N,N-Di-n-butyl-N'-pivaloylthio­urea

The title compound, C₁₄H₂₈N₂OS, is found to adopt a distorted S conformation, with the carbonyl of the pivaloyl group facing in the opposite direction to the N-H amine bond, which lies in roughly the same direction as the C=S of the thio­urea. The C-N bond of the thio­urea on the acyl side of the mol­ecule is much longer than the corresponding bond on the opposite disubstituted side.

Key indicators

• Single-crystal X-ray study
• T = 103 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.041
• wR factor = 0.095
• Data-to-parameter ratio = 17.4

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low .......       0.96

Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.01 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.50 Ratio

Alert level G
REFLT03_ALERT_4_G  WARNING: Large fraction of Friedel related reflns may
                     be needed to determine absolute structure
           From the CIF: _diffrn_reflns_theta_max           28.30
           From the CIF: _reflns_number_total               2926
           Count of symmetry unique reflns         2099
           Completeness (_total/calc)            139.40%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       827
           Fraction of Friedel pairs measured     0.394
           Are heavy atom types Z>Si present        yes

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   2 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
   1 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

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Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: X-SEED (Barbour, 2001).

N,N-Di-n-butyl-N'-pivaloylthiourea

Crystal data

C14H28N2OS	F(000) = 600
Mr = 272.44	Dx = 1.122 Mg m^−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P2c-2n	Cell parameters from 9342 reflections
a = 10.0259 (8) Å	θ = 2.3–28.3°
b = 13.2126 (10) Å	µ = 0.19 mm^−1
c = 12.1805 (10) Å	T = 103 K
V = 1613.5 (2) Å^3	Block, white
Z = 4	0.20 × 0.20 × 0.10 mm

Data collection

Bruker APEX CCD area-detector diffractometer	2926 independent reflections
Radiation source: fine-focus sealed tube	2760 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
ω scans	θmax = 28.3°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −13→12
Tmin = 0.960, Tmax = 0.980	k = −17→16
9342 measured reflections	l = −16→8

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.041	H-atom parameters constrained
wR(F^2) = 0.095	w = 1/[σ^2(Fo^2) + (0.0557P)^2 + 0.0826P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.001
2926 reflections	Δρmax = 0.33 e Å^−3
168 parameters	Δρmin = −0.18 e Å^−3
1 restraint	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.05 (8)

