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Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296

Hydrogen-bonded sheet structures in methyl 4-(4-chloro­anilino)-3-nitro­benzoate and methyl 1-benzyl-2-(4-chloro­phen­yl)-1H-benzimidazole-5-carboxyl­ate

aDepartamento de Química, Universidad de Valle, AA 25360 Cali, Colombia, bDepartamento de Química Inorgánica y Orgánica, Universidad de Jaén, 23071 Jaén, Spain, and cSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 3 December 2012; accepted 3 December 2012; online 13 December 2012)

In methyl 4-(4-chloro­anilino)-3-nitro­benzoate, C14H11ClN2O4, (I), there is an intra­molecular N—H⋯O hydrogen bond and the intra­molecular distances provide evidence for electronic polarization of the o-quinonoid type. The mol­ecules are linked into sheets built from N—H⋯O, C—H⋯O and C—H⋯π(arene) hydrogen bonds, together with an aromatic ππ stacking inter­action. The mol­ecules of methyl 1-benzyl-2-(4-chloro­phenyl)-1H-benzimidazole-5-carboxyl­ate, C22H17ClN2O2, (II), are also linked into sheets, this time by a combination of C—H⋯π(arene) hydrogen bonds and aromatic ππ stacking inter­actions.

Comment

We report here the mol­ecular structures and the supra­molecular assembly of the two title compounds, (I)[link] (Fig. 1[link]) and (II)[link] (Fig. 2[link]). Benzimidazoles are compounds of wide inter­est because of their diverse biological activities and clinical applications (Ansari & Lal, 2009[Ansari, K. F. & Lal, C. (2009). Eur. J. Med. Chem. 44, 4028-4033.]). They are regarded as a promising class of bioactive heterocyclic compounds, exhibiting a wide range of biological properties such as anti­fungal, anti­parasitic and anti­viral activity. They are also active as analgesics, anti­coagulants, anti­convulsants, anti­histamines and anti-inflammatory agents, and they show anti­cancer, anti­hypertensive and anti-ulcer activity, as well as acting as proton-pump inhibitors (Bansal & Silakari, 2012[Bansal, Y. & Silakari, O. (2012). Bioorg. Med. Chem. 20, 6208-6236.]). Consequently, substituted benzimidazoles have attracted inter­est, especially since it has been reported that the influence of the substitution at the 1-, 2- and 5-positions of the benzimidazole framework is important for their pharmacological effects (Kılcıgil & Altanlar, 2006[Kılcıgil, G. A. & Altanlar, N. (2006). Turk. J. Chem. 30, 223-228.]). We have recently reported the design of a four-step synthesis of novel 1,2,5-tri­substituted benzimidazoles bearing the 4-chloro­phenyl or quinolin-2-one pharmacophores at position 2, which exhibit high activity against a range of cancer cell lines (Abonía et al., 2011[Abonía, R., Cortés, E., Insuasty, B., Quiroga, J., Nogueras, M. & Cobo, J. (2011). Eur. J. Med. Chem. 46, 4062-4070.]). As part of our current synthetic programme aimed at the development of potential anti­tumour agents, we have now prepared the benzimidazole derivative, (II),[link] using a two-step synthesis involving the in situ reduction of the nitro­aniline precursor, (I)[link], followed by cyclo­condensation with 4-chloro­benz­al­de­hyde.

[Scheme 1]

Within the mol­ecule of (I)[link], the plane of the nitro group makes a dihedral angle of only 9.4 (2)° with that of the adjacent aryl ring, and this may be associated with the presence of an intra­molecular N—H⋯O hydrogen bond (Fig. 1[link] and Table 2[link]) which gives rise to an S(6) motif (Bernstein et al., 1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]). On the other hand, the two rings within the mol­ecule make a dihedral angle of 49.8 (2)°.

The bond lengths in the mol­ecule of (I)[link] provide evidence for polarization of the electronic structure. Thus, the C12—C13 and C15—C16 bond lengths are significantly shorter than the other C—C bond lengths in the C11–C16 ring (Table 1[link]); the C13—N31 bond is short for its type [mean value (Allen et al., 1987[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-S19.]) = 1.468 Å, lower quartile value = 1.460 Å], while the C14—N41 bond is significantly shorter than the N41—C41 bond; and the N31—O31 and N31—O32 bonds are both long for their type (mean value = 1.217 Å, upper quartile value = 1.225 Å). These observations, taken as a whole, indicate that the polarized form, (Ia)[link] (see Scheme[link]), makes a significant contribution to the overall electronic structure, alongside the classically delocalized form, (I)[link]. Polarization of this type has been observed previously both in simple 2-nitro­anilines containing unsubstituted amino groups (Cannon et al., 2001[Cannon, D., Glidewell, C., Low, J. N., Quesada, A. & Wardell, J. L. (2001). Acta Cryst. C57, 216-221.]; Glidewell et al., 2001[Glidewell, C., Cannon, D., Quesada, A., Low, J. N., McWilliam, S. A., Skakle, J. M. S. & Wardell, J. L. (2001). Acta Cryst. C57, 455-458.]) and in N-(2-nitro­phenyl)aniline (McWilliam et al., 2001[McWilliam, S. A., Skakle, J. M. S., Wardell, J. L., Low, J. N. & Glidewell, C. (2001). Acta Cryst. C57, 946-948.]).

As noted above, the mol­ecules of (I)[link] contain an intra­molecular N—H⋯O hydrogen bond. In addition, the mol­ecules are linked by a combination of inter­molecular N—H⋯O, C—H⋯O and C—H⋯π(arene) hydrogen bonds (Table 2[link]), augmented by an aromatic ππ stacking inter­action. The resulting rather complex sheet structure can be readily analysed in terms of two one-dimensional substructures (Ferguson et al., 1998a[Ferguson, G., Glidewell, C., Gregson, R. M. & Meehan, P. R. (1998a). Acta Cryst. B54, 129-138.],b[Ferguson, G., Glidewell, C., Gregson, R. M. & Meehan, P. R. (1998b). Acta Cryst. B54, 139-150.]; Gregson et al., 2000[Gregson, R. M., Glidewell, C., Ferguson, G. & Lough, A. J. (2000). Acta Cryst. B56, 39-57.]).

The first substructure is built from a combination of N—H⋯O and C—H⋯O hydrogen bonds, which link mol­ecules related by inversion to form a chain of rings running parallel to the [010] direction. Pairs of inversion-related N—H⋯O hydrogen bonds generate R22(4) rings centred at ([{1 \over 2}]n[{1 \over 2}]), where n represents an integer, and pairs of inversion-related C—H⋯O hydrogen bonds generate R22(10) rings centred at ([{1 \over 2}]n + [{1 \over 2}][{1 \over 2}]), where n again represents an integer (Fig. 3[link]).

The second substructure in (I)[link] is built from the combination of a C—H⋯π(arene) hydrogen bond and an aromatic ππ stacking inter­action. Aryl atom C46 in the mol­ecule at (x, y, z) acts as hydrogen-bond donor to the C41–C46 aryl ring in the mol­ecule at (x, −y + [{1\over 2}], z − [{1\over 2}]), so linking mol­ecules related by the c-glide plane at y = [{1 \over 4}] into a chain running parallel to the [001] direction (Fig. 4[link]). In addition, the plane of the tri­substituted C11–C16 ring in the mol­ecule at (x, y, z) makes a dihedral angle of only 2.0 (2)° with the planes of the corresponding rings of the two mol­ecules at (x, −y + [{1\over 2}], z − [{1\over 2}]) and (x, −y + [{1\over 2}], z + [{1\over 2}]). The shortest ring-centroid separation is 3.722 (2) Å and the shortest perpendicular distance between the ring planes is ca 3.34 Å, corresponding to a ring-centroid offset of ca 1.64 Å. The effect of this stacking inter­action is to reinforce the chain formation along [001] generated by the C—H⋯π(arene) hydrogen bond (Fig. 4[link]). The combination of the [010] and [001] chains generates a complex sheet lying parallel to (100).

