Crystal structure of di-μ2-chlorido-bis­[(1-aza-4-azoniabi­cyclo­[2.2.2]octane-κN1)di­chlorido­dicadmium]

Yan, J.-J.; Pan, Q.-J.; Chen, L.-Z.

doi:10.1107/S2056989015023361

metal-organic compounds

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Volume 71| Part 12| December 2015| Pages m259-m260

https://doi.org/10.1107/S2056989015023361

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Crystal structure of di-μ₂-chlorido-bis[(1-aza-4-azoniabicyclo[2.2.2]octane-κN¹)dichloridodicadmium]

Jing-Jing Yan,^a Qi-Jian Pan ^a and Li-Zhuang Chen ^a ^*

^aSchool of Environmental and Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, People's Republic of China
^*Correspondence e-mail: clz1977@sina.com

Edited by M. Weil, Vienna University of Technology, Austria (Received 19 November 2015; accepted 5 December 2015; online 12 December 2015)

In the structure of the binuclear title compound, [Cd₂(C₆H₁₃N₂)₂Cl₆], two Cd^II atoms are bridged by two Cl⁻ ligands, defining a centrosymmetric Cd₂Cl₂ motif. Each metal cation is additionally coordinated by two Cl⁻ ligands and the N atom of a protonated 1,4-diazabicyclo[2.2.2]octane (H-DABCO)⁺ ligand, leading to an overall trigonal–bipyramidal coordination environment with one of the bridging Cl⁻ ligands and the N atom at the apical sites. In the crystal, the neutral dimers are linked via N—H⋯Cl hydrogen bonds, forming a two-dimensional network expanding parallel to (100).

Keywords: crystal structure; cadmium; DABCO; hydrogen bonding.

CCDC reference: 1440782

1. Related literature

For a study on phase transition of related Cd₂(DABCO-CH₂Cl)₂(μ-Cl₂), see: Chen et al. (2014 ). Mononuclear and dinuclear bromide-nitrite cadmium complexes with DABCO derivatives were reported by Cai (2011 ).

2. Experimental

2.1. Crystal data

[Cd₂(C₆H₁₃N₂)₂Cl₆]
M_r = 663.86
Orthorhombic, P b c a
a = 12.317 (2) Å
b = 12.289 (2) Å
c = 14.440 (2) Å
V = 2185.7 (6) Å³
Z = 4
Mo Kα radiation
μ = 2.68 mm⁻¹
T = 296 K
0.3 × 0.2 × 0.2 mm

2.2. Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.500, T_max = 0.616
14939 measured reflections
1924 independent reflections
1752 reflections with I > 2σ(I)
R_int = 0.025

2.3. Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.183
S = 1.12
1924 reflections
109 parameters
30 restraints
H-atom parameters constrained
Δρ_max = 1.98 e Å⁻³
Δρ_min = −1.65 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯Cl3ⁱ	0.91	2.33	3.205 (3)	162
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 1440782

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989015023361/wm5244sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015023361/wm5244Isup2.hkl

checkCIF report

Synthesis and crystallization top

CdCl₂·2.5H₂O (2.28 g, 10 mmol) and 1,4-diazabicyclo [2.2.2]octan (1.12 g, 10 mmol) were mixed in water (20 ml). After being stirred for 30 min, the reaction mixture was filtered and evaporated slowly at room temperature for 3 days. Colourless block-like crystals were obtained.

Refinement top

C-bound H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.97 Å and U_iso(H) = 1.2U_eq(C). The H atom of the protonated N2 atom was discernible from a difference map. It was modelled with N—H = 0.91 Å and U_iso(H) = 1.2U_eq(N). The maximum and minimum electron density peaks are found 0.20 Å from atom Cl3 and 0.27 Å from atom Cd1, respectively.

Related literature top

For a study on phase transition of related Cd₂(DABCO-CH₂Cl)₂(µ-Cl₂), see: Chen et al. (2014). Mononuclear and dinuclear bromide-nitrite cadmium complexes with DABCO derivatives were reported by Cai (2011).

Structure description top

Synthesis and crystallization top

Refinement details top

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

	Fig. 1. The molecular structure of the dinuclear complex in the title compound. Displacement ellipsoids are drawn at the 30% probability level. The left part of the binuclear complex is generated by symmetry code -x + 1, -y, -z + 1.
	Fig. 2. View onto a layer of complexes in the title compound with N—H···Cl hydrogen bonds drawn as dashed lines.

