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Short halogen–halogen and sulfur–sulfur inter­actions have been exploited in the design of supra­molecular assemblies. The inter­molecular Cl...Cl (3.581 Å) and S...S (3.282 Å) distances in the crystal structure of the title compound, C9H8ClN3S, are shorter than the sum of the van der Waals radii. Classical N—H...N and C—H...N hydrogen bonds also contribute to the stabilization of the crystal structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807024130/fj2024sup1.cif
Contains datablocks I, fj2024

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807024130/fj2024Isup2.hkl
Contains datablock I

CCDC reference: 651513

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.058
  • wR factor = 0.132
  • Data-to-parameter ratio = 14.2

checkCIF/PLATON results

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Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 5 PLAT480_ALERT_4_C Long H...A H-Bond Reported H5A .. N2 .. 2.66 Ang.
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

N-(4-chlorophenyl)-N'-cyano-carbamimidothioic acid, methyl ester (I) has been used as an intermediate in the synthesis of potassium channel openers, which show considerable biomolecular current-voltage rectification characteristics. (Lan et al., 2005, 2006)It is also an important reagent for heterocyclic drugs, such as triazoles and oxadiazoles(Wu, 1977; Tilley & Ramuz, 1980).

The molecular structure and atom-labeling scheme are shown in Fig. 1. The bonds N2—C3, N2—C2 and N3—C3 [1.320 (5), 1.322 (5) and 1.331 (5) Å, respectively] have partial double-bond character. The triple-bond character of C2—N1 [1.157 (5) Å] and the N1—C2—N2 angle of 173.8 (4) ° defining the linearity of the cyano moiety, are typical of this group of N-cyano compounds.

The distances of Cl1···Cl1i [symmetry code: (i) 1/2 - x, y - 1/2, z] (3.581 Å) and S1···S1ii [symmetry code: (ii) -x, y, 3/2 - z] (3.282 Å) in the lattice, lower than the sum of the van der Waals for the corresponding atoms, demonstrate the existence of short contacts (Dai et al., 2004; Karan & Arunan, 2004; Zou et al., 2005). The Cl1···Cl1 interactions are responsible for the formation of one-dimensional chains, and the S1···S1 interactions bridge them, as shown in Fig. 2.

There also exists classical hydrogen bonds in the structure, C5—H5a···N2iii [symmetry code: (iii) x,-y + 1,z - 1/2] and N3—H3a···N1 [symmetry code: (iv) x,y,z - 1].

Related literature top

For related literature, see: Dai et al. (2004); Karan & Arunan (2004); Lan et al. (2005, 2006); Tilley & Ramuz (1980); Wu (1977); Zou et al. (2005).

Experimental top

The title compound was synthesized by the reaction of 4-chloroaniline and dimethyl cyanoimidodithiocarbonate according to the method of Lan et al. (2005) in a yield of 80%. Single crystals of (I) were grown by slow evaporation, in air, of an ethanol/tetrahydrofuran (1/1, v/v) solution. Selected analytical data: m.p. 464–466 K; 1H NMR (CDCl3, 500 MHz): δ 1.57 (s, 3H), 2.49 (s, 1H), 7.27–7.91 (m, 4H).

Refinement top

H atoms were included using a riding model with C—H = 0.96 or 0.97 Å and Uiso = 1.2Ueq of the parent C atom.

Structure description top

N-(4-chlorophenyl)-N'-cyano-carbamimidothioic acid, methyl ester (I) has been used as an intermediate in the synthesis of potassium channel openers, which show considerable biomolecular current-voltage rectification characteristics. (Lan et al., 2005, 2006)It is also an important reagent for heterocyclic drugs, such as triazoles and oxadiazoles(Wu, 1977; Tilley & Ramuz, 1980).

The molecular structure and atom-labeling scheme are shown in Fig. 1. The bonds N2—C3, N2—C2 and N3—C3 [1.320 (5), 1.322 (5) and 1.331 (5) Å, respectively] have partial double-bond character. The triple-bond character of C2—N1 [1.157 (5) Å] and the N1—C2—N2 angle of 173.8 (4) ° defining the linearity of the cyano moiety, are typical of this group of N-cyano compounds.

The distances of Cl1···Cl1i [symmetry code: (i) 1/2 - x, y - 1/2, z] (3.581 Å) and S1···S1ii [symmetry code: (ii) -x, y, 3/2 - z] (3.282 Å) in the lattice, lower than the sum of the van der Waals for the corresponding atoms, demonstrate the existence of short contacts (Dai et al., 2004; Karan & Arunan, 2004; Zou et al., 2005). The Cl1···Cl1 interactions are responsible for the formation of one-dimensional chains, and the S1···S1 interactions bridge them, as shown in Fig. 2.

