Planar packing of tetrachlorodicyanobenzenes. II

Britton, D.

doi:10.1107/S0108768108035234

Planar packing of tetrachlorodicyanobenzenes. II

Equimolar mixtures of ortho- and meta-, or ortho- and para-, or meta- and para-tetrachlorodicyanobenzene, C₆Cl₄(CN)₂, form structures with disordered layers containing both kinds of molecules in rhombohedral or pseudo-rhombohedral cells. These structures are similar to the structure of the rhombohedral form of the meta isomer. The guiding force appears to be an intermolecular synthon, in which a nitrile group in one molecule interacts with Cl atoms in two adjacent molecules with N

Cl distances of approximately 3.1 Å.

Keywords: planar packing; disorder; polymorphism; synthons.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768108035234/bs5066sup1.cif Contains datablocks M-II, O-P, M-P-II
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768108035234/bs5066M-IIsup2.hkl Contains datablock M-II
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768108035234/bs5066O-Psup3.hkl Contains datablock O-P
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768108035234/bs5066M-P-IIsup4.hkl Contains datablock M-P-II

CCDC references: 722681; 722682; 722683

Computing details top

For all 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

(M-II) m-tetrachlorodicyanobenzene polymorph II top

Crystal data top

C₈Cl₄N₂	F(000) = 390
M_r = 265.90	D_x = 1.812 Mg m⁻³
Rhombohedral, R3m:H	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -R 3 2"	Cell parameters from 2211 reflections
a = 9.2171 (14) Å	θ = 3.3–27.4°
c = 9.935 (2) Å	µ = 1.17 mm⁻¹
α = 90°	T = 173 K
γ = 120°	Prism, colorless
V = 731.0 (2) Å³	0.50 × 0.35 × 0.25 mm
Z = 3

Data collection top

Bruker 1X CCD area detector duiffractometer	226 independent reflections
Radiation source: fine-focus sealed tube	216 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ω scans	θ_max = 27.5°, θ_min = 3.3°
Absorption correction: multi-scan SADABS; Sheldrick, 1996; Blessing, 1995	h = −11→11
T_min = 0.64, T_max = 0.75	k = −11→11
2730 measured reflections	l = −12→12

Refinement top

Refinement on F²	4 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F² > 2σ(F²)] = 0.031	Secondary atom site location: difference Fourier map
wR(F²) = 0.086	w = 1/[σ²(F_o²) + (0.045P)² + 0.495P] where P = (F_o² + 2F_c²)/3
S = 1.24	(Δ/σ)_max = 0.001
226 reflections	Δρ_max = 0.21 e Å⁻³
21 parameters	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₈Cl₄N₂	V = 731.0 (2) Å³
M_r = 265.90	Z = 3
Rhombohedral, R3m:H	Mo Kα radiation
a = 9.2171 (14) Å	µ = 1.17 mm⁻¹
c = 9.935 (2) Å	T = 173 K
α = 90°	0.50 × 0.35 × 0.25 mm
γ = 120°

Data collection top

Bruker 1X CCD area detector duiffractometer	226 independent reflections
Absorption correction: multi-scan SADABS; Sheldrick, 1996; Blessing, 1995	216 reflections with I > 2σ(I)
T_min = 0.64, T_max = 0.75	R_int = 0.031
2730 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	21 parameters
wR(F²) = 0.086	4 restraints
S = 1.24	Δρ_max = 0.21 e Å⁻³
226 reflections	Δρ_min = −0.27 e Å⁻³

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.17335 (10)	0.08667 (5)	−0.00031 (18)	0.0379 (5)
Cl1	0.38779 (10)	0.19390 (5)	−0.00679 (15)	0.0506 (4)	0.66667
C2	0.35431 (12)	0.17715 (6)	0.0037 (16)	0.0506 (4)	0.33333
N1	0.49728 (10)	0.24864 (5)	0.0077 (7)	0.0534 (14)	0.33333

