1-Benzoyl-3,3-bis­(2-methyl­prop­yl)thio­urea

The title compound, C₁₆H₂₄N₂OS, is twisted about the central N(H)—C bond with the C—N—C—S torsion angle being 119.6 (3)°. The carbonyl O and thione S atoms are directed to opposite sides of the mol­ecule, a conformation that allows for the formation of a linear supra­molecular chain comprising alternating eight-membered {...HNCS}₂ and 14-membered {...HCNCNCO}₂ synthons.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.074
• wR factor = 0.219
• Data-to-parameter ratio = 20.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.96
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C14
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds (x 1000) Ang ..          6
PLAT414_ALERT_2_C Short Intra D-H..H-X       H1     ..  H6      ..       1.99 Ang.
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          1
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          2
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600        150

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         12

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 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

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S1. Comment

N,N-Dialkyl-N'-benzoylthioureas are versatile ligands which can coordinate to transition metal centres either as neutral species or in an anionic form. The complexation capacity of thiourea derivatives has been reported in several studies (Binzet et al., 2009; Gunasekaran et al., 2010). Chiral and achiral platinum(II) complexes of these ligands have been used as chemotherapeutic agents (Sacht et al., 2000) while cadmium(II) complexes of N,N-diethyl-N'-benzoylthiourea have been used as single-source precursors for the preparation of CdS nanoparticles (Bruce et al., 2007). In addition, thioureas have been shown to possess anti-tubercular, anti-helmintic, anti-bacterial, insecticidal and rodenticidal properties (Arslan et al., 2006). In continuation of structural studies of these derivatives (Gunasekaran et al., 2010a; Gunasekaran et al., 2010b), the title compound, (I), was investigated.

In (I), Fig. 1, the molecule exhibits a significant twist about the central N(H)–C bond as seen in the value of the C7–N1–C8–S1 torsion angle of 119.6 (3) °. This arrangement causes the carbonyl-O and thione-S atoms to lie on opposite sides of the molecule. Similarly, the carbonyl and N–H groups are directed away from each other. This conformation allows for the formation of N–H···S hydrogen bonds, Table 1, via an eight-membered {···HNCS}₂ ring which has the shape of an elongated chair. These are connected into supramolecular chains along [1 1 1] via C–H···O contacts that close 14-membered {···HCNCNCO}₂ synthons, also adopting the shape of an elongated chair, Table 1 and Fig. 2. Chains are arranged into layers via weak π···π interactions [Cg(C1–C6)···Cg(C1–C6)ⁱ = 3.806 (3) Å for i: 2 - x, 1 - y, 2 - z] and these stack as shown in Fig. 3.

Related literature

For the coordinating ability of N,N-dialkyl-N'-benzoylthioureas; see: Binzet et al. (2009); Gunasekaran et al. (2010); Sacht et al. (2000). For the utility of Cd derivatives to serve as synthetic precursors for CdS nanoparticles, see: Bruce et al. (2007). For their biological activity, see: Arslan et al. (2006). For related structures, see: Gunasekaran et al. (2010a,b).

S2. Experimental

A solution of benzoyl chloride (0.7029 g, 5 mmol) in acetone (50 ml) was added drop wise to a suspension of potassium thiocyanate (0.4859 g, 5 mmol) in anhydrous acetone (50 ml). The reaction mixture was heated under reflux for 45 min. and then cooled to room temperature. A solution of diisobutyl amine (0.6462 g, 5 mmol) in acetone (30 ml) was added and the resulting mixture was stirred for 2 h. Hydrochloric acid (0.1 N, 300 ml) was added and the resulting white solid was filtered, washed with water and dried in vacuo. Single crystals for X-ray diffraction were grown at room temperature from an acetonitrile solution of the compound. Yield 72%; M.Pt. 415 K. FT—IR (KBr) ν(N—H) 3268, ν(C═O) 1688, ν(C=S) 1264 cm^-1.

S3. Refinement

The H-atoms were placed in calculated positions (N—H = 0.88; C—H 0.93 to 0.98 Å) and were included in the refinement in the riding model approximation, with U_iso(H) set to 1.2 to 1.5U_equiv(N, C).

Computing details

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. The molecular structure of (I) showing the atom-labelling scheme and displacement ellipsoids at the 35% probability level.
	Fig. 2. Supramolecular chain in (I) mediated by N–H···S hydrogen bonds and C–H···O contacts, shown as orange and blue dashed lines, respectively.
	Fig. 3. View in projection down the b axis of the unit cell contents of (I). The N–H···S hydrogen bonds and C–H···O contacts are shown as orange and blue dashed lines, respectively.