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
S	0.12031 (5)	0.94513 (3)	0.83835 (5)	0.02149 (13)
O	−0.08767 (13)	0.72979 (10)	0.95873 (17)	0.0289 (4)
N1	0.12803 (14)	0.77524 (11)	0.95608 (15)	0.0147 (3)
H1	0.2115	0.7552	0.9610	0.018*
N2	0.05594 (16)	0.91911 (12)	1.04906 (15)	0.0153 (3)
C1	0.02934 (18)	0.70538 (14)	0.94968 (18)	0.0170 (4)
C2	0.09818 (16)	0.88111 (13)	0.95496 (17)	0.0139 (4)
C3	0.06921 (18)	0.59450 (13)	0.92888 (17)	0.0165 (4)
C4	0.2179 (2)	0.57364 (14)	0.9451 (2)	0.0265 (5)
H4A	0.2450	0.5961	1.0185	0.040*
H4B	0.2693	0.6106	0.8896	0.040*
H4C	0.2348	0.5009	0.9377	0.040*
C5	−0.0133 (2)	0.52915 (15)	1.0076 (2)	0.0251 (5)
H5A	0.0064	0.4575	0.9946	0.038*
H5B	−0.1085	0.5416	0.9951	0.038*
H5C	0.0093	0.5466	1.0836	0.038*
C6	0.0294 (2)	0.57128 (15)	0.80995 (19)	0.0243 (5)
H6A	0.0775	0.6168	0.7602	0.036*
H6B	−0.0668	0.5813	0.8011	0.036*
H6C	0.0522	0.5009	0.7926	0.036*
C7	0.0579 (2)	0.86088 (14)	1.15248 (18)	0.0186 (4)
H7A	0.0194	0.7930	1.1390	0.022*
H7B	0.0009	0.8955	1.2072	0.022*
C8	0.1980 (2)	0.84873 (16)	1.19985 (19)	0.0242 (4)
H8A	0.2376	0.9166	1.2112	0.029*
H8B	0.2543	0.8120	1.1462	0.029*
C9	0.1987 (2)	0.79133 (17)	1.30873 (19)	0.0292 (5)
H9A	0.2900	0.7931	1.3396	0.035*
H9B	0.1389	0.8265	1.3610	0.035*
C10	0.1548 (3)	0.68231 (19)	1.2988 (3)	0.0419 (7)
H10A	0.0598	0.6799	1.2799	0.063*
H10B	0.1693	0.6476	1.3688	0.063*
H10C	0.2067	0.6488	1.2411	0.063*
C11	0.01613 (18)	1.02617 (13)	1.05623 (18)	0.0170 (4)
H11A	−0.0584	1.0325	1.1091	0.020*
H11B	−0.0169	1.0485	0.9836	0.020*
C12	0.12906 (18)	1.09584 (14)	1.09195 (19)	0.0195 (4)
H12A	0.1559	1.0785	1.1679	0.023*
H12B	0.2071	1.0849	1.0436	0.023*
C13	0.08881 (19)	1.20659 (14)	1.0874 (2)	0.0217 (5)
H13A	0.0129	1.2179	1.1379	0.026*
H13B	0.0585	1.2230	1.0121	0.026*
C14	0.2023 (2)	1.27753 (15)	1.1187 (2)	0.0258 (5)
H14A	0.2316	1.2625	1.1937	0.039*
H14B	0.1713	1.3478	1.1146	0.039*
H14C	0.2770	1.2679	1.0678	0.039*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S	0.0270 (3)	0.0214 (2)	0.0161 (2)	0.00421 (19)	0.0005 (2)	0.0032 (2)
O	0.0117 (6)	0.0181 (7)	0.0568 (12)	0.0013 (5)	−0.0002 (7)	−0.0071 (8)
N1	0.0092 (7)	0.0140 (7)	0.0208 (9)	0.0014 (5)	−0.0008 (7)	−0.0013 (7)
N2	0.0133 (7)	0.0147 (7)	0.0179 (8)	−0.0009 (6)	−0.0008 (7)	0.0009 (7)
C1	0.0140 (9)	0.0155 (8)	0.0216 (10)	−0.0007 (6)	−0.0013 (8)	−0.0013 (8)
C2	0.0078 (7)	0.0159 (8)	0.0181 (10)	−0.0016 (6)	−0.0027 (7)	−0.0009 (7)
C3	0.0119 (9)	0.0128 (8)	0.0249 (11)	0.0011 (7)	0.0005 (8)	−0.0024 (8)
C4	0.0155 (10)	0.0150 (8)	0.0490 (16)	0.0043 (7)	−0.0044 (10)	−0.0077 (9)
C5	0.0278 (11)	0.0189 (9)	0.0285 (12)	−0.0008 (8)	0.0023 (10)	0.0027 (9)
C6	0.0270 (11)	0.0197 (9)	0.0263 (13)	0.0001 (8)	0.0013 (9)	−0.0037 (8)
C7	0.0237 (10)	0.0168 (9)	0.0154 (9)	0.0008 (7)	0.0031 (8)	−0.0008 (8)
C8	0.0297 (11)	0.0230 (10)	0.0197 (11)	−0.0046 (8)	−0.0048 (9)	0.0052 (9)
C9	0.0344 (12)	0.0318 (11)	0.0214 (12)	−0.0005 (9)	−0.0052 (9)	0.0058 (9)
C10	0.0491 (15)	0.0293 (12)	0.0474 (17)	−0.0044 (11)	−0.0107 (13)	0.0172 (12)
C11	0.0150 (9)	0.0139 (9)	0.0220 (10)	0.0014 (7)	−0.0005 (8)	−0.0024 (8)
C12	0.0163 (9)	0.0160 (9)	0.0261 (11)	0.0003 (7)	−0.0049 (8)	−0.0011 (8)
C13	0.0168 (9)	0.0167 (9)	0.0315 (12)	0.0008 (7)	−0.0038 (9)	−0.0027 (9)
C14	0.0232 (10)	0.0172 (9)	0.0370 (14)	−0.0016 (7)	−0.0058 (10)	−0.0045 (9)

Geometric parameters (Å, º)

