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Acta Cryst. (2007). C63, o14-o16
https://doi.org/10.1107/S0108270106048451
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o-Chloro- and o-bromo­benzonitrile: pseudosymmetry and pseudo-isostructural packing

D. Britton
The structures of o-chloro­benzonitrile, C7H4ClN, (I), and o-bromo­benzonitrile, C7H4BrN, (II), have similar packing arrangements, even though Z' = 4 in (I) and Z' = 1 in (II). Both structures involve X...N inter­actions, as well as weak C-H...X and C-H...N hydrogen bonds. The four crystallographically independent mol­ecules in (I) are related by pseudosymmetry.
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Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106048451/sq3046sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106048451/sq3046Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106048451/sq3046IIsup3.hkl
Contains datablock II

CCDC references: 634885; 634886

Comment top

The structures of the title compounds, (I) and (II), have been determined as part of a series of studies on halogen–nitrile intermolecular interactions. Although many examples of X···NC intermolecular interactions are known, in o-iodobenzonitrile (Lam & Britton, 1974) there are no I···NC contacts, but short I···I contacts are important. The question of interest was whether the same situation occurred with the lighter halogens.

Fig. 1 shows the atom labelling and displacement ellispoids for one of the four crystallographically non-equivalent molecules in (I), and for a molecule of (II). The displacement ellipsoids in the remaining three independent molecules in (I) are similar. The bond lengths and angles are normal (Standard reference?).

Fig. 2 shows one view of the packing in (I). The four crystallographically independent molecules, A, B, C and D, are tilted by 25.8 (1), 25.4 (1), 23.9 (1) and 24.1 (1)°, respectively, with respect to (010). Fig. 3 shows a view of the packing in (II). The moleclules of (II) are all tilted by 27.5° with respect to the (100) plane. In both figures, the X···N interactions are shown as dashed lines. Geometric details are given in Table 1. The Cl···N distances are not shorter than the usual van der Waals distances but the Br···N distance is. The similarity in the geometries suggests that the same type of interaction is occurring in both cases. There are a number of C—H···X (X = N, Cl or Br) interactions which are not shown in the figures but are listed in Table 2. These are at about the normal van der Waals distances, but could be regarded as C—H···X hydrogen bonds. They are shown to emphasize the packing similarities between (I) and (II), and also to show the extent of the differences between the four independent molecules of (I). There are X···X interlayer contacts separated by a in (I) and by b in (II); none is closer than the usual van der Waals distances.

The similarity in the packing for (I) and (II) (see Figs. 2 and 3) suggests that there are pseudosymmetric relationships between the independent molecules in (I). Closer inspection shows that this is, indeed, the case. The pseudo conversions are shown in Table 3. As part of the pseudosymmetric relationship, the matrix (400/010/001) converts the cell in (I) to a nearly orthogonal cell, with a' = 63.768 (16) ~ 4a(sinβ), b' = b, c'= c, and β' = 89.89 (1)°. In this cell, the glide planes perpendicular to a* are also perpendicular to a'.

Experimental top

Both compounds were obtained from Aldrich Chemical Co. Inc. A crystal of (I) selected from the original sample and a crystal of (II) grown from an acetone solution were used for the data collection. Both (I) and (II), as well as the iodine analogue, were recrystallized from acetone, acetonitrile, benzene, dichloromethane, chloroform and carbon tetrachloride solutions in efforts to find additional polymorphs of the three compounds, but none was found.

Refinement top

H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.95 Å and with Uiso(H) = 1.2Ueq(C).

Structure description top

The structures of the title compounds, (I) and (II), have been determined as part of a series of studies on halogen–nitrile intermolecular interactions. Although many examples of X···NC intermolecular interactions are known, in o-iodobenzonitrile (Lam & Britton, 1974) there are no I···NC contacts, but short I···I contacts are important. The question of interest was whether the same situation occurred with the lighter halogens.

Fig. 1 shows the atom labelling and displacement ellispoids for one of the four crystallographically non-equivalent molecules in (I), and for a molecule of (II). The displacement ellipsoids in the remaining three independent molecules in (I) are similar. The bond lengths and angles are normal (Standard reference?).

