By the reaction of benzoyl chloride, potassium isothiocyanate and the appropriate halogenoaniline,
i.e. 2/3/4-(bromo/iodo)aniline, we have obtained five new 1-benzoyl-3-(halogenophenyl)thioureas, namely, 1-benzoyl-3-(2-bromophenyl)thiourea and 1-benzoyl-3-(3-bromophenyl)thiourea, C
14H
11BrN
2OS, and 1-benzoyl-3-(2-iodophenyl)thiourea, 1-benzoyl-3-(3-iodophenyl)thiourea and 1-benzoyl-3-(4-iodophenyl)thiourea, C
14H
11IN
2OS. Structural and conformational features of the compounds have been analyzed using X-ray diffraction and theoretical calculations. The novel compounds were characterized by solid-state IR and
1H/
13C NMR spectroscopy. The conformations and intermolecular interactions, such as hydrogen bonds, π–π and
S(6)
π stacking, and
XO (
X = I or Br), I
S and I
π, have been examined and rationalized, together with four analogous compounds described previously in the literature. The set of nine compounds was chosen to examine how a change of the halogen atom and its position on the phenyl ring affects the molecular and crystal structures.
Supporting information
CCDC references: 1824002; 1824001; 1824005; 1824004; 1824003
For all structures, data collection: X-AREA (Stoe & Cie, 2009); cell refinement: X-AREA (Stoe & Cie, 2009); data reduction: X-RED32 (Stoe & Cie, 2009); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).
1-Benzoyl-3-(2-iodophenyl)thiourea (7)
top
Crystal data top
C14H11IN2OS | Z = 2 |
Mr = 382.21 | F(000) = 372 |
Triclinic, P1 | Dx = 1.850 Mg m−3 |
a = 6.2410 (7) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 7.2420 (8) Å | Cell parameters from 15454 reflections |
c = 16.709 (2) Å | θ = 5.0–58.9° |
α = 84.408 (9)° | µ = 2.48 mm−1 |
β = 89.142 (9)° | T = 125 K |
γ = 65.933 (8)° | Needle, colourless |
V = 686.02 (14) Å3 | 0.38 × 0.36 × 0.20 mm |
Data collection top
Stoe IPDS 2T diffractometer | 3508 reflections with I > 2σ(I) |
Detector resolution: 6.67 pixels mm-1 | Rint = 0.026 |
rotation method, ω scans | θmax = 29.0°, θmin = 2.5° |
Absorption correction: integration [X-RED32 (Stoe & Cie, 2009), by Gaussian integration,
analogous to Coppens (1970)] | h = −8→8 |
Tmin = 0.405, Tmax = 0.644 | k = −9→9 |
7847 measured reflections | l = −22→22 |
3616 independent reflections | |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.028 | H-atom parameters constrained |
wR(F2) = 0.072 | w = 1/[σ2(Fo2) + (0.039P)2 + 0.7088P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.001 |
3616 reflections | Δρmax = 0.70 e Å−3 |
172 parameters | Δρmin = −0.94 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
I1 | 0.90242 (2) | 0.02230 (2) | 0.15049 (2) | 0.03196 (7) | |
S1 | 0.15430 (10) | 0.46926 (10) | 0.22234 (3) | 0.03037 (13) | |
O1 | 0.7747 (3) | 0.2798 (3) | 0.39791 (9) | 0.0285 (3) | |
N2 | 0.6016 (3) | 0.4070 (3) | 0.24851 (10) | 0.0211 (3) | |
H2 | 0.723735 | 0.364016 | 0.281876 | 0.025* | |
N1 | 0.3991 (3) | 0.3503 (3) | 0.35827 (10) | 0.0220 (3) | |
H1 | 0.265397 | 0.351322 | 0.376215 | 0.026* | |
C26 | 0.7606 (3) | 0.3342 (3) | 0.11447 (12) | 0.0228 (4) | |
C22 | 0.5295 (4) | 0.6780 (4) | 0.14173 (13) | 0.0261 (4) | |
H22 | 0.440446 | 0.772704 | 0.177811 | 0.031* | |
C11 | 0.5187 (4) | 0.2440 (3) | 0.49911 (11) | 0.0210 (4) | |
C21 | 0.6289 (3) | 0.4723 (3) | 0.16703 (11) | 0.0207 (4) | |
C1 | 0.4010 (3) | 0.4079 (3) | 0.27636 (12) | 0.0208 (3) | |
C10 | 0.5784 (4) | 0.2919 (3) | 0.41490 (12) | 0.0210 (3) | |
C12 | 0.7032 (4) | 0.1607 (4) | 0.55539 (13) | 0.0282 (4) | |
H12 | 0.858015 | 0.137499 | 0.539275 | 0.034* | |
C25 | 0.7944 (4) | 0.4025 (4) | 0.03653 (13) | 0.0298 (5) | |
H25 | 0.886598 | 0.308343 | 0.000756 | 0.036* | |
C23 | 0.5600 (4) | 0.7459 (4) | 0.06345 (14) | 0.0326 (5) | |
H23 | 0.489514 | 0.886869 | 0.045740 | 0.039* | |
C16 | 0.2916 (4) | 0.2777 (3) | 0.52341 (13) | 0.0261 (4) | |
H16 | 0.164269 | 0.333137 | 0.485342 | 0.031* | |
C24 | 0.6928 (4) | 0.6084 (5) | 0.01139 (14) | 0.0342 (5) | |
H24 | 0.714536 | 0.655435 | −0.041909 | 0.041* | |
C13 | 0.6637 (5) | 0.1113 (4) | 0.63477 (14) | 0.0340 (5) | |
H13 | 0.791269 | 0.052973 | 0.672691 | 0.041* | |
C14 | 0.4383 (5) | 0.1469 (4) | 0.65881 (13) | 0.0309 (5) | |
H14 | 0.410940 | 0.114186 | 0.713373 | 0.037* | |
C15 | 0.2522 (4) | 0.2301 (4) | 0.60339 (14) | 0.0301 (4) | |
H15 | 0.097554 | 0.254730 | 0.620068 | 0.036* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
I1 | 0.02866 (9) | 0.03127 (10) | 0.03389 (10) | −0.00873 (7) | 0.00216 (6) | −0.00997 (6) |
S1 | 0.0253 (2) | 0.0501 (3) | 0.0197 (2) | −0.0211 (2) | −0.00379 (18) | 0.0045 (2) |
O1 | 0.0241 (7) | 0.0369 (9) | 0.0218 (7) | −0.0112 (6) | −0.0010 (5) | 0.0036 (6) |
N2 | 0.0195 (7) | 0.0264 (8) | 0.0163 (7) | −0.0087 (6) | −0.0008 (6) | 0.0002 (6) |
N1 | 0.0230 (8) | 0.0279 (8) | 0.0155 (7) | −0.0114 (7) | 0.0003 (6) | 0.0006 (6) |
C26 | 0.0178 (8) | 0.0339 (10) | 0.0198 (9) | −0.0136 (8) | −0.0008 (6) | −0.0030 (7) |
C22 | 0.0273 (10) | 0.0285 (10) | 0.0241 (9) | −0.0138 (8) | −0.0048 (7) | 0.0015 (8) |
C11 | 0.0282 (9) | 0.0187 (8) | 0.0165 (8) | −0.0100 (7) | −0.0006 (7) | −0.0008 (6) |
C21 | 0.0197 (8) | 0.0295 (10) | 0.0158 (8) | −0.0135 (7) | −0.0012 (6) | 0.0007 (7) |
C1 | 0.0229 (9) | 0.0226 (9) | 0.0172 (8) | −0.0098 (7) | −0.0002 (6) | −0.0009 (6) |
C10 | 0.0255 (9) | 0.0187 (8) | 0.0172 (8) | −0.0078 (7) | −0.0017 (7) | 0.0001 (6) |
C12 | 0.0314 (10) | 0.0358 (11) | 0.0203 (9) | −0.0173 (9) | −0.0037 (8) | 0.0020 (8) |
C25 | 0.0218 (9) | 0.0546 (14) | 0.0197 (9) | −0.0220 (10) | 0.0034 (7) | −0.0057 (9) |
C23 | 0.0348 (11) | 0.0409 (13) | 0.0278 (11) | −0.0243 (10) | −0.0088 (9) | 0.0124 (9) |
C16 | 0.0272 (10) | 0.0264 (10) | 0.0210 (9) | −0.0077 (8) | 0.0014 (7) | −0.0003 (7) |
C24 | 0.0299 (11) | 0.0612 (16) | 0.0210 (9) | −0.0306 (11) | −0.0028 (8) | 0.0070 (10) |
C13 | 0.0422 (13) | 0.0455 (14) | 0.0192 (9) | −0.0242 (11) | −0.0079 (9) | 0.0043 (9) |
