Crystal structure of N-(propan-2-yl­carbamo­thio­yl)benzamide

In the crystal structure of the title compound, C₁₁H₁₄N₂OS, the six atoms of the central C₂N₂OS residue are coplanar (r.m.s. deviation = 0.002 Å), which facilitates the formation of an intra­molecular N—H...O hydrogen bond, which closes an S(6) loop. The terminal phenyl ring is inclined with respect to the central plane [dihedral angle = 42.10 (6)°]. The most prominent feature of the crystal packing is the formation of {...HNCS}₂ synthons resulting in centrosymmetric dimers.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.049
• wR factor = 0.146
• Data-to-parameter ratio = 15.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O1     --  C7      ..        5.3 su
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         15 Report

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          4 Note
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT432_ALERT_2_G Short Inter X...Y Contact  S1     ..  C1      ..       3.23 Ang.
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          2 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         63 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   7 ALERT level G = General information/check it is not something unexpected

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Structural commentary

Compounds containing thio­urea linkage are very useful building blocks for the synthesis of a wide range of multiheterocyclic and macromolecular compounds. Thio­ureas have proved to be useful substances in drug research in recent years (Burgeson et al., 2012; Vega-Pérez et al., 2012; Yao et al., 2012; Shantharam et al., 2013; Yang et al., 2013). Symmetrical and unsymmetrical thio­ureas have shown anti-fungal activity against the plant pathogens like Penicillium expansum and Fusarium oxysporum (Rodriguez-Fernandez et al., 2005). Also, 1,3-di­alkyl or di­aryl thio­ureas exhibited significant anti-fungal activity against Pyricularia oryzae and Drechslera oryzae (Rauf et al., 2012). In light of this, and following to our on-going study in synthesis of bio-active molecules, we report here the synthesis and crystal structure of the title compound.

In the structure of the title compound, Fig. 1, intra­molecular N—H···O and inter­molecular N—H···S inter­actions are noted (Table 1).

S2. Synthesis and crystallization

Freshly prepared benzoyl chloride 5 ml (0.043 mol) was added drop wise to a solution of 3.2 g (0.042 mol) of ammonium thio­cyanate in 20 ml dry acetone with stirring. The reaction mixture was refluxed for 3 h. The obtained solid precipitate ammonium chloride was filtered off. The formed benzoyl iso­thio­cyanate in the filtrate was added to a solution of 3.1 ml (0.0425 mol) of 2-amino-iso­propane in 20 ml dry acetone. The reaction mixture was heated under reflux for 5 h, then poured into a beaker containing some ice cubes. The resulting precipitate was collected by filtration, washed several times with cold ethanol/water and purified by recrystallization from ethanol/di­chloro­methane mixture (1:1). Yield (63%); colourless solid, m.p 418 K.

S3. Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H = 0.93 to 0.98 Å) and were included in the refinement in the riding model approximation, with U_iso(H) = 1.2–1.5U_eq(C). The hydrogen atoms attached to N1 and N2 were found from difference Fourier maps and were refined with the distance contratin N—H = 0.86±0.02 Å with unrestrained U_iso.

Related literature

For use of thioureas as building blocks in the synthesis of various organic compounds, see: Burgeson et al. (2012); Vega-Pérez et al. (2012); Yao et al. (2012); Shantharam et al. (2013); Yang et al. (2013). For use of thiourea-containing compounds in medicinal applications, see: Rodriguez-Fernandez et al. (2005); Rauf et al. (2012).

Structure description

Compounds containing thio­urea linkage are very useful building blocks for the synthesis of a wide range of multiheterocyclic and macromolecular compounds. Thio­ureas have proved to be useful substances in drug research in recent years (Burgeson et al., 2012; Vega-Pérez et al., 2012; Yao et al., 2012; Shantharam et al., 2013; Yang et al., 2013). Symmetrical and unsymmetrical thio­ureas have shown anti-fungal activity against the plant pathogens like Penicillium expansum and Fusarium oxysporum (Rodriguez-Fernandez et al., 2005). Also, 1,3-di­alkyl or di­aryl thio­ureas exhibited significant anti-fungal activity against Pyricularia oryzae and Drechslera oryzae (Rauf et al., 2012). In light of this, and following to our on-going study in synthesis of bio-active molecules, we report here the synthesis and crystal structure of the title compound.

