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The title compounds are isomorphous, with two half-molecules in the asymmetric unit of a monoclinic unit cell in the space group C2/m. For the chloro compound: a = 18.0525 (8), b = 20.7374 (10), c = 3.8334 (2) Å, β = 101.143 (1)°; for the bromo compound: a = 18.2269 (15), b = 21.349 (2), c = 3.9663 (3) Å, β = 101.446 (2)°. The dominant intermolecular interactions are between halogen atoms rather than between halogen and nitrile, as is the case in the corresponding 2,4,6-trihalobenzonitriles. The molecules pack into layers with a fourfold pseudosymmetry. The pseudosymmetry appears to be the consequence of halogen–halogen intermolecular interactions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768100003773/bk0072sup1.cif
Contains datablocks Cl2, Br2, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108768100003773/bk0072Cl2sup2.hkl
Contains datablock cl

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108768100003773/bk0072Br2sup3.hkl
Contains datablock br

CCDC references: 153323; 153324

Computing details top

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.

Figures top
[Figure 1]
[Figure 2]
[Figure 3]
[Figure 4]
(Cl2) 2,6-dichlorobenzonitrile top
Crystal data top
C7H3Cl2NF(000) = 688
Mr = 172.00Dx = 1.623 Mg m3
Monoclinic, C2/mMo Kα radiation, λ = 0.71073 Å
a = 18.0525 (8) ÅCell parameters from 2740 reflections
b = 20.7374 (10) Åθ = 1.5–25.0°
c = 3.8334 (2) ŵ = 0.83 mm1
β = 101.143 (1)°T = 172 K
V = 1408.02 (12) Å3Thick needle, colorless
Z = 80.45 × 0.15 × 0.15 mm
Data collection top
Siemens SMART area detector
diffractometer
1289 independent reflections
Radiation source: fine-focus sealed tube1114 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.021
w scansθmax = 25.0°, θmin = 1.5°
Absorption correction: multi-scan
SADABS (Sheldrick, 1996; Blessing, 1995)
h = 2118
Tmin = 0.69, Tmax = 0.88k = 2424
3625 measured reflectionsl = 44
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030Riding
wR(F2) = 0.081Calculated w = 1/[σ2(Fo2) + (0.045P)2 + 0.920P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.001
1289 reflectionsΔρmax = 0.25 e Å3
100 parametersΔρmin = 0.24 e Å3
0 restraintsExtinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0077 (7)
Crystal data top
C7H3Cl2NV = 1408.02 (12) Å3
Mr = 172.00Z = 8
Monoclinic, C2/mMo Kα radiation
a = 18.0525 (8) ŵ = 0.83 mm1
b = 20.7374 (10) ÅT = 172 K
c = 3.8334 (2) Å0.45 × 0.15 × 0.15 mm
β = 101.143 (1)°
Data collection top
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 = 0.88Rint = 0.021
3625 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.081Riding
S = 1.02Δρmax = 0.25 e Å3
1289 reflectionsΔρmin = 0.24 e Å3
100 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl120.36135 (3)0.24609 (2)0.16576 (13)0.0335 (2)
N110.50000.12857 (11)0.00000.0393 (6)
C110.50000.25326 (11)0.00000.0252 (6)
C120.43829 (9)0.28813 (8)0.0742 (4)0.0270 (4)
C130.43795 (10)0.35460 (9)0.0742 (5)0.0320 (4)
H130.39580.37770.12450.038*
C140.50000.38722 (13)0.00000.0345 (6)
H140.50000.43300.00000.041*
C170.50000.18391 (13)0.00000.0288 (6)
Cl220.24617 (2)0.13011 (2)0.51158 (12)0.0350 (2)
N210.12163 (13)0.00000.6686 (7)0.0378 (6)
C210.25257 (12)0.00000.4900 (6)0.0245 (5)
C220.28927 (9)0.05788 (8)0.4425 (4)0.0265 (4)
C230.35903 (10)0.05818 (9)0.3443 (5)0.0314 (4)
H230.38330.09770.31090.038*
C240.39295 (14)0.00000.2954 (7)0.0319 (6)
H240.44080.00000.22650.038*
C270.17964 (14)0.00000.5879 (6)0.0276 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl120.0268 (3)0.0342 (3)0.0423 (3)0.0026 (2)0.0134 (2)0.0022 (2)
N110.0354 (13)0.0286 (14)0.059 (2)0.0000.0214 (12)0.000
C110.0254 (13)0.0257 (13)0.0240 (12)0.0000.0037 (10)0.000
C120.0244 (9)0.0305 (10)0.0259 (9)0.0015 (7)0.0049 (7)0.0016 (7)
C130.0295 (10)0.0294 (10)0.0369 (10)0.0039 (7)0.0059 (8)0.0037 (8)
C140.0359 (15)0.0228 (13)0.044 (2)0.0000.0068 (12)0.000
C170.0242 (13)0.033 (2)0.0314 (14)0.0000.0099 (10)0.000
Cl220.0383 (3)0.0239 (3)0.0448 (3)0.0000 (2)0.0132 (2)0.0007 (2)
N210.0330 (13)0.0302 (13)0.055 (2)0.0000.0200 (11)0.000
C210.0237 (13)0.0275 (14)0.0218 (12)0.0000.0034 (10)0.000
C220.0277 (9)0.0269 (10)0.0242 (9)0.0006 (7)0.0030 (7)0.0007 (7)
C230.0283 (9)0.0351 (11)0.0310 (9)0.0061 (8)0.0059 (7)0.0019 (8)
C240.0225 (13)0.045 (2)0.0291 (13)0.0000.0066 (11)0.000
C270.0323 (15)0.0215 (12)0.0289 (13)0.0000.0062 (11)0.000
Geometric parameters (Å, º) top
Cl12—C121.732 (2)Cl22—C221.732 (2)
N11—C171.148 (3)N21—C271.148 (3)
C11—C121.403 (2)C21—C22ii1.400 (2)
C11—C12i1.403 (2)C21—C221.400 (2)
C11—C171.438 (3)C21—C271.437 (3)
C12—C131.378 (3)C22—C231.382 (2)
C13—C141.384 (2)C23—C241.382 (2)
C13—H130.950 (2)C23—H230.950 (2)
C14—C13i1.384 (2)C24—C23ii1.382 (2)