Fig. 2 shows one view of the packing in (I). The four crystallographically independent molecules, A, B, C and D, are tilted by 25.8 (1), 25.4 (1), 23.9 (1) and 24.1 (1)°, respectively, with respect to (010). Fig. 3 shows a view of the packing in (II). The moleclules of (II) are all tilted by 27.5° with respect to the (100) plane. In both figures, the X···N interactions are shown as dashed lines. Geometric details are given in Table 1. The Cl···N distances are not shorter than the usual van der Waals distances but the Br···N distance is. The similarity in the geometries suggests that the same type of interaction is occurring in both cases. There are a number of C—H···X (X = N, Cl or Br) interactions which are not shown in the figures but are listed in Table 2. These are at about the normal van der Waals distances, but could be regarded as C—H···X hydrogen bonds. They are shown to emphasize the packing similarities between (I) and (II), and also to show the extent of the differences between the four independent molecules of (I). There are X···X interlayer contacts separated by a in (I) and by b in (II); none is closer than the usual van der Waals distances.

The similarity in the packing for (I) and (II) (see Figs. 2 and 3) suggests that there are pseudosymmetric relationships between the independent molecules in (I). Closer inspection shows that this is, indeed, the case. The pseudo conversions are shown in Table 3. As part of the pseudosymmetric relationship, the matrix (400/010/001) converts the cell in (I) to a nearly orthogonal cell, with a' = 63.768 (16) ~ 4a(sinβ), b' = b, c'= c, and β' = 89.89 (1)°. In this cell, the glide planes perpendicular to a* are also perpendicular to a'.

Computing details top

For both compounds, data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); 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.