C14 | 0.0464 (13) | 0.0365 (12) | 0.0176 (9) | −0.0254 (11) | 0.0011 (8) | −0.0002 (8) |
C15 | 0.0357 (11) | 0.0344 (11) | 0.0224 (10) | −0.0161 (10) | 0.0070 (8) | −0.0053 (8) |
Geometric parameters (Å, º) top
I1—C26 | 2.090 (2) | C11—C16 | 1.397 (3) |
S1—C1 | 1.670 (2) | C12—H12 | 0.9500 |
O1—C10 | 1.224 (3) | C12—C13 | 1.385 (3) |
N2—H2 | 0.8800 | C25—H25 | 0.9500 |
N2—C21 | 1.428 (2) | C25—C24 | 1.385 (4) |
N2—C1 | 1.326 (3) | C23—H23 | 0.9500 |
N1—H1 | 0.8800 | C23—C24 | 1.381 (4) |
N1—C1 | 1.393 (2) | C16—H16 | 0.9500 |
N1—C10 | 1.376 (3) | C16—C15 | 1.391 (3) |
C26—C21 | 1.388 (3) | C24—H24 | 0.9500 |
C26—C25 | 1.392 (3) | C13—H13 | 0.9500 |
C22—H22 | 0.9500 | C13—C14 | 1.384 (4) |
C22—C21 | 1.384 (3) | C14—H14 | 0.9500 |
C22—C23 | 1.390 (3) | C14—C15 | 1.386 (3) |
C11—C10 | 1.494 (3) | C15—H15 | 0.9500 |
C11—C12 | 1.389 (3) | | |
| | | |
C21—N2—H2 | 118.4 | C11—C12—H12 | 119.7 |
C1—N2—H2 | 118.4 | C13—C12—C11 | 120.6 (2) |
C1—N2—C21 | 123.21 (17) | C13—C12—H12 | 119.7 |
C1—N1—H1 | 115.7 | C26—C25—H25 | 120.2 |
C10—N1—H1 | 115.7 | C24—C25—C26 | 119.6 (2) |
C10—N1—C1 | 128.69 (17) | C24—C25—H25 | 120.2 |
C21—C26—I1 | 120.46 (15) | C22—C23—H23 | 120.0 |
C21—C26—C25 | 120.1 (2) | C24—C23—C22 | 120.0 (2) |
C25—C26—I1 | 119.44 (17) | C24—C23—H23 | 120.0 |
C21—C22—H22 | 120.0 | C11—C16—H16 | 120.0 |
C21—C22—C23 | 119.9 (2) | C15—C16—C11 | 119.9 (2) |
C23—C22—H22 | 120.0 | C15—C16—H16 | 120.0 |
C12—C11—C10 | 116.82 (19) | C25—C24—H24 | 119.8 |
C12—C11—C16 | 119.26 (19) | C23—C24—C25 | 120.3 (2) |
C16—C11—C10 | 123.92 (18) | C23—C24—H24 | 119.8 |
C26—C21—N2 | 121.15 (19) | C12—C13—H13 | 120.0 |
C22—C21—N2 | 118.82 (19) | C14—C13—C12 | 120.0 (2) |
C22—C21—C26 | 119.98 (19) | C14—C13—H13 | 120.0 |
N2—C1—S1 | 126.10 (15) | C13—C14—H14 | 120.0 |
N2—C1—N1 | 116.28 (17) | C13—C14—C15 | 120.1 (2) |
N1—C1—S1 | 117.62 (15) | C15—C14—H14 | 120.0 |
O1—C10—N1 | 122.48 (18) | C16—C15—H15 | 119.9 |
O1—C10—C11 | 121.69 (18) | C14—C15—C16 | 120.1 (2) |
N1—C10—C11 | 115.83 (18) | C14—C15—H15 | 119.9 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O1 | 0.88 | 1.97 | 2.659 (2) | 135 |
1-Benzoyl-3-(3-iodophenyl)thiourea (8)
top
Crystal data top
C14H11IN2OS | F(000) = 744 |
Mr = 382.21 | Dx = 1.870 Mg m−3 |
Monoclinic, Pc | Mo Kα radiation, λ = 0.71073 Å |
a = 4.5639 (5) Å | Cell parameters from 2158 reflections |
b = 15.375 (3) Å | θ = 2.5–29.4° |
c = 19.355 (2) Å | µ = 2.51 mm−1 |
β = 91.404 (9)° | T = 125 K |
V = 1357.7 (3) Å3 | Needle, colourless |
Z = 4 | 0.7 × 0.08 × 0.05 mm |
Data collection top
Stoe_IPDS_2T diffractometer | 5820 independent reflections |
Radiation source: microfocus sealed X-ray tube, GeniX Mo, 0.05 x 0.05 mm2 | 5398 reflections with I > 2σ(I) |
Parabolic x-ray mirror monochromator | Rint = 0.070 |
Detector resolution: 6.67 pixels mm-1 | θmax = 27.5°, θmin = 2.5° |
rotation method scans | h = −5→5 |
Absorption correction: integration [X-RED32 (Stoe & Cie, 2009), by Gaussian integration,
analogous to Coppens (1970)] | k = −19→19 |
Tmin = 0.393, Tmax = 0.885 | l = −25→23 |
13551 measured reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.054 | w = 1/[σ2(Fo2) + (0.1066P)2 + 0.9908P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.148 | (Δ/σ)max < 0.001 |
S = 1.07 | Δρmax = 1.24 e Å−3 |
5820 reflections | Δρmin = −1.27 e Å−3 |
343 parameters | Absolute structure: Flack (1983), 2156 Friedel pairs |
2 restraints | Absolute structure parameter: 0.30 (4) |
Primary atom site location: dual | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
I1A | 0.87867 (10) | 0.35387 (4) | 0.39772 (4) | 0.0328 (2) | |
I1 | 0.14942 (12) | 0.40415 (4) | 0.61116 (4) | 0.0338 (2) | |
S1 | 0.7822 (7) | −0.05110 (18) | 0.57618 (16) | 0.0368 (6) | |
S1A | 0.1700 (7) | 0.80028 (19) | 0.41313 (17) | 0.0393 (7) | |
O1A | −0.1126 (19) | 0.5770 (6) | 0.5497 (4) | 0.0330 (17) | |
O1 | 1.123 (2) | 0.1767 (5) | 0.4527 (4) | 0.0341 (17) | |
N2A | 0.189 (2) | 0.6285 (7) | 0.4449 (5) | 0.0280 (19) | |
H2A | 0.124794 | 0.589646 | 0.474320 | 0.034* | |
C12 | 1.478 (3) | 0.1371 (8) | 0.3423 (6) | 0.030 (2) | |
H12 | 1.395714 | 0.193753 | 0.345652 | 0.036* | |
N2 | 0.794 (2) | 0.1221 (7) | 0.5524 (5) | 0.0288 (19) | |
H2 | 0.868530 | 0.162280 | 0.525647 | 0.035* | |
N1 | 1.101 (2) | 0.0358 (6) | 0.4888 (5) | 0.0282 (18) | |
H1 | 1.179490 | −0.015895 | 0.482922 | 0.034* | |
N1A | −0.130 (2) | 0.7143 (6) | 0.5053 (5) | 0.0306 (18) | |
H1A | −0.220421 | 0.764534 | 0.508664 | 0.037* | |
C25A | 0.666 (3) | 0.5976 (7) | 0.2925 (6) | 0.032 (2) | |
H25A | 0.717177 | 0.625646 | 0.250752 | 0.038* | |
C23 | 0.299 (2) | 0.2779 (7) | 0.6325 (6) | 0.029 (2) | |
C21 | 0.591 (2) | 0.1540 (7) | 0.6007 (6) | 0.027 (2) | |
C22 | 0.494 (2) | 0.2395 (7) | 0.5876 (6) | 0.029 (2) | |
H22 | 0.560848 | 0.270554 | 0.548633 | 0.035* | |
C24A | 0.788 (3) | 0.5167 (8) | 0.3096 (7) | 0.033 (2) | |
H24A | 0.923610 | 0.489731 | 0.279989 | 0.040* | |
C10 | 1.201 (3) | 0.1003 (8) | 0.4464 (6) | 0.029 (2) | |
C22A | 0.508 (2) | 0.5159 (7) | 0.4143 (6) | 0.027 (2) | |
H22A | 0.453406 | 0.487322 | 0.455542 | 0.033* | |
C26A | 0.468 (3) | 0.6375 (9) | 0.3372 (7) | 0.032 (3) | |
H26A | 0.387924 | 0.692794 | 0.325606 | 0.039* | |
C1 | 0.891 (2) | 0.0417 (7) | 0.5403 (6) | 0.028 (2) | |
C11A | −0.418 (2) | 0.6775 (7) | 0.6071 (6) | 0.026 (2) | |
C14 | 1.788 (2) | 0.0358 (8) | 0.2847 (6) | 0.032 (2) | |
H14 | 1.919888 | 0.023232 | 0.248821 | 0.038* | |
C23A | 0.707 (2) | 0.4762 (7) | 0.3703 (5) | 0.027 (2) | |
C13 | 1.660 (3) | 0.1178 (9) | 0.2890 (6) | 0.033 (2) | |
H13 | 1.698782 | 0.160457 | 0.254936 | 0.040* | |
C11 | 1.411 (3) | 0.0736 (7) | 0.3919 (6) | 0.027 (2) | |
C21A | 0.388 (3) | 0.5969 (6) | 0.3980 (6) | 0.029 (2) | |
C16A | −0.573 (2) | 0.7558 (7) | 0.6067 (6) | 0.031 (2) | |
H16A | −0.549717 | 0.795796 | 0.569802 | 0.037* | |
C24 | 0.199 (3) | 0.2334 (8) | 0.6895 (6) | 0.033 (2) | |
H24 | 0.065033 | 0.259819 | 0.719880 | 0.039* | |