Di-µ₂-chlorido-bis[(1-aza-4-azoniabicyclo[2.2.2]octane-κN¹)dichloridodicadmium] top

Crystal data top

[Cd₂(C₆H₁₃N₂)₂Cl₆]	D_x = 2.017 Mg m⁻³
M_r = 663.86	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 6044 reflections
a = 12.317 (2) Å	θ = 2.7–27.4°
b = 12.289 (2) Å	µ = 2.68 mm⁻¹
c = 14.440 (2) Å	T = 296 K
V = 2185.7 (6) Å³	Block, colorless
Z = 4	0.3 × 0.2 × 0.2 mm
F(000) = 1296

Data collection top

Bruker APEXII CCD diffractometer	1924 independent reflections
Radiation source: fine-focus sealed tube	1752 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
phi and ω scans	θ_max = 25.0°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −13→14
T_min = 0.500, T_max = 0.616	k = −14→14
14939 measured reflections	l = −17→16

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.183	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.1089P)² + 19.3777P] where P = (F_o² + 2F_c²)/3
1924 reflections	(Δ/σ)_max = 0.006
109 parameters	Δρ_max = 1.98 e Å⁻³
30 restraints	Δρ_min = −1.65 e Å⁻³

Crystal data top

[Cd₂(C₆H₁₃N₂)₂Cl₆]	V = 2185.7 (6) Å³
M_r = 663.86	Z = 4
Orthorhombic, Pbca	Mo Kα radiation
a = 12.317 (2) Å	µ = 2.68 mm⁻¹
b = 12.289 (2) Å	T = 296 K
c = 14.440 (2) Å	0.3 × 0.2 × 0.2 mm

Data collection top

Bruker APEXII CCD diffractometer	1924 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	1752 reflections with I > 2σ(I)
T_min = 0.500, T_max = 0.616	R_int = 0.025
14939 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	30 restraints
wR(F²) = 0.183	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.1089P)² + 19.3777P] where P = (F_o² + 2F_c²)/3
1924 reflections	Δρ_max = 1.98 e Å⁻³
109 parameters	Δρ_min = −1.65 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 (Å²) top

	x	y	z	U_iso*/U_eq
Cd1	0.42960 (2)	0.138551 (19)	0.535783 (17)	0.03153 (7)
Cl2	0.37788 (6)	0.25484 (6)	0.40100 (5)	0.02553 (17)
Cl3	0.28196 (6)	0.11273 (6)	0.65621 (5)	0.02369 (17)
Cl4	0.61656 (7)	0.05552 (8)	0.54294 (8)	0.0606 (3)
C1	0.4234 (3)	0.3697 (3)	0.6469 (3)	0.0453 (12)
H1A	0.3732	0.3344	0.6890	0.054*
H1B	0.3833	0.3921	0.5923	0.054*
C3	0.5670 (3)	0.2551 (3)	0.7038 (2)	0.0401 (9)
H3A	0.6263	0.2078	0.6853	0.048*
H3B	0.5177	0.2128	0.7418	0.048*
N1	0.5090 (2)	0.2930 (2)	0.62028 (18)	0.0284 (7)
C4	0.5890 (3)	0.3502 (3)	0.5617 (3)	0.0418 (10)
H4A	0.5526	0.3799	0.5078	0.050*
H4B	0.6432	0.2987	0.5404	0.050*
C2	0.4742 (3)	0.4710 (3)	0.6946 (3)	0.0512 (12)
H2A	0.4624	0.5352	0.6568	0.061*
H2B	0.4403	0.4829	0.7544	0.061*
N2	0.5912 (3)	0.4521 (3)	0.7064 (2)	0.0429 (8)
H2	0.6208	0.5096	0.7370	0.051*
C5	0.6446 (4)	0.4414 (3)	0.6140 (3)	0.0553 (12)
H5A	0.7211	0.4251	0.6218	0.066*
H5B	0.6381	0.5091	0.5799	0.066*
C6	0.6123 (4)	0.3495 (3)	0.7611 (3)	0.0537 (10)
H6A	0.5763	0.3531	0.8208	0.064*
H6B	0.6895	0.3400	0.7713	0.064*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.03132 (14)	0.02795 (13)	0.03533 (14)	0.00383 (9)	−0.00315 (9)	−0.00071 (9)
Cl2	0.0293 (3)	0.0249 (3)	0.0224 (3)	0.0010 (3)	−0.0047 (3)	0.0066 (3)
Cl3	0.0201 (3)	0.0231 (3)	0.0278 (3)	0.0002 (3)	0.0055 (3)	0.0068 (3)
Cl4	0.0362 (4)	0.0375 (4)	0.1082 (7)	0.0139 (4)	−0.0311 (4)	−0.0347 (4)
C1	0.0315 (19)	0.042 (2)	0.062 (2)	0.0035 (15)	0.0005 (17)	−0.0087 (17)
C3	0.0468 (17)	0.0325 (15)	0.0408 (16)	0.0022 (13)	−0.0054 (14)	0.0003 (14)
N1	0.0269 (12)	0.0237 (12)	0.0346 (13)	−0.0007 (10)	0.0030 (11)	0.0011 (11)
C4	0.0393 (18)	0.0414 (19)	0.0448 (19)	−0.0063 (16)	0.0128 (17)	0.0046 (16)
C2	0.041 (2)	0.0406 (19)	0.072 (2)	0.0050 (17)	0.003 (2)	−0.0175 (19)
N2	0.0411 (14)	0.0361 (14)	0.0515 (15)	−0.0060 (12)	−0.0063 (13)	−0.0092 (12)
C5	0.054 (2)	0.0381 (19)	0.074 (3)	−0.0152 (17)	0.024 (2)	0.0006 (19)
C6	0.0584 (17)	0.0475 (16)	0.0551 (17)	−0.0017 (15)	−0.0138 (16)	−0.0050 (15)

