Crystal structure of (E)-4-{[2-(2,4-di-nitro-phen-yl)hydrazin-1-yl-idene]meth-yl}-3-methyl-1-phenyl-5-(1H-pyrrol-1-yl)-1H-pyrazole.

The title compound, C21H17N7O4, is in an 'extended' conformation aided by an intra-molecular N-H⋯O hydrogen bond. The pyrazole ring makes dihedral angles of 29.17 (6), 65.47 (4) and 9.91 (7)°, respectively, with the phenyl, pyrrole and benzene rings. In the crystal, mol-ecules are connected by pairs of N-H⋯O and C-H⋯O hydrogen bonds, forming inversion dimers which associate into ribbons running along the b axis through complementary C-H⋯O inter-actions.

Related literature

For the use of pyrazole compounds as building blocks of various heterocyclic compounds, see: Abramov et al. (2001 ▶); Quiroga et al. (2001 ▶); Wu et al. (2006 ▶); El-Emary (2006 ▶); Rangnekar & Dhamnaskar (1988 ▶). For the bioactivity of pyrazole-containing compounds, see: Mashevskaya et al. (2001 ▶); Janus et al. (1999 ▶); Park et al. (2005 ▶); Bouabdallah et al. (2006 ▶); Yıldırım et al. (2005 ▶); Bailey et al. (1985 ▶); Chu & Cutler (1986 ▶). For industrial applications of azo­pyrazole derivatives, see: Karci & Demircah (2006 ▶); Vicentini et al. (1998 ▶).

Experimental

Crystal data

C21H17N7O4

M = 431.42

Monoclinic,

a = 5.7955 (1) Å

b = 15.4472 (4) Å

c = 21.9289 (5) Å

β = 93.831 (1)°

V = 1958.78 (8) Å3

Z = 4

Cu Kα radiation

μ = 0.88 mm−1

T = 150 K

0.17 × 0.10 × 0.09 mm

Data collection

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer

Absorption correction: numerical (SADABS; Bruker, 2014 ▶) T min = 0.89, T max = 0.93

30722 measured reflections

3854 independent reflections

3425 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.089

S = 1.03

3854 reflections

290 parameters

H-atom parameters constrained

Δρmax = 0.20 e Å−3

Δρmin = −0.27 e Å−3

Data collection: APEX2 (Bruker, 2014 ▶); cell refinement: SAINT (Bruker, 2014 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXT (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2012 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814024039/is5380sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814024039/is5380Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814024039/is5380Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S1600536814024039/is5380fig1.tif

Numbering scheme for the title mol­ecule. Ellipsoids are drawn at the 50% probability level.

Click here for additional data file.

c . DOI: 10.1107/S1600536814024039/is5380fig2.tif

Packing diagram looking down the c axis showing two chains formed by complementary N—H⋯O and C—H⋯O inter­actions and their association through additional C—H⋯O inter­actions.

Click here for additional data file.

a . DOI: 10.1107/S1600536814024039/is5380fig3.tif

Packing diagram viewed down the a axis showing an edge view of several ribbons.

CCDC reference: 1031959

Additional supporting information: crystallographic information; 3D view; checkCIF report

C21H17N7O4	F(000) = 896
Mr = 431.42	Dx = 1.463 Mg m−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54178 Å
a = 5.7955 (1) Å	Cell parameters from 9846 reflections
b = 15.4472 (4) Å	θ = 6.3–72.1°
c = 21.9289 (5) Å	µ = 0.88 mm−1
β = 93.831 (1)°	T = 150 K
V = 1958.78 (8) Å3	Column, red-orange
Z = 4	0.17 × 0.10 × 0.09 mm

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	3854 independent reflections
Radiation source: INCOATEC IµS micro–focus source	3425 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.034
Detector resolution: 10.4167 pixels mm-1	θmax = 72.1°, θmin = 3.5°
ω scans	h = −7→6
Absorption correction: numerical (SADABS; Bruker, 2014)	k = −19→19
Tmin = 0.89, Tmax = 0.93	l = −26→26
30722 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033	Hydrogen site location: mixed
wR(F2) = 0.089	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0466P)2 + 0.6128P] where P = (Fo2 + 2Fc2)/3
3854 reflections	(Δ/σ)max < 0.001
290 parameters	Δρmax = 0.20 e Å−3
0 restraints	Δρmin = −0.27 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. H-atoms attached to carbon were placed in calculated positions (C—H = 0.95 - 0.98 Å) while that attached to nitrogen was placed in a location derived from a difference map and its parameters adjusted to give N—H = 0.91 Å. All were included as riding contributions with isotropic displacement parameters 1.2 - 1.5 times those of the attached atoms.

