1-(3-Bromo­phen­yl)-3-pivaloylthio­urea

The crystal structure of the title compound, C₁₂H₁₅BrN₂OS, is composed of discrete mol­ecules with bond lengths and angles quite typical for thio­urea compounds of this class. The mol­ecule exists in the solid state in its thione form with typical thio­urea C—S and C—O bonds lengths, as well as shortened C—N bonds. Stabilized by an intra­molecular N—H...O hydrogen bond, the thio­carbonyl and carbonyl groups are almost coplanar. The three methyl groups are disordered over two positions with occupancy factors in an approximate 4:1 ratio.

Key indicators

• Single-crystal X-ray study
• T = 113 K
• Mean [sigma](C-C) = 0.006 Å
• Disorder in main residue
• R factor = 0.041
• wR factor = 0.082
• Data-to-parameter ratio = 16.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.55 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.05 Ratio
PLAT301_ALERT_3_C Main Residue  Disorder .........................      15.00 Perc.
PLAT420_ALERT_2_C D-H Without Acceptor       N2     -   H2     ...          ?
PLAT431_ALERT_2_C Short Inter HL..A Contact  Br1    ..  O1      ..       3.25 Ang.

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.48
           From the CIF: _reflns_number_total               3073
           Count of symmetry unique reflns         1803
           Completeness (_total/calc)            170.44%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1270
           Fraction of Friedel pairs measured     0.704
           Are heavy atom types Z>Si present        yes

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 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
   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
   0 ALERT type 5 Informative message, check

---

S1. Comment

The background to this study has been set out in our previous work for the structural chemistry of N,N'-disubstituted thioureas (Shoukat et al., 2007). Herein, as a continuation of these studies, the structure of the title compound (I) is described. A depiction of the molecule is given in Fig. 1. Bond lengths and angles, see the selected geometric parameters table, can be regarded as typical for N,N'-disubstituted thiourea compounds as found in the Cambridge Structural Database v5.28 (Allen, 2002; Khawar Rauf et al., 2006). The molecule exists in its thione form with typical thiourea C—S and C—O bond distances, as well as shortened C—N bonds (See selected geometric parameters table). The molecule also features an intramolecular N—H···O hydrogen bond (See hydrogen-bond geometry table) which stears the thiocarbonyl and carbonyl groups to be almost coplanar, as reflected by the torsion angles of 0.5 (7)° for O(1)—C(2)—N(2)—C(1) and -5.8 (6)° for N(1)—C(1)—N(2)—C(2). The plane containing the S1, O1, N1, N2, C1 & C2 atoms is almost perpendicular to the phenyl ring with a dihedral angle of 86.13 (11)°.

Related literature

For related literature, see: Shoukat et al. (2007); Khawar Rauf et al. (2006); Allen (2002).

S2. Experimental

Freshly prepared pivaloylisothiocyanate (1.43 g, 10 mmol) in acetone (30 ml) was stirred for 15 minutes. Neat 3-bromoaniline (1.72 g, 10 mmol) was then added and the resulting mixture was stirred for 1 h. The reaction mixture was poured into acidified water and stirred well. The solid product was separated and washed with deionized water and purified by recrystallization from methanol/ 1,1-dichloromethane (1:1 v/v) to give fine crystals of (I), with an overall yield of 85%.

S3. Refinement

The C atoms of the t-butyl group were found to be disordered over two sites and were refined using similarity restraints (DELU and SIMU). Refinement of the occupancies converged to 0.819 (12) for C10 to C12 and 0.191 (12) for C13 to C15. H atoms were included using the riding model approximation with N—H 0.88 and C—H 0.95 - 0.98 Å, and with U_iso(H) = 1.2 U_eq(C and N) or U_iso(H) = 1.5 U_eq(C_methyl).

Computing details

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2001); cell refinement: CrystalClear; data reduction: TEXSAN (Molecular Structure Corporation & Rigaku, 2004); program(s) used to solve structure: SIR97 (Altomare, 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 and TEXSAN.

Figures

Fig. 1. The molecular structure of (I) showing the atom labelling scheme. Thermal displacement ellipsoids are drawn at the 50% probability level. The hydrogen bond is shown as a dashed line and the white/unfilled bonds depict the minor disordered moiety of the t-butyl group.

