(E)-1-(3-Nitro-phen-yl)-2-({5-[(1E)-2-(3-nitro-phen-yl)hydrazin-1-ylidenemeth-yl]-2-thien-yl}methyl-idene)hydrazine.

The title mol-ecule, C(18)H(14)N(6)O(4)S, adopts a U-shape with the aromatic groups lying syn and oriented in the same direction as the thio-phene S atom. Twists away from planarity are evident with the maximum deviation being found for a terminal nitro group: C/C/N/O = 19.0 (3)°. The conformation about each of the C=N bonds is E. In the crystal, centrosymmetrically related mol-ecules are connected via N-H⋯O(nitro) hydrogen bonds, forming 14-membered {⋯HNC(3)NO}(2) synthons. These are linked into layers via C-H⋯O(nitro) inter-actions with the primary inter-actions between layers being of the type C-H⋯π, where the π-system is the thio-phene ring.

Related literature

For the preparation of hydrazones of thio­phene­carbaldehydes, see: Kwon et al. (2009 ▶); Wardell et al. (2007 ▶); Vaysse & Pastour (1964 ▶). For general uses of 2-substituted-thio­phenes, see: Campaigne (1984 ▶). For their specific uses as materials, see: Michaleviciute et al. (2007 ▶, 2009 ▶); Kwon et al. (2009 ▶). For their specific uses as pharmacological agents, see: Kleemann et al. (2006 ▶); Sonar & Crooks (2009 ▶); Mellado et al. (2009 ▶); Satyanarayana et al. (2008 ▶); Lourenço et al. (2007 ▶). For related structures, see: Wardell et al. (2007 ▶, 2010 ▶); Ferreira et al. (2009 ▶); Nogueira et al. (2010 ▶).

Experimental

Crystal data

C18H14N6O4S

M = 410.41

Monoclinic,

a = 11.1790 (5) Å

b = 20.6993 (9) Å

c = 8.0334 (2) Å

β = 100.513 (2)°

V = 1827.70 (12) Å3

Z = 4

Mo Kα radiation

μ = 0.22 mm−1

T = 120 K

0.62 × 0.10 × 0.06 mm

Data collection

Nonius KappaCCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ▶) T min = 0.668, T max = 0.746

21780 measured reflections

4183 independent reflections

3001 reflections with I > 2σ(I)

R int = 0.071

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.133

S = 1.08

4183 reflections

268 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.27 e Å−3

Δρmin = −0.34 e Å−3

Data collection: COLLECT (Hooft, 1998 ▶); cell refinement: DENZO (Otwinowski & Minor, 1997 ▶) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810002771/hg2635sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810002771/hg2635Isup2.hkl

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

C18H14N6O4S	F(000) = 848
Mr = 410.41	Dx = 1.492 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 13699 reflections
a = 11.1790 (5) Å	θ = 2.9–27.5°
b = 20.6993 (9) Å	µ = 0.22 mm−1
c = 8.0334 (2) Å	T = 120 K
β = 100.513 (2)°	Rod, red
V = 1827.70 (12) Å3	0.62 × 0.10 × 0.06 mm
Z = 4

