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The mol­ecules of the title compound, C22H21ClN4O, are conformationally chiral, and in the space group P212121 each crystal contains only one conformational enantio­mer. The intra­molecular dimensions provide evidence for polarization of the electronic structure. Mol­ecules are linked by a single C—H...π(arene) hydrogen bond into chains, which are themselves weakly linked into sheets by an aromatic π–π stacking inter­action.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110012023/gg3232sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110012023/gg3232Isup2.hkl
Contains datablock I

CCDC reference: 779960

Comment top

We are exploring the use of 5-amino-4-formylpyrazoles as building blocks in the synthesis of new heterocyclic compounds containing fused pyrazole ring systems, as such compounds have a wide range of potential applications (Elguero, 1984, 1996). In connection with this synthetic study, we report here the structure of the title compound, (I) (Fig. 1), which forms an interesting structure consisting of π-stacked hydrogen-bonded chains.

Compound (I) was prepared by base-catalysed condensation of 4'-chloroacetophenone with the intermediate (E)-N'-(4-formyl-3-methyl-1-phenyl-1H-pyrazol-5-yl)-N,N-dimethylformamidine, denoted (A) in the scheme, which itself had been prepared in a single step by reaction of the simple precursor 5-amino-3-methyl-1-phenylpyrazole with an excess of N,N-dimethylformamide and phosphorus(V) trichloride oxide, in a process which leads not only to formylation of the pyrazole ring at the hitherto-vacant 4-position, but also to conversion of the 5-amino group to a formamidine function by condensation with N,N-dimethylformamide.

The molecular conformation of (I) is conveniently considered in terms of the orientations of the various peripheral substituents relative to the central pyrazole ring, as defined by the relevant torsion angles (Table 1). Thus, while the chain between atoms C4 and C41 (Fig. 1) is nearly coplanar with the pyrazole ring, the two phenyl rings are both markedly twisted out of this plane: the dihedral angles between the pyrazole ring and the two aryl rings C11–C16 and C41–C46 are 25.1 (2) and 15.7 (2)°, respectively. Similarly, the dimethylaminomethine unit is significantly twisted out of the plane of the pyrazole ring. Consequently, the molecule of (I) has no internal symmetry and hence it is chiral. In space group P212121, therefore, each crystal contains only a single conformational enantiomer. However, this has no chemical significance and it may be expected that, in solution for example, all accessible molecular conformations are populated in a dynamic equilibrium.

The intramolecular dimensions (Table 1) provide evidence for polarization of the electronic structure. The C47—O47 and C48—C49 bonds are both long for their types [mean values (Allen et al., 1987) 1.222 and 1.340 Å, respectively; upper quartile values 1.229 and 1.348 Å, respectively], while the C47—C48 and C4—C49 bonds are both short for their types (mean vales 1.464 and 1.455 Å respectively; lower quartile values 1.453 and 1.447 Å, respectively). In addition, the C52—N53 bond is significantly shorter than the N1—C5 bond. The C5—N51 and N51—C52 distances can be compared with the context-specific examples found in the series of simple Schiff bases, (II) (see scheme), where the substituent Ar represents a range of substituted phenyl, or exceptionally pyridyl, groups (Castillo et al., 2010). For the C5—N51 bond, 15 independent values in the series of compounds (II) range from 1.381 (4) to 1.401 (3) Å, all longer than the comparable bond in (I), while for the N51—C52 bond, the values in the series (II) span the range 1.268 (3) to 1.294 (3) Å, all shorter than the corresponding bond in (I). Similarly, in compound (III) [Cambridge Structural Database (CSD; Allen, 2002) refcode CIZQEH; Moreno-Fuquen et al., 1999), the distances corresponding to the C5—N51 and N51—C52 bonds in (I) are 1.383 (2) and 1.289 (2) Å, respectively. The conclusion to be drawn from all of these observations is that the polarized form (Ia) is a significant contributor to the overall electronic structure, in addition to the conventional form (I). Electronic polarization of this type is not possible in the series (II), nor in compound (III).

