1-(2-Chloro-benzyl-idene)-2-(2,4-dinitro-phen-yl)hydrazine.

In the title compound, C(13)H(9)ClN(4)O(4), there are two crystallographically independent mol-ecules in the asymmetric unit, which have very similar conformations. The C=N-N angles in each independent mol-ecule are 115.0 (2) and 116.6 (2)°, which are significantly smaller than the ideal value of 120° expected for sp(2)-hybridized N atoms. This is probably a consequence of repulsion between the nitro-gen lone pairs and the adjacent N-N bonds. Two bifurcated intra-molecular N-H⋯O hydrogen bonds help to establish the mol-ecular conformation and consolidate the crystal packing.

Related literature

For general background, see: Garnovskii et al. (1993 ▶); Anderson et al. (1997 ▶); Musie et al. (2001 ▶); Paul et al. (2002 ▶); Shi et al. (2007 ▶); For related structures, see: Baughman et al. (2004 ▶); Zare et al. (2005 ▶); El-Seify & El-Dossoki (2006 ▶); Kim & Yoon (1998 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C13H9ClN4O4

M = 320.69

Triclinic,

a = 7.2286 (7) Å

b = 7.6596 (8) Å

c = 25.145 (2) Å

α = 95.691 (2)°

β = 93.030 (2)°

γ = 99.728 (3)°

V = 1362.0 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.31 mm−1

T = 295 (2) K

0.15 × 0.12 × 0.08 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.956, T max = 0.976

7216 measured reflections

4776 independent reflections

3273 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.125

S = 1.07

4776 reflections

397 parameters

H-atom parameters constrained

Δρmax = 0.42 e Å−3

Δρmin = −0.36 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005 ▶); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808033357/fj2153sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808033357/fj2153Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C13H9ClN4O4	Z = 4
Mr = 320.69	F(000) = 656
Triclinic, P1	Dx = 1.564 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2286 (7) Å	Cell parameters from 1793 reflections
b = 7.6596 (8) Å	θ = 2.7–24.9°
c = 25.145 (2) Å	µ = 0.31 mm−1
α = 95.691 (2)°	T = 295 K
β = 93.030 (2)°	Block, yellow
γ = 99.728 (3)°	0.15 × 0.12 × 0.08 mm
V = 1362.0 (2) Å3

Bruker APEXII CCD area-detector diffractometer	4776 independent reflections
Radiation source: fine-focus sealed tube	3273 reflections with I > 2σ(I)
graphite	Rint = 0.021
φ and ω scans	θmax = 25.0°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −8→8
Tmin = 0.956, Tmax = 0.976	k = −9→5
7216 measured reflections	l = −28→29

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.125	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0511P)2 + 0.2987P] where P = (Fo2 + 2Fc2)/3
4776 reflections	(Δ/σ)max = 0.001
397 parameters	Δρmax = 0.42 e Å−3
0 restraints	Δρmin = −0.36 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.

