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In the title compound, C29H35ClN4O2, the bond lengths provide evidence for aromatic delocalization in the pyrazole ring but bond fixation in the fused imidazole ring, and the octyl chain is folded, rather than adopting an all-trans chain-extended conformation. A combination of N—H...N, C—H...N and C—H...O hydrogen bonds links the mol­ecules into sheets, in which the hydrogen bonds occupy the central layer with the tert-butyl and octyl groups arranged on either side, such that the closest contacts between adjacent sheets involve only the octyl groups. Comparisons are made with the supra­molecular assembly in some simpler analogues.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614011760/fg3321sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229614011760/fg3321Isup2.hkl
Contains datablock I

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229614011760/fg3321Isup3.cml
Supplementary material

CCDC reference: 1004427

Introduction top

The imidazole nucleus is a common group in a large number of natural products and pharmacologically active compounds (Adams et al., 1998). In particular, benzimidazoles may be considered as structural isosteres of nucleotide bases, owing to the fused heterocyclic nuclei in their structures, and they inter­act easily with biopolymers and possess potential activity for chemotherapeutic applications (Ören et al., 1998). The benzimidazole group itself is a crucial pharmacophore in modern drug discovery (Tebbe et al., 1997), owing to the broad spectrum of important biological and pharmacological properties exhibited for a large number of benzimidazole-containing compounds, such as anti-ulcerative and anti­hypertensive (Zarrinmayeh et al., 1999), anti­fungal (Taggart et al., 1998), anti­tumour (Zhou & Skibo, 1996; Craigo et al., 1999) and anti-allergic actions (Nakano et al., 2000); as topoisomerase inhibitors (Kim et al., 1996); and as selective neuropeptide YY1 receptor antagonists (Zarrinmayeh et al., 1998). In addition, some benzimidazole derivatives are effective against several human viruses, such as cytomegalovirus (HCMV) (Zhu et al., 2000), HIV (Roth et al., 1997) and herpes (HSV-1) (Migawa et al., 1998).

Continuing with our current studies of the synthesis of benzimidazole-based compounds of potential anti­tumour activity (Abonía et al., 2010, 2011; Cortés et al.,2011), we have now prepared octyl 1-(5-tert-butyl-1H-pyrazol-3-yl)-2-(4-chloro­phenyl)-1H-benzimidazole-5-carboxyl­ate, (I), through a two-step one-pot synthesis using the reduction of nitro derivative (II) [octyl 4-[(5-tert-butyl-1H-pyrazol-3-yl)amino]-3-nitro­benzoate; see scheme] to a di­amine followed by a condensation reaction with 4-chloro­benzaldehyde, without isolation of the inter­mediate di­amine, and here we report the molecular and supra­molecular structure of (I) which we compare with the simpler analogues, (III) [methyl 2-(4-bromo­phenyl)-1-(5-tert-butyl-1H-pyrazol-3-yl)-1H-benzimidazole-5-carboxyl­ate; Cortés et al., 2011] and (IV) [methyl 1-(5-tert-butyl-1H-pyrazol-3-yl)-1H-benzimidazole-5-carboxyl­ate; Portilla et al., 2007] (see scheme), which had been prepared using a similar condensation reaction between a pre-formed di­amine and 4-bromo­benzaldehyde or tri­methyl orthoformate, respectively.

Experimental top

Synthesis and crystallization top

A mixture of octyl 4-[(5-tert-butyl-1H-pyrazol-3-yl)amino]-3-nitro­benzoate, (II) (1 mmol) (see scheme), zinc powder (5 mmol) and acetic acid (2 ml) was stirred at ambient temperature for 15 min. After complete disappearance of starting compound (II) [as monitored by thin-layer chromatography (TLC)], the by-product zinc acetate and the excess of zinc metal were removed by filtration. To the resulting solution, 4-chloro­benzaldehyde (1.05 mmol) was added, and it was subjected to heating at 373 K for 1 h. After consumption of the starting materials (as monitored by TLC), the solution was allowed to cool at ambient temperature, excess acetic acid was removed under reduced pressure and the resulting solid product was washed with ethanol (2 × 1 ml). Colourless crystals of (I) suitable for single-crystal X-ray diffraction were grown by slow evaporation, at ambient temperature and in the presence of air, from a solution in ethanol (yield 88%; m.p. 439 K). Spectroscopic analysis: FT–IR (KBr, ν cm-1): 3184 (NH), 2959, 2854, 1710 (CO), 1615 (C C), 1570 (CN), 1511, 1472, 1279 (C—O); EIMS (70 eV) m/z = 508/506 (26/68) [M+], 449 (21), 396/394 (33/86), 377 (52), 350 (100), 337 (12); analysis, found: C 68.8, H 7.1, N 10.9%; C29H35ClN4O2 requires: C 68.7, H 7.0, N 11.1%.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were located in a difference map and then treated as riding atoms. C-bound H atoms were treated as riding in geometrically idealized positions, with C—H = 0.95 (aromatic and pyrazole), 0.98 (methyl) or 0.99 Å (methyl­ene), and with Uiso(H) = kUeq(C), where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and 1.2 for all other C-bound H atoms. The H atom bonded to atom N11 was permitted to ride at the position located in a difference map, with Uiso(H) = 1.2Ueq(N), giving the N···H distance shown in Table 3. Six low-angle reflections (202, 220, 221, 112, 311 and 400), which had been wholly or partially attenuated by the beam stop, were omitted from the refinement. Examination of the refined structure using PLATON (Spek, 2009) showed the presence of four symmetry-related cavities per unit cell, each of volume ca 12 Å3, and centred at (0, 0, 0), (1/2, 1/2, 0), (1/2, 1/2, 0) and (1/2, 1/2, 1/2). These cavities are too small to accommodate any solvent species and, consistent with this, application of the SQUEEZE procedure in PLATON returned a count of zero additional electrons per unit cell; accordingly, no modification of the reflection file was required.

