Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768100003773/bk0072sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108768100003773/bk0072Cl2sup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108768100003773/bk0072Br2sup3.hkl |
CCDC references: 153323; 153324
For both compounds, data collection: SAINT (Siemens, 1995); cell refinement: SAINT; data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1994); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C7H3Cl2N | F(000) = 688 |
Mr = 172.00 | Dx = 1.623 Mg m−3 |
Monoclinic, C2/m | Mo Kα radiation, λ = 0.71073 Å |
a = 18.0525 (8) Å | Cell parameters from 2740 reflections |
b = 20.7374 (10) Å | θ = 1.5–25.0° |
c = 3.8334 (2) Å | µ = 0.83 mm−1 |
β = 101.143 (1)° | T = 172 K |
V = 1408.02 (12) Å3 | Thick needle, colorless |
Z = 8 | 0.45 × 0.15 × 0.15 mm |
Siemens SMART area detector diffractometer | 1289 independent reflections |
Radiation source: fine-focus sealed tube | 1114 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
w scans | θmax = 25.0°, θmin = 1.5° |
Absorption correction: multi-scan SADABS (Sheldrick, 1996; Blessing, 1995) | h = −21→18 |
Tmin = 0.69, Tmax = 0.88 | k = −24→24 |
3625 measured reflections | l = −4→4 |
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)] = 0.030 | Riding |
wR(F2) = 0.081 | Calculated w = 1/[σ2(Fo2) + (0.045P)2 + 0.920P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
1289 reflections | Δρmax = 0.25 e Å−3 |
100 parameters | Δρmin = −0.24 e Å−3 |
0 restraints | Extinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0077 (7) |
C7H3Cl2N | V = 1408.02 (12) Å3 |
Mr = 172.00 | Z = 8 |
Monoclinic, C2/m | Mo Kα radiation |
a = 18.0525 (8) Å | µ = 0.83 mm−1 |
b = 20.7374 (10) Å | T = 172 K |
c = 3.8334 (2) Å | 0.45 × 0.15 × 0.15 mm |
β = 101.143 (1)° |
Siemens SMART area detector diffractometer | 1289 independent reflections |
Absorption correction: multi-scan SADABS (Sheldrick, 1996; Blessing, 1995) | 1114 reflections with I > 2σ(I) |
Tmin = 0.69, Tmax = 0.88 | Rint = 0.021 |
3625 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.081 | Riding |
S = 1.02 | Δρmax = 0.25 e Å−3 |
1289 reflections | Δρmin = −0.24 e Å−3 |
100 parameters |
x | y | z | Uiso*/Ueq | ||
Cl12 | 0.36135 (3) | 0.24609 (2) | 0.16576 (13) | 0.0335 (2) | |
N11 | 0.5000 | 0.12857 (11) | 0.0000 | 0.0393 (6) | |
C11 | 0.5000 | 0.25326 (11) | 0.0000 | 0.0252 (6) | |
C12 | 0.43829 (9) | 0.28813 (8) | 0.0742 (4) | 0.0270 (4) | |
C13 | 0.43795 (10) | 0.35460 (9) | 0.0742 (5) | 0.0320 (4) | |
H13 | 0.3958 | 0.3777 | 0.1245 | 0.038* | |
C14 | 0.5000 | 0.38722 (13) | 0.0000 | 0.0345 (6) | |
H14 | 0.5000 | 0.4330 | 0.0000 | 0.041* | |
C17 | 0.5000 | 0.18391 (13) | 0.0000 | 0.0288 (6) | |
Cl22 | 0.24617 (2) | 0.13011 (2) | 0.51158 (12) | 0.0350 (2) | |
N21 | 0.12163 (13) | 0.0000 | 0.6686 (7) | 0.0378 (6) | |
C21 | 0.25257 (12) | 0.0000 | 0.4900 (6) | 0.0245 (5) | |
C22 | 0.28927 (9) | 0.05788 (8) | 0.4425 (4) | 0.0265 (4) | |
C23 | 0.35903 (10) | 0.05818 (9) | 0.3443 (5) | 0.0314 (4) | |