The crystal structure of (I)[link] also contains a rather short inter­molecular Cl⋯O contact of 2.924 (3) Å between atom Cl44 in the mol­ecule at (x, y, z) and atom O31 in the mol­ecule at (x + 1, y + 1, z + 1). This contact distance is certainly shorter than the sum of the van der Waals radii (3.2 Å; Bondi, 1964[Bondi, A. (1964). J. Phys. Chem. 68, 441-451.]), but it is unclear whether the contact is attractive, or, as seems more likely, repulsive.

In the mol­ecule of (II)[link] (Fig. 2[link]), the bond lengths within the fused bicyclic system (Table 3[link]) indicate strong bond fixation in the imidazole portion, with typical aromatic delocalization in the carbocyclic ring. The plane of the chlorinated aryl ring makes a dihedral angle of 50.2 (2)° with that of the adjacent imidazole ring, while the benzyl ring plane is almost orthogonal to that of the imidazole ring, with a dihedral angle of 81.7 (2)°.

The supra­molecular assembly in (II)[link] depends on the combination of a C—H⋯π(arene) hydrogen bond (Table 4[link]) and an aromatic ππ stacking inter­action, both of which involve the fused aryl ring. In the π-stacking inter­action, the fused rings of the mol­ecules at (x, y, z) and (−x + 1, −y + 1, −z + 1), which are strictly parallel, have an inter­planar spacing of 3.481 (2) Å and a ring-centroid separation of 3.568 (2) Å, corresponding to a ring-centroid offset of ca 0.78 Å (Fig. 5[link]). The C—H⋯π(arene) hydrogen bond links mol­ecules related by the 21 screw axis along (0, [{3 \over 4}], z) to form a chain running parallel to the [001] direction (Fig. 6[link]).

The combination of these two inter­actions generates a sheet structure in which, for example, the reference π-stacked dimer centred at ([{1 \over 2}][{1 \over 2}][{1 \over 2}]) is directly linked by C—H⋯π(arene) hydrogen bonds to the four symmetry-related dimers centred at ([{1 \over 2}], 0, 0), ([{1 \over 2}], 1, 0), ([{1 \over 2}], 0, 1) and ([{1 \over 2}], 1, 1), so forming a sheet lying parallel to (100) (Fig. 7[link]).

The details of the supra­molecular assembly in (I)[link] and (II)[link] provide some inter­esting comparisons. In each compound, the supra­molecular assembly leads to the formation of a sheet parallel to (100) in the space group P21/c, and in both compounds it is the ring carrying the ester function which participates in the ππ stacking inter­action. However, the acceptor in the C—H⋯π(arene) hydrogen bond is the chlorinated aryl ring in (I)[link] but the fused aryl ring in (II)[link], while the donor in this inter­action forms part of the chlorinated aryl ring in (I)[link] as opposed to the benzyl ring in (II)[link]. Finally, the ester function participates in the assembly in (I)[link], where the ester carbonyl O atom acts as the acceptor in the C—H⋯O hydrogen bond, while in (II)[link] the ester function plays no part in the supra­molecular assembly.

[Figure 1]
Figure 1
The mol­ecular structure of (I)[link], showing the atom-labelling scheme and the intra­molecular N—H⋯O hydrogen bond (dashed line). Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2]
Figure 2
The mol­ecular structure of (II)[link], showing the atom-labelling scheme Displacement ellipsoids are drawn at the 30% probability level.
[Figure 3]
Figure 3
A stereoview of part of the crystal structure of (I)[link], showing the formation of a chain of alternating R22(4) and R22(10) rings running parallel to the [010] direction. For the sake of clarity, H atoms not involved in the motifs shown have been omitted.
[Figure 4]
Figure 4
A stereoview of part of the crystal structure of (I)[link], showing the formation of a chain running parallel to the [001] direction and built from C—H⋯π(arene) hydrogen bonds augmented by aromatic ππ stacking inter­actions. For the sake of clarity, H atoms not involved in the motifs shown have been omitted.
[Figure 5]
Figure 5
Part of the crystal structure of (II)[link], showing the formation of a π-stacked dimer centred at ([{1 \over 2}][{1 \over 2}][{1 \over 2}]). For the sake of clarity, all H atoms have been omitted. The atom marked with an asterisk (*) is at the symmetry position (−x + 1, −y + 1, −z + 1).
[Figure 6]
Figure 6
A stereoview of part of the crystal structure of (II)[link], showing the formation of a chain running parallel to the [001] direction and built from C—H⋯π(arene) hydrogen bonds. For the sake of clarity, H atoms not involved in the motif shown have been omitted.
[Figure 7]
Figure 7
A stereoview of part of the crystal structure of (II)[link], showing the formation of a sheet lying parallel to (100). For the sake of clarity, H atoms not involved in the motifs shown have been omitted.

Experimental

For the synthesis of (I)[link], a mixture of methyl 4-fluoro-3-nitro­benzoate (0.199 g, 1 mmol) and 4-chloro­aniline (1 mmol) in dimethyl ­sulfoxide (2 ml) was stirred at ambient temperature for 2 h. After complete disappearance of the starting materials [as monitored by thin-layer chromatography (TLC)], the solid thus formed was collected by filtration and washed with a methanol–water mixture (1:2 v/v; 3 × 2 ml) to afford (I)[link] (yield 84%; orange crystals, m.p. 421 K). FT–IR (KBr, ν, cm−1): 3312 (NH), 1770 (C=O), 1718 (C=C), 1622 (C=N), 1524, 1324 (NO2). MS (70 eV) m/z (%): 308/306 (100/34) [M+], 277/275 (15/5) [M − OCH3], 243/241 (29/9), 230/228 (38/13), 201 (30), 111 (3).

For the synthesis of (II)[link], a mixture of inter­mediate (A)[link] (see Scheme[link]) (0.306 g, 1 mmol), which had been prepared in a manner analogous to that for (I)[link] but using benzyl­amine in place of 4-choloro­aniline, acetic acid (2 ml) and zinc powder (5 equivalents) was stirred at ambient temperature for 15 min. After complete disappearance of starting compound (I)[link] (as monitored by TLC), the by-product zinc acetate and excess zinc were removed by filtration. The resulting solution was then heated with 4-chloro­benz­aldehyde (1.05 mmol) at 373 K for 1 h. After complete disappearance of the starting materials (as monitored by TLC), the solution was allowed to cool to ambient temperature and the excess of acetic acid was removed under reduced pressure. The solid product was washed with ethanol (2 × 1 ml) to afford (II)[link] (yield 88%; colourless crystals, m.p. 437 K). FT–IR (KBr, ν, cm−1): 3028, 2951, 1719 (C=O), 1612 (C=C), 1521 (C=N), 1438, 1287 (C—O). MS (70 eV) m/z (%): 378/376 (3/12) [M+], 345 (1) [M − 28], 137 (3), 91 (28).

Crystals of (I)[link] and (II)[link] suitable for single-crystal X-ray diffraction were grown by slow evaporation, at ambient temperature and in air, from solutions in ethanol.

