Weak interactions in chain polymers [M(μ-X)₂L₂]_∞ (M = Zn, Cd; X = Cl, Br; L = substituted pyridine) – an electron density study

The experimental electron-density distributions in crystals of five chain polymers [M(μ-X)₂(py)₂] (M = Zn, Cd; X = Cl, Br; py = 3,5-substituted pyridine) have been obtained from high-resolution X-ray diffraction data sets (sin θ/λ > 1.1 Å⁻¹) at 100 K. Topological analyses following Bader's `Atoms in Molecules' approach not only confirmed the existence of (3, −1) critical points for the chemically reasonable and presumably strong covalent and coordinative bonds, but also for four different secondary interactions which are expected to play a role in stabilizing the polymeric structures which are unusual for Zn as the metal center. These weaker contacts comprise intra- and inter-strand C—H...X—M hydrogen bonds on the one hand and C—X...X—C interhalogen contacts on the other hand. According to the experimental electron-density studies, the non-classical hydrogen bonds are associated with higher electron density in the (3, −1) critical points than the halogen bonds and hence are the dominant interactions both with respect to intra- and inter-chain contacts.

Computing details

For all compounds, data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a). Program(s) used to refine structure: SHELXL97 (Sheldrick, 1997b) for comp1iam, comp2iam, comp3iam, comp4iam, comp5iam; XD2006 (Volkov et al., (2006)) for comp1multi; Volkov et al., (2006) for comp2multi, comp3multi, comp4multi, comp5multi. Molecular graphics: PLATON (Spek, 2003) for comp1iam, comp1multi, comp2iam, comp3iam, comp4iam, comp5iam, comp5multi; Volkov et al., (2006) for comp2multi, comp3multi, comp4multi. Software used to prepare material for publication: SHELXL97 (Sheldrick, 1997b) for comp1iam, comp1multi, comp2iam, comp3iam, comp4iam, comp5iam; Volkov et al., (2006) for comp2multi, comp3multi, comp4multi, comp5multi.

Figures

(comp1iam)

Crystal data

C10H6Cl6N2Zn	Dx = 2.074 Mg m^−3
Mr = 432.24	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4b2	Cell parameters from 7837 reflections
Hall symbol: P -4 -2ab	θ = 3.0–52.6°
a = 13.7958 (4) Å	µ = 2.91 mm^−1
c = 3.6371 (2) Å	T = 100 K
V = 692.23 (5) Å^3	Rod, colorless
Z = 2	0.60 × 0.15 × 0.15 mm
F(000) = 424

Data collection

CCD area detector diffractometer	4347 independent reflections
Radiation source: fine-focus sealed tube	3850 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.053
ω scans	θmax = 54.4°, θmin = 3.0°
Absorption correction: numerical J. De Meulenaer, H. Tompa, Acta Crystallogr. 19 (1965) 1014.	h = −31→31
Tmin = 0.241, Tmax = 0.678	k = −31→31
54172 measured reflections	l = −8→8

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.023	H-atom parameters constrained
wR(F^2) = 0.049	w = 1/[σ^2(Fo^2) + (0.021P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.003
4347 reflections	Δρmax = 0.45 e Å^−3
46 parameters	Δρmin = −0.39 e Å^−3
0 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.014 (6)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Zn1	1.0000	0.5000	0.5000	0.00882 (2)
Cl1	0.913154 (9)	0.413154 (9)	1.0000	0.00976 (3)
Cl2	0.608693 (11)	0.629607 (13)	0.75111 (6)	0.01630 (3)
N1	0.88761 (3)	0.61239 (3)	0.5000	0.01034 (8)
C1	0.79635 (4)	0.59074 (5)	0.60068 (18)	0.01091 (8)
H1	0.7804	0.5240	0.6711	0.014*
C2	0.72398 (5)	0.66115 (5)	0.60688 (18)	0.01124 (8)
C3	0.74396 (4)	0.75604 (4)	0.5000	0.01247 (10)
H3	0.6937	0.8063	0.5000	0.016*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.00845 (3)	0.00845 (3)	0.00956 (4)	0.00140 (3)	0.000	0.000
Cl1	0.00974 (4)	0.00974 (4)	0.00980 (5)	−0.00107 (4)	−0.00090 (5)	0.00090 (5)
Cl2	0.00990 (5)	0.02002 (6)	0.01897 (6)	0.00157 (4)	0.00225 (6)	0.00139 (6)
N1	0.00961 (12)	0.00961 (12)	0.0118 (2)	0.00165 (15)	−0.0001 (2)	−0.0001 (2)
C1	0.00928 (19)	0.0107 (2)	0.01271 (19)	0.00155 (15)	−0.00045 (16)	0.00026 (17)
C2	0.00935 (19)	0.0136 (2)	0.01079 (18)	0.00216 (15)	−0.00019 (16)	0.00015 (17)
C3	0.01213 (15)	0.01213 (15)	0.0131 (2)	0.0037 (2)	0.0002 (2)	0.0002 (2)

Geometric parameters (Å, º)

Zn1—N1	2.1927 (6)	N1—C1	1.3449 (7)
Zn1—N1^i	2.1927 (6)	N1—C1^iv	1.3449 (7)
Zn1—Cl1^i	2.4856 (1)	C1—C2	1.3931 (9)
Zn1—Cl1^ii	2.4856 (1)	C1—H1	0.9800
Zn1—Cl1	2.4856 (1)	C2—C3	1.3932 (8)
Zn1—Cl1^iii	2.4856 (1)	C3—C2^iv	1.3931 (8)
Cl2—C2	1.7304 (7)	C3—H3	0.9800
N1—Zn1—N1^i	180.0	C1—N1—Zn1	120.33 (4)
N1—Zn1—Cl1^i	90.0	C1^iv—N1—Zn1	120.33 (4)
N1—Zn1—Cl1^ii	90.0	N1—C1—C2	121.36 (6)
N1^i—Zn1—Cl1^ii	90.0	N1—C1—H1	119.3
Cl1^i—Zn1—Cl1^ii	94.050 (7)	C2—C1—H1	119.3
Cl1^i—Zn1—Cl1	85.951 (7)	C1—C2—C3	120.59 (6)
Cl1^ii—Zn1—Cl1	180.0	C1—C2—Cl2	119.23 (5)
N1—Zn1—Cl1^iii	90.0	C3—C2—Cl2	120.18 (5)
N1^i—Zn1—Cl1^iii	90.0	C2^iv—C3—C2	116.72 (7)
Zn1^v—Cl1—Zn1	94.049 (7)	C2^iv—C3—H3	121.6
C1—N1—C1^iv	119.34 (7)	C2—C3—H3	121.6

Symmetry codes: (i) −x+2, −y+1, z; (ii) −x+2, −y+1, z−1; (iii) x, y, z−1; (iv) −y+3/2, −x+3/2, −z+1; (v) x, y, z+1.

