Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803004422/su6016sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803004422/su6016Isup2.hkl |
CCDC reference: 209911
A solution of 4-bromoaniline (1.411 g, 8.2 mmol) was added dropwise to 50 ml of ethanol containing an equimolar amount of 2-chlorobenzoyl chloride and ammonium thiocynate in a two-neck round-bottomed flask. The solution was refluxed for ca 1 h and then cooled in ice. The orange precipitate was filtered off and washed with methanol–distilled water, then dried at room temperature. Recrystallization from DMSO yielded single crystals suitable for X-ray analysis.
After checking their presence in difference Fourier maps, all H atoms were fixed geometrically at ideal positions and allowed to ride on the parent C or N atoms, with C—H = 0.97 Å and N—H = 0.89 Å.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).
C14H10BrClN2O2 | F(000) = 704 |
Mr = 353.60 | Dx = 1.725 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 7.6761 (7) Å | Cell parameters from 2647 reflections |
b = 17.7520 (17) Å | θ = 2.3–27.5° |
c = 10.3654 (10) Å | µ = 3.22 mm−1 |
β = 105.479 (2)° | T = 293 K |
V = 1361.2 (2) Å3 | Block, colourless |
Z = 4 | 0.38 × 0.21 × 0.16 mm |
Bruker SMART APEX CCD area-detector diffractometer | 3130 independent reflections |
Radiation source: fine-focus sealed tube | 2322 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
Detector resolution: 83.66 pixels mm-1 | θmax = 27.5°, θmin = 2.3° |
ω scans | h = −9→9 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −23→22 |
Tmin = 0.374, Tmax = 0.627 | l = −13→13 |
9216 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.049P)2 + 0.3187P] where P = (Fo2 + 2Fc2)/3 |
3130 reflections | (Δ/σ)max < 0.001 |
181 parameters | Δρmax = 0.61 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
C14H10BrClN2O2 | V = 1361.2 (2) Å3 |
Mr = 353.60 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.6761 (7) Å | µ = 3.22 mm−1 |
b = 17.7520 (17) Å | T = 293 K |
c = 10.3654 (10) Å | 0.38 × 0.21 × 0.16 mm |
β = 105.479 (2)° |
Bruker SMART APEX CCD area-detector diffractometer | 3130 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 2322 reflections with I > 2σ(I) |
Tmin = 0.374, Tmax = 0.627 | Rint = 0.022 |
9216 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.61 e Å−3 |
3130 reflections | Δρmin = −0.28 e Å−3 |
181 parameters |
x | y | z | Uiso*/Ueq | ||
Br1 | 0.84987 (5) | 0.035482 (19) | 0.09409 (3) | 0.07391 (15) | |
Cl1 | −0.11560 (11) | 0.31030 (4) | 0.43300 (7) | 0.0637 (2) | |
O1 | 0.2248 (2) | 0.21736 (9) | 0.55813 (19) | 0.0543 (4) | |
O2 | 0.1713 (2) | −0.00241 (10) | 0.42736 (17) | 0.0520 (4) | |
N1 | 0.0960 (3) | 0.10119 (10) | 0.52699 (19) | 0.0422 (4) | |
H1A | 0.0129 | 0.0747 | 0.5467 | 0.051* | |
N2 | 0.3382 (3) | 0.10369 (10) | 0.43313 (19) | 0.0426 (4) | |
H2A | 0.3548 | 0.1478 | 0.4684 | 0.051* | |
