The title compound, C
15H
19N
3O
2S, is one of the thiourea herbicides in which 1-
tert-butylurea replaces 4,6-disubstituted pyrimidine. The crystal structure reveals intramolecular N—H
O and N—H
S hydrogen bonds that form six-membered rings, whereas intermolecular N—H
O hydrogen bonds connect molecules along the
b axis.
Supporting information
CCDC reference: 618253
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.007 Å
- R factor = 0.076
- wR factor = 0.172
- Data-to-parameter ratio = 10.9
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT031_ALERT_4_B Refined Extinction Parameter within Range ...... 1.29 Sigma
Alert level C
STRVA01_ALERT_4_C Flack test results are meaningless.
From the CIF: _refine_ls_abs_structure_Flack 0.200
From the CIF: _refine_ls_abs_structure_Flack_su 1.000
PLAT032_ALERT_4_C Std. Uncertainty in Flack Parameter too High ... 1.00
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ?
PLAT150_ALERT_1_C Volume as Calculated Differs from that Given ... 3309.00 Ang-3
PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 4.00 Ratio
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C12
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 7
PLAT350_ALERT_3_C Short C-H Bond (0.96A) C14 - H14C ... 0.83 Ang.
PLAT390_ALERT_3_C Deviating Methyl C15 X-C-H Bond Angle ...... 117.00 Deg.
0 ALERT level A = In general: serious problem
1 ALERT level B = Potentially serious problem
9 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
2 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
4 ALERT type 3 Indicator that the structure quality may be low
3 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998) and SHELXTL (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
(
E)-5-
tert-Butyl-1-cinnamoylthiobiuret
top
Crystal data top
C15H19N3O2S | Dx = 1.226 Mg m−3 |
Mr = 305.39 | Melting point: 457 K |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 2644 reflections |
a = 7.898 (2) Å | θ = 2.8–21.6° |
b = 11.910 (5) Å | µ = 0.20 mm−1 |
c = 35.170 (16) Å | T = 298 K |
V = 3309 (2) Å3 | Prism, yellow |
Z = 8 | 0.35 × 0.10 × 0.05 mm |
F(000) = 1296 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2908 independent reflections |
Radiation source: fine-focus sealed tube | 2209 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.055 |
φ and ω scans | θmax = 25.0°, θmin = 1.2° |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | h = −9→8 |
Tmin = 0.932, Tmax = 0.990 | k = −12→14 |