Compound (I)[link]

Crystal data
  • C14H11ClN2O4

  • Mr = 306.70

  • Monoclinic, P 21 /c

  • a = 12.4413 (10) Å

  • b = 15.8116 (18) Å

  • c = 7.1805 (10) Å

  • β = 103.037 (9)°

  • V = 1376.1 (3) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.30 mm−1

  • T = 120 K

  • 0.32 × 0.16 × 0.08 mm

Data collection
  • Bruker–Nonius KappaCCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. University of Göttingen, Germany.]) Tmin = 0.912, Tmax = 0.977

  • 20301 measured reflections

  • 2572 independent reflections

  • 1600 reflections with I > 2σ(I)

  • Rint = 0.111

Refinement
  • R[F2 > 2σ(F2)] = 0.059

  • wR(F2) = 0.163

  • S = 1.04

  • 2572 reflections

  • 191 parameters

  • H-atom parameters constrained

  • Δρmax = 0.37 e Å−3

  • Δρmin = −0.35 e Å−3

Table 1
Selected geometric parameters (Å, °) for (I)[link]

C11—C121.380 (5)
C12—C131.397 (5)
C13—C141.418 (5)
C14—C151.426 (5)
C15—C161.366 (5)
C16—C111.412 (5)
C13—N311.447 (4)
N31—O311.231 (4)
N31—O321.242 (4)
C14—N411.364 (4)
N41—C411.420 (4)
C11—C1—O2—C2178.9 (3)
O1—C1—C11—C12167.0 (4)
O2—C1—C11—C12−13.9 (5)
C12—C13—N31—O318.9 (5)
C12—C13—N31—O32−171.0 (3)
C13—C14—N41—C41174.9 (3)
C14—N41—C41—C42135.8 (4)

Table 2
Hydrogen-bond geometry (Å, °) for (I)[link]

Cg1 represents the centroid of the C41–C46 ring.

D—H⋯AD—HH⋯ADAD—H⋯A
N41—H41⋯O320.881.932.617 (4)133
N41—H41⋯O32i0.882.373.158 (4)149
C16—H16⋯O1ii0.952.493.302 (4)144
C46—H46⋯Cg1iii0.952.723.560 (4)147
Symmetry codes: (i) -x+1, -y, -z+1; (ii) -x+1, -y+1, -z+1; (iii) [x, -y+{\script{1\over 2}}], [z-{\script{1\over 2}}].

Compound (II)[link]

Crystal data
  • C22H17ClN2O2

  • Mr = 376.83

  • Monoclinic, P 21 /c

  • a = 14.214 (2) Å

  • b = 11.7391 (10) Å

  • c = 11.0580 (14) Å

  • β = 98.908 (10)°

  • V = 1822.9 (4) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.23 mm−1

  • T = 120 K

  • 0.31 × 0.28 × 0.20 mm

Data collection
  • Bruker–Nonius KappaCCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. University of Göttingen, Germany.]) Tmin = 0.932, Tmax = 0.956

  • 24459 measured reflections

  • 4183 independent reflections

  • 3040 reflections with I > 2σ(I)

  • Rint = 0.065

Refinement
  • R[F2 > 2σ(F2)] = 0.046

  • wR(F2) = 0.117

  • S = 1.05

  • 4183 reflections

  • 245 parameters

  • H-atom parameters constrained

  • Δρmax = 0.32 e Å−3

  • Δρmin = −0.43 e Å−3

Table 3
Selected geometric parameters (Å, °) for (II)[link]

N1—C21.381 (2)
C2—N31.322 (2)
N3—C3a1.392 (2)
C3a—C41.394 (3)
C4—C51.393 (3)
C5—C61.417 (3)
C6—C71.383 (3)
C7—C7a1.399 (3)
C7a—N11.383 (2)
C3a—C7a1.406 (2)
C2—N1—C17—C11−115.9 (2)
N1—C17—C11—C1221.2 (3)
N1—C2—C21—C2251.5 (3)
C4—C5—C51—O51−8.5 (3)
C4—C5—C51—O52171.38 (17)
C5—C51—O52—C52179.72 (16)

Table 4
Hydrogen-bond geometry (Å, °) for (II)[link]

Cg2 represents the centroid of the C3a/C4–C7/C7a ring.

D—H⋯AD—HH⋯ADAD—H⋯A
C16—H16⋯Cg2i0.952.523.388 (2)153
Symmetry code: (i) [x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}].

All H atoms were located in difference maps and subsequently treated as riding in geometrically idealized positions, with C—H = 0.95 (aromatic), 0.98 (CH3) or 0.99 Å (CH2) and N—H = 0.88 Å, and with Uiso(H) = kUeq(carrier), where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and 1.2 for all other H atoms.

For both compounds, data collection: COLLECT (Nonius, 1999[Nonius (1999). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000[Duisenberg, A. J. M., Hooft, R. W. W., Schreurs, A. M. M. & Kroon, J. (2000). J. Appl. Cryst. 33, 893-898.]); data reduction: EVALCCD (Duisenberg et al., 2003[Duisenberg, A. J. M., Kroon-Batenburg, L. M. J. & Schreurs, A. M. M. (2003). J. Appl. Cryst. 36, 220-229.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: SHELXL97 and PLATON.

Supporting information


Comment top

We report here the molecular structures and the supramolecular assembly of the two title compounds, (I) (Fig. 1) and (II) (Fig. 2). Benzimidazoles are compounds of wide interest because of their diverse biological activities and clinical applications (Ansari & Lal, 2009). They are regarded as a promising class of bioactive heterocyclic compounds, exhibiting a wide range of biological properties such as antifungal, antiparasitic and antiviral activity. They are also active as analgesics, anticoagulants, anticonvulsants, antihistamines and anti-inflammatory agents, and they show anticancer, antihypertensive and anti-ulcer activity, as well as acting as proton-pump inhibitors (Bansal & Silakari, 2012). Consequently, substituted benzimidazoles have attracted interest, especially since it has been reported that the influence of the substitution at the 1-, 2- and 5-positions of the benzimidazole framework is important for their pharmacological effects (Kılcıgil & Altanlar, 2006). We have recently reported the design of a four-step synthesis of novel 1,2,5-trisubstituted benzimidazoles bearing the 4-chlorophenyl or quinolin-2-one pharmacophores at position 2, which exhibit high activity against a range of cancer cell lines (Abonía et al., 2011). As part of our current synthetic programme aimed at the development of potential antitumour agents, we have now prepared the benzimidazole derivative (II) using a two-step synthesis involving the in situ reduction of the nitroaniline precursor, (I), followed by cyclocondensation with 4-chlorobenzaldehyde

Within the molecule of (I), the nitro group makes a dihedral angle of only 9.4 (2)° with the adjacent aryl ring, and this may be associated with the presence of an intramolecular N—H···O hydrogen bond (Fig. 1, Table 2) which gives rise to an S(6) motif (Bernstein et al., 1995). On the other hand, the two rings within the molecule make a dihedral angle of 49.8 (2)°.

The bond distances in the molecule of (I) provide evidence for polarization of the electronic structure. Thus, the distances C12—C13 and C15—C16 are significantly shorter than the other C—C distances in the C11–C16 ring (Table 1); the bond C13—N31 is short for its type [mean value (Allen et al., 1987) = 1.468 Å, lower quartile value = 1.460 Å], while the C14—N41 bond is significantly shorter than the N41—C41 bond; and the N31—O31 and N31—O32 bonds are both long for their type (mean value = 1.217 Å, upper quartile value = 1.225 Å). These observations, taken as a whole, indicate that the polarized form, (Ia) (see scheme), makes a significant contribution to the overall electronic structure, alongside the classically delocalized form, (I). Polarization of this type has been observed previously in both simple 2-nitroanilines containing unsubstituted amino groups (Cannon et al., 2001; Glidewell et al., 2001) and N-(2-nitrophenyl)phenylamine (McWilliam et al., 2001).

As noted above, the molecules of (I) contain an intramolecular N—H···O hydrogen bond. In addition, the molecules are linked by a combination of intermolecular N—H···O, C—H···O and C—H···π(arene) hydrogen bonds (Table 2), augmented by an aromatic ππ stacking interaction. The resulting rather complex sheet structure can be readily analysed in terms of two one-dimensional substructures (Ferguson et al., 1998a,b; Gregson et al., 2000).