C14—H140.950 (3)C24—H240.950 (2)
C12—C11—C12i117.9 (2)C22ii—C21—C22118.1 (2)
C12—C11—C17121.04 (10)C22ii—C21—C27120.97 (10)
C12i—C11—C17121.04 (10)C22—C21—C27120.97 (10)
C13—C12—C11121.3 (2)C23—C22—C21121.2 (2)
C13—C12—Cl12119.96 (13)C23—C22—Cl22119.84 (13)
C11—C12—Cl12118.75 (14)C21—C22—Cl22118.94 (13)
C12—C13—C14119.0 (2)C24—C23—C22118.9 (2)
C12—C13—H13120.5 (2)C24—C23—H23120.5 (2)
C14—C13—H13120.5 (2)C22—C23—H23120.5 (2)
C13—C14—C13i121.5 (2)C23—C24—C23ii121.6 (2)
C13—C14—H14119.25 (12)C23—C24—H24119.19 (11)
C13i—C14—H14119.25 (12)C23ii—C24—H24119.19 (11)
N11—C17—C11180.0N21—C27—C21179.5 (3)
Symmetry codes: (i) x+1, y, z; (ii) x, y, z.
(Br2) 2,6-dibromobenzonitrile top
Crystal data top
C7H3Br2NF(000) = 976
Mr = 260.92Dx = 2.291 Mg m3
Monoclinic, C2/mMo Kα radiation, λ = 0.71073 Å
a = 18.2269 (15) ÅCell parameters from 2694 reflections
b = 21.349 (2) Åθ = 1.5–25.0°
c = 3.9663 (3) ŵ = 10.63 mm1
β = 101.446 (2)°T = 174 K
V = 1512.7 (2) Å3Thick needle, colorless
Z = 80.50 × 0.21 × 0.16 mm
Data collection top
Siemens SMART area detector
diffractometer
1378 independent reflections
Radiation source: fine-focus sealed tube1148 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
w scansθmax = 25.1°, θmin = 1.5°
Absorption correction: multi-scan
SADABS (Sheldrick, 1996; Blessing, 1995)
h = 1421
Tmin = 0.086, Tmax = 0.183k = 2325
3985 measured reflectionsl = 44
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036Riding
wR(F2) = 0.104Calculated w = 1/[σ2(Fo2) + (0.056P)2 + 1.940P]
where P = (Fo2 + 2Fc2)/3
S = 1.13(Δ/σ)max = 0.001
1378 reflectionsΔρmax = 0.99 e Å3
100 parametersΔρmin = 1.07 e Å3
0 restraintsExtinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0014 (2)
Crystal data top
C7H3Br2NV = 1512.7 (2) Å3
Mr = 260.92Z = 8
Monoclinic, C2/mMo Kα radiation
a = 18.2269 (15) ŵ = 10.63 mm1
b = 21.349 (2) ÅT = 174 K
c = 3.9663 (3) Å0.50 × 0.21 × 0.16 mm
β = 101.446 (2)°
Data collection top
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 = 0.183Rint = 0.033
3985 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.104Riding
S = 1.13Δρmax = 0.99 e Å3
1378 reflectionsΔρmin = 1.07 e Å3
100 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br120.35939 (3)0.24585 (2)0.19831 (13)0.0243 (2)
N110.50000.1362 (3)0.00000.038 (2)
C110.50000.2567 (3)0.00000.0182 (14)
C120.4402 (2)0.2904 (2)0.0864 (11)0.0188 (10)
C130.4401 (3)0.3559 (2)0.0843 (12)0.0245 (11)
H130.3992 (3)0.3784 (2)0.1402 (12)0.029*
C140.50000.3874 (3)0.00000.030 (2)
H140.50000.4319 (3)0.00000.036*
C170.50000.1901 (3)0.00000.024 (2)
Br220.24603 (3)0.13240 (2)0.51581 (12)0.0267 (2)
N210.1297 (4)0.00000.6772 (18)0.037 (2)
C210.2566 (3)0.00000.4871 (14)0.0184 (14)
C220.2923 (3)0.0560 (2)0.4366 (11)0.0196 (10)
C230.3616 (2)0.0562 (2)0.3386 (11)0.0221 (11)
H230.3860 (2)0.0945 (2)0.3092 (11)0.027*
C240.3936 (4)0.00000.2856 (18)0.029 (2)
H240.4398 (4)0.00000.2091 (18)0.035*
C270.1857 (4)0.00000.5918 (17)0.0211 (14)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br120.0177 (4)0.0237 (4)0.0345 (4)0.0025 (2)0.0123 (3)0.0023 (2)
N110.033 (4)0.019 (4)0.068 (5)0.0000.026 (4)0.000
C110.017 (4)0.013 (3)0.024 (4)0.0000.003 (3)0.000
C120.012 (2)0.021 (2)0.025 (2)0.005 (2)0.006 (2)0.001 (2)
C130.017 (3)0.022 (2)0.035 (3)0.003 (2)0.006 (2)0.006 (2)
C140.026 (4)0.015 (4)0.048 (5)0.0000.007 (4)0.000
C170.016 (4)0.025 (4)0.034 (4)0.0000.012 (3)0.000
Br220.0293 (4)0.0158 (3)0.0384 (4)0.0001 (2)0.0150 (3)0.0007 (2)
N210.036 (4)0.034 (4)0.048 (4)0.0000.024 (3)0.000
C210.014 (3)0.022 (4)0.020 (3)0.0000.004 (3)0.000
C220.023 (3)0.015 (2)0.021 (2)0.002 (2)0.004 (2)0.001 (2)
C230.014 (2)0.025 (3)0.027 (3)0.004 (2)0.006 (2)0.002 (2)
C240.013 (4)0.041 (5)0.037 (4)0.0000.013 (3)0.000
C270.020 (4)0.012 (3)0.033 (4)0.0000.010 (3)0.000
Geometric parameters (Å, º) top
Br12—C121.879 (4)Br22—C221.892 (4)
N11—C171.150 (9)N21—C271.138 (9)
C11—C121.404 (5)C21—C221.394 (5)
C11—C12i1.404 (5)C21—C22ii1.394 (5)
C11—C171.423 (9)C21—C271.434 (8)
C12—C131.398 (7)C22—C231.393 (6)
C13—C141.379 (6)C23—C241.369 (6)
C13—H130.95C23—H230.95
C14—C13i1.379 (6)C24—C23ii1.369 (6)
C14—H140.95C24—H240.95
C12—C11—C12i118.3 (5)C22—C21—C22ii118.0 (5)
C12—C11—C17120.8 (3)C22—C21—C27121.0 (3)
C12i—C11—C17120.8 (3)C22ii—C21—C27121.0 (3)
C13—C12—C11120.8 (4)C23—C22—C21121.2 (4)
C13—C12—Br12120.5 (3)C23—C22—Br22120.1 (4)
C11—C12—Br12118.7 (3)C21—C22—Br22118.7 (3)
C14—C13—C12119.2 (5)C24—C23—C22118.5 (5)
C14—C13—H13120.4 (3)C24—C23—H23120.8 (3)
C12—C13—H13120.4 (3)C22—C23—H23120.8 (3)
C13—C14—C13i121.6 (6)C23—C24—C23ii122.5 (6)
C13—C14—H14119.2 (3)C23—C24—H24118.7 (3)
C13i—C14—H14119.2 (3)C23ii—C24—H24118.7 (3)
N11—C17—C11180.0N21—C27—C21179.5 (8)
Symmetry codes: (i) x+1, y, z; (ii) x, y, z.

