Crystal structure of N'-[(E)-3,5-di-chloro-2-hy-droxy-benzyl-idene]-4-nitro-benzo-hydrazide di-methyl-formamide monosolvate.

In the title compound, C14H9Cl2N3O4·C3H7NO, the hydrazone mol-ecule adopts an E conformation with respect to azomethine bond, and the dihedral angle between the two aromatic rings [8.96 (11)°] shows that the rings are almost co-planar. The planar conformation of the mol-ecule is stabilized by the intra-molecular O-H⋯N hydrogen bond involving the OH group and azomethine N atom. The azomethine and keto bond distances [1.269 (2) and 1.210 (2) Å, respectively] are very close to the formal C=N and C=O bond lengths. The di-methyl-formamide solvent mol-ecule is connected to the hydrazone NH group via an N-H⋯O hydrogen bond. In the crystal, non-classical C-H⋯O and C-H⋯Cl hydrogen bonds link the mol-ecules into chains along [322]. A supra-molecular three-dimensional architecture is created by weak C-Cl⋯π [4.163 (3) Å, 83.26 (9)°] and π-π [centroid-centroid distance = 4.0395 (14) Å] inter-actions.

Related literature

For applications of hydrazones in supra­molecular chemistry, see: Su & Aprahamian (2014 ▸). For biological applications of hydrazones and derivatives, see: Nair et al. (2014 ▸); Prasanna & Kumar (2013 ▸); Holló et al. (2014 ▸). For the synthesis of related compounds, see: Bessy et al. (2006 ▸).

Experimental

Crystal data

C14H9Cl2N3O4·C3H7NO

M = 427.24

Triclinic,

a = 7.8853 (6) Å

b = 11.9445 (10) Å

c = 11.9521 (15) Å

α = 114.408 (6)°

β = 102.895 (7)°

γ = 98.939 (5)°

V = 959.60 (17) Å3

Z = 2

Mo Kα radiation

μ = 0.38 mm−1

T = 296 K

0.40 × 0.11 × 0.09 mm

Data collection

Bruker Kappa APEXII CCD Diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▸) T min = 0.834, T max = 0.929

7569 measured reflections

4660 independent reflections

3000 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.159

S = 0.95

4660 reflections

263 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.23 e Å−3

Δρmin = −0.19 e Å−3

Data collection: APEX2 (Bruker, 2004 ▸); cell refinement: APEX2 and SAINT (Bruker, 2004 ▸); data reduction: SAINT and XPREP (Bruker, 2004 ▸); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▸); software used to prepare material for publication: publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015018290/yk2106sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015018290/yk2106Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015018290/yk2106Isup3.cml

Click here for additional data file.

ORTEP . DOI: 10.1107/S2056989015018290/yk2106fig1.tif

ORTEP view of the title compound, drawn with 50% probability displacement ellipsoids for the non-H atoms.

Click here for additional data file.

c . DOI: 10.1107/S2056989015018290/yk2106fig2.tif

Diagram showing mol­ecular packing viewed along the c axis along with inter­molecular inter­actions..

CCDC reference: 1428612

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

C14H9Cl2N3O4·C3H7NO	Z = 2
Mr = 427.24	F(000) = 440
Triclinic, P1	Dx = 1.479 Mg m−3
a = 7.8853 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.9445 (10) Å	Cell parameters from 2537 reflections
c = 11.9521 (15) Å	θ = 2.8–28.1°
α = 114.408 (6)°	µ = 0.38 mm−1
β = 102.895 (7)°	T = 296 K
γ = 98.939 (5)°	Needle, pale yellow
V = 959.60 (17) Å3	0.40 × 0.11 × 0.09 mm

Bruker Kappa APEXII CCD Diffractometer	3000 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.019
ω and φ scan	θmax = 28.4°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −10→9
Tmin = 0.834, Tmax = 0.929	k = −15→15
7569 measured reflections	l = −15→15
4660 independent reflections

