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The mol­ecules of the title compound, C26H19Cl2N5, are conformationally chiral, with none of the aryl groups coplanar with the pyrazolo[3,4-b]pyridine core of the mol­ecule. A single unique N-H...N hydrogen bond links the mol­ecules into two symmetry-related sets of C(11) chains running parallel to the [011] and [01\overline{1}] directions, respectively, and these two sets of chains are linked into a continuous three-dimensional framework structure by a single unique C-H...N hydrogen bond which forms a chain parallel to the [100] direction.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110004026/sk3364sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110004026/sk3364Isup2.hkl
Contains datablock I

CCDC reference: 774089

Comment top

Simple nitrogen heterocycles, such pyridines, pyrazoles, pyrimidines or pyrroles, are of interest in chemical biology or medicinal chemistry, and also for the preparation of new fused pyrazolo-heterocyclic derivatives. We are currently exploring the use of 6-chloro-4-(4-chlorophenyl)-3-methyl-1-phenyl-1H- pyrazolo[3,4-b]pyridine-5-carbaldehyde, itself readily prepared under Vilsmeier–Haack formylation conditions from 4-(4-chlorophenyl)-3-methyl-1-phenyl-4,5-dihydro-1H- pyrazolo[3,4-b]pyridin-6(7H)-one, as a building-block for the synthesis of polyannellated heterocyclic systems (Verdecía et al., 1996; Girreser et al., 2004; Quiroga et al., 1998, 2005). It was hoped that the reaction of this carbaldehyde with 1,2-benzenediamine would lead to a cyclization, forming a dihydropyrazolo[4',3':5,6]pyrido[2,3-b][1,5]benzodiazepine system, but instead this reaction led to the formation and isolation of the intermediate title compound, (I) (Fig. 1). In the formation of (I), condensation has occurred between the aldehyde function and one of the amino groups in the benzenediamine reactant (see first scheme), but the cyclization step, involving nucleophilic displacement of the 6-chloro atom on the pyridine ring by the second amino group, has not occurred. We report here the structure of (I), which proves to be of interest as the molecules are linked into a single three-dimensional framework structure by the action of just two hydrogen bonds.

The molecular conformation of (I) can readily be defined in terms of five torsion angles (Fig. 1, Table 1), which show that while the Schiff base-type space unit comprising atoms C57, N57 and C51 is almost coplanar with the pyrazolopyridine unit, the three pendent aryl rings are all markedly rotated out of this plane. The dihedral angles made between the plane of the pyrazolopyridine unit and the planes of the aryl rings C11–C16, C41–C46 and C51–C56 are 21.4 (2), 75.3 (2) and 29.9 (2)°, respectively. It is reasonable to associate the much large dihedral angle involving ring C41–C46 with the greater steric congestion in the vicinity of this ring. In particular, a small dihedral angle between this ring and the heterocyclic unit is almost certainly prevented by the presence of both the methyl group containing atom C31 and the C—H bond at atom C57 (Fig. 1). Consistent with this idea, the smallest dihedral angle is found for ring C11–C16, where the intramolecular steric constraints are the least for any of the rings. This conformation means that the molecule of (I) exhibits no internal symmetry and so is conformationally chiral. However, the space group accommodates equal numbers of the two conformational enantiomers, and the choice of the selected asymmetric unit has no chemical significance. The bond distances (Table 1) in the heterocyclic fragment of the molecule, which show the same pattern as found in similar pyrazolo[3,4-b]pyridines (Low et al., 2002, 2007; Abonia et al., 2005; Quiroga et al., 2009), having due regard to the differences between the peripheral substituents, are consistent with the occurrence of aromatic-type electronic delocalization within the pyridine and strong bond fixation in the pyrazole ring. Likewise, there is strong bond fixation, as expected, in the spacer unit between the pyridine and the aminophenyl rings.

