Crystal structure of 1-(4-formyl-benzyl-idene)thio-semicarbazone.

The asymmetric unit of the title compound, C9H9N3OS, contains two approximately planar mol-ecules (r.m.s. deviations for 14 non-H atoms = 0.094 and 0.045 Å), with different conformations. In one of them, the C=O group is syn to the S atom and in the other it is anti. Each mol-ecule features an intra-molecular N-H⋯N hydrogen bond, which generates an S(5) ring. In the crystal, mol-ecules are linked by N-H⋯O and N-H⋯S hydrogen bonds, generating discrete networks; the syn mol-ecules form [010] chains and the anti mol-ecules form (100) sheets.

Related literature

For further synthetic details, see: Jagst et al. (2005 ▶). For structure–biological activity relationships in thio­semicarbazones, see: Lukmantara et al. (2013 ▶). For their biological properties, see: Serda et al. (2012 ▶).

Experimental

Crystal data

C9H9N3OS

M = 207.25

Monoclinic,

a = 12.3888 (9) Å

b = 11.7972 (8) Å

c = 14.9428 (11) Å

β = 110.286 (1)°

V = 2048.5 (3) Å3

Z = 8

Mo Kα radiation

μ = 0.29 mm−1

T = 293 K

0.51 × 0.44 × 0.33 mm

Data collection

Bruker SMART 1000 CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.693, T max = 0.746

19018 measured reflections

4920 independent reflections

3344 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.119

S = 1.03

4920 reflections

277 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.36 e Å−3

Δρmin = −0.35 e Å−3

Data collection: SMART (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814017255/hb7254sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814017255/hb7254Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814017255/hb7254Isup3.cml

Click here for additional data file.

ORTEP . DOI: 10.1107/S1600536814017255/hb7254fig1.tif

ORTEP view of the two mol­ecules of the title compound. Displacement ellipsoids shown at the 50% probability level.

Click here for additional data file.

. DOI: 10.1107/S1600536814017255/hb7254fig2.tif

View of the crystal packing showing the two different chains.

CCDC reference: 1016158

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

C9H9N3OS	F(000) = 864
Mr = 207.25	Dx = 1.344 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.3888 (9) Å	Cell parameters from 6097 reflections
b = 11.7972 (8) Å	θ = 2.3–27.2°
c = 14.9428 (11) Å	µ = 0.29 mm−1
β = 110.286 (1)°	T = 293 K
V = 2048.5 (3) Å3	Prism, yellow
Z = 8	0.51 × 0.44 × 0.33 mm

Bruker SMART 1000 CCD diffractometer	3344 reflections with I > 2σ(I)
Radiation source: sealed X-ray tube	Rint = 0.022
φ and ω scans	θmax = 28.1°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→16
Tmin = 0.693, Tmax = 0.746	k = −15→15
19018 measured reflections	l = −19→19
4920 independent reflections