Figures top
[Figure 1] Fig. 1. (a) Molecule A in (I); molecules B, C, and D are similar. (b) The molecule of (II). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. The structure of (I), viewed along b. X···CN contacts are shown as dashed lines.
[Figure 3] Fig. 3. The structure of (II), viewed normal to (100). X···CN contacts are shown as dashed lines.
(I) 2-chlorobenzonitrile top
Crystal data top
C7H4ClNF(000) = 1120
Mr = 137.56Dx = 1.432 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 18.999 (4) ÅCell parameters from 3716 reflections
b = 3.8410 (8) Åθ = 2.5–26.7°
c = 41.690 (8) ŵ = 0.49 mm−1
β = 122.96 (3)°T = 174 K
V = 2552.7 (12) Å3Needle, colourless
Z = 160.40 × 0.10 × 0.10 mm
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer		5797 independent reflections
Radiation source: fine-focus sealed tube4186 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.052
ω scansθmax = 27.5°, θmin = 1.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003; Blessing, 1995)		h = −24→24
Tmin = 0.91, Tmax = 0.95k = −4→4
27524 measured reflectionsl = −54→54
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.102H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.041P)2 + 1.039P]
where P = (Fo2 + 2Fc2)/3
5797 reflections(Δ/σ)max = 0.001
325 parametersΔρmax = 0.26 e Å−3
0 restraintsΔρmin = −0.32 e Å−3
Crystal data top
C7H4ClNV = 2552.7 (12) Å3
Mr = 137.56Z = 16
Monoclinic, P21/cMo Kα radiation
a = 18.999 (4) ŵ = 0.49 mm−1
b = 3.8410 (8) ÅT = 174 K
c = 41.690 (8) Å0.40 × 0.10 × 0.10 mm
β = 122.96 (3)°
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer		5797 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003; Blessing, 1995)		4186 reflections with I > 2σ(I)
Tmin = 0.91, Tmax = 0.95Rint = 0.052
27524 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.102H-atom parameters constrained
S = 1.03Δρmax = 0.26 e Å−3
5797 reflectionsΔρmin = −0.32 e Å−3
325 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C1A0.31201 (13)−0.3242 (6)0.01648 (6)0.0294 (5)
C2A0.37756 (13)−0.3054 (6)0.05488 (6)0.0279 (5)
C3A0.45624 (13)−0.4274 (6)0.06649 (6)0.0339 (5)
H3A0.5010−0.41110.09260.041*
C4A0.46964 (14)−0.5742 (6)0.03984 (7)0.0374 (5)
H4A0.5236−0.66130.04790.045*
C5A0.40538 (14)−0.5949 (6)0.00178 (7)0.0373 (5)
H5A0.4152−0.6951−0.01630.045*
C6A0.32659 (14)−0.4694 (6)−0.00999 (6)0.0353 (5)
H6A0.2824−0.4823−0.03620.042*
C7A0.22949 (14)−0.1918 (6)0.00394 (6)0.0357 (5)
N8A0.16474 (13)−0.0856 (7)−0.00629 (6)0.0548 (6)
Cl9A0.36008 (4)−0.13311 (16)0.088429 (16)0.03917 (15)
C1B0.18169 (12)0.3180 (6)0.10952 (6)0.0289 (5)
C2B0.11944 (13)0.3475 (6)0.11744 (6)0.0303 (5)
C3B0.04242 (13)0.4904 (6)0.09073 (6)0.0362 (5)
H3B−0.00020.50730.09600.043*
C4B0.02760 (14)0.6088 (6)0.05625 (6)0.0388 (6)
H4B−0.02520.70900.03800.047*
C5B0.08905 (14)0.5822 (6)0.04820 (6)0.0377 (5)
H5B0.07850.66480.02450.045*
C6B0.16574 (13)0.4356 (6)0.07462 (6)0.0346 (5)
H6B0.20770.41510.06890.042*
C7B0.26237 (14)0.1656 (6)0.13723 (6)0.0327 (5)
N8B0.32562 (12)0.0410 (6)0.15826 (6)0.0460 (5)
Cl9B0.13878 (4)0.20881 (18)0.161085 (17)0.04416 (17)
C1C0.32918 (12)0.7121 (6)0.27157 (6)0.0274 (5)
C2C0.39284 (13)0.7400 (6)0.31023 (6)0.0283 (5)
C3C0.47007 (13)0.8745 (6)0.32110 (6)0.0324 (5)
H3C0.51350.88900.34740.039*
C4C0.48405 (13)0.9885 (6)0.29351 (6)0.0338 (5)
H4C0.53701.08450.30100.041*
C5C0.42156 (13)0.9635 (6)0.25512 (6)0.0332 (5)
H5C0.43171.04120.23640.040*
C6C0.34437 (13)0.8257 (6)0.24406 (6)0.0326 (5)
H6C0.30150.80820.21770.039*