(comp1multi)

Crystal data

C10H6Cl6N2Zn	Dx = 2.074 Mg m^−3
Mr = 432.24	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4b2	Cell parameters from 7837 reflections
Hall symbol: P -4 -2ab	θ = 3.0–52.6°
a = 13.7958 (4) Å	µ = 2.91 mm^−1
c = 3.6371 (2) Å	T = 100 K
V = 692.23 (5) Å^3	Rod, colorless
Z = 2	0.60 × 0.15 × 0.15 mm
F(000) = 424

Data collection

CCD area detector diffractometer	4347 independent reflections
Radiation source: fine-focus sealed tube	3850 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.053
ω scans	θmax = 54.4°, θmin = 3.0°
Absorption correction: numerical J. De Meulenaer, H. Tompa, Acta Crystallogr. 19 (1965) 1014.	h = −31→31
Tmin = 0.38, Tmax = 0.50	k = −31→31
54172 measured reflections	l = −8→8

Refinement

Refinement on F	180 parameters
Least-squares matrix: full	0 restraints
R[F^2 > 2σ(F^2)] = 0.02	w1 = 1/[s^2(Fo)]
wR(F^2) = 0.018	(Δ/σ)max = 0.003
S = 1.75	Δρmax = 0.11 e Å^−3
3963 reflections	Δρmin = −0.19 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	0.5	0	0.5	0.009
Cl1	0.586859 (8)	0.086859 (8)	0	0.01
Cl2	0.370387 (13)	0.391274 (11)	0.24873 (6)	0.017
N1	0.38763 (4)	0.11237 (4)	0.5	0.011
C3	0.24388 (3)	0.25612 (3)	0.5	0.013
C1	0.40932 (4)	0.20365 (4)	0.39982 (18)	0.011
C2	0.33884 (5)	0.27615 (4)	0.39285 (17)	0.012
H3	0.18837	0.311631	0.5	0.025
H1	0.483114	0.216077	0.309848	0.025
DUM0	0.5	0	0	0	0

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.00881 (3)	0.00881 (3)	0.00967 (4)	0.00138 (3)	0	0
Cl1	0.01022 (4)	0.01022 (4)	0.01010 (6)	−0.00105 (4)	0.00098 (6)	−0.00098 (6)
Cl2	0.02056 (7)	0.01051 (5)	0.01908 (6)	0.00163 (5)	0.00143 (7)	0.00220 (6)
N1	0.00983 (12)	0.00983 (12)	0.0128 (2)	0.00182 (18)	0.0008 (3)	0.0008 (3)
C3	0.01247 (14)	0.01247 (14)	0.0143 (2)	0.0038 (2)	0.0007 (3)	0.0007 (3)
C1	0.01083 (19)	0.00947 (18)	0.01374 (18)	0.00152 (14)	0.00076 (16)	−0.00003 (16)
C2	0.0137 (2)	0.00994 (18)	0.01147 (18)	0.00223 (15)	0.00048 (17)	−0.00021 (16)

Geometric parameters (Å, º)

Zn1—Cl1	2.4857 (1)	C3—C2^i	1.3945 (7)
Cl2—C2	1.7282 (6)	C3—H3	1.083
N1—C1	1.3447 (7)	C1—C2	1.3951 (8)
N1—C1^i	1.3447 (7)	C1—H1	1.083
C3—C2	1.3945 (7)
Cl1—Zn1—Cl1^ii	94.040 (5)	N1^i—C1—H1	116.06
Zn1^iii—Cl1—Zn1^i	94.040 (5)	C2—C1—H1	122.42
C1—N1—C1^i	119.35 (7)	Cl2—C2—C3	120.23 (4)
C2—C3—C2^i	116.77 (7)	Cl2—C2—C3^i	120.23 (4)
C2—C3—H3	121.62	Cl2—C2—C1	119.27 (5)
N1—C1—C2	121.42 (6)	C3—C2—C1	120.51 (6)
N1—C1—H1	116.06	C3^i—C2—C1	120.51 (6)
N1^i—C1—C2	121.42 (6)

Symmetry codes: (i) −y+1/2, −x+1/2, −z+1; (ii) x, y, z+1; (iii) −y+1/2, −x+1/2, −z.

(comp2iam)

Crystal data

C10H6Br4Cl2N2Zn	Dx = 2.861 Mg m^−3
Mr = 610.08	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4b2	Cell parameters from 6095 reflections
Hall symbol: P -4 -2ab	θ = 3.0–44.9°
a = 13.8260 (2) Å	µ = 13.38 mm^−1
c = 3.7044 (1) Å	T = 100 K
V = 708.13 (2) Å^3	Rod, colourless
Z = 2	0.24 × 0.09 × 0.09 mm
F(000) = 568

Data collection

CCD area detector diffractometer	4284 independent reflections
Radiation source: fine-focus sealed tube	3189 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.074
ω scans	θmax = 54.5°, θmin = 3.0°
Absorption correction: numerical J. De Meulenaer, H. Tompa, Acta Crystallogr. 19 (1965) 1014.	h = −30→31
Tmin = 0.151, Tmax = 0.397	k = −28→30
35317 measured reflections	l = −7→8

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.028	H-atom parameters constrained
wR(F^2) = 0.050	w = 1/[σ^2(Fo^2) + (0.015P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
4284 reflections	Δρmax = 1.99 e Å^−3
46 parameters	Δρmin = −1.23 e Å^−3
0 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.002 (6)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.601880 (9)	0.630241 (10)	0.79139 (4)	0.00951 (3)
Zn1	1.0000	0.5000	0.5000	0.00737 (5)
Cl1	0.91425 (2)	0.41425 (2)	1.0000	0.00815 (6)
N1	0.88778 (8)	0.61222 (8)	0.5000	0.0088 (2)
C1	0.79759 (9)	0.59182 (9)	0.6136 (4)	0.00827 (19)
H1	0.7826	0.5281	0.6914	0.010*
C2	0.72656 (9)	0.66163 (9)	0.6191 (3)	0.00796 (18)
C3	0.74504 (8)	0.75496 (8)	0.5000	0.0086 (2)
H3	0.6965	0.8035	0.5000	0.010*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.00631 (4)	0.01021 (5)	0.01202 (5)	0.00025 (4)	0.00118 (4)	0.00108 (4)
Zn1	0.00620 (7)	0.00620 (7)	0.00970 (11)	0.00119 (8)	0.000	0.000
Cl1	0.00693 (9)	0.00693 (9)	0.01058 (15)	−0.00050 (11)	−0.00056 (9)	0.00056 (9)
N1	0.0080 (3)	0.0080 (3)	0.0105 (6)	0.0008 (4)	−0.0002 (3)	−0.0002 (3)
C1	0.0060 (4)	0.0074 (4)	0.0114 (5)	0.0001 (4)	−0.0004 (3)	0.0007 (3)
C2	0.0056 (4)	0.0088 (5)	0.0095 (5)	0.0001 (3)	0.0004 (3)	−0.0004 (4)
C3	0.0077 (4)	0.0077 (4)	0.0104 (6)	0.0019 (5)	−0.0001 (4)	−0.0001 (4)