	x	y	z	Uiso*/Ueq
Cl1	0.32732 (10)	0.39535 (11)	0.21587 (3)	0.0647 (2)
Cl2	0.43812 (11)	0.46461 (12)	0.65151 (3)	0.0739 (3)
O1	1.1413 (3)	0.8066 (3)	0.24502 (8)	0.0769 (6)
O2	1.4364 (3)	0.8957 (4)	0.23973 (8)	0.0901 (8)
O3	1.6810 (3)	1.1413 (4)	0.08840 (11)	0.1047 (9)
O4	1.4958 (3)	1.1774 (3)	0.02231 (9)	0.0754 (6)
O5	−0.0518 (4)	−0.1695 (3)	0.37193 (10)	0.0957 (8)
O6	0.0550 (3)	−0.0357 (3)	0.44708 (4)	0.0817 (7)
O7	−0.1612 (4)	0.1254 (4)	0.22106 (9)	0.0899 (8)
O8	−0.1463 (3)	0.4102 (3)	0.23032 (8)	0.0804 (7)
N1	0.7500 (3)	0.6855 (3)	0.12714 (8)	0.0490 (5)
N2	0.9138 (3)	0.7485 (3)	0.15793 (8)	0.0506 (6)
H2	0.9218	0.7309	0.1912	0.061*
N3	1.2749 (4)	0.8647 (3)	0.21971 (9)	0.0586 (6)
N4	1.5265 (4)	1.1204 (3)	0.06490 (11)	0.0626 (7)
N5	0.2250 (3)	0.4769 (3)	0.48803 (9)	0.0544 (6)
N6	0.1464 (3)	0.3138 (3)	0.46212 (8)	0.0555 (6)
H6	0.1359	0.2206	0.4790	0.067*
N7	0.0038 (3)	−0.0334 (3)	0.40054 (10)	0.0584 (6)
N8	−0.1249 (3)	0.2712 (4)	0.24773 (9)	0.0613 (6)
C1	0.2909 (3)	0.4329 (3)	0.14910 (10)	0.0440 (6)
C2	0.4356 (3)	0.5294 (3)	0.12368 (10)	0.0428 (6)
C3	0.3991 (4)	0.5523 (4)	0.07027 (10)	0.0508 (7)
H3	0.4928	0.6154	0.0522	0.061*
C4	0.2273 (4)	0.4835 (4)	0.04363 (11)	0.0565 (7)
H4	0.2058	0.5001	0.0078	0.068*
C5	0.0867 (4)	0.3899 (4)	0.06992 (11)	0.0558 (7)
H5	−0.0295	0.3438	0.0518	0.067*
C6	0.1179 (4)	0.3646 (3)	0.12285 (11)	0.0506 (7)
H6A	0.0232	0.3020	0.1407	0.061*
C7	0.6178 (3)	0.6038 (3)	0.15160 (10)	0.0470 (6)
H7	0.6378	0.5915	0.1878	0.056*
C8	1.0634 (3)	0.8386 (3)	0.13611 (10)	0.0436 (6)
C9	1.2406 (3)	0.8962 (3)	0.16462 (10)	0.0450 (6)
C10	1.3931 (3)	0.9855 (3)	0.14090 (10)	0.0466 (6)
H10	1.5096	1.0204	0.1599	0.056*
C11	1.3680 (4)	1.0207 (3)	0.08927 (10)	0.0479 (6)
C12	1.1976 (4)	0.9667 (4)	0.05948 (11)	0.0522 (7)
H12	1.1849	0.9913	0.0241	0.063*
C13	1.0483 (4)	0.8770 (3)	0.08255 (10)	0.0501 (7)
H13	0.9341	0.8404	0.0625	0.060*
C14	0.4405 (4)	0.6574 (4)	0.62064 (11)	0.0555 (7)
C15	0.3642 (4)	0.6497 (4)	0.56796 (10)	0.0517 (7)
C16	0.3711 (4)	0.8103 (4)	0.54624 (12)	0.0626 (8)
H16	0.3214	0.8099	0.5113	0.075*
C17	0.4496 (4)	0.9698 (5)	0.57508 (13)	0.0700 (9)
H17	0.4537	1.0755	0.5595	0.084*
C18	0.5230 (4)	0.9733 (5)	0.62741 (13)	0.0713 (9)
H18	0.5753	1.0813	0.6471	0.086*
C19	0.5181 (4)	0.8170 (5)	0.65008 (12)	0.0664 (8)
H19	0.5669	0.8187	0.6851	0.080*
C20	0.2786 (4)	0.4815 (4)	0.53736 (10)	0.0548 (7)
H20	0.2629	0.3771	0.5539	0.066*
C21	0.0852 (3)	0.2998 (4)	0.40979 (10)	0.0451 (6)
C22	0.0134 (3)	0.1353 (3)	0.37897 (10)	0.0461 (6)
C23	−0.0515 (3)	0.1268 (4)	0.32600 (10)	0.0482 (6)
H23	−0.0975	0.0172	0.3064	0.058*
C24	−0.0474 (3)	0.2805 (4)	0.30277 (9)	0.0462 (6)
C25	0.0247 (4)	0.4448 (4)	0.33107 (10)	0.0512 (7)
H25	0.0282	0.5484	0.3145	0.061*
C26	0.0902 (4)	0.4542 (4)	0.38328 (10)	0.0513 (7)
H26	0.1394	0.5649	0.4018	0.062*