The molecules of (I) are linked into a continuous three-dimensional framework structure by just two hydrogen bonds, one each of N—H···N and C—H···N types (Table 2), and the formation of the framework structure is readily analysed in terms of two simple one-dimensional sub-structures, each of which depends on only one hydrogen bond. The N—H···N hydrogen bond links molecules related by an n-glide plane. Amino atom N52 in the molecule at (x, y, z) acts as hydrogen-bond donor to the pyrazole ring atom N2 in the molecule at (1/2 − x, 1/2 + y, −1/2 + z), so linking molecules related by the n-glide plane at x = 1/4 into a C(11) [see Bernstein et al. (1995) for graph-set notation] chain running parallel to the [011] direction (Fig. 2). A similar chain is formed by molecules related by the n-glide plane at x = 3/4, and this second chain is related to the first by the action of the 21 screw axes parallel to [001]. Hence, the chain based on the n-glide plane at x = 3/4 runs parallel to [011] (Fig. 2), so that the structure consists of alternating layers of C(11) chains along [011] and [011], stacked in the [100] direction. Within each layer, the chains are related to one another by unit translations along [010] or [001].

The second sub-structure is simpler and consists of just a simple chain. The aryl atom C46 in the molecule at (x, y, z) acts as hydrogen-bond donor to the pyridine ring atom N7 in the molecule at (1/2 + x, 3/2 − y, z), so forming a C(7) chain running parallel to the [100] direction and containing molecules related by the a-glide plane at y = 3/4 (Fig. 3). Within this chain, adjacent molecules, for example those at (x, y, z) and (1/2 + x, 3/2 − y, z), are components of C(11) chains along [011] and [011], respectively. Hence, the overall action of all the chains parallel to [100] is to link each chain along [011] to each chain along [011], so linking all of the molecules into a single three-dimensional framework. There are neither C—H···π(arene) nor C—H···π(pyridine) hydrogen bonds, nor any ππ stacking interactions, in the structure of (I).

It is of interest briefly to compare the crystal structure of (I) reported here with those of some close analogues, compounds (II)–(VI) (see second scheme). The crystallization characteristics of (II)-(VI) differ markedly from those of (I). Firstly, (IV) and (V) both crystallize as stoichiometric monosolvates with dimethylformamide (Low et al., 2007). Secondly, unlike (I), which crystallizes in the Sohnke space group Pna21, compounds (II)–(VI) all crystallize in the centrosymmetric space groups P1 [for (II) (Low et al., 2002), (III) (Abonia et al., 2005) and (IV) (Low et al., 2007)] or C2/c [for (V) (Low et al., 2007) and (VI) (Quiroga et al., 2009)]. In addition, the crystal structures of (II)–(VI) all contain C—H···π(arene) hydrogen bonds, whereas such interactions are absent from the structure of (I).

In the structure of (II), there are two independent C—H···π(arene) hydrogen bonds, each using a different arene ring as acceptor, and their action is to link the molecules into chains of centrosymmetric rings. These chains are linked into sheets by a ππ stacking interaction between pairs of pyridine rings, giving a two-dimensional supramolecular structure. In (III), the supramolecular structure is one-dimensional and contains two types of centrosymmetric ring built alternately from pairs of C—H···π(arene) hydrogen bonds and pairs of C—H···O hydrogen bonds. Symmetry-related pairs of C—H···π(arene) hydrogen bonds in the structure of (IV) link pairs of molecules into centrosymmetric dimers, i.e. a finite zero-dimensional hydrogen-bonded structure, while in (V) C—H···π(arene) and C—H···N hydrogen bonds once again generate a chain in which two types of centrosymmetric ring alternate. Finally, in the structure of (VI), the molecules are linked into rather complex double chains by a combination of N—H···N, C—H···N and C—H···π(arene) hydrogen bonds. Thus, overall, the supramolecular structures generated by direction-specific interactions are zero-dimensional in (IV), one-dimensional for (III), (V) and (VI), two-dimensional for (II), and three-dimensional for (I). However, in terms just of hydrogen bonds, as opposed to ππ stacking interactions, the hydrogen-bonded structures in (II), (III), (V) and (VI) are one-dimensional. The sharp contrast between this behaviour and that of (I) can be traced directly to the space group for (I), Pna21, where the combination of two hydrogen bonds connecting molecules related by a glide plane and a screw axis, respectively, generates a three-dimensional array. But this simply raises the question of why (I) crystallizes in the relatively uncommon space group Pna21, representing only ca 1.4% of the entries in the Cambridge Strcutural Database (release 5.31, November 2009; Allen, 2002), rather than P1 (23.0% of entries) or C2/c (8.0% of entries).