Refinement on F2	2 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.159	w = 1/[σ2(Fo2) + (0.0998P)2 + 0.0446P] where P = (Fo2 + 2Fc2)/3
S = 0.95	(Δ/σ)max = 0.001
4660 reflections	Δρmax = 0.23 e Å−3
263 parameters	Δρmin = −0.19 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.

	x	y	z	Uiso*/Ueq
Cl1	1.35723 (9)	1.29047 (6)	1.47197 (6)	0.0756 (2)
Cl2	1.23273 (9)	1.51632 (6)	1.17091 (7)	0.0756 (2)
O1	1.0508 (2)	1.08266 (15)	1.27329 (15)	0.0576 (4)
O2	0.6756 (2)	0.77509 (15)	1.08867 (15)	0.0652 (4)
O3	−0.0311 (3)	0.25861 (16)	0.6472 (2)	0.0864 (6)
O4	−0.0770 (3)	0.3439 (2)	0.5227 (2)	0.0989 (7)
O5	0.4796 (2)	1.06202 (17)	0.22900 (16)	0.0668 (4)
N1	0.78454 (19)	0.97794 (15)	1.05922 (16)	0.0457 (4)
N2	0.6378 (2)	0.87905 (15)	0.96978 (16)	0.0454 (4)
N3	0.0045 (2)	0.34550 (18)	0.6219 (2)	0.0619 (5)
N4	0.5894 (3)	0.96448 (18)	0.34168 (18)	0.0616 (5)
C1	1.0866 (2)	1.18037 (18)	1.24598 (19)	0.0441 (4)
C2	1.2306 (3)	1.2870 (2)	1.3331 (2)	0.0512 (5)
C3	1.2741 (3)	1.39056 (18)	1.3111 (2)	0.0529 (5)
H3	1.3694	1.4622	1.3714	0.063*
C4	1.1756 (3)	1.38669 (19)	1.1995 (2)	0.0521 (5)
C5	1.0326 (2)	1.28330 (19)	1.1101 (2)	0.0489 (5)
H5	0.9675	1.2824	1.0344	0.059*
C6	0.9853 (2)	1.17920 (17)	1.13350 (19)	0.0426 (4)
C7	0.8316 (2)	1.07285 (19)	1.03936 (19)	0.0464 (4)
H7	0.7673	1.0738	0.9645	0.056*
C8	0.5925 (2)	0.77882 (18)	0.99269 (18)	0.0428 (4)
C9	0.4325 (2)	0.67029 (17)	0.89195 (18)	0.0397 (4)
C10	0.3727 (3)	0.57541 (19)	0.9227 (2)	0.0496 (5)
H10	0.4276	0.5841	1.0044	0.060*
C11	0.2333 (3)	0.4681 (2)	0.8348 (2)	0.0548 (5)
H11	0.1944	0.4034	0.8551	0.066*
C12	0.1536 (2)	0.45939 (18)	0.7164 (2)	0.0470 (4)
C13	0.2077 (3)	0.5529 (2)	0.6837 (2)	0.0507 (5)
H13	0.1497	0.5449	0.6029	0.061*
C14	0.3485 (2)	0.65882 (19)	0.77184 (19)	0.0456 (4)
H14	0.3873	0.7228	0.7506	0.055*
C15	0.4196 (5)	0.8698 (3)	0.2961 (4)	0.1047 (11)
H15A	0.3223	0.9022	0.2699	0.157*
H15B	0.4052	0.8506	0.3645	0.157*
H15C	0.4177	0.7934	0.2236	0.157*
C16	0.7510 (5)	0.9501 (3)	0.4148 (3)	0.0998 (10)
H16A	0.7692	0.8691	0.3641	0.150*
H16B	0.7365	0.9538	0.4938	0.150*
H16C	0.8541	1.0179	0.4349	0.150*
C17	0.6030 (3)	1.0510 (2)	0.3016 (2)	0.0531 (5)
H17	0.7162	1.1087	0.3310	0.064*
H2	0.589 (3)	0.888 (2)	0.9019 (17)	0.072 (8)*
H1	0.962 (3)	1.028 (2)	1.2106 (19)	0.090 (9)*