H23 | 0.3833 | 0.0977 | 0.3109 | 0.038* | |
C24 | 0.39295 (14) | 0.0000 | 0.2954 (7) | 0.0319 (6) | |
H24 | 0.4408 | 0.0000 | 0.2265 | 0.038* | |
C27 | 0.17964 (14) | 0.0000 | 0.5879 (6) | 0.0276 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl12 | 0.0268 (3) | 0.0342 (3) | 0.0423 (3) | −0.0026 (2) | 0.0134 (2) | −0.0022 (2) |
N11 | 0.0354 (13) | 0.0286 (14) | 0.059 (2) | 0.000 | 0.0214 (12) | 0.000 |
C11 | 0.0254 (13) | 0.0257 (13) | 0.0240 (12) | 0.000 | 0.0037 (10) | 0.000 |
C12 | 0.0244 (9) | 0.0305 (10) | 0.0259 (9) | −0.0015 (7) | 0.0049 (7) | −0.0016 (7) |
C13 | 0.0295 (10) | 0.0294 (10) | 0.0369 (10) | 0.0039 (7) | 0.0059 (8) | −0.0037 (8) |
C14 | 0.0359 (15) | 0.0228 (13) | 0.044 (2) | 0.000 | 0.0068 (12) | 0.000 |
C17 | 0.0242 (13) | 0.033 (2) | 0.0314 (14) | 0.000 | 0.0099 (10) | 0.000 |
Cl22 | 0.0383 (3) | 0.0239 (3) | 0.0448 (3) | 0.0000 (2) | 0.0132 (2) | −0.0007 (2) |
N21 | 0.0330 (13) | 0.0302 (13) | 0.055 (2) | 0.000 | 0.0200 (11) | 0.000 |
C21 | 0.0237 (13) | 0.0275 (14) | 0.0218 (12) | 0.000 | 0.0034 (10) | 0.000 |
C22 | 0.0277 (9) | 0.0269 (10) | 0.0242 (9) | 0.0006 (7) | 0.0030 (7) | −0.0007 (7) |
C23 | 0.0283 (9) | 0.0351 (11) | 0.0310 (9) | −0.0061 (8) | 0.0059 (7) | 0.0019 (8) |
C24 | 0.0225 (13) | 0.045 (2) | 0.0291 (13) | 0.000 | 0.0066 (11) | 0.000 |
C27 | 0.0323 (15) | 0.0215 (12) | 0.0289 (13) | 0.000 | 0.0062 (11) | 0.000 |
Cl12—C12 | 1.732 (2) | Cl22—C22 | 1.732 (2) |
N11—C17 | 1.148 (3) | N21—C27 | 1.148 (3) |
C11—C12 | 1.403 (2) | C21—C22ii | 1.400 (2) |
C11—C12i | 1.403 (2) | C21—C22 | 1.400 (2) |
C11—C17 | 1.438 (3) | C21—C27 | 1.437 (3) |
C12—C13 | 1.378 (3) | C22—C23 | 1.382 (2) |
C13—C14 | 1.384 (2) | C23—C24 | 1.382 (2) |
C13—H13 | 0.950 (2) | C23—H23 | 0.950 (2) |
C14—C13i | 1.384 (2) | C24—C23ii | 1.382 (2) |
C14—H14 | 0.950 (3) | C24—H24 | 0.950 (2) |
C12—C11—C12i | 117.9 (2) | C22ii—C21—C22 | 118.1 (2) |
C12—C11—C17 | 121.04 (10) | C22ii—C21—C27 | 120.97 (10) |
C12i—C11—C17 | 121.04 (10) | C22—C21—C27 | 120.97 (10) |
C13—C12—C11 | 121.3 (2) | C23—C22—C21 | 121.2 (2) |
C13—C12—Cl12 | 119.96 (13) | C23—C22—Cl22 | 119.84 (13) |
C11—C12—Cl12 | 118.75 (14) | C21—C22—Cl22 | 118.94 (13) |
C12—C13—C14 | 119.0 (2) | C24—C23—C22 | 118.9 (2) |
C12—C13—H13 | 120.5 (2) | C24—C23—H23 | 120.5 (2) |
C14—C13—H13 | 120.5 (2) | C22—C23—H23 | 120.5 (2) |
C13—C14—C13i | 121.5 (2) | C23—C24—C23ii | 121.6 (2) |
C13—C14—H14 | 119.25 (12) | C23—C24—H24 | 119.19 (11) |
C13i—C14—H14 | 119.25 (12) | C23ii—C24—H24 | 119.19 (11) |
N11—C17—C11 | 180.0 | N21—C27—C21 | 179.5 (3) |
Symmetry codes: (i) −x+1, y, −z; (ii) x, −y, z. |
C7H3Br2N | F(000) = 976 |
Mr = 260.92 | Dx = 2.291 Mg m−3 |
Monoclinic, C2/m | Mo Kα radiation, λ = 0.71073 Å |
a = 18.2269 (15) Å | Cell parameters from 2694 reflections |
b = 21.349 (2) Å | θ = 1.5–25.0° |
c = 3.9663 (3) Å | µ = 10.63 mm−1 |
β = 101.446 (2)° | T = 174 K |
V = 1512.7 (2) Å3 | Thick needle, colorless |
Z = 8 | 0.50 × 0.21 × 0.16 mm |
Siemens SMART area detector diffractometer | 1378 independent reflections |