The first substructure is built from a combination of N—H···O and C—H···O hydrogen bonds, which link molecules related by inversion to form a chain of rings running parallel to the [010] direction. Pairs of inversion-related N—H···O hydrogen bonds generate R22(4) rings centred at (1/2, n, 1/2), where n represents an integer, and pairs of inversion-related C—H···O hydrogen bonds generate R22(10) rings centred at (1/2, n + 1/2, 1/2), where n again represents an integer (Fig. 3).

The second substructure in (I) is built from the combination of a C—H···π(Arene) hydrogen bond and an aromatic ππ stacking interaction. Aryl atom C46 in the molecule at (x, y, z) acts as hydrogen-bond donor to the C41–C46 aryl ring in the molecule at (x, -y + 1/2, z - 1/2), so linking molecules related by the c-glide plane at y = 1/4 into a chain running parallel to the [001] direction (Fig. 4). In addition, the trisubstituted C11–C16 ring in the molecule at (x, y, z) makes a dihedral angle of only 2.0 (2)° with the corresponding rings of the two molecules at (x, -y + 1/2, z - 1/2) and (x, -y + 1/2, z + 1/2). The shortest ring-centroid separation is 3.722 (2) Å and the shortest perpendicular distance between the ring planes is ca 3.34 Å, corresponding to a ring-centroid offset of ca 1.64 Å. The effect of this stacking interaction is to reinforce the chain formation along [001] generated by the C—H···π(arene) hydrogen bond (Fig. 4). The combination of the [010] and [001] chains generates a complex sheet lying parallel to (100).

The crystal structure of (I) also contains a rather short intermolecular Cl···O contact of 2.924 (3) Å between atom Cl44 in the molecule at (x, y, z) and atom O31 in the molecule at (x + 1, y + 1, z + 1). This contact distance is certainly shorter than the sum of the van der Waals radii (3.2 Å; Bondi, 1964), but it is unclear whether this contact is attractive, or, as seems more likely, repulsive.

In the molecule of (II) (Fig. 2), the bond distances within the fused bicyclic system (Table 3) indicate strong bond fixation in the imidazole portion, with typical aromatic delocalization in the carbocyclic ring. The chlorinated aryl ring makes a dihedral angle of 50.2 (2)° with the adjacent imidazole ring, while the benzyl ring is almost orthogonal to the imidazole ring, with a dihedral angle of 81.7 (2)°.

The supramolecular assembly in (II) depends on the combination of a C—H···π(arene) hydrogen bond (Table 4) and an aromatic ππ stacking interaction, both of which involve the fused aryl ring. In the π-stacking interaction, the fused rings of the molecules at (x, y, z) and (-x + 1, -y + 1, -z + 1), which are strictly parallel, have an interplanar spacing of 3.481 (2) Å, with a ring-centroid separation of 3.568 (2) Å corresponding to a ring-centroid offset of ca 0.78 Å (Fig 5). The C—H···π(arene) hydrogen bond links molecules related by the 21 screw axis along (0, 3/4, z) to form a chain running parallel to the [001] direction (Fig. 6).

The combination of these two interactions generates a sheet structure in which, for example, the reference π-stacked dimer centred at (1/2, 1/2, 1/2) is directly linked by C—H···π(arene) hydrogen bonds to the four symmetry-related dimers centred at (1/2, 0, 0), (1/2, 1, 0), (1/2, 0, 1) and (1/2, 1, 1), so forming a sheet lying parallel to (100) (Fig. 7).

The details of the supramolecular assembly in (I) and (II) provide some interesting comparisons. In each compound, the supramolecular assembly leads to the formation of a sheet parallel to (100) in space group P21/c, and in both compounds it is the ring carrying the ester function which participates in the ππ stacking interaction. However, the acceptor in the C—H···π(arene) hydrogen bond is the chlorinated aryl ring in (I) but the fused aryl ring in (II), while the donor in this interaction forms part of the chlorinated aryl ring in (I) as opposed to the benzyl ring in (II). Finally, the ester function participates in the assembly in (I), where the ester carbonyl O atom acts as the acceptor in the C—H···O hydrogen bond, while in (II) the ester function plays no part in the supramolecular assembly.

Related literature top

For related literature, see: Abonía et al. (2011); Allen et al. (1987); Ansari & Lal (2009); Bansal & Silakari (2012); Bernstein et al. (1995); Bondi (1964); Cannon et al. (2001); Ferguson et al. (1998a, 1998b); Glidewell et al. (2001); Gregson et al. (2000); Kılcıgil & Altanlar (2006); McWilliam et al. (2001).

Experimental top

For the synthesis of (I), a mixture of methyl 4-fluoro-3-nitrobenzoate (0.199 g, 1 mmol) and 4-chloroaniline (1 mmol) in dimethylsulfoxide (2 ml) was stirred at ambient temperature for 2 h. After complete disappearance of the starting materials [as monitored by thin-layer chromatography (TLC)], the solid thus formed was collected by filtration and washed with a methanol–water mixture (1:2 v/v; 3 × 2 ml), to afford (I) (yield 84%; orange crystals, m.p. 421 K). Spectroscopic analysis: FT–IR (KBr, ν, cm-1): 3312 (NH), 1770 (CO), 1718 (CC), 1622 (CN), 1524, 1324 (NO2). MS (70 eV) m/z (%): 308/306 (100/34) [M+], 277/275 (15/5) [M - OCH3], 243/241 (29/9), 230/228 (38/13), 201 (30), 111 (3).

For the synthesis of (II), a mixture of the intermediate (A) (see scheme) (0.306 g, 1 mmol), which had been prepared in a manner analogous to that for (I) but using benzylamine in place of 4-choloroaniline, acetic acid (2 ml) and zinc powder (5 equivalents) was stirred at ambient temperature for 15 min. After complete disappearance of the starting compound, (I) (as monitored by TLC), the by-product zinc acetate and excess zinc were removed by filtration. The resulting solution was then heated with 4-chlorobenzaldehyde (1.05 mmol) at 373 K for 1 h. After complete disappearance of the starting materials (as monitored by TLC), the solution was allowed to cool to ambient temperature and the excess of acetic acid was removed under reduced pressure. The solid product was washed with ethanol (2 × 1 ml) to afford (II) (yield 88%; colourless crystals, m.p. 437 K). Spectroscopic analysis: FT–IR (KBr, ν, cm-1): 3028, 2951, 1719 (CO), 1612 (CC), 1521 (CN), 1438, 1287 (C—O). MS (70 eV) m/z (%): 378/376 (3/12) [M+], 345 (1) [M - 28], 137 (3), 91 (28).

Crystals of (I) and (II) suitable for single-crystal X-ray diffraction were grown by slow evaporation, at ambient temperature and in air, from solutions in ethanol.

Refinement top

All H atoms were located in difference maps and subsequently treated as riding atoms in geometrically idealized positions, with C—H = 0.95 (aromatic), 0.98 (CH3) or 0.99 Å (CH2) and N—H = 0.88 Å, and with Uiso(H) = kUeq(carrier), where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and 1.2 for all other H atoms.

Computing details top

For both compounds, data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
Fig. 1. The molecular structure of (I), showing the atom-labelling scheme and the intramolecular N—H···O hydrogen bond (dashed line). Displacement ellipsoids are drawn at the 30% probability level.

Fig. 2. The molecular structure of (II), showing the atom-labelling scheme Displacement ellipsoids are drawn at the 30% probability level.

Fig. 3. A stereoview of part of the crystal structure of (I), showing the formation of a chain of alternating R22(4) and R22(10) rings running parallel to the [010] direction. For the sake of clarity, H atoms not involved in the motifs shown have been omitted.