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0381 (10)	0.0451 (8)	0.0282 (8)	0.0191 (5)	0.0003 (7)	0.0002 (4)
Cl1	0.0343 (5)	0.0629 (5)	0.0450 (6)	0.0172 (3)	0.0017 (5)	0.0008 (2)
C2	0.0343 (5)	0.0629 (5)	0.0450 (6)	0.0172 (3)	0.0017 (5)	0.0008 (2)
N1	0.044 (4)	0.056 (3)	0.056 (4)	0.0218 (19)	0.001 (3)	0.0006 (14)

Geometric parameters (Å, º) top

C1—C1ⁱ	1.3837 (8)	C1—Cl1	1.7130 (3)
C1—C1ⁱⁱ	1.3837 (8)	Cl1—N1	0.8858 (10)
C1—C2	1.4450 (2)	C2—N1	1.1420 (2)

C1ⁱ—C1—C1ⁱⁱ	119.998 (3)	C1ⁱ—C1—Cl1	119.987 (7)
C1ⁱ—C1—C2	119.979 (15)	C1ⁱⁱ—C1—Cl1	119.988 (8)
C1ⁱⁱ—C1—C2	119.980 (15)	N1—C2—C1	179.5 (14)

Symmetry codes: (i) y, −x+y, −z; (ii) x−y, x, −z.

(O-P) o-tetrachlordicyanobenzene/p-tetrachlordicyanobenzene 1/1 top

Crystal data top

C₈Cl₄N₂	D_x = 1.796 Mg m⁻³
M_r = 265.90	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, R3m:H	Cell parameters from 1173 reflections
Hall symbol: - R 3 2"	θ = 3.3–25.0°
a = 9.2473 (8) Å	µ = 1.16 mm⁻¹
c = 9.9590 (13) Å	T = 173 K
V = 737.52 (13) Å³	Prism, colorless
Z = 3	0.45 × 0.35 × 0.30 mm
F(000) = 390

Data collection top

Bruker 1K area CCD area detector diffractometer	176 independent reflections
Radiation source: fine-focus sealed tube	167 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
ω scans	θ_max = 25.0°, θ_min = 3.3°
Absorption correction: multi-scan SADABS; Sheldrick, 1996; Blessing, 1995	h = −8→10
T_min = 0.64, T_max = 0.71	k = −10→10
1227 measured reflections	l = −11→9

Refinement top

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)] = 0.029	w = 1/[σ²(F_o²) + (0.058P)² + 0.025P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.086	(Δ/σ)_max = 0.001
S = 1.28	Δρ_max = 0.22 e Å⁻³
176 reflections	Δρ_min = −0.22 e Å⁻³
22 parameters	Extinction correction: SHELXTL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
4 restraints	Extinction coefficient: 0.036 (10)

Crystal data top

C₈Cl₄N₂	Z = 3
M_r = 265.90	Mo Kα radiation
Hexagonal, R3m:H	µ = 1.16 mm⁻¹
a = 9.2473 (8) Å	T = 173 K
c = 9.9590 (13) Å	0.45 × 0.35 × 0.30 mm
V = 737.52 (13) Å³

Data collection top

Bruker 1K area CCD area detector diffractometer	176 independent reflections
Absorption correction: multi-scan SADABS; Sheldrick, 1996; Blessing, 1995	167 reflections with I > 2σ(I)
T_min = 0.64, T_max = 0.71	R_int = 0.038
1227 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	22 parameters
wR(F²) = 0.086	4 restraints
S = 1.28	Δρ_max = 0.22 e Å⁻³
176 reflections	Δρ_min = −0.22 e Å⁻³

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl1	0.38797 (10)	0.19398 (5)	−0.00711 (11)	0.0536 (6)	0.66667
C1	0.17423 (10)	0.08712 (5)	−0.00036 (19)	0.0375 (7)
C2	0.35453 (12)	0.17726 (6)	0.0053 (11)	0.0536 (6)	0.33333
N1	0.49708 (11)	0.24854 (5)	0.0083 (6)	0.0537 (14)	0.33333

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0355 (7)	0.0698 (7)	0.0439 (8)	0.0178 (4)	0.0019 (4)	0.00093 (18)
C1	0.0385 (10)	0.0446 (10)	0.0272 (10)	0.0193 (5)	0.0003 (7)	0.0002 (3)
C2	0.0355 (7)	0.0698 (7)	0.0439 (8)	0.0178 (4)	0.0019 (4)	0.00093 (18)
N1	0.044 (3)	0.058 (2)	0.054 (4)	0.0218 (17)	−0.003 (3)	−0.0017 (13)

