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

Tahir, M.N.; Anwar-ul-Haq, M.; Choudhary, M.A.

doi:10.1107/S2056989015017594

organic compounds

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Volume 71| Part 10| October 2015| Page o772

doi:10.1107/S2056989015017594

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

Muhammad Nawaz Tahir,^a ^* Muhammad Anwar-ul-Haq ^a and Muhammad Aziz Choudhary ^b

^aDepartment of Physics, University of Sargodha, Sargodha, Punjab, Pakistan, and ^bDepartment of Chemistry, Mirpur University of Science and Technology (MUST), Mirpur, Azad Jammu and Kashmir, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 15 September 2015; accepted 20 September 2015; online 26 September 2015)

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 R₂²(8) type by pairs of O—H⋯O interactions. The dimers are further connected by pairs of N—H⋯S interactions, which also complete R₂²(8) ring motifs. The chains of dimers are cross-linked by N—H⋯O bonds and hence R₄²(28) rings are completed. Taken together, these interactions lead to infinite sheets propagating in the (122) plane.

Keywords: crystal structure; hydrazinecarbothioamide; hydrogen bonding.

CCDC reference: 1426244

1. Related literature

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

2. Experimental

2.1. Crystal data

C₉H₉N₃O₂S
M_r = 223.25
Triclinic, $[P \overline 1]$
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

2.2. 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

2.3. Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 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

Table 1
Hydrogen-bond geometry (Å, °)

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.

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.

Supporting information

CCDC reference: 1426244

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2056989015017594/hb7508sup1.cif

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

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

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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 (Spek, 2009).

Figures top

	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.

4-[(E)-(2-Carbamothioylhydrazinylidene)methyl]benzoic acid top

Crystal data top

C₉H₉N₃O₂S	Z = 2
M_r = 223.25	F(000) = 232
Triclinic, P1	D_x = 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 top

Bruker Kappa APEXII CCD diffractometer	2286 independent reflections
Radiation source: fine-focus sealed tube	1566 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
Detector resolution: 7.70 pixels mm^-1	θ_max = 27.0°, θ_min = 1.6°
ω scans	h = −5→6
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −10→10
T_min = 0.895, T_max = 0.958	l = −17→17
5971 measured reflections

Refinement top

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(F_o²) + (0.0687P)² + 0.105P] where P = (F_o² + 2F_c²)/3
2286 reflections	(Δ/σ)_max < 0.001
143 parameters	Δρ_max = 0.55 e Å⁻³
3 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₉H₉N₃O₂S	γ = 79.416 (6)°
M_r = 223.25	V = 526.52 (10) Å³
Triclinic, P1	Z = 2
a = 4.7454 (5) Å	Mo Kα radiation
b = 8.5691 (10) Å	µ = 0.29 mm⁻¹
c = 13.3886 (15) Å	T = 296 K
α = 81.386 (6)°	0.40 × 0.22 × 0.16 mm
β = 82.878 (6)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2286 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1566 reflections with I > 2σ(I)
T_min = 0.895, T_max = 0.958	R_int = 0.030
5971 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	3 restraints
wR(F²) = 0.146	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.55 e Å⁻³
2286 reflections	Δρ_min = −0.23 e Å⁻³
143 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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) top

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) top

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.

Hydrogen-bond geometry (Å, º) top

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	0.853 (10)	2.136 (19)	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.

Acknowledgements

The authors acknowledge the provision of funds for the purchase of a diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan.

References

Bruker (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Carballo, R., Pino-Cuevas, A. & Vázquez-López, E. M. (2014). Acta Cryst. E70, o970. CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 10| October 2015| Page o772

doi:10.1107/S2056989015017594

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

1. Related literature

2. Experimental

2.1. Crystal data

2.2. Data collection

2.3. Refinement

Supporting information

Acknowledgements

References

organic compounds

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