KappaCCD area-detector diffractometer	4183 independent reflections
Radiation source: Enraf Nonius FR591 rotating anode	3001 reflections with I > 2σ(I)
10 cm confocal mirrors	Rint = 0.071
Detector resolution: 9.091 pixels mm-1	θmax = 27.5°, θmin = 3.1°
φ and ω scans	h = −14→14
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	k = −26→26
Tmin = 0.668, Tmax = 0.746	l = −10→9
21780 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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.133	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0678P)2 + 0.3581P] where P = (Fo2 + 2Fc2)/3
4183 reflections	(Δ/σ)max = 0.001
268 parameters	Δρmax = 0.27 e Å−3
0 restraints	Δρmin = −0.34 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
S1	0.51694 (5)	0.64771 (3)	0.10731 (6)	0.01767 (15)
O1	0.86026 (16)	0.47833 (10)	1.1894 (2)	0.0440 (5)
O2	0.66466 (16)	0.47631 (9)	1.16581 (19)	0.0344 (4)
O3	1.09960 (18)	0.66615 (11)	−0.6358 (3)	0.0553 (6)
O4	0.91528 (19)	0.66409 (11)	−0.7736 (2)	0.0519 (6)
N1	0.50139 (16)	0.59578 (9)	0.4425 (2)	0.0182 (4)
N2	0.50940 (17)	0.56838 (9)	0.5969 (2)	0.0191 (4)
H2N	0.446 (2)	0.5655 (12)	0.649 (3)	0.029*
N3	0.75746 (18)	0.48377 (10)	1.1061 (2)	0.0267 (5)
N4	0.60955 (16)	0.69295 (9)	−0.1986 (2)	0.0181 (4)
N5	0.65934 (16)	0.70405 (9)	−0.3383 (2)	0.0184 (4)
H5N	0.611 (2)	0.7106 (11)	−0.442 (3)	0.028*
N6	0.9889 (2)	0.66605 (11)	−0.6418 (3)	0.0340 (5)
C1	0.38972 (19)	0.64722 (10)	0.2032 (2)	0.0171 (4)
C2	0.29149 (19)	0.67487 (10)	0.1014 (3)	0.0194 (5)
H2	0.2137	0.6787	0.1322	0.023*
C3	0.31778 (19)	0.69709 (10)	−0.0543 (2)	0.0186 (4)
H3	0.2596	0.7175	−0.1389	0.022*
C4	0.43575 (19)	0.68609 (10)	−0.0706 (2)	0.0173 (4)
C5	0.3983 (2)	0.61919 (10)	0.3698 (2)	0.0189 (5)
H5	0.3297	0.6181	0.4242	0.023*
C6	0.6201 (2)	0.54271 (10)	0.6765 (3)	0.0184 (5)
C7	0.6332 (2)	0.52533 (10)	0.8470 (3)	0.0189 (5)
H7	0.5680	0.5303	0.9069	0.023*
C8	0.7441 (2)	0.50061 (11)	0.9255 (2)	0.0208 (5)
C9	0.8416 (2)	0.49104 (11)	0.8444 (3)	0.0245 (5)
H9	0.9165	0.4740	0.9028	0.029*
C10	0.8256 (2)	0.50743 (11)	0.6740 (3)	0.0240 (5)
H10	0.8903	0.5008	0.6140	0.029*
C11	0.7166 (2)	0.53338 (10)	0.5900 (3)	0.0216 (5)
H11	0.7076	0.5448	0.4738	0.026*
C12	0.49410 (19)	0.70092 (10)	−0.2128 (2)	0.0174 (4)
H12	0.4474	0.7164	−0.3159	0.021*
C13	0.77989 (19)	0.68714 (10)	−0.3355 (2)	0.0162 (4)
C14	0.8226 (2)	0.68469 (10)	−0.4875 (3)	0.0193 (5)
H14	0.7703	0.6936	−0.5921	0.023*
C15	0.9433 (2)	0.66899 (11)	−0.4818 (3)	0.0223 (5)
C16	1.0241 (2)	0.65534 (12)	−0.3337 (3)	0.0264 (5)
H16	1.1069	0.6452	−0.3345	0.032*
C17	0.9786 (2)	0.65709 (11)	−0.1840 (3)	0.0253 (5)
H17	1.0311	0.6473	−0.0802	0.030*
C18	0.8583 (2)	0.67280 (10)	−0.1833 (3)	0.0200 (5)
H18	0.8289	0.6738	−0.0796	0.024*