12822 measured reflections | l = −36→41 |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.076 | w = 1/[σ2(Fo2) + (0.051P)2 + 4.2027P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.172 | (Δ/σ)max = 0.001 |
S = 1.15 | Δρmax = 0.34 e Å−3 |
2908 reflections | Δρmin = −0.21 e Å−3 |
267 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0009 (7) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983) |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.2 (10) |
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 | |
S1 | 0.16144 (15) | 0.73310 (10) | 0.32335 (4) | 0.0739 (5) | |
O1 | 0.4501 (3) | 0.9575 (2) | 0.40536 (8) | 0.0610 (8) | |
O2 | −0.0025 (3) | 1.0721 (2) | 0.36750 (8) | 0.0570 (7) | |
N1 | 0.3883 (4) | 0.7959 (3) | 0.37290 (9) | 0.0470 (8) | |
H1A | 0.423 (5) | 0.719 (4) | 0.3702 (11) | 0.066 (12)* | |
N2 | 0.1803 (4) | 0.9276 (3) | 0.36252 (9) | 0.0481 (8) | |
H2A | 0.232 (5) | 0.965 (3) | 0.3817 (10) | 0.056 (11)* | |
N3 | −0.0327 (4) | 0.9544 (3) | 0.31710 (10) | 0.0529 (8) | |
H3A | −0.006 (5) | 0.877 (4) | 0.3112 (11) | 0.063 (12)* | |
C1 | 1.0301 (5) | 0.9040 (4) | 0.45964 (12) | 0.0599 (11) | |
H1 | 0.992 (5) | 0.982 (4) | 0.4634 (12) | 0.071 (13)* | |
C2 | 1.1865 (6) | 0.8699 (5) | 0.47467 (13) | 0.0677 (13) | |
H2 | 1.247 (6) | 0.925 (4) | 0.4890 (13) | 0.090 (16)* | |
C3 | 1.2404 (6) | 0.7622 (5) | 0.46988 (13) | 0.0711 (13) | |
H3 | 1.353 (6) | 0.737 (4) | 0.4811 (13) | 0.087 (15)* | |
C4 | 1.1430 (6) | 0.6864 (4) | 0.45010 (14) | 0.0729 (13) | |
H4 | 1.175 (6) | 0.605 (4) | 0.4481 (13) | 0.088 (15)* | |
C5 | 0.9878 (6) | 0.7183 (4) | 0.43555 (13) | 0.0636 (12) | |
H5 | 0.932 (5) | 0.663 (4) | 0.4219 (11) | 0.062 (12)* | |
C6 | 0.9292 (5) | 0.8279 (3) | 0.44034 (10) | 0.0482 (9) | |
C7 | 0.7641 (5) | 0.8663 (4) | 0.42626 (11) | 0.0522 (10) | |
H7 | 0.737 (5) | 0.943 (3) | 0.4332 (10) | 0.055 (11)* | |
C8 | 0.6464 (5) | 0.8061 (3) | 0.40861 (11) | 0.0514 (10) | |
H8 | 0.658 (5) | 0.728 (4) | 0.4032 (11) | 0.064 (12)* | |
C9 | 0.4872 (5) | 0.8613 (3) | 0.39656 (11) | 0.0488 (9) | |
C10 | 0.2406 (5) | 0.8256 (3) | 0.35380 (10) | 0.0472 (9) | |
C11 | 0.0373 (4) | 0.9894 (3) | 0.34902 (11) | 0.0458 (9) | |
C12 | −0.1769 (5) | 1.0081 (4) | 0.29738 (12) | 0.0572 (11) | |
C13 | −0.1352 (10) | 1.1288 (5) | 0.2880 (2) | 0.096 (2) | |
H13A | −0.217 (9) | 1.149 (6) | 0.2695 (18) | 0.14 (3)* | |
H13B | −0.128 (7) | 1.179 (5) | 0.3123 (16) | 0.102 (19)* | |
H13C | −0.036 (8) | 1.133 (6) | 0.2762 (17) | 0.12 (3)* | |