Experimental top

Glacial acetic acid (3 drops) was added to a solution of 6-chloro-4-(4-chlorophenyl)-3-methyl-1-phenyl-1H- pyrazolo[3,4-b]pyridine-5-carbaldehyde (0.64 mmol) and 1,2-benzenediamine (0.64 mmol) in ethanol (5 ml) and the mixture was heated under reflux for 1 h. The mixture was then cooled to ambient temperature, and the resulting precipitate was collected by filtration, washed with cold ethanol and recrystallized from ethanol to afford yellow crystals of (I) suitable for single-crystal X-ray diffraction (yield 80%, m.p. 474–476 K). MS (EI, 70 eV) m/z (%): 475/473/471 (M+, 2/5/10), 359 (5), 119 (100), 77 (11). Analysis: found: C 66.3, H 4.0, N 14.6%; C26H19Cl2N5 requires: C 66.1, H 4.1, N 14.8%.

Refinement top

All H atoms were located in difference maps. H atoms bonded to C atoms were then treated as riding atoms in geometrically idealized positions, with C—H = 0.95 (aromatic and alkenyl) or 0.98 Å (methyl), and with Uiso(H) = kUeq(C), where k = 1.5 for the methyl group, which was permitted to rotate but not to tilt, and 1.2 for all other H atoms bonded to C atoms. The coordinates of the H atoms bonded to N52 were refined with Uiso(H) = 1.2Ueq(N), giving N—H distances of 1.00 (6) and 1.02 (6) Å. The correct orientation of the structure with respect to the polar axis direction was established by means of the Flack x parameter (Flack, 1983), x = 0.12 (10), and the Hooft y parameter (Hooft et al., 2008), y = 0.15 (8), both calculated with 1792 Bijvoet pairs (96.4% coverage).

