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Acta Crystallogr Sect E Struct Rep Online. Nov 1, 2011; 67(Pt 11): o2965.
Published online Oct 12, 2011. doi:  10.1107/S1600536811041894
PMCID: PMC3247371
1,3-Bis(2-chloro­phen­yl)thio­urea: a monoclinic polymorph
Chien Ing Yeoa and Edward R. T. Tiekinka*
aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
Correspondence e-mail: edward.tiekink/at/gmail.com
Received October 6, 2011; Accepted October 11, 2011.
Abstract
The title compound, C13H10Cl2N2S, represents a monoclinic polymorph of the previously reported ortho­rhom­bic form [Ramnathan et al. (1996 [triangle]). Acta Cryst. C52, 134–136]. The mol­ecule is twisted with the dihedral angle between the benzene rings being 55.37 (7)°. The N—H atoms are syn to each other, which contrasts their anti disposition in the ortho­rhom­bic form. In the crystal, mol­ecules assemble into zigzag chains along the c axis via N—H(...)S hydrogen bonds. Chains are connected into layers via C—H(...)Cl inter­actions, and these stack along the a axis.
Related literature
For background to the structural chemistry of thio­carbamides, see: Ho et al. (2005 [triangle]). For a related diaryl­thio­urea structure, see: Kuan & Tiekink (2007 [triangle]). For the structure of the ortho­rhom­bic polymorph, see: Ramnathan et al. (1996 [triangle]).
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Object name is e-67-o2965-scheme1.jpg Object name is e-67-o2965-scheme1.jpg
Crystal data
  • C13H10Cl2N2S
  • M r = 297.19
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-67-o2965-efi1.jpg
  • a = 11.9999 (3) Å
  • b = 14.6811 (3) Å
  • c = 8.0806 (2) Å
  • β = 109.509 (1)°
  • V = 1341.84 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.62 mm−1
  • T = 100 K
  • 0.20 × 0.06 × 0.02 mm
Data collection
  • Bruker SMART APEX diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.644, T max = 0.746
  • 12491 measured reflections
  • 3090 independent reflections
  • 2291 reflections with I > 2σ(I)
  • R int = 0.052
Refinement
  • R[F 2 > 2σ(F 2)] = 0.038
  • wR(F 2) = 0.090
  • S = 1.02
  • 3090 reflections
  • 169 parameters
  • 2 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.35 e Å−3
  • Δρmin = −0.43 e Å−3
Data collection: APEX2 (Bruker, 2009 [triangle]); cell refinement: SAINT (Bruker, 2009 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]), DIAMOND (Brandenburg, 2006 [triangle]) and Qmol (Gans & Shalloway, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2010 [triangle]).
Table 1
Table 1
Hydrogen-bond geometry (Å, °)
Supplementary Material
Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811041894/vm2125sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811041894/vm2125Isup2.hkl
Supplementary material file. DOI: 10.1107/S1600536811041894/vm2125Isup3.cml
Additional supplementary materials: crystallographic information; 3D view; checkCIF report
Acknowledgments
The Ministry of Higher Education, Malaysia, is thanked for the award of a research grant (RG125/10AFR).
supplementary crystallographic information
Comment
In connection with the synthesis and structural studies of thiocarbamides (Ho et al., 2005), diarylthioureas are sometimes isolated as the undesired hydrolysis by-product (Kuan & Tiekink, 2007). The title compound, (I), was isolated in crystalline form during the attempted synthesis of (C6H4Cl-o)N(H)C(═S)O-i-Pr. The structure of (I) is reported herein. A previously reported orthorhombic form of (I) exists in the literature (Ramnathan et al., 1996).
The molecular structure of (I), Fig. 1, is twisted about the central N—C bonds. With reference to the central plane through the CN2S chromophore [r.m.s. deviation = 0.0029 Å], the C2-benzene ring is almost perpendicular [dihedral angle = 85.20 (6)°] and the C8-ring is twisted [dihedral angle = 49.32 (6)°]; the dihedral angle between the benzene rings is 55.37 (7)°. The amide-H atoms are syn to each other. The syn conformation observed for the thiourea chromophore in (I) is quite distinct to that found in the orthorhombic polymorph (Ramnathan et al., 1996).