Results and discussion top

Within the pyrazole ring of (I), the two independent C—C distances (C13—C14 and C14—C15) differ by less than 0.02 Å (Table 2), despite the fact that these bonds are formally single and double bonds, respectively. Similarly, the two independent C—N distances (N11—C15 and N12—C13) differ by less than 0.03 Å, although these two bonds are again formally single and double bonds, respectively. These observations indicate a degree of aromatic delocalization within this ring. By contrast, the bond lengths within the imidazole ring point to strong bond fixation in this ring.

The molecular conformation of (I) can be specified in terms of (a) the dihedral angles between the imidazole ring and the two pendent rings (N11/N12/C13–C15 and C21–C26; Fig. 1), (b) the orientations of the tert-butyl and 4-chloro­phenyl substituents relative to the adjacent rings, and (c) the folding of the octyl chain. The imidazole ring makes dihedral angles with the pyrazole ring and the chlorinated aryl ring of 60.01 (12) and 34.63 (11)°, respectively. The corresponding dihedral angles in (III) (Cortés et al., 2011) are 83.30 (15) and 26.90 (14)°, respectively, while in (IV), which crystallizes with Z' = 2 (Portilla et al., 2007), the dihedral angles between the imidazole and pyrazole rings in the two independent molecules are 5.5 (2) and 5.9 (2)°, indicating considerable flexibility about the N1—C13 and C2—C21 bonds. The relative orientation of the pyrazole and chlorinated aryl rings in (I) may be influenced by the intra­molecular C—H···π(pyrazole) contact (Table 3), although no such contact is apparent in (III) nor possible in (IV). The tert-butyl group adopts an orientation in which the projection of one of the C—Me bonds is almost orthogonal to the plane of the adjacent pyrazole ring, while the ester function is nearly coplanar with the fused aryl ring, as shown by the torsion angles within the fragment between atoms C4 and C52 (Table 2).

Perhaps the least expected aspect of the molecular conformation of (I) is the folding of the octyl chain. Instead of adopting an all-trans chain-extended conformation in which all of the C atoms are effectively coplanar, with the torsion angles along the chain all close to 180° in each four-carbon fragment, the O52—C52—C53—C54 and C53—C54—C55—C56 torsion angles are close to ±60°, indicating a synclinal arrangement about the C52—C53 and C54—C55 bonds, rather than the usual anti­periplanar arrangement. In view of the supra­molecular arrangement discussed below, it seems possible that this chain folding represents the most effective means of accommodating the octyl substituents between the hydrogen-bonded c sheets.

A combination of N—H···N, C—H···O and C—H···N hydrogen bonds (Table 3) links the molecules of (I) into complex sheets, the formation of which can readily be analysed in terms of two substructures (Ferguson et al., 1998a,b; Gregson et al., 2000); one of these substructures is finite and thus zero-dimensional, while the other is one-dimensional. In the finite substructure, inversion-related pairs of molecules are linked by C—H···O hydrogen bonds to form cyclic centrosymmetric dimers characterized by an R22(20) (Bernstein et al., 1995) motif (Fig. 2), where the reference dimer is centred across (1/4, 3/4, 1/2). In the second substructure, molecules related by the 21 screw axis along (1/4, y, 1/4) are linked by a combination of N—H···N and C—H···N hydrogen bonds to form a C(7)C(7)[R22(8)] chain of rings running parallel to the [010] direction (Fig. 3). Four chains of this type pass through each unit cell, associated with the screw axes along (1/4, y, 1/4), (1/4, y, 3/4), (3/4, y, 1/4) and (3/4, y, 3/4), and they link the R22(20) dimers into sheets. Thus, the reference dimer centred at (1/4, 3/4, 1/2) is directly linked to four other dimers centred at (1/4, 1/4, 0), (1/4, 1/4, 1), (1/4, 5/4, 0) and (1/4, 5/4, 1), respectively, so forming a sheet lying parallel to (100) and containing rings of R22(8), R22(20) and R66(36) types, where the inter­ior of the R66(36) ring is occupied by an inversion-related pair of chlorinated aryl rings engaged in ππ stacking, as discussed below.