1-(3-Bromophenyl)-3-pivaloylthiourea

Crystal data

C12H15BrN2OS	F(000) = 640
Mr = 315.23	Dx = 1.552 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: P 2ac 2ab	Cell parameters from 4509 reflections
a = 6.188 (4) Å	θ = 3.3–27.5°
b = 10.250 (7) Å	µ = 3.19 mm^−1
c = 21.268 (14) Å	T = 113 K
V = 1348.9 (15) Å^3	Block, colorless
Z = 4	0.51 × 0.42 × 0.21 mm

Data collection

Rigaku/MSC Mercury CCD diffractometer	3073 independent reflections
Graphite monochromator	2965 reflections with I > 2σ(I)
Detector resolution: 14.62 pixels mm^-1	Rint = 0.051
ω scans	θmax = 27.5°, θmin = 3.4°
Absorption correction: integration (NUMABS; Higashi, 1999)	h = −8→5
Tmin = 0.537, Tmax = 0.715	k = −13→12
10869 measured reflections	l = −26→27

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.042	w = 1/[σ^2(Fo^2) + 2.2104P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.082	(Δ/σ)max = 0.003
S = 1.21	Δρmax = 0.66 e Å^−3
3073 reflections	Δρmin = −0.45 e Å^−3
189 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
66 restraints	Extinction coefficient: 0.0030 (8)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1275 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.012 (12)

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 > 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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.6304 (6)	0.3939 (4)	0.97247 (17)	0.0152 (7)
S1	0.70985 (18)	0.32987 (9)	1.04111 (5)	0.0182 (2)
N1	0.4986 (5)	0.4961 (3)	0.96633 (15)	0.0172 (7)
H1	0.4677	0.5232	0.9281	0.021*
C2	0.6416 (7)	0.3735 (4)	0.85578 (18)	0.0191 (8)
O1	0.5088 (6)	0.4596 (3)	0.84607 (13)	0.0300 (8)
N2	0.7040 (6)	0.3399 (3)	0.91598 (15)	0.0156 (7)
H2	0.8010	0.2774	0.9192	0.019*
C3	0.4040 (7)	0.5643 (4)	1.01863 (18)	0.0176 (8)
C4	0.5135 (6)	0.6714 (3)	1.04368 (18)	0.0166 (8)
H4	0.6531	0.6954	1.0291	0.020*
C5	0.4098 (7)	0.7419 (3)	1.09107 (18)	0.0174 (8)
C6	0.2083 (7)	0.7088 (4)	1.11360 (18)	0.0201 (8)
H6	0.1426	0.7581	1.1463	0.024*
C7	0.1024 (7)	0.6014 (4)	1.08742 (19)	0.0223 (9)
H7	−0.0371	0.5776	1.1021	0.027*
C8	0.2004 (8)	0.5286 (4)	1.03973 (19)	0.0203 (8)
H8	0.1283	0.4555	1.0220	0.024*
Br1	0.55861 (7)	0.88797 (4)	1.125472 (19)	0.02269 (12)
C9	0.7379 (8)	0.2956 (4)	0.80096 (19)	0.0210 (8)
C10	0.9613 (13)	0.2404 (8)	0.8134 (3)	0.0386 (17)	0.819 (12)
H10A	1.0588	0.3110	0.8261	0.058*	0.819 (12)
H10B	1.0166	0.1992	0.7751	0.058*	0.819 (12)
H10C	0.9530	0.1753	0.8471	0.058*	0.819 (12)
