organic compounds
E)-(2-carbamothioylhydrazinylidene)methyl]benzoic acid
of 4-[(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
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
2. Experimental
2.1. Crystal data
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2.3. Refinement
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Data collection: APEX2 (Bruker, 2007); cell 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
10.1107/S2056989015017594/hb7508sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989015017594/hb7508Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989015017594/hb7508Isup3.cml
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
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 Uiso(H) = xUeq(C, N O), where x = 1.5 for hydroxy and NH2 groups and x = 1.2 for other H-atoms.
Data collection: APEX2 (Bruker, 2007); cell
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).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. |
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 |
C9H9N3O2S | γ = 79.416 (6)° |
Mr = 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)° |
Bruker Kappa APEXII CCD diffractometer | 2286 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | 1566 reflections with I > 2σ(I) |
Tmin = 0.895, Tmax = 0.958 | Rint = 0.030 |
5971 measured reflections |
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 | Δρmax = 0.55 e Å−3 |
2286 reflections | Δρmin = −0.23 e Å−3 |
143 parameters |
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) |
Symmetry codes: (i) −x−2, −y+1, −z+1; (ii) −x+2, −y, −z; (iii) x+2, y−1, z. |
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
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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.