Geometric parameters (Å, º)

Br1—C2	1.8887 (13)	N1—C1	1.3460 (15)
Zn1—N1^i	2.1942 (15)	N1—C1^iv	1.3460 (15)
Zn1—N1	2.1942 (15)	C1—C2	1.3771 (17)
Zn1—Cl1	2.4984 (3)	C1—H1	0.9500
Zn1—Cl1^ii	2.4984 (3)	C2—C3	1.3874 (15)
Zn1—Cl1^i	2.4984 (3)	C3—C2^iv	1.3874 (15)
Zn1—Cl1^iii	2.4984 (3)	C3—H3	0.9500
N1^i—Zn1—N1	180.0	Zn1—Cl1—Zn1^v	95.695 (14)
N1^i—Zn1—Cl1	90.0	C1—N1—C1^iv	119.08 (15)
N1—Zn1—Cl1	90.00 (2)	C1—N1—Zn1	120.46 (8)
N1^i—Zn1—Cl1^ii	90.0	C1^iv—N1—Zn1	120.46 (8)
N1—Zn1—Cl1^ii	90.0	N1—C1—C2	121.23 (12)
Cl1—Zn1—Cl1^ii	95.694 (14)	N1—C1—H1	119.4
Cl1—Zn1—Cl1^i	84.306 (14)	C2—C1—H1	119.4
Cl1^ii—Zn1—Cl1^i	180.0	C1—C2—C3	121.05 (13)
N1^i—Zn1—Cl1^iii	90.0	C1—C2—Br1	119.66 (10)
N1—Zn1—Cl1^iii	90.0	C3—C2—Br1	119.29 (10)
Cl1—Zn1—Cl1^iii	180.0	C2^iv—C3—C2	116.34 (16)
Cl1^ii—Zn1—Cl1^iii	84.307 (14)	C2^iv—C3—H3	121.8
Cl1^i—Zn1—Cl1^iii	95.693 (14)	C2—C3—H3	121.8

Symmetry codes: (i) −x+2, −y+1, z; (ii) x, y, z−1; (iii) −x+2, −y+1, z−1; (iv) −y+3/2, −x+3/2, −z+1; (v) x, y, z+1.

(comp2multi)

Crystal data

C10H6Br4Cl2N2Zn	Dx = 2.861 Mg m^−3
Mr = 610.08	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4b2	Cell parameters from 6095 reflections
Hall symbol: P -4 -2ab	θ = 3.0–44.9°
a = 13.8260 (2) Å	µ = 13.38 mm^−1
c = 3.7044 (1) Å	T = 100 K
V = 708.13 (2) Å^3	Rod, colourless
Z = 2	0.24 × 0.09 × 0.09 mm
F(000) = 568

Data collection

CCD area detector diffractometer	4284 independent reflections
Radiation source: fine-focus sealed tube	3189 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.074
ω scans	θmax = 54.5°, θmin = 3.0°
Absorption correction: numerical J. De Meulenaer, H. Tompa, Acta Crystallogr. 19 (1965) 1014.	h = −30→31
Tmin = 0.151, Tmax = 0.397	k = −28→30
35317 measured reflections	l = −7→8

Refinement

Refinement on F	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.024	w1 = 1/[s^2(Fo)]
wR(F^2) = 0.017	(Δ/σ)max < 0.001
S = 1.21	Δρmax = 0.41 e Å^−3
2834 reflections	Δρmin = −0.29 e Å^−3
173 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
BR(1)	0.601883 (10)	0.630238 (11)	0.79146 (4)	0.009
Zn(1)	1	0.5	0.5	0.007
Cl(1)	0.91425 (2)	0.41425 (2)	1	0.008
N(1)	0.88785 (13)	0.61215 (13)	0.5	0.008
C(1)	0.79794 (14)	0.59142 (13)	0.6135 (5)	0.008
C(2)	0.72650 (14)	0.66173 (15)	0.6205 (5)	0.008
C(3)	0.74484 (13)	0.75516 (13)	0.5	0.009
H(1)	0.78042	0.518941	0.703111	0.011
H(3)	0.689453	0.810549	0.500001	0.011
DUM0	1	0.5	1	0	0

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
BR(1)	0.00606 (5)	0.00995 (6)	0.01161 (6)	0.00027 (4)	0.00116 (5)	0.00108 (5)
Zn(1)	0.00604 (18)	0.00604 (18)	0.0085 (4)	0.0012 (3)	0	0
Cl(1)	0.00677 (11)	0.00677 (11)	0.01004 (19)	−0.00051 (14)	−0.00048 (11)	0.00048 (11)
N(1)	0.0061 (5)	0.0061 (5)	0.0118 (10)	0.0009 (7)	0.0006 (6)	0.0006 (6)
C(1)	0.0059 (6)	0.0069 (7)	0.0116 (7)	0.0008 (5)	0.0002 (5)	0.0017 (5)
C(2)	0.0067 (6)	0.0073 (7)	0.0100 (7)	0.0000 (6)	−0.0001 (5)	−0.0001 (6)
C(3)	0.0069 (5)	0.0069 (5)	0.0122 (9)	0.0013 (7)	0.0008 (6)	0.0008 (6)

Geometric parameters (Å, º)

Br(1)—C(2)	1.8866 (19)	C(1)—H(1)	1.083
Zn(1)—Cl(1)^i	2.4984 (3)	C(2)—C(3)	1.390 (2)
Cl(1)—Cl(1)^ii	3.3535 (9)	C(2)—C(3)^iii	1.390 (2)
N(1)—C(1)	1.343 (2)	C(3)—H(3)	1.083
C(1)—C(2)	1.386 (2)
Cl(1)^i—Zn(1)—Cl(1)	95.692 (15)	C(2)—C(1)—H(1)	118.94
Cl(1)^iv—Zn(1)—Cl(1)^v	180.00 (2)	Br(1)—C(2)—C(1)	119.68 (16)
Zn(1)—Cl(1)—Zn(1)^vi	95.692 (15)	Br(1)—C(2)—C(3)	119.27 (15)
C(1)—N(1)—C(1)^iii	119.5 (2)	Br(1)—C(2)—C(3)^iii	119.27 (15)
N(1)—C(1)—C(2)	121.0 (2)	C(1)—C(2)—C(3)	121.0 (2)
N(1)—C(1)—H(1)	120.02	C(1)—C(2)—C(3)^iii	121.0 (2)
N(1)^iii—C(1)—C(2)	121.0 (2)	C(2)—C(3)—C(2)^iii	116.2 (2)
N(1)^iii—C(1)—H(1)	120.02	C(2)—C(3)—H(3)	121.88

Symmetry codes: (i) x, y, z−1; (ii) −y+3/2, −x+3/2, −z+2; (iii) −y+3/2, −x+3/2, −z+1; (iv) −x+2, −y+1, z; (v) y+1/2, x−1/2, −z+1; (vi) y+1/2, x−1/2, −z+2.