C7C0.24798 (14)0.5687 (6)0.25980 (6)0.0336 (5)
N8C0.18396 (12)0.4559 (7)0.25034 (6)0.0516 (6)
Cl9C0.37437 (3)0.60385 (16)0.344633 (15)0.03758 (15)
C1D0.18629 (13)0.2610 (6)0.35901 (6)0.0291 (5)
C2D0.11674 (13)0.2795 (6)0.36207 (6)0.0289 (5)
C3D0.03917 (13)0.1641 (6)0.33246 (6)0.0345 (5)
H3D−0.00820.17810.33450.041*
C4D0.03116 (14)0.0281 (6)0.29986 (6)0.0358 (5)
H4D−0.0220−0.05290.27960.043*
C5D0.09928 (14)0.0086 (6)0.29645 (6)0.0363 (5)
H5D0.0930−0.08480.27390.044*
C6D0.17698 (13)0.1256 (6)0.32598 (6)0.0327 (5)
H6D0.22400.11330.32370.039*
C7D0.26761 (14)0.3845 (6)0.38975 (6)0.0334 (5)
N8D0.33197 (13)0.4831 (6)0.41312 (6)0.0531 (6)
Cl9D0.12838 (4)0.44516 (16)0.403487 (16)0.04135 (16)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C1A0.0261 (11)0.0290 (12)0.0336 (12)0.0000 (9)0.0165 (10)0.0059 (9)
C2A0.0308 (11)0.0261 (12)0.0306 (11)−0.0013 (9)0.0192 (10)0.0038 (9)
C3A0.0270 (11)0.0360 (13)0.0325 (12)0.0011 (10)0.0122 (10)0.0067 (10)
C4A0.0334 (12)0.0332 (13)0.0499 (14)0.0054 (10)0.0255 (11)0.0083 (11)
C5A0.0457 (14)0.0337 (13)0.0441 (14)−0.0047 (11)0.0318 (12)−0.0033 (11)
C6A0.0365 (12)0.0371 (13)0.0317 (12)−0.0057 (11)0.0182 (10)0.0004 (10)
C7A0.0336 (13)0.0374 (14)0.0335 (12)0.0016 (11)0.0166 (11)0.0070 (10)
N8A0.0356 (12)0.0662 (16)0.0594 (14)0.0093 (11)0.0237 (11)0.0170 (12)
Cl9A0.0429 (3)0.0416 (3)0.0380 (3)0.0002 (3)0.0252 (3)−0.0023 (3)
C1B0.0245 (11)0.0285 (12)0.0294 (11)−0.0018 (9)0.0118 (9)−0.0039 (9)
C2B0.0317 (12)0.0294 (12)0.0291 (11)−0.0011 (9)0.0162 (10)−0.0032 (9)
C3B0.0288 (12)0.0381 (14)0.0402 (13)0.0023 (10)0.0179 (10)−0.0058 (11)
C4B0.0311 (12)0.0348 (14)0.0348 (13)0.0032 (10)0.0077 (10)−0.0011 (11)
C5B0.0395 (13)0.0359 (13)0.0281 (12)−0.0055 (11)0.0122 (10)0.0006 (10)
C6B0.0307 (12)0.0382 (14)0.0337 (12)−0.0067 (10)0.0167 (10)−0.0033 (10)
C7B0.0311 (12)0.0349 (13)0.0319 (12)−0.0013 (10)0.0169 (10)−0.0020 (10)
N8B0.0338 (11)0.0536 (14)0.0427 (12)0.0058 (10)0.0156 (10)0.0021 (11)
Cl9B0.0469 (4)0.0545 (4)0.0371 (3)0.0062 (3)0.0267 (3)0.0043 (3)
C1C0.0243 (11)0.0267 (12)0.0316 (11)0.0026 (9)0.0154 (9)0.0004 (9)
C2C0.0317 (12)0.0262 (12)0.0306 (11)0.0030 (9)0.0192 (10)0.0009 (9)
C3C0.0298 (12)0.0327 (13)0.0320 (12)−0.0012 (10)0.0150 (10)−0.0021 (10)
C4C0.0281 (11)0.0290 (12)0.0480 (14)0.0005 (10)0.0231 (11)−0.0010 (11)
C5C0.0365 (12)0.0319 (13)0.0403 (13)0.0042 (10)0.0269 (11)0.0045 (10)
C6C0.0316 (12)0.0357 (13)0.0297 (12)0.0042 (10)0.0162 (10)0.0020 (10)
C7C0.0299 (12)0.0422 (14)0.0287 (12)0.0004 (11)0.0159 (10)−0.0001 (10)
N8C0.0337 (12)0.0751 (17)0.0447 (12)−0.0089 (12)0.0205 (10)−0.0036 (12)
Cl9C0.0388 (3)0.0443 (3)0.0323 (3)−0.0041 (3)0.0210 (3)0.0016 (3)
C1D0.0275 (11)0.0267 (12)0.0286 (11)−0.0005 (9)0.0124 (9)0.0056 (9)
C2D0.0337 (12)0.0235 (11)0.0301 (11)0.0005 (9)0.0177 (10)0.0027 (9)
C3D0.0282 (11)0.0328 (13)0.0405 (13)0.0010 (10)0.0173 (10)0.0074 (10)
C4D0.0295 (12)0.0320 (13)0.0327 (12)−0.0037 (10)0.0084 (10)0.0042 (10)
C5D0.0428 (14)0.0312 (13)0.0291 (12)−0.0006 (11)0.0158 (11)0.0009 (10)
C6D0.0327 (12)0.0322 (13)0.0354 (12)0.0028 (10)0.0199 (10)0.0037 (10)
C7D0.0335 (12)0.0372 (13)0.0306 (12)−0.0029 (11)0.0182 (11)0.0030 (10)
N8D0.0400 (12)0.0689 (16)0.0414 (12)−0.0165 (12)0.0163 (10)−0.0023 (12)
Cl9D0.0473 (3)0.0436 (4)0.0404 (3)−0.0029 (3)0.0285 (3)−0.0036 (3)
Geometric parameters (Å, º) top
C1A—C6A1.392 (3)C1C—C2C1.397 (3)
C1A—C2A1.396 (3)C1C—C6C1.396 (3)
C1A—C7A1.448 (3)C1C—C7C1.449 (3)
C2A—C3A1.379 (3)C2C—C3C1.379 (3)