Fig. 4. A stereoview of part of the crystal structure of (I), showing the formation of a chain running parallel to the [001] direction and built from C—H···π(arene) hydrogen bonds augmented by aromatic ππ stacking interactions. For the sake of clarity, H atoms not involved in the motifs shown have been omitted.

Fig. 5. Part of the crystal structure of (II), showing the formation of a π-stacked dimer centred at (1/2, 1/2, 1/2). For the sake of clarity, all H atoms have been omitted. The atom marked with an asterisk (*) is at the symmetry position (-x + 1, -y + 1, -z + 1).

Fig. 6. A stereoview of part of the crystal structure of (II), showing the formation of a chain running parallel to the [001] direction and built from C—H···π(arene) hydrogen bonds. For the sake of clarity, H atoms not involved in the motif shown have been omitted.

Fig. 7. A stereoview of part of the crystal structure of (II), showing the formation of a sheet lying parallel to (100). For the sake of clarity, H atoms not involved in the motifs shown have been omitted.
(I) Methyl 4-(4-chloroanilino)-3-nitrobenzoate top
Crystal data top
C14H11ClN2O4F(000) = 632
Mr = 306.70Dx = 1.480 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3170 reflections
a = 12.4413 (10) Åθ = 3.1–27.5°
b = 15.8116 (18) ŵ = 0.30 mm1
c = 7.1805 (10) ÅT = 120 K
β = 103.037 (9)°Plate, orange
V = 1376.1 (3) Å30.32 × 0.16 × 0.08 mm
Z = 4
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
2572 independent reflections
Radiation source: Bruker–Nonius FR591 rotating anode1600 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.111
Detector resolution: 9.091 pixels mm-1θmax = 25.6°, θmin = 3.1°
ϕ and ω scansh = 1515
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1919
Tmin = 0.912, Tmax = 0.977l = 88
20301 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.059Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.163H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0792P)2 + 1.1147P]
where P = (Fo2 + 2Fc2)/3
2572 reflections(Δ/σ)max = 0.001
191 parametersΔρmax = 0.37 e Å3
0 restraintsΔρmin = 0.35 e Å3
Crystal data top
C14H11ClN2O4V = 1376.1 (3) Å3
Mr = 306.70Z = 4
Monoclinic, P21/cMo Kα radiation
a = 12.4413 (10) ŵ = 0.30 mm1
b = 15.8116 (18) ÅT = 120 K
c = 7.1805 (10) Å0.32 × 0.16 × 0.08 mm
β = 103.037 (9)°
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
2572 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
1600 reflections with I > 2σ(I)
Tmin = 0.912, Tmax = 0.977Rint = 0.111
20301 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0590 restraints
wR(F2) = 0.163H-atom parameters constrained
S = 1.04Δρmax = 0.37 e Å3
2572 reflectionsΔρmin = 0.35 e Å3
191 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.3117 (3)0.4227 (2)0.2714 (5)0.0278 (8)
O10.3299 (2)0.49519 (15)0.3259 (4)0.0347 (7)
O20.22506 (19)0.39896 (15)0.1329 (3)0.0303 (6)
C20.1486 (3)0.4650 (2)0.0504 (6)0.0367 (10)
H2A0.10740.48370.14440.055*
H2B0.09700.44310.06320.055*
H2C0.18950.51290.01410.055*
C110.3824 (3)0.3493 (2)0.3463 (5)0.0238 (8)
C120.3467 (3)0.2672 (2)0.3069 (5)0.0252 (8)
H120.27530.25680.22980.030*
C130.4153 (3)0.1993 (2)0.3798 (5)0.0225 (8)
C140.5244 (3)0.2110 (2)0.4889 (5)0.0235 (8)
C150.5571 (3)0.2966 (2)0.5303 (5)0.0238 (8)
H150.62840.30800.60720.029*
C160.4887 (3)0.3627 (2)0.4624 (5)0.0245 (8)
H160.51330.41880.49390.029*
N310.3685 (2)0.11608 (18)0.3335 (4)0.0259 (7)
O310.2797 (2)0.10904 (15)0.2170 (4)0.0323 (6)
O320.41931 (19)0.05350 (15)0.4133 (4)0.0343 (7)
N410.5935 (2)0.14530 (18)0.5553 (4)0.0250 (7)
H410.56450.09440.53510.030*
C410.7062 (3)0.1486 (2)0.6529 (5)0.0236 (8)
C420.7405 (3)0.0972 (2)0.8112 (5)0.0246 (8)
H420.68810.06350.85530.029*
C430.8501 (3)0.0945 (2)0.9056 (5)0.0274 (8)
H430.87320.05891.01370.033*
C440.9259 (3)0.1438 (2)0.8419 (5)0.0271 (8)
Cl441.06412 (7)0.14155 (6)0.96463 (14)0.0371 (3)
C450.8938 (3)0.1960 (2)0.6835 (5)0.0289 (9)
H450.94660.23000.64130.035*
C460.7837 (3)0.1978 (2)0.5876 (5)0.0280 (8)
H460.76090.23230.47750.034*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.029 (2)0.025 (2)0.030 (2)0.0033 (16)0.0075 (16)0.0026 (16)
O10.0418 (17)0.0223 (14)0.0385 (16)0.0026 (12)0.0057 (12)0.0007 (12)
O20.0268 (13)0.0261 (14)0.0360 (15)0.0050 (11)0.0027 (11)0.0025 (11)
C20.032 (2)0.032 (2)0.042 (2)0.0094 (18)0.0003 (18)0.0092 (18)
C110.0295 (19)0.0183 (18)0.0257 (19)0.0031 (15)0.0107 (15)0.0004 (14)
C120.0232 (18)0.030 (2)0.0229 (19)0.0002 (16)0.0055 (15)0.0001 (15)
C130.0185 (17)0.0260 (19)0.0223 (18)0.0004 (15)0.0032 (14)0.0016 (15)
C140.0236 (18)0.0241 (19)0.0234 (19)0.0011 (15)0.0070 (14)0.0009 (15)
C150.0218 (18)0.0257 (19)0.0246 (19)0.0033 (15)0.0070 (15)0.0023 (15)
C160.0274 (18)0.0187 (17)0.0286 (19)0.0022 (15)0.0087 (15)0.0000 (15)
N310.0249 (16)0.0231 (16)0.0289 (17)0.0007 (13)0.0040 (13)0.0018 (13)
O310.0258 (14)0.0272 (14)0.0379 (15)0.0013 (11)0.0052 (12)0.0001 (11)
O320.0287 (14)0.0186 (13)0.0500 (17)0.0010 (11)0.0030 (12)0.0048 (12)
N410.0240 (15)0.0180 (15)0.0307 (17)0.0003 (13)0.0013 (12)0.0028 (12)
C410.0191 (17)0.0212 (18)0.0292 (19)0.0006 (15)0.0025 (14)0.0003 (15)
C420.0275 (18)0.0182 (18)0.029 (2)0.0026 (15)0.0078 (15)0.0004 (15)
C430.0288 (19)0.0221 (19)0.029 (2)0.0062 (16)0.0012 (16)0.0003 (15)
C440.0218 (18)0.0251 (19)0.031 (2)0.0035 (16)0.0004 (15)0.0069 (16)
Cl440.0222 (5)0.0411 (6)0.0439 (6)0.0045 (4)0.0013 (4)0.0023 (5)
C450.0264 (19)0.026 (2)0.035 (2)0.0026 (16)0.0100 (16)0.0005 (16)
C460.0268 (19)0.028 (2)0.027 (2)0.0013 (16)0.0028 (15)0.0028 (16)
Geometric parameters (Å, º) top
C1—O11.216 (4)N31—O321.242 (4)
C1—O21.344 (4)C14—N411.364 (4)
C1—C111.482 (5)N41—C411.420 (4)
O2—C21.446 (4)N41—H410.8800
C2—H2A0.9800C16—H160.9500
C2—H2B0.9800C41—C421.384 (5)
C2—H2C0.9800C41—C461.399 (5)