1-Benzoyl-3,3-bis(2-methylpropyl)thiourea

Crystal data

C16H24N2OS	Z = 2
Mr = 292.43	F(000) = 316
Triclinic, P1	Dx = 1.160 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.9331 (10) Å	Cell parameters from 1845 reflections
b = 10.1023 (9) Å	θ = 2.2–29.2°
c = 11.0725 (12) Å	µ = 0.19 mm^−1
α = 105.776 (9)°	T = 295 K
β = 112.734 (10)°	Block, colourless
γ = 100.782 (9)°	0.35 × 0.30 × 0.25 mm
V = 837.47 (19) Å^3

Data collection

Agilent Supernova Dual diffractometer with an Atlas detector	3693 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2232 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.025
Detector resolution: 10.4041 pixels mm^-1	θmax = 27.5°, θmin = 2.2°
ω scans	h = −10→11
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −13→12
Tmin = 0.936, Tmax = 0.954	l = −14→12
6265 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.074	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.219	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.078P)^2 + 0.7593P] where P = (Fo^2 + 2Fc^2)/3
3693 reflections	(Δ/σ)max = 0.001
181 parameters	Δρmax = 0.86 e Å^−3
12 restraints	Δρmin = −0.58 e Å^−3

Special details

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 > 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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.74828 (14)	0.92803 (11)	0.99096 (12)	0.0711 (4)
O1	0.6998 (3)	0.5295 (2)	0.7153 (3)	0.0585 (7)
N1	0.8690 (3)	0.7638 (3)	0.8494 (3)	0.0512 (7)
H1	0.9753	0.8236	0.8909	0.061*
N2	0.6172 (3)	0.7981 (3)	0.7098 (3)	0.0515 (7)
C1	0.9961 (4)	0.5699 (3)	0.8524 (3)	0.0431 (7)
C2	0.9697 (5)	0.4222 (4)	0.8112 (4)	0.0535 (9)
H2	0.8597	0.3566	0.7487	0.064*
C3	1.1045 (5)	0.3706 (4)	0.8615 (5)	0.0653 (11)
H3	1.0847	0.2708	0.8335	0.078*
C4	1.2664 (5)	0.4656 (5)	0.9522 (5)	0.0669 (11)
H4	1.3568	0.4306	0.9866	0.080*
C5	1.2961 (5)	0.6133 (5)	0.9929 (5)	0.0661 (11)
H5	1.4069	0.6780	1.0542	0.079*
C6	1.1618 (4)	0.6657 (4)	0.9431 (4)	0.0538 (9)
H6	1.1826	0.7656	0.9705	0.065*
C7	0.8421 (4)	0.6165 (3)	0.7986 (3)	0.0426 (7)
C8	0.7372 (4)	0.8250 (3)	0.8392 (4)	0.0513 (9)
C9	0.6351 (4)	0.7432 (3)	0.5811 (4)	0.0526 (9)
H9A	0.5352	0.6588	0.5122	0.063*
H9B	0.7353	0.7118	0.6035	0.063*
C10	0.6535 (5)	0.8564 (4)	0.5150 (4)	0.0654 (11)