In the structure of the title compound, Fig. 1, intra­molecular N—H···O and inter­molecular N—H···S inter­actions are noted (Table 1).

For use of thioureas as building blocks in the synthesis of various organic compounds, see: Burgeson et al. (2012); Vega-Pérez et al. (2012); Yao et al. (2012); Shantharam et al. (2013); Yang et al. (2013). For use of thiourea-containing compounds in medicinal applications, see: Rodriguez-Fernandez et al. (2005); Rauf et al. (2012).

Synthesis and crystallization

Freshly prepared benzoyl chloride 5 ml (0.043 mol) was added drop wise to a solution of 3.2 g (0.042 mol) of ammonium thio­cyanate in 20 ml dry acetone with stirring. The reaction mixture was refluxed for 3 h. The obtained solid precipitate ammonium chloride was filtered off. The formed benzoyl iso­thio­cyanate in the filtrate was added to a solution of 3.1 ml (0.0425 mol) of 2-amino-iso­propane in 20 ml dry acetone. The reaction mixture was heated under reflux for 5 h, then poured into a beaker containing some ice cubes. The resulting precipitate was collected by filtration, washed several times with cold ethanol/water and purified by recrystallization from ethanol/di­chloro­methane mixture (1:1). Yield (63%); colourless solid, m.p 418 K.

Refinement details

Carbon-bound H-atoms were placed in calculated positions (C—H = 0.93 to 0.98 Å) and were included in the refinement in the riding model approximation, with U_iso(H) = 1.2–1.5U_eq(C). The hydrogen atoms attached to N1 and N2 were found from difference Fourier maps and were refined with the distance contratin N—H = 0.86±0.02 Å with unrestrained U_iso.

Computing details

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXS2014 (Gruene et al., 2014); program(s) used to refine structure: SHELXL2014 (Gruene et al., 2014); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009).

Figures

	Fig. 1. Perspective view of the title molecule with atom labeling scheme and 50% probability ellipsoids.
	Fig. 2. Packing viewed down the b axis showing stacks of pairs of molecules connected by N—H···S interactions.

N-(Propan-2-ylcarbamothioyl)benzamide

Crystal data

C11H14N2OS	F(000) = 472
Mr = 222.30	Dx = 1.267 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybc	Cell parameters from 1804 reflections
a = 11.2147 (4) Å	θ = 4.0–71.4°
b = 5.3988 (2) Å	µ = 2.27 mm^−1
c = 19.6834 (7) Å	T = 293 K
β = 102.031 (4)°	Prism, colourless
V = 1165.57 (7) Å^3	0.28 × 0.22 × 0.18 mm
Z = 4

Data collection

Agilent Xcalibur, Eos, Gemini diffractometer	2189 independent reflections
Radiation source: Enhance (Cu) X-ray Source	1944 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
Detector resolution: 16.0416 pixels mm^-1	θmax = 71.3°, θmin = 4.0°
ω scans	h = −12→13
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −6→5
Tmin = 0.828, Tmax = 1.000	l = −18→24
3844 measured reflections