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); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. Part of the crystal structure of (I), showing symmetry-related hydrogen-bonded C(11) chains running parallel to the [011] and [011] directions, and linked by the C—H···N hydrogen bond. For the sake of clarity, H atoms bonded to C atoms not involved in the motifs shown have been omitted.
[Figure 3] Fig. 3. Part of the crystal structure of (I), showing a hydrogen-bonded C(7) chain running parallel to the [100] direction, in which alternate molecules lie in C(11) chains along [011] and [011]. Hydrogen bonds are shown as dashed lines. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*), a hash (#) or a dollar sign ($) are at the symmetry positions (1/2 + x, 3/2 − y, z), (1 + x, y, z) and (−1/2 + x, 3/2 − y, z), respectively.
(E)-N-{[6-Chloro-4-(4-chlorophenyl)-3-methyl-1-phenyl-1H- pyrazolo[3,4-b]pyridin-5-yl]methylene}benzene-1,2-diamine top
Crystal data top
C26H19Cl2N5F(000) = 976
Mr = 472.36Dx = 1.436 Mg m3
Orthorhombic, Pna21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2nCell parameters from 3777 reflections
a = 10.013 (2) Åθ = 2.9–25.1°
b = 12.3487 (12) ŵ = 0.32 mm1
c = 17.666 (4) ÅT = 120 K
V = 2184.4 (7) Å3Needle, yellow
Z = 40.37 × 0.06 × 0.04 mm
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
3777 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode2630 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.104
Detector resolution: 9.091 pixels mm-1θmax = 25.1°, θmin = 2.9°
ϕ and ω scansh = 1111
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1414
Tmin = 0.899, Tmax = 0.987l = 2021
15595 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.057H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.127 w = 1/[σ2(Fo2) + (0.0407P)2 + 1.7541P]
where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max = 0.001
3777 reflectionsΔρmax = 0.39 e Å3
306 parametersΔρmin = 0.34 e Å3
1 restraintAbsolute structure: Flack (1983), with 1792 pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.12 (10)
Crystal data top
C26H19Cl2N5V = 2184.4 (7) Å3
Mr = 472.36Z = 4
Orthorhombic, Pna21Mo Kα radiation
a = 10.013 (2) ŵ = 0.32 mm1
b = 12.3487 (12) ÅT = 120 K
c = 17.666 (4) Å0.37 × 0.06 × 0.04 mm
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
3777 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2630 reflections with I > 2σ(I)
Tmin = 0.899, Tmax = 0.987Rint = 0.104
15595 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.057H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.127Δρmax = 0.39 e Å3
S = 1.10Δρmin = 0.34 e Å3
3777 reflectionsAbsolute structure: Flack (1983), with 1792 pairs
306 parametersAbsolute structure parameter: 0.12 (10)
1 restraint
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.0770 (4)0.7263 (3)0.8465 (2)0.0271 (10)
N20.0567 (5)0.6149 (3)0.8539 (3)0.0321 (11)
C30.1374 (6)0.5667 (4)0.8067 (3)0.0260 (13)
C3A0.2136 (5)0.6443 (4)0.7656 (3)0.0244 (12)
C40.3103 (5)0.6428 (4)0.7105 (3)0.0254 (13)
C50.3612 (5)0.7420 (4)0.6849 (3)0.0243 (11)
C60.3053 (6)0.8363 (4)0.7174 (3)0.0269 (13)
N70.2149 (4)0.8408 (3)0.7708 (2)0.0250 (10)
C7A0.1703 (5)0.7441 (4)0.7935 (3)0.0246 (12)
C110.0024 (5)0.7974 (4)0.8919 (3)0.0281 (13)
C120.0496 (6)0.9013 (5)0.9051 (3)0.0357 (14)
H120.13190.92470.88390.043*
C130.0261 (6)0.9706 (5)0.9501 (3)0.0400 (15)
H130.00421.04230.95910.048*
C140.1446 (7)0.9362 (5)0.9815 (3)0.0392 (15)
H140.19600.98421.01170.047*
C150.1877 (6)0.8329 (4)0.9691 (3)0.0341 (14)
H150.26870.80890.99150.041*
C160.1147 (5)0.7631 (4)0.9243 (3)0.0273 (13)
H160.14540.69130.91600.033*
C310.1393 (7)0.4479 (4)0.8027 (3)0.0358 (15)
H31A0.22960.42160.81380.054*
H31B0.11300.42460.75190.054*
H31C0.07660.41820.84000.054*