C1 | −0.0901 (3) | 0.16094 (14) | 0.7237 (2) | 0.0488 (6) | |
H1B | −0.0232 | 0.1186 | 0.7596 | 0.059* | |
C2 | −0.2285 (4) | 0.18459 (16) | 0.7751 (3) | 0.0585 (7) | |
H2B | −0.2524 | 0.1592 | 0.8470 | 0.070* | |
C3 | −0.3310 (4) | 0.24545 (17) | 0.7204 (3) | 0.0595 (7) | |
H3A | −0.4264 | 0.2606 | 0.7538 | 0.071* | |
C4 | −0.2937 (4) | 0.28428 (15) | 0.6163 (3) | 0.0526 (6) | |
H4A | −0.3632 | 0.3257 | 0.5791 | 0.063* | |
C5 | −0.1530 (3) | 0.26132 (13) | 0.5677 (2) | 0.0418 (5) | |
C6 | −0.0487 (3) | 0.19917 (12) | 0.6194 (2) | 0.0388 (5) | |
C7 | 0.1046 (3) | 0.17463 (12) | 0.5658 (2) | 0.0400 (5) | |
C8 | 0.2048 (3) | 0.06300 (13) | 0.4591 (2) | 0.0398 (5) | |
C9 | 0.4545 (3) | 0.08285 (12) | 0.3550 (2) | 0.0380 (5) | |
C10 | 0.5758 (3) | 0.13703 (13) | 0.3378 (2) | 0.0452 (5) | |
H10A | 0.5785 | 0.1836 | 0.3793 | 0.054* | |
C11 | 0.6920 (3) | 0.12328 (14) | 0.2607 (3) | 0.0493 (6) | |
H11A | 0.7720 | 0.1604 | 0.2490 | 0.059* | |
C12 | 0.6892 (3) | 0.05486 (14) | 0.2014 (2) | 0.0467 (6) | |
C13 | 0.5710 (4) | 0.00010 (15) | 0.2172 (3) | 0.0609 (7) | |
H13A | 0.5707 | −0.0466 | 0.1764 | 0.073* | |
C14 | 0.4522 (4) | 0.01414 (14) | 0.2937 (3) | 0.0564 (7) | |
H14A | 0.3709 | −0.0228 | 0.3036 | 0.068* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0782 (2) | 0.0794 (3) | 0.0848 (3) | 0.01496 (16) | 0.0577 (2) | 0.00629 (15) |
Cl1 | 0.0755 (5) | 0.0600 (4) | 0.0656 (4) | 0.0126 (3) | 0.0362 (4) | 0.0185 (3) |
O1 | 0.0501 (10) | 0.0420 (9) | 0.0824 (12) | −0.0100 (7) | 0.0381 (9) | −0.0136 (8) |
O2 | 0.0555 (11) | 0.0349 (9) | 0.0779 (12) | −0.0074 (7) | 0.0389 (9) | −0.0088 (8) |
N1 | 0.0411 (10) | 0.0349 (10) | 0.0593 (12) | −0.0013 (8) | 0.0283 (9) | −0.0020 (8) |
N2 | 0.0436 (11) | 0.0327 (10) | 0.0604 (12) | −0.0047 (8) | 0.0293 (9) | −0.0076 (8) |
C1 | 0.0536 (15) | 0.0458 (13) | 0.0533 (14) | −0.0001 (11) | 0.0252 (12) | 0.0018 (10) |
C2 | 0.0662 (18) | 0.0627 (17) | 0.0586 (16) | −0.0057 (13) | 0.0375 (14) | −0.0013 (12) |
C3 | 0.0516 (16) | 0.0703 (18) | 0.0673 (17) | −0.0009 (13) | 0.0346 (14) | −0.0147 (14) |
C4 | 0.0466 (14) | 0.0548 (15) | 0.0592 (15) | 0.0085 (11) | 0.0187 (12) | −0.0058 (12) |
C5 | 0.0448 (13) | 0.0436 (13) | 0.0425 (12) | −0.0004 (10) | 0.0209 (11) | −0.0040 (9) |
C6 | 0.0400 (12) | 0.0374 (12) | 0.0445 (12) | −0.0027 (9) | 0.0209 (10) | −0.0057 (9) |
C7 | 0.0405 (12) | 0.0378 (12) | 0.0461 (12) | 0.0007 (9) | 0.0193 (10) | −0.0016 (9) |
C8 | 0.0404 (12) | 0.0363 (11) | 0.0479 (13) | 0.0011 (9) | 0.0207 (10) | 0.0007 (9) |
C9 | 0.0385 (12) | 0.0328 (11) | 0.0468 (12) | 0.0017 (9) | 0.0186 (10) | 0.0022 (9) |
C10 | 0.0426 (13) | 0.0389 (12) | 0.0597 (14) | −0.0030 (10) | 0.0233 (12) | −0.0059 (10) |
C11 | 0.0423 (13) | 0.0491 (14) | 0.0640 (15) | −0.0032 (10) | 0.0271 (12) | 0.0044 (11) |
C12 | 0.0418 (13) | 0.0561 (15) | 0.0496 (13) | 0.0095 (11) | 0.0253 (11) | 0.0061 (11) |
