Crystal structure of 4-[(E)-(2-carbamo-thio-ylhydrazinyl-idene)meth-yl]benzoic acid.

The title compound, C9H9N3O2S, is close to planar with an r.m.s. deviation of 0.032 Å. An intra-molecular N-H⋯N hydrogen bond closes an S(5) ring. In the crystal, mol-ecules are connected into inversion dimers of the R 2 (2)(8) type by pairs of O-H⋯O inter-actions. The dimers are further connected by pairs of N-H⋯S inter-actions, which also complete R 2 (2)(8) ring motifs. The chains of dimers are cross-linked by N-H⋯O bonds and hence R 4 (2)(28) rings are completed. Taken together, these inter-actions lead to infinite sheets propagating in the (122) plane.

Related literature

For related structures, see: Carballo et al. (2014 ▸); Wu et al., (2009 ▸).

Experimental

Crystal data

C9H9N3O2S

M = 223.25

Triclinic,

a = 4.7454 (5) Å

b = 8.5691 (10) Å

c = 13.3886 (15) Å

α = 81.386 (6)°

β = 82.878 (6)°

γ = 79.416 (6)°

V = 526.52 (10) Å3

Z = 2

Mo Kα radiation

μ = 0.29 mm−1

T = 296 K

0.40 × 0.22 × 0.16 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▸) T min = 0.895, T max = 0.958

5971 measured reflections

2286 independent reflections

1566 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.051

wR(F 2) = 0.146

S = 1.06

2286 reflections

143 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.55 e Å−3

Δρmin = −0.23 e Å−3

Data collection: APEX2 (Bruker, 2007 ▸); cell refinement: SAINT (Bruker, 2007 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014/6 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸) and PLATON (Spek, 2009 ▸); software used to prepare material for publication: WinGX (Farrugia, 2012 ▸) and PLATON.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015017594/hb7508sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015017594/hb7508Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015017594/hb7508Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015017594/hb7508fig1.tif

View of the title compound with displacement ellipsoids drawn at the 50% probability level. The dotted line indicate the intra­molecular H-inter­action.

Click here for additional data file.

PLATON . DOI: 10.1107/S2056989015017594/hb7508fig2.tif

The partial packing (PLATON; Spek, 2009), which shows that mol­ecules are dimerized and form a two-dimensional network with various ring motifs.

CCDC reference: 1426244

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

C9H9N3O2S	Z = 2
Mr = 223.25	F(000) = 232
Triclinic, P1	Dx = 1.408 Mg m−3
a = 4.7454 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.5691 (10) Å	Cell parameters from 1566 reflections
c = 13.3886 (15) Å	θ = 1.6–27.0°
α = 81.386 (6)°	µ = 0.29 mm−1
β = 82.878 (6)°	T = 296 K
γ = 79.416 (6)°	Needle, colourless
V = 526.52 (10) Å3	0.40 × 0.22 × 0.16 mm