Despite the polarization of the electronic structure in (I), there are no hydrogen bonds involving the O atom as the acceptor. Instead, molecules related by translation are linked by a single C—H···π(arene) hydrogen bond (Table 2) into simple chains running parallel to the [010] direction (Fig. 2). These chains are weakly linked into sheets by an aromatic ππ stacking interaction. The unsubstituted phenyl ring C11–C16 in the molecule at (x, y, z) makes a dihedral angle of 13.4 (2)° with the substituted phenyl ring C41–C46 in the molecule at (-1 + x, 1 + y, z). The ring centroid separation is 3.867 (2) Å and the interplanar spacing is ca 3.8 Å. The effect of this interaction is to link the hydrogen-bonded chain, albeit weakly, into a sheet parallel to (001) (Fig. 2). Four sheets of this type pass through each unit cell, in the domains 0 < z < 1/4, 1/4 < z < 1/2, 1/2 < z < 3/4 and 3/4 < z < 1.0, respectively, but there are no direction-specific interactions between adjacent sheets.

It is of interest briefly to compare the supramolecular aggregation in (I) with that in the closely related amino-substituted analogues (III) (CSD refcode CIZQEH) and (IV) (CSD refcode YICWUD; Zhang et al., 2007). Neither of the original reports mentioned any intermolecular interactions, but analysis using the deposited atomic coordinates shows that in (III), molecules related by a 21 screw axis in space group P21/n are linked into chains along [010] by a single C—H···π(arene) hydrogen bond (Fig. 3), while in compound (IV), molecules related by translation are linked by two independent N—H···N hydrogen bonds into a C(7)C(7)[R12(6)] (Bernstein et al., 1995) chain of rings along [100] (Fig. 4).

Experimental top

To a solution containing 1 mmol each of 4'-chloroacetophenone and (E)-N'-(4-formyl-3-methyl-1-phenyl-1H-pyrazol-5-yl)-N,N-dimethylformamidine, prepared from 5-amino-3-methyl-1-phenylpyrazole under Vilsmaier conditions (Häufel & Breitmaier, 1974), in absolute ethanol (10 ml), a catalytic quantity of sodium hydroxide (0.5 ml of a 30% w/v aqueous solution) was added, and the mixture was then stirred at room temperature for 2 h. The resulting solid product was collected by filtration and recrystallized by slow evaporation, at ambient temperature and in air, of a solution in ethanol, yielding crystals of (I) suitable for single-crystal X-ray diffraction. MS (70 eV) m/z (%): 392 (M+,100), 321 (11), 253 (44), 139 (43), 44 (16); HRMS, found: 392.1404; C22H2135ClN4O requires: 392.1404.