	U11	U22	U33	U12	U13	U23
S1	0.0173 (3)	0.0206 (3)	0.0161 (3)	0.0015 (2)	0.00585 (19)	0.0015 (2)
O1	0.0278 (11)	0.0719 (15)	0.0297 (10)	0.0132 (10)	−0.0019 (8)	0.0147 (9)
O2	0.0306 (10)	0.0526 (12)	0.0217 (8)	0.0002 (8)	0.0090 (7)	0.0075 (7)
O3	0.0333 (12)	0.0913 (18)	0.0497 (12)	0.0191 (11)	0.0300 (10)	0.0196 (11)
O4	0.0481 (13)	0.0905 (17)	0.0198 (10)	0.0207 (11)	0.0136 (9)	0.0044 (9)
N1	0.0241 (10)	0.0195 (10)	0.0122 (8)	−0.0030 (8)	0.0065 (7)	−0.0013 (7)
N2	0.0215 (10)	0.0240 (10)	0.0132 (8)	−0.0002 (8)	0.0069 (7)	0.0020 (7)
N3	0.0290 (12)	0.0286 (11)	0.0230 (10)	0.0034 (9)	0.0061 (9)	0.0030 (8)
N4	0.0212 (10)	0.0197 (10)	0.0152 (9)	−0.0012 (8)	0.0080 (7)	−0.0006 (7)
N5	0.0165 (9)	0.0272 (10)	0.0126 (9)	0.0029 (8)	0.0052 (7)	0.0040 (7)
N6	0.0326 (13)	0.0449 (14)	0.0297 (12)	0.0129 (10)	0.0192 (10)	0.0116 (9)
C1	0.0188 (11)	0.0167 (11)	0.0171 (10)	−0.0050 (9)	0.0070 (8)	−0.0024 (8)
C2	0.0161 (11)	0.0241 (12)	0.0186 (11)	−0.0013 (9)	0.0051 (8)	−0.0013 (8)
C3	0.0172 (11)	0.0227 (11)	0.0154 (10)	−0.0010 (9)	0.0020 (8)	0.0006 (8)
C4	0.0204 (11)	0.0164 (11)	0.0148 (10)	−0.0018 (9)	0.0025 (8)	−0.0001 (8)
C5	0.0208 (11)	0.0198 (11)	0.0174 (10)	−0.0039 (9)	0.0068 (8)	−0.0021 (8)
C6	0.0212 (12)	0.0151 (11)	0.0190 (10)	−0.0044 (9)	0.0042 (8)	−0.0020 (8)
C7	0.0219 (12)	0.0176 (11)	0.0181 (10)	−0.0018 (9)	0.0063 (8)	−0.0009 (8)
C8	0.0258 (13)	0.0207 (12)	0.0156 (10)	−0.0034 (9)	0.0032 (9)	0.0009 (8)
C9	0.0202 (12)	0.0260 (13)	0.0274 (12)	0.0003 (10)	0.0049 (9)	0.0012 (9)
C10	0.0211 (12)	0.0261 (13)	0.0274 (12)	−0.0029 (10)	0.0112 (9)	0.0001 (9)
C11	0.0245 (12)	0.0225 (12)	0.0186 (11)	−0.0053 (9)	0.0059 (9)	0.0009 (8)
C12	0.0190 (11)	0.0183 (11)	0.0150 (10)	0.0006 (9)	0.0033 (8)	−0.0009 (8)
C13	0.0173 (11)	0.0163 (11)	0.0162 (10)	−0.0012 (8)	0.0061 (8)	0.0001 (8)
C14	0.0200 (12)	0.0201 (11)	0.0186 (10)	0.0004 (9)	0.0060 (8)	0.0031 (8)
C15	0.0237 (12)	0.0255 (12)	0.0207 (11)	0.0030 (9)	0.0116 (9)	0.0019 (8)
C16	0.0149 (11)	0.0340 (14)	0.0313 (12)	0.0040 (10)	0.0070 (9)	0.0018 (10)
C17	0.0193 (12)	0.0349 (14)	0.0196 (11)	0.0007 (10)	−0.0016 (9)	−0.0011 (9)
C18	0.0234 (12)	0.0236 (12)	0.0137 (10)	−0.0002 (9)	0.0050 (8)	−0.0002 (8)