This sheet lies in the domain 0 < x < 1/2 and a second sheet, related to the first by inversion, lies in the domain 1/2 < x < 1.0. Each sheet is effectively tripartite, with a central layer containing the hydrogen bonds, and with all of the octyl and tert-butyl groups arranged on either side of the central layer (Fig. 5). The only close contacts between adjacent sheets involve the octyl groups, so that there are no direction-specific inter­actions between adjacent sheets. The only C—H···π contact in the structure is intra­molecular (Table 3), but two inter­molecular ππ stacking inter­actions are present. The chlorinated aryl rings in the molecules at (x, y, z) and (-x + 1/2, -y + 3/2, -z) are strictly parallel, with an inter­planar spacing of 3.297 Å; the ring-centroid separation is 3.6476 (13) Å, corresponding to a ring-centroid offset of 1.560 Å. In addition, the imidazole ring of the molecule at (x, y, z) and the fused aryl ring in the molecule at (-x + 1/2, -y + 3/2, -z + 1) make a dihedral angle of only 1.94 (11)°; the ring-centroid separation here is 3.6881 (13) Å and the shortest perpendicular distance from the centroid of one ring to the plane of the other is 3.449 Å, corresponding to a ring-centroid offset of ca 1.31 Å. Both of these inter­actions involve molecules in the same hydrogen-bonded sheet and, indeed, the first of them lies within the hydrogen-bonded R22(20) dimer (cf. Fig. 2).

It is of inter­est briefly to compare the rather complex sheet structure in (I) with the supra­molecular assembly in (III) (Cortés et al., 2011) and (IV) (Portilla et al., 2007). In (III), a combination of N—H···O and C—H···π(arene) hydrogen bonds links the molecules into a chain of centrosymmetric edge-fused rings. Compound (IV), where there is no pendent aryl group, crystallizes (Z' = 2) with no direction-specific inter­actions between the two independent molecules. Each type of molecule forms a hydrogen-bonded sheet, in which molecules related by translation only are linked by a combination of N—H···N and C—H···O hydrogen bonds to form a single type of R44(28) ring. In each of (I), (III) and (IV), atoms N11 and C14 of the pyrazole ring act as hydrogen-bond donors, but the two acceptors in these two hydrogen bonds are not always the same. In (I) and (IV), the acceptors from the pyrazole donors are, respectively, the two-coordinate N atom of the imidazole ring and the carbonyl O atom of the ester group, but in (III) these acceptors are, respectively, the carbonyl O atom of the ester group and the pendent aryl ring. However, the assembly in (I) and (IV) differs in the relationship between the molecules within the hydrogen-bonded sheet, i.e. translation only in (IV), but a combination of inversion and translation in (I), where there is also an addition hydrogen bond involving the pyrazole ring as an acceptor, rather than as a donor. Only in (III) is there an inter­molecular C—H···π hydrogen bond.

Related literature top

For related literature, see: Abonía et al. (2010, 2011); Adams et al. (1998); Bernstein et al. (1995); Cortés et al. (2011); Craigo et al. (1999); Ferguson et al. (1998a, 1998b); Gregson et al. (2000); Kim et al. (1996); Migawa et al. (1998); Nakano et al. (2000); Portilla et al. (2007); Roth et al. (1997); Spek (2009); Taggart et al. (1998); Tebbe et al. (1997); Zarrinmayeh et al. (1998, 1999); Zhou & Skibo (1996); Zhu et al. (2000); Ören et al. (1998).

Computing details top

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: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and SHELXL2013 (Sheldrick, 2013); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), SHELXL2013 (Sheldrick, 2013) and PLATON (Spek, 2009).

Figures top
Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Fig. 2. Part of the crystal structure of (I), showing the formation of a cyclic centrosymmetric R22(20) dimer built from C—H···O hydrogen bonds (dashed lines). For the sake of clarity, the unit-cell outline and H atoms not involved in the motif shown have been omitted. The atoms marked with an asterisk (*) are at the symmetry position (1/2 - x, 3/2 - y, 1 - z).

Fig. 3. A stereoview of part of the crystal structure of (I), showing the formation of a C(7)C(7)[R22(8)] chain of rings along the [010] direction. Dashed lines indicate hydrogen bonds. For the sake of clarity, H atoms not involved in the motifs shown have been omitted.

Fig. 4. Part of the crystal structure of (I), showing the formation of a centrosymmetric hydrogen-bonded R66(36) ring lying within the (100) sheet and centred at (1/4, 1/4, 1/2). Dashed lines indicate hydrogen bonds. For the sake of clarity, H atoms not involved in the motif shown have been omitted, as have atoms C17–C19 and C53–C59. [Symmetry codes: (i) -x + 1/2, -y + 3/2, -z + 1; (ii) x, -y + 1, z + 1/2; (iii) -x + 1/2, -y + 1/2, -z + 1; (iv) x, y - 1, z; (v) -x + 1/2, y - 1/2, -z + 1/2.]