C15 | 1.722 (3) | −0.0272 (8) | 0.3328 (6) | 0.035 (2) | |
H15 | 1.803195 | −0.083840 | 0.328833 | 0.042* | |
C25 | 0.300 (3) | 0.1495 (7) | 0.7013 (6) | 0.032 (2) | |
H25 | 0.236230 | 0.118764 | 0.740804 | 0.039* | |
C15A | −0.760 (2) | 0.7754 (8) | 0.6592 (6) | 0.032 (2) | |
H15A | −0.866389 | 0.828518 | 0.658524 | 0.038* | |
C13A | −0.635 (3) | 0.6399 (8) | 0.7136 (7) | 0.034 (3) | |
H13A | −0.658159 | 0.599928 | 0.750468 | 0.041* | |
C14A | −0.792 (3) | 0.7163 (8) | 0.7139 (6) | 0.034 (2) | |
H14A | −0.919502 | 0.728911 | 0.750532 | 0.041* | |
C16 | 1.538 (3) | −0.0082 (7) | 0.3870 (6) | 0.032 (2) | |
H16 | 1.499738 | −0.051296 | 0.420745 | 0.038* | |
C10A | −0.210 (3) | 0.6517 (7) | 0.5523 (6) | 0.030 (2) | |
C12A | −0.447 (3) | 0.6194 (9) | 0.6618 (6) | 0.030 (2) | |
H12A | −0.338093 | 0.566679 | 0.663213 | 0.036* | |
C1A | 0.078 (2) | 0.7089 (7) | 0.4525 (6) | 0.029 (2) | |
C26 | 0.492 (3) | 0.1092 (9) | 0.6568 (7) | 0.033 (3) | |
H26 | 0.554691 | 0.051109 | 0.665226 | 0.039* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
I1A | 0.0339 (4) | 0.0383 (3) | 0.0266 (4) | 0.0024 (3) | 0.0080 (3) | −0.0009 (3) |
I1 | 0.0359 (4) | 0.0374 (3) | 0.0285 (4) | 0.0035 (3) | 0.0086 (3) | 0.0000 (3) |
S1 | 0.0428 (15) | 0.0374 (13) | 0.0310 (14) | 0.0015 (11) | 0.0172 (12) | 0.0045 (10) |
S1A | 0.0478 (17) | 0.0380 (14) | 0.0330 (15) | 0.0021 (11) | 0.0180 (13) | 0.0066 (11) |
O1A | 0.035 (4) | 0.040 (4) | 0.025 (4) | 0.003 (3) | 0.009 (3) | 0.003 (3) |
O1 | 0.041 (5) | 0.036 (4) | 0.026 (4) | 0.002 (4) | 0.006 (3) | 0.001 (3) |
N2A | 0.023 (4) | 0.041 (5) | 0.021 (5) | 0.004 (4) | 0.008 (4) | 0.006 (4) |
C12 | 0.025 (6) | 0.039 (6) | 0.027 (6) | −0.002 (4) | 0.007 (4) | 0.004 (4) |
N2 | 0.029 (5) | 0.035 (5) | 0.022 (4) | 0.004 (4) | 0.009 (4) | 0.005 (4) |
N1 | 0.029 (4) | 0.032 (4) | 0.024 (4) | 0.004 (3) | 0.008 (4) | −0.001 (3) |
N1A | 0.033 (5) | 0.034 (4) | 0.025 (4) | 0.002 (3) | 0.010 (4) | 0.004 (4) |
C25A | 0.037 (6) | 0.043 (6) | 0.017 (5) | −0.001 (4) | 0.006 (5) | 0.001 (4) |
C23 | 0.029 (5) | 0.034 (5) | 0.025 (5) | −0.003 (4) | 0.003 (4) | 0.001 (4) |
C21 | 0.020 (5) | 0.043 (5) | 0.018 (5) | 0.003 (4) | 0.004 (4) | −0.002 (4) |
C22 | 0.030 (5) | 0.040 (5) | 0.018 (5) | 0.001 (4) | 0.004 (4) | 0.002 (4) |
C24A | 0.028 (5) | 0.039 (6) | 0.032 (6) | 0.002 (4) | 0.005 (4) | 0.004 (4) |
C10 | 0.022 (5) | 0.041 (6) | 0.024 (5) | −0.003 (4) | −0.002 (4) | −0.001 (4) |
C22A | 0.021 (5) | 0.033 (5) | 0.028 (5) | 0.000 (4) | 0.006 (4) | 0.002 (4) |
C26A | 0.023 (6) | 0.048 (7) | 0.027 (6) | 0.001 (4) | 0.005 (5) | 0.008 (5) |
C1 | 0.025 (5) | 0.040 (5) | 0.020 (5) | −0.002 (4) | 0.000 (4) | 0.000 (4) |
C11A | 0.023 (5) | 0.035 (5) | 0.021 (5) | −0.001 (4) | 0.002 (4) | −0.002 (4) |
C14 | 0.026 (5) | 0.047 (6) | 0.022 (5) | 0.000 (4) | 0.007 (4) | 0.002 (4) |
C23A | 0.023 (5) | 0.039 (5) | 0.019 (5) | 0.000 (4) | 0.003 (4) | −0.002 (4) |
C13 | 0.032 (6) | 0.045 (6) | 0.023 (6) | −0.009 (5) | 0.006 (4) | 0.009 (5) |
C11 | 0.022 (5) | 0.036 (4) | 0.023 (5) | −0.005 (4) | 0.006 (4) | 0.000 (4) |
C21A | 0.032 (5) | 0.036 (5) | 0.018 (5) | 0.000 (5) | 0.007 (4) | −0.002 (5) |
C16A | 0.022 (5) | 0.042 (6) | 0.029 (6) | 0.002 (4) | 0.005 (4) | 0.004 (4) |
C24 | 0.034 (6) | 0.044 (6) | 0.021 (5) | 0.002 (4) | 0.009 (4) | −0.001 (4) |
C15 | 0.040 (6) | 0.039 (6) | 0.026 (6) | 0.003 (5) | 0.007 (5) | −0.003 (4) |
C25 | 0.045 (7) | 0.040 (6) | 0.012 (5) | 0.003 (4) | 0.009 (5) | 0.008 (4) |
C15A | 0.030 (5) | 0.041 (5) | 0.025 (5) | 0.001 (4) | 0.009 (4) | −0.004 (4) |
C13A | 0.032 (6) | 0.042 (6) | 0.028 (6) | −0.001 (4) | 0.002 (5) | 0.004 (4) |
C14A | 0.029 (6) | 0.044 (6) | 0.029 (6) | 0.000 (4) | 0.004 (4) | 0.000 (4) |
C16 | 0.035 (6) | 0.035 (5) | 0.026 (5) | −0.001 (4) | 0.005 (4) | 0.002 (4) |
C10A | 0.025 (5) | 0.039 (6) | 0.025 (5) | −0.005 (4) | 0.008 (4) | 0.002 (4) |
C12A | 0.025 (6) | 0.041 (6) | 0.024 (5) | 0.001 (5) | 0.009 (4) | 0.005 (5) |
C1A | 0.025 (5) | 0.037 (5) | 0.025 (5) | 0.001 (4) | 0.007 (4) | −0.004 (4) |
C26 | 0.029 (6) | 0.045 (6) | 0.023 (6) | 0.003 (5) | −0.002 (5) | 0.003 (5) |
Geometric parameters (Å, º) top
I1A—C23A | 2.101 (11) | C21—C22 | 1.408 (16) |
I1—C23 | 2.095 (11) | C21—C26 | 1.373 (17) |
S1—C1 | 1.668 (11) | C24A—C23A | 1.389 (15) |
S1A—C1A | 1.658 (11) | C10—C11 | 1.501 (16) |
O1A—C10A | 1.232 (15) | C22A—C23A | 1.399 (14) |
O1—C10 | 1.233 (15) | C22A—C21A | 1.392 (15) |
N2A—C21A | 1.388 (14) | C26A—C21A | 1.389 (17) |
N2A—C1A | 1.345 (15) | C11A—C16A | 1.397 (15) |
C12—C13 | 1.374 (17) | C11A—C10A | 1.494 (15) |
C12—C11 | 1.408 (16) | C11A—C12A | 1.394 (16) |
N2—C21 | 1.420 (14) | C14—C13 | 1.393 (18) |
N2—C1 | 1.335 (16) | C14—C15 | 1.382 (16) |
N1—C10 | 1.371 (14) | C11—C16 | 1.391 (16) |
N1—C1 | 1.403 (14) | C16A—C15A | 1.376 (15) |
N1A—C10A | 1.380 (14) | C24—C25 | 1.388 (16) |
N1A—C1A | 1.414 (13) | C15—C16 | 1.390 (15) |
C25A—C24A | 1.399 (17) | C25—C26 | 1.390 (18) |
C25A—C26A | 1.406 (18) | C15A—C14A | 1.405 (17) |
C23—C22 | 1.389 (15) | C13A—C14A | 1.374 (17) |
C23—C24 | 1.385 (15) | C13A—C12A | 1.374 (17) |
| | | |
C1A—N2A—C21A | 130.3 (10) | C24A—C23A—I1A | 120.6 (8) |
C13—C12—C11 | 120.4 (11) | C24A—C23A—C22A | 120.6 (10) |
C1—N2—C21 | 131.3 (11) | C22A—C23A—I1A | 118.8 (8) |
C10—N1—C1 | 128.3 (9) | C12—C13—C14 | 120.3 (10) |
C10A—N1A—C1A | 129.0 (9) | C12—C11—C10 | 116.2 (11) |
C24A—C25A—C26A | 120.0 (11) | C16—C11—C12 | 118.9 (11) |
C22—C23—I1 | 118.8 (8) | C16—C11—C10 | 124.9 (11) |
C24—C23—I1 | 120.1 (8) | N2A—C21A—C22A | 115.1 (10) |
C24—C23—C22 | 121.1 (10) | N2A—C21A—C26A | 125.9 (10) |
C22—C21—N2 | 114.4 (10) | C26A—C21A—C22A | 119.0 (11) |
C26—C21—N2 | 125.4 (11) | C15A—C16A—C11A | 120.5 (11) |
C26—C21—C22 | 120.2 (11) | C23—C24—C25 | 118.4 (10) |
C23—C22—C21 | 119.2 (10) | C14—C15—C16 | 120.4 (11) |
C23A—C24A—C25A | 119.1 (11) | C24—C25—C26 | 121.6 (10) |