	x	y	z	Uiso*/Ueq
O1	−0.33378 (17)	0.99482 (6)	0.45404 (5)	0.0375 (2)
O2	−0.58503 (18)	0.90272 (7)	0.41597 (5)	0.0501 (3)
O3	−0.49349 (16)	0.60444 (6)	0.45127 (4)	0.0358 (2)
O4	−0.18232 (15)	0.54965 (6)	0.49537 (4)	0.0332 (2)
N1	0.97263 (17)	0.60556 (6)	0.70725 (5)	0.0242 (2)
N2	0.94167 (18)	0.69340 (6)	0.70316 (5)	0.0269 (2)
N3	0.80335 (16)	0.47264 (6)	0.66558 (4)	0.0232 (2)
N4	0.33730 (17)	0.67100 (7)	0.58210 (5)	0.0256 (2)
N5	0.14465 (17)	0.64891 (6)	0.54543 (5)	0.0258 (2)
H5A	0.1113	0.5925	0.5350	0.031*
N6	−0.40360 (19)	0.92045 (7)	0.44522 (5)	0.0327 (3)
N7	−0.30076 (17)	0.61280 (7)	0.47743 (5)	0.0260 (2)
C1	1.14907 (19)	0.57328 (8)	0.75003 (5)	0.0241 (2)
C2	1.3424 (2)	0.62502 (8)	0.76363 (6)	0.0276 (3)
H2	1.3569	0.6794	0.7440	0.033*
C3	1.5137 (2)	0.59637 (8)	0.80620 (6)	0.0304 (3)
H3	1.6455	0.6315	0.8159	0.036*
C4	1.4935 (2)	0.51679 (9)	0.83452 (6)	0.0312 (3)
H4	1.6119	0.4971	0.8632	0.037*
C5	1.3000 (2)	0.46609 (9)	0.82076 (6)	0.0312 (3)
H5	1.2866	0.4115	0.8402	0.037*
C6	1.1250 (2)	0.49398 (8)	0.77893 (6)	0.0276 (3)
H6	0.9912	0.4594	0.7702	0.033*
C7	0.81077 (19)	0.56305 (8)	0.67051 (5)	0.0226 (2)
C8	0.6671 (2)	0.62469 (7)	0.64242 (5)	0.0230 (2)
C9	0.7576 (2)	0.70498 (8)	0.66482 (5)	0.0249 (2)
C10	0.6691 (2)	0.79431 (8)	0.65187 (6)	0.0316 (3)
H10A	0.7726	0.8365	0.6729	0.047*
H10B	0.5136	0.8000	0.6664	0.047*
H10C	0.6630	0.8050	0.6077	0.047*
C11	0.9756 (2)	0.42083 (8)	0.64524 (6)	0.0304 (3)
H11	1.1119	0.4404	0.6277	0.036*
C12	0.9170 (3)	0.33692 (9)	0.65452 (6)	0.0365 (3)
H12	1.0042	0.2874	0.6445	0.044*
C13	0.7022 (2)	0.33657 (9)	0.68190 (6)	0.0348 (3)
H13	0.6194	0.2868	0.6936	0.042*
C14	0.6360 (2)	0.42042 (8)	0.68838 (6)	0.0284 (3)
H14	0.4988	0.4396	0.7056	0.034*
C15	0.4654 (2)	0.60777 (8)	0.60170 (5)	0.0236 (2)
H15	0.4279	0.5502	0.5895	0.028*
C16	0.0083 (2)	0.71292 (8)	0.52114 (5)	0.0247 (2)
C17	0.0773 (2)	0.80070 (8)	0.52864 (6)	0.0304 (3)
H17	0.2187	0.8136	0.5512	0.037*
C18	−0.0544 (2)	0.86720 (8)	0.50421 (6)	0.0320 (3)
H18	−0.0038	0.9254	0.5096	0.038*
C19	−0.2638 (2)	0.84940 (8)	0.47125 (6)	0.0285 (3)
C20	−0.3414 (2)	0.76630 (8)	0.46297 (5)	0.0269 (3)
H20	−0.4847	0.7551	0.4408	0.032*
C21	−0.2072 (2)	0.69842 (7)	0.48756 (5)	0.0241 (2)