C11	0.7487 (14)	0.3872 (6)	0.7432 (3)	0.0330 (15)	0.819 (12)
H11A	0.8357	0.4642	0.7535	0.049*	0.819 (12)
H11B	0.6023	0.4146	0.7316	0.049*	0.819 (12)
H11C	0.8151	0.3408	0.7078	0.049*	0.819 (12)
C12	0.5761 (14)	0.1849 (6)	0.7871 (3)	0.0336 (15)	0.819 (12)
H12A	0.6288	0.1327	0.7517	0.050*	0.819 (12)
H12B	0.4351	0.2225	0.7764	0.050*	0.819 (12)
H12C	0.5615	0.1293	0.8243	0.050*	0.819 (12)
C13	0.995 (5)	0.303 (3)	0.8023 (15)	0.030 (3)	0.181 (12)
H13A	1.0447	0.3064	0.8460	0.045*	0.181 (12)
H13B	1.0432	0.3809	0.7799	0.045*	0.181 (12)
H13C	1.0547	0.2249	0.7819	0.045*	0.181 (12)
C14	0.645 (6)	0.350 (3)	0.7436 (13)	0.028 (3)	0.181 (12)
H14A	0.6911	0.4404	0.7386	0.042*	0.181 (12)
H14B	0.4866	0.3461	0.7462	0.042*	0.181 (12)
H14C	0.6935	0.2984	0.7073	0.042*	0.181 (12)
C15	0.650 (6)	0.160 (3)	0.8086 (16)	0.033 (3)	0.181 (12)
H15A	0.6254	0.1212	0.7671	0.049*	0.181 (12)
H15B	0.5132	0.1633	0.8318	0.049*	0.181 (12)
H15C	0.7541	0.1065	0.8320	0.049*	0.181 (12)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0096 (17)	0.0164 (15)	0.0195 (18)	−0.0053 (15)	0.0030 (13)	0.0002 (16)
S1	0.0173 (5)	0.0204 (4)	0.0171 (5)	0.0018 (4)	−0.0001 (4)	0.0012 (4)
N1	0.0178 (19)	0.0157 (14)	0.0182 (16)	0.0035 (12)	0.0013 (13)	−0.0010 (12)
C2	0.019 (2)	0.0200 (18)	0.0186 (19)	−0.0002 (16)	0.0028 (15)	−0.0007 (15)
O1	0.037 (2)	0.0329 (16)	0.0199 (15)	0.0177 (14)	−0.0019 (13)	−0.0036 (12)
N2	0.0150 (17)	0.0140 (13)	0.0177 (16)	0.0019 (13)	0.0001 (14)	−0.0034 (12)
C3	0.022 (2)	0.0170 (15)	0.0137 (18)	0.0051 (15)	0.0039 (16)	0.0008 (14)
C4	0.014 (2)	0.0164 (16)	0.0193 (18)	0.0037 (14)	0.0029 (15)	0.0028 (15)
C5	0.021 (2)	0.0158 (16)	0.0152 (18)	0.0016 (16)	−0.0041 (17)	−0.0010 (14)
C6	0.020 (2)	0.0239 (18)	0.017 (2)	0.0050 (16)	0.0047 (17)	−0.0005 (15)
C7	0.020 (2)	0.0239 (19)	0.023 (2)	−0.0046 (18)	0.0061 (16)	0.0000 (17)
C8	0.024 (2)	0.0168 (18)	0.020 (2)	−0.0010 (16)	0.0006 (18)	−0.0021 (15)
Br1	0.0280 (2)	0.01807 (17)	0.02199 (19)	−0.00228 (18)	−0.00135 (19)	−0.00341 (17)
C9	0.027 (2)	0.0192 (16)	0.0172 (18)	0.0047 (15)	−0.0005 (16)	−0.0038 (14)
C10	0.034 (3)	0.057 (4)	0.025 (3)	0.019 (3)	−0.003 (3)	−0.016 (3)
C11	0.052 (4)	0.023 (2)	0.024 (2)	0.009 (3)	0.014 (3)	0.001 (2)
C12	0.039 (3)	0.032 (3)	0.030 (3)	−0.009 (3)	0.004 (3)	−0.009 (2)
C13	0.028 (4)	0.039 (7)	0.024 (7)	0.006 (5)	−0.001 (5)	−0.009 (7)
C14	0.036 (7)	0.031 (6)	0.018 (5)	0.018 (6)	0.002 (6)	−0.008 (5)
C15	0.044 (7)	0.025 (5)	0.029 (7)	−0.003 (5)	0.004 (7)	−0.009 (5)