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.119	w = 1/[σ2(Fo2) + (0.0442P)2 + 0.8755P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.001
4920 reflections	Δρmax = 0.36 e Å−3
277 parameters	Δρmin = −0.35 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
N3A	0.89210 (14)	0.63007 (12)	−0.01356 (11)	0.0479 (4)
S1A	0.90693 (5)	0.91696 (4)	−0.13892 (4)	0.06120 (17)
O1A	0.89088 (17)	0.16790 (14)	0.29083 (12)	0.0778 (5)
N1A	0.97843 (19)	0.83357 (16)	0.03697 (14)	0.0646 (5)
C1A	0.92577 (17)	0.81529 (15)	−0.05446 (14)	0.0488 (4)
N2A	0.88481 (15)	0.71091 (13)	−0.08158 (13)	0.0519 (4)
C2A	0.84890 (17)	0.53375 (15)	−0.04474 (14)	0.0499 (4)
H2A	0.8172	0.5214	−0.1102	0.060*
C3A	0.84875 (16)	0.44243 (14)	0.02136 (13)	0.0446 (4)
C4A	0.80002 (18)	0.33905 (16)	−0.01569 (14)	0.0536 (5)
H4A	0.7659	0.3300	−0.0813	0.064*
C5A	0.80199 (18)	0.24931 (15)	0.04467 (14)	0.0549 (5)
H5A	0.7691	0.1803	0.0195	0.066*
C6A	0.85265 (17)	0.26217 (15)	0.14207 (14)	0.0487 (4)
C7A	0.9008 (2)	0.36573 (16)	0.17931 (14)	0.0576 (5)
H7A	0.9348	0.3746	0.2450	0.069*
C8A	0.89848 (19)	0.45524 (16)	0.11987 (14)	0.0550 (5)
H8A	0.9302	0.5245	0.1455	0.066*
C9A	0.8559 (2)	0.16499 (18)	0.20519 (17)	0.0615 (5)
H9A	0.8286	0.0959	0.1763	0.074*
H1NA	0.990 (2)	0.782 (2)	0.0779 (17)	0.069 (7)*
H2NA	1.007 (2)	0.900 (2)	0.0570 (17)	0.075 (7)*
H3NA	0.8488 (18)	0.6956 (18)	−0.1392 (16)	0.054 (6)*
S1B	0.70719 (7)	0.87078 (5)	0.20508 (5)	0.0836 (2)
O1B	0.36864 (17)	−0.02352 (14)	0.06781 (17)	0.1027 (7)
N1B	0.5055 (2)	0.77556 (19)	0.11523 (17)	0.0728 (6)
C1B	0.6141 (2)	0.76241 (17)	0.16872 (15)	0.0633 (6)
N2B	0.6506 (2)	0.65472 (15)	0.19199 (15)	0.0659 (5)
C2B	0.61285 (19)	0.46749 (17)	0.18659 (16)	0.0596 (5)
H2B	0.6866	0.4587	0.2310	0.072*
N3B	0.57577 (16)	0.56654 (14)	0.15795 (13)	0.0591 (4)
C3B	0.54146 (18)	0.36782 (16)	0.15082 (15)	0.0539 (5)
C4B	0.5824 (2)	0.26093 (18)	0.18761 (17)	0.0636 (6)
H4B	0.6538	0.2549	0.2358	0.076*
C5B	0.5189 (2)	0.16464 (18)	0.15366 (18)	0.0663 (6)
H5B	0.5477	0.0941	0.1784	0.080*
C6B	0.41212 (19)	0.17280 (17)	0.08275 (16)	0.0574 (5)
C7B	0.37016 (19)	0.27858 (17)	0.04567 (16)	0.0592 (5)
H6B	0.2983	0.2843	−0.0020	0.071*
C8B	0.43420 (19)	0.37484 (17)	0.07894 (16)	0.0583 (5)
H7B	0.4056	0.4451	0.0532	0.070*
C9B	0.3412 (2)	0.07213 (19)	0.0444 (2)	0.0723 (6)
H9B	0.2691	0.0838	−0.0017	0.087*
H1NB	0.463 (3)	0.712 (3)	0.093 (2)	0.107 (10)*
H2NB	0.478 (2)	0.844 (2)	0.1003 (19)	0.085 (8)*
H3NB	0.717 (2)	0.642 (2)	0.2304 (17)	0.065 (7)*