(comp3iam)

Crystal data

C14H18Br2CdN2	Dx = 1.968 Mg m^−3
Mr = 486.52	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4b2	Cell parameters from 7959 reflections
Hall symbol: P -4 -2ab	θ = 2.8–39.9°
a = 14.4457 (3) Å	µ = 6.19 mm^−1
c = 3.9345 (1) Å	T = 100 K
V = 821.04 (3) Å^3	Rod, colorless
Z = 2	0.28 × 0.07 × 0.07 mm
F(000) = 468

Data collection

CCD area detector diffractometer	5146 independent reflections
Radiation source: fine-focus sealed tube	3889 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.067
ω scans	θmax = 54.5°, θmin = 2.8°
Absorption correction: numerical J. De Meulenaer, H. Tompa, Acta Crystallogr. 19 (1965) 1014.	h = −32→31
Tmin = 0.276, Tmax = 0.671	k = −32→30
45933 measured reflections	l = −8→8

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.026	H-atom parameters constrained
wR(F^2) = 0.045	w = 1/[σ^2(Fo^2) + (0.010P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
5146 reflections	Δρmax = 1.24 e Å^−3
47 parameters	Δρmin = −2.62 e Å^−3
0 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.010 (9)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cd	0.5000	0.0000	0.5000	0.00945 (2)
Br1	0.404724 (5)	0.095276 (5)	1.0000	0.01117 (2)
N	0.61526 (5)	0.11526 (5)	0.5000	0.01338 (16)
C1	0.59616 (8)	0.20127 (8)	0.6038 (3)	0.01419 (17)
H1	0.5349	0.2148	0.6768	0.017*
C2	0.66155 (8)	0.27183 (8)	0.6101 (3)	0.01422 (18)
C3	0.75039 (6)	0.25039 (6)	0.5000	0.01605 (19)
H3	0.7969	0.2969	0.5000	0.019*
C4	0.63666 (11)	0.36715 (9)	0.7325 (4)	0.0221 (2)
H4A	0.6883	0.3928	0.8635	0.033*
H4B	0.5815	0.3637	0.8770	0.033*
H4C	0.6239	0.4071	0.5368	0.033*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd	0.00905 (3)	0.00905 (3)	0.01024 (4)	−0.00118 (3)	0.000	0.000
Br1	0.01150 (3)	0.01150 (3)	0.01051 (4)	0.00262 (3)	0.00110 (9)	0.00110 (9)
N	0.0124 (2)	0.0124 (2)	0.0154 (4)	−0.0023 (3)	−0.0012 (8)	0.0012 (8)
C1	0.0135 (4)	0.0123 (4)	0.0168 (4)	−0.0025 (3)	0.0006 (3)	0.0002 (3)
C2	0.0174 (5)	0.0118 (4)	0.0135 (4)	−0.0036 (3)	−0.0001 (3)	0.0002 (3)
C3	0.0166 (3)	0.0166 (3)	0.0149 (4)	−0.0072 (4)	0.0001 (9)	−0.0001 (9)
C4	0.0265 (7)	0.0144 (5)	0.0253 (6)	−0.0037 (4)	0.0024 (5)	−0.0032 (4)

Geometric parameters (Å, º)

Cd—N	2.3546 (10)	C1—H1	0.9500
Cd—N^i	2.3547 (10)	C2—C3	1.3894 (14)
Cd—Br1	2.7674 (1)	C2—C4	1.5024 (17)
Cd—Br1^ii	2.7674 (1)	C3—C2^iv	1.3894 (14)
Cd—Br1^iii	2.7674 (1)	C3—H3	0.9500
Cd—Br1^i	2.7674 (1)	C4—H4A	0.9800
N—C1	1.3368 (12)	C4—H4B	0.9800
N—C1^iv	1.3368 (12)	C4—H4C	0.9800
C1—C2	1.3899 (16)
N—Cd—N^i	180.00 (5)	C1^iv—N—Cd	120.75 (6)
N—Cd—Br1	90.00 (1)	N—C1—C2	123.15 (11)
N^i—Cd—Br1	90.00 (1)	N—C1—H1	118.4
N—Cd—Br1^ii	90.00 (1)	C2—C1—H1	118.4
N^i—Cd—Br1^ii	90.00 (1)	C1—C2—C3	117.30 (11)
Br1—Cd—Br1^ii	90.610 (4)	C1—C2—C4	121.00 (12)
N—Cd—Br1^iii	90.00 (1)	C3—C2—C4	121.69 (11)
N^i—Cd—Br1^iii	90.00 (1)	C2—C3—C2^iv	120.60 (13)
Br1^ii—Cd—Br1^iii	89.390 (4)	C2—C3—H3	119.7
N^i—Cd—Br1^i	90.0	C2^iv—C3—H3	119.7
Br1—Cd—Br1^i	89.390 (4)	C2—C4—H4A	109.5
Br1^ii—Cd—Br1^i	180.000 (3)	C2—C4—H4B	109.5
Br1^iii—Cd—Br1^i	90.610 (4)	H4A—C4—H4B	109.5
Cd^v—Br1—Cd	90.610 (4)	C2—C4—H4C	109.5
C1—N—C1^iv	118.50 (12)	H4A—C4—H4C	109.5
C1—N—Cd	120.75 (6)	H4B—C4—H4C	109.5

Symmetry codes: (i) −x+1, −y, z; (ii) x, y, z−1; (iii) −x+1, −y, z−1; (iv) y+1/2, x−1/2, −z+1; (v) x, y, z+1.

(comp3multi)

Crystal data

C14H18Br2CdN2	Dx = 1.968 Mg m^−3
Mr = 486.52	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4b2	Cell parameters from 7959 reflections
Hall symbol: P -4 -2ab	θ = 2.8–39.9°
a = 14.4457 (3) Å	µ = 6.19 mm^−1
c = 3.9345 (1) Å	T = 100 K
V = 821.04 (3) Å^3	Rod, colorless
Z = 2	0.28 × 0.07 × 0.07 mm
F(000) = 468

Data collection

CCD area detector diffractometer	5146 independent reflections
Radiation source: fine-focus sealed tube	3889 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.067
ω scans	θmax = 54.5°, θmin = 2.8°
Absorption correction: numerical J. De Meulenaer, H. Tompa, Acta Crystallogr. 19 (1965) 1014.	h = −32→31
Tmin = 0.276, Tmax = 0.671	k = −32→30
45933 measured reflections	l = −8→8