Refinement top

All H atoms were located in difference maps and 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 groups, which were permitted to rotate but not to tilt, and 1.2 for all other H atoms. The correct enantiomorph in the crystal selected for data collection was established by means of the Flack x parameter (Flack, 1983), x = -0.03 (9), and the Hooft y parameter (Hooft et al., 2008), y = 0.02 (7), calculated from 1620 Bijvoet pairs, equivalent to 99.1% 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. A stereoview of part of the crystal structure of (I), showing the formation of a sheet parallel to (001) built from the π-stacking of hydrogen-bonded chains parallel to [010]. For the sake of clarity, H atoms not involved in the motif shown have been omitted.
[Figure 3] Fig. 3. A stereoview of part of the crystal structure of (III) (CSD refcode CIZQEH; Moreno-Fuquen et al., 1999), showing the formation of a hydrogen-bonded chain running parallel to the [010] direction. The deposited atomic coordinates have been used and, for the sake of clarity, H atoms not involved in the motif shown have been omitted.
[Figure 4] Fig. 4. A stereoview of part of the crystal structure of (IV) (CSD refcode YICWUD; Zhang et al., 2007), showing the formation of a hydrogen-bonded chain of rings running parallel to the [100] direction. The deposited atomic coordinates have been used and, for the sake of clarity, H atoms not involved in the motif shown have been omitted.
(E)-N2-{4-[(E)-2-(4-Chlorobenzoyl)ethenyl]-3-methyl- 1-phenyl-1H-pyrazol-5-yl}-N1,N1-dimethylformamidine top
Crystal data top
C22H21ClN4OF(000) = 824
Mr = 392.88Dx = 1.324 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 3871 reflections
a = 8.2228 (3) Åθ = 3.2–26.1°
b = 8.3506 (2) ŵ = 0.21 mm1
c = 28.7043 (10) ÅT = 120 K
V = 1970.99 (11) Å3Block, colourless
Z = 40.12 × 0.06 × 0.06 mm
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
3871 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode2849 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.082
Detector resolution: 9.091 pixels mm-1θmax = 26.1°, θmin = 3.2°
ϕ and ω scansh = 109
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 810
Tmin = 0.978, Tmax = 0.987l = 3535
13638 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)] = 0.056H-atom parameters constrained
wR(F2) = 0.134 w = 1/[σ2(Fo2) + (0.0461P)2 + 0.2898P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
3871 reflectionsΔρmax = 0.25 e Å3
256 parametersΔρmin = 0.28 e Å3
0 restraintsAbsolute structure: Flack (1983), with 1620 Bijvoet pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.03 (9)
Crystal data top
C22H21ClN4OV = 1970.99 (11) Å3
Mr = 392.88Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 8.2228 (3) ŵ = 0.21 mm1
b = 8.3506 (2) ÅT = 120 K
c = 28.7043 (10) Å0.12 × 0.06 × 0.06 mm
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
3871 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2849 reflections with I > 2σ(I)
Tmin = 0.978, Tmax = 0.987Rint = 0.082
13638 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.056H-atom parameters constrained
wR(F2) = 0.134Δρmax = 0.25 e Å3
S = 1.05Δρmin = 0.28 e Å3
3871 reflectionsAbsolute structure: Flack (1983), with 1620 Bijvoet pairs
256 parametersAbsolute structure parameter: 0.03 (9)
0 restraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.5564 (4)1.0206 (3)0.41684 (9)0.0250 (7)
N20.5913 (4)0.9255 (3)0.45538 (9)0.0283 (7)
C30.6663 (4)0.7989 (4)0.43830 (11)0.0270 (8)
C40.6819 (4)0.8061 (4)0.38857 (10)0.0237 (7)
C50.6091 (4)0.9523 (4)0.37648 (10)0.0226 (7)