Geometric parameters (Å, º)

C1—N1	1.334 (5)	C9—C10	1.517 (8)
C1—N2	1.399 (5)	C9—C12	1.542 (8)
C1—S1	1.674 (4)	C9—C11	1.548 (7)
N1—C3	1.439 (5)	C9—C13	1.59 (3)
N1—H1	0.8800	C10—H10A	0.9800
C2—O1	1.224 (5)	C10—H10B	0.9800
C2—N2	1.381 (5)	C10—H10C	0.9800
C2—C9	1.533 (5)	C11—H11A	0.9800
N2—H2	0.8800	C11—H11B	0.9800
C3—C8	1.387 (6)	C11—H11C	0.9800
C3—C4	1.396 (5)	C12—H12A	0.9800
C4—C5	1.396 (5)	C12—H12B	0.9800
C4—H4	0.9500	C12—H12C	0.9800
C5—C6	1.378 (6)	C13—H13A	0.9800
C5—Br1	1.904 (4)	C13—H13B	0.9800
C6—C7	1.397 (6)	C13—H13C	0.9800
C6—H6	0.9500	C14—H14A	0.9800
C7—C8	1.397 (6)	C14—H14B	0.9800
C7—H7	0.9500	C14—H14C	0.9800
C8—H8	0.9500	C15—H15A	0.9800
C9—C14	1.46 (3)	C15—H15B	0.9800
C9—C15	1.50 (3)	C15—H15C	0.9800
N1—C1—N2	115.2 (3)	C2—C9—C12	106.0 (4)
N1—C1—S1	124.9 (3)	C10—C9—C11	109.0 (5)
N2—C1—S1	119.9 (3)	C2—C9—C11	107.8 (4)
C1—N1—C3	123.7 (3)	C12—C9—C11	108.8 (4)
C1—N1—H1	118.1	C14—C9—C13	113.1 (17)
C3—N1—H1	118.1	C15—C9—C13	113.7 (18)
O1—C2—N2	121.6 (4)	C2—C9—C13	110.6 (11)
O1—C2—C9	120.5 (4)	C9—C10—H10A	109.5
N2—C2—C9	117.8 (3)	C9—C10—H10B	109.5
C2—N2—C1	127.3 (3)	C9—C10—H10C	109.5
C2—N2—H2	116.3	C9—C11—H11A	109.5
C1—N2—H2	116.3	C9—C11—H11B	109.5
C8—C3—C4	121.7 (4)	C9—C11—H11C	109.5
C8—C3—N1	119.4 (4)	C9—C12—H12A	109.5
C4—C3—N1	118.7 (4)	C9—C12—H12B	109.5
C3—C4—C5	117.3 (4)	C9—C12—H12C	109.5
C3—C4—H4	121.3	C9—C13—H13A	109.5
C5—C4—H4	121.3	C9—C13—H13B	109.5
C6—C5—C4	122.6 (4)	H13A—C13—H13B	109.5
C6—C5—Br1	119.8 (3)	C9—C13—H13C	109.5
C4—C5—Br1	117.5 (3)	H13A—C13—H13C	109.5
C5—C6—C7	118.7 (4)	H13B—C13—H13C	109.5
C5—C6—H6	120.7	C9—C14—H14A	109.5
C7—C6—H6	120.7	C9—C14—H14B	109.5
C6—C7—C8	120.5 (4)	H14A—C14—H14B	109.5
C6—C7—H7	119.8	C9—C14—H14C	109.5
C8—C7—H7	119.8	H14A—C14—H14C	109.5
C3—C8—C7	119.2 (4)	H14B—C14—H14C	109.5
C3—C8—H8	120.4	C9—C15—H15A	109.5
C7—C8—H8	120.4	C9—C15—H15B	109.5
C14—C9—C15	107.3 (18)	H15A—C15—H15B	109.5
C14—C9—C2	106.6 (11)	C9—C15—H15C	109.5
C15—C9—C2	105.0 (12)	H15A—C15—H15C	109.5
C10—C9—C2	114.6 (4)	H15B—C15—H15C	109.5
C10—C9—C12	110.5 (5)
N2—C1—N1—C3	179.3 (3)	C4—C3—C8—C7	−0.2 (6)
S1—C1—N1—C3	−0.9 (5)	N1—C3—C8—C7	−175.3 (4)
O1—C2—N2—C1	0.5 (7)	C6—C7—C8—C3	0.0 (6)
C9—C2—N2—C1	−177.3 (4)	O1—C2—C9—C14	1.7 (17)
N1—C1—N2—C2	−5.8 (6)	N2—C2—C9—C14	179.5 (17)
S1—C1—N2—C2	174.4 (3)	O1—C2—C9—C15	−112.0 (17)
C1—N1—C3—C8	−93.5 (5)	N2—C2—C9—C15	65.8 (17)
C1—N1—C3—C4	91.3 (4)	O1—C2—C9—C10	153.2 (5)
C8—C3—C4—C5	−0.1 (6)	N2—C2—C9—C10	−29.0 (6)
N1—C3—C4—C5	175.0 (3)	O1—C2—C9—C12	−84.6 (6)
C3—C4—C5—C6	0.6 (6)	N2—C2—C9—C12	93.2 (5)
C3—C4—C5—Br1	179.9 (3)	O1—C2—C9—C11	31.7 (6)
C4—C5—C6—C7	−0.8 (6)	N2—C2—C9—C11	−150.5 (5)
Br1—C5—C6—C7	179.9 (3)	O1—C2—C9—C13	125.0 (14)
C5—C6—C7—C8	0.5 (6)	N2—C2—C9—C13	−57.2 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.88	1.88	2.586 (5)	136