Refinement

Refinement on F	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.024	w1 = 1/[s^2(Fo)]
wR(F^2) = 0.019	(Δ/σ)max < 0.001
S = 1.28	Δρmax = 0.37 e Å^−3
3549 reflections	Δρmin = −0.14 e Å^−3
172 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cd(1)	0.5	0	0.5	0.009
Br(1)	0.404714 (6)	0.095286 (6)	1	0.011
N(1)	0.61535 (10)	0.11535 (10)	0.5	0.013
C(1)	0.59600 (14)	0.20153 (12)	0.6029 (5)	0.014
C(2)	0.66179 (14)	0.27184 (13)	0.6092 (6)	0.014
C(3)	0.75067 (11)	0.25067 (11)	0.5	0.016
C(4)	0.63650 (17)	0.36713 (15)	0.7318 (6)	0.023
H(1)	0.526272	0.216752	0.687133	0.017
H(3)	0.803687	0.303686	0.500001	0.019
H(4A)	0.693568	0.395448	0.876863	0.033
H(4B)	0.5757	0.363297	0.892237	0.033
H(4C)	0.622537	0.411436	0.515751	0.033
DUM0	0.5	0	1	0	0

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd(1)	0.00893 (4)	0.00893 (4)	0.01026 (6)	−0.00113 (6)	0	0
Br(1)	0.01150 (4)	0.01150 (4)	0.01057 (5)	0.00259 (4)	0.00127 (12)	0.00127 (12)
N(1)	0.0119 (4)	0.0119 (4)	0.0167 (8)	−0.0028 (6)	−0.0009 (17)	0.0009 (17)
C(1)	0.0135 (7)	0.0114 (7)	0.0179 (6)	−0.0035 (5)	0.0016 (6)	−0.0007 (5)
C(2)	0.0157 (7)	0.0112 (7)	0.0160 (7)	−0.0032 (6)	0.0005 (6)	−0.0002 (5)
C(3)	0.0162 (4)	0.0162 (4)	0.0156 (7)	−0.0071 (6)	0.0013 (16)	−0.0013 (16)
C(4)	0.0258 (10)	0.0155 (8)	0.0273 (9)	−0.0049 (6)	0.0018 (8)	−0.0052 (7)

Geometric parameters (Å, º)

N(1)—C(1)	1.339 (2)	C(2)—C(4)	1.504 (3)
N(1)—C(1)^i	1.339 (2)	C(3)—H(3)	1.083
C(1)—C(2)	1.391 (2)	C(4)—H(4A)	1.083
C(1)—H(1)	1.083	C(4)—H(4B)	1.083
C(2)—C(3)	1.388 (2)	C(4)—H(4C)	1.083
C(2)—C(3)^i	1.388 (2)
C(1)—N(1)—C(1)^i	118.7 (2)	C(3)^i—C(2)—C(4)	121.72 (18)
N(1)—C(1)—C(2)	122.8 (2)	C(2)—C(3)—C(2)^i	120.2 (2)
N(1)—C(1)—H(1)	118.40	C(2)—C(3)—H(3)	119.89
N(1)^i—C(1)—C(2)	122.8 (2)	C(2)—C(4)—H(4A)	109.26
N(1)^i—C(1)—H(1)	118.40	C(2)—C(4)—H(4B)	109.71
C(2)—C(1)—H(1)	118.79	C(2)—C(4)—H(4C)	109.55
C(1)—C(2)—C(3)	117.7 (2)	H(4A)—C(4)—H(4B)	109.23
C(1)—C(2)—C(3)^i	117.7 (2)	H(4A)—C(4)—H(4C)	109.4
C(1)—C(2)—C(4)	120.5 (2)	H(4B)—C(4)—H(4C)	109.7
C(3)—C(2)—C(4)	121.72 (18)

Symmetry code: (i) y+1/2, x−1/2, −z+1.

(comp4iam)

Crystal data

C10H6Br2CdCl4N2	F(000) = 1064
Mr = 568.19	Dx = 2.421 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 9254 reflections
a = 20.0345 (5) Å	θ = 2.9–41.8°
b = 20.4024 (6) Å	µ = 7.20 mm^−1
c = 3.8561 (2) Å	T = 100 K
β = 98.518 (2)°	Rod, colourless
V = 1558.80 (10) Å^3	0.23 × 0.07 × 0.05 mm
Z = 4

Data collection

CCD area detector diffractometer	8536 independent reflections
Radiation source: fine-focus sealed tube	6007 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.058
ω scans	θmax = 52.2°, θmin = 2.9°
Absorption correction: multi-scan SADABS (1996)	h = −44→41
Tmin = 0.278, Tmax = 0.702	k = −45→43
39526 measured reflections	l = −7→8

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.048	H-atom parameters constrained
S = 0.96	w = 1/[σ^2(Fo^2) + (0.010P)^2] where P = (Fo^2 + 2Fc^2)/3
8536 reflections	(Δ/σ)max < 0.001
96 parameters	Δρmax = 1.35 e Å^−3
0 restraints	Δρmin = −1.61 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cd2	0.0000	0.5000	0.0000	0.00815 (3)
Br2	−0.097939 (7)	0.5000	0.42274 (4)	0.01006 (3)
Cl2	0.128212 (16)	0.241967 (14)	0.33822 (8)	0.01940 (6)
N2	0.0000	0.38317 (6)	0.0000	0.0122 (2)
C4	0.05528 (6)	0.35004 (5)	0.1406 (3)	0.01215 (18)
H4	0.0945	0.3735	0.2388	0.015*
C5	0.05604 (6)	0.28210 (5)	0.1450 (3)	0.01260 (18)
C6	0.0000	0.24661 (7)	0.0000	0.0141 (3)
H6	0.0000	0.2000	0.0000	0.017*
Cd1	0.0000	0.0000	0.0000	0.00833 (3)
Br1	0.0000	0.094906 (7)	0.5000	0.01087 (3)
Cl1	0.254588 (16)	0.132311 (16)	−0.12422 (9)	0.02354 (6)
N1	0.12005 (6)	0.0000	0.0589 (3)	0.0125 (2)
C1	0.15195 (5)	0.05676 (6)	0.0216 (3)	0.01333 (18)
H1	0.1300	0.0970	0.0566	0.016*
C2	0.21661 (6)	0.05775 (6)	−0.0675 (3)	0.01438 (19)
C3	0.24969 (8)	0.0000	−0.1191 (4)	0.0147 (3)
H3	0.2934	0.0000	−0.1872	0.018*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd2	0.00872 (6)	0.00762 (5)	0.00819 (6)	0.000	0.00154 (4)	0.000
Br2	0.00772 (6)	0.01415 (6)	0.00836 (6)	0.000	0.00142 (4)	0.000
Cl2	0.01807 (13)	0.01373 (12)	0.02496 (14)	0.00476 (10)	−0.00157 (10)	0.00268 (10)
N2	0.0118 (5)	0.0099 (5)	0.0151 (6)	0.000	0.0031 (4)	0.000
C4	0.0125 (4)	0.0101 (4)	0.0140 (5)	0.0001 (3)	0.0024 (3)	0.0001 (3)
C5	0.0142 (5)	0.0114 (4)	0.0124 (4)	0.0029 (4)	0.0024 (3)	0.0010 (3)
C6	0.0204 (7)	0.0086 (6)	0.0135 (6)	0.000	0.0031 (5)	0.000
Cd1	0.00726 (6)	0.00943 (6)	0.00860 (6)	0.000	0.00220 (4)	0.000
Br1	0.01541 (7)	0.00824 (6)	0.00916 (6)	0.000	0.00250 (5)	0.000
Cl1	0.01582 (13)	0.02229 (14)	0.03306 (17)	−0.00652 (11)	0.00539 (11)	0.00490 (12)
N1	0.0092 (5)	0.0146 (6)	0.0137 (6)	0.000	0.0024 (4)	0.000
C1	0.0098 (4)	0.0144 (5)	0.0158 (5)	0.0000 (4)	0.0021 (3)	0.0001 (4)
C2	0.0099 (4)	0.0192 (5)	0.0138 (5)	−0.0038 (4)	0.0012 (3)	0.0019 (4)
C3	0.0089 (6)	0.0245 (8)	0.0107 (6)	0.000	0.0015 (5)	0.000