H10	0.5463	0.8792	0.4831	0.079*
C11	0.6790 (7)	0.7906 (5)	0.3856 (4)	0.0892 (15)
H11A	0.5849	0.7025	0.3204	0.134*
H11B	0.7847	0.7691	0.4149	0.134*
H11C	0.6835	0.8587	0.3403	0.134*
C12	0.7998 (6)	0.9970 (4)	0.6237 (5)	0.0877 (15)
H12A	0.8091	1.0661	0.5801	0.132*
H12B	0.9057	0.9765	0.6583	0.132*
H12C	0.7765	1.0367	0.7012	0.132*
C13	0.4659 (4)	0.8426 (4)	0.6909 (5)	0.0662 (11)
H13A	0.4206	0.8536	0.6005	0.079*
H13B	0.5025	0.9377	0.7640	0.079*
C14	0.3240 (5)	0.7441 (4)	0.6949 (7)	0.106 (2)
H14	0.3640	0.7625	0.7957	0.127*
C15	0.1645 (5)	0.7914 (5)	0.6518 (6)	0.0888 (15)
H15A	0.1979	0.8950	0.6987	0.133*
H15B	0.0863	0.7435	0.6785	0.133*
H15C	0.1094	0.7655	0.5512	0.133*
C16	0.2816 (6)	0.5830 (4)	0.6261 (6)	0.0816 (13)
H16A	0.3853	0.5586	0.6554	0.122*
H16B	0.2264	0.5542	0.5251	0.122*
H16C	0.2058	0.5330	0.6536	0.122*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0676 (7)	0.0507 (6)	0.0765 (7)	0.0191 (5)	0.0294 (6)	0.0036 (5)
O1	0.0434 (13)	0.0383 (13)	0.0653 (16)	0.0071 (11)	0.0031 (12)	0.0157 (12)
N1	0.0344 (14)	0.0355 (15)	0.0622 (18)	0.0091 (12)	0.0100 (13)	0.0078 (13)
N2	0.0364 (14)	0.0400 (15)	0.0659 (19)	0.0137 (12)	0.0144 (14)	0.0156 (14)
C1	0.0428 (17)	0.0444 (18)	0.0423 (17)	0.0167 (15)	0.0181 (14)	0.0176 (14)
C2	0.054 (2)	0.0427 (19)	0.059 (2)	0.0190 (16)	0.0215 (17)	0.0169 (17)
C3	0.069 (3)	0.054 (2)	0.088 (3)	0.034 (2)	0.040 (2)	0.034 (2)
C4	0.055 (2)	0.077 (3)	0.089 (3)	0.039 (2)	0.035 (2)	0.046 (3)
C5	0.0419 (19)	0.071 (3)	0.077 (3)	0.0192 (19)	0.0186 (18)	0.029 (2)
C6	0.0451 (19)	0.050 (2)	0.060 (2)	0.0171 (16)	0.0180 (16)	0.0193 (17)
C7	0.0417 (17)	0.0384 (17)	0.0383 (16)	0.0125 (14)	0.0111 (14)	0.0128 (14)
C8	0.0403 (17)	0.0325 (17)	0.067 (2)	0.0098 (14)	0.0173 (16)	0.0118 (16)
C9	0.0438 (18)	0.0412 (19)	0.060 (2)	0.0136 (15)	0.0125 (16)	0.0183 (17)
C10	0.055 (2)	0.052 (2)	0.075 (3)	0.0160 (18)	0.0104 (19)	0.032 (2)
C11	0.113 (4)	0.077 (3)	0.071 (3)	0.025 (3)	0.033 (3)	0.038 (3)
C12	0.092 (3)	0.052 (3)	0.089 (3)	0.000 (2)	0.021 (3)	0.030 (2)
C13	0.046 (2)	0.057 (2)	0.089 (3)	0.0247 (18)	0.022 (2)	0.027 (2)
C14	0.065 (3)	0.072 (3)	0.203 (7)	0.033 (3)	0.070 (4)	0.065 (4)
C15	0.060 (3)	0.097 (4)	0.139 (5)	0.039 (3)	0.057 (3)	0.060 (4)
C16	0.071 (3)	0.057 (3)	0.113 (4)	0.012 (2)	0.047 (3)	0.027 (3)