S1—C1	1.737 (2)	C5—H5	0.9500
S1—C4	1.739 (2)	C6—C11	1.399 (3)
O1—N3	1.225 (3)	C6—C7	1.398 (3)
O2—N3	1.229 (2)	C7—C8	1.382 (3)
O3—N6	1.230 (3)	C7—H7	0.9500
O4—N6	1.217 (3)	C8—C9	1.382 (3)
N1—C5	1.288 (3)	C9—C10	1.390 (3)
N1—N2	1.352 (2)	C9—H9	0.9500
N2—C6	1.391 (3)	C10—C11	1.389 (3)
N2—H2N	0.89 (3)	C10—H10	0.9500
N3—C8	1.473 (3)	C11—H11	0.9500
N4—C12	1.285 (3)	C12—H12	0.9500
N4—N5	1.360 (2)	C13—C14	1.391 (3)
N5—C13	1.389 (3)	C13—C18	1.400 (3)
N5—H5N	0.92 (2)	C14—C15	1.380 (3)
N6—C15	1.468 (3)	C14—H14	0.9500
C1—C2	1.369 (3)	C15—C16	1.385 (3)
C1—C5	1.445 (3)	C16—C17	1.388 (3)
C2—C3	1.413 (3)	C16—H16	0.9500
C2—H2	0.9500	C17—C18	1.385 (3)
C3—C4	1.368 (3)	C17—H17	0.9500
C3—H3	0.9500	C18—H18	0.9500
C4—C12	1.449 (3)
C1—S1—C4	91.17 (10)	C6—C7—H7	121.1
C5—N1—N2	118.56 (18)	C9—C8—C7	123.82 (19)
N1—N2—C6	119.09 (18)	C9—C8—N3	118.9 (2)
N1—N2—H2N	122.5 (16)	C7—C8—N3	117.29 (19)
C6—N2—H2N	118.4 (16)	C8—C9—C10	117.3 (2)
O1—N3—O2	123.37 (19)	C8—C9—H9	121.4
O1—N3—C8	118.43 (19)	C10—C9—H9	121.4
O2—N3—C8	118.20 (19)	C9—C10—C11	121.2 (2)
C12—N4—N5	117.41 (17)	C9—C10—H10	119.4
N4—N5—C13	119.06 (17)	C11—C10—H10	119.4
N4—N5—H5N	121.3 (16)	C10—C11—C6	119.9 (2)
C13—N5—H5N	117.1 (16)	C10—C11—H11	120.0
O4—N6—O3	123.4 (2)	C6—C11—H11	120.0
O4—N6—C15	118.4 (2)	N4—C12—C4	119.47 (18)
O3—N6—C15	118.2 (2)	N4—C12—H12	120.3
C2—C1—C5	129.17 (19)	C4—C12—H12	120.3
C2—C1—S1	111.39 (15)	N5—C13—C14	118.84 (18)
C5—C1—S1	119.43 (16)	N5—C13—C18	121.25 (18)
C1—C2—C3	113.04 (19)	C14—C13—C18	119.9 (2)
C1—C2—H2	123.5	C15—C14—C13	118.01 (19)
C3—C2—H2	123.5	C15—C14—H14	121.0
C4—C3—C2	112.95 (19)	C13—C14—H14	121.0
C4—C3—H3	123.5	C14—C15—C16	123.8 (2)
C2—C3—H3	123.5	C14—C15—N6	118.30 (19)
C3—C4—C12	128.36 (19)	C16—C15—N6	117.9 (2)
C3—C4—S1	111.45 (15)	C15—C16—C17	117.0 (2)
C12—C4—S1	120.17 (16)	C15—C16—H16	121.5
N1—C5—C1	118.30 (19)	C17—C16—H16	121.5
N1—C5—H5	120.9	C18—C17—C16	121.3 (2)