C110.4718 (4)1.1668 (4)0.42500 (10)0.0257 (8)
C120.4837 (5)1.2967 (4)0.39485 (11)0.0308 (8)
H120.54931.29000.36770.037*
C130.3993 (5)1.4354 (4)0.40470 (12)0.0368 (10)
H130.40641.52390.38400.044*
C140.3045 (5)1.4475 (4)0.44432 (12)0.0348 (9)
H140.24681.54350.45080.042*
C150.2945 (5)1.3192 (4)0.47420 (12)0.0349 (9)
H150.23001.32710.50150.042*
C160.3770 (5)1.1794 (4)0.46493 (11)0.0318 (8)
H160.36911.09150.48580.038*
C310.7189 (5)0.6694 (4)0.47107 (11)0.0374 (9)
H31A0.67950.69370.50250.056*
H31B0.83790.66310.47140.056*
H31C0.67380.56670.46080.056*
C410.9566 (4)0.2875 (4)0.34752 (11)0.0257 (8)
C420.9335 (5)0.2233 (4)0.39144 (11)0.0306 (8)
H420.86650.27830.41310.037*
C431.0066 (5)0.0795 (4)0.40447 (11)0.0307 (9)
H430.98800.03490.43440.037*
C441.1064 (5)0.0036 (4)0.37285 (12)0.0284 (8)
Cl441.20021 (12)0.17507 (10)0.38921 (3)0.0366 (3)
C451.1357 (4)0.0665 (4)0.32902 (12)0.0301 (9)
H451.20740.01390.30810.036*
C461.0592 (5)0.2071 (4)0.31624 (11)0.0313 (9)
H461.07620.24970.28590.038*
C470.8720 (4)0.4386 (4)0.33153 (11)0.0273 (8)
O470.8453 (3)0.4586 (3)0.28954 (8)0.0350 (7)
C480.8263 (4)0.5537 (4)0.36722 (11)0.0285 (8)
H480.85540.53310.39870.034*
C490.7437 (4)0.6889 (4)0.35703 (11)0.0274 (8)
H490.72430.70840.32490.033*
N510.5738 (4)1.0229 (3)0.33425 (9)0.0252 (7)
C520.6879 (5)1.0237 (4)0.30291 (10)0.0260 (8)
H520.79030.97700.31000.031*
N530.6641 (4)1.0890 (3)0.26078 (9)0.0309 (7)
C540.5089 (6)1.1657 (5)0.24972 (14)0.0494 (11)
H54A0.46351.21400.27800.074*
H54B0.43301.08540.23760.074*
H54C0.52631.24900.22620.074*
C550.7916 (5)1.0957 (4)0.22658 (12)0.0431 (10)
H55A0.88901.04280.23880.065*
H55B0.81671.20770.21940.065*
H55C0.75611.04100.19810.065*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0270 (18)0.0222 (14)0.0257 (14)0.0009 (13)0.0006 (13)0.0028 (11)
N20.0319 (19)0.0255 (14)0.0276 (14)0.0021 (14)0.0025 (13)0.0015 (13)
C30.031 (2)0.0220 (17)0.0286 (17)0.0019 (16)0.0025 (16)0.0015 (14)
C40.0199 (19)0.0230 (16)0.0282 (16)0.0009 (15)0.0029 (15)0.0002 (15)
C50.0197 (19)0.0236 (16)0.0246 (17)0.0037 (15)0.0019 (15)0.0031 (14)
C110.023 (2)0.0249 (17)0.0288 (17)0.0003 (17)0.0033 (15)0.0026 (14)
C120.035 (2)0.0265 (18)0.0306 (17)0.0023 (17)0.0042 (17)0.0008 (15)
C130.044 (3)0.0302 (19)0.036 (2)0.005 (2)0.0017 (18)0.0034 (16)
C140.037 (2)0.0270 (19)0.040 (2)0.0108 (19)0.0007 (19)0.0018 (16)
C150.037 (2)0.0351 (19)0.0324 (18)0.004 (2)0.0053 (17)0.0038 (16)
C160.033 (2)0.0283 (17)0.0339 (18)0.0002 (18)0.0023 (17)0.0032 (16)
C310.053 (3)0.0285 (18)0.0305 (18)0.009 (2)0.0071 (18)0.0012 (15)
C410.023 (2)0.0227 (17)0.0315 (17)0.0007 (16)0.0045 (16)0.0022 (14)
C420.037 (2)0.0264 (17)0.0284 (18)0.0002 (17)0.0006 (18)0.0034 (14)
C430.033 (2)0.0298 (18)0.0291 (18)0.0038 (18)0.0012 (16)0.0045 (15)
C440.025 (2)0.0240 (17)0.0362 (19)0.0015 (16)0.0082 (17)0.0008 (15)
Cl440.0387 (6)0.0276 (5)0.0436 (5)0.0081 (4)0.0044 (4)0.0018 (4)
C450.026 (2)0.0255 (18)0.039 (2)0.0034 (17)0.0032 (17)0.0004 (16)
C460.034 (2)0.0299 (18)0.0300 (18)0.0041 (18)0.0015 (17)0.0025 (14)
C470.025 (2)0.0243 (18)0.0329 (19)0.0027 (16)0.0002 (16)0.0037 (15)
O470.0417 (19)0.0358 (13)0.0275 (13)0.0100 (13)0.0010 (12)0.0047 (11)
C480.032 (2)0.0264 (18)0.0267 (17)0.0016 (17)0.0023 (16)0.0008 (14)
C490.030 (2)0.0260 (18)0.0266 (17)0.0026 (17)0.0021 (15)0.0039 (15)
N510.0269 (19)0.0233 (15)0.0255 (14)0.0028 (13)0.0030 (14)0.0027 (11)
C520.031 (2)0.0209 (17)0.0255 (17)0.0042 (17)0.0027 (17)0.0017 (13)
N530.032 (2)0.0331 (16)0.0281 (15)0.0010 (15)0.0032 (13)0.0056 (13)
C540.045 (3)0.058 (2)0.045 (2)0.003 (2)0.009 (2)0.0214 (19)
C550.061 (3)0.039 (2)0.0293 (19)0.001 (2)0.008 (2)0.0005 (17)