Geometric parameters (Å, º) top

Cl1—C1	1.7130 (2)	C1—C2	1.4450 (2)
C1—C1ⁱ	1.3953 (8)	C2—N1	1.1420 (1)
C1—C1ⁱⁱ	1.3953 (8)

C1ⁱ—C1—C1ⁱⁱ	119.997 (3)	C1ⁱ—C1—Cl1	119.988 (8)
C1ⁱ—C1—C2	119.961 (16)	C1ⁱⁱ—C1—Cl1	119.987 (8)
C1ⁱⁱ—C1—C2	119.960 (16)	N1—C2—C1	179.2 (10)

Symmetry codes: (i) y, −x+y, −z; (ii) x−y, x, −z.

(M-P-II) m-tetrachlorodicyanobenzene/p- tetrachlorodicyanobenzene 1/1 polymorpth II top

Crystal data top

C₈Cl₄N₂	F(000) = 260
M_r = 265.90	D_x = 1.812 Mg m⁻³
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 2359 reflections
a = 7.9237 (9) Å	θ = 3.1–27.5°
b = 9.4546 (11) Å	µ = 1.17 mm⁻¹
c = 6.5157 (7) Å	T = 173 K
β = 93.106 (2)°	Prism, colorless
V = 487.41 (9) Å³	0.35 × 0.35 × 0.30 mm
Z = 2

Data collection top

BRUKER 1K CCD area detector diffractometer	589 independent reflections
Radiation source: fine-focus sealed tube	562 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ω scans	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan SADABS; Sheldrick, 1996; Blessing, 1995	h = −10→10
T_min = 0.58, T_max = 0.70	k = −12→12
2825 measured reflections	l = −8→8

Refinement top

Refinement on F²	9 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F² > 2σ(F²)] = 0.031	Secondary atom site location: difference Fourier map
wR(F²) = 0.080	w = 1/[σ²(F_o²) + (0.039P)² + 0.594P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
589 reflections	Δρ_max = 0.40 e Å⁻³
53 parameters	Δρ_min = −0.46 e Å⁻³

Crystal data top

C₈Cl₄N₂	V = 487.41 (9) Å³
M_r = 265.90	Z = 2
Monoclinic, C2/m	Mo Kα radiation
a = 7.9237 (9) Å	µ = 1.17 mm⁻¹
b = 9.4546 (11) Å	T = 173 K
c = 6.5157 (7) Å	0.35 × 0.35 × 0.30 mm
β = 93.106 (2)°

Data collection top

BRUKER 1K CCD area detector diffractometer	589 independent reflections
Absorption correction: multi-scan SADABS; Sheldrick, 1996; Blessing, 1995	562 reflections with I > 2σ(I)
T_min = 0.58, T_max = 0.70	R_int = 0.016
2825 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	53 parameters
wR(F²) = 0.080	9 restraints
S = 1.08	Δρ_max = 0.40 e Å⁻³
589 reflections	Δρ_min = −0.46 e Å⁻³

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl2	0.59393 (11)	0.21874 (6)	0.28866 (9)	0.0420 (2)	0.7852 (19)
Cl1	0.7036 (3)	0.5000	0.1082 (3)	0.0525 (6)	0.430 (4)
C1	0.58745 (19)	0.5000	0.3224 (2)	0.0328 (5)
C2	0.54348 (19)	0.37247 (10)	0.4102 (2)	0.0326 (4)
N1	0.7474 (3)	0.5000	−0.0133 (3)	0.0434 (10)	0.570 (4)
N2	0.6256 (6)	0.1252 (3)	0.2781 (11)	0.0491 (19)	0.2148 (19)
C11	0.6774 (12)	0.5000	0.1353 (9)	0.0525 (6)	0.570 (4)
C12	0.589 (2)	0.2337 (4)	0.3385 (14)	0.0420 (2)	0.2148 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl2	0.0470 (4)	0.0327 (4)	0.0459 (4)	0.0042 (2)	−0.0004 (3)	−0.0099 (2)
Cl1	0.0405 (11)	0.0844 (11)	0.0330 (9)	0.000	0.0062 (5)	0.000
C1	0.0300 (11)	0.0408 (13)	0.0274 (10)	0.000	−0.0006 (8)	0.000
C2	0.0316 (8)	0.0323 (8)	0.0332 (8)	0.0018 (6)	−0.0035 (6)	−0.0040 (6)
N1	0.051 (2)	0.044 (2)	0.036 (2)	0.000	0.0121 (18)	0.000
N2	0.059 (5)	0.041 (5)	0.048 (4)	0.000 (4)	0.007 (3)	−0.002 (3)
C11	0.0405 (11)	0.0844 (11)	0.0330 (9)	0.000	0.0062 (5)	0.000
C12	0.0470 (4)	0.0327 (4)	0.0459 (4)	0.0042 (2)	−0.0004 (3)	−0.0099 (2)