S—C2	1.668 (2)	C7—H7B	0.9900
O—C1	1.222 (2)	C8—C9	1.528 (3)
N1—C1	1.355 (2)	C8—H8A	0.9900
N1—C2	1.431 (2)	C8—H8B	0.9900
N1—H1	0.8800	C9—C10	1.511 (3)
N2—C2	1.321 (3)	C9—H9A	0.9900
N2—C11	1.472 (2)	C9—H9B	0.9900
N2—C7	1.476 (3)	C10—H10A	0.9800
C1—C3	1.540 (2)	C10—H10B	0.9800
C3—C4	1.529 (3)	C10—H10C	0.9800
C3—C5	1.533 (3)	C11—C12	1.523 (3)
C3—C6	1.533 (3)	C11—H11A	0.9900
C4—H4A	0.9800	C11—H11B	0.9900
C4—H4B	0.9800	C12—C13	1.519 (3)
C4—H4C	0.9800	C12—H12A	0.9900
C5—H5A	0.9800	C12—H12B	0.9900
C5—H5B	0.9800	C13—C14	1.522 (3)
C5—H5C	0.9800	C13—H13A	0.9900
C6—H6A	0.9800	C13—H13B	0.9900
C6—H6B	0.9800	C14—H14A	0.9800
C6—H6C	0.9800	C14—H14B	0.9800
C7—C8	1.527 (3)	C14—H14C	0.9800
C7—H7A	0.9900
C1—N1—C2	120.84 (14)	C7—C8—C9	112.61 (18)
C1—N1—H1	119.6	C7—C8—H8A	109.1
C2—N1—H1	119.6	C9—C8—H8A	109.1
C2—N2—C11	120.23 (17)	C7—C8—H8B	109.1
C2—N2—C7	122.55 (15)	C9—C8—H8B	109.1
C11—N2—C7	116.98 (16)	H8A—C8—H8B	107.8
O—C1—N1	121.07 (17)	C10—C9—C8	113.7 (2)
O—C1—C3	121.03 (16)	C10—C9—H9A	108.8
N1—C1—C3	117.90 (16)	C8—C9—H9A	108.8
N2—C2—N1	115.49 (17)	C10—C9—H9B	108.8
N2—C2—S	126.07 (14)	C8—C9—H9B	108.8
N1—C2—S	118.43 (15)	H9A—C9—H9B	107.7
C4—C3—C5	110.10 (17)	C9—C10—H10A	109.5
C4—C3—C6	109.87 (18)	C9—C10—H10B	109.5
C5—C3—C6	109.75 (16)	H10A—C10—H10B	109.5
C4—C3—C1	113.79 (15)	C9—C10—H10C	109.5
C5—C3—C1	107.03 (16)	H10A—C10—H10C	109.5
C6—C3—C1	106.16 (16)	H10B—C10—H10C	109.5
C3—C4—H4A	109.5	N2—C11—C12	113.33 (15)
C3—C4—H4B	109.5	N2—C11—H11A	108.9
H4A—C4—H4B	109.5	C12—C11—H11A	108.9
C3—C4—H4C	109.5	N2—C11—H11B	108.9
H4A—C4—H4C	109.5	C12—C11—H11B	108.9
H4B—C4—H4C	109.5	H11A—C11—H11B	107.7
C3—C5—H5A	109.5	C13—C12—C11	111.98 (15)
C3—C5—H5B	109.5	C13—C12—H12A	109.2
H5A—C5—H5B	109.5	C11—C12—H12A	109.2
C3—C5—H5C	109.5	C13—C12—H12B	109.2
H5A—C5—H5C	109.5	C11—C12—H12B	109.2
H5B—C5—H5C	109.5	H12A—C12—H12B	107.9
C3—C6—H6A	109.5	C12—C13—C14	112.67 (16)
C3—C6—H6B	109.5	C12—C13—H13A	109.1
H6A—C6—H6B	109.5	C14—C13—H13A	109.1
C3—C6—H6C	109.5	C12—C13—H13B	109.1
H6A—C6—H6C	109.5	C14—C13—H13B	109.1
H6B—C6—H6C	109.5	H13A—C13—H13B	107.8
N2—C7—C8	112.92 (17)	C13—C14—H14A	109.5
N2—C7—H7A	109.0	C13—C14—H14B	109.5
C8—C7—H7A	109.0	H14A—C14—H14B	109.5
N2—C7—H7B	109.0	C13—C14—H14C	109.5
C8—C7—H7B	109.0	H14A—C14—H14C	109.5
H7A—C7—H7B	107.8	H14B—C14—H14C	109.5
C2—N1—C1—O	−10.7 (3)	N1—C1—C3—C5	135.7 (2)
C2—N1—C1—C3	168.42 (18)	O—C1—C3—C6	71.9 (3)
C11—N2—C2—N1	−177.07 (15)	N1—C1—C3—C6	−107.1 (2)
C7—N2—C2—N1	8.7 (2)	C2—N2—C7—C8	73.8 (2)
C11—N2—C2—S	3.5 (2)	C11—N2—C7—C8	−100.62 (19)
C7—N2—C2—S	−170.72 (14)	N2—C7—C8—C9	178.16 (17)
C1—N1—C2—N2	79.1 (2)	C7—C8—C9—C10	65.3 (3)
C1—N1—C2—S	−101.4 (2)	C2—N2—C11—C12	−92.9 (2)
O—C1—C3—C4	−167.1 (2)	C7—N2—C11—C12	81.7 (2)
N1—C1—C3—C4	13.8 (3)	N2—C11—C12—C13	174.21 (18)
O—C1—C3—C5	−45.2 (3)	C11—C12—C13—C14	−177.8 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O^i	0.88	2.02	2.8514 (19)	156

Symmetry code: (i) x+1/2, −y+3/2, z.