Fig. 5. Part of the crystal structure of (I), viewed approximately along [001], showing the tripartite nature of two adjacent sheets comprising central hydrogen-bonded layers and exterior layers of octyl groups. Dashed lines indicate hydrogen bonds. For the sake of clarity, H atoms not involved in hydrogen bonding have been omitted.
Octyl 1-(5-(tert-butyl)-1H-pyrazol-3-yl)-2- (4-chlorophenyl)-1H-benzo[d]imidazole-5-carboxylate top
Crystal data top
C29H35ClN4O2F(000) = 2160
Mr = 507.06Dx = 1.226 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 6308 reflections
a = 29.768 (4) Åθ = 2.7–27.5°
b = 15.6022 (12) ŵ = 0.17 mm1
c = 11.8465 (15) ÅT = 120 K
β = 93.247 (11)°Block, colourless
V = 5493.2 (11) Å30.30 × 0.30 × 0.24 mm
Z = 8
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
6303 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode4127 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.076
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.1°
ϕ and ω scansh = 3838
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 2020
Tmin = 0.904, Tmax = 0.960l = 1215
44941 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)] = 0.053Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116H-atom parameters constrained
S = 1.09 w = 1/[σ2(Fo2) + (0.0289P)2 + 10.0795P]
where P = (Fo2 + 2Fc2)/3
6303 reflections(Δ/σ)max = 0.001
329 parametersΔρmax = 0.42 e Å3
0 restraintsΔρmin = 0.32 e Å3
Crystal data top
C29H35ClN4O2V = 5493.2 (11) Å3
Mr = 507.06Z = 8
Monoclinic, C2/cMo Kα radiation
a = 29.768 (4) ŵ = 0.17 mm1
b = 15.6022 (12) ÅT = 120 K
c = 11.8465 (15) Å0.30 × 0.30 × 0.24 mm
β = 93.247 (11)°
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
6303 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
4127 reflections with I > 2σ(I)
Tmin = 0.904, Tmax = 0.960Rint = 0.076
44941 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0530 restraints
wR(F2) = 0.116H-atom parameters constrained
S = 1.09 w = 1/[σ2(Fo2) + (0.0289P)2 + 10.0795P]
where P = (Fo2 + 2Fc2)/3
6303 reflectionsΔρmax = 0.42 e Å3
329 parametersΔρmin = 0.32 e Å3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.25787 (6)0.63868 (10)0.31816 (15)0.0163 (4)
C20.25340 (7)0.71904 (13)0.26995 (17)0.0153 (4)
N30.22407 (6)0.76752 (11)0.32052 (15)0.0164 (4)
C3a0.20796 (7)0.71655 (13)0.40562 (17)0.0160 (4)
C40.17557 (7)0.73311 (13)0.48333 (18)0.0176 (4)
H40.16130.78750.48600.021*
C50.16466 (7)0.66763 (13)0.55689 (18)0.0175 (4)
C60.18684 (7)0.58772 (13)0.55630 (18)0.0192 (5)
H60.17900.54460.60830.023*
C70.21981 (7)0.57093 (13)0.48158 (18)0.0183 (5)
H70.23550.51790.48230.022*
C7a0.22872 (7)0.63584 (13)0.40526 (17)0.0164 (4)
N110.30521 (6)0.44808 (11)0.23533 (15)0.0185 (4)
H110.30020.39590.21480.022*
N120.26881 (6)0.49649 (11)0.25719 (15)0.0188 (4)
C130.28705 (7)0.57072 (13)0.28947 (17)0.0160 (4)
C140.33396 (7)0.57130 (13)0.28929 (18)0.0175 (4)
H140.35390.61700.30990.021*
C150.34474 (7)0.49032 (13)0.25235 (17)0.0171 (4)
C160.38979 (7)0.45298 (14)0.22397 (19)0.0202 (5)
C170.39329 (8)0.35878 (14)0.2602 (2)0.0268 (5)
H17A0.39120.35470.34230.040*
H17B0.42220.33540.23930.040*
H17C0.36870.32610.22230.040*
C180.39383 (9)0.46020 (17)0.0951 (2)0.0320 (6)
H18A0.36910.42860.05600.048*
H18B0.42260.43590.07480.048*
H18C0.39230.52060.07270.048*
C190.42779 (7)0.50463 (16)0.2846 (2)0.0279 (5)
H19A0.42570.56470.26060.042*
H19B0.45690.48110.26530.042*
H19C0.42510.50110.36650.042*
C210.27871 (7)0.74611 (13)0.17284 (18)0.0161 (4)