O1—C10—N1 | 122.0 (11) | C16A—C15A—C14A | 119.4 (11) |
O1—C10—C11 | 121.3 (11) | C12A—C13A—C14A | 122.3 (12) |
N1—C10—C11 | 116.7 (10) | C13A—C14A—C15A | 119.1 (11) |
C21A—C22A—C23A | 120.6 (10) | C15—C16—C11 | 120.2 (11) |
C21A—C26A—C25A | 120.7 (11) | O1A—C10A—N1A | 121.4 (10) |
N2—C1—S1 | 127.9 (9) | O1A—C10A—C11A | 120.8 (10) |
N2—C1—N1 | 114.8 (9) | N1A—C10A—C11A | 117.8 (10) |
N1—C1—S1 | 117.2 (8) | C13A—C12A—C11A | 118.7 (12) |
C16A—C11A—C10A | 123.8 (10) | N2A—C1A—S1A | 129.0 (9) |
C12A—C11A—C16A | 120.0 (11) | N2A—C1A—N1A | 113.2 (10) |
C12A—C11A—C10A | 116.3 (10) | N1A—C1A—S1A | 117.6 (8) |
C15—C14—C13 | 119.7 (10) | C21—C26—C25 | 119.4 (12) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2A—H2A···O1A | 0.88 | 1.85 | 2.602 (13) | 142 |
N2—H2···O1 | 0.88 | 1.86 | 2.614 (13) | 142 |
N1—H1···S1Ai | 0.88 | 3.13 | 3.922 (10) | 150 |
N1A—H1A···S1ii | 0.88 | 3.12 | 3.884 (10) | 146 |
Symmetry codes: (i) x+1, y−1, z; (ii) x−1, y+1, z. |
1-Benzoyl-3-(4-iodophenyl)thiourea (9)
top
Crystal data top
C14H11IN2OS | Z = 2 |
Mr = 382.21 | F(000) = 372 |
Triclinic, P1 | Dx = 1.861 Mg m−3 |
a = 4.4279 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 13.0767 (14) Å | Cell parameters from 17633 reflections |
c = 13.4410 (14) Å | θ = 3.0–29.6° |
α = 61.622 (7)° | µ = 2.49 mm−1 |
β = 86.203 (9)° | T = 120 K |
γ = 85.241 (9)° | Needle, colourless |
V = 682.06 (13) Å3 | 0.33 × 0.08 × 0.05 mm |
Data collection top
Stoe IPDS 2T diffractometer | 3348 reflections with I > 2σ(I) |
Detector resolution: 6.67 pixels mm-1 | Rint = 0.020 |
rotation method scans | θmax = 29.0°, θmin = 3.0° |
Absorption correction: integration [X-RED32 (Stoe & Cie, 2009), by Gaussian integration,
analogous to Coppens (1970)] | h = −6→5 |
Tmin = 0.734, Tmax = 0.932 | k = −17→17 |
9681 measured reflections | l = −18→18 |
3617 independent reflections | |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.021 | H-atom parameters constrained |
wR(F2) = 0.054 | w = 1/[σ2(Fo2) + (0.0365P)2 + 0.1682P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.002 |
3617 reflections | Δρmax = 0.80 e Å−3 |
172 parameters | Δρmin = −0.39 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
I1 | 1.54166 (3) | 0.97722 (2) | 0.30315 (2) | 0.02325 (5) | |
S1 | 0.69441 (13) | 0.63634 (4) | 0.85377 (4) | 0.02636 (10) | |
O1 | 0.4225 (3) | 0.43021 (12) | 0.68414 (11) | 0.0242 (3) | |
N2 | 0.7238 (4) | 0.60053 (13) | 0.67111 (13) | 0.0195 (3) | |
H2 | 0.659541 | 0.556723 | 0.644375 | 0.023* | |
N1 | 0.4100 (4) | 0.48760 (13) | 0.82067 (13) | 0.0198 (3) | |
H1 | 0.322999 | 0.474879 | 0.886008 | 0.024* | |
C24 | 1.2997 (4) | 0.84543 (15) | 0.43373 (15) | 0.0191 (3) | |
C21 | 0.9269 (4) | 0.68403 (15) | 0.59760 (14) | 0.0176 (3) | |
C23 | 1.1904 (4) | 0.86015 (16) | 0.52524 (16) | 0.0221 (3) | |
H23 | 1.243847 | 0.925496 | 0.531840 | 0.026* | |
C22 | 1.0024 (4) | 0.77975 (16) | 0.60781 (16) | 0.0220 (3) | |
H22 | 0.926668 | 0.790207 | 0.670373 | 0.026* | |
C11 | 0.1253 (4) | 0.32291 (15) | 0.85074 (14) | 0.0178 (3) | |
C12 | 0.0857 (4) | 0.23904 (16) | 0.81704 (16) | 0.0214 (3) | |
H12 | 0.183570 | 0.245258 | 0.749489 | 0.026* | |
C1 | 0.6126 (4) | 0.57668 (15) | 0.77422 (15) | 0.0195 (3) | |
C25 | 1.2329 (4) | 0.74801 (16) | 0.42476 (15) | 0.0212 (3) | |
H25 | 1.314542 | 0.736362 | 0.363510 | 0.025* | |
C26 | 1.0454 (4) | 0.66836 (16) | 0.50665 (15) | 0.0209 (3) | |
H26 | 0.996650 | 0.602062 | 0.500796 | 0.025* | |
C10 | 0.3288 (4) | 0.41730 (15) | 0.77783 (15) | 0.0182 (3) | |
C14 | −0.2385 (5) | 0.13765 (17) | 0.98032 (16) | 0.0239 (4) | |
H14 | −0.361951 | 0.074328 | 1.024676 | 0.029* | |
C16 | −0.0220 (4) | 0.31351 (16) | 0.94942 (15) | 0.0216 (3) | |
H16 | 0.000485 | 0.370853 | 0.972299 | 0.026* | |
C15 | −0.2017 (5) | 0.22064 (17) | 1.01444 (16) | 0.0241 (4) | |
H15 | −0.299221 | 0.213934 | 1.082217 | 0.029* | |
C13 | −0.0951 (5) | 0.14698 (17) | 0.88137 (17) | 0.0246 (4) | |
H13 | −0.121186 | 0.090296 | 0.857955 | 0.030* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
I1 | 0.02755 (7) | 0.02270 (7) | 0.01967 (7) | −0.00760 (4) | 0.00314 (4) | −0.00969 (5) |
S1 | 0.0372 (3) | 0.0277 (2) | 0.0205 (2) | −0.01240 (19) | 0.00619 (18) | −0.01575 (18) |
O1 | 0.0316 (7) | 0.0244 (6) | 0.0199 (6) | −0.0064 (5) | 0.0042 (5) | −0.0129 (5) |
N2 | 0.0220 (7) | 0.0199 (7) | 0.0195 (7) | −0.0042 (6) | 0.0020 (6) | −0.0115 (6) |
N1 | 0.0218 (7) | 0.0211 (7) | 0.0199 (7) | −0.0045 (6) | 0.0037 (6) | −0.0124 (6) |
C24 | 0.0196 (8) | 0.0181 (7) | 0.0178 (7) | −0.0028 (6) | 0.0003 (6) | −0.0069 (6) |
C21 | 0.0185 (8) | 0.0172 (7) | 0.0169 (7) | −0.0004 (6) | −0.0008 (6) | −0.0079 (6) |
C23 | 0.0272 (9) | 0.0208 (8) | 0.0215 (8) | −0.0047 (7) | 0.0007 (7) | −0.0123 (7) |
C22 | 0.0262 (9) | 0.0219 (8) | 0.0222 (8) | −0.0039 (7) | 0.0031 (7) | −0.0139 (7) |
C11 | 0.0188 (8) | 0.0179 (7) | 0.0175 (7) | 0.0002 (6) | −0.0022 (6) | −0.0090 (6) |
C12 | 0.0232 (8) | 0.0229 (8) | 0.0207 (8) | −0.0030 (7) | −0.0002 (6) | −0.0122 (7) |
C1 | 0.0206 (8) | 0.0184 (7) | 0.0211 (8) | −0.0008 (6) | −0.0008 (6) | −0.0107 (6) |
C25 | 0.0258 (9) | 0.0220 (8) | 0.0183 (8) | −0.0015 (7) | 0.0018 (6) | −0.0118 (7) |
C26 | 0.0264 (9) | 0.0189 (8) | 0.0213 (8) | −0.0022 (7) | 0.0000 (7) | −0.0126 (7) |
C10 | 0.0192 (8) | 0.0179 (7) | 0.0189 (7) | −0.0001 (6) | −0.0013 (6) | −0.0099 (6) |
C14 | 0.0255 (9) | 0.0211 (8) | 0.0229 (8) | −0.0052 (7) | 0.0007 (7) | −0.0082 (7) |
C16 | 0.0269 (9) | 0.0206 (8) | 0.0185 (8) | −0.0025 (7) | −0.0001 (7) | −0.0102 (7) |
C15 | 0.0286 (9) | 0.0238 (8) | 0.0194 (8) | −0.0037 (7) | 0.0026 (7) | −0.0100 (7) |
C13 | 0.0297 (10) | 0.0223 (8) | 0.0261 (9) | −0.0050 (7) | −0.0001 (7) | −0.0144 (7) |
Geometric parameters (Å, º) top
I1—C24 | 2.0930 (18) | C11—C12 | 1.398 (2) |
S1—C1 | 1.6656 (19) | C11—C10 | 1.488 (2) |
O1—C10 | 1.236 (2) | C11—C16 | 1.394 (2) |
N2—H2 | 0.8800 | C12—H12 | 0.9500 |
N2—C21 | 1.413 (2) | C12—C13 | 1.384 (3) |