	U11	U22	U33	U12	U13	U23
N3A	0.0572 (9)	0.0343 (7)	0.0505 (8)	0.0015 (7)	0.0167 (7)	0.0081 (6)
S1A	0.0797 (4)	0.0362 (2)	0.0594 (3)	−0.0022 (2)	0.0134 (3)	0.0123 (2)
O1A	0.1133 (14)	0.0633 (10)	0.0600 (10)	0.0069 (9)	0.0341 (9)	0.0169 (8)
N1A	0.0936 (15)	0.0363 (9)	0.0541 (10)	−0.0053 (9)	0.0130 (10)	0.0050 (8)
C1A	0.0554 (11)	0.0351 (9)	0.0545 (11)	0.0034 (8)	0.0174 (9)	0.0043 (8)
N2A	0.0682 (11)	0.0343 (7)	0.0479 (9)	−0.0020 (7)	0.0135 (8)	0.0067 (7)
C2A	0.0602 (11)	0.0375 (9)	0.0477 (10)	−0.0014 (8)	0.0131 (8)	0.0043 (8)
C3A	0.0498 (10)	0.0347 (8)	0.0480 (10)	0.0006 (7)	0.0151 (8)	0.0032 (7)
C4A	0.0647 (12)	0.0430 (9)	0.0447 (10)	−0.0084 (9)	0.0082 (9)	0.0010 (8)
C5A	0.0638 (12)	0.0367 (9)	0.0586 (12)	−0.0116 (8)	0.0141 (10)	−0.0017 (8)
C6A	0.0576 (11)	0.0383 (9)	0.0507 (10)	−0.0004 (8)	0.0193 (9)	0.0057 (8)
C7A	0.0817 (15)	0.0445 (10)	0.0439 (10)	−0.0040 (10)	0.0183 (10)	−0.0002 (8)
C8A	0.0774 (14)	0.0351 (9)	0.0498 (10)	−0.0068 (9)	0.0187 (10)	−0.0045 (8)
C9A	0.0775 (15)	0.0449 (10)	0.0641 (13)	−0.0005 (10)	0.0271 (11)	0.0082 (9)
S1B	0.1164 (6)	0.0470 (3)	0.0657 (4)	−0.0135 (3)	0.0042 (3)	0.0020 (3)
O1B	0.0916 (13)	0.0436 (9)	0.158 (2)	−0.0036 (9)	0.0239 (13)	−0.0026 (11)
N1B	0.0818 (15)	0.0507 (11)	0.0826 (14)	0.0090 (11)	0.0243 (12)	0.0030 (11)
C1B	0.0916 (17)	0.0453 (11)	0.0517 (11)	0.0007 (11)	0.0233 (11)	−0.0012 (9)
N2B	0.0739 (13)	0.0445 (9)	0.0669 (12)	−0.0017 (9)	0.0088 (10)	−0.0003 (8)
C2B	0.0632 (13)	0.0471 (11)	0.0647 (13)	0.0019 (10)	0.0172 (10)	0.0008 (9)
N3B	0.0685 (11)	0.0429 (9)	0.0635 (10)	−0.0031 (8)	0.0199 (9)	−0.0036 (8)
C3B	0.0603 (12)	0.0434 (10)	0.0616 (12)	0.0037 (9)	0.0259 (10)	−0.0003 (9)
C4B	0.0605 (13)	0.0517 (11)	0.0738 (14)	0.0066 (10)	0.0172 (11)	0.0103 (10)
C5B	0.0705 (15)	0.0419 (10)	0.0884 (16)	0.0083 (10)	0.0299 (13)	0.0111 (10)
C6B	0.0607 (13)	0.0434 (10)	0.0742 (14)	0.0031 (9)	0.0312 (11)	−0.0022 (9)
C7B	0.0583 (12)	0.0483 (11)	0.0697 (13)	0.0068 (9)	0.0207 (10)	−0.0036 (10)
C8B	0.0650 (13)	0.0423 (10)	0.0672 (13)	0.0103 (9)	0.0225 (11)	0.0015 (9)
C9B	0.0709 (15)	0.0517 (12)	0.0965 (18)	−0.0014 (11)	0.0320 (13)	−0.0068 (12)