	U11	U22	U33	U12	U13	U23
Cl1	0.0735 (4)	0.0650 (4)	0.0560 (3)	−0.0053 (3)	−0.0032 (3)	0.0191 (3)
Cl2	0.0772 (4)	0.0489 (3)	0.1074 (5)	0.0066 (3)	0.0394 (4)	0.0413 (4)
O1	0.0540 (8)	0.0471 (9)	0.0590 (9)	−0.0035 (7)	0.0066 (7)	0.0249 (8)
O2	0.0644 (9)	0.0599 (10)	0.0530 (9)	−0.0038 (7)	−0.0047 (7)	0.0286 (8)
O3	0.0830 (12)	0.0449 (10)	0.1029 (15)	−0.0120 (8)	0.0080 (11)	0.0295 (10)
O4	0.0887 (13)	0.0704 (12)	0.0839 (13)	−0.0243 (10)	−0.0282 (10)	0.0310 (11)
O5	0.0629 (9)	0.0687 (11)	0.0651 (10)	0.0103 (8)	0.0063 (8)	0.0375 (9)
N1	0.0368 (8)	0.0370 (8)	0.0492 (9)	0.0012 (6)	0.0089 (7)	0.0128 (7)
N2	0.0367 (8)	0.0378 (8)	0.0467 (9)	−0.0013 (6)	0.0027 (7)	0.0152 (8)
N3	0.0514 (10)	0.0408 (10)	0.0705 (13)	−0.0025 (8)	0.0058 (9)	0.0171 (9)
N4	0.0783 (12)	0.0453 (10)	0.0564 (11)	0.0101 (9)	0.0138 (9)	0.0257 (9)
C1	0.0418 (9)	0.0370 (10)	0.0489 (11)	0.0042 (7)	0.0173 (8)	0.0169 (9)
C2	0.0449 (10)	0.0446 (11)	0.0487 (11)	0.0018 (8)	0.0140 (9)	0.0119 (9)
C3	0.0440 (10)	0.0368 (11)	0.0579 (12)	−0.0015 (8)	0.0172 (9)	0.0078 (10)
C4	0.0468 (10)	0.0365 (10)	0.0702 (14)	0.0055 (8)	0.0282 (10)	0.0197 (10)
C5	0.0441 (10)	0.0433 (11)	0.0584 (12)	0.0096 (8)	0.0187 (9)	0.0228 (10)
C6	0.0363 (8)	0.0342 (9)	0.0487 (10)	0.0052 (7)	0.0155 (8)	0.0122 (8)
C7	0.0389 (9)	0.0423 (11)	0.0495 (11)	0.0074 (8)	0.0094 (8)	0.0174 (9)
C8	0.0372 (9)	0.0391 (10)	0.0424 (10)	0.0035 (7)	0.0080 (7)	0.0150 (8)
C9	0.0349 (8)	0.0351 (9)	0.0441 (9)	0.0061 (7)	0.0098 (7)	0.0165 (8)
C10	0.0497 (10)	0.0467 (11)	0.0499 (11)	0.0057 (8)	0.0082 (9)	0.0267 (10)
C11	0.0526 (11)	0.0412 (11)	0.0673 (13)	0.0016 (8)	0.0121 (10)	0.0298 (11)
C12	0.0399 (9)	0.0345 (10)	0.0540 (11)	0.0019 (7)	0.0092 (8)	0.0149 (9)
C13	0.0478 (10)	0.0463 (11)	0.0484 (11)	0.0042 (8)	0.0053 (9)	0.0214 (9)
C14	0.0424 (9)	0.0399 (10)	0.0507 (11)	0.0031 (8)	0.0093 (8)	0.0232 (9)
C15	0.121 (3)	0.072 (2)	0.111 (2)	−0.0127 (17)	0.039 (2)	0.0468 (19)
C16	0.128 (3)	0.086 (2)	0.0810 (19)	0.041 (2)	0.0054 (18)	0.0460 (18)
C17	0.0537 (11)	0.0449 (11)	0.0524 (12)	0.0040 (9)	0.0108 (9)	0.0216 (10)