C410.3566 (5)0.5375 (4)0.6806 (3)0.0229 (11)
C420.2732 (6)0.4787 (4)0.6345 (3)0.0317 (13)
H420.19040.50880.61880.038*
C430.3085 (5)0.3779 (4)0.6111 (3)0.0339 (13)
H430.25190.33870.57770.041*
C440.4259 (6)0.3327 (4)0.6359 (3)0.0294 (13)
Cl440.46779 (14)0.20246 (10)0.61010 (9)0.0367 (3)
C450.5117 (6)0.3897 (4)0.6819 (4)0.0426 (15)
H450.59330.35870.69860.051*
C460.4753 (6)0.4941 (4)0.7033 (3)0.0373 (14)
H460.53390.53560.73410.045*
C570.4555 (5)0.7422 (4)0.6223 (3)0.0300 (13)
H570.47330.67480.59850.036*
N570.5150 (5)0.8236 (4)0.5970 (2)0.0337 (11)
C510.5980 (6)0.8139 (5)0.5336 (3)0.0306 (13)
C520.5967 (5)0.9016 (4)0.4832 (3)0.0271 (12)
C530.6762 (6)0.8957 (5)0.4201 (3)0.0411 (16)
H530.67410.95330.38450.049*
C540.7583 (6)0.8094 (5)0.4072 (3)0.0412 (15)
H540.81320.80760.36330.049*
C550.7611 (7)0.7254 (5)0.4577 (3)0.0431 (16)
H550.81910.66580.44930.052*
C560.6805 (6)0.7270 (5)0.5205 (3)0.0381 (15)
H560.68190.66800.55500.046*
N520.5177 (5)0.9882 (4)0.4982 (3)0.0369 (12)
H52A0.495 (6)1.038 (5)0.454 (3)0.044*
H52B0.442 (6)0.987 (4)0.535 (3)0.044*
Cl610.35055 (15)0.96467 (10)0.68734 (8)0.0361 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.023 (2)0.031 (3)0.028 (2)0.0010 (19)0.001 (2)0.0001 (19)
N20.037 (3)0.022 (2)0.037 (2)0.005 (2)0.005 (2)0.008 (2)
C30.026 (3)0.024 (3)0.027 (3)0.007 (3)0.001 (3)0.003 (2)
C3A0.031 (3)0.021 (3)0.021 (3)0.003 (2)0.005 (2)0.001 (2)
C40.023 (3)0.023 (3)0.031 (3)0.001 (2)0.009 (2)0.002 (2)
C50.019 (3)0.031 (3)0.023 (2)0.002 (2)0.003 (3)0.003 (2)
C60.034 (3)0.016 (3)0.031 (3)0.006 (2)0.012 (3)0.002 (2)
N70.025 (3)0.027 (2)0.024 (2)0.001 (2)0.003 (2)0.0035 (18)
C7A0.024 (3)0.025 (3)0.025 (3)0.006 (2)0.006 (2)0.002 (2)
C110.026 (3)0.026 (3)0.032 (3)0.005 (3)0.004 (2)0.005 (2)
C120.027 (3)0.036 (4)0.044 (3)0.001 (3)0.001 (3)0.001 (3)
C130.035 (4)0.032 (3)0.053 (4)0.000 (3)0.008 (3)0.009 (3)
C140.036 (4)0.038 (3)0.043 (3)0.007 (3)0.001 (3)0.002 (3)
C150.023 (3)0.038 (4)0.041 (3)0.003 (3)0.005 (3)0.008 (3)
C160.026 (3)0.032 (3)0.024 (2)0.002 (2)0.001 (2)0.007 (2)
C310.054 (4)0.018 (3)0.035 (3)0.001 (3)0.005 (3)0.004 (2)
C410.022 (3)0.020 (2)0.027 (3)0.002 (2)0.003 (3)0.004 (2)
C420.029 (3)0.034 (3)0.033 (3)0.000 (3)0.008 (3)0.001 (2)
C430.028 (3)0.029 (3)0.045 (3)0.002 (2)0.012 (3)0.006 (3)
C440.031 (3)0.014 (3)0.043 (3)0.002 (2)0.002 (3)0.000 (2)
Cl440.0341 (8)0.0258 (7)0.0501 (8)0.0040 (6)0.0012 (8)0.0056 (6)
C450.032 (4)0.037 (3)0.059 (4)0.009 (3)0.013 (3)0.011 (3)
C460.034 (4)0.030 (3)0.048 (4)0.003 (3)0.005 (3)0.011 (3)
C570.028 (3)0.023 (3)0.039 (3)0.002 (2)0.001 (3)0.002 (2)
N570.034 (3)0.033 (3)0.033 (3)0.004 (2)0.002 (2)0.002 (2)
C510.024 (3)0.039 (3)0.029 (3)0.007 (3)0.001 (3)0.001 (3)
C520.013 (3)0.030 (3)0.039 (3)0.000 (2)0.006 (3)0.002 (2)
C530.036 (4)0.046 (4)0.042 (3)0.018 (3)0.005 (3)0.010 (3)
C540.036 (4)0.048 (4)0.039 (3)0.001 (3)0.007 (3)0.005 (3)
C550.048 (4)0.032 (4)0.049 (4)0.004 (3)0.004 (3)0.001 (3)
C560.035 (4)0.043 (4)0.036 (3)0.006 (3)0.002 (3)0.001 (3)
N520.038 (3)0.028 (3)0.044 (3)0.003 (2)0.005 (3)0.005 (2)
Cl610.0420 (9)0.0241 (7)0.0423 (7)0.0014 (7)0.0091 (8)0.0039 (6)
Geometric parameters (Å, º) top
N1—N21.397 (6)C31—H31C0.9800
N2—C31.304 (7)C41—C461.365 (7)
C3—C3A1.424 (7)C41—C421.374 (7)
C3A—C41.373 (7)C42—C431.358 (7)
C4—C51.402 (7)C42—H420.9500
C5—C61.414 (7)C43—C441.373 (7)
C6—N71.308 (7)C43—H430.9500
N7—C7A1.336 (6)C44—C451.376 (8)
C7A—N11.341 (6)C44—Cl441.724 (5)
C3A—C7A1.397 (7)C45—C461.392 (7)
N1—C111.404 (7)C45—H450.9500
C3—C311.470 (7)C46—H460.9500
C4—C411.478 (7)C57—N571.250 (6)
C5—C571.454 (7)C57—H570.9500
C6—Cl611.732 (5)N57—C511.400 (7)
C11—C161.372 (7)C51—C561.373 (8)
C11—C121.388 (8)C51—C521.402 (8)
C12—C131.392 (8)C52—N521.356 (7)
C12—H120.9500C52—C531.371 (8)
C13—C141.377 (8)C53—C541.366 (8)
C13—H130.9500C53—H530.9500