Radiation source: fine-focus sealed tube | 1148 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
w scans | θmax = 25.1°, θmin = 1.5° |
Absorption correction: multi-scan SADABS (Sheldrick, 1996; Blessing, 1995) | h = −14→21 |
Tmin = 0.086, Tmax = 0.183 | k = −23→25 |
3985 measured reflections | l = −4→4 |
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)] = 0.036 | Riding |
wR(F2) = 0.104 | Calculated w = 1/[σ2(Fo2) + (0.056P)2 + 1.940P] where P = (Fo2 + 2Fc2)/3 |
S = 1.13 | (Δ/σ)max = −0.001 |
1378 reflections | Δρmax = 0.99 e Å−3 |
100 parameters | Δρmin = −1.07 e Å−3 |
0 restraints | Extinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0014 (2) |
C7H3Br2N | V = 1512.7 (2) Å3 |
Mr = 260.92 | Z = 8 |
Monoclinic, C2/m | Mo Kα radiation |
a = 18.2269 (15) Å | µ = 10.63 mm−1 |
b = 21.349 (2) Å | T = 174 K |
c = 3.9663 (3) Å | 0.50 × 0.21 × 0.16 mm |
β = 101.446 (2)° |
Siemens SMART area detector diffractometer | 1378 independent reflections |
Absorption correction: multi-scan SADABS (Sheldrick, 1996; Blessing, 1995) | 1148 reflections with I > 2σ(I) |
Tmin = 0.086, Tmax = 0.183 | Rint = 0.033 |
3985 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.104 | Riding |
S = 1.13 | Δρmax = 0.99 e Å−3 |
1378 reflections | Δρmin = −1.07 e Å−3 |
100 parameters |
Refinement. The highest peaks and lowest depressions in the final difference map were all about 1 Å from one or the other of the Br positions. |
x | y | z | Uiso*/Ueq | ||
Br12 | 0.35939 (3) | 0.24585 (2) | 0.19831 (13) | 0.0243 (2) | |
N11 | 0.5000 | 0.1362 (3) | 0.0000 | 0.038 (2) | |
C11 | 0.5000 | 0.2567 (3) | 0.0000 | 0.0182 (14) | |
C12 | 0.4402 (2) | 0.2904 (2) | 0.0864 (11) | 0.0188 (10) | |
C13 | 0.4401 (3) | 0.3559 (2) | 0.0843 (12) | 0.0245 (11) | |
H13 | 0.3992 (3) | 0.3784 (2) | 0.1402 (12) | 0.029* | |
C14 | 0.5000 | 0.3874 (3) | 0.0000 | 0.030 (2) | |
H14 | 0.5000 | 0.4319 (3) | 0.0000 | 0.036* | |
C17 | 0.5000 | 0.1901 (3) | 0.0000 | 0.024 (2) | |
Br22 | 0.24603 (3) | 0.13240 (2) | 0.51581 (12) | 0.0267 (2) | |
N21 | 0.1297 (4) | 0.0000 | 0.6772 (18) | 0.037 (2) | |
C21 | 0.2566 (3) | 0.0000 | 0.4871 (14) | 0.0184 (14) | |
C22 | 0.2923 (3) | 0.0560 (2) | 0.4366 (11) | 0.0196 (10) | |
C23 | 0.3616 (2) | 0.0562 (2) | 0.3386 (11) | 0.0221 (11) | |
H23 | 0.3860 (2) | 0.0945 (2) | 0.3092 (11) | 0.027* | |
C24 | 0.3936 (4) | 0.0000 | 0.2856 (18) | 0.029 (2) | |
H24 | 0.4398 (4) | 0.0000 | 0.2091 (18) | 0.035* | |
C27 | 0.1857 (4) | 0.0000 | 0.5918 (17) | 0.0211 (14) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br12 | 0.0177 (4) | 0.0237 (4) | 0.0345 (4) | −0.0025 (2) | 0.0123 (3) | −0.0023 (2) |
N11 | 0.033 (4) | 0.019 (4) | 0.068 (5) | 0.000 | 0.026 (4) | 0.000 |
C11 | 0.017 (4) | 0.013 (3) | 0.024 (4) | 0.000 | 0.003 (3) | 0.000 |
C12 | 0.012 (2) | 0.021 (2) | 0.025 (2) | −0.005 (2) | 0.006 (2) | 0.001 (2) |
C13 | 0.017 (3) | 0.022 (2) | 0.035 (3) | 0.003 (2) | 0.006 (2) | −0.006 (2) |
C14 | 0.026 (4) | 0.015 (4) | 0.048 (5) | 0.000 | 0.007 (4) | 0.000 |