N2—C1 | 1.336 (2) | C25—H25 | 0.9500 |
N1—H1 | 0.8800 | C25—C26 | 1.385 (3) |
N1—C1 | 1.400 (2) | C26—H26 | 0.9500 |
N1—C10 | 1.375 (2) | C14—H14 | 0.9500 |
C24—C23 | 1.384 (2) | C14—C15 | 1.388 (3) |
C24—C25 | 1.392 (3) | C14—C13 | 1.391 (3) |
C21—C22 | 1.392 (2) | C16—H16 | 0.9500 |
C21—C26 | 1.395 (2) | C16—C15 | 1.389 (3) |
C23—H23 | 0.9500 | C15—H15 | 0.9500 |
C23—C22 | 1.394 (3) | C13—H13 | 0.9500 |
C22—H22 | 0.9500 | | |
| | | |
C21—N2—H2 | 114.5 | N2—C1—S1 | 128.09 (15) |
C1—N2—H2 | 114.5 | N2—C1—N1 | 114.60 (16) |
C1—N2—C21 | 131.06 (16) | N1—C1—S1 | 117.28 (13) |
C1—N1—H1 | 115.7 | C24—C25—H25 | 120.6 |
C10—N1—H1 | 115.7 | C26—C25—C24 | 118.89 (16) |
C10—N1—C1 | 128.66 (15) | C26—C25—H25 | 120.6 |
C23—C24—I1 | 119.07 (13) | C21—C26—H26 | 119.5 |
C23—C24—C25 | 120.57 (17) | C25—C26—C21 | 121.00 (16) |
C25—C24—I1 | 120.23 (13) | C25—C26—H26 | 119.5 |
C22—C21—N2 | 124.91 (16) | O1—C10—N1 | 122.06 (17) |
C22—C21—C26 | 119.73 (17) | O1—C10—C11 | 121.19 (16) |
C26—C21—N2 | 115.30 (15) | N1—C10—C11 | 116.74 (15) |
C24—C23—H23 | 119.8 | C15—C14—H14 | 119.9 |
C24—C23—C22 | 120.46 (17) | C15—C14—C13 | 120.15 (18) |
C22—C23—H23 | 119.8 | C13—C14—H14 | 119.9 |
C21—C22—C23 | 119.28 (17) | C11—C16—H16 | 119.9 |
C21—C22—H22 | 120.4 | C15—C16—C11 | 120.28 (17) |
C23—C22—H22 | 120.4 | C15—C16—H16 | 119.9 |
C12—C11—C10 | 116.82 (16) | C14—C15—C16 | 119.97 (17) |
C16—C11—C12 | 119.22 (17) | C14—C15—H15 | 120.0 |
C16—C11—C10 | 123.95 (16) | C16—C15—H15 | 120.0 |
C11—C12—H12 | 119.8 | C12—C13—C14 | 119.86 (18) |
C13—C12—C11 | 120.50 (17) | C12—C13—H13 | 120.1 |
C13—C12—H12 | 119.8 | C14—C13—H13 | 120.1 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O1 | 0.88 | 1.87 | 2.620 (2) | 142 |
N1—H1···S1i | 0.88 | 3.08 | 3.8864 (17) | 153 |
C22—H22···S1 | 0.95 | 2.54 | 3.200 (2) | 126 |
Symmetry code: (i) −x+1, −y+1, −z+2. |
1-Benzoyl-3-(2-bromophenyl)thiourea (4)
top
Crystal data top
C14H11BrN2OS | F(000) = 672 |
Mr = 335.23 | Dx = 1.676 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 3.9592 (4) Å | Cell parameters from 7760 reflections |
b = 15.142 (2) Å | θ = 2.7–29.7° |
c = 22.250 (2) Å | µ = 3.24 mm−1 |
β = 95.183 (8)° | T = 120 K |
V = 1328.4 (3) Å3 | Needle, colourless |
Z = 4 | 0.76 × 0.05 × 0.03 mm |
Data collection top
Stoe IPDS 2T diffractometer | 3566 independent reflections |
Radiation source: GeniX Mo, 0.05 x 0.05 mm2 microfocus, GeniX Mo, 0.05 x 0.05 mm2 | 2917 reflections with I ≥ 2u(I) |
Parabolic x-ray mirror monochromator | Rint = 0.057 |
Detector resolution: 6.67 pixels mm-1 | θmax = 29.0°, θmin = 2.7° |
rotation method, ω scans | h = −5→4 |
Absorption correction: integration [X-RED32 (Stoe & Cie, 2009), by Gaussian integration,
analogous to Coppens (1970)] | k = −20→20 |
Tmin = 0.379, Tmax = 0.892 | l = −30→28 |
7908 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.145 | w = 1/[σ2(Fo2) + (0.0967P)2 + 0.6126P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.001 |
3530 reflections | Δρmax = 1.06 e Å−3 |
172 parameters | Δρmin = −1.47 e Å−3 |
0 restraints | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1 | 0.83362 (8) | 0.34433 (2) | 0.77092 (2) | 0.01943 (14) | |
S1 | 0.6259 (2) | 0.54961 (5) | 0.58644 (4) | 0.01665 (18) | |
O1 | 0.2706 (9) | 0.27419 (16) | 0.62856 (12) | 0.0297 (6) | |
N1 | 0.3562 (7) | 0.39130 (16) | 0.56653 (12) | 0.0161 (5) | |
H1 | 0.353938 | 0.406926 | 0.528399 | 0.019* | |
N2 | 0.4080 (8) | 0.43571 (16) | 0.66660 (13) | 0.0173 (5) | |
H2 | 0.329777 | 0.382603 | 0.673484 | 0.021* | |
C26 | 0.6616 (8) | 0.46142 (19) | 0.76882 (15) | 0.0162 (6) | |
C21 | 0.4747 (8) | 0.49224 (19) | 0.71708 (14) | 0.0154 (6) | |
C23 | 0.3934 (9) | 0.6301 (2) | 0.76853 (16) | 0.0189 (6) | |
H23 | 0.297239 | 0.687607 | 0.768823 | 0.023* | |
C25 | 0.7230 (8) | 0.5146 (2) | 0.81993 (15) | 0.0190 (6) | |
H25 | 0.853494 | 0.492943 | 0.854762 | 0.023* | |
C22 | 0.3352 (8) | 0.5774 (2) | 0.71732 (15) | 0.0175 (6) | |
H22 | 0.201802 | 0.598914 | 0.682784 | 0.021* | |
C1 | 0.4536 (8) | 0.45618 (19) | 0.60940 (14) | 0.0140 (5) | |
C11 | 0.1546 (8) | 0.25167 (18) | 0.52290 (14) | 0.0160 (6) | |
C14 | −0.0510 (9) | 0.1466 (2) | 0.42403 (17) | 0.0221 (7) | |
H14 | −0.119601 | 0.110393 | 0.390232 | 0.026* | |
C24 | 0.5898 (9) | 0.5998 (2) | 0.81905 (16) | 0.0201 (6) | |
H24 | 0.633754 | 0.637177 | 0.853146 | 0.024* | |
C16 | −0.0313 (8) | 0.2886 (2) | 0.47280 (15) | 0.0171 (6) | |
H16 | −0.084947 | 0.349728 | 0.472294 | 0.021* | |
C12 | 0.2344 (9) | 0.16178 (19) | 0.52423 (16) | 0.0192 (6) | |
H12 | 0.353727 | 0.136073 | 0.558862 | 0.023* | |
C10 | 0.2633 (9) | 0.30534 (19) | 0.57767 (15) | 0.0185 (6) | |
C13 | 0.1350 (9) | 0.1106 (2) | 0.47352 (17) | 0.0227 (7) | |
H13 | 0.196328 | 0.049976 | 0.473065 | 0.027* | |
C15 | −0.1383 (9) | 0.2354 (2) | 0.42343 (15) | 0.0201 (6) | |
H15 | −0.269855 | 0.259882 | 0.389659 | 0.024* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0214 (2) | 0.01716 (18) | 0.0198 (2) | 0.00371 (10) | 0.00254 (13) | 0.00192 (10) |
S1 | 0.0205 (4) | 0.0149 (3) | 0.0147 (4) | −0.0040 (2) | 0.0020 (3) | 0.0016 (2) |
O1 | 0.0553 (19) | 0.0163 (11) | 0.0179 (12) | −0.0079 (11) | 0.0043 (12) | 0.0027 (9) |
N1 | 0.0226 (13) | 0.0130 (10) | 0.0129 (12) | −0.0018 (9) | 0.0018 (10) | 0.0009 (9) |
N2 | 0.0244 (13) | 0.0139 (10) | 0.0137 (12) | −0.0035 (9) | 0.0030 (11) | 0.0014 (9) |
C26 | 0.0136 (12) | 0.0163 (12) | 0.0188 (15) | −0.0009 (10) | 0.0021 (12) | 0.0022 (11) |
C21 | 0.0163 (13) | 0.0159 (12) | 0.0147 (14) | −0.0013 (10) | 0.0050 (11) | 0.0027 (10) |
C23 | 0.0203 (14) | 0.0141 (13) | 0.0232 (16) | −0.0032 (11) | 0.0072 (13) | −0.0003 (11) |
C25 | 0.0185 (14) | 0.0229 (14) | 0.0151 (14) | −0.0017 (11) | −0.0005 (12) | −0.0023 (11) |
C22 | 0.0187 (14) | 0.0157 (12) | 0.0183 (14) | −0.0028 (10) | 0.0034 (12) | 0.0007 (11) |
C1 | 0.0141 (12) | 0.0142 (12) | 0.0136 (13) | 0.0004 (9) | −0.0002 (11) | −0.0005 (10) |