C11—C121.380 (5)C42—C431.380 (5)
C12—C131.397 (5)C42—H420.9500
C12—H120.9500C43—C441.379 (5)
C13—C141.418 (5)C43—H430.9500
C14—C151.426 (5)C44—C451.389 (5)
C15—C161.366 (5)C44—Cl441.747 (3)
C15—H150.9500C45—C461.388 (5)
C16—C111.412 (5)C45—H450.9500
C13—N311.447 (4)C46—H460.9500
N31—O311.231 (4)
O1—C1—O2124.1 (3)C15—C16—H16119.3
O1—C1—C11124.7 (3)C11—C16—H16119.3
O2—C1—C11111.2 (3)O31—N31—O32121.8 (3)
C1—O2—C2116.4 (3)O31—N31—C13119.4 (3)
O2—C2—H2A109.5O32—N31—C13118.8 (3)
O2—C2—H2B109.5C14—N41—C41128.2 (3)
H2A—C2—H2B109.5C14—N41—H41115.9
O2—C2—H2C109.5C41—N41—H41115.9
H2A—C2—H2C109.5C42—C41—C46119.6 (3)
H2B—C2—H2C109.5C42—C41—N41118.1 (3)
C12—C11—C16118.5 (3)C46—C41—N41122.2 (3)
C12—C11—C1121.7 (3)C43—C42—C41120.6 (3)
C16—C11—C1119.8 (3)C43—C42—H42119.7
C11—C12—C13120.3 (3)C41—C42—H42119.7
C11—C12—H12119.8C44—C43—C42119.6 (3)
C13—C12—H12119.8C44—C43—H43120.2
C12—C13—C14122.3 (3)C42—C43—H43120.2
C12—C13—N31115.6 (3)C43—C44—C45121.1 (3)
C14—C13—N31122.1 (3)C43—C44—Cl44119.3 (3)
N41—C14—C13122.9 (3)C45—C44—Cl44119.6 (3)
N41—C14—C15121.5 (3)C46—C45—C44119.2 (3)
C13—C14—C15115.6 (3)C46—C45—H45120.4
C16—C15—C14121.7 (3)C44—C45—H45120.4
C16—C15—H15119.1C45—C46—C41120.0 (3)
C14—C15—H15119.1C45—C46—H46120.0
C15—C16—C11121.5 (3)C41—C46—H46120.0
O1—C1—O2—C21.9 (5)C12—C13—N31—O318.9 (5)
C11—C1—O2—C2178.9 (3)C14—C13—N31—O31170.0 (3)
O1—C1—C11—C12167.0 (4)C12—C13—N31—O32171.0 (3)
O2—C1—C11—C1213.9 (5)C14—C13—N31—O3210.2 (5)
O1—C1—C11—C1612.5 (5)C13—C14—N41—C41174.9 (3)
O2—C1—C11—C16166.6 (3)C15—C14—N41—C417.0 (5)
C16—C11—C12—C130.4 (5)C14—N41—C41—C42135.8 (4)
C1—C11—C12—C13179.9 (3)C14—N41—C41—C4648.3 (5)
C11—C12—C13—C142.7 (5)C46—C41—C42—C430.5 (5)
C11—C12—C13—N31178.5 (3)N41—C41—C42—C43176.6 (3)
C12—C13—C14—N41177.7 (3)C41—C42—C43—C440.3 (5)
N31—C13—C14—N411.0 (5)C42—C43—C44—C450.3 (5)
C12—C13—C14—C154.1 (5)C42—C43—C44—Cl44178.8 (3)
N31—C13—C14—C15177.2 (3)C43—C44—C45—C460.4 (5)
N41—C14—C15—C16179.3 (3)Cl44—C44—C45—C46179.6 (3)
C13—C14—C15—C162.4 (5)C44—C45—C46—C411.2 (5)
C14—C15—C16—C110.5 (5)C42—C41—C46—C451.2 (5)
C12—C11—C16—C152.0 (5)N41—C41—C46—C45177.2 (3)
C1—C11—C16—C15178.5 (3)
Hydrogen-bond geometry (Å, º) top
Cg1 represents the centroid of the C41–C46 ring.
D—H···AD—HH···AD···AD—H···A
N41—H41···O320.881.932.617 (4)133
N41—H41···O32i0.882.373.158 (4)149
C16—H16···O1ii0.952.493.302 (4)144
C46—H46···Cg1iii0.952.723.560 (4)147
Symmetry codes: (i) x+1, y, z+1; (ii) x+1, y+1, z+1; (iii) x, y+1/2, z1/2.
(II) Methyl 1-benzyl-2-(4-chlorophenyl)-1H-benzimidazole-5-carboxylate top
Crystal data top
C22H17ClN2O2F(000) = 784
Mr = 376.83Dx = 1.373 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4183 reflections
a = 14.214 (2) Åθ = 2.8–27.5°
b = 11.7391 (10) ŵ = 0.23 mm1
c = 11.0580 (14) ÅT = 120 K
β = 98.908 (10)°Block, colourless
V = 1822.9 (4) Å30.31 × 0.28 × 0.20 mm
Z = 4
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
4183 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode3040 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.065
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 2.8°
ϕ and ω scansh = 1818
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1515
Tmin = 0.932, Tmax = 0.956l = 1414
24459 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.117H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0449P)2 + 1.0641P]
where P = (Fo2 + 2Fc2)/3
4183 reflections(Δ/σ)max = 0.001
245 parametersΔρmax = 0.32 e Å3
0 restraintsΔρmin = 0.43 e Å3
Crystal data top
C22H17ClN2O2V = 1822.9 (4) Å3
Mr = 376.83Z = 4
Monoclinic, P21/cMo Kα radiation
a = 14.214 (2) ŵ = 0.23 mm1
b = 11.7391 (10) ÅT = 120 K
c = 11.0580 (14) Å0.31 × 0.28 × 0.20 mm
β = 98.908 (10)°
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
4183 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
3040 reflections with I > 2σ(I)
Tmin = 0.932, Tmax = 0.956Rint = 0.065
24459 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.117H-atom parameters constrained
S = 1.05Δρmax = 0.32 e Å3
4183 reflectionsΔρmin = 0.43 e Å3
245 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.69848 (11)0.57451 (13)0.45316 (14)0.0219 (3)
C20.73360 (13)0.46478 (15)0.46699 (17)0.0215 (4)
N30.69613 (11)0.40547 (13)0.54929 (14)0.0240 (4)
C3a0.63269 (13)0.48000 (15)0.59228 (16)0.0218 (4)
C40.57395 (13)0.46255 (15)0.68054 (17)0.0230 (4)
H40.57180.39070.71960.028*
C50.51849 (13)0.55328 (15)0.70979 (17)0.0225 (4)
C60.52074 (14)0.65955 (16)0.64954 (17)0.0240 (4)
H60.48230.72020.67120.029*
C70.57724 (14)0.67767 (15)0.56017 (17)0.0241 (4)
H70.57790.74870.51920.029*
C7a0.63340 (13)0.58599 (15)0.53325 (16)0.0218 (4)
C170.71419 (14)0.66023 (15)0.36200 (16)0.0239 (4)
H17A0.65170.68390.31660.029*
H17B0.75080.62490.30250.029*
C110.76685 (13)0.76488 (15)0.41551 (16)0.0217 (4)
C120.82367 (15)0.76704 (17)0.52964 (18)0.0269 (4)
H120.82960.70070.57950.032*
C130.87194 (16)0.86605 (18)0.57100 (19)0.0324 (5)
H130.91070.86690.64910.039*
C140.86405 (16)0.96298 (18)0.4997 (2)0.0345 (5)
H140.89771.03010.52820.041*
C150.80687 (16)0.96185 (17)0.3867 (2)0.0343 (5)
H150.80081.02860.33750.041*
C160.75846 (15)0.86392 (16)0.34512 (18)0.0274 (4)
H160.71890.86410.26750.033*
C210.80203 (14)0.41651 (16)0.39352 (17)0.0234 (4)
C220.88719 (14)0.47085 (17)0.37947 (18)0.0274 (4)
H220.90310.54140.41950.033*
C230.94890 (15)0.42279 (18)0.30757 (19)0.0301 (5)
H231.00720.45930.29930.036*
C240.92384 (15)0.32070 (17)0.24829 (18)0.0281 (4)
Cl240.99602 (4)0.26432 (5)0.14922 (5)0.03969 (17)
C250.84068 (15)0.26460 (17)0.26202 (18)0.0285 (4)
H250.82470.19450.22100.034*
C260.78075 (15)0.31173 (16)0.33641 (18)0.0271 (4)
H260.72460.27220.34860.032*
C510.45824 (14)0.53386 (16)0.80648 (17)0.0235 (4)
O510.44658 (10)0.44172 (11)0.85107 (12)0.0300 (3)
O520.41778 (10)0.62973 (11)0.84006 (12)0.0288 (3)