Refinement

Refinement on F^2	2 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.049	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.146	w = 1/[σ^2(Fo^2) + (0.0871P)^2 + 0.3862P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
2189 reflections	Δρmax = 0.37 e Å^−3
146 parameters	Δρmin = −0.34 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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	0.60730 (5)	0.80543 (14)	0.08368 (3)	0.0464 (2)
O1	0.86531 (13)	1.0046 (3)	−0.05679 (8)	0.0392 (5)
N1	0.69070 (16)	1.0345 (3)	−0.01498 (9)	0.0321 (5)
N2	0.82704 (16)	0.7717 (3)	0.05595 (9)	0.0337 (5)
C1	0.63795 (19)	1.4665 (4)	−0.10695 (11)	0.0334 (6)
C2	0.5930 (2)	1.6272 (4)	−0.16095 (12)	0.0392 (6)
C3	0.6171 (2)	1.5865 (4)	−0.22650 (11)	0.0414 (7)
C4	0.6865 (2)	1.3853 (5)	−0.23779 (11)	0.0402 (7)
C5	0.73328 (19)	1.2248 (4)	−0.18386 (11)	0.0342 (6)
C6	0.70827 (17)	1.2641 (4)	−0.11803 (10)	0.0293 (5)
C7	0.76319 (18)	1.0900 (4)	−0.06135 (10)	0.0310 (6)
C8	0.71668 (19)	0.8697 (4)	0.04084 (10)	0.0322 (6)
C9	0.8684 (2)	0.5923 (4)	0.11200 (11)	0.0389 (7)
C10	0.9666 (2)	0.4305 (4)	0.09293 (13)	0.0452 (7)
C11	0.9154 (3)	0.7308 (6)	0.17988 (13)	0.0592 (9)
H1	0.62120	1.49370	−0.06320	0.0400*
H1N	0.6216 (16)	1.085 (4)	−0.0236 (11)	0.022 (5)*
H2	0.54640	1.76300	−0.15340	0.0470*
H2N	0.880 (2)	0.814 (5)	0.0317 (14)	0.048 (8)*
H3	0.58660	1.69470	−0.26270	0.0500*
H4	0.70190	1.35740	−0.28180	0.0480*
H5	0.78120	1.09110	−0.19140	0.0410*
H9	0.79950	0.48790	0.11730	0.0470*
H10A	0.93400	0.34290	0.05070	0.0680*
H10B	0.99470	0.31390	0.12960	0.0680*
H10C	1.03360	0.53220	0.08640	0.0680*
H11A	0.98180	0.83660	0.17480	0.0890*
H11B	0.94320	0.61370	0.21650	0.0890*
H11C	0.85090	0.82920	0.19110	0.0890*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0297 (3)	0.0743 (5)	0.0364 (3)	0.0061 (2)	0.0096 (2)	0.0129 (3)
O1	0.0309 (8)	0.0465 (9)	0.0415 (8)	0.0072 (6)	0.0106 (6)	0.0113 (7)
N1	0.0278 (8)	0.0390 (9)	0.0293 (8)	0.0046 (7)	0.0056 (6)	0.0054 (7)
N2	0.0306 (9)	0.0383 (10)	0.0314 (9)	0.0010 (7)	0.0046 (7)	0.0076 (7)
C1	0.0350 (10)	0.0309 (10)	0.0331 (10)	−0.0033 (8)	0.0041 (8)	−0.0023 (8)
C2	0.0400 (11)	0.0299 (10)	0.0448 (12)	−0.0012 (9)	0.0019 (9)	0.0025 (9)
C3	0.0418 (12)	0.0405 (12)	0.0377 (11)	−0.0059 (9)	−0.0014 (9)	0.0124 (9)
C4	0.0369 (11)	0.0544 (14)	0.0291 (10)	−0.0081 (10)	0.0064 (8)	0.0062 (9)
C5	0.0284 (10)	0.0408 (11)	0.0341 (10)	−0.0027 (8)	0.0080 (8)	0.0032 (8)
C6	0.0260 (9)	0.0304 (9)	0.0300 (9)	−0.0055 (7)	0.0022 (7)	0.0023 (8)
C7	0.0321 (10)	0.0314 (10)	0.0286 (9)	−0.0038 (8)	0.0043 (7)	−0.0007 (8)
C8	0.0336 (10)	0.0363 (10)	0.0255 (9)	−0.0020 (8)	0.0033 (7)	−0.0004 (8)
C9	0.0367 (11)	0.0412 (12)	0.0379 (11)	0.0022 (9)	0.0059 (9)	0.0114 (9)
C10	0.0487 (13)	0.0347 (11)	0.0506 (13)	0.0075 (10)	0.0065 (10)	0.0043 (10)
C11	0.0607 (16)	0.079 (2)	0.0334 (12)	0.0280 (14)	−0.0003 (11)	0.0010 (12)

Geometric parameters (Å, º)