C220.28925 (7)0.68977 (14)0.08616 (18)0.0186 (5)
H220.28030.63140.08960.022*
C230.31252 (7)0.71816 (14)0.00445 (19)0.0201 (5)
H230.31950.67990.06330.024*
C240.32557 (7)0.80348 (14)0.00809 (19)0.0201 (5)
Cl240.35460 (2)0.84130 (4)0.12188 (5)0.03072 (16)
C250.31546 (7)0.86065 (13)0.07603 (18)0.0189 (5)
H250.32470.91880.07230.023*
C260.29161 (7)0.83199 (13)0.16592 (18)0.0169 (4)
H260.28400.87110.22330.020*
C510.12816 (7)0.68442 (14)0.63483 (18)0.0189 (5)
O510.11099 (5)0.75352 (10)0.64901 (14)0.0246 (4)
O520.11534 (5)0.61234 (9)0.68670 (13)0.0225 (4)
C520.07993 (8)0.62233 (15)0.7656 (2)0.0264 (5)
H52A0.05630.66160.73400.032*
H52B0.09240.64630.83810.032*
C530.06049 (8)0.53415 (15)0.7840 (2)0.0283 (5)
H53A0.03450.53990.83220.034*
H53B0.04900.51120.71000.034*
C540.09297 (8)0.46972 (16)0.8382 (2)0.0277 (5)
H54A0.10190.48890.91600.033*
H54B0.12040.46780.79480.033*
C550.07286 (8)0.37921 (15)0.8432 (2)0.0261 (5)
H55A0.06130.36260.76630.031*
H55B0.09710.33850.86700.031*
C560.03485 (8)0.37089 (15)0.9238 (2)0.0262 (5)
H56A0.00860.40430.89310.031*
H56B0.04480.39620.99760.031*
C570.02003 (8)0.27838 (15)0.9425 (2)0.0264 (5)
H57A0.00950.25330.86890.032*
H57B0.04630.24460.97200.032*
C580.01726 (9)0.27096 (18)1.0243 (2)0.0372 (6)
H58A0.04470.29890.99050.045*
H58B0.00810.30221.09460.045*
C590.02851 (12)0.1784 (2)1.0542 (3)0.0606 (10)
H59A0.03650.14630.98490.091*
H59B0.05390.17781.10330.091*
H59C0.00230.15171.09380.091*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0180 (9)0.0123 (8)0.0187 (9)0.0007 (7)0.0018 (7)0.0002 (7)
C20.0169 (10)0.0110 (10)0.0176 (11)0.0017 (8)0.0020 (8)0.0009 (8)
N30.0174 (9)0.0133 (8)0.0184 (9)0.0008 (7)0.0009 (7)0.0018 (7)
C3a0.0188 (11)0.0123 (10)0.0166 (11)0.0014 (8)0.0014 (8)0.0000 (8)
C40.0182 (11)0.0135 (10)0.0208 (11)0.0012 (8)0.0016 (9)0.0006 (9)
C50.0186 (11)0.0170 (10)0.0166 (11)0.0036 (9)0.0014 (8)0.0011 (9)
C60.0237 (12)0.0147 (10)0.0190 (11)0.0052 (9)0.0001 (9)0.0027 (9)
C70.0220 (11)0.0127 (10)0.0200 (11)0.0002 (9)0.0012 (9)0.0007 (9)
C7a0.0173 (10)0.0155 (10)0.0164 (11)0.0017 (8)0.0007 (8)0.0014 (8)
N110.0203 (9)0.0113 (8)0.0242 (10)0.0006 (7)0.0033 (7)0.0037 (7)
N120.0204 (9)0.0142 (9)0.0220 (10)0.0002 (7)0.0020 (7)0.0005 (7)
C130.0212 (11)0.0116 (10)0.0152 (11)0.0008 (8)0.0003 (8)0.0011 (8)
C140.0186 (11)0.0146 (10)0.0192 (11)0.0024 (9)0.0011 (9)0.0006 (9)
C150.0203 (11)0.0161 (10)0.0149 (11)0.0026 (9)0.0014 (8)0.0017 (9)
C160.0208 (11)0.0182 (11)0.0222 (12)0.0009 (9)0.0071 (9)0.0002 (9)
C170.0252 (12)0.0213 (12)0.0344 (14)0.0061 (10)0.0079 (10)0.0012 (10)
C180.0393 (14)0.0329 (14)0.0249 (13)0.0033 (12)0.0124 (11)0.0006 (11)
C190.0209 (12)0.0295 (13)0.0339 (14)0.0002 (10)0.0071 (10)0.0025 (11)
C210.0148 (10)0.0163 (10)0.0169 (11)0.0017 (8)0.0009 (8)0.0026 (8)
C220.0210 (11)0.0145 (10)0.0197 (11)0.0007 (9)0.0022 (9)0.0021 (9)
C230.0228 (12)0.0187 (11)0.0187 (11)0.0023 (9)0.0007 (9)0.0020 (9)
C240.0150 (11)0.0243 (11)0.0212 (12)0.0009 (9)0.0043 (9)0.0056 (9)
Cl240.0378 (3)0.0283 (3)0.0275 (3)0.0043 (3)0.0143 (3)0.0025 (3)
C250.0179 (11)0.0144 (10)0.0242 (12)0.0004 (9)0.0008 (9)0.0016 (9)
C260.0178 (11)0.0145 (10)0.0183 (11)0.0014 (8)0.0012 (8)0.0011 (9)
C510.0178 (11)0.0201 (11)0.0185 (12)0.0049 (9)0.0027 (9)0.0016 (9)
O510.0239 (8)0.0176 (8)0.0329 (10)0.0012 (7)0.0076 (7)0.0019 (7)
O520.0230 (8)0.0189 (8)0.0266 (9)0.0018 (6)0.0097 (7)0.0029 (7)
C520.0215 (12)0.0278 (12)0.0308 (13)0.0007 (10)0.0104 (10)0.0017 (10)