C11 | 0.0201 (13) | 0.0134 (12) | 0.0152 (14) | −0.0039 (10) | 0.0047 (12) | 0.0007 (10) |
C14 | 0.0232 (16) | 0.0233 (15) | 0.0204 (16) | −0.0073 (12) | 0.0053 (14) | −0.0074 (12) |
C24 | 0.0225 (15) | 0.0187 (13) | 0.0197 (15) | −0.0029 (11) | 0.0057 (13) | −0.0048 (11) |
C16 | 0.0157 (13) | 0.0170 (12) | 0.0188 (15) | −0.0023 (10) | 0.0024 (12) | −0.0007 (11) |
C12 | 0.0220 (15) | 0.0155 (13) | 0.0197 (16) | 0.0003 (10) | 0.0001 (13) | 0.0010 (11) |
C10 | 0.0251 (15) | 0.0133 (13) | 0.0173 (15) | −0.0019 (10) | 0.0023 (13) | 0.0019 (10) |
C13 | 0.0262 (16) | 0.0158 (13) | 0.0268 (17) | −0.0019 (12) | 0.0058 (14) | −0.0029 (12) |
C15 | 0.0207 (15) | 0.0229 (14) | 0.0164 (15) | −0.0030 (11) | 0.0003 (12) | −0.0006 (11) |
Geometric parameters (Å, º) top
Br1—C26 | 1.898 (3) | C25—C24 | 1.394 (5) |
S1—C1 | 1.671 (3) | C22—H22 | 0.9500 |
O1—C10 | 1.225 (4) | C11—C16 | 1.396 (5) |
N1—H1 | 0.8800 | C11—C12 | 1.397 (4) |
N1—C1 | 1.399 (4) | C11—C10 | 1.495 (4) |
N1—C10 | 1.381 (4) | C14—H14 | 0.9500 |
N2—H2 | 0.8800 | C14—C13 | 1.380 (6) |
N2—C21 | 1.418 (4) | C14—C15 | 1.389 (5) |
N2—C1 | 1.338 (4) | C24—H24 | 0.9500 |
C26—C21 | 1.392 (5) | C16—H16 | 0.9500 |
C26—C25 | 1.396 (4) | C16—C15 | 1.396 (5) |
C21—C22 | 1.402 (4) | C12—H12 | 0.9500 |
C23—H23 | 0.9500 | C12—C13 | 1.396 (5) |
C23—C22 | 1.394 (5) | C13—H13 | 0.9500 |
C23—C24 | 1.386 (5) | C15—H15 | 0.9500 |
C25—H25 | 0.9500 | | |
| | | |
C1—N1—H1 | 116.5 | C16—C11—C12 | 120.6 (3) |
C10—N1—H1 | 116.5 | C16—C11—C10 | 121.7 (3) |
C10—N1—C1 | 126.9 (3) | C12—C11—C10 | 117.7 (3) |
C21—N2—H2 | 117.2 | C13—C14—H14 | 119.9 |
C1—N2—H2 | 117.2 | C13—C14—C15 | 120.3 (3) |
C1—N2—C21 | 125.6 (3) | C15—C14—H14 | 119.9 |
C21—C26—Br1 | 119.8 (2) | C23—C24—C25 | 120.2 (3) |
C21—C26—C25 | 121.4 (3) | C23—C24—H24 | 119.9 |
C25—C26—Br1 | 118.9 (2) | C25—C24—H24 | 119.9 |
C26—C21—N2 | 120.0 (3) | C11—C16—H16 | 120.1 |
C26—C21—C22 | 119.0 (3) | C11—C16—C15 | 119.9 (3) |
C22—C21—N2 | 120.8 (3) | C15—C16—H16 | 120.1 |
C22—C23—H23 | 119.6 | C11—C12—H12 | 120.8 |
C24—C23—H23 | 119.6 | C13—C12—C11 | 118.5 (3) |
C24—C23—C22 | 120.8 (3) | C13—C12—H12 | 120.8 |
C26—C25—H25 | 120.5 | O1—C10—N1 | 123.0 (3) |
C24—C25—C26 | 119.0 (3) | O1—C10—C11 | 121.7 (3) |
C24—C25—H25 | 120.5 | N1—C10—C11 | 115.3 (3) |
C21—C22—H22 | 120.2 | C14—C13—C12 | 121.1 (3) |
C23—C22—C21 | 119.6 (3) | C14—C13—H13 | 119.4 |
C23—C22—H22 | 120.2 | C12—C13—H13 | 119.4 |
N1—C1—S1 | 118.8 (2) | C14—C15—C16 | 119.6 (3) |
N2—C1—S1 | 125.5 (2) | C14—C15—H15 | 120.2 |
N2—C1—N1 | 115.7 (3) | C16—C15—H15 | 120.2 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S1i | 0.88 | 2.65 | 3.526 (3) | 177 |
N2—H2···O1 | 0.88 | 1.93 | 2.629 (4) | 136 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
1-Benzoyl-3-(3-bromophenyl)thiourea (5)
top
Crystal data top
C14H11BrN2OS | F(000) = 672 |
Mr = 335.22 | Dx = 1.675 Mg m−3 |
Monoclinic, Pc | Mo Kα radiation, λ = 0.71073 Å |
a = 4.6404 (7) Å | Cell parameters from 6776 reflections |
b = 15.017 (2) Å | θ = 2.5–29.4° |
c = 19.074 (3) Å | µ = 3.24 mm−1 |
β = 91.052 (12)° | T = 125 K |
V = 1329.0 (3) Å3 | Needle, colourless |
Z = 4 | 0.68 × 0.05 × 0.04 mm |
Data collection top
Stoe IPDS 2T diffractometer | 4537 independent reflections |
Radiation source: GeniX Mo, 0.05 x 0.05 mm2 microfocus, GeniX Mo, 0.05 x 0.05 mm2 | 4294 reflections with I > 2σ(I) |
Parabolic x-ray mirror monochromator | Rint = 0.087 |
Detector resolution: 6.67 pixels mm-1 | θmax = 26.0°, θmin = 2.5° |
rotation method, ω scans | h = −5→5 |
Absorption correction: integration [X-RED32 (Stoe & Cie, 2009), by Gaussian integration,
analogous to Coppens (1970)] | k = −18→18 |
Tmin = 0.354, Tmax = 0.875 | l = −23→23 |
15213 measured reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.066 | w = 1/[σ2(Fo2) + (0.1436P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.183 | (Δ/σ)max < 0.001 |
S = 1.02 | Δρmax = 1.97 e Å−3 |
4909 reflections | Δρmin = −0.65 e Å−3 |
343 parameters | Absolute structure: Flack (1983), 2288 Friedel pairs |
2 restraints | Absolute structure parameter: 0.01 (2) |
Primary atom site location: dual | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1A | 0.1216 (2) | 0.36015 (7) | 0.60049 (6) | 0.0339 (3) | |
Br1 | 0.8472 (2) | 0.39778 (7) | 0.38804 (7) | 0.0363 (3) | |
S1 | 0.2193 (7) | −0.05182 (18) | 0.42320 (16) | 0.0331 (6) | |
S1A | 0.8356 (7) | 0.7992 (2) | 0.58713 (17) | 0.0372 (7) | |
O1A | 1.1114 (18) | 0.5705 (5) | 0.4491 (4) | 0.0292 (17) | |
O1 | −0.1229 (18) | 0.1826 (5) | 0.5461 (4) | 0.0288 (17) | |
N2 | 0.201 (2) | 0.1267 (7) | 0.4461 (5) | 0.0238 (19) | |
H2 | 0.116675 | 0.168717 | 0.470412 | 0.029* | |
N2A | 0.814 (2) | 0.6247 (7) | 0.5548 (5) | 0.027 (2) | |
H2A | 0.886318 | 0.584080 | 0.526870 | 0.032* | |
N1A | 1.130 (2) | 0.7115 (6) | 0.4936 (5) | 0.0257 (18) | |
H1A | 1.221915 | 0.762601 | 0.490681 | 0.031* | |
N1 | −0.099 (2) | 0.0382 (6) | 0.5108 (5) | 0.0253 (18) | |
H1 | −0.172561 | −0.015048 | 0.517202 | 0.030* | |
C12 | −0.484 (3) | 0.1445 (8) | 0.6559 (7) | 0.030 (3) | |
H12 | −0.404248 | 0.202517 | 0.652126 | 0.036* | |
C10 | −0.204 (2) | 0.1046 (7) | 0.5528 (6) | 0.022 (2) | |
C1 | 0.111 (2) | 0.0441 (7) | 0.4592 (6) | 0.026 (2) | |
C22A | 0.527 (3) | 0.6346 (8) | 0.6633 (6) | 0.027 (2) | |
H22A | 0.609316 | 0.690436 | 0.675859 | 0.032* | |
C24 | 0.806 (3) | 0.2363 (8) | 0.3099 (6) | 0.029 (2) | |
H24 | 0.940707 | 0.263197 | 0.279534 | 0.035* | |
C11A | 1.418 (2) | 0.6723 (7) | 0.3926 (5) | 0.022 (2) | |
C23A | 0.331 (3) | 0.5941 (9) | 0.7058 (6) | 0.033 (3) | |
H23A | 0.278747 | 0.622390 | 0.748276 | 0.039* | |
C26 | 0.510 (2) | 0.2446 (7) | 0.4119 (6) | 0.025 (2) | |
H26 | 0.441157 | 0.277844 | 0.450456 | 0.030* | |
C21 | 0.410 (3) | 0.1569 (8) | 0.3993 (6) | 0.028 (2) | |
C25 | 0.707 (3) | 0.2807 (8) | 0.3680 (6) | 0.029 (2) | |
C26A | 0.485 (2) | 0.5093 (8) | 0.5829 (6) | 0.026 (2) | |