Cl1—C2	1.716 (2)	C5—C6	1.397 (3)
Cl2—C4	1.734 (2)	C5—H5	0.9300
O1—C1	1.342 (2)	C6—C7	1.442 (3)
O1—H1	0.835 (10)	C7—H7	0.9300
O2—C8	1.210 (2)	C8—C9	1.498 (2)
O3—N3	1.206 (2)	C9—C10	1.378 (3)
O4—N3	1.207 (3)	C9—C14	1.380 (3)
O5—C17	1.214 (2)	C10—C11	1.375 (3)
N1—C7	1.269 (2)	C10—H10	0.9300
N1—N2	1.363 (2)	C11—C12	1.367 (3)
N2—C8	1.348 (2)	C11—H11	0.9300
N2—H2	0.872 (10)	C12—C13	1.367 (3)
N3—C12	1.466 (3)	C13—C14	1.372 (3)
N4—C17	1.306 (3)	C13—H13	0.9300
N4—C15	1.437 (3)	C14—H14	0.9300
N4—C16	1.454 (3)	C15—H15A	0.9600
C1—C2	1.386 (3)	C15—H15B	0.9600
C1—C6	1.396 (3)	C15—H15C	0.9600
C2—C3	1.376 (3)	C16—H16A	0.9600
C3—C4	1.363 (3)	C16—H16B	0.9600
C3—H3	0.9300	C16—H16C	0.9600
C4—C5	1.370 (3)	C17—H17	0.9300
C1—O1—H1	105 (2)	N2—C8—C9	116.40 (16)
C7—N1—N2	118.71 (16)	C10—C9—C14	119.48 (17)
C8—N2—N1	117.36 (15)	C10—C9—C8	116.28 (16)
C8—N2—H2	128.4 (18)	C14—C9—C8	124.20 (16)
N1—N2—H2	114.1 (18)	C11—C10—C9	121.12 (18)
O3—N3—O4	123.3 (2)	C11—C10—H10	119.4
O3—N3—C12	118.6 (2)	C9—C10—H10	119.4
O4—N3—C12	118.07 (19)	C12—C11—C10	117.92 (18)
C17—N4—C15	120.0 (2)	C12—C11—H11	121.0
C17—N4—C16	120.2 (2)	C10—C11—H11	121.0
C15—N4—C16	119.0 (2)	C13—C12—C11	122.36 (18)
O1—C1—C2	118.66 (18)	C13—C12—N3	119.26 (19)
O1—C1—C6	122.82 (16)	C11—C12—N3	118.38 (18)
C2—C1—C6	118.52 (17)	C12—C13—C14	119.15 (18)
C3—C2—C1	121.57 (19)	C12—C13—H13	120.4
C3—C2—Cl1	119.12 (16)	C14—C13—H13	120.4
C1—C2—Cl1	119.31 (16)	C13—C14—C9	119.95 (17)
C4—C3—C2	119.06 (18)	C13—C14—H14	120.0
C4—C3—H3	120.5	C9—C14—H14	120.0
C2—C3—H3	120.5	N4—C15—H15A	109.5
C3—C4—C5	121.61 (19)	N4—C15—H15B	109.5
C3—C4—Cl2	119.00 (16)	H15A—C15—H15B	109.5
C5—C4—Cl2	119.39 (18)	N4—C15—H15C	109.5
C4—C5—C6	119.5 (2)	H15A—C15—H15C	109.5
C4—C5—H5	120.2	H15B—C15—H15C	109.5
C6—C5—H5	120.2	N4—C16—H16A	109.5
C1—C6—C5	119.70 (17)	N4—C16—H16B	109.5