C14—C151.364 (8)C54—C551.368 (8)
C14—H140.9500C54—H540.9500
C15—C161.380 (7)C55—C561.372 (8)
C15—H150.9500C55—H550.9500
C16—H160.9500C56—H560.9500
C31—H31A0.9800N52—H52A1.02 (6)
C31—H31B0.9800N52—H52B1.00 (6)
C7A—N1—N2109.2 (4)H31A—C31—H31C109.5
C7A—N1—C11131.8 (4)H31B—C31—H31C109.5
N2—N1—C11119.0 (4)C46—C41—C42119.8 (5)
C3—N2—N1107.4 (4)C46—C41—C4120.9 (5)
N2—C3—C3A110.6 (5)C42—C41—C4119.1 (5)
N2—C3—C31119.6 (5)C43—C42—C41120.4 (5)
C3A—C3—C31129.8 (5)C43—C42—H42119.8
C4—C3A—C7A118.7 (5)C41—C42—H42119.8
C4—C3A—C3137.0 (5)C42—C43—C44119.9 (5)
C7A—C3A—C3104.3 (5)C42—C43—H43120.1
C3A—C4—C5118.3 (5)C44—C43—H43120.1
C3A—C4—C41119.1 (4)C43—C44—C45121.0 (5)
C5—C4—C41122.6 (5)C43—C44—Cl44120.2 (4)
C4—C5—C6116.4 (5)C45—C44—Cl44118.8 (4)
C4—C5—C57118.9 (4)C44—C45—C46118.1 (5)
C6—C5—C57124.4 (5)C44—C45—H45120.9
N7—C6—C5127.0 (5)C46—C45—H45120.9
N7—C6—Cl61111.3 (4)C41—C46—C45120.8 (5)
C5—C6—Cl61121.7 (4)C41—C46—H46119.6
C6—N7—C7A114.2 (5)C45—C46—H46119.6
N7—C7A—N1126.1 (5)N57—C57—C5125.6 (5)
N7—C7A—C3A125.4 (5)N57—C57—H57117.2
N1—C7A—C3A108.5 (4)C5—C57—H57117.2
C16—C11—C12120.4 (5)C57—N57—C51120.0 (5)
C16—C11—N1120.0 (5)C56—C51—N57123.9 (5)
C12—C11—N1119.6 (5)C56—C51—C52120.1 (5)
C11—C12—C13118.6 (6)N57—C51—C52115.9 (5)
C11—C12—H12120.7N52—C52—C53122.6 (5)
C13—C12—H12120.7N52—C52—C51119.4 (5)
C14—C13—C12120.7 (6)C53—C52—C51118.0 (5)
C14—C13—H13119.7C54—C53—C52121.8 (5)
C12—C13—H13119.7C54—C53—H53119.1
C15—C14—C13119.8 (6)C52—C53—H53119.1
C15—C14—H14120.1C53—C54—C55119.6 (6)
C13—C14—H14120.1C53—C54—H54120.2
C14—C15—C16120.6 (6)C55—C54—H54120.2
C14—C15—H15119.7C54—C55—C56120.3 (6)
C16—C15—H15119.7C54—C55—H55119.8
C11—C16—C15119.9 (5)C56—C55—H55119.8
C11—C16—H16120.0C55—C56—C51120.1 (6)
C15—C16—H16120.0C55—C56—H56120.0
C3—C31—H31A109.5C51—C56—H56120.0
C3—C31—H31B109.5C52—N52—H52A117 (3)
H31A—C31—H31B109.5C52—N52—H52B124 (3)
C3—C31—H31C109.5H52A—N52—H52B110 (5)
C7A—N1—N2—C30.7 (5)N1—C11—C12—C13179.8 (5)
C11—N1—N2—C3179.5 (4)C11—C12—C13—C140.8 (9)
N1—N2—C3—C3A0.6 (6)C12—C13—C14—C150.6 (9)
N1—N2—C3—C31179.2 (5)C13—C14—C15—C161.0 (9)
N2—C3—C3A—C4180.0 (6)C12—C11—C16—C151.5 (7)
C31—C3—C3A—C40.2 (10)N1—C11—C16—C15179.8 (5)
N2—C3—C3A—C7A0.4 (6)C14—C15—C16—C110.0 (8)
C31—C3—C3A—C7A179.5 (5)C3A—C4—C41—C46102.5 (6)
C7A—C3A—C4—C50.0 (7)C5—C4—C41—C4677.6 (7)
C3—C3A—C4—C5179.7 (6)C3A—C4—C41—C4271.8 (7)
C7A—C3A—C4—C41179.9 (5)C5—C4—C41—C42108.1 (6)
C3—C3A—C4—C410.4 (9)C46—C41—C42—C430.3 (8)
C3A—C4—C5—C61.3 (7)C4—C41—C42—C43174.6 (5)
C41—C4—C5—C6178.6 (5)C41—C42—C43—C442.3 (9)
C3A—C4—C5—C57174.9 (5)C42—C43—C44—C452.5 (9)
C41—C4—C5—C575.0 (7)C42—C43—C44—Cl44177.0 (4)
C4—C5—C6—N72.7 (8)C43—C44—C45—C460.6 (9)
C57—C5—C6—N7175.9 (5)Cl44—C44—C45—C46178.9 (5)
C4—C5—C6—Cl61175.9 (4)C42—C41—C46—C451.6 (9)
C57—C5—C6—Cl612.8 (7)C4—C41—C46—C45172.6 (5)
C5—C6—N7—C7A2.3 (8)C44—C45—C46—C411.5 (9)
Cl61—C6—N7—C7A176.5 (3)C4—C5—C57—N57175.1 (5)
C6—N7—C7A—N1179.2 (5)C6—C5—C57—N5711.9 (9)
C6—N7—C7A—C3A0.7 (7)C5—C57—N57—C51176.5 (5)
N2—N1—C7A—N7179.5 (5)C57—N57—C51—C5638.9 (8)
C11—N1—C7A—N70.3 (9)C57—N57—C51—C52143.2 (5)
N2—N1—C7A—C3A0.5 (5)C56—C51—C52—N52177.9 (5)
C11—N1—C7A—C3A179.8 (5)N57—C51—C52—N520.0 (7)
C4—C3A—C7A—N70.4 (8)C56—C51—C52—C532.2 (8)
C3—C3A—C7A—N7179.8 (5)N57—C51—C52—C53179.9 (5)
C4—C3A—C7A—N1179.7 (4)N52—C52—C53—C54177.8 (6)
C3—C3A—C7A—N10.1 (5)C51—C52—C53—C542.2 (8)
C7A—N1—C11—C16159.5 (5)C52—C53—C54—C550.7 (9)
N2—N1—C11—C1620.3 (7)C53—C54—C55—C561.0 (9)
C7A—N1—C11—C1222.2 (8)C54—C55—C56—C511.0 (9)
N2—N1—C11—C12158.1 (5)N57—C51—C56—C55178.4 (5)
C16—C11—C12—C131.8 (8)C52—C51—C56—C550.6 (9)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N52—H52A···N2i1.02 (6)2.07 (6)3.082 (7)170 (5)
C46—H46···N7ii0.952.463.367 (7)160
Symmetry codes: (i) x+1/2, y+1/2, z1/2; (ii) x+1/2, y+3/2, z.