Geometric parameters (Å, º)

Cd2—N2	2.3837 (13)	Cd1—N1^v	2.3821 (13)
Cd2—N2^i	2.3838 (13)	Cd1—N1	2.3822 (13)
Cd2—Br2	2.7304 (2)	Cd1—Br1^vi	2.7325 (1)
Cd2—Br2^i	2.7304 (2)	Cd1—Br1^v	2.7325 (1)
Cd2—Br2^ii	2.7406 (2)	Cd1—Br1^ii	2.7325 (1)
Cd2—Br2^iii	2.7407 (2)	Cd1—Br1	2.7325 (1)
Cl2—C5	1.7312 (11)	Cl1—C2	1.7292 (12)
N2—C4^iv	1.3415 (13)	N1—C1^vii	1.3407 (13)
N2—C4	1.3415 (13)	N1—C1	1.3407 (13)
C4—C5	1.3863 (15)	C1—C2	1.3886 (15)
C4—H4	0.9500	C1—H1	0.9500
C5—C6	1.3826 (14)	C2—C3	1.3806 (14)
C6—C5^iv	1.3826 (14)	C3—C2^vii	1.3806 (14)
C6—H6	0.9500	C3—H3	0.9500
N2—Cd2—N2^i	180.0	N1^v—Cd1—N1	180.0
N2—Cd2—Br2	90.00 (1)	N1—Cd1—Br1^vi	92.19 (2)
N2—Cd2—Br2^i	90.00 (1)	N1—Cd1—Br1^v	87.81 (2)
Br2—Cd2—Br2^i	180.0	Br1^vi—Cd1—Br1^v	89.755 (5)
N2—Cd2—Br2^ii	90.00 (1)	N1—Cd1—Br1^ii	87.81 (2)
Br2—Cd2—Br2^ii	89.630 (5)	Br1^vi—Cd1—Br1^ii	180.000 (4)
Br2^i—Cd2—Br2^ii	90.370 (5)	Br1^v—Cd1—Br1^ii	90.245 (6)
N2—Cd2—Br2^iii	90.00 (1)	N1—Cd1—Br1	92.19 (2)
Br2—Cd2—Br2^iii	90.370 (5)	Br1^vi—Cd1—Br1	90.245 (6)
Br2^i—Cd2—Br2^iii	89.630 (5)	Br1^v—Cd1—Br1	180.0
Br2^ii—Cd2—Br2^iii	180.0	Br1^ii—Cd1—Br1	89.755 (5)
Cd2—Br2—Cd2^viii	89.630 (5)	Cd1^viii—Br1—Cd1	89.755 (6)
C4^iv—N2—C4	119.49 (13)	C1^vii—N1—C1	119.48 (13)
C4^iv—N2—Cd2	120.25 (7)	C1^vii—N1—Cd1	118.71 (7)
C4—N2—Cd2	120.25 (7)	C1—N1—Cd1	118.71 (7)
N2—C4—C5	121.04 (11)	N1—C1—C2	121.07 (11)
N2—C4—H4	119.5	N1—C1—H1	119.5
C5—C4—H4	119.5	C2—C1—H1	119.5
C6—C5—C4	120.79 (11)	C3—C2—C1	120.57 (11)
C6—C5—Cl2	120.19 (9)	C3—C2—Cl1	120.20 (9)
C4—C5—Cl2	119.02 (9)	C1—C2—Cl1	119.21 (9)
C5—C6—C5^iv	116.84 (14)	C2—C3—C2^vii	117.17 (14)
C5—C6—H6	121.6	C2—C3—H3	121.4
C5^iv—C6—H6	121.6	C2^vii—C3—H3	121.4

Symmetry codes: (i) −x, −y+1, −z; (ii) x, y, z−1; (iii) −x, −y+1, −z+1; (iv) −x, y, −z; (v) −x, −y, −z; (vi) −x, −y, −z+1; (vii) x, −y, z; (viii) x, y, z+1.

(comp4multi)

Crystal data

C10H6Br2CdCl4N2	F(000) = 1064
Mr = 568.19	Dx = 2.421 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 9254 reflections
a = 20.0345 (5) Å	θ = 2.9–41.8°
b = 20.4024 (6) Å	µ = 7.20 mm^−1
c = 3.8561 (2) Å	T = 100 K
β = 98.518 (2)°	Rod, colourless
V = 1558.80 (10) Å^3	0.23 × 0.07 × 0.05 mm
Z = 4

Data collection

CCD area detector diffractometer	8536 independent reflections
Radiation source: fine-focus sealed tube	6007 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.058
ω scans	θmax = 52.2°, θmin = 2.9°
Absorption correction: multi-scan SADABS (1996)	h = −44→41
Tmin = 0.278, Tmax = 0.702	k = −45→43
39526 measured reflections	l = −7→8

Refinement

Refinement on F	304 parameters
Least-squares matrix: full	0 restraints
R[F^2 > 2σ(F^2)] = 0.024	w1 = 1/[s^2(Fo)]
wR(F^2) = 0.016	(Δ/σ)max = 0.00034
S = 0.96	Δρmax = 0.51 e Å^−3
5082 reflections	Δρmin = −0.51 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cd(2)	0	0.5	0	0.008
Cd(1)	0	0	0	0.008
Br(1)	0	0.094906 (8)	0.5	0.011
Br(2)	−0.097946 (8)	0.5	0.42275 (4)	0.01
CL(2)	0.128242 (19)	0.242009 (17)	0.33837 (10)	0.019
CL(1)	0.25458 (2)	0.13231 (2)	−0.12441 (12)	0.023
N(2)	0	0.38314 (12)	0	0.012
N(1)	0.12047 (13)	0	0.0605 (7)	0.012
C(4)	0.05517 (9)	0.35016 (9)	0.1410 (4)	0.013
C(5)	0.05615 (9)	0.28189 (8)	0.1454 (4)	0.013
C(6)	0	0.24644 (12)	0	0.015
C(1)	0.15185 (9)	0.05659 (9)	0.0229 (4)	0.014
C(2)	0.21649 (9)	0.05819 (9)	−0.0676 (4)	0.014
C(3)	0.24981 (12)	0	−0.1198 (6)	0.015
H(4)	0.100027	0.376769	0.252595	0.015
H(6)	0.00000	0.193358	0.00000	0.017
H(1)	0.12692	0.102552	0.061503	0.016
H(3)	0.299678	0	−0.196408	0.018
DUM0	0.055118	0.383132	0.140988	0	0
DUM1	−0.097946	0	0.422758	0	0
DUM2	0	0.5	0.5	0	0
DUM3	0	0.094909	0	0	0
DUM4	0.11996	0.5	0.05929	0	0
DUM5	0.249855	0.5	−0.119417	0	0
DUM6	0.299693	0.5	−0.196437	0	0