	U11	U22	U33	U12	U13	U23
Cl1	0.0580 (4)	0.0837 (5)	0.0489 (4)	−0.0052 (4)	0.0051 (3)	0.0196 (4)
Cl2	0.0731 (5)	0.0892 (6)	0.0596 (5)	0.0129 (4)	−0.0076 (4)	0.0178 (4)
O1	0.0683 (14)	0.1072 (18)	0.0515 (12)	−0.0034 (13)	0.0101 (10)	0.0190 (12)
O2	0.0658 (15)	0.131 (2)	0.0598 (13)	−0.0178 (14)	−0.0154 (11)	0.0137 (13)
O3	0.0540 (14)	0.142 (2)	0.1053 (19)	−0.0302 (15)	0.0087 (14)	0.0299 (17)
O4	0.0938 (17)	0.0597 (13)	0.0773 (15)	0.0076 (12)	0.0342 (12)	0.0249 (12)
O5	0.158 (3)	0.0482 (13)	0.0751 (16)	0.0065 (15)	−0.0070 (15)	0.0038 (12)
O6	0.123 (2)	0.0665 (14)	0.0573 (13)	0.0157 (13)	−0.0011 (13)	0.0240 (11)
O7	0.110 (2)	0.0898 (18)	0.0566 (13)	−0.0106 (15)	−0.0197 (13)	0.0052 (13)
O8	0.0857 (16)	0.1023 (18)	0.0622 (13)	0.0302 (14)	−0.0007 (11)	0.0327 (13)
N1	0.0405 (12)	0.0503 (13)	0.0541 (13)	0.0000 (10)	0.0056 (10)	0.0075 (11)
N2	0.0407 (12)	0.0596 (14)	0.0483 (12)	−0.0026 (11)	0.0055 (10)	0.0087 (11)
N3	0.0588 (15)	0.0641 (16)	0.0468 (13)	−0.0031 (13)	0.0014 (12)	0.0015 (11)
N4	0.0632 (17)	0.0517 (15)	0.0701 (17)	−0.0032 (13)	0.0235 (14)	0.0057 (13)
N5	0.0539 (14)	0.0647 (16)	0.0447 (13)	0.0106 (12)	0.0054 (11)	0.0056 (12)
N6	0.0634 (15)	0.0572 (15)	0.0458 (13)	0.0082 (12)	0.0013 (11)	0.0114 (11)
N7	0.0695 (16)	0.0589 (16)	0.0513 (15)	0.0147 (13)	0.0099 (12)	0.0185 (13)
N8	0.0507 (14)	0.086 (2)	0.0468 (14)	0.0045 (14)	0.0041 (11)	0.0180 (15)
C1	0.0436 (14)	0.0430 (14)	0.0459 (14)	0.0060 (12)	0.0066 (11)	0.0081 (12)
C2	0.0395 (14)	0.0403 (14)	0.0508 (15)	0.0089 (11)	0.0069 (11)	0.0109 (12)
C3	0.0467 (15)	0.0534 (16)	0.0559 (16)	0.0097 (13)	0.0110 (13)	0.0187 (13)
C4	0.0537 (17)	0.0669 (19)	0.0502 (16)	0.0106 (15)	−0.0001 (13)	0.0155 (14)
C5	0.0441 (15)	0.0583 (18)	0.0625 (18)	0.0037 (13)	−0.0058 (13)	0.0088 (14)
C6	0.0418 (15)	0.0514 (16)	0.0577 (17)	0.0015 (13)	0.0051 (12)	0.0120 (13)
C7	0.0423 (14)	0.0480 (16)	0.0512 (15)	0.0060 (12)	0.0058 (12)	0.0093 (13)
C8	0.0425 (14)	0.0393 (14)	0.0478 (15)	0.0030 (12)	0.0095 (11)	0.0026 (11)
C9	0.0478 (15)	0.0415 (14)	0.0425 (14)	0.0007 (12)	0.0047 (12)	0.0006 (11)
C10	0.0399 (14)	0.0411 (15)	0.0544 (16)	−0.0018 (12)	0.0038 (12)	−0.0015 (12)
C11	0.0480 (16)	0.0392 (14)	0.0545 (16)	−0.0011 (12)	0.0132 (13)	0.0049 (12)
C12	0.0544 (17)	0.0531 (17)	0.0491 (15)	0.0055 (14)	0.0079 (13)	0.0095 (13)
C13	0.0446 (15)	0.0510 (16)	0.0519 (16)	0.0013 (13)	0.0005 (12)	0.0058 (13)
C14	0.0407 (15)	0.075 (2)	0.0496 (16)	0.0070 (14)	0.0036 (12)	0.0078 (15)
C15	0.0413 (15)	0.0687 (19)	0.0446 (15)	0.0058 (14)	0.0084 (12)	0.0073 (14)
C16	0.0589 (18)	0.077 (2)	0.0512 (17)	0.0058 (16)	0.0117 (14)	0.0091 (16)
C17	0.067 (2)	0.069 (2)	0.075 (2)	0.0072 (17)	0.0198 (17)	0.0153 (18)
C18	0.0606 (19)	0.078 (2)	0.070 (2)	0.0016 (17)	0.0130 (16)	−0.0064 (18)
C19	0.0544 (18)	0.089 (2)	0.0519 (17)	0.0091 (17)	0.0009 (14)	−0.0013 (18)
C20	0.0517 (16)	0.069 (2)	0.0442 (16)	0.0088 (15)	0.0039 (13)	0.0126 (14)
C21	0.0395 (14)	0.0584 (17)	0.0399 (14)	0.0102 (13)	0.0087 (11)	0.0115 (13)
C22	0.0455 (15)	0.0498 (16)	0.0459 (15)	0.0095 (13)	0.0096 (12)	0.0142 (13)
C23	0.0443 (15)	0.0559 (17)	0.0440 (15)	0.0046 (13)	0.0080 (11)	0.0074 (13)
C24	0.0393 (14)	0.0624 (18)	0.0375 (14)	0.0067 (13)	0.0046 (11)	0.0108 (13)
C25	0.0495 (16)	0.0574 (18)	0.0499 (16)	0.0083 (14)	0.0100 (12)	0.0202 (14)
C26	0.0513 (16)	0.0526 (16)	0.0499 (16)	0.0066 (13)	0.0063 (12)	0.0082 (13)