C520.35773 (16)0.61510 (18)0.93410 (19)0.0329 (5)
H52A0.30750.55970.90620.049*
H52B0.32880.68830.95000.049*
H52C0.39640.58751.00950.049*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0277 (9)0.0146 (7)0.0236 (8)0.0007 (6)0.0046 (6)0.0011 (6)
C20.0247 (10)0.0140 (8)0.0252 (9)0.0001 (7)0.0020 (7)0.0006 (7)
N30.0284 (9)0.0156 (8)0.0286 (8)0.0008 (6)0.0064 (7)0.0002 (6)
C3a0.0257 (10)0.0136 (8)0.0253 (9)0.0008 (7)0.0013 (7)0.0003 (7)
C40.0273 (10)0.0144 (8)0.0270 (9)0.0021 (8)0.0033 (8)0.0001 (7)
C50.0255 (10)0.0156 (9)0.0257 (9)0.0023 (7)0.0015 (8)0.0021 (7)
C60.0282 (10)0.0162 (9)0.0271 (10)0.0011 (8)0.0021 (8)0.0025 (7)
C70.0302 (11)0.0132 (9)0.0280 (10)0.0011 (8)0.0017 (8)0.0005 (7)
C7a0.0256 (10)0.0164 (9)0.0233 (9)0.0021 (7)0.0031 (8)0.0004 (7)
C170.0319 (11)0.0168 (9)0.0226 (9)0.0000 (8)0.0028 (8)0.0032 (7)
C110.0249 (10)0.0167 (9)0.0243 (9)0.0005 (7)0.0065 (8)0.0004 (7)
C120.0343 (11)0.0213 (10)0.0253 (10)0.0002 (8)0.0055 (8)0.0028 (8)
C130.0371 (12)0.0313 (11)0.0281 (10)0.0036 (9)0.0028 (9)0.0045 (9)
C140.0391 (13)0.0229 (11)0.0420 (12)0.0084 (9)0.0079 (10)0.0074 (9)
C150.0420 (13)0.0184 (10)0.0425 (12)0.0020 (9)0.0068 (10)0.0063 (9)
C160.0325 (11)0.0197 (10)0.0287 (10)0.0000 (8)0.0010 (8)0.0036 (8)
C210.0281 (10)0.0188 (9)0.0231 (9)0.0028 (8)0.0034 (8)0.0024 (7)
C220.0304 (11)0.0206 (10)0.0310 (10)0.0044 (8)0.0044 (8)0.0004 (8)
C230.0272 (11)0.0294 (11)0.0345 (11)0.0030 (9)0.0069 (8)0.0062 (9)
C240.0323 (11)0.0241 (10)0.0294 (10)0.0077 (9)0.0092 (8)0.0072 (8)
Cl240.0467 (3)0.0333 (3)0.0443 (3)0.0125 (2)0.0234 (3)0.0071 (2)
C250.0363 (12)0.0187 (9)0.0316 (10)0.0033 (8)0.0081 (9)0.0019 (8)
C260.0310 (11)0.0188 (9)0.0322 (10)0.0016 (8)0.0075 (8)0.0023 (8)
C510.0253 (10)0.0169 (9)0.0269 (10)0.0009 (8)0.0003 (8)0.0043 (7)
O510.0382 (8)0.0177 (7)0.0361 (8)0.0006 (6)0.0120 (6)0.0000 (6)
O520.0358 (8)0.0201 (7)0.0330 (7)0.0042 (6)0.0135 (6)0.0006 (6)
C520.0393 (12)0.0293 (11)0.0328 (11)0.0074 (9)0.0141 (9)0.0025 (9)
Geometric parameters (Å, º) top
N1—C21.381 (2)C13—H130.9500
C2—N31.322 (2)C14—C151.381 (3)
N3—C3a1.392 (2)C14—H140.9500
C3a—C41.394 (3)C15—C161.382 (3)
C4—C51.393 (3)C15—H150.9500
C4—H40.9500C16—H160.9500
C5—C61.417 (3)C21—C261.394 (3)
C6—H60.9500C21—C221.398 (3)
C6—C71.383 (3)C22—C231.391 (3)
C7—C7a1.399 (3)C22—H220.9500
C7—H70.9500C23—C241.386 (3)
C7a—N11.383 (2)C23—H230.9500
C3a—C7a1.406 (2)C24—C251.382 (3)
N1—C171.466 (2)C24—Cl241.743 (2)
C2—C211.474 (3)C25—C261.388 (3)
C5—C511.487 (3)C25—H250.9500
C17—C111.511 (3)C26—H260.9500
C17—H17A0.9900C51—O511.211 (2)
C17—H17B0.9900C51—O521.342 (2)
C11—C121.389 (3)O52—C521.454 (2)
C11—C161.394 (3)C52—H52A0.9800
C12—C131.391 (3)C52—H52B0.9800
C12—H120.9500C52—H52C0.9800
C13—C141.379 (3)
C2—N1—C7a106.63 (15)C12—C13—H13119.7
C2—N1—C17128.71 (16)C13—C14—C15119.58 (19)
C7a—N1—C17124.19 (15)C13—C14—H14120.2
N3—C2—N1112.97 (16)C15—C14—H14120.2
N3—C2—C21123.22 (16)C14—C15—C16120.15 (19)
N1—C2—C21123.75 (16)C14—C15—H15119.9
C2—N3—C3a104.80 (15)C16—C15—H15119.9
N3—C3a—C4129.53 (17)C15—C16—C11120.86 (18)
N3—C3a—C7a110.26 (16)C15—C16—H16119.6
C4—C3a—C7a120.21 (17)C11—C16—H16119.6
C5—C4—C3a118.17 (17)C26—C21—C22118.89 (18)
C5—C4—H4120.9C26—C21—C2118.25 (18)
C3a—C4—H4120.9C22—C21—C2122.86 (17)
C4—C5—C6120.62 (18)C23—C22—C21120.78 (18)
C4—C5—C51117.35 (16)C23—C22—H22119.6
C6—C5—C51122.03 (17)C21—C22—H22119.6
C7—C6—C5121.96 (17)C24—C23—C22118.84 (19)
C7—C6—H6119.0C24—C23—H23120.6
C5—C6—H6119.0C22—C23—H23120.6
C6—C7—C7a116.57 (17)C25—C24—C23121.45 (19)
C6—C7—H7121.7C25—C24—Cl24119.00 (16)
C7a—C7—H7121.7C23—C24—Cl24119.50 (16)
N1—C7a—C7132.19 (17)C24—C25—C26119.29 (19)
N1—C7a—C3a105.34 (16)C24—C25—H25120.4
C7—C7a—C3a122.46 (17)C26—C25—H25120.4
N1—C17—C11114.08 (15)C25—C26—C21120.67 (19)
N1—C17—H17A108.7C25—C26—H26119.7
C11—C17—H17A108.7C21—C26—H26119.7
N1—C17—H17B108.7O51—C51—O52123.02 (18)
C11—C17—H17B108.7O51—C51—C5124.06 (17)
H17A—C17—H17B107.6O52—C51—C5112.92 (16)
C12—C11—C16118.65 (17)C51—O52—C52115.02 (15)
C12—C11—C17123.62 (17)O52—C52—H52A109.5
C16—C11—C17117.72 (16)O52—C52—H52B109.5
C11—C12—C13120.12 (18)H52A—C52—H52B109.5
C11—C12—H12119.9O52—C52—H52C109.5
C13—C12—H12119.9H52A—C52—H52C109.5
C14—C13—C12120.63 (19)H52B—C52—H52C109.5
C14—C13—H13119.7
C7a—N1—C2—N30.0 (2)C16—C11—C12—C130.9 (3)
C17—N1—C2—N3172.18 (17)C17—C11—C12—C13178.22 (19)
C7a—N1—C2—C21177.12 (17)C11—C12—C13—C140.1 (3)
C17—N1—C2—C214.9 (3)C12—C13—C14—C150.6 (3)
N1—C2—N3—C3a0.0 (2)C13—C14—C15—C160.4 (3)
C21—C2—N3—C3a177.07 (17)C14—C15—C16—C110.4 (3)
C2—N3—C3a—C4179.70 (19)C12—C11—C16—C151.1 (3)
C2—N3—C3a—C7a0.1 (2)C17—C11—C16—C15178.08 (19)
N3—C3a—C4—C5178.13 (18)N3—C2—C21—C2647.9 (3)
C7a—C3a—C4—C51.5 (3)N1—C2—C21—C26128.9 (2)
C3a—C4—C5—C61.1 (3)N3—C2—C21—C22131.7 (2)
C3a—C4—C5—C51178.42 (17)N1—C2—C21—C2251.5 (3)
C4—C5—C6—C70.1 (3)C26—C21—C22—C231.4 (3)
C51—C5—C6—C7179.60 (17)C2—C21—C22—C23178.98 (18)
C5—C6—C7—C7a0.9 (3)C21—C22—C23—C241.0 (3)
C2—N1—C7a—C7178.9 (2)C22—C23—C24—C251.9 (3)
C17—N1—C7a—C78.4 (3)C22—C23—C24—Cl24175.46 (15)
C2—N1—C7a—C3a0.09 (19)C23—C24—C25—C260.3 (3)
C17—N1—C7a—C3a172.58 (16)Cl24—C24—C25—C26177.09 (15)
C6—C7—C7a—N1178.33 (19)C24—C25—C26—C212.3 (3)
C6—C7—C7a—C3a0.6 (3)C22—C21—C26—C253.1 (3)
N3—C3a—C7a—N10.1 (2)C2—C21—C26—C25177.30 (17)
C4—C3a—C7a—N1179.77 (16)C4—C5—C51—O518.5 (3)
N3—C3a—C7a—C7179.04 (17)C6—C5—C51—O51171.99 (18)
C4—C3a—C7a—C70.6 (3)C4—C5—C51—O52171.38 (17)
C2—N1—C17—C11115.9 (2)C6—C5—C51—O528.2 (3)
C7a—N1—C17—C1173.1 (2)O51—C51—O52—C520.4 (3)
N1—C17—C11—C1221.2 (3)C5—C51—O52—C52179.72 (16)
N1—C17—C11—C16159.68 (17)
Hydrogen-bond geometry (Å, º) top
Cg2 represents the centroid of the C3a/C4–C7/C7a ring.
D—H···AD—HH···AD···AD—H···A
C16—H16···Cg2i0.952.523.388 (2)153
Symmetry code: (i) x, y+3/2, z1/2.