H26A | 0.539187 | 0.479402 | 0.541306 | 0.031* | |
C13A | 1.635 (3) | 0.6325 (7) | 0.2841 (6) | 0.028 (2) | |
H13A | 1.656135 | 0.591839 | 0.246407 | 0.033* | |
C11 | −0.413 (2) | 0.0790 (7) | 0.6073 (6) | 0.023 (2) | |
C23 | 0.702 (3) | 0.1510 (8) | 0.2973 (6) | 0.031 (2) | |
H23 | 0.768490 | 0.119194 | 0.257672 | 0.037* | |
C13 | −0.667 (3) | 0.1251 (9) | 0.7088 (6) | 0.031 (2) | |
H13 | −0.711529 | 0.169799 | 0.742179 | 0.037* | |
C21A | 0.606 (3) | 0.5914 (7) | 0.6007 (6) | 0.025 (2) | |
C10A | 1.206 (3) | 0.6462 (7) | 0.4466 (6) | 0.024 (2) | |
C16 | −0.535 (3) | −0.0054 (8) | 0.6132 (6) | 0.027 (2) | |
H16 | −0.488645 | −0.050385 | 0.580284 | 0.033* | |
C1A | 0.922 (2) | 0.7045 (7) | 0.5458 (6) | 0.025 (2) | |
C24A | 0.205 (2) | 0.5125 (8) | 0.6881 (6) | 0.028 (2) | |
H24A | 0.067460 | 0.485458 | 0.717769 | 0.034* | |
C14A | 1.792 (3) | 0.7102 (9) | 0.2849 (7) | 0.034 (3) | |
H14A | 1.921841 | 0.722651 | 0.248208 | 0.041* | |
C22 | 0.504 (3) | 0.1106 (8) | 0.3413 (7) | 0.030 (3) | |
H22 | 0.434508 | 0.052300 | 0.331595 | 0.036* | |
C25A | 0.285 (2) | 0.4723 (7) | 0.6266 (6) | 0.027 (2) | |
C12A | 1.447 (3) | 0.6125 (8) | 0.3374 (7) | 0.027 (2) | |
H12A | 1.339264 | 0.558708 | 0.336270 | 0.033* | |
C14 | −0.790 (2) | 0.0423 (8) | 0.7147 (6) | 0.027 (2) | |
H14 | −0.919974 | 0.030087 | 0.751344 | 0.032* | |
C15 | −0.722 (3) | −0.0239 (8) | 0.6663 (6) | 0.031 (2) | |
H15 | −0.804361 | −0.081564 | 0.670121 | 0.037* | |
C15A | 1.760 (3) | 0.7709 (8) | 0.3398 (6) | 0.031 (2) | |
H15A | 1.865168 | 0.825140 | 0.340197 | 0.037* | |
C16A | 1.574 (3) | 0.7518 (8) | 0.3932 (6) | 0.029 (2) | |
H16A | 1.552695 | 0.792864 | 0.430674 | 0.035* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1A | 0.0415 (6) | 0.0233 (6) | 0.0370 (6) | −0.0043 (5) | 0.0063 (4) | 0.0017 (5) |
Br1 | 0.0474 (7) | 0.0215 (6) | 0.0404 (6) | −0.0066 (5) | 0.0091 (5) | 0.0002 (5) |
S1 | 0.0476 (17) | 0.0193 (12) | 0.0329 (14) | −0.0021 (11) | 0.0147 (12) | −0.0033 (10) |
S1A | 0.0550 (19) | 0.0226 (13) | 0.0347 (14) | −0.0013 (13) | 0.0202 (13) | −0.0072 (11) |
O1A | 0.037 (4) | 0.022 (4) | 0.029 (4) | −0.007 (3) | 0.005 (3) | −0.001 (3) |
O1 | 0.037 (4) | 0.020 (4) | 0.029 (4) | −0.001 (3) | 0.006 (3) | 0.001 (3) |
N2 | 0.030 (5) | 0.021 (4) | 0.021 (4) | −0.001 (4) | 0.005 (4) | −0.005 (4) |
N2A | 0.029 (5) | 0.024 (4) | 0.028 (5) | −0.001 (4) | 0.006 (4) | −0.004 (4) |
N1A | 0.029 (5) | 0.020 (4) | 0.029 (4) | −0.005 (4) | 0.008 (4) | −0.002 (4) |
N1 | 0.027 (4) | 0.019 (4) | 0.030 (5) | −0.003 (4) | 0.006 (4) | 0.002 (4) |
C12 | 0.033 (6) | 0.026 (6) | 0.030 (6) | 0.007 (5) | 0.005 (5) | −0.004 (5) |
C10 | 0.020 (5) | 0.022 (6) | 0.024 (5) | −0.003 (4) | 0.000 (4) | 0.000 (4) |
C1 | 0.030 (5) | 0.025 (5) | 0.023 (5) | 0.001 (4) | 0.003 (4) | 0.001 (4) |
C22A | 0.033 (6) | 0.029 (6) | 0.020 (5) | −0.004 (4) | 0.007 (4) | −0.003 (4) |
C24 | 0.034 (6) | 0.028 (6) | 0.027 (5) | −0.006 (5) | 0.006 (4) | 0.006 (4) |
C11A | 0.024 (5) | 0.020 (5) | 0.023 (5) | 0.003 (4) | 0.002 (4) | −0.001 (4) |
C23A | 0.036 (6) | 0.036 (7) | 0.026 (6) | 0.006 (5) | −0.003 (5) | −0.004 (4) |
C26 | 0.029 (5) | 0.018 (5) | 0.028 (5) | 0.009 (4) | 0.002 (4) | 0.001 (4) |
C21 | 0.031 (6) | 0.026 (5) | 0.026 (5) | 0.003 (4) | −0.001 (4) | 0.002 (4) |
C25 | 0.036 (6) | 0.024 (5) | 0.028 (5) | 0.008 (5) | −0.001 (5) | −0.004 (4) |
C26A | 0.030 (6) | 0.028 (5) | 0.020 (5) | 0.007 (4) | 0.004 (4) | −0.003 (4) |
C13A | 0.031 (6) | 0.024 (5) | 0.029 (6) | 0.001 (4) | 0.007 (5) | −0.005 (4) |
C11 | 0.019 (5) | 0.022 (4) | 0.029 (5) | 0.002 (4) | −0.003 (4) | −0.001 (4) |
C23 | 0.040 (7) | 0.028 (6) | 0.025 (5) | −0.003 (5) | 0.005 (5) | 0.000 (4) |
C13 | 0.030 (6) | 0.033 (6) | 0.030 (6) | 0.001 (5) | 0.004 (5) | −0.009 (5) |
C21A | 0.027 (5) | 0.023 (5) | 0.023 (5) | 0.005 (5) | 0.001 (4) | 0.000 (4) |
C10A | 0.028 (5) | 0.023 (6) | 0.020 (5) | 0.001 (4) | 0.004 (4) | −0.004 (4) |
C16 | 0.033 (6) | 0.024 (5) | 0.026 (5) | 0.000 (4) | 0.004 (4) | −0.001 (4) |
C1A | 0.026 (5) | 0.023 (5) | 0.027 (5) | −0.002 (4) | −0.002 (4) | −0.002 (4) |
C24A | 0.027 (5) | 0.027 (5) | 0.030 (6) | 0.000 (4) | 0.004 (4) | 0.010 (4) |
C14A | 0.028 (6) | 0.041 (7) | 0.033 (6) | 0.000 (5) | 0.001 (4) | −0.002 (5) |
C22 | 0.036 (7) | 0.022 (6) | 0.033 (6) | 0.000 (4) | −0.001 (5) | −0.003 (4) |
C25A | 0.033 (6) | 0.017 (5) | 0.030 (6) | 0.003 (4) | −0.003 (5) | 0.000 (4) |
C12A | 0.028 (6) | 0.023 (6) | 0.031 (6) | −0.008 (4) | 0.008 (4) | −0.003 (5) |
C14 | 0.023 (5) | 0.033 (6) | 0.024 (5) | 0.000 (4) | 0.003 (4) | 0.002 (4) |
C15 | 0.036 (6) | 0.026 (5) | 0.030 (6) | −0.004 (4) | 0.003 (5) | 0.003 (4) |
C15A | 0.034 (6) | 0.026 (5) | 0.034 (6) | −0.008 (4) | 0.003 (5) | 0.002 (5) |
C16A | 0.031 (6) | 0.022 (5) | 0.036 (6) | 0.005 (4) | 0.001 (5) | −0.006 (4) |
Geometric parameters (Å, º) top
Br1A—C25A | 1.909 (11) | C23A—H23A | 0.9500 |
Br1—C25 | 1.911 (12) | C23A—C24A | 1.396 (18) |
S1—C1 | 1.678 (12) | C26—H26 | 0.9500 |
S1A—C1A | 1.678 (11) | C26—C21 | 1.416 (16) |
O1A—C10A | 1.219 (14) | C26—C25 | 1.362 (18) |
O1—C10 | 1.238 (14) | C21—C22 | 1.383 (19) |
N2—H2 | 0.8800 | C26A—H26A | 0.9500 |
N2—C1 | 1.334 (15) | C26A—C21A | 1.395 (16) |
N2—C21 | 1.406 (17) | C26A—C25A | 1.375 (17) |
N2A—H2A | 0.8800 | C13A—H13A | 0.9500 |
N2A—C21A | 1.408 (17) | C13A—C14A | 1.376 (17) |
N2A—C1A | 1.311 (15) | C13A—C12A | 1.384 (18) |
N1A—H1A | 0.8800 | C11—C16 | 1.393 (16) |
N1A—C10A | 1.379 (14) | C23—H23 | 0.9500 |
N1A—C1A | 1.405 (15) | C23—C22 | 1.40 (2) |
N1—H1 | 0.8800 | C13—H13 | 0.9500 |
N1—C10 | 1.374 (15) | C13—C14 | 1.373 (18) |
N1—C1 | 1.398 (15) | C16—H16 | 0.9500 |
C12—H12 | 0.9500 | C16—C15 | 1.374 (17) |
C12—C11 | 1.396 (16) | C24A—H24A | 0.9500 |
C12—C13 | 1.36 (2) | C24A—C25A | 1.378 (17) |
C10—C11 | 1.483 (17) | C14A—H14A | 0.9500 |
C22A—H22A | 0.9500 | C14A—C15A | 1.399 (18) |
C22A—C23A | 1.37 (2) | C22—H22 | 0.9500 |