Experimental details

Crystal data
Chemical formulaC26H19Cl2N5
Mr472.36
Crystal system, space groupOrthorhombic, Pna21
Temperature (K)120
a, b, c (Å)10.013 (2), 12.3487 (12), 17.666 (4)
V3)2184.4 (7)
Z4
Radiation typeMo Kα
µ (mm1)0.32
Crystal size (mm)0.37 × 0.06 × 0.04
Data collection
DiffractometerBruker Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.899, 0.987
No. of measured, independent and
observed [I > 2σ(I)] reflections
15595, 3777, 2630
Rint0.104
(sin θ/λ)max1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.057, 0.127, 1.10
No. of reflections3777
No. of parameters306
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.39, 0.34
Absolute structureFlack (1983), with 1792 pairs
Absolute structure parameter0.12 (10)

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 PLATON (Spek, 2009).

Selected geometric parameters (Å, º) top
N1—N21.397 (6)C5—C61.414 (7)
N2—C31.304 (7)C6—N71.308 (7)
C3—C3A1.424 (7)N7—C7A1.336 (6)
C3A—C41.373 (7)C7A—N11.341 (6)
C4—C51.402 (7)C3A—C7A1.397 (7)
N2—N1—C11—C12158.1 (5)C5—C57—N57—C51176.5 (5)
C3A—C4—C41—C4271.8 (7)C57—N57—C51—C52143.2 (5)
C4—C5—C57—N57175.1 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N52—H52A···N2i1.02 (6)2.07 (6)3.082 (7)170 (5)
C46—H46···N7ii0.952.463.367 (7)160
Symmetry codes: (i) x+1/2, y+1/2, z1/2; (ii) x+1/2, y+3/2, z.
 

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