C2A—Cl9A1.735 (2)C2C—Cl9C1.732 (2)
C3A—C4A1.388 (3)C3C—C4C1.385 (3)
C3A—H3A0.9500C3C—H3C0.9500
C4A—C5A1.381 (3)C4C—C5C1.383 (3)
C4A—H4A0.9500C4C—H4C0.9500
C5A—C6A1.384 (3)C5C—C6C1.381 (3)
C5A—H5A0.9500C5C—H5C0.9500
C6A—H6A0.9500C6C—H6C0.9500
C7A—N8A1.136 (3)C7C—N8C1.141 (3)
C1B—C6B1.390 (3)C1D—C6D1.390 (3)
C1B—C2B1.395 (3)C1D—C2D1.397 (3)
C1B—C7B1.449 (3)C1D—C7D1.449 (3)
C2B—C3B1.382 (3)C2D—C3D1.383 (3)
C2B—Cl9B1.733 (2)C2D—Cl9D1.738 (2)
C3B—C4B1.383 (3)C3D—C4D1.385 (3)
C3B—H3B0.9500C3D—H3D0.9500
C4B—C5B1.383 (3)C4D—C5D1.379 (3)
C4B—H4B0.9500C4D—H4D0.9500
C5B—C6B1.381 (3)C5D—C6D1.385 (3)
C5B—H5B0.9500C5D—H5D0.9500
C6B—H6B0.9500C6D—H6D0.9500
C7B—N8B1.138 (3)C7D—N8D1.137 (3)
C6A—C1A—C2A119.44 (19)C2C—C1C—C6C119.19 (19)
C6A—C1A—C7A119.8 (2)C2C—C1C—C7C120.92 (19)
C2A—C1A—C7A120.7 (2)C6C—C1C—C7C119.89 (19)
C3A—C2A—C1A120.3 (2)C3C—C2C—C1C120.4 (2)
C3A—C2A—Cl9A119.54 (17)C3C—C2C—Cl9C119.98 (17)
C1A—C2A—Cl9A120.10 (16)C1C—C2C—Cl9C119.60 (16)
C2A—C3A—C4A119.6 (2)C2C—C3C—C4C119.7 (2)
C2A—C3A—H3A120.2C2C—C3C—H3C120.1
C4A—C3A—H3A120.2C4C—C3C—H3C120.1
C5A—C4A—C3A120.7 (2)C5C—C4C—C3C120.5 (2)
C5A—C4A—H4A119.6C5C—C4C—H4C119.7
C3A—C4A—H4A119.6C3C—C4C—H4C119.7
C4A—C5A—C6A119.8 (2)C6C—C5C—C4C120.0 (2)
C4A—C5A—H5A120.1C6C—C5C—H5C120.0
C6A—C5A—H5A120.1C4C—C5C—H5C120.0
C5A—C6A—C1A120.1 (2)C5C—C6C—C1C120.1 (2)
C5A—C6A—H6A119.9C5C—C6C—H6C119.9
C1A—C6A—H6A119.9C1C—C6C—H6C119.9
N8A—C7A—C1A179.1 (3)N8C—C7C—C1C179.6 (2)
C6B—C1B—C2B119.4 (2)C6D—C1D—C2D119.5 (2)
C6B—C1B—C7B119.96 (19)C6D—C1D—C7D119.89 (19)
C2B—C1B—C7B120.6 (2)C2D—C1D—C7D120.6 (2)
C3B—C2B—C1B120.3 (2)C3D—C2D—C1D120.3 (2)
C3B—C2B—Cl9B119.67 (17)C3D—C2D—Cl9D120.13 (17)
C1B—C2B—Cl9B120.07 (17)C1D—C2D—Cl9D119.62 (17)
C4B—C3B—C2B119.7 (2)C2D—C3D—C4D119.4 (2)
C4B—C3B—H3B120.1C2D—C3D—H3D120.3
C2B—C3B—H3B120.1C4D—C3D—H3D120.3
C3B—C4B—C5B120.4 (2)C5D—C4D—C3D120.9 (2)
C3B—C4B—H4B119.8C5D—C4D—H4D119.6
C5B—C4B—H4B119.8C3D—C4D—H4D119.6
C4B—C5B—C6B120.0 (2)C4D—C5D—C6D119.8 (2)
C4B—C5B—H5B120.0C4D—C5D—H5D120.1
C6B—C5B—H5B120.0C6D—C5D—H5D120.1
C5B—C6B—C1B120.1 (2)C5D—C6D—C1D120.1 (2)
C5B—C6B—H6B119.9C5D—C6D—H6D120.0
C1B—C6B—H6B119.9C1D—C6D—H6D120.0
N8B—C7B—C1B178.2 (3)N8D—C7D—C1D178.1 (2)
C6A—C1A—C2A—C3A0.4 (3)C6C—C1C—C2C—C3C−0.7 (3)
C7A—C1A—C2A—C3A−179.0 (2)C7C—C1C—C2C—C3C179.5 (2)
C6A—C1A—C2A—Cl9A−178.76 (17)C6C—C1C—C2C—Cl9C179.36 (17)
C7A—C1A—C2A—Cl9A1.8 (3)C7C—C1C—C2C—Cl9C−0.4 (3)
C1A—C2A—C3A—C4A−1.0 (3)C1C—C2C—C3C—C4C1.2 (3)
Cl9A—C2A—C3A—C4A178.21 (17)Cl9C—C2C—C3C—C4C−178.90 (17)
C2A—C3A—C4A—C5A0.9 (3)C2C—C3C—C4C—C5C−1.0 (3)
C3A—C4A—C5A—C6A−0.2 (4)C3C—C4C—C5C—C6C0.3 (3)
C4A—C5A—C6A—C1A−0.3 (3)C4C—C5C—C6C—C1C0.1 (3)
C2A—C1A—C6A—C5A0.2 (3)C2C—C1C—C6C—C5C0.0 (3)
C7A—C1A—C6A—C5A179.7 (2)C7C—C1C—C6C—C5C179.8 (2)
C6B—C1B—C2B—C3B0.4 (3)C6D—C1D—C2D—C3D0.0 (3)
C7B—C1B—C2B—C3B−179.4 (2)C7D—C1D—C2D—C3D179.4 (2)
C6B—C1B—C2B—Cl9B−178.95 (17)C6D—C1D—C2D—Cl9D179.44 (17)
C7B—C1B—C2B—Cl9B1.2 (3)C7D—C1D—C2D—Cl9D−1.1 (3)
C1B—C2B—C3B—C4B−0.9 (3)C1D—C2D—C3D—C4D0.4 (3)
Cl9B—C2B—C3B—C4B178.47 (18)Cl9D—C2D—C3D—C4D−179.05 (17)
C2B—C3B—C4B—C5B0.6 (4)C2D—C3D—C4D—C5D−0.5 (3)
C3B—C4B—C5B—C6B0.2 (4)C3D—C4D—C5D—C6D0.1 (3)
C4B—C5B—C6B—C1B−0.7 (4)C4D—C5D—C6D—C1D0.2 (3)
C2B—C1B—C6B—C5B0.4 (3)C2D—C1D—C6D—C5D−0.3 (3)
C7B—C1B—C6B—C5B−179.8 (2)C7D—C1D—C6D—C5D−179.7 (2)
(II) 2-bromobenzonitrile top
Crystal data top
C7H4BrNF(000) = 352
Mr = 182.02Dx = 1.824 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 3.9247 (10) ÅCell parameters from 3997 reflections
b = 10.348 (3) Åθ = 2.3–27.4°