C1—C6—C7	121.85 (16)	H16A—C16—H16B	109.5
C5—C6—C7	118.44 (18)	N4—C16—H16C	109.5
N1—C7—C6	119.61 (18)	H16A—C16—H16C	109.5
N1—C7—H7	120.2	H16B—C16—H16C	109.5
C6—C7—H7	120.2	O5—C17—N4	125.3 (2)
O2—C8—N2	122.52 (17)	O5—C17—H17	117.4
O2—C8—C9	121.07 (17)	N4—C17—H17	117.4
C7—N1—N2—C8	179.15 (17)	N1—N2—C8—C9	−179.03 (15)
O1—C1—C2—C3	−179.80 (17)	O2—C8—C9—C10	8.0 (3)
C6—C1—C2—C3	0.3 (3)	N2—C8—C9—C10	−172.24 (16)
O1—C1—C2—Cl1	0.0 (3)	O2—C8—C9—C14	−169.75 (19)
C6—C1—C2—Cl1	−179.94 (14)	N2—C8—C9—C14	10.0 (3)
C1—C2—C3—C4	−1.5 (3)	C14—C9—C10—C11	1.4 (3)
Cl1—C2—C3—C4	178.75 (15)	C8—C9—C10—C11	−176.44 (18)
C2—C3—C4—C5	1.2 (3)	C9—C10—C11—C12	−1.1 (3)
C2—C3—C4—Cl2	−179.09 (15)	C10—C11—C12—C13	−0.1 (3)
C3—C4—C5—C6	0.3 (3)	C10—C11—C12—N3	−179.89 (18)
Cl2—C4—C5—C6	−179.43 (13)	O3—N3—C12—C13	173.37 (19)
O1—C1—C6—C5	−178.71 (16)	O4—N3—C12—C13	−7.0 (3)
C2—C1—C6—C5	1.2 (3)	O3—N3—C12—C11	−6.8 (3)
O1—C1—C6—C7	1.2 (3)	O4—N3—C12—C11	172.8 (2)
C2—C1—C6—C7	−178.87 (18)	C11—C12—C13—C14	0.9 (3)
C4—C5—C6—C1	−1.5 (3)	N3—C12—C13—C14	−179.30 (18)
C4—C5—C6—C7	178.56 (17)	C12—C13—C14—C9	−0.5 (3)
N2—N1—C7—C6	179.29 (15)	C10—C9—C14—C13	−0.6 (3)
C1—C6—C7—N1	1.0 (3)	C8—C9—C14—C13	177.11 (18)
C5—C6—C7—N1	−179.11 (16)	C15—N4—C17—O5	2.2 (4)
N1—N2—C8—O2	0.7 (3)	C16—N4—C17—O5	172.0 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O5i	0.87 (1)	1.90 (1)	2.757 (2)	169 (3)
C3—H3···Cl1ii	0.93	2.92	3.836 (2)	169
C7—H7···O5i	0.93	2.38	3.145 (3)	139
C13—H13···O4iii	0.93	2.42	3.231 (3)	146
O1—H1···N1	0.84 (1)	1.82 (2)	2.581 (2)	151 (3)

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
O1H1N1	0.84(1)	1.82(2)	2.581(2)	151(3)
N2H2O5i	0.87(1)	1.90(1)	2.757(2)	169(3)
C3H3Cl1ii	0.93	2.92	3.836(2)	169
C7H7O5i	0.93	2.38	3.145(3)	139
C13H13O4iii	0.93	2.42	3.231(3)	146

Symmetry codes: (i) ; (ii) ; (iii) .