Experimental details

(I)(II)
Crystal data
Chemical formulaC14H11ClN2O4C22H17ClN2O2
Mr306.70376.83
Crystal system, space groupMonoclinic, P21/cMonoclinic, P21/c
Temperature (K)120120
a, b, c (Å)12.4413 (10), 15.8116 (18), 7.1805 (10)14.214 (2), 11.7391 (10), 11.0580 (14)
β (°) 103.037 (9) 98.908 (10)
V3)1376.1 (3)1822.9 (4)
Z44
Radiation typeMo KαMo Kα
µ (mm1)0.300.23
Crystal size (mm)0.32 × 0.16 × 0.080.31 × 0.28 × 0.20
Data collection
DiffractometerBruker Nonius KappaCCD area-detector
diffractometer
Bruker Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.912, 0.9770.932, 0.956
No. of measured, independent and
observed [I > 2σ(I)] reflections
20301, 2572, 1600 24459, 4183, 3040
Rint0.1110.065
(sin θ/λ)max1)0.6070.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.059, 0.163, 1.04 0.046, 0.117, 1.05
No. of reflections25724183
No. of parameters191245
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.37, 0.350.32, 0.43

Computer programs: COLLECT (Nonius, 1999), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Selected geometric parameters (Å, º) for (I) top
C11—C121.380 (5)C13—N311.447 (4)
C12—C131.397 (5)N31—O311.231 (4)
C13—C141.418 (5)N31—O321.242 (4)
C14—C151.426 (5)C14—N411.364 (4)
C15—C161.366 (5)N41—C411.420 (4)
C16—C111.412 (5)
C11—C1—O2—C2178.9 (3)C12—C13—N31—O32171.0 (3)
O1—C1—C11—C12167.0 (4)C13—C14—N41—C41174.9 (3)
O2—C1—C11—C1213.9 (5)C14—N41—C41—C42135.8 (4)
C12—C13—N31—O318.9 (5)
Hydrogen-bond geometry (Å, º) for (I) top
Cg1 represents the centroid of the C41–C46 ring.
D—H···AD—HH···AD···AD—H···A
N41—H41···O320.881.932.617 (4)133
N41—H41···O32i0.882.373.158 (4)149
C16—H16···O1ii0.952.493.302 (4)144
C46—H46···Cg1iii0.952.723.560 (4)147
Symmetry codes: (i) x+1, y, z+1; (ii) x+1, y+1, z+1; (iii) x, y+1/2, z1/2.
Selected geometric parameters (Å, º) for (II) top
N1—C21.381 (2)C5—C61.417 (3)
C2—N31.322 (2)C6—C71.383 (3)
N3—C3a1.392 (2)C7—C7a1.399 (3)
C3a—C41.394 (3)C7a—N11.383 (2)
C4—C51.393 (3)C3a—C7a1.406 (2)
C2—N1—C17—C11115.9 (2)C4—C5—C51—O518.5 (3)
N1—C17—C11—C1221.2 (3)C4—C5—C51—O52171.38 (17)
N1—C2—C21—C2251.5 (3)C5—C51—O52—C52179.72 (16)
Hydrogen-bond geometry (Å, º) for (II) top
Cg2 represents the centroid of the C3a/C4–C7/C7a ring.
D—H···AD—HH···AD···AD—H···A
C16—H16···Cg2i0.952.523.388 (2)153
Symmetry code: (i) x, y+3/2, z1/2.
 

Acknowledgements

The authors thank the Centro de Instrumentación Científico-Técnica of the Universidad de Jaén and the staff for the data collection. EC and RA thank COLCIENCIAS and the Universidad del Valle for financial support. JC thanks the Consejería de Innovación, Ciencia y Empresa (Junta de Andalucía, Spain) and the Universidad de Jaén for financial support.

References

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