	U11	U22	U33	U12	U13	U23
O1	0.0399 (5)	0.0267 (5)	0.0456 (6)	0.0029 (4)	0.0011 (4)	0.0057 (4)
O2	0.0423 (6)	0.0412 (6)	0.0629 (7)	0.0049 (5)	−0.0245 (5)	0.0074 (5)
O3	0.0296 (5)	0.0349 (5)	0.0410 (5)	−0.0028 (4)	−0.0129 (4)	−0.0048 (4)
O4	0.0302 (5)	0.0241 (5)	0.0442 (5)	0.0018 (4)	−0.0058 (4)	−0.0011 (4)
N1	0.0234 (5)	0.0212 (5)	0.0272 (5)	0.0005 (4)	−0.0034 (4)	−0.0015 (4)
N2	0.0285 (5)	0.0212 (5)	0.0305 (5)	0.0007 (4)	−0.0028 (4)	−0.0014 (4)
N3	0.0242 (5)	0.0210 (5)	0.0240 (5)	0.0003 (4)	−0.0023 (4)	−0.0007 (4)
N4	0.0224 (5)	0.0259 (5)	0.0276 (5)	0.0003 (4)	−0.0039 (4)	−0.0006 (4)
N5	0.0237 (5)	0.0232 (5)	0.0297 (5)	−0.0004 (4)	−0.0052 (4)	−0.0014 (4)
N6	0.0317 (6)	0.0313 (6)	0.0343 (6)	0.0039 (5)	−0.0024 (5)	0.0050 (4)
N7	0.0252 (5)	0.0278 (5)	0.0248 (5)	0.0003 (4)	−0.0012 (4)	−0.0024 (4)
C1	0.0217 (5)	0.0265 (6)	0.0237 (6)	0.0024 (5)	−0.0016 (4)	−0.0029 (5)
C2	0.0267 (6)	0.0250 (6)	0.0306 (6)	−0.0015 (5)	−0.0011 (5)	−0.0014 (5)
C3	0.0241 (6)	0.0318 (7)	0.0343 (7)	−0.0025 (5)	−0.0050 (5)	−0.0052 (5)
C4	0.0273 (6)	0.0343 (7)	0.0308 (6)	0.0015 (5)	−0.0075 (5)	−0.0015 (5)
C5	0.0320 (7)	0.0303 (6)	0.0304 (6)	−0.0020 (5)	−0.0041 (5)	0.0044 (5)
C6	0.0241 (6)	0.0300 (6)	0.0282 (6)	−0.0042 (5)	−0.0024 (5)	0.0011 (5)
C7	0.0219 (5)	0.0229 (6)	0.0228 (6)	−0.0005 (4)	−0.0006 (4)	−0.0016 (4)
C8	0.0232 (6)	0.0229 (6)	0.0229 (6)	0.0006 (4)	0.0008 (4)	−0.0002 (4)
C9	0.0251 (6)	0.0240 (6)	0.0255 (6)	0.0004 (5)	0.0003 (4)	−0.0010 (4)
C10	0.0351 (7)	0.0226 (6)	0.0359 (7)	0.0012 (5)	−0.0053 (5)	−0.0012 (5)
C11	0.0312 (6)	0.0287 (6)	0.0317 (6)	0.0048 (5)	0.0047 (5)	−0.0013 (5)
C12	0.0490 (8)	0.0243 (6)	0.0362 (7)	0.0084 (6)	0.0033 (6)	−0.0006 (5)
C13	0.0465 (8)	0.0247 (6)	0.0329 (7)	−0.0059 (6)	−0.0009 (6)	0.0029 (5)
C14	0.0271 (6)	0.0295 (6)	0.0281 (6)	−0.0031 (5)	−0.0009 (5)	0.0007 (5)
C15	0.0244 (6)	0.0215 (6)	0.0246 (6)	−0.0010 (4)	−0.0001 (4)	−0.0004 (4)
C16	0.0232 (6)	0.0257 (6)	0.0251 (6)	0.0015 (5)	0.0002 (4)	0.0011 (4)
C17	0.0264 (6)	0.0268 (6)	0.0371 (7)	−0.0019 (5)	−0.0059 (5)	0.0011 (5)
C18	0.0306 (7)	0.0250 (6)	0.0396 (7)	−0.0020 (5)	−0.0033 (5)	0.0027 (5)
C19	0.0273 (6)	0.0280 (6)	0.0299 (6)	0.0040 (5)	−0.0014 (5)	0.0045 (5)
C20	0.0243 (6)	0.0310 (6)	0.0251 (6)	0.0019 (5)	−0.0018 (4)	0.0001 (5)
C21	0.0241 (6)	0.0244 (6)	0.0235 (6)	−0.0011 (5)	0.0002 (4)	−0.0012 (4)