Bruker Kappa APEXII CCD diffractometer	2286 independent reflections
Radiation source: fine-focus sealed tube	1566 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
Detector resolution: 7.70 pixels mm-1	θmax = 27.0°, θmin = 1.6°
ω scans	h = −5→6
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −10→10
Tmin = 0.895, Tmax = 0.958	l = −17→17
5971 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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.146	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0687P)2 + 0.105P] where P = (Fo2 + 2Fc2)/3
2286 reflections	(Δ/σ)max < 0.001
143 parameters	Δρmax = 0.55 e Å−3
3 restraints	Δρmin = −0.23 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
S1	1.16213 (14)	−0.24283 (8)	0.07250 (5)	0.0516 (3)
O1	−0.7098 (4)	0.3266 (3)	0.50791 (14)	0.0659 (6)
H1	−0.8389	0.3791	0.5417	0.099*
O2	−0.8294 (4)	0.5276 (2)	0.38826 (14)	0.0598 (6)
N1	0.4804 (4)	0.0209 (2)	0.19255 (16)	0.0417 (5)
N2	0.7068 (4)	−0.0327 (2)	0.12477 (16)	0.0426 (5)
H2	0.7307	0.0194	0.0651	0.051*
N3	0.8427 (6)	−0.2352 (3)	0.24762 (19)	0.0635 (7)
H3A	0.951 (6)	−0.321 (3)	0.270 (2)	0.095*
H3B	0.702 (5)	−0.199 (4)	0.289 (2)	0.095*
C1	−0.6710 (5)	0.4042 (3)	0.41755 (19)	0.0443 (6)
C2	−0.4179 (5)	0.3333 (3)	0.35245 (19)	0.0409 (6)
C3	−0.3616 (5)	0.4082 (3)	0.2550 (2)	0.0426 (6)
H3	−0.4830	0.5005	0.2308	0.051*
C4	−0.1243 (5)	0.3456 (3)	0.1935 (2)	0.0434 (6)
H4	−0.0858	0.3969	0.1282	0.052*
C5	0.0572 (4)	0.2066 (3)	0.22859 (19)	0.0380 (6)
C6	−0.0038 (5)	0.1310 (3)	0.3255 (2)	0.0488 (7)
H6	0.1146	0.0372	0.3493	0.059*
C7	−0.2402 (5)	0.1942 (3)	0.3875 (2)	0.0495 (7)
H7	−0.2795	0.1430	0.4527	0.059*
C8	0.3065 (5)	0.1441 (3)	0.16108 (19)	0.0406 (6)
H8	0.3370	0.1949	0.0952	0.049*
C9	0.8922 (5)	−0.1683 (3)	0.15277 (19)	0.0415 (6)

	U11	U22	U33	U12	U13	U23
S1	0.0457 (4)	0.0493 (4)	0.0491 (4)	0.0093 (3)	0.0097 (3)	−0.0059 (3)
O1	0.0503 (11)	0.0888 (16)	0.0404 (11)	0.0235 (10)	0.0101 (8)	−0.0059 (11)
O2	0.0497 (11)	0.0690 (13)	0.0463 (11)	0.0202 (10)	0.0079 (8)	−0.0087 (10)
N1	0.0345 (10)	0.0446 (12)	0.0429 (12)	−0.0032 (9)	0.0093 (9)	−0.0108 (10)
N2	0.0366 (10)	0.0457 (12)	0.0378 (12)	0.0032 (9)	0.0092 (8)	−0.0041 (9)
N3	0.0702 (17)	0.0557 (16)	0.0458 (15)	0.0152 (12)	0.0145 (12)	0.0054 (12)
C1	0.0340 (13)	0.0574 (17)	0.0390 (15)	0.0029 (12)	−0.0009 (10)	−0.0133 (13)
C2	0.0306 (12)	0.0519 (15)	0.0393 (14)	0.0012 (10)	0.0003 (10)	−0.0160 (12)
C3	0.0330 (12)	0.0452 (14)	0.0461 (15)	0.0034 (10)	0.0014 (10)	−0.0115 (12)
C4	0.0381 (13)	0.0483 (15)	0.0402 (14)	−0.0027 (11)	0.0046 (10)	−0.0069 (12)
C5	0.0273 (11)	0.0465 (14)	0.0407 (14)	−0.0036 (10)	0.0014 (9)	−0.0143 (11)
C6	0.0382 (13)	0.0536 (16)	0.0466 (16)	0.0088 (11)	0.0018 (11)	−0.0060 (13)
C7	0.0419 (14)	0.0632 (18)	0.0359 (14)	0.0025 (12)	0.0048 (11)	−0.0039 (13)
C8	0.0324 (12)	0.0458 (14)	0.0406 (14)	0.0007 (10)	0.0023 (10)	−0.0094 (12)
C9	0.0382 (13)	0.0395 (14)	0.0444 (15)	−0.0050 (10)	−0.0033 (10)	−0.0007 (12)