Geometric parameters (Å, º) top

Cl2—C2	1.7130 (2)	C2—C2ⁱⁱ	1.389 (3)
Cl1—C1	1.7130 (2)	C2—C12	1.4451 (2)
C1—C2ⁱ	1.3871 (15)	N1—C11	1.1420 (1)
C1—C2	1.3871 (16)	N2—C12	1.1421 (2)
C1—C11	1.4450 (2)

C2ⁱ—C1—C2	120.74 (11)	C1—C2—C12	125.7 (4)
C2ⁱ—C1—C11	119.63 (6)	C2ⁱⁱ—C2—C12	114.6 (3)
C2—C1—C11	119.63 (6)	C1—C2—Cl2	118.47 (10)
C2ⁱ—C1—Cl1	119.61 (6)	C2ⁱⁱ—C2—Cl2	121.88 (6)
C2—C1—Cl1	119.61 (6)	N1—C11—C1	179.5 (10)
C1—C2—C2ⁱⁱ	119.63 (6)	N2—C12—C2	178.6 (6)

Symmetry codes: (i) x, −y+1, z; (ii) −x+1, y, −z+1.

Experimental details

	(M-II)	(O-P)	(M-P-II)
Crystal data
Chemical formula	C₈Cl₄N₂	C₈Cl₄N₂	C₈Cl₄N₂
M_r	265.90	265.90	265.90
Crystal system, space group	Rhombohedral, R3m:H	Hexagonal, R3m:H	Monoclinic, C2/m
Temperature (K)	173	173	173
a, b, c (Å)	9.2171 (14), 9.2171 (14), 9.935 (2)	9.2473 (8), 9.2473 (8), 9.9590 (13)	7.9237 (9), 9.4546 (11), 6.5157 (7)
α, β, γ (°)	90, 90, 120	90, 90, 120	90, 93.106 (2), 90
V (Å³)	731.0 (2)	737.52 (13)	487.41 (9)
Z	3	3	2
Radiation type	Mo Kα	Mo Kα	Mo Kα
µ (mm⁻¹)	1.17	1.16	1.17
Crystal size (mm)	0.50 × 0.35 × 0.25	0.45 × 0.35 × 0.30	0.35 × 0.35 × 0.30

Data collection
Diffractometer	Bruker 1X CCD area detector duiffractometer	Bruker 1K area CCD area detector diffractometer	BRUKER 1K CCD area detector diffractometer
Absorption correction	Multi-scan SADABS; Sheldrick, 1996; Blessing, 1995	Multi-scan SADABS; Sheldrick, 1996; Blessing, 1995	Multi-scan SADABS; Sheldrick, 1996; Blessing, 1995
T_min, T_max	0.64, 0.75	0.64, 0.71	0.58, 0.70
No. of measured, independent and observed [I > 2σ(I)] reflections	2730, 226, 216	1227, 176, 167	2825, 589, 562
R_int	0.031	0.038	0.016
(sin θ/λ)_max (Å⁻¹)	0.650	0.594	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.086, 1.24	0.029, 0.086, 1.28	0.031, 0.080, 1.08
No. of reflections	226	176	589
No. of parameters	21	22	53
No. of restraints	4	4	9
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.27	0.22, −0.22	0.40, −0.46

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

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