C1—C5—H5	120.9	C18—C17—H17	119.4
N2—C6—C11	121.80 (19)	C16—C17—H17	119.4
N2—C6—C7	118.27 (19)	C17—C18—C13	119.98 (19)
C11—C6—C7	119.9 (2)	C17—C18—H18	120.0
C8—C7—C6	117.9 (2)	C13—C18—H18	120.0
C8—C7—H7	121.1
C5—N1—N2—C6	179.76 (19)	N3—C8—C9—C10	179.9 (2)
C12—N4—N5—C13	−170.79 (19)	C8—C9—C10—C11	1.1 (3)
C4—S1—C1—C2	0.37 (17)	C9—C10—C11—C6	−0.8 (3)
C4—S1—C1—C5	179.95 (17)	N2—C6—C11—C10	−179.8 (2)
C5—C1—C2—C3	−179.9 (2)	C7—C6—C11—C10	−0.6 (3)
S1—C1—C2—C3	−0.4 (2)	N5—N4—C12—C4	176.44 (18)
C1—C2—C3—C4	0.2 (3)	C3—C4—C12—N4	173.0 (2)
C2—C3—C4—C12	178.6 (2)	S1—C4—C12—N4	−8.6 (3)
C2—C3—C4—S1	0.1 (2)	N4—N5—C13—C14	165.61 (18)
C1—S1—C4—C3	−0.26 (17)	N4—N5—C13—C18	−14.5 (3)
C1—S1—C4—C12	−178.90 (17)	N5—C13—C14—C15	178.8 (2)
N2—N1—C5—C1	−178.75 (17)	C18—C13—C14—C15	−1.1 (3)
C2—C1—C5—N1	−180.0 (2)	C13—C14—C15—C16	0.2 (3)
S1—C1—C5—N1	0.5 (3)	C13—C14—C15—N6	179.7 (2)
N1—N2—C6—C11	−12.2 (3)	O4—N6—C15—C14	−15.1 (3)
N1—N2—C6—C7	168.57 (18)	O3—N6—C15—C14	164.4 (2)
N2—C6—C7—C8	−179.20 (19)	O4—N6—C15—C16	164.5 (2)
C11—C6—C7—C8	1.5 (3)	O3—N6—C15—C16	−16.0 (3)
C6—C7—C8—C9	−1.2 (3)	C14—C15—C16—C17	0.8 (4)
C6—C7—C8—N3	178.75 (18)	N6—C15—C16—C17	−178.7 (2)
O1—N3—C8—C9	19.0 (3)	C15—C16—C17—C18	−1.0 (4)
O2—N3—C8—C9	−161.5 (2)	C16—C17—C18—C13	0.1 (3)
O1—N3—C8—C7	−161.0 (2)	N5—C13—C18—C17	−178.9 (2)
O2—N3—C8—C7	18.6 (3)	C14—C13—C18—C17	0.9 (3)
C7—C8—C9—C10	−0.1 (3)

Cg1 is the centroid of the S1,C1–C4 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2n···O2i	0.89 (2)	2.27 (2)	3.103 (2)	156 (2)
C2—H2···O3ii	0.95	2.46	3.278 (3)	145
C18—H18···O4iii	0.95	2.48	3.241 (3)	137
C12—H12···Cg1iv	0.95	2.58	3.323 (2)	135

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2n⋯O2i	0.89 (2)	2.27 (2)	3.103 (2)	156 (2)
C2—H2⋯O3ii	0.95	2.46	3.278 (3)	145
C18—H18⋯O4iii	0.95	2.48	3.241 (3)	137
C12—H12⋯Cg1iv	0.95	2.58	3.323 (2)	135

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