C530.0210 (12)0.0304 (13)0.0341 (14)0.0039 (10)0.0070 (10)0.0039 (11)
C540.0190 (12)0.0351 (14)0.0292 (13)0.0022 (10)0.0033 (10)0.0038 (11)
C550.0262 (12)0.0249 (12)0.0277 (13)0.0014 (10)0.0072 (10)0.0028 (10)
C560.0263 (12)0.0238 (12)0.0293 (13)0.0012 (10)0.0075 (10)0.0037 (10)
C570.0283 (13)0.0251 (12)0.0256 (13)0.0042 (10)0.0009 (10)0.0022 (10)
C580.0361 (15)0.0404 (16)0.0357 (15)0.0085 (12)0.0065 (12)0.0063 (13)
C590.071 (2)0.054 (2)0.058 (2)0.0285 (18)0.0091 (18)0.0178 (17)
Geometric parameters (Å, º) top
N1—C21.381 (3)C21—C221.401 (3)
N1—C131.424 (3)C22—C231.383 (3)
C2—N31.324 (3)C22—H220.9500
C2—C211.472 (3)C23—C241.388 (3)
N3—C3a1.391 (3)C23—H230.9500
C3a—C41.394 (3)C24—C251.383 (3)
C3a—C7a1.403 (3)C24—Cl241.745 (2)
C7a—N11.386 (3)C25—C261.387 (3)
C4—C51.393 (3)C25—H250.9500
C4—H40.9500C26—H260.9500
C5—C61.411 (3)C51—O511.209 (3)
C5—C511.488 (3)C51—O521.347 (3)
C6—C71.383 (3)O52—C521.457 (3)
C6—H60.9500C52—C531.513 (3)
C7—C7a1.393 (3)C52—H52A0.9900
C7—H70.9500C52—H52B0.9900
N11—N121.358 (2)C53—C541.513 (3)
N11—H110.8601C53—H53A0.9900
N12—C131.326 (3)C53—H53B0.9900
C13—C141.397 (3)C54—C551.536 (3)
C14—C151.381 (3)C54—H54A0.9900
C15—N111.354 (3)C54—H54B0.9900
C14—H140.9500C55—C561.526 (3)
C15—C161.517 (3)C55—H55A0.9900
C16—C171.533 (3)C55—H55B0.9900
C16—C191.534 (3)C56—C571.529 (3)
C16—C181.542 (3)C56—H56A0.9900
C17—H17A0.9800C56—H56B0.9900
C17—H17B0.9800C57—C581.519 (3)
C17—H17C0.9800C57—H57A0.9900
C18—H18A0.9800C57—H57B0.9900
C18—H18B0.9800C58—C591.529 (4)
C18—H18C0.9800C58—H58A0.9900
C19—H19A0.9800C58—H58B0.9900
C19—H19B0.9800C59—H59A0.9800
C19—H19C0.9800C59—H59B0.9800
C21—C261.397 (3)C59—H59C0.9800
C2—N1—C7a106.69 (17)C23—C22—H22119.6
C2—N1—C13128.55 (17)C21—C22—H22119.6
C7a—N1—C13124.75 (17)C22—C23—C24119.0 (2)
N3—C2—N1112.47 (18)C22—C23—H23120.5
N3—C2—C21124.71 (18)C24—C23—H23120.5
N1—C2—C21122.82 (18)C25—C24—C23121.5 (2)
C2—N3—C3a105.35 (17)C25—C24—Cl24118.43 (17)
N3—C3a—C4130.73 (19)C23—C24—Cl24120.01 (17)
N3—C3a—C7a109.94 (18)C24—C25—C26119.1 (2)
C4—C3a—C7a119.31 (19)C24—C25—H25120.4
C5—C4—C3a118.14 (19)C26—C25—H25120.4
C5—C4—H4120.9C25—C26—C21120.6 (2)
C3a—C4—H4120.9C25—C26—H26119.7
C4—C5—C6121.3 (2)C21—C26—H26119.7
C4—C5—C51117.60 (19)O51—C51—O52123.2 (2)
C6—C5—C51121.12 (19)O51—C51—C5124.9 (2)
C7—C6—C5121.3 (2)O52—C51—C5111.82 (18)
C7—C6—H6119.3C51—O52—C52115.94 (17)
C5—C6—H6119.3O52—C52—C53106.96 (19)
C6—C7—C7a116.47 (19)O52—C52—H52A110.3
C6—C7—H7121.8C53—C52—H52A110.3
C7a—C7—H7121.8O52—C52—H52B110.3
N1—C7a—C7131.05 (19)C53—C52—H52B110.3
N1—C7a—C3a105.55 (17)H52A—C52—H52B108.6
C7—C7a—C3a123.40 (19)C54—C53—C52115.1 (2)
C15—N11—N12113.41 (17)C54—C53—H53A108.5
C15—N11—H11129.7C52—C53—H53A108.5
N12—N11—H11116.9C54—C53—H53B108.5
C13—N12—N11102.86 (16)C52—C53—H53B108.5
N12—C13—C14113.48 (18)H53A—C53—H53B107.5
N12—C13—N1118.29 (18)C53—C54—C55112.70 (19)
C14—C13—N1128.23 (18)C53—C54—H54A109.1
C15—C14—C13104.17 (18)C55—C54—H54A109.1
C15—C14—H14127.9C53—C54—H54B109.1
C13—C14—H14127.9C55—C54—H54B109.1
N11—C15—C14106.08 (18)H54A—C54—H54B107.8
N11—C15—C16123.49 (18)C56—C55—C54114.0 (2)
C14—C15—C16130.22 (19)C56—C55—H55A108.8
C15—C16—C17110.67 (17)C54—C55—H55A108.8
C15—C16—C19109.41 (18)C56—C55—H55B108.8
C17—C16—C19109.62 (19)C54—C55—H55B108.8
C15—C16—C18108.11 (18)H55A—C55—H55B107.6
C17—C16—C18109.84 (19)C55—C56—C57113.6 (2)
C19—C16—C18109.15 (19)C55—C56—H56A108.8
C16—C17—H17A109.5C57—C56—H56A108.8
C16—C17—H17B109.5C55—C56—H56B108.8
H17A—C17—H17B109.5C57—C56—H56B108.8