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd(2)	0.00828 (9)	0.00724 (9)	0.00823 (10)	0	0.00145 (7)	0
Cd(1)	0.00699 (9)	0.00900 (9)	0.00847 (10)	0	0.00204 (7)	0
Br(1)	0.01504 (8)	0.00799 (7)	0.00887 (8)	0	0.00249 (6)	0
Br(2)	0.00751 (7)	0.01380 (8)	0.00805 (7)	0	0.00141 (5)	0
CL(2)	0.01814 (17)	0.01308 (16)	0.02498 (18)	0.00453 (13)	−0.00157 (13)	0.00275 (12)
CL(1)	0.01536 (17)	0.02229 (19)	0.0328 (2)	−0.00622 (14)	0.00537 (15)	0.00483 (16)
N(2)	0.0117 (10)	0.0077 (8)	0.0169 (10)	0	0.0010 (8)	0
N(1)	0.0084 (9)	0.0122 (10)	0.0173 (10)	0	0.0044 (7)	0
C(4)	0.0122 (6)	0.0086 (6)	0.0163 (7)	−0.0002 (6)	0.0009 (5)	0.0000 (5)
C(5)	0.0137 (7)	0.0096 (6)	0.0153 (7)	0.0021 (6)	0.0019 (5)	0.0006 (5)
C(6)	0.0193 (10)	0.0077 (8)	0.0161 (10)	0	0.0002 (8)	0
C(1)	0.0079 (6)	0.0132 (7)	0.0208 (7)	−0.0007 (6)	0.0037 (5)	0.0002 (5)
C(2)	0.0099 (6)	0.0171 (7)	0.0169 (7)	−0.0019 (6)	0.0034 (5)	0.0022 (6)
C(3)	0.0071 (9)	0.0222 (11)	0.0156 (10)	0	0.0034 (7)	0

Geometric parameters (Å, º)

Cl(2)—C(5)	1.7272 (17)	C(5)—C(6)	1.384 (2)
Cl(1)—C(2)	1.7225 (18)	C(5)—C(6)^i	1.384 (2)
N(2)—C(4)	1.339 (2)	C(6)—H(6)	1.083
N(2)—C(4)^i	1.339 (2)	C(1)—C(2)	1.391 (2)
N(1)—C(1)	1.333 (2)	C(1)—H(1)	1.083
N(1)—C(1)^ii	1.333 (2)	C(2)—C(3)	1.391 (2)
C(4)—C(5)	1.393 (2)	C(2)—C(3)^ii	1.391 (2)
C(4)—H(4)	1.083	C(3)—H(3)	1.083
C(4)—N(2)—C(4)^i	119.6 (2)	C(5)—C(6)—H(6)	121.50
C(1)—N(1)—C(1)^ii	120.1 (2)	N(1)—C(1)—C(2)	121.29 (19)
N(2)—C(4)—C(5)	121.12 (19)	N(1)—C(1)—H(1)	120.04 (16)
N(2)—C(4)—H(4)	119.73	N(1)^ii—C(1)—C(2)	121.29 (19)
N(2)^i—C(4)—C(5)	121.12 (19)	N(1)^ii—C(1)—H(1)	120.04
N(2)^i—C(4)—H(4)	119.73	C(2)—C(1)—H(1)	118.67
C(5)—C(4)—H(4)	119.15	CL(1)—C(2)—C(1)	119.93 (15)
CL(2)—C(5)—C(4)	119.05 (15)	CL(1)—C(2)—C(3)	119.99 (14)
CL(2)—C(5)—C(6)	120.40 (14)	CL(1)—C(2)—C(3)^ii	119.99 (14)
CL(2)—C(5)—C(6)^i	120.40 (14)	C(1)—C(2)—C(3)	120.06 (18)
C(4)—C(5)—C(6)	120.55 (18)	C(1)—C(2)—C(3)^ii	120.06 (18)
C(4)—C(5)—C(6)^i	120.55 (18)	C(2)—C(3)—C(2)^ii	117.2 (2)
C(5)—C(6)—C(5)^i	117.0 (2)	C(2)—C(3)—H(3)	121.42

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

(comp5iam)

Crystal data

C10H6Br6CdN2	Dx = 3.078 Mg m^−3
Mr = 746.03	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4b2	Cell parameters from 7789 reflections
Hall symbol: P -4 -2ab	θ = 2.8–39.7°
a = 14.3513 (2) Å	µ = 16.23 mm^−1
c = 3.9082 (1) Å	T = 100 K
V = 804.93 (3) Å^3	Rod, colourless
Z = 2	0.18 × 0.06 × 0.06 mm
F(000) = 676

Data collection

CCD area detector diffractometer	5090 independent reflections
Radiation source: Incoatec Microfocus Source	4364 reflections with I > 2σ(I)
Multilayer optics monochromator	Rint = 0.049
ω scans	θmax = 54.8°, θmin = 2.8°
Absorption correction: multi-scan SADABS (1996)	h = −32→32
Tmin = 0.158, Tmax = 0.443	k = −32→32
42311 measured reflections	l = −8→8

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.025	H-atom parameters constrained
wR(F^2) = 0.051	w = 1/[σ^2(Fo^2) + (0.017P)^2 + 0.050P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.002
5090 reflections	Δρmax = 3.10 e Å^−3
46 parameters	Δρmin = −0.86 e Å^−3
0 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.030 (5)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cd	0.5000	−0.0000	0.5000	0.00838 (2)
Br1	0.405530 (7)	0.094470 (7)	1.0000	0.00990 (2)
Br2	0.632768 (9)	0.393627 (8)	0.76783 (4)	0.01475 (2)
N	0.61772 (6)	0.11772 (6)	0.5000	0.01188 (18)
C1	0.59743 (8)	0.20423 (8)	0.6049 (3)	0.01169 (16)
H1	0.5359	0.2184	0.6775	0.014*
C2	0.66496 (8)	0.27374 (8)	0.6092 (3)	0.01126 (15)
C3	0.75516 (7)	0.25516 (7)	0.5000	0.01203 (19)
H3	0.8020	0.3020	0.5000	0.014*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd	0.00750 (3)	0.00750 (3)	0.01014 (4)	−0.00098 (3)	−0.000	−0.000
Br1	0.00947 (3)	0.00947 (3)	0.01076 (5)	0.00225 (4)	0.00099 (4)	0.00099 (4)
Br2	0.01565 (5)	0.00959 (4)	0.01902 (5)	−0.00134 (3)	0.00133 (4)	−0.00232 (4)
N	0.0101 (2)	0.0101 (2)	0.0155 (5)	−0.0021 (3)	−0.0004 (4)	0.0004 (4)
C1	0.0098 (4)	0.0096 (4)	0.0157 (4)	−0.0014 (3)	0.0006 (3)	0.0012 (3)
C2	0.0123 (4)	0.0087 (3)	0.0128 (4)	−0.0015 (3)	0.0009 (3)	−0.0002 (3)
C3	0.0111 (3)	0.0111 (3)	0.0139 (5)	−0.0030 (4)	−0.0006 (4)	0.0006 (4)

