N'-(3,5-Dichloro-2-hy-droxy-benzyl-idene)-4-nitro-benzohydrazide methanol solvate.

In the title compound, C(14)H(9)Cl(2)N(3)O(4)·CH(4)O, the dihedral angle between the two benzene rings in the hydrazone mol-ecule is 6.3 (3)°. An intra-molecular N-H⋯O hydrogen bond stabilizes the mol-ecular conformation. In the crystal, centrosymmetrically related mol-ecules are linked through inter-molecular O-H⋯O and N-H⋯O hydrogen bonds.

Related literature

For general background to hydrazone compounds, see: Rasras et al. (2010 ▶); Fan et al. (2010 ▶); Ajani et al. (2010 ▶); Avaji et al. (2009 ▶). For the crystal structures of related hydrazone compounds, see: Khaledi et al. (2010 ▶); Han et al. (2010 ▶); Hussain et al. (2010 ▶); Ji & Lu (2010 ▶). For reference bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C14H9Cl2N3O4·CH4O

M = 386.18

Monoclinic,

a = 7.415 (3) Å

b = 13.408 (3) Å

c = 16.674 (2) Å

β = 99.716 (3)°

V = 1634.0 (8) Å3

Z = 4

Mo Kα radiation

μ = 0.43 mm−1

T = 298 K

0.15 × 0.13 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.938, T max = 0.958

8410 measured reflections

3467 independent reflections

2099 reflections with I > 2σ(I)

R int = 0.046

Refinement

R[F 2 > 2σ(F 2)] = 0.054

wR(F 2) = 0.124

S = 1.02

3467 reflections

232 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.21 e Å−3

Δρmin = −0.31 e Å−3

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; 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/S1600536810036184/rz2485sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810036184/rz2485Isup2.hkl

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

C14H9Cl2N3O4·CH4O	F(000) = 792
Mr = 386.18	Dx = 1.570 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1245 reflections
a = 7.415 (3) Å	θ = 2.4–24.5°
b = 13.408 (3) Å	µ = 0.43 mm−1
c = 16.674 (2) Å	T = 298 K
β = 99.716 (3)°	Cut from needle, yellow
V = 1634.0 (8) Å3	0.15 × 0.13 × 0.10 mm
Z = 4

Bruker SMART CCD area-detector diffractometer	3467 independent reflections
Radiation source: fine-focus sealed tube	2099 reflections with I > 2σ(I)
graphite	Rint = 0.046
ω scans	θmax = 27.0°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −9→9
Tmin = 0.938, Tmax = 0.958	k = −14→17
8410 measured reflections	l = −21→17

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.124	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0478P)2 + 0.0676P] where P = (Fo2 + 2Fc2)/3
3467 reflections	(Δ/σ)max < 0.001
232 parameters	Δρmax = 0.21 e Å−3
1 restraint	Δρmin = −0.31 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	0.46614 (12)	−0.21402 (6)	0.15195 (5)	0.0565 (3)
Cl2	0.37115 (12)	0.17025 (6)	0.06479 (5)	0.0538 (3)
N1	0.2955 (3)	−0.01141 (17)	0.40697 (13)	0.0378 (6)
N2	0.2663 (3)	0.02375 (17)	0.48171 (14)	0.0388 (6)
N3	0.0804 (4)	0.1043 (3)	0.84113 (17)	0.0567 (8)
O1	0.3717 (3)	−0.14918 (14)	0.30523 (12)	0.0481 (6)
H1	0.3572	−0.1275	0.3497	0.072*
O2	0.2382 (3)	−0.13351 (15)	0.52776 (12)	0.0552 (6)
O3	0.0317 (4)	0.1905 (2)	0.84516 (15)	0.0786 (8)
O4	0.1004 (4)	0.0463 (2)	0.89825 (15)	0.0911 (9)
O5	0.4237 (3)	0.21205 (16)	0.51288 (15)	0.0619 (7)
H5	0.5275	0.2100	0.5021	0.093*
C1	0.3366 (4)	0.0260 (2)	0.27209 (16)	0.0329 (6)
C2	0.3712 (4)	−0.0733 (2)	0.25280 (16)	0.0356 (7)
C3	0.4095 (4)	−0.0933 (2)	0.17535 (16)	0.0349 (7)
C4	0.4077 (4)	−0.0197 (2)	0.11735 (17)	0.0410 (7)
H4	0.4311	−0.0353	0.0657	0.049*
C5	0.3705 (4)	0.0773 (2)	0.13695 (16)	0.0370 (7)
C6	0.3342 (4)	0.1002 (2)	0.21322 (16)	0.0363 (7)
H6	0.3079	0.1656	0.2256	0.044*
C7	0.3046 (4)	0.0552 (2)	0.35267 (16)	0.0373 (7)
H7	0.2908	0.1223	0.3647	0.045*
C8	0.2371 (4)	−0.0435 (2)	0.53888 (17)	0.0369 (7)
C9	0.1972 (4)	−0.0003 (2)	0.61643 (16)	0.0332 (7)
C10	0.1438 (4)	0.0976 (2)	0.62461 (17)	0.0395 (7)
H10	0.1332	0.1406	0.5803	0.047*
C11	0.1061 (4)	0.1320 (2)	0.69819 (18)	0.0440 (8)
H11	0.0710	0.1978	0.7040	0.053*
C12	0.1216 (4)	0.0669 (2)	0.76247 (17)	0.0405 (7)
C13	0.1716 (4)	−0.0309 (2)	0.75640 (17)	0.0439 (8)
H13	0.1796	−0.0737	0.8008	0.053*
C14	0.2096 (4)	−0.0643 (2)	0.68295 (17)	0.0400 (7)
H14	0.2439	−0.1304	0.6777	0.048*
C15	0.3910 (5)	0.3073 (2)	0.5430 (2)	0.0592 (9)
H15A	0.4591	0.3147	0.5970	0.089*
H15B	0.2628	0.3147	0.5444	0.089*
H15C	0.4288	0.3574	0.5082	0.089*
H2	0.300 (5)	0.0871 (11)	0.494 (2)	0.080*