There also exists classical hydrogen bonds in the structure, C5—H5a···N2iii [symmetry code: (iii) x,-y + 1,z - 1/2] and N3—H3a···N1 [symmetry code: (iv) x,y,z - 1].

For related literature, see: Dai et al. (2004); Karan & Arunan (2004); Lan et al. (2005, 2006); Tilley & Ramuz (1980); Wu (1977); Zou et al. (2005).

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SAINT (Bruker, 1999) and SHELXTL (Sheldrick, 1997b); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. The crystal structure of (I), viewed along the c axis. Dashed lines indicate S···S and Cl···Cl short contacts, H atoms are omitted for clarity.
Methyl N-(4-chlorophenyl)-N'-cyanocarbamimidothioate top
Crystal data top
C9H8ClN3SF(000) = 928
Mr = 225.69Dx = 1.461 Mg m3
Orthorhombic, PbcnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2abCell parameters from 797 reflections
a = 38.708 (17) Åθ = 2.9–26.9°
b = 7.160 (3) ŵ = 0.54 mm1
c = 7.407 (3) ÅT = 293 K
V = 2052.8 (16) Å3Prism, colourless
Z = 80.15 × 0.12 × 0.08 mm
Data collection top
Bruker APEX CCD area-detector
diffractometer
1809 independent reflections
Radiation source: fine-focus sealed tube1498 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.046
φ and ω scansθmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1997b)
h = 4631
Tmin = 0.924, Tmax = 0.958k = 78
7728 measured reflectionsl = 88
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.132H-atom parameters constrained
S = 1.25 w = 1/[σ2(Fo2) + (0.0297P)2 + 3.8026P]
where P = (Fo2 + 2Fc2)/3
1809 reflections(Δ/σ)max = 0.002
127 parametersΔρmax = 0.33 e Å3
0 restraintsΔρmin = 0.24 e Å3
Crystal data top
C9H8ClN3SV = 2052.8 (16) Å3
Mr = 225.69Z = 8
Orthorhombic, PbcnMo Kα radiation
a = 38.708 (17) ŵ = 0.54 mm1
b = 7.160 (3) ÅT = 293 K
c = 7.407 (3) Å0.15 × 0.12 × 0.08 mm
Data collection top
Bruker APEX CCD area-detector
diffractometer
1809 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1997b)
1498 reflections with I > 2σ(I)
Tmin = 0.924, Tmax = 0.958Rint = 0.046
7728 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0580 restraints
wR(F2) = 0.132H-atom parameters constrained
S = 1.25Δρmax = 0.33 e Å3
1809 reflectionsΔρmin = 0.24 e Å3
127 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
xyzUiso*/Ueq
Cl10.25094 (2)0.21867 (15)0.35499 (15)0.0468 (3)
S10.03929 (2)0.24739 (17)0.66683 (12)0.0438 (3)
N10.07780 (9)0.2476 (6)1.1032 (5)0.0581 (11)
N20.10311 (7)0.2383 (5)0.7964 (4)0.0392 (8)
N30.09994 (7)0.2402 (4)0.4876 (4)0.0342 (7)
H3A0.08710.24300.39290.041*
C10.02332 (10)0.2496 (7)0.4414 (5)0.0572 (13)
H1A0.00150.25300.44330.086*
H1B0.03090.13910.37960.086*
H1C0.03190.35800.37970.086*
C20.08802 (9)0.2437 (6)0.9566 (5)0.0379 (9)
C30.08436 (9)0.2411 (5)0.6478 (5)0.0320 (8)
C40.13666 (8)0.2348 (5)0.4620 (4)0.0299 (8)
C50.15109 (9)0.3549 (5)0.3371 (5)0.0379 (9)
H5A0.13720.43980.27580.045*
C60.18627 (10)0.3491 (6)0.3029 (5)0.0406 (10)
H6A0.19600.42880.21780.049*
C70.20661 (9)0.2253 (5)0.3951 (5)0.0331 (8)
C80.19262 (10)0.1033 (5)0.5193 (5)0.0392 (9)
H8A0.20670.01940.58060.047*
C90.15734 (9)0.1071 (6)0.5517 (5)0.0391 (9)