Cl1—C1	1.745 (2)	C5—H5	0.9300
Cl2—C14	1.733 (3)	C6—H6A	0.9300
O1—N3	1.229 (3)	C7—H7	0.9300
O2—N3	1.222 (3)	C8—C13	1.409 (3)
O3—N4	1.214 (3)	C8—C9	1.413 (3)
O4—N4	1.220 (3)	C9—C10	1.391 (3)
O5—N7	1.202 (3)	C10—C11	1.361 (3)
O6—N7	1.211 (3)	C10—H10	0.9300
O7—N8	1.224 (3)	C11—C12	1.385 (4)
O8—N8	1.221 (3)	C12—C13	1.367 (3)
N1—C7	1.272 (3)	C12—H12	0.9300
N1—N2	1.368 (3)	C13—H13	0.9300
N2—C8	1.354 (3)	C14—C19	1.379 (4)
N2—H2	0.8600	C14—C15	1.399 (4)
N3—O1	1.229 (3)	C15—C16	1.389 (4)
N3—C9	1.445 (3)	C15—C20	1.456 (4)
N4—C11	1.464 (3)	C16—C17	1.374 (4)
N5—C20	1.275 (3)	C16—H16	0.9300
N5—N6	1.367 (3)	C17—C18	1.389 (4)
N6—C21	1.354 (3)	C17—H17	0.9300
N6—H6	0.8600	C18—C19	1.372 (4)
N7—O6	1.211 (3)	C18—H18	0.9300
N7—C22	1.443 (3)	C19—H19	0.9300
N8—C24	1.456 (3)	C20—H20	0.9300
C1—C6	1.377 (3)	C21—C26	1.410 (4)
C1—C2	1.396 (3)	C21—C22	1.414 (4)
C2—C3	1.389 (3)	C22—C23	1.380 (3)
C2—C7	1.457 (3)	C23—C24	1.362 (4)
C3—C4	1.375 (4)	C23—H23	0.9300
C3—H3	0.9300	C24—C25	1.386 (4)
C4—C5	1.379 (4)	C25—C26	1.363 (4)
C4—H4	0.9300	C25—H25	0.9300
C5—C6	1.376 (4)	C26—H26	0.9300
C7—N1—N2	115.0 (2)	C11—C10—C9	118.5 (2)
C8—N2—N1	120.0 (2)	C11—C10—H10	120.7
C8—N2—H2	120.0	C9—C10—H10	120.7
N1—N2—H2	120.0	C10—C11—C12	122.1 (2)
O2—N3—O1	121.8 (2)	C10—C11—N4	118.6 (2)
O2—N3—O1	121.8 (2)	C12—C11—N4	119.3 (2)
O2—N3—C9	118.9 (2)	C13—C12—C11	119.4 (2)
O1—N3—C9	119.2 (2)	C13—C12—H12	120.3
O1—N3—C9	119.2 (2)	C11—C12—H12	120.3
O3—N4—O4	123.9 (3)	C12—C13—C8	121.5 (2)
O3—N4—C11	117.9 (3)	C12—C13—H13	119.3
O4—N4—C11	118.2 (3)	C8—C13—H13	119.3
C20—N5—N6	116.6 (2)	C19—C14—C15	121.8 (3)
C21—N6—N5	119.6 (2)	C19—C14—Cl2	117.5 (2)
C21—N6—H6	120.2	C15—C14—Cl2	120.7 (2)