	U11	U22	U33	U12	U13	U23
Cl1	0.0704 (6)	0.0374 (5)	0.0641 (6)	0.0041 (4)	0.0181 (4)	−0.0126 (4)
Cl2	0.0633 (6)	0.0514 (5)	0.0479 (5)	−0.0048 (4)	0.0127 (4)	0.0148 (4)
N1	0.0435 (15)	0.0393 (14)	0.0321 (13)	−0.0018 (12)	0.0109 (11)	−0.0040 (11)
N2	0.0501 (16)	0.0345 (14)	0.0334 (13)	−0.0035 (13)	0.0120 (11)	−0.0031 (11)
N3	0.0562 (19)	0.072 (2)	0.0457 (18)	−0.0123 (17)	0.0203 (14)	−0.0134 (16)
O1	0.0704 (16)	0.0325 (12)	0.0429 (12)	−0.0015 (11)	0.0138 (12)	0.0040 (9)
O2	0.0864 (18)	0.0301 (12)	0.0527 (14)	−0.0008 (12)	0.0223 (12)	−0.0067 (10)
O3	0.098 (2)	0.076 (2)	0.0684 (18)	0.0053 (17)	0.0328 (15)	−0.0264 (15)
O4	0.143 (3)	0.093 (2)	0.0445 (15)	−0.0060 (19)	0.0359 (16)	−0.0005 (15)
O5	0.0673 (17)	0.0488 (14)	0.0767 (17)	−0.0132 (12)	0.0326 (14)	−0.0180 (12)
C1	0.0328 (16)	0.0336 (16)	0.0335 (15)	−0.0002 (13)	0.0089 (12)	−0.0015 (12)
C2	0.0350 (17)	0.0346 (17)	0.0375 (16)	−0.0021 (13)	0.0065 (13)	0.0027 (13)
C3	0.0342 (17)	0.0311 (16)	0.0406 (16)	0.0007 (13)	0.0094 (13)	−0.0066 (13)
C4	0.0444 (19)	0.0441 (18)	0.0354 (16)	−0.0056 (15)	0.0095 (13)	−0.0027 (14)
C5	0.0375 (17)	0.0383 (17)	0.0357 (16)	−0.0036 (14)	0.0081 (13)	0.0039 (13)
C6	0.0371 (17)	0.0290 (15)	0.0423 (17)	0.0011 (13)	0.0056 (13)	0.0008 (13)
C7	0.0401 (18)	0.0323 (16)	0.0406 (16)	0.0026 (14)	0.0099 (13)	−0.0024 (13)
C8	0.0384 (18)	0.0350 (17)	0.0378 (16)	−0.0028 (14)	0.0078 (13)	−0.0025 (14)
C9	0.0307 (16)	0.0351 (16)	0.0344 (15)	−0.0016 (13)	0.0075 (12)	−0.0028 (13)
C10	0.0459 (19)	0.0368 (17)	0.0387 (17)	0.0034 (14)	0.0157 (14)	0.0019 (13)
C11	0.048 (2)	0.0404 (18)	0.0461 (18)	0.0010 (15)	0.0150 (15)	−0.0044 (15)
C12	0.0340 (17)	0.054 (2)	0.0356 (16)	−0.0081 (15)	0.0132 (13)	−0.0094 (15)
C13	0.048 (2)	0.047 (2)	0.0368 (17)	−0.0054 (16)	0.0068 (14)	0.0039 (14)
C14	0.0417 (18)	0.0332 (17)	0.0458 (18)	−0.0059 (14)	0.0094 (14)	−0.0009 (14)
C15	0.058 (2)	0.047 (2)	0.074 (2)	0.0044 (17)	0.0156 (18)	−0.0058 (18)