Geometric parameters (Å, º) top
N1—N21.392 (3)C42—H420.9500
N2—C31.318 (4)C43—C441.378 (5)
C3—C41.434 (4)C43—H430.9500
C4—C51.404 (4)C44—C451.385 (5)
C5—N11.362 (4)C44—Cl441.744 (3)
N1—C111.425 (4)C45—C461.381 (5)
C3—C311.497 (4)C45—H450.9500
C4—C491.427 (4)C46—H460.9500
C11—C161.390 (5)C47—O471.236 (4)
C11—C121.391 (4)C47—C481.454 (4)
C12—C131.379 (5)C48—C491.350 (5)
C12—H120.9500C48—H480.9500
C13—C141.382 (5)C49—H490.9500
C13—H130.9500C5—N511.379 (4)
C14—C151.375 (5)N51—C521.300 (4)
C14—H140.9500C52—N531.341 (4)
C15—C161.376 (5)C52—H520.9500
C15—H150.9500N53—C551.438 (5)
C16—H160.9500N53—C541.463 (5)
C31—H31A0.9800C54—H54A0.9800
C31—H31B0.9800C54—H54B0.9800
C31—H31C0.9800C54—H54C0.9800
C41—C421.383 (4)C55—H55A0.9800
C41—C461.403 (5)C55—H55B0.9800
C41—C471.512 (5)C55—H55C0.9800
C42—C431.394 (5)
C5—N1—N2111.8 (2)C43—C42—H42119.4
C5—N1—C11130.8 (3)C44—C43—C42118.4 (3)
N2—N1—C11117.3 (2)C44—C43—H43120.8
C3—N2—N1105.0 (2)C42—C43—H43120.8
N2—C3—C4112.2 (3)C43—C44—C45121.9 (3)
N2—C3—C31118.7 (3)C43—C44—Cl44118.7 (3)
C4—C3—C31129.0 (3)C45—C44—Cl44119.5 (3)
C5—C4—C49126.3 (3)C46—C45—C44119.0 (3)
C5—C4—C3104.1 (3)C46—C45—H45120.5
C49—C4—C3129.4 (3)C44—C45—H45120.5
N1—C5—N51120.1 (3)C45—C46—C41120.7 (3)
N1—C5—C4106.8 (3)C45—C46—H46119.6
N51—C5—C4132.8 (3)C41—C46—H46119.6
C16—C11—C12119.5 (3)O47—C47—C48123.5 (3)
C16—C11—N1118.3 (3)O47—C47—C41119.4 (3)
C12—C11—N1122.2 (3)C48—C47—C41117.2 (3)
C13—C12—C11119.5 (3)C49—C48—C47122.0 (3)
C13—C12—H12120.3C49—C48—H48119.0
C11—C12—H12120.3C47—C48—H48119.0
C12—C13—C14120.9 (3)C48—C49—C4128.0 (3)
C12—C13—H13119.6C48—C49—H49116.0
C14—C13—H13119.6C4—C49—H49116.0
C15—C14—C13119.4 (3)C52—N51—C5117.3 (3)
C15—C14—H14120.3N51—C52—N53121.4 (3)
C13—C14—H14120.3N51—C52—H52119.3
C14—C15—C16120.7 (3)N53—C52—H52119.3
C14—C15—H15119.6C52—N53—C55121.7 (3)
C16—C15—H15119.6C52—N53—C54120.1 (3)
C15—C16—C11120.0 (3)C55—N53—C54118.1 (3)
C15—C16—H16120.0N53—C54—H54A109.5
C11—C16—H16120.0N53—C54—H54B109.5
C3—C31—H31A109.5H54A—C54—H54B109.5
C3—C31—H31B109.5N53—C54—H54C109.5
H31A—C31—H31B109.5H54A—C54—H54C109.5
C3—C31—H31C109.5H54B—C54—H54C109.5
H31A—C31—H31C109.5N53—C55—H55A109.5
H31B—C31—H31C109.5N53—C55—H55B109.5
C42—C41—C46118.7 (3)H55A—C55—H55B109.5
C42—C41—C47122.5 (3)N53—C55—H55C109.5
C46—C41—C47118.8 (3)H55A—C55—H55C109.5
C41—C42—C43121.3 (3)H55B—C55—H55C109.5
C41—C42—H42119.4
C5—N1—N2—C30.2 (4)C12—C11—C16—C150.6 (5)
C11—N1—N2—C3179.1 (3)N1—C11—C16—C15179.5 (3)
N1—N2—C3—C40.4 (4)C46—C41—C42—C431.6 (5)
N1—N2—C3—C31179.0 (3)C47—C41—C42—C43176.7 (3)
N2—C3—C4—C50.4 (4)C41—C42—C43—C441.5 (5)
C31—C3—C4—C5178.9 (4)C42—C43—C44—C450.2 (5)
N2—C3—C4—C49174.8 (3)C42—C43—C44—Cl44179.2 (3)
C31—C3—C4—C493.7 (6)C43—C44—C45—C461.8 (5)
N2—N1—C5—N51174.8 (3)Cl44—C44—C45—C46179.2 (3)
C11—N1—C5—N513.9 (5)C44—C45—C46—C411.7 (5)
N2—N1—C5—C40.0 (4)C42—C41—C46—C450.1 (5)
C11—N1—C5—C4178.7 (3)C47—C41—C46—C45178.4 (3)
C49—C4—C5—N1175.2 (3)C42—C41—C47—O47152.6 (4)
C3—C4—C5—N10.2 (4)C46—C41—C47—O4725.7 (5)
C49—C4—C5—N511.3 (6)C3—C4—C49—C4811.8 (6)
C3—C4—C5—N51174.1 (4)C4—C49—C48—C47175.5 (3)
C5—N1—C11—C16154.5 (3)C49—C48—C47—C41176.9 (3)
N2—N1—C11—C1624.1 (4)C48—C47—C41—C4227.4 (5)
C5—N1—C11—C1226.6 (6)C46—C41—C47—C48154.4 (3)
N2—N1—C11—C12154.8 (3)O47—C47—C48—C493.1 (6)
C16—C11—C12—C130.9 (5)C5—C4—C49—C48174.0 (4)
N1—C11—C12—C13179.8 (3)N1—C5—N51—C52139.7 (3)
C11—C12—C13—C140.6 (6)C4—C5—N51—C5247.1 (5)
C12—C13—C14—C150.0 (6)C5—N51—C52—N53179.7 (3)
C13—C14—C15—C160.3 (6)N51—C52—N53—C541.9 (5)
C14—C15—C16—C110.1 (6)N51—C52—N53—C55177.6 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C52—H52···Cg1i0.952.833.432 (4)122
Symmetry code: (i) x, y+1, z.

