Crystal structure of 4-[(E)-(2-carbamo­thio­ylhydrazinyl­idene)meth­yl]benzoic acid

Abstract

The title compound, C₉H₉N₃O₂S, is close to planar with an r.m.s. deviation of 0.032 Å. An intra­molecular N—H⋯N hydrogen bond closes an S(5) ring. In the crystal, mol­ecules are connected into inversion dimers of the R ₂ ²(8) type by pairs of O—H⋯O inter­actions. The dimers are further connected by pairs of N—H⋯S inter­actions, 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 inter­actions 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 _r = 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) ų

• 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

• Δρ_max = 0.55 e Å⁻³

• Δρ_min = −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.

Supplementary Material

CCDC reference: 1426244

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

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) .

supplementary crystallographic information

S1. Comment

The title compound (I, Fig. 1) has been synthesized for the complexation and other studies. The crystal structures of 2-(4-cyanobenzylidene)hydrazinecarbothioamide (Wu et al., 2009) and 2-(4-formylbenzylidene)hydrazinecarbothioamide (Carballo et al., 2014) have been published which are related to (I).

The heavy atoms of (I) i.e (C1–C9/N1/M2/M3/O1/O2/S1) are almost in a plane. The r. m. s. deviation from the mean square plane is 0.0312 Å. S (5) ring motif is present due to intramolecular H-interaction of N–H···N type (Table 1, Fig. 1). The molecules are dimerzed due to conventional O–H···O interaction with R₂²(8) rings (Table 1, Fig. 2). These dimmers are connected from opposite ends due to N–H···S interactions and also complete R₂²(8) ring motifs. R₄²(28) rings are completed (Table 1, Fig. 2), when we consider N–H···O and O–H···O contacts (Table 1, Fig. 2). The molecules are overall stabilized in the form of a two dimensional network with base vectors [4 - 1 -1] and [2 - 1 0] in the (1 2 2) plane.

S2. Experimental

Equimolar quantities of 4-formylbenzoic acid and thiosemicarbazide were dissolved separately in methanol and then mixed. The mixture was refluxed for 3 h. The resulting solution was kept at room temperature for crystallization which afforded white needle after 48 h. m.p. 455 K

S3. Refinement

The coordinates of H-atoms of NH₂ group were refined with constraints. The other H-atoms were positioned geometrically (C–H = 0.93 Å, N–H = 0.86 Å, O–H = 0.82 Å)and refined as riding with U_iso(H) = xU_eq(C, N O), where x = 1.5 for hydroxy and NH₂ groups and x = 1.2 for other H-atoms.

Figures

Fig. 1.

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

Fig. 2.

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

Crystal data

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

Data collection

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

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

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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)

Atomic displacement parameters (Ų)

	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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

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)

Symmetry codes: (i) −x−2, −y+1, −z+1; (ii) −x+2, −y, −z; (iii) x+2, y−1, z.