N3A—C2A	1.274 (2)	S1B—C1B	1.681 (2)
N3A—N2A	1.374 (2)	O1B—C9B	1.195 (3)
S1A—C1A	1.6976 (18)	N1B—C1B	1.314 (3)
O1A—C9A	1.201 (3)	N1B—H1NB	0.91 (3)
N1A—C1A	1.312 (3)	N1B—H2NB	0.88 (3)
N1A—H1NA	0.84 (3)	C1B—N2B	1.353 (3)
N1A—H2NA	0.87 (3)	N2B—N3B	1.369 (2)
C1A—N2A	1.340 (2)	N2B—H3NB	0.84 (2)
N2A—H3NA	0.84 (2)	C2B—N3B	1.274 (3)
C2A—C3A	1.462 (2)	C2B—C3B	1.457 (3)
C2A—H2A	0.9300	C2B—H2B	0.9300
C3A—C4A	1.388 (2)	C3B—C8B	1.392 (3)
C3A—C8A	1.393 (3)	C3B—C4B	1.399 (3)
C4A—C5A	1.386 (3)	C4B—C5B	1.375 (3)
C4A—H4A	0.9300	C4B—H4B	0.9300
C5A—C6A	1.379 (3)	C5B—C6B	1.382 (3)
C5A—H5A	0.9300	C5B—H5B	0.9300
C6A—C7A	1.388 (3)	C6B—C7B	1.391 (3)
C6A—C9A	1.476 (3)	C6B—C9B	1.470 (3)
C7A—C8A	1.374 (3)	C7B—C8B	1.376 (3)
C7A—H7A	0.9300	C7B—H6B	0.9300
C8A—H8A	0.9300	C8B—H7B	0.9300
C9A—H9A	0.9300	C9B—H9B	0.9300
C2A—N3A—N2A	115.92 (16)	C1B—N1B—H1NB	118 (2)
C1A—N1A—H1NA	122.5 (16)	C1B—N1B—H2NB	119.2 (18)
C1A—N1A—H2NA	120.1 (16)	H1NB—N1B—H2NB	122 (3)
H1NA—N1A—H2NA	117 (2)	N1B—C1B—N2B	116.6 (2)
N1A—C1A—N2A	117.74 (17)	N1B—C1B—S1B	123.36 (18)
N1A—C1A—S1A	123.28 (15)	N2B—C1B—S1B	120.0 (2)
N2A—C1A—S1A	118.98 (15)	C1B—N2B—N3B	119.7 (2)
C1A—N2A—N3A	119.56 (17)	C1B—N2B—H3NB	120.4 (17)
C1A—N2A—H3NA	121.2 (15)	N3B—N2B—H3NB	119.7 (16)
N3A—N2A—H3NA	119.0 (15)	N3B—C2B—C3B	121.0 (2)
N3A—C2A—C3A	120.60 (17)	N3B—C2B—H2B	119.5
N3A—C2A—H2A	119.7	C3B—C2B—H2B	119.5
C3A—C2A—H2A	119.7	C2B—N3B—N2B	116.96 (19)
C4A—C3A—C8A	119.25 (16)	C8B—C3B—C4B	118.45 (19)
C4A—C3A—C2A	118.70 (17)	C8B—C3B—C2B	122.07 (18)
C8A—C3A—C2A	122.03 (16)	C4B—C3B—C2B	119.5 (2)
C5A—C4A—C3A	120.31 (17)	C5B—C4B—C3B	121.1 (2)
C5A—C4A—H4A	119.8	C5B—C4B—H4B	119.5
C3A—C4A—H4A	119.8	C3B—C4B—H4B	119.5
C6A—C5A—C4A	120.11 (17)	C4B—C5B—C6B	119.92 (19)
C6A—C5A—H5A	119.9	C4B—C5B—H5B	120.0
C4A—C5A—H5A	119.9	C6B—C5B—H5B	120.0
C5A—C6A—C7A	119.67 (17)	C5B—C6B—C7B	119.61 (19)
C5A—C6A—C9A	119.37 (17)	C5B—C6B—C9B	121.8 (2)
C7A—C6A—C9A	120.96 (18)	C7B—C6B—C9B	118.6 (2)
C8A—C7A—C6A	120.50 (18)	C8B—C7B—C6B	120.5 (2)
C8A—C7A—H7A	119.8	C8B—C7B—H6B	119.7
C6A—C7A—H7A	119.8	C6B—C7B—H6B	119.7
C7A—C8A—C3A	120.15 (17)	C7B—C8B—C3B	120.43 (19)
C7A—C8A—H8A	119.9	C7B—C8B—H7B	119.8
C3A—C8A—H8A	119.9	C3B—C8B—H7B	119.8
O1A—C9A—C6A	125.3 (2)	O1B—C9B—C6B	125.3 (3)
O1A—C9A—H9A	117.3	O1B—C9B—H9B	117.4
C6A—C9A—H9A	117.3	C6B—C9B—H9B	117.4

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1NA···N3A	0.84 (3)	2.32 (2)	2.630 (2)	102.0 (19)
N1A—H1NA···O1Ai	0.84 (3)	2.41 (3)	3.190 (3)	154 (2)
N1A—H2NA···S1Aii	0.87 (3)	2.52 (3)	3.391 (2)	172 (2)
N2A—H3NA···S1Biii	0.84 (2)	2.50 (2)	3.3270 (19)	166.1 (19)
N1B—H1NB···N3B	0.91 (3)	2.21 (3)	2.619 (3)	106 (3)
N1B—H2NB···O1Biv	0.88 (3)	2.01 (3)	2.857 (3)	161 (3)
N2B—H3NB···S1Av	0.84 (2)	2.58 (2)	3.409 (2)	171 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1NA⋯N3A	0.84 (3)	2.32 (2)	2.630 (2)	102.0 (19)
N1A—H1NA⋯O1A i	0.84 (3)	2.41 (3)	3.190 (3)	154 (2)
N1A—H2NA⋯S1A ii	0.87 (3)	2.52 (3)	3.391 (2)	172 (2)
N2A—H3NA⋯S1B iii	0.84 (2)	2.50 (2)	3.3270 (19)	166.1 (19)
N1B—H1NB⋯N3B	0.91 (3)	2.21 (3)	2.619 (3)	106 (3)
N1B—H2NB⋯O1B iv	0.88 (3)	2.01 (3)	2.857 (3)	161 (3)
N2B—H3NB⋯S1A v	0.84 (2)	2.58 (2)	3.409 (2)	171 (2)

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