Experimental details

Crystal data
Chemical formulaC22H21ClN4O
Mr392.88
Crystal system, space groupOrthorhombic, P212121
Temperature (K)120
a, b, c (Å)8.2228 (3), 8.3506 (2), 28.7043 (10)
V3)1970.99 (11)
Z4
Radiation typeMo Kα
µ (mm1)0.21
Crystal size (mm)0.12 × 0.06 × 0.06
Data collection
DiffractometerBruker Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.978, 0.987
No. of measured, independent and
observed [I > 2σ(I)] reflections
13638, 3871, 2849
Rint0.082
(sin θ/λ)max1)0.618
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.056, 0.134, 1.05
No. of reflections3871
No. of parameters256
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.25, 0.28
Absolute structureFlack (1983), with 1620 Bijvoet pairs
Absolute structure parameter0.03 (9)

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—N21.392 (3)C47—O471.236 (4)
N2—C31.318 (4)C47—C481.454 (4)
C3—C41.434 (4)C48—C491.350 (5)
C4—C51.404 (4)C5—N511.379 (4)
C5—N11.362 (4)N51—C521.300 (4)
C4—C491.427 (4)C52—N531.341 (4)
N2—N1—C11—C12154.8 (3)N1—C5—N51—C52139.7 (3)
C3—C4—C49—C4811.8 (6)C5—N51—C52—N53179.7 (3)
C4—C49—C48—C47175.5 (3)N51—C52—N53—C541.9 (5)
C49—C48—C47—C41176.9 (3)N51—C52—N53—C55177.6 (3)
C48—C47—C41—C4227.4 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C52—H52···Cg1i0.952.833.432 (4)122
Symmetry code: (i) x, y+1, z.
 

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