S1—C8	1.664 (2)	C9—C11	1.526 (3)
O1—C7	1.220 (3)	C9—C10	1.513 (3)
N1—C7	1.376 (3)	C1—H1	0.9300
N1—C8	1.397 (3)	C2—H2	0.9300
N2—C8	1.322 (3)	C3—H3	0.9300
N2—C9	1.469 (3)	C4—H4	0.9300
C1—C2	1.383 (3)	C5—H5	0.9300
C1—C6	1.391 (3)	C9—H9	0.9800
N1—H1N	0.806 (19)	C10—H10A	0.9600
N2—H2N	0.87 (2)	C10—H10B	0.9600
C2—C3	1.390 (3)	C10—H10C	0.9600
C3—C4	1.381 (3)	C11—H11A	0.9600
C4—C5	1.386 (3)	C11—H11B	0.9600
C5—C6	1.398 (3)	C11—H11C	0.9600
C6—C7	1.490 (3)
C7—N1—C8	127.26 (18)	C6—C1—H1	120.00
C8—N2—C9	124.57 (18)	C1—C2—H2	120.00
C2—C1—C6	120.0 (2)	C3—C2—H2	120.00
C7—N1—H1N	117.5 (15)	C2—C3—H3	120.00
C8—N1—H1N	114.5 (15)	C4—C3—H3	120.00
C1—C2—C3	120.3 (2)	C3—C4—H4	120.00
C8—N2—H2N	119.2 (17)	C5—C4—H4	120.00
C9—N2—H2N	116.2 (17)	C4—C5—H5	120.00
C2—C3—C4	119.9 (2)	C6—C5—H5	120.00
C3—C4—C5	120.3 (2)	N2—C9—H9	109.00
C4—C5—C6	119.9 (2)	C10—C9—H9	109.00
C1—C6—C7	122.51 (18)	C11—C9—H9	109.00
C5—C6—C7	117.82 (18)	C9—C10—H10A	109.00
C1—C6—C5	119.63 (19)	C9—C10—H10B	110.00
O1—C7—N1	122.96 (19)	C9—C10—H10C	109.00
O1—C7—C6	121.90 (18)	H10A—C10—H10B	110.00
N1—C7—C6	115.14 (17)	H10A—C10—H10C	109.00
S1—C8—N1	118.47 (16)	H10B—C10—H10C	109.00
S1—C8—N2	123.87 (16)	C9—C11—H11A	110.00
N1—C8—N2	117.65 (19)	C9—C11—H11B	109.00
N2—C9—C11	109.39 (19)	C9—C11—H11C	109.00
C10—C9—C11	111.3 (2)	H11A—C11—H11B	109.00
N2—C9—C10	109.06 (18)	H11A—C11—H11C	109.00
C2—C1—H1	120.00	H11B—C11—H11C	110.00
C7—N1—C8—N2	7.1 (3)	C2—C1—C6—C7	177.6 (2)
C7—N1—C8—S1	−172.18 (17)	C1—C2—C3—C4	−0.2 (3)
C8—N1—C7—O1	−3.3 (3)	C2—C3—C4—C5	−0.6 (3)
C8—N1—C7—C6	176.95 (19)	C3—C4—C5—C6	1.2 (3)
C9—N2—C8—S1	0.4 (3)	C4—C5—C6—C7	−178.5 (2)
C9—N2—C8—N1	−178.83 (18)	C4—C5—C6—C1	−0.9 (3)
C8—N2—C9—C10	151.8 (2)	C1—C6—C7—O1	−140.9 (2)
C8—N2—C9—C11	−86.2 (3)	C5—C6—C7—O1	36.7 (3)
C6—C1—C2—C3	0.4 (3)	C5—C6—C7—N1	−143.55 (19)
C2—C1—C6—C5	0.1 (3)	C1—C6—C7—N1	38.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···S1^i	0.81 (2)	2.66 (2)	3.4439 (19)	165 (2)
N2—H2N···O1	0.87 (2)	2.00 (3)	2.662 (2)	132 (2)

Symmetry code: (i) −x+1, −y+2, −z.