O1—N6	1.2291 (15)	C5—H5	0.9500
O2—N6	1.2255 (15)	C6—H6	0.9500
O3—N7	1.2279 (13)	C7—C8	1.3822 (16)
O4—N7	1.2416 (13)	C8—C9	1.4213 (16)
N1—C7	1.3636 (15)	C8—C15	1.4469 (16)
N1—N2	1.3708 (14)	C9—C10	1.4928 (16)
N1—C1	1.4305 (14)	C10—H10A	0.9800
N2—C9	1.3254 (15)	C10—H10B	0.9800
N3—C11	1.3769 (16)	C10—H10C	0.9800
N3—C14	1.3806 (16)	C11—C12	1.3589 (19)
N3—C7	1.4012 (15)	C11—H11	0.9500
N4—C15	1.2834 (16)	C12—C13	1.418 (2)
N4—N5	1.3747 (14)	C12—H12	0.9500
N5—C16	1.3527 (15)	C13—C14	1.3609 (19)
N5—H5A	0.9184	C13—H13	0.9500
N6—C19	1.4579 (16)	C14—H14	0.9500
N7—C21	1.4410 (15)	C15—H15	0.9500
C1—C6	1.3906 (17)	C16—C17	1.4201 (17)
C1—C2	1.3921 (17)	C16—C21	1.4246 (16)
C2—C3	1.3891 (17)	C17—C18	1.3677 (18)
C2—H2	0.9500	C17—H17	0.9500
C3—C4	1.3858 (19)	C18—C19	1.3973 (18)
C3—H3	0.9500	C18—H18	0.9500
C4—C5	1.3847 (18)	C19—C20	1.3683 (18)
C4—H4	0.9500	C20—C21	1.3924 (17)
C5—C6	1.3898 (17)	C20—H20	0.9500
C7—N1—N2	110.87 (9)	N2—C9—C10	119.82 (11)
C7—N1—C1	130.77 (10)	C8—C9—C10	128.81 (11)
N2—N1—C1	118.20 (9)	C9—C10—H10A	109.5
C9—N2—N1	105.75 (9)	C9—C10—H10B	109.5
C11—N3—C14	108.66 (10)	H10A—C10—H10B	109.5
C11—N3—C7	125.81 (10)	C9—C10—H10C	109.5
C14—N3—C7	124.97 (10)	H10A—C10—H10C	109.5
C15—N4—N5	115.85 (10)	H10B—C10—H10C	109.5
C16—N5—N4	118.63 (10)	C12—C11—N3	108.17 (12)
C16—N5—H5A	119.2	C12—C11—H11	125.9
N4—N5—H5A	122.1	N3—C11—H11	125.9
O2—N6—O1	123.59 (11)	C11—C12—C13	107.61 (12)
O2—N6—C19	118.15 (11)	C11—C12—H12	126.2
O1—N6—C19	118.26 (11)	C13—C12—H12	126.2
O3—N7—O4	122.13 (10)	C14—C13—C12	107.58 (12)
O3—N7—C21	119.32 (10)	C14—C13—H13	126.2
O4—N7—C21	118.55 (9)	C12—C13—H13	126.2
C6—C1—C2	120.80 (11)	C13—C14—N3	107.98 (11)
C6—C1—N1	121.12 (11)	C13—C14—H14	126.0
C2—C1—N1	118.04 (11)	N3—C14—H14	126.0
C3—C2—C1	119.34 (12)	N4—C15—C8	119.65 (11)
C3—C2—H2	120.3	N4—C15—H15	120.2
C1—C2—H2	120.3	C8—C15—H15	120.2
C4—C3—C2	120.38 (12)	N5—C16—C17	119.99 (11)
C4—C3—H3	119.8	N5—C16—C21	123.88 (11)
C2—C3—H3	119.8	C17—C16—C21	116.13 (11)
C5—C4—C3	119.70 (12)	C18—C17—C16	121.76 (12)
C5—C4—H4	120.1	C18—C17—H17	119.1
C3—C4—H4	120.1	C16—C17—H17	119.1
C4—C5—C6	120.88 (12)	C17—C18—C19	119.82 (12)
C4—C5—H5	119.6	C17—C18—H18	120.1
C6—C5—H5	119.6	C19—C18—H18	120.1
C5—C6—C1	118.87 (11)	C20—C19—C18	121.32 (11)
C5—C6—H6	120.6	C20—C19—N6	119.01 (11)
C1—C6—H6	120.6	C18—C19—N6	119.67 (11)
N1—C7—C8	107.55 (10)	C19—C20—C21	118.99 (11)