In the orthorhombic form of (I), the amide-H atoms are anti to each other. This key difference between the molecular structures in the two polymorphs is highlighted in the overlay diagram shown in Fig. 2. The anti orientation allows for the formation of eight-membered {···HNCS}2 synthons in the crystal packing in the orthorhombic polymorph. By contrast, the crystal structure of (I) features supramolecular zigzag chains along the c axis mediated by N—H···S hydrogen bonds (Table 1 and Fig. 3); the S1 atom is bifurcated. Chains assemble into layers by C—H···Cl interactions (Fig. 4) and the layers thus formed stack along the a axis (Fig. 5).
Experimental
2-Chlorophenyl isothiocyanate (2 ml) was added drop-wise to a stirred solution of NaOH (1 mol equiv.) in i-PrOH (25 ml) and stirred for 3 h. Excess HCl (50% M/v) was then added and the solution was stirred for a further 2 h. The product was then extracted with CHCl3 and left for evaporation at room temperature yielding colourless crystals after 3 days; M.pt: 394–396 K. IR (cm-1): ν(N—H) 3348; ν(C—N) 1498; ν(C═ S) 1201.
Refinement
Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 Å) and were included in the refinement in the riding model approximation, with Uiso(H) set to 1.2Ueq(C). The N-bound H-atoms were located in a difference Fourier map but were refined with a distance restraint of N—H = 0.88±0.01 Å, and with Uiso(H) = 1.2Ueq(N).
Figures
Fig. 1.
Fig. 1.
The molecular structure of (I) showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level.
Fig. 2.
Fig. 2.
Overlay diagram of (I) (shown in blue) with the two independent molecules found in the orthorhombic polymorph (see text), shown in red and green. The central thiourea fragments have been fitted.
Fig. 3.
Fig. 3.
Supramolecular zigzag chain in (I) mediated by N—H···S hydrogen bonds, shown as orange dashed lines.
Fig. 4.
Fig. 4.
A view of the supramolecular two-dimensional array in the bc plane for (I). The N—H···S and C—H···Cl contacts are shown as orange and blue dashed lines, respectively.
Fig. 5.
Fig. 5.
Unit-cell contents for (I) shown in projection down the c axis, showing the stacking of supramolecular layers along the a axis. The N—H···S and C—H···Cl contacts are shown as orange and blue (more ...)
Crystal data
C13H10Cl2N2SF(000) = 608
Mr = 297.19Dx = 1.471 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2105 reflections
a = 11.9999 (3) Åθ = 2.3–25.4°
b = 14.6811 (3) ŵ = 0.62 mm1
c = 8.0806 (2) ÅT = 100 K
β = 109.509 (1)°Prism, colourless
V = 1341.84 (5) Å30.20 × 0.06 × 0.02 mm
Z = 4
Data collection
Bruker SMART APEX diffractometer3090 independent reflections