Cl1—C3	1.733 (3)	C4—C5	1.380 (4)
Cl2—C5	1.733 (3)	C4—H4	0.9300
N1—C7	1.282 (3)	C5—C6	1.378 (4)
N1—N2	1.383 (3)	C6—H6	0.9300
N2—C8	1.356 (4)	C7—H7	0.9300
N2—H2	0.898 (10)	C8—C9	1.492 (4)
N3—O3	1.217 (4)	C9—C10	1.385 (4)
N3—O4	1.219 (3)	C9—C14	1.393 (4)
N3—C12	1.483 (4)	C10—C11	1.383 (4)
O1—C2	1.341 (3)	C10—H10	0.9300
O1—H1	0.8200	C11—C12	1.372 (4)
O2—C8	1.221 (3)	C11—H11	0.9300
O5—C15	1.409 (3)	C12—C13	1.371 (4)
O5—H5	0.8200	C13—C14	1.377 (4)
C1—C6	1.396 (4)	C13—H13	0.9300
C1—C2	1.403 (4)	C14—H14	0.9300
C1—C7	1.457 (4)	C15—H15A	0.9600
C2—C3	1.394 (4)	C15—H15B	0.9600
C3—C4	1.380 (4)	C15—H15C	0.9600
C7—N1—N2	115.7 (2)	C1—C7—H7	120.0
C8—N2—N1	118.3 (2)	O2—C8—N2	123.0 (3)
C8—N2—H2	123 (2)	O2—C8—C9	121.5 (3)
N1—N2—H2	116 (2)	N2—C8—C9	115.4 (2)
O3—N3—O4	124.2 (3)	C10—C9—C14	119.1 (3)
O3—N3—C12	118.5 (3)	C10—C9—C8	123.7 (3)
O4—N3—C12	117.3 (3)	C14—C9—C8	117.1 (3)
C2—O1—H1	109.5	C11—C10—C9	120.5 (3)
C15—O5—H5	109.5	C11—C10—H10	119.8
C6—C1—C2	119.7 (2)	C9—C10—H10	119.8
C6—C1—C7	118.2 (3)	C12—C11—C10	118.6 (3)
C2—C1—C7	122.1 (3)	C12—C11—H11	120.7
O1—C2—C3	118.6 (3)	C10—C11—H11	120.7
O1—C2—C1	123.4 (3)	C13—C12—C11	122.6 (3)
C3—C2—C1	118.0 (2)	C13—C12—N3	119.2 (3)
C4—C3—C2	122.1 (3)	C11—C12—N3	118.2 (3)
C4—C3—Cl1	119.0 (2)	C12—C13—C14	118.4 (3)
C2—C3—Cl1	118.9 (2)	C12—C13—H13	120.8
C5—C4—C3	119.1 (3)	C14—C13—H13	120.8
C5—C4—H4	120.4	C13—C14—C9	120.8 (3)
C3—C4—H4	120.4	C13—C14—H14	119.6
C6—C5—C4	120.4 (3)	C9—C14—H14	119.6
C6—C5—Cl2	120.3 (2)	O5—C15—H15A	109.5
C4—C5—Cl2	119.3 (2)	O5—C15—H15B	109.5
C5—C6—C1	120.6 (3)	H15A—C15—H15B	109.5
C5—C6—H6	119.7	O5—C15—H15C	109.5
C1—C6—H6	119.7	H15A—C15—H15C	109.5
N1—C7—C1	120.0 (3)	H15B—C15—H15C	109.5
N1—C7—H7	120.0

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.92	2.633 (3)	145
N2—H2···O5	0.90 (1)	1.91 (1)	2.793 (3)	167 (3)
O5—H5···O2i	0.82	2.15	2.903 (3)	153

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.82	1.92	2.633 (3)	145
N2—H2⋯O5	0.90 (1)	1.91 (1)	2.793 (3)	167 (3)
O5—H5⋯O2i	0.82	2.15	2.903 (3)	153

Symmetry code: (i) .