C13 | 0.0691 (18) | 0.0440 (14) | 0.0836 (19) | −0.0025 (13) | 0.0445 (16) | −0.0160 (13) |
C14 | 0.0605 (16) | 0.0398 (13) | 0.0831 (19) | −0.0099 (11) | 0.0438 (15) | −0.0103 (12) |
Br1—C12 | 1.900 (2) | C3—H3A | 0.9300 |
Cl1—C5 | 1.733 (2) | C4—C5 | 1.369 (3) |
O1—C7 | 1.213 (3) | C4—H4A | 0.9300 |
O2—C8 | 1.215 (3) | C5—C6 | 1.384 (3) |
N1—C7 | 1.361 (3) | C6—C7 | 1.494 (3) |
N1—C8 | 1.402 (3) | C9—C14 | 1.373 (3) |
N1—H1A | 0.8600 | C9—C10 | 1.383 (3) |
N2—C8 | 1.338 (3) | C10—C11 | 1.369 (3) |
N2—C9 | 1.406 (3) | C10—H10A | 0.9300 |
N2—H2A | 0.8600 | C11—C12 | 1.359 (4) |
C1—C2 | 1.375 (4) | C11—H11A | 0.9300 |
C1—C6 | 1.383 (3) | C12—C13 | 1.369 (4) |
C1—H1B | 0.9300 | C13—C14 | 1.381 (4) |
C2—C3 | 1.367 (4) | C13—H13A | 0.9300 |
C2—H2B | 0.9300 | C14—H14A | 0.9300 |
C3—C4 | 1.374 (4) | ||
C7—N1—C8 | 128.58 (19) | O1—C7—N1 | 123.9 (2) |
C7—N1—H1A | 115.7 | O1—C7—C6 | 122.0 (2) |
C8—N1—H1A | 115.7 | N1—C7—C6 | 114.11 (19) |
C8—N2—C9 | 127.73 (19) | O2—C8—N2 | 125.4 (2) |
C8—N2—H2A | 116.1 | O2—C8—N1 | 119.13 (19) |
C9—N2—H2A | 116.1 | N2—C8—N1 | 115.48 (19) |
C2—C1—C6 | 121.0 (2) | C14—C9—C10 | 119.0 (2) |
C2—C1—H1B | 119.5 | C14—C9—N2 | 124.7 (2) |
C6—C1—H1B | 119.5 | C10—C9—N2 | 116.37 (19) |
C3—C2—C1 | 119.9 (3) | C11—C10—C9 | 121.1 (2) |
C3—C2—H2B | 120.0 | C11—C10—H10A | 119.4 |
C1—C2—H2B | 120.0 | C9—C10—H10A | 119.4 |
C2—C3—C4 | 120.3 (2) | C12—C11—C10 | 119.3 (2) |
C2—C3—H3A | 119.8 | C12—C11—H11A | 120.4 |
C4—C3—H3A | 119.8 | C10—C11—H11A | 120.4 |
C5—C4—C3 | 119.3 (2) | C11—C12—C13 | 120.8 (2) |
C5—C4—H4A | 120.3 | C11—C12—Br1 | 119.48 (19) |
C3—C4—H4A | 120.3 | C13—C12—Br1 | 119.73 (19) |
C4—C5—C6 | 121.7 (2) | C12—C13—C14 | 120.0 (2) |
C4—C5—Cl1 | 117.60 (19) | C12—C13—H13A | 120.0 |
C6—C5—Cl1 | 120.59 (17) | C14—C13—H13A | 120.0 |
C1—C6—C5 | 117.7 (2) | C9—C14—C13 | 119.8 (2) |
C1—C6—C7 | 121.0 (2) | C9—C14—H14A | 120.1 |
C5—C6—C7 | 121.3 (2) | C13—C14—H14A | 120.1 |
C6—C1—C2—C3 | 1.9 (4) | C9—N2—C8—O2 | 6.4 (4) |
C1—C2—C3—C4 | −1.6 (4) | C9—N2—C8—N1 | −172.6 (2) |
C2—C3—C4—C5 | 0.1 (4) | C7—N1—C8—O2 | −176.7 (2) |
C3—C4—C5—C6 | 1.0 (4) | C7—N1—C8—N2 | 2.4 (3) |
C3—C4—C5—Cl1 | 178.1 (2) | C8—N2—C9—C14 | −1.8 (4) |
C2—C1—C6—C5 | −0.8 (4) | C8—N2—C9—C10 | 176.6 (2) |
C2—C1—C6—C7 | 178.4 (2) | C14—C9—C10—C11 | 0.3 (4) |
C4—C5—C6—C1 | −0.7 (3) | N2—C9—C10—C11 | −178.3 (2) |
Cl1—C5—C6—C1 | −177.62 (18) | C9—C10—C11—C12 | −0.8 (4) |
C4—C5—C6—C7 | −179.9 (2) | C10—C11—C12—C13 | 0.5 (4) |
Cl1—C5—C6—C7 | 3.1 (3) | C10—C11—C12—Br1 | 179.93 (18) |
C8—N1—C7—O1 | −7.9 (4) | C11—C12—C13—C14 | 0.3 (5) |
C8—N1—C7—C6 | 171.9 (2) | Br1—C12—C13—C14 | −179.2 (2) |
C1—C6—C7—O1 | −125.5 (3) | C10—C9—C14—C13 | 0.5 (4) |
C5—C6—C7—O1 | 53.7 (3) | N2—C9—C14—C13 | 178.9 (3) |
C1—C6—C7—N1 | 54.7 (3) | C12—C13—C14—C9 | −0.8 (5) |
C5—C6—C7—N1 | −126.1 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2i | 0.86 | 1.98 | 2.833 (3) | 171 |
N2—H2A···O1 | 0.86 | 1.97 | 2.667 (2) | 137 |