Radiation source: fine-focus sealed tube2291 reflections with I > 2σ(I)
graphiteRint = 0.052
ω scansθmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −15→15
Tmin = 0.644, Tmax = 0.746k = −19→19
12491 measured reflectionsl = −10→10
Refinement
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.090H atoms treated by a mixture of independent and constrained refinement
S = 1.02w = 1/[σ2(Fo2) + (0.0375P)2 + 0.4482P] where P = (Fo2 + 2Fc2)/3
3090 reflections(Δ/σ)max < 0.001
169 parametersΔρmax = 0.35 e Å3
2 restraintsΔρmin = −0.43 e Å3
Special details
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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)
xyzUiso*/Ueq
Cl20.95110 (5)0.44450 (4)0.76829 (8)0.03177 (16)
Cl10.51862 (5)0.24151 (4)0.54764 (9)0.03412 (17)
S10.80893 (5)0.11833 (4)0.59792 (7)0.01789 (13)
N10.73545 (16)0.18714 (12)0.8464 (2)0.0200 (4)
H1N0.740 (2)0.2301 (12)0.923 (2)0.024*
N20.90127 (15)0.25343 (12)0.8279 (2)0.0189 (4)
H2N0.891 (2)0.2893 (13)0.907 (2)0.023*
C10.81669 (17)0.18925 (14)0.7647 (3)0.0171 (4)
C20.63988 (18)0.12309 (15)0.7997 (3)0.0192 (4)
C30.53473 (19)0.14084 (15)0.6660 (3)0.0223 (5)
C40.4428 (2)0.07777 (17)0.6227 (3)0.0280 (5)
H40.37080.09040.53110.034*
C50.4575 (2)−0.00316 (17)0.7142 (3)0.0290 (6)
H50.3955−0.04680.68450.035*
C60.5615 (2)−0.02114 (16)0.8484 (3)0.0274 (5)
H60.5708−0.07690.91120.033*
C70.6528 (2)0.04214 (15)0.8918 (3)0.0223 (5)
H70.72420.02980.98490.027*
C81.00456 (18)0.26531 (15)0.7822 (3)0.0190 (5)
C91.03988 (19)0.35296 (15)0.7568 (3)0.0227 (5)
C101.1449 (2)0.36828 (17)0.7252 (3)0.0292 (6)
H101.16870.42860.71040.035*
C111.2144 (2)0.2954 (2)0.7154 (3)0.0340 (6)
H111.28610.30540.69270.041*
C121.1804 (2)0.20762 (18)0.7386 (3)0.0308 (6)
H121.22840.15750.73030.037*
C131.07637 (19)0.19243 (16)0.7739 (3)0.0248 (5)
H131.05430.13210.79250.030*
Atomic displacement parameters (Å2)
U11U22U33U12U13U23
Cl20.0352 (3)0.0165 (3)0.0443 (4)−0.0053 (2)0.0142 (3)0.0001 (3)
Cl10.0332 (3)0.0314 (3)0.0386 (4)0.0093 (3)0.0131 (3)0.0113 (3)
S10.0192 (3)0.0152 (3)0.0199 (3)−0.0022 (2)0.0072 (2)−0.0024 (2)
N10.0229 (9)0.0184 (9)0.0211 (10)−0.0073 (8)0.0105 (8)−0.0070 (8)
N20.0195 (9)0.0151 (9)0.0231 (10)−0.0049 (7)0.0083 (8)−0.0045 (7)
C10.0179 (10)0.0135 (10)0.0179 (11)0.0006 (8)0.0034 (8)0.0024 (8)
C20.0181 (10)0.0202 (11)0.0229 (11)−0.0039 (9)0.0115 (9)−0.0062 (9)
C30.0243 (12)0.0221 (12)0.0242 (12)−0.0004 (9)0.0130 (9)−0.0013 (9)
C40.0197 (11)0.0412 (15)0.0239 (12)−0.0041 (10)0.0083 (9)−0.0069 (11)
C50.0287 (13)0.0330 (14)0.0307 (13)−0.0163 (11)0.0170 (11)−0.0129 (11)
C60.0358 (13)0.0212 (12)0.0312 (13)−0.0065 (10)0.0193 (11)−0.0015 (10)
C70.0228 (11)0.0225 (11)0.0232 (12)−0.0032 (9)0.0099 (9)−0.0019 (9)