N1—C7—N3	122.82 (10)	C19—C20—H20	120.5
C8—C7—N3	129.63 (10)	C21—C20—H20	120.5
C7—C8—C9	104.47 (10)	C20—C21—C16	121.97 (11)
C7—C8—C15	126.04 (11)	C20—C21—N7	115.90 (10)
C9—C8—C15	129.44 (11)	C16—C21—N7	122.13 (10)
N2—C9—C8	111.35 (10)
C7—N1—N2—C9	1.25 (13)	C14—N3—C11—C12	0.56 (14)
C1—N1—N2—C9	−174.68 (10)	C7—N3—C11—C12	172.24 (11)
C15—N4—N5—C16	−177.12 (11)	N3—C11—C12—C13	−0.41 (15)
C7—N1—C1—C6	−26.82 (18)	C11—C12—C13—C14	0.11 (16)
N2—N1—C1—C6	148.16 (11)	C12—C13—C14—N3	0.22 (15)
C7—N1—C1—C2	155.46 (12)	C11—N3—C14—C13	−0.48 (14)
N2—N1—C1—C2	−29.57 (15)	C7—N3—C14—C13	−172.26 (11)
C6—C1—C2—C3	0.61 (18)	N5—N4—C15—C8	−177.73 (10)
N1—C1—C2—C3	178.34 (11)	C7—C8—C15—N4	175.05 (11)
C1—C2—C3—C4	0.50 (19)	C9—C8—C15—N4	−1.91 (19)
C2—C3—C4—C5	−0.8 (2)	N4—N5—C16—C17	6.28 (17)
C3—C4—C5—C6	−0.1 (2)	N4—N5—C16—C21	−173.53 (11)
C4—C5—C6—C1	1.2 (2)	N5—C16—C17—C18	179.26 (12)
C2—C1—C6—C5	−1.45 (19)	C21—C16—C17—C18	−0.92 (19)
N1—C1—C6—C5	−179.11 (11)	C16—C17—C18—C19	0.5 (2)
N2—N1—C7—C8	−1.12 (13)	C17—C18—C19—C20	0.3 (2)
C1—N1—C7—C8	174.14 (11)	C17—C18—C19—N6	−179.94 (12)
N2—N1—C7—N3	179.54 (10)	O2—N6—C19—C20	−1.03 (18)
C1—N1—C7—N3	−5.19 (19)	O1—N6—C19—C20	178.62 (12)
C11—N3—C7—N1	−60.95 (16)	O2—N6—C19—C18	179.19 (13)
C14—N3—C7—N1	109.43 (13)	O1—N6—C19—C18	−1.16 (18)
C11—N3—C7—C8	119.87 (14)	C18—C19—C20—C21	−0.56 (19)
C14—N3—C7—C8	−69.75 (17)	N6—C19—C20—C21	179.67 (11)
N1—C7—C8—C9	0.52 (12)	C19—C20—C21—C16	0.08 (18)
N3—C7—C8—C9	179.80 (11)	C19—C20—C21—N7	179.52 (11)
N1—C7—C8—C15	−177.05 (11)	N5—C16—C21—C20	−179.55 (11)
N3—C7—C8—C15	2.2 (2)	C17—C16—C21—C20	0.64 (17)
N1—N2—C9—C8	−0.90 (13)	N5—C16—C21—N7	1.04 (18)
N1—N2—C9—C10	177.49 (11)	C17—C16—C21—N7	−178.78 (11)
C7—C8—C9—N2	0.25 (13)	O3—N7—C21—C20	−3.71 (16)
C15—C8—C9—N2	177.71 (11)	O4—N7—C21—C20	176.00 (11)
C7—C8—C9—C10	−177.97 (12)	O3—N7—C21—C16	175.74 (11)
C15—C8—C9—C10	−0.5 (2)	O4—N7—C21—C16	−4.56 (16)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···O4	0.92	1.97	2.6208 (13)	126
N5—H5A···O4i	0.92	2.34	3.2065 (13)	158
C15—H15···O3i	0.95	2.59	3.4853 (15)	158
C18—H18···O1ii	0.95	2.40	3.1887 (16)	140

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N5H5AO4	0.92	1.97	2.6208(13)	126
N5H5AO4i	0.92	2.34	3.2065(13)	158
C15H15O3i	0.95	2.59	3.4853(15)	158
C18H18O1ii	0.95	2.40	3.1887(16)	140

Symmetry codes: (i) ; (ii) .