C14—H14A···O2 | 0.93 | 2.27 | 2.873 (3) | 122 |
Symmetry code: (i) −x, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C14H10BrClN2O2 |
Mr | 353.60 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 7.6761 (7), 17.7520 (17), 10.3654 (10) |
β (°) | 105.479 (2) |
V (Å3) | 1361.2 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.22 |
Crystal size (mm) | 0.38 × 0.21 × 0.16 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.374, 0.627 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9216, 3130, 2322 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.098, 1.02 |
No. of reflections | 3130 |
No. of parameters | 181 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.61, −0.28 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).
Br1—C12 | 1.900 (2) | N1—C7 | 1.361 (3) |
Cl1—C5 | 1.733 (2) | N1—C8 | 1.402 (3) |
O1—C7 | 1.213 (3) | N2—C8 | 1.338 (3) |
O2—C8 | 1.215 (3) | N2—C9 | 1.406 (3) |
C7—N1—C8 | 128.58 (19) | O2—C8—N1 | 119.13 (19) |
C8—N2—C9 | 127.73 (19) | N2—C8—N1 | 115.48 (19) |
O1—C7—N1 | 123.9 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2i | 0.86 | 1.98 | 2.833 (3) | 171 |
N2—H2A···O1 | 0.86 | 1.97 | 2.667 (2) | 137 |
C14—H14A···O2 | 0.93 | 2.27 | 2.873 (3) | 122 |
Symmetry code: (i) −x, −y, −z+1. |
It is known that conversion of thiocarbonyls to their carbonyl compounds can be carried out with the help of reagents such as sodium peroxide (Kalm, 1961), dimethyl selenoxide (Mikolajczyk & Luczak, 1978), dimethyl sulfoxide/iodine (Mikolajczyk & Luczak, 1975) and bismuth nitrate (Mohammadpoor-Baltork, 2003). In the course of our work to synthesize a series of chlorobenzoylthiourea derivatives, including p-bromophenylchlorobenzoylthiourea, the title compound, (I), was obtained instead.
The bond lengths and angles in (I) are in the normal ranges (Allen et al., 1987) and in agreement with most urea and thiourea derivatives (Stoyanova et al., 2002; Yamin & Yusof, 2003). The bromophenyl and chlorobenzoyl groups lie cis and trans, respectively, to atom O2 across the urea C—N bonds. Both aryl rings, Cl1/C1—C6 and Br1/C9—C14, are essentially planar, with atoms Br1 and Cl1 deviating by 0.046 (1) and 0.020 (1) Å, respectively, from their mean planes, and an angle between the planes of 57.12 (10)°. The central carbonyl-urea carbonyl fragment (atoms O1/O2/N1/N2/C7/C8) is also planar, with a maximum deviation of 0.039 (2)° for atom C7. The bromophenyl and chlorophenyl planes are inclined to the central carbonyl-urea plane by 7.65 (11) and 55.12 (10)°, respectively. There are two intramolecular interactions N2—H2A···O1 and C14—H14···O2 forming the two pseduo-six-membered rings O1—C7—N1—C8—N2—H2A and O2—C8—N2—C9—C14—H14, respectively. In the crystal, the molecules are arranged as dimers by intermolecular hydrogen bonding, N1—H1A···O2i, and are arranged almost perpendicular to the ac plane, stackng in the a direction (Fig. 2).