c = 16.387 (4) ŵ = 6.10 mm−1
β = 95.011 (4)°T = 174 K
V = 663.0 (3) Å3Prism, colourless
Z = 40.40 × 0.30 × 0.20 mm
Data collection top
Bruker SMART 1K area-detector
diffractometer		1518 independent reflections
Radiation source: fine-focus sealed tube1301 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.027
ω scansθmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003; Blessing, 1995)		h = −5→5
Tmin = 0.15, Tmax = 0.30k = −13→13
7557 measured reflectionsl = −21→21
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)] = 0.022H-atom parameters constrained
wR(F2) = 0.051 w = 1/[σ2(Fo2) + (0.019P)2 + 0.386P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.001
1518 reflectionsΔρmax = 0.31 e Å−3
83 parametersΔρmin = −0.29 e Å−3
0 restraintsExtinction correction: SHELXTL (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0049 (8)
Crystal data top
C7H4BrNV = 663.0 (3) Å3
Mr = 182.02Z = 4
Monoclinic, P21/cMo Kα radiation
a = 3.9247 (10) ŵ = 6.10 mm−1
b = 10.348 (3) ÅT = 174 K
c = 16.387 (4) Å0.40 × 0.30 × 0.20 mm
β = 95.011 (4)°
Data collection top
Bruker SMART 1K area-detector
diffractometer		1518 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003; Blessing, 1995)		1301 reflections with I > 2σ(I)
Tmin = 0.15, Tmax = 0.30Rint = 0.027
7557 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0220 restraints
wR(F2) = 0.051H-atom parameters constrained
S = 1.07Δρmax = 0.31 e Å−3
1518 reflectionsΔρmin = −0.29 e Å−3
83 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.1563 (5)0.25777 (18)0.18031 (12)0.0262 (4)
C20.2026 (5)0.34281 (18)0.11627 (12)0.0250 (4)
C30.0904 (5)0.3110 (2)0.03661 (12)0.0309 (4)
H30.12490.3688−0.00690.037*
C4−0.0736 (6)0.1934 (2)0.02070 (13)0.0348 (5)
H4−0.15470.1717−0.03390.042*
C5−0.1196 (5)0.1079 (2)0.08341 (14)0.0346 (5)
H5−0.23090.02770.07180.042*
C6−0.0033 (5)0.1391 (2)0.16325 (13)0.0321 (5)
H6−0.03230.07980.20630.038*
C70.2738 (6)0.29029 (19)0.26484 (13)0.0321 (5)
N80.3638 (6)0.3131 (2)0.32969 (12)0.0495 (5)
Br90.40752 (5)0.506505 (18)0.138088 (13)0.03229 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0263 (10)0.0259 (9)0.0267 (10)0.0059 (8)0.0036 (8)−0.0001 (7)
C20.0203 (9)0.0245 (9)0.0302 (10)0.0032 (7)0.0029 (7)−0.0008 (7)
C30.0326 (11)0.0341 (11)0.0263 (10)0.0070 (9)0.0037 (8)0.0038 (8)
C40.0349 (12)0.0404 (12)0.0283 (11)0.0046 (9)−0.0020 (8)−0.0075 (9)
C50.0320 (12)0.0284 (11)0.0437 (13)−0.0003 (9)0.0049 (9)−0.0063 (9)
C60.0354 (11)0.0278 (10)0.0342 (11)0.0016 (9)0.0103 (9)0.0029 (8)
C70.0391 (12)0.0237 (10)0.0334 (12)0.0058 (8)0.0031 (9)0.0033 (8)
N80.0698 (15)0.0421 (11)0.0352 (12)0.0114 (11)−0.0039 (10)0.0014 (9)
Br90.03043 (13)0.02811 (13)0.03863 (14)−0.00228 (9)0.00474 (8)0.00046 (9)
Geometric parameters (Å, º) top
C1—C21.394 (3)C4—C51.379 (3)
C1—C61.396 (3)C4—H40.9500
C1—C71.461 (3)C5—C61.386 (3)
C2—C31.381 (3)C5—H50.9500
C2—Br91.896 (2)C6—H60.9500
C3—C41.390 (3)C7—N81.115 (3)
C3—H30.9500
C2—C1—C6119.37 (18)C5—C4—H4119.7
C2—C1—C7121.17 (18)C3—C4—H4119.7
C6—C1—C7119.46 (18)C4—C5—C6120.0 (2)
C3—C2—C1120.63 (18)C4—C5—H5120.0
C3—C2—Br9119.12 (15)C6—C5—H5120.0
C1—C2—Br9120.22 (14)C5—C6—C1119.94 (19)
C2—C3—C4119.36 (19)C5—C6—H6120.0
C2—C3—H3120.3C1—C6—H6120.0
C4—C3—H3120.3N8—C7—C1178.9 (2)
C5—C4—C3120.65 (19)
C6—C1—C2—C30.4 (3)C2—C3—C4—C5−1.1 (3)
C7—C1—C2—C3180.00 (19)C3—C4—C5—C60.3 (3)
C6—C1—C2—Br9178.29 (15)C4—C5—C6—C10.8 (3)
C7—C1—C2—Br9−2.1 (3)C2—C1—C6—C5−1.2 (3)
C1—C2—C3—C40.7 (3)C7—C1—C6—C5179.21 (19)
Br9—C2—C3—C4−177.20 (15)