C17 | 0.016 (4) | 0.025 (4) | 0.034 (4) | 0.000 | 0.012 (3) | 0.000 |
Br22 | 0.0293 (4) | 0.0158 (3) | 0.0384 (4) | −0.0001 (2) | 0.0150 (3) | −0.0007 (2) |
N21 | 0.036 (4) | 0.034 (4) | 0.048 (4) | 0.000 | 0.024 (3) | 0.000 |
C21 | 0.014 (3) | 0.022 (4) | 0.020 (3) | 0.000 | 0.004 (3) | 0.000 |
C22 | 0.023 (3) | 0.015 (2) | 0.021 (2) | 0.002 (2) | 0.004 (2) | 0.001 (2) |
C23 | 0.014 (2) | 0.025 (3) | 0.027 (3) | −0.004 (2) | 0.006 (2) | 0.002 (2) |
C24 | 0.013 (4) | 0.041 (5) | 0.037 (4) | 0.000 | 0.013 (3) | 0.000 |
C27 | 0.020 (4) | 0.012 (3) | 0.033 (4) | 0.000 | 0.010 (3) | 0.000 |
Br12—C12 | 1.879 (4) | Br22—C22 | 1.892 (4) |
N11—C17 | 1.150 (9) | N21—C27 | 1.138 (9) |
C11—C12 | 1.404 (5) | C21—C22 | 1.394 (5) |
C11—C12i | 1.404 (5) | C21—C22ii | 1.394 (5) |
C11—C17 | 1.423 (9) | C21—C27 | 1.434 (8) |
C12—C13 | 1.398 (7) | C22—C23 | 1.393 (6) |
C13—C14 | 1.379 (6) | C23—C24 | 1.369 (6) |
C13—H13 | 0.95 | C23—H23 | 0.95 |
C14—C13i | 1.379 (6) | C24—C23ii | 1.369 (6) |
C14—H14 | 0.95 | C24—H24 | 0.95 |
C12—C11—C12i | 118.3 (5) | C22—C21—C22ii | 118.0 (5) |
C12—C11—C17 | 120.8 (3) | C22—C21—C27 | 121.0 (3) |
C12i—C11—C17 | 120.8 (3) | C22ii—C21—C27 | 121.0 (3) |
C13—C12—C11 | 120.8 (4) | C23—C22—C21 | 121.2 (4) |
C13—C12—Br12 | 120.5 (3) | C23—C22—Br22 | 120.1 (4) |
C11—C12—Br12 | 118.7 (3) | C21—C22—Br22 | 118.7 (3) |
C14—C13—C12 | 119.2 (5) | C24—C23—C22 | 118.5 (5) |
C14—C13—H13 | 120.4 (3) | C24—C23—H23 | 120.8 (3) |
C12—C13—H13 | 120.4 (3) | C22—C23—H23 | 120.8 (3) |
C13—C14—C13i | 121.6 (6) | C23—C24—C23ii | 122.5 (6) |
C13—C14—H14 | 119.2 (3) | C23—C24—H24 | 118.7 (3) |
C13i—C14—H14 | 119.2 (3) | C23ii—C24—H24 | 118.7 (3) |
N11—C17—C11 | 180.0 | N21—C27—C21 | 179.5 (8) |
Symmetry codes: (i) −x+1, y, −z; (ii) x, −y, z. |
Experimental details
(Cl2) | (Br2) | |
Crystal data | ||
Chemical formula | C7H3Cl2N | C7H3Br2N |
Mr | 172.00 | 260.92 |
Crystal system, space group | Monoclinic, C2/m | Monoclinic, C2/m |
Temperature (K) | 172 | 174 |
a, b, c (Å) | 18.0525 (8), 20.7374 (10), 3.8334 (2) | 18.2269 (15), 21.349 (2), 3.9663 (3) |
β (°) | 101.143 (1) | 101.446 (2) |
V (Å3) | 1408.02 (12) | 1512.7 (2) |
Z | 8 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.83 | 10.63 |
Crystal size (mm) | 0.45 × 0.15 × 0.15 | 0.50 × 0.21 × 0.16 |
Data collection | ||
Diffractometer | Siemens SMART area detector diffractometer | Siemens SMART area detector diffractometer |
Absorption correction | Multi-scan SADABS (Sheldrick, 1996; Blessing, 1995) | Multi-scan SADABS (Sheldrick, 1996; Blessing, 1995) |
Tmin, Tmax | 0.69, 0.88 | 0.086, 0.183 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3625, 1289, 1114 | 3985, 1378, 1148 |
Rint | 0.021 | 0.033 |
(sin θ/λ)max (Å−1) | 0.595 | 0.596 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.081, 1.02 | 0.036, 0.104, 1.13 |
No. of reflections | 1289 | 1378 |
No. of parameters | 100 | 100 |
H-atom treatment | Riding | Riding |
Δρmax, Δρmin (e Å−3) | 0.25, −0.24 | 0.99, −1.07 |
Computer programs: SAINT (Siemens, 1995), SAINT, SHELXTL (Sheldrick, 1994), SHELXTL.