C16—C17—H17C109.5H56A—C56—H56B107.7
H17A—C17—H17C109.5C58—C57—C56113.1 (2)
H17B—C17—H17C109.5C58—C57—H57A109.0
C16—C18—H18A109.5C56—C57—H57A109.0
C16—C18—H18B109.5C58—C57—H57B109.0
H18A—C18—H18B109.5C56—C57—H57B109.0
C16—C18—H18C109.5H57A—C57—H57B107.8
H18A—C18—H18C109.5C57—C58—C59113.4 (2)
H18B—C18—H18C109.5C57—C58—H58A108.9
C16—C19—H19A109.5C59—C58—H58A108.9
C16—C19—H19B109.5C57—C58—H58B108.9
H19A—C19—H19B109.5C59—C58—H58B108.9
C16—C19—H19C109.5H58A—C58—H58B107.7
H19A—C19—H19C109.5C58—C59—H59A109.5
H19B—C19—H19C109.5C58—C59—H59B109.5
C26—C21—C22119.02 (19)H59A—C59—H59B109.5
C26—C21—C2118.38 (19)C58—C59—H59C109.5
C22—C21—C2122.58 (19)H59A—C59—H59C109.5
C23—C22—C21120.7 (2)H59B—C59—H59C109.5
C7a—N1—C2—N30.7 (2)C13—C14—C15—N110.9 (2)
C13—N1—C2—N3177.69 (19)N1—C2—C21—C2235.2 (3)
C7a—N1—C2—C21179.10 (18)N1—C2—C21—C26146.5 (2)
C13—N1—C2—C212.5 (3)N3—C2—C21—C22144.6 (2)
N1—C2—N3—C3a0.6 (2)N3—C2—C21—C2633.7 (3)
C21—C2—N3—C3a179.14 (19)C13—C14—C15—C16173.9 (2)
C2—N3—C3a—C4177.9 (2)N11—C15—C16—C1742.5 (3)
C2—N3—C3a—C7a0.3 (2)C14—C15—C16—C17143.4 (2)
N3—C3a—C4—C5177.2 (2)N11—C15—C16—C19163.4 (2)
C7a—C3a—C4—C50.9 (3)N11—C15—C16—C1877.8 (3)
C3a—C4—C5—C62.4 (3)C14—C15—C16—C1896.2 (3)
C3a—C4—C5—C51176.51 (19)C14—C15—C16—C1922.5 (3)
C4—C5—C6—C70.9 (3)C26—C21—C22—C230.8 (3)
C51—C5—C6—C7177.96 (19)C2—C21—C22—C23179.03 (19)
C5—C6—C7—C7a2.0 (3)C21—C22—C23—C240.3 (3)
C2—N1—C7a—C7179.7 (2)C22—C23—C24—C250.7 (3)
C13—N1—C7a—C71.2 (3)C22—C23—C24—Cl24179.52 (16)
C2—N1—C7a—C3a0.4 (2)C23—C24—C25—C260.2 (3)
C13—N1—C7a—C3a178.03 (18)Cl24—C24—C25—C26178.72 (16)
C6—C7—C7a—N1177.3 (2)C24—C25—C26—C211.3 (3)
C6—C7—C7a—C3a3.6 (3)C22—C21—C26—C251.6 (3)
N3—C3a—C7a—N10.1 (2)C2—C21—C26—C25179.93 (18)
C4—C3a—C7a—N1178.55 (18)C4—C5—C51—O519.4 (3)
N3—C3a—C7a—C7179.37 (19)C6—C5—C51—O51171.6 (2)
C4—C3a—C7a—C72.1 (3)C4—C5—C51—O52168.98 (18)
C15—N11—N12—C130.5 (2)C6—C5—C51—O5210.0 (3)
N11—N12—C13—C140.2 (2)O51—C51—O52—C522.1 (3)
N11—N12—C13—N1179.17 (17)C5—C51—O52—C52179.49 (18)
C2—N1—C13—N12120.5 (2)C51—O52—C52—C53161.93 (19)
C2—N1—C13—C1458.7 (3)O52—C52—C53—C5463.2 (3)
C7a—N1—C13—N1261.4 (3)C52—C53—C54—C55173.9 (2)
C7a—N1—C13—C14119.4 (2)C53—C54—C55—C5668.1 (3)
N12—C13—C14—C150.7 (2)C54—C55—C56—C57170.9 (2)
N1—C13—C14—C15178.6 (2)C55—C56—C57—C58179.0 (2)
N12—N11—C15—C140.9 (2)C56—C57—C58—C59173.3 (2)
N12—N11—C15—C16174.38 (18)
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the N11/N12/C13–C15 ring.
D—H···AD—HH···AD···AD—H···A
N11—H11···N3i0.862.163.011 (2)169
C14—H14···O51ii0.952.313.249 (3)168
C26—H26···N12iii0.952.533.292 (3)137
C22—H22···Cg10.952.843.472 (3)125
Symmetry codes: (i) x+1/2, y1/2, z+1/2; (ii) x+1/2, y+3/2, z+1; (iii) x+1/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC29H35ClN4O2
Mr507.06
Crystal system, space groupMonoclinic, C2/c
Temperature (K)120
a, b, c (Å)29.768 (4), 15.6022 (12), 11.8465 (15)
β (°) 93.247 (11)
V3)5493.2 (11)
Z8
Radiation typeMo Kα
µ (mm1)0.17
Crystal size (mm)0.30 × 0.30 × 0.24
Data collection
DiffractometerBruker Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.904, 0.960
No. of measured, independent and
observed [I > 2σ(I)] reflections
44941, 6303, 4127
Rint0.076
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.053, 0.116, 1.09
No. of reflections6303
No. of parameters329
H-atom treatmentH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0289P)2 + 10.0795P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)0.42, 0.32