Experimental details

(I)(II)
Crystal data
Chemical formulaC7H4ClNC7H4BrN
Mr137.56182.02
Crystal system, space groupMonoclinic, P21/cMonoclinic, P21/c
Temperature (K)174174
a, b, c (Å)18.999 (4), 3.8410 (8), 41.690 (8)3.9247 (10), 10.348 (3), 16.387 (4)
β (°) 122.96 (3) 95.011 (4)
V (Å3)2552.7 (12)663.0 (3)
Z164
Radiation typeMo KαMo Kα
µ (mm−1)0.496.10
Crystal size (mm)0.40 × 0.10 × 0.100.40 × 0.30 × 0.20
Data collection
DiffractometerBruker SMART 1K CCD area-detectorBruker SMART 1K area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003; Blessing, 1995)		Multi-scan
(SADABS; Sheldrick, 2003; Blessing, 1995)
Tmin, Tmax0.91, 0.950.15, 0.30
No. of measured, independent and
observed [I > 2σ(I)] reflections		27524, 5797, 4186 7557, 1518, 1301
Rint0.0520.027
(sin θ/λ)max (Å−1)0.6500.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.102, 1.03 0.022, 0.051, 1.07
No. of reflections57971518
No. of parameters32583
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.26, −0.320.31, −0.29

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL.