H9A0.14760.02400.63370.047*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0281 (5)0.0518 (6)0.0605 (6)0.0003 (4)0.0086 (5)0.0044 (5)
S10.0271 (5)0.0766 (8)0.0277 (5)0.0002 (5)0.0040 (4)0.0015 (5)
N10.048 (2)0.098 (3)0.0285 (18)0.003 (2)0.0025 (16)0.0017 (19)
N20.0275 (15)0.066 (2)0.0236 (15)0.0017 (15)0.0002 (12)0.0048 (15)
N30.0263 (15)0.054 (2)0.0229 (14)0.0006 (14)0.0002 (12)0.0020 (14)
C10.029 (2)0.108 (4)0.034 (2)0.003 (2)0.0016 (17)0.000 (3)
C20.0252 (18)0.060 (3)0.029 (2)0.0022 (17)0.0018 (15)0.0022 (19)
C30.0298 (18)0.038 (2)0.0285 (18)0.0021 (15)0.0024 (15)0.0050 (17)
C40.0242 (17)0.041 (2)0.0246 (17)0.0002 (15)0.0027 (14)0.0056 (16)
C50.0329 (19)0.045 (2)0.036 (2)0.0035 (17)0.0017 (17)0.0049 (18)
C60.037 (2)0.046 (2)0.039 (2)0.0054 (17)0.0092 (17)0.0082 (18)
C70.0273 (18)0.038 (2)0.0340 (19)0.0029 (15)0.0023 (15)0.0049 (16)
C80.038 (2)0.043 (2)0.037 (2)0.0065 (17)0.0011 (17)0.0090 (18)
C90.035 (2)0.050 (2)0.032 (2)0.0015 (18)0.0059 (17)0.0108 (19)
Geometric parameters (Å, º) top
Cl1—C71.742 (4)C1—H1C0.9600
S1—C31.751 (4)C4—C51.381 (5)
S1—C11.781 (4)C4—C91.385 (5)
N1—C21.156 (5)C5—C61.386 (5)
N2—C31.318 (5)C5—H5A0.9300
N2—C21.323 (5)C6—C71.368 (5)
N3—C31.331 (4)C6—H6A0.9300
N3—C41.435 (4)C7—C81.379 (5)
N3—H3A0.8600C8—C91.387 (5)
C1—H1A0.9600C8—H8A0.9300
C1—H1B0.9600C9—H9A0.9300
C3—S1—C1105.72 (18)C9—C4—N3121.8 (3)
C3—N2—C2120.3 (3)C4—C5—C6120.0 (4)
C3—N3—C4124.5 (3)C4—C5—H5A120.0
C3—N3—H3A117.7C6—C5—H5A120.0
C4—N3—H3A117.7C7—C6—C5119.6 (4)
S1—C1—H1A109.5C7—C6—H6A120.2
S1—C1—H1B109.5C5—C6—H6A120.2
H1A—C1—H1B109.5C6—C7—C8121.1 (3)
S1—C1—H1C109.5C6—C7—Cl1120.0 (3)
H1A—C1—H1C109.5C8—C7—Cl1118.9 (3)
H1B—C1—H1C109.5C7—C8—C9119.3 (3)
N1—C2—N2173.8 (4)C7—C8—H8A120.3
N2—C3—N3119.7 (3)C9—C8—H8A120.3
N2—C3—S1118.8 (3)C4—C9—C8119.9 (3)
N3—C3—S1121.5 (3)C4—C9—H9A120.0
C5—C4—C9119.9 (3)C8—C9—H9A120.0
C5—C4—N3118.2 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5A···N2i0.932.663.467 (5)146
N3—H3A···N1ii0.862.182.974 (5)154
Symmetry codes: (i) x, y+1, z1/2; (ii) x, y, z1.

Experimental details

Crystal data
Chemical formulaC9H8ClN3S
Mr225.69
Crystal system, space groupOrthorhombic, Pbcn
Temperature (K)293
a, b, c (Å)38.708 (17), 7.160 (3), 7.407 (3)
V3)2052.8 (16)
Z8
Radiation typeMo Kα
µ (mm1)0.54
Crystal size (mm)0.15 × 0.12 × 0.08
Data collection
DiffractometerBruker APEX CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1997b)
Tmin, Tmax0.924, 0.958
No. of measured, independent and
observed [I > 2σ(I)] reflections
7728, 1809, 1498
Rint0.046
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.058, 0.132, 1.25
No. of reflections1809
No. of parameters127
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.33, 0.24

Computer programs: SMART (Bruker, 1999), SMART, SAINT (Bruker, 1999) and SHELXTL (Sheldrick, 1997b), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL and ORTEP-3 (Farrugia, 1997), SHELXTL.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5A···N2i0.932.663.467 (5)146
N3—H3A···N1ii0.862.182.974 (5)154
Symmetry codes: (i) x, y+1, z1/2; (ii) x, y, z1.
 

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