C22A—C21A | 1.412 (17) | C12A—H12A | 0.9500 |
C24—H24 | 0.9500 | C14—H14 | 0.9500 |
C24—C25 | 1.380 (17) | C14—C15 | 1.396 (17) |
C24—C23 | 1.388 (17) | C15—H15 | 0.9500 |
C11A—C10A | 1.490 (16) | C15A—H15A | 0.9500 |
C11A—C12A | 1.392 (17) | C15A—C16A | 1.375 (18) |
C11A—C16A | 1.398 (16) | C16A—H16A | 0.9500 |
| | | |
C1—N2—H2 | 115.0 | C12—C11—C10 | 116.6 (11) |
C1—N2—C21 | 130.0 (11) | C16—C11—C12 | 119.0 (12) |
C21—N2—H2 | 115.0 | C16—C11—C10 | 124.4 (10) |
C21A—N2A—H2A | 113.8 | C24—C23—H23 | 119.1 |
C1A—N2A—H2A | 113.8 | C24—C23—C22 | 121.8 (12) |
C1A—N2A—C21A | 132.3 (10) | C22—C23—H23 | 119.1 |
C10A—N1A—H1A | 116.7 | C12—C13—H13 | 119.4 |
C10A—N1A—C1A | 126.5 (9) | C12—C13—C14 | 121.2 (11) |
C1A—N1A—H1A | 116.7 | C14—C13—H13 | 119.4 |
C10—N1—H1 | 115.7 | N2A—C21A—C22A | 123.6 (10) |
C10—N1—C1 | 128.6 (9) | C26A—C21A—N2A | 116.2 (10) |
C1—N1—H1 | 115.7 | C26A—C21A—C22A | 120.2 (12) |
C11—C12—H12 | 120.0 | O1A—C10A—N1A | 122.8 (11) |
C13—C12—H12 | 120.0 | O1A—C10A—C11A | 121.0 (10) |
C13—C12—C11 | 120.0 (12) | N1A—C10A—C11A | 116.2 (9) |
O1—C10—N1 | 120.9 (11) | C11—C16—H16 | 119.7 |
O1—C10—C11 | 121.4 (10) | C15—C16—C11 | 120.5 (11) |
N1—C10—C11 | 117.7 (9) | C15—C16—H16 | 119.7 |
N2—C1—S1 | 128.6 (10) | N2A—C1A—S1A | 128.2 (10) |
N2—C1—N1 | 114.6 (10) | N2A—C1A—N1A | 115.4 (10) |
N1—C1—S1 | 116.8 (8) | N1A—C1A—S1A | 116.3 (8) |
C23A—C22A—H22A | 120.7 | C23A—C24A—H24A | 120.9 |
C23A—C22A—C21A | 118.7 (11) | C25A—C24A—C23A | 118.1 (11) |
C21A—C22A—H22A | 120.7 | C25A—C24A—H24A | 120.9 |
C25—C24—H24 | 121.1 | C13A—C14A—H14A | 120.1 |
C25—C24—C23 | 117.8 (11) | C13A—C14A—C15A | 119.8 (12) |
C23—C24—H24 | 121.1 | C15A—C14A—H14A | 120.1 |
C12A—C11A—C10A | 115.3 (10) | C21—C22—C23 | 118.9 (11) |
C12A—C11A—C16A | 120.0 (11) | C21—C22—H22 | 120.6 |
C16A—C11A—C10A | 124.6 (10) | C23—C22—H22 | 120.6 |
C22A—C23A—H23A | 119.1 | C26A—C25A—Br1A | 117.9 (8) |
C22A—C23A—C24A | 121.8 (12) | C26A—C25A—C24A | 122.3 (11) |
C24A—C23A—H23A | 119.1 | C24A—C25A—Br1A | 119.8 (9) |
C21—C26—H26 | 120.4 | C11A—C12A—H12A | 120.5 |
C25—C26—H26 | 120.4 | C13A—C12A—C11A | 119.1 (11) |
C25—C26—C21 | 119.2 (11) | C13A—C12A—H12A | 120.5 |
N2—C21—C26 | 114.9 (10) | C13—C14—H14 | 120.3 |
C22—C21—N2 | 125.2 (11) | C13—C14—C15 | 119.5 (11) |
C22—C21—C26 | 119.8 (12) | C15—C14—H14 | 120.3 |
C24—C25—Br1 | 119.2 (9) | C16—C15—C14 | 119.7 (11) |
C26—C25—Br1 | 118.2 (9) | C16—C15—H15 | 120.1 |
C26—C25—C24 | 122.5 (11) | C14—C15—H15 | 120.1 |
C21A—C26A—H26A | 120.6 | C14A—C15A—H15A | 120.1 |
C25A—C26A—H26A | 120.6 | C16A—C15A—C14A | 119.8 (11) |
C25A—C26A—C21A | 118.9 (10) | C16A—C15A—H15A | 120.1 |
C14A—C13A—H13A | 119.4 | C11A—C16A—H16A | 119.9 |
C14A—C13A—C12A | 121.1 (11) | C15A—C16A—C11A | 120.2 (10) |
C12A—C13A—H13A | 119.4 | C15A—C16A—H16A | 119.9 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O1 | 0.88 | 1.85 | 2.590 (13) | 141 |
N2A—H2A···O1A | 0.88 | 1.84 | 2.595 (14) | 142 |
N1A—H1A···S1i | 0.88 | 3.07 | 3.825 (9) | 145 |
N1—H1···S1Aii | 0.88 | 3.09 | 3.888 (10) | 151 |
Symmetry codes: (i) x+1, y+1, z; (ii) x−1, y−1, z. |
Compounds under consideration. For explanation of symbols, see Fig. 3. topCompound | Substituent and position in ring C | Reference [CSD refcode] |
(1) | 2-Cl | Yusof & Yamin (2004) [IZAMIF] |
(2) | 3-Cl | Khawar Rauf et al. (2006) [MEGNIW] |
(3) | 4-Cl | Rauf et al. (2006) [VEGMEA] |
(4) | 2-Br | This work |
(5) | 3-Br | This work |
(6) | 4-Br | Yamin & Yusof (2003) [GUWFIN] |
(7) | 2-I | This work |
(8) | 3-I | This work |
(9) | 4-I | This work |
Parameters of halogen bonding in structures (5)–(8). topType C═E···X | Angle C═E···X (°) | Distance E···X (Å) | Structure |
C10═O1···Br1A | 153.9 (7) | 3.071 (8) | (5) |
C10A═O1A···Br1 | 155.3 (8) | 3.088 (8) | (5) |
C10═O1···I1A | 154.0 (8) | 3.121 (8) | (8) |
C10A═O1A···I1A | 155.3 (8) | 3.137 (9) | (8) |
C1═S1···I1 | 109.97 (9) | 3.7333 (8) | (7) |
Type X···X | | | |
C1—Br1···Br1i | 156.22 (7) | 3.8829 (8) | (6) |
C1—Br1···Br1ii | 88.74 (7) | 3.8829 (8) | (6) |
Notes: E = O or S.
Symmetry codes: (i) -x, y-1/2, -z+5/2;
(ii) -x, y+1/2, -z+5/2. |
Parameters of stacking interactions in the investigated structures topStructure | Ring 1 | Ring 2 | Cg1···Cg2 (Å) | Dihedral angle between rings 1 and 2 (°) | Slippage (Å) |
(1) | B | A(x, -y+1/2, z+1/2) | 3.4092 (13) | 1.28 (8) | |
| B | C[x, -y+1/2, z-1/2) | 3.6302 (16) | 15.12 (6) | |
(2) | B | A(x, y+1, z) | 3.7423 (12) | 17.73 (5) | |
| B | C(x, y-1, z) | 3.2584 (10) | 2.77 (5) | |
(3) | B | A(x-1, y, z) | 3.834 (2) | 8.15 (7) | |
| B | C(x+1, y, z) | 3.274 (3) | 8.78 (6) | |
(4) | A | A(x+1, y, z) | 3.9592 (4) | 0 | 1.804 |
| B | B(x+1, y, z) | | | |
| C | C(x+1, y, z) | | | |
(5) | B | A(x+1, y, z) | 3.668 (6) | 4.1 (4) | |
| B | C(x-1, y, z) | 3.501 (6) | 1.6 (4) | |
| BA | AA(x+1, y, z) | 3.492 (6) | 3.8 (4) | |
| BA | CA(x-1, y, z) | 3.709 (6) | 9.0 (4) | |
(7) | B | A(-x+1, -y+1, -z+1) | 3.646 | 4.11 | |
| C | C(-x+1, -y+1, -z) | 3.836 | 0.0 | 2.16 |
(8) | B | A(x-1, y, z) | 3.687 | 10.28 | |
| B | C(x+1, y, z) | 3.552 | 13.07 | |
| BA | AA(x+1, y, z) | 3.772 | 13.20 | |
| BA | CA(x-1, y, z) | 3.551 | 13.80 | |
(9) | B | A(x+1, y, z) | 3.734 | 5.70 | |
| B | C(x-1, y, z) | 3.620 | 2.39 | |
Notes: The third column lists the inter-centroid distances (Å). For ring 2,
the symmetry operation applied to get ring 2 from the asymmetric unit to the
correct position to interact is given. Subscript A denotes the next
independent molecule in the asymmetric unit. |
The values of dihedral angles φ1 and φ2 (for definition, see Fig. 3). topSubstitution of ring C | 2-Cl | 2-Br | 2-I | 3-Cl | 3-Br | 3-I | 4-Cl | 4-Br | 4-I |
Structure | (1) | (4) | (7) | (2) | (5) | (8) | (3) | (6) | (9) |
φ1 (°) | 15.83 | 40.34 | 7.78 | 22.12 | 10.21; 14.15 | 10.28; 13.20 | 36.81 | 30.01 | 11.59 |
φ2 (°) | 23.51 | 45.26 | 73.05 | 4.23 | 15.44; 15.39 | 13.07; 13.80 | 10.36 | 21.06 | 13.09 |