Table 1. A comparison of the geometry (Å, °) of the X···N contacts in compounds (I) and (II). For comparison, the van der Waals contact distances (Bondi, 1964; Rowland & Taylor, 1996) are Cl···N = 3.30 Å and Br···N = 3.40 Å. top
X···NC-X···NX···NX···N≡C
(I)Cl9A···N8B169.0 (2)3.380 (2)92.2 (2)
Cl9B···N8C146.2 (2)3.466 (2)94.0 (2)
Cl9C···N8D170.2 (2)3.394 (2)87.8 (2)
Cl9D···N8Ai167.1 (2)3.477 (2)89.9 (2)
(II)Br9···N8ii170.4 (2)3.327 (2)90.5 (2)
Symmetry codes: (i) x, 1/2-y, 1/2+z; (ii) 1-x, 1/2+y, 1/2-z.
Table 2. A comparison of the geometries (Å, °) of the C–H···X interactions in (I) and (II), where X = N, Cl or Br. For comparison, the van der Waals contact distances (Bondi, 1964; Rowland & Taylor, 1996=) are Cl···N = 3.30 Å and Br···N = 3.40 Å. top
HXC-H···XH···XH···X-CC···X
Chlorobenzonitrile
H3ACl9Ci1383.03973.788 (2)
H3ACl9Cii1443.101193.908 (2)
H4AN8Dii1612.681643.592 (3)
H5AN8Diii1412.711213.496 (3)
H6ACl9Diii1433.17983.969 (2)
H3BCl9Div1343.261243.978 (2)
H3BCl9Dv1482.97983.807 (2)
H4BN8Avi1622.661653.573 (3)
H5BN8Avii1402.751203.523 (3)
H6BCl9Avii1333.08983.794 (2)
H3CCl9Aviii1363.161223.898 (2)
H3CCl9Aix1453.05943.869 (2)
H4CN8Bix1552.821663.703 (3)
H5CN8Bvii1292.741353.422 (3)
H6CCl9Bvii1363.091213.832 (2)
H3DCl9Biv1423.15993.944 (2)
H3DCl9Bv1453.291214.107 (2)
H4DN8Civ1462.621583.443 (3)
H5DN8Cx1402.991113.763 (3)
H6DCl9Cxi1393.17983.939 (2)
H6DCl9C1353.121213.856 (2)
Bromobenzonitrile
H3Br9vi1303.14903.822 (2)
H3Br9xii1523.221194.078 (2)
H4N8xiii1522.801553.670 (3)
H5N8iv1332.821313.535 (3)
H6Br9iv1493.15983.987 (2)
Symmetry codes: (i) 1-x, -3/2+y, 1/2-z; (ii) 1-x, -1/2+y, 1/2-z; (iii) x, -1/2-y, -1/2+z; (iv) -x, -1/2+y, 1/2-z;; (v) -x, 1/2+y, 1/2-z; (vi) -x, 1-y, -z; (vii) x, 1+y, z; (viii) 1-x, 1/2+y, 1/2-z; (ix) 1-x, 3/2+y, 3/2-z; (x) x, -1+y, z; (xi)x, -1+y, z; (xii) 1-x, 1-y, -z; (xiii) -1+x, 1/2-y, -1/2+z.
Pseudo-conversions for the four independent molecules of (I) top
conversionpseudo-symmetry elementapproximate translationaverage discrepancy between corresponding atoms
A→Bscrew axis parallel to cc/80.16 Å
A→Cc glide perpendicular to bc/40.14 Å
A→Dc glide perpendicular to a*3c/80.13 Å
B→Cc glide perpendicular to a*c/80.06 Å
B→Dc glide perpendicular to bc/40.23 Å
C→Dscrew axis parallel to cc/80.19 Å
 

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