Geometric parameters (Å, º)

S1—C8	1.673 (4)	C9—H9B	0.9700
O1—C7	1.214 (4)	C10—C12	1.528 (4)
N1—C7	1.377 (4)	C10—C11	1.529 (4)
N1—C8	1.410 (4)	C10—H10	0.9800
N1—H1	0.8800	C11—H11A	0.9600
N2—C8	1.330 (4)	C11—H11B	0.9600
N2—C13	1.461 (4)	C11—H11C	0.9600
N2—C9	1.464 (5)	C12—H12A	0.9600
C1—C2	1.380 (5)	C12—H12B	0.9600
C1—C6	1.386 (5)	C12—H12C	0.9600
C1—C7	1.493 (4)	C13—C14	1.482 (4)
C2—C3	1.381 (5)	C13—H13A	0.9700
C2—H2	0.9300	C13—H13B	0.9700
C3—C4	1.362 (6)	C14—C16	1.498 (4)
C3—H3	0.9300	C14—C15	1.530 (4)
C4—C5	1.376 (6)	C14—H14	0.9800
C4—H4	0.9300	C15—H15A	0.9600
C5—C6	1.382 (5)	C15—H15B	0.9600
C5—H5	0.9300	C15—H15C	0.9600
C6—H6	0.9300	C16—H16A	0.9600
C9—C10	1.533 (4)	C16—H16B	0.9600
C9—H9A	0.9700	C16—H16C	0.9600
C7—N1—C8	124.2 (3)	C12—C10—H10	108.2
C7—N1—H1	117.9	C11—C10—H10	108.2
C8—N1—H1	117.9	C9—C10—H10	108.2
C8—N2—C13	120.0 (3)	C10—C11—H11A	109.5
C8—N2—C9	124.2 (3)	C10—C11—H11B	109.5
C13—N2—C9	115.2 (3)	H11A—C11—H11B	109.5
C2—C1—C6	118.6 (3)	C10—C11—H11C	109.5
C2—C1—C7	117.4 (3)	H11A—C11—H11C	109.5
C6—C1—C7	124.0 (3)	H11B—C11—H11C	109.5
C1—C2—C3	120.9 (4)	C10—C12—H12A	109.5
C1—C2—H2	119.6	C10—C12—H12B	109.5
C3—C2—H2	119.6	H12A—C12—H12B	109.5
C4—C3—C2	120.1 (4)	C10—C12—H12C	109.5
C4—C3—H3	119.9	H12A—C12—H12C	109.5
C2—C3—H3	119.9	H12B—C12—H12C	109.5
C3—C4—C5	120.0 (3)	N2—C13—C14	116.6 (3)
C3—C4—H4	120.0	N2—C13—H13A	108.1
C5—C4—H4	120.0	C14—C13—H13A	108.1
C4—C5—C6	120.2 (4)	N2—C13—H13B	108.1
C4—C5—H5	119.9	C14—C13—H13B	108.1
C6—C5—H5	119.9	H13A—C13—H13B	107.3
C5—C6—C1	120.2 (3)	C13—C14—C16	118.4 (4)
C5—C6—H6	119.9	C13—C14—C15	111.0 (3)
C1—C6—H6	119.9	C16—C14—C15	112.5 (4)
O1—C7—N1	121.4 (3)	C13—C14—H14	104.5
O1—C7—C1	122.1 (3)	C16—C14—H14	104.5
N1—C7—C1	116.6 (3)	C15—C14—H14	104.5
N2—C8—N1	117.1 (3)	C14—C15—H15A	109.5
N2—C8—S1	125.9 (3)	C14—C15—H15B	109.5
N1—C8—S1	117.1 (3)	H15A—C15—H15B	109.5
N2—C9—C10	113.3 (3)	C14—C15—H15C	109.5
N2—C9—H9A	108.9	H15A—C15—H15C	109.5
C10—C9—H9A	108.9	H15B—C15—H15C	109.5
N2—C9—H9B	108.9	C14—C16—H16A	109.5
C10—C9—H9B	108.9	C14—C16—H16B	109.5
H9A—C9—H9B	107.7	H16A—C16—H16B	109.5
C12—C10—C11	112.2 (3)	C14—C16—H16C	109.5
C12—C10—C9	110.9 (3)	H16A—C16—H16C	109.5
C11—C10—C9	109.1 (3)	H16B—C16—H16C	109.5
C6—C1—C2—C3	1.4 (5)	C13—N2—C8—N1	172.5 (3)
C7—C1—C2—C3	−177.1 (3)	C9—N2—C8—N1	−16.3 (5)
C1—C2—C3—C4	−0.5 (6)	C13—N2—C8—S1	−9.0 (5)
C2—C3—C4—C5	−0.5 (6)	C9—N2—C8—S1	162.2 (3)
C3—C4—C5—C6	0.6 (7)	C7—N1—C8—N2	−61.8 (5)
C4—C5—C6—C1	0.4 (6)	C7—N1—C8—S1	119.6 (3)
C2—C1—C6—C5	−1.4 (5)	C8—N2—C9—C10	−109.9 (4)
C7—C1—C6—C5	177.1 (3)	C13—N2—C9—C10	61.7 (4)
C8—N1—C7—O1	15.7 (5)	N2—C9—C10—C12	53.6 (4)
C8—N1—C7—C1	−163.6 (3)	N2—C9—C10—C11	177.6 (3)
C2—C1—C7—O1	−4.2 (5)	C8—N2—C13—C14	−82.1 (5)
C6—C1—C7—O1	177.4 (3)	C9—N2—C13—C14	105.9 (4)
C2—C1—C7—N1	175.2 (3)	N2—C13—C14—C16	−39.2 (7)
C6—C1—C7—N1	−3.3 (5)	N2—C13—C14—C15	−171.4 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1^i	0.88	2.74	3.586 (3)	162
C9—H9a···O1^ii	0.97	2.49	3.424 (5)	162

Symmetry codes: (i) −x+2, −y+2, −z+2; (ii) −x+1, −y+1, −z+1.