S1—C9	1.664 (2)	C2—C3	1.383 (4)
O1—C1	1.299 (3)	C2—C7	1.383 (3)
O1—H1	0.8200	C3—C4	1.383 (3)
O2—C1	1.222 (3)	C3—H3	0.9300
N1—C8	1.268 (3)	C4—C5	1.392 (3)
N1—N2	1.375 (3)	C4—H4	0.9300
N2—C9	1.357 (3)	C5—C6	1.383 (4)
N2—H2	0.8600	C5—C8	1.466 (3)
N3—C9	1.325 (3)	C6—C7	1.386 (3)
N3—H3A	0.853 (10)	C6—H6	0.9300
N3—H3B	0.851 (10)	C7—H7	0.9300
C1—C2	1.484 (3)	C8—H8	0.9300
C1—O1—H1	109.5	C3—C4—H4	119.7
C8—N1—N2	116.9 (2)	C5—C4—H4	119.7
C9—N2—N1	119.5 (2)	C6—C5—C4	119.1 (2)
C9—N2—H2	120.3	C6—C5—C8	122.0 (2)
N1—N2—H2	120.3	C4—C5—C8	118.8 (2)
C9—N3—H3A	120 (2)	C5—C6—C7	120.4 (2)
C9—N3—H3B	124 (2)	C5—C6—H6	119.8
H3A—N3—H3B	116 (3)	C7—C6—H6	119.8
O2—C1—O1	122.6 (2)	C2—C7—C6	120.1 (2)
O2—C1—C2	122.2 (2)	C2—C7—H7	119.9
O1—C1—C2	115.2 (2)	C6—C7—H7	119.9
C3—C2—C7	119.9 (2)	N1—C8—C5	120.0 (2)
C3—C2—C1	118.9 (2)	N1—C8—H8	120.0
C7—C2—C1	121.2 (2)	C5—C8—H8	120.0
C4—C3—C2	119.9 (2)	N3—C9—N2	115.3 (2)
C4—C3—H3	120.0	N3—C9—S1	123.1 (2)
C2—C3—H3	120.0	N2—C9—S1	121.62 (19)
C3—C4—C5	120.5 (2)
C8—N1—N2—C9	−177.0 (2)	C4—C5—C6—C7	−0.9 (4)
O2—C1—C2—C3	−0.8 (4)	C8—C5—C6—C7	179.5 (2)
O1—C1—C2—C3	179.8 (2)	C3—C2—C7—C6	0.9 (4)
O2—C1—C2—C7	179.5 (3)	C1—C2—C7—C6	−179.5 (2)
O1—C1—C2—C7	0.1 (4)	C5—C6—C7—C2	0.3 (4)
C7—C2—C3—C4	−1.3 (4)	N2—N1—C8—C5	179.0 (2)
C1—C2—C3—C4	179.0 (2)	C6—C5—C8—N1	−2.9 (4)
C2—C3—C4—C5	0.7 (4)	C4—C5—C8—N1	177.6 (2)
C3—C4—C5—C6	0.5 (4)	N1—N2—C9—N3	−2.7 (4)
C3—C4—C5—C8	180.0 (2)	N1—N2—C9—S1	177.48 (17)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···N1	0.86 (3)	2.28 (3)	2.600 (3)	102 (2)
O1—H1···O2i	0.82	1.84	2.653 (2)	170
N2—H2···S1ii	0.86	2.53	3.347 (2)	160
N3—H3A···O2iii	0.85 (1)	2.14 (2)	2.918 (3)	152 (3)

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N3H3BN1	0.86(3)	2.28(3)	2.600(3)	102(2)
O1H1O2i	0.82	1.84	2.653(2)	170
N2H2S1ii	0.86	2.53	3.347(2)	160
N3H3AO2iii	0.85(1)	2.14(2)	2.918(3)	152(3)

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