C14 | −0.3350 (7) | 0.9975 (8) | 0.3221 (2) | 0.089 (2) | |
H14A | −0.315 (5) | 1.042 (4) | 0.3488 (13) | 0.072 (13)* | |
H14B | −0.343 (12) | 0.929 (9) | 0.329 (3) | 0.22 (5)* | |
H14C | −0.418 (7) | 1.023 (5) | 0.3103 (15) | 0.10 (2)* | |
C15 | −0.2018 (7) | 0.9414 (6) | 0.26092 (16) | 0.0758 (15) | |
H15A | −0.294 (6) | 0.974 (4) | 0.2448 (13) | 0.084 (14)* | |
H15B | −0.105 (7) | 0.931 (4) | 0.2455 (15) | 0.097 (18)* | |
H15C | −0.238 (8) | 0.867 (5) | 0.2692 (15) | 0.11 (2)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0714 (7) | 0.0471 (7) | 0.1032 (9) | 0.0106 (5) | −0.0323 (7) | −0.0271 (6) |
O1 | 0.0536 (16) | 0.0470 (16) | 0.0825 (19) | 0.0052 (13) | −0.0082 (14) | −0.0223 (14) |
O2 | 0.0541 (16) | 0.0374 (15) | 0.0796 (19) | 0.0013 (12) | 0.0068 (14) | −0.0106 (13) |
N1 | 0.0450 (17) | 0.0296 (16) | 0.066 (2) | 0.0008 (14) | −0.0069 (15) | −0.0052 (14) |
N2 | 0.0456 (18) | 0.0388 (18) | 0.060 (2) | 0.0047 (14) | −0.0055 (15) | −0.0122 (15) |
N3 | 0.0459 (18) | 0.046 (2) | 0.067 (2) | 0.0080 (15) | −0.0034 (15) | −0.0050 (17) |
C1 | 0.056 (3) | 0.054 (3) | 0.069 (3) | −0.003 (2) | −0.006 (2) | −0.006 (2) |
C2 | 0.062 (3) | 0.075 (3) | 0.067 (3) | −0.011 (3) | −0.012 (2) | −0.013 (2) |
C3 | 0.061 (3) | 0.084 (4) | 0.068 (3) | 0.008 (3) | −0.011 (2) | 0.002 (3) |
C4 | 0.075 (3) | 0.060 (3) | 0.084 (3) | 0.014 (3) | −0.013 (3) | −0.007 (3) |
C5 | 0.065 (3) | 0.054 (3) | 0.071 (3) | −0.002 (2) | −0.013 (2) | −0.013 (2) |
C6 | 0.051 (2) | 0.044 (2) | 0.049 (2) | −0.0028 (18) | −0.0002 (17) | −0.0045 (17) |
C7 | 0.051 (2) | 0.044 (2) | 0.061 (2) | 0.0018 (19) | −0.0030 (19) | −0.0112 (19) |
C8 | 0.053 (2) | 0.040 (2) | 0.062 (2) | −0.0015 (18) | −0.0055 (19) | −0.0073 (19) |
C9 | 0.045 (2) | 0.044 (2) | 0.057 (2) | −0.0032 (17) | 0.0016 (17) | −0.0103 (18) |
C10 | 0.045 (2) | 0.040 (2) | 0.058 (2) | −0.0019 (16) | 0.0032 (18) | −0.0070 (17) |
C11 | 0.041 (2) | 0.036 (2) | 0.060 (2) | −0.0015 (16) | 0.0072 (17) | −0.0047 (18) |
C12 | 0.039 (2) | 0.061 (3) | 0.071 (3) | 0.0044 (19) | −0.0014 (19) | 0.004 (2) |
C13 | 0.097 (5) | 0.069 (4) | 0.120 (6) | −0.001 (4) | −0.032 (5) | 0.024 (4) |
C14 | 0.044 (3) | 0.137 (7) | 0.086 (4) | 0.015 (3) | 0.008 (3) | −0.001 (4) |
C15 | 0.050 (3) | 0.098 (5) | 0.080 (4) | 0.006 (3) | −0.009 (3) | −0.003 (3) |
Geometric parameters (Å, º) top
S1—C10 | 1.659 (4) | C4—H4 | 1.01 (5) |
O1—C9 | 1.222 (4) | C5—C6 | 1.395 (6) |
O2—C11 | 1.222 (4) | C5—H5 | 0.92 (4) |
N1—C9 | 1.382 (5) | C6—C7 | 1.468 (5) |