C80.0161 (10)0.0221 (11)0.0176 (11)−0.0049 (9)0.0041 (8)−0.0021 (9)
C90.0234 (11)0.0225 (11)0.0206 (11)−0.0055 (9)0.0051 (9)−0.0026 (9)
C100.0287 (13)0.0324 (14)0.0274 (13)−0.0157 (11)0.0104 (10)−0.0035 (11)
C110.0210 (12)0.0528 (17)0.0298 (14)−0.0131 (12)0.0108 (10)−0.0079 (12)
C120.0210 (12)0.0378 (14)0.0325 (14)0.0013 (11)0.0075 (10)−0.0076 (11)
C130.0202 (11)0.0252 (12)0.0261 (12)−0.0016 (10)0.0037 (9)−0.0023 (10)
Geometric parameters (Å, °)
Cl2—C91.737 (2)C5—H50.9500
Cl1—C31.736 (2)C6—C71.389 (3)
S1—C11.681 (2)C6—H60.9500
N1—C11.348 (3)C7—H70.9500
N1—C21.433 (3)C8—C91.391 (3)
N1—H1N0.871 (10)C8—C131.389 (3)
N2—C11.354 (3)C9—C101.385 (3)
N2—C81.417 (3)C10—C111.375 (4)
N2—H2N0.872 (9)C10—H100.9500
C2—C71.383 (3)C11—C121.383 (4)
C2—C31.384 (3)C11—H110.9500
C3—C41.392 (3)C12—C131.388 (3)
C4—C51.379 (3)C12—H120.9500
C4—H40.9500C13—H130.9500
C5—C61.379 (3)
C1—N1—C2122.16 (18)C7—C6—H6120.0
C1—N1—H1N116.2 (16)C2—C7—C6120.1 (2)
C2—N1—H1N121.4 (16)C2—C7—H7120.0
C1—N2—C8126.73 (18)C6—C7—H7120.0
C1—N2—H2N115.1 (15)C9—C8—C13118.7 (2)
C8—N2—H2N118.1 (15)C9—C8—N2119.22 (19)
N1—C1—N2113.90 (18)C13—C8—N2121.9 (2)
N1—C1—S1121.53 (16)C10—C9—C8121.2 (2)
N2—C1—S1124.56 (16)C10—C9—Cl2119.76 (18)
C7—C2—C3119.4 (2)C8—C9—Cl2119.03 (17)
C7—C2—N1119.08 (19)C11—C10—C9119.4 (2)
C3—C2—N1121.5 (2)C11—C10—H10120.3
C2—C3—C4120.7 (2)C9—C10—H10120.3
C2—C3—Cl1119.68 (17)C10—C11—C12120.4 (2)
C4—C3—Cl1119.65 (18)C10—C11—H11119.8
C5—C4—C3119.3 (2)C12—C11—H11119.8
C5—C4—H4120.3C11—C12—C13120.2 (2)
C3—C4—H4120.3C11—C12—H12119.9
C4—C5—C6120.4 (2)C13—C12—H12119.9
C4—C5—H5119.8C12—C13—C8120.1 (2)
C6—C5—H5119.8C12—C13—H13120.0
C5—C6—C7120.1 (2)C8—C13—H13120.0
C5—C6—H6120.0
Hydrogen-bond geometry (Å, °)
D—H···AD—HH···AD···AD—H···A
N1—H1n···S1i0.873 (17)2.618 (17)3.4449 (18)158.6 (19)
N2—H2n···S1i0.868 (18)2.49 (2)3.3389 (18)166 (2)
C13—H13···Cl2ii0.952.793.660 (2)152
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+2, y−1/2, −z+3/2.
Footnotes
Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: VM2125).
  • Brandenburg, K. (2006). DIAMOND Crystal Impact GbR, Bonn, Germany.
  • Bruker (2009). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
  • Gans, J. & Shalloway, D. (2001). J. Mol. Graph. Model. 19, 557–559. [PubMed]
  • Ho, S. Y., Bettens, R. P. A., Dakternieks, D., Duthie, A. & Tiekink, E. R. T. (2005). CrystEngComm, 7, 682–689.
  • Kuan, F. S. & Tiekink, E. R. T. (2007). Acta Cryst. E63, o4692.
  • Ramnathan, A., Sivakumar, K., Subramanian, K., Janarthanan, N., Ramadas, K. & Fun, H.-K. (1996). Acta Cryst. C52, 134–136.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.
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