N5—N6—H6	120.2	C16—C15—C14	117.1 (3)
O5—N7—O6	120.9 (2)	C16—C15—C20	121.2 (3)
O5—N7—O6	120.9 (2)	C14—C15—C20	121.7 (3)
O5—N7—C22	119.6 (2)	C17—C16—C15	121.6 (3)
O6—N7—C22	119.4 (3)	C17—C16—H16	119.2
O6—N7—C22	119.4 (3)	C15—C16—H16	119.2
O8—N8—O7	123.5 (3)	C16—C17—C18	120.0 (3)
O8—N8—C24	118.0 (3)	C16—C17—H17	120.0
O7—N8—C24	118.5 (3)	C18—C17—H17	120.0
C6—C1—C2	121.8 (2)	C19—C18—C17	119.8 (3)
C6—C1—Cl1	118.19 (19)	C19—C18—H18	120.1
C2—C1—Cl1	119.98 (19)	C17—C18—H18	120.1
C3—C2—C1	117.3 (2)	C18—C19—C14	119.7 (3)
C3—C2—C7	120.8 (2)	C18—C19—H19	120.2
C1—C2—C7	121.9 (2)	C14—C19—H19	120.2
C4—C3—C2	121.3 (2)	N5—C20—C15	120.2 (3)
C4—C3—H3	119.4	N5—C20—H20	119.9
C2—C3—H3	119.4	C15—C20—H20	119.9
C3—C4—C5	120.1 (3)	N6—C21—C26	120.1 (3)
C3—C4—H4	120.0	N6—C21—C22	123.4 (2)
C5—C4—H4	120.0	C26—C21—C22	116.5 (2)
C6—C5—C4	120.2 (3)	C23—C22—C21	121.7 (2)
C6—C5—H5	119.9	C23—C22—N7	115.8 (2)
C4—C5—H5	119.9	C21—C22—N7	122.5 (2)
C1—C6—C5	119.3 (2)	C24—C23—C22	119.3 (3)
C1—C6—H6A	120.3	C24—C23—H23	120.4
C5—C6—H6A	120.3	C22—C23—H23	120.4
N1—C7—C2	120.9 (2)	C23—C24—C25	121.1 (2)
N1—C7—H7	119.6	C23—C24—N8	119.0 (3)
C2—C7—H7	119.6	C25—C24—N8	119.8 (2)
N2—C8—C13	120.4 (2)	C26—C25—C24	119.9 (2)
N2—C8—C9	122.8 (2)	C26—C25—H25	120.0
C13—C8—C9	116.8 (2)	C24—C25—H25	120.0
C10—C9—C8	121.7 (2)	C25—C26—C21	121.4 (3)
C10—C9—N3	116.1 (2)	C25—C26—H26	119.3
C8—C9—N3	122.3 (2)	C21—C26—H26	119.3

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6···O6	0.86	2.02	2.631 (3)	127
N2—H2···O1	0.86	2.00	2.622 (3)	129

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N6—H6⋯O6	0.86	2.02	2.631 (3)	127
N2—H2⋯O1	0.86	2.00	2.622 (3)	129