Geometric parameters (Å, º)

Cd—N	2.3892 (12)	N—C1^v	1.3395 (14)
Cd—N^i	2.3892 (12)	N—C1	1.3395 (13)
Cd—Br1^ii	2.7376 (1)	C1—C2	1.3909 (16)
Cd—Br1^i	2.7377 (1)	C1—H1	0.9500
Cd—Br1^iii	2.7377 (1)	C2—C3	1.3889 (14)
Cd—Br1	2.7377 (1)	C3—C2^v	1.3889 (14)
Br1—Cd^iv	2.7376 (1)	C3—H3	0.9500
Br2—C2	1.8862 (12)
N—Cd—N^i	180.0	Br1^iii—Cd—Br1	180.0
N—Cd—Br1^ii	90.0	Cd^iv—Br1—Cd	91.088 (4)
N^i—Cd—Br1^ii	90.0	C1^v—N—C1	119.78 (13)
N—Cd—Br1^i	90.0	C1^v—N—Cd	120.11 (7)
N^i—Cd—Br1^i	90.0	C1—N—Cd	120.11 (7)
Br1^ii—Cd—Br1^i	180.0	N—C1—C2	121.14 (11)
N—Cd—Br1^iii	89.999 (1)	N—C1—H1	119.4
N^i—Cd—Br1^iii	90.00 (2)	C2—C1—H1	119.4
Br1^ii—Cd—Br1^iii	88.912 (4)	C3—C2—C1	120.52 (11)
Br1^i—Cd—Br1^iii	91.088 (4)	C3—C2—Br2	120.29 (8)
N—Cd—Br1	90.00 (2)	C1—C2—Br2	119.18 (9)
N^i—Cd—Br1	90.0	C2—C3—C2^v	116.90 (13)
Br1^ii—Cd—Br1	91.088 (4)	C2—C3—H3	121.6
Br1^i—Cd—Br1	88.912 (4)	C2^v—C3—H3	121.6

Symmetry codes: (i) −x+1, −y, z; (ii) x, y, z−1; (iii) −x+1, −y, z−1; (iv) x, y, z+1; (v) y+1/2, x−1/2, −z+1.

(comp5multi)

Crystal data

C10H6Br6CdN2	Dx = 3.078 Mg m^−3
Mr = 746.03	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4b2	Cell parameters from 7789 reflections
a = 14.3513 (2) Å	θ = 2.8–39.7°
c = 3.9082 (1) Å	µ = 16.23 mm^−1
V = 804.93 (3) Å^3	T = 100 K
Z = 2	Rod, colourless
F(000) = 676	0.18 × 0.06 × 0.06 mm

Data collection

CCD area detector diffractometer	5090 independent reflections
Radiation source: Incoatec Microfocus Source	4364 reflections with I > 2σ(I)
Multilayer optics monochromator	Rint = 0.049
ω scans	θmax = 54.8°, θmin = 2.8°
Absorption correction: multi-scan SADABS (1996)	h = −32→32
Tmin = 0.158, Tmax = 0.443	k = −32→32
42311 measured reflections	l = −8→8

Refinement

Refinement on F	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.021	w1 = 1/[s^2(Fo)]
wR(F^2) = 0.019	(Δ/σ)max < 0.001
S = 1.12	Δρmax = 0.46 e Å^−3
4088 reflections	Δρmin = −0.28 e Å^−3
174 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
CD(1)	0.5	0	0.5	0.008
BR(1)	0.405529 (6)	0.094471 (6)	1	0.010
BR(2)	0.632768 (9)	0.393619 (8)	0.76790 (4)	0.015
N(1)	0.61772 (8)	0.11772 (8)	0.5	0.012
C(1)	0.59762 (9)	0.20429 (10)	0.6042 (4)	0.012
C(2)	0.66479 (10)	0.27392 (9)	0.6091 (4)	0.011
C(3)	0.75528 (8)	0.25528 (8)	0.5	0.012
H(1)	0.527063	0.220746	0.681774	0.014
H(3)	0.808639	0.308638	0.5	0.013
DUM0	0.5	0	1	0	0

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
CD(1)	0.00758 (3)	0.00758 (3)	0.00993 (5)	−0.00098 (4)	0	0
BR(1)	0.00938 (3)	0.00938 (3)	0.01075 (5)	0.00226 (4)	0.00097 (4)	0.00097 (4)
BR(2)	0.01556 (5)	0.00958 (4)	0.01891 (5)	−0.00134 (3)	0.00135 (4)	−0.00238 (4)
N(1)	0.0093 (3)	0.0093 (3)	0.0171 (7)	−0.0018 (4)	−0.0001 (6)	0.0001 (6)
C(1)	0.0100 (4)	0.0094 (4)	0.0156 (5)	−0.0022 (4)	0.0008 (4)	0.0002 (4)
C(2)	0.0115 (5)	0.0086 (4)	0.0139 (5)	−0.0019 (4)	0.0012 (4)	−0.0005 (4)
C(3)	0.0107 (3)	0.0107 (3)	0.0145 (6)	−0.0029 (4)	−0.0000 (6)	0.0000 (6)

Geometric parameters (Å, º)

BR(2)—C(2)	1.8834 (13)	C(1)—H(1)	1.083
N(1)—C(1)	1.3389 (16)	C(2)—C(3)	1.3928 (16)
N(1)—C(1)^i	1.3389 (16)	C(2)—C(3)^i	1.3928 (16)
C(1)—C(2)	1.3887 (18)	C(3)—H(3)	1.083
C(1)—N(1)—C(1)^i	119.49 (17)	BR(2)—C(2)—C(3)	120.24 (10)
N(1)—C(1)—C(2)	121.49 (14)	BR(2)—C(2)—C(3)^i	120.24 (10)
N(1)—C(1)—H(1)	119.27	C(1)—C(2)—C(3)	120.32 (13)
N(1)^i—C(1)—C(2)	121.49 (14)	C(1)—C(2)—C(3)^i	120.32 (13)
N(1)^i—C(1)—H(1)	119.27	C(2)—C(3)—C(2)^i	116.87 (15)
C(2)—C(1)—H(1)	119.23	C(2)—C(3)—H(3)	121.56
BR(2)—C(2)—C(1)	119.44 (11)

Symmetry code: (i) y+1/2, x−1/2, −z+1.