N1—C10 | 1.392 (5) | C7—C8 | 1.328 (5) |
N1—H1A | 0.97 (4) | C7—H7 | 0.97 (4) |
N2—C10 | 1.341 (5) | C8—C9 | 1.480 (5) |
N2—C11 | 1.429 (5) | C8—H8 | 0.95 (4) |
N2—H2A | 0.90 (4) | C12—C13 | 1.511 (7) |
N3—C11 | 1.319 (5) | C12—C15 | 1.522 (7) |
N3—C12 | 1.479 (5) | C12—C14 | 1.526 (7) |
N3—H3A | 0.97 (4) | C13—H13A | 0.95 (7) |
C1—C6 | 1.385 (5) | C13—H13B | 1.04 (6) |
C1—C2 | 1.403 (6) | C13—H13C | 0.89 (6) |
C1—H1 | 0.99 (5) | C14—H14A | 1.09 (5) |
C2—C3 | 1.363 (7) | C14—H14B | 0.86 (10) |
C2—H2 | 0.95 (5) | C14—H14C | 0.83 (6) |
C3—C4 | 1.376 (7) | C15—H15A | 1.00 (5) |
C3—H3 | 1.02 (5) | C15—H15B | 0.94 (5) |
C4—C5 | 1.382 (6) | C15—H15C | 0.98 (6) |
| | | |
C9—N1—C10 | 128.4 (3) | O1—C9—N1 | 123.0 (4) |
C9—N1—H1A | 116 (2) | O1—C9—C8 | 123.2 (3) |
C10—N1—H1A | 116 (2) | N1—C9—C8 | 113.7 (3) |
C10—N2—C11 | 132.2 (3) | N2—C10—N1 | 114.7 (3) |
C10—N2—H2A | 117 (3) | N2—C10—S1 | 128.0 (3) |
C11—N2—H2A | 111 (3) | N1—C10—S1 | 117.3 (3) |
C11—N3—C12 | 125.9 (3) | O2—C11—N3 | 126.8 (4) |
C11—N3—H3A | 113 (2) | O2—C11—N2 | 116.2 (3) |
C12—N3—H3A | 119 (2) | N3—C11—N2 | 116.9 (3) |
C6—C1—C2 | 120.1 (4) | N3—C12—C13 | 110.2 (4) |
C6—C1—H1 | 120 (3) | N3—C12—C15 | 105.6 (4) |
C2—C1—H1 | 119 (3) | C13—C12—C15 | 109.9 (5) |
C3—C2—C1 | 120.1 (4) | N3—C12—C14 | 109.1 (4) |
C3—C2—H2 | 124 (3) | C13—C12—C14 | 112.4 (6) |
C1—C2—H2 | 116 (3) | C15—C12—C14 | 109.3 (4) |
C2—C3—C4 | 120.4 (5) | C12—C13—H13A | 104 (4) |
C2—C3—H3 | 120 (3) | C12—C13—H13B | 112 (3) |
C4—C3—H3 | 119 (3) | H13A—C13—H13B | 117 (5) |
C3—C4—C5 | 120.2 (5) | C12—C13—H13C | 111 (5) |
C3—C4—H4 | 122 (3) | H13A—C13—H13C | 105 (6) |
C5—C4—H4 | 118 (3) | H13B—C13—H13C | 108 (5) |
C4—C5—C6 | 120.5 (4) | C12—C14—H14A | 109 (2) |
C4—C5—H5 | 115 (3) | C12—C14—H14B | 108 (6) |
C6—C5—H5 | 125 (3) | H14A—C14—H14B | 102 (7) |
C1—C6—C5 | 118.7 (4) | C12—C14—H14C | 109 (4) |
C1—C6—C7 | 118.2 (4) | H14A—C14—H14C | 111 (5) |
C5—C6—C7 | 123.1 (4) | H14B—C14—H14C | 116 (8) |
C8—C7—C6 | 127.7 (4) | C12—C15—H15A | 111 (3) |
C8—C7—H7 | 118 (2) | C12—C15—H15B | 117 (3) |
C6—C7—H7 | 114 (2) | H15A—C15—H15B | 108 (4) |
C7—C8—C9 | 119.2 (4) | C12—C15—H15C | 105 (3) |
C7—C8—H8 | 124 (2) | H15A—C15—H15C | 108 (4) |
C9—C8—H8 | 117 (2) | H15B—C15—H15C | 107 (5) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···S1 | 0.97 (4) | 2.21 (4) | 3.058 (4) | 146 (3) |
N2—H2A···O1 | 0.90 (4) | 1.92 (4) | 2.634 (4) | 135 (3) |
N1—H1A···O2i | 0.97 (4) | 1.86 (5) | 2.820 (4) | 176 (4) |
Symmetry code: (i) −x+1/2, y−1/2, z. |