Computer programs: COLLECT (Nonius, 1999), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008) and SHELXL2013 (Sheldrick, 2013), PLATON (Spek, 2009), SHELXL97 (Sheldrick, 2008), SHELXL2013 (Sheldrick, 2013) and PLATON (Spek, 2009).

Selected geometric parameters (Å, º) top
N1—C21.381 (3)N11—N121.358 (2)
C2—N31.324 (3)N12—C131.326 (3)
N3—C3a1.391 (3)C13—C141.397 (3)
C3a—C7a1.403 (3)C14—C151.381 (3)
C7a—N11.386 (3)C15—N111.354 (3)
C2—N1—C13—N12120.5 (2)C4—C5—C51—O519.4 (3)
C2—N1—C13—C1458.7 (3)C4—C5—C51—O52168.98 (18)
C7a—N1—C13—N1261.4 (3)C5—C51—O52—C52179.49 (18)
C7a—N1—C13—C14119.4 (2)C51—O52—C52—C53161.93 (19)
N1—C2—C21—C2235.2 (3)O52—C52—C53—C5463.2 (3)
N1—C2—C21—C26146.5 (2)C52—C53—C54—C55173.9 (2)
N3—C2—C21—C22144.6 (2)C53—C54—C55—C5668.1 (3)
N3—C2—C21—C2633.7 (3)C54—C55—C56—C57170.9 (2)
C14—C15—C16—C17143.4 (2)C55—C56—C57—C58179.0 (2)
C14—C15—C16—C1896.2 (3)C56—C57—C58—C59173.3 (2)
C14—C15—C16—C1922.5 (3)
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the N11/N12/C13–C15 ring.
D—H···AD—HH···AD···AD—H···A
N11—H11···N3i0.862.163.011 (2)169
C14—H14···O51ii0.952.313.249 (3)168
C26—H26···N12iii0.952.533.292 (3)137
C22—H22···Cg10.952.843.472 (3)125
Symmetry codes: (i) x+1/2, y1/2, z+1/2; (ii) x+1/2, y+3/2, z+1; (iii) x+1/2, y+1/2, z+1/2.
 

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