Experimental details

(Cl2)(Br2)
Crystal data
Chemical formulaC7H3Cl2NC7H3Br2N
Mr172.00260.92
Crystal system, space groupMonoclinic, C2/mMonoclinic, C2/m
Temperature (K)172174
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)
V3)1408.02 (12)1512.7 (2)
Z88
Radiation typeMo KαMo Kα
µ (mm1)0.8310.63
Crystal size (mm)0.45 × 0.15 × 0.150.50 × 0.21 × 0.16
Data collection
DiffractometerSiemens SMART area detector
diffractometer
Siemens SMART area detector
diffractometer
Absorption correctionMulti-scan
SADABS (Sheldrick, 1996; Blessing, 1995)
Multi-scan
SADABS (Sheldrick, 1996; Blessing, 1995)
Tmin, Tmax0.69, 0.880.086, 0.183
No. of measured, independent and
observed [I > 2σ(I)] reflections
3625, 1289, 1114 3985, 1378, 1148
Rint0.0210.033
(sin θ/λ)max1)0.5950.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.081, 1.02 0.036, 0.104, 1.13
No. of reflections12891378
No. of parameters100100
H-atom treatmentRidingRiding
Δρmax, Δρmin (e Å3)0.25, 0.240.99, 1.07

Computer programs: SAINT (Siemens, 1995), SAINT, SHELXTL (Sheldrick, 1994), SHELXTL.

 

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