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.
Supporting information
CCDC reference: 627640
Key indicators
- Single-crystal X-ray study
- T = 103 K
- Mean (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
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
top
Crystal data top
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) Å3 | Block, white |
Z = 4 | 0.20 × 0.20 × 0.10 mm |
Data collection top
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 top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.041 | H-atom parameters constrained |
wR(F2) = 0.095 | w = 1/[σ2(Fo2) + (0.0557P)2 + 0.0826P] where P = (Fo2 + 2Fc2)/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 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 | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Oi | 0.88 | 2.02 | 2.8514 (19) | 156 |
Symmetry code: (i) x+1/2, −y+3/2, z. |