Geometric parameters (Å, º) top

Cd1—Cl2	2.4972 (8)	N1—C4	1.477 (5)
Cd1—Cl3	2.5361 (8)	C4—H4A	0.9700
Cd1—Cl4ⁱ	2.7025 (11)	C4—H4B	0.9700
Cd1—Cl4	2.5207 (10)	C4—C5	1.515 (6)
Cd1—N1	2.460 (3)	C2—H2A	0.9700
Cl4—Cd1ⁱ	2.7025 (11)	C2—H2B	0.9700
C1—H1A	0.9700	C2—N2	1.470 (5)
C1—H1B	0.9700	N2—H2	0.9100
C1—N1	1.465 (5)	N2—C5	1.493 (5)
C1—C2	1.555 (6)	N2—C6	1.510 (5)
C3—H3A	0.9700	C5—H5A	0.9700
C3—H3B	0.9700	C5—H5B	0.9700
C3—N1	1.477 (4)	C6—H6A	0.9700
C3—C6	1.530 (6)	C6—H6B	0.9700

Cl2—Cd1—Cl3	115.03 (3)	N1—C4—H4B	109.3
Cl2—Cd1—Cl4	119.78 (3)	N1—C4—C5	111.6 (3)
Cl2—Cd1—Cl4ⁱ	97.09 (3)	H4A—C4—H4B	108.0
Cl3—Cd1—Cl4ⁱ	91.56 (3)	C5—C4—H4A	109.3
Cl4—Cd1—Cl3	125.19 (3)	C5—C4—H4B	109.3
Cl4—Cd1—Cl4ⁱ	81.50 (3)	C1—C2—H2A	110.0
N1—Cd1—Cl2	92.66 (6)	C1—C2—H2B	110.0
N1—Cd1—Cl3	92.39 (6)	H2A—C2—H2B	108.3
N1—Cd1—Cl4	85.91 (7)	N2—C2—C1	108.6 (3)
N1—Cd1—Cl4ⁱ	166.77 (6)	N2—C2—H2A	110.0
Cd1—Cl4—Cd1ⁱ	98.50 (3)	N2—C2—H2B	110.0
H1A—C1—H1B	108.2	C2—N2—H2	109.0
N1—C1—H1A	109.7	C2—N2—C5	110.0 (3)
N1—C1—H1B	109.7	C2—N2—C6	111.2 (3)
N1—C1—C2	110.0 (3)	C5—N2—H2	109.0
C2—C1—H1A	109.7	C5—N2—C6	108.5 (3)
C2—C1—H1B	109.7	C6—N2—H2	109.0
H3A—C3—H3B	107.9	C4—C5—H5A	110.1
N1—C3—H3A	109.2	C4—C5—H5B	110.1
N1—C3—H3B	109.2	N2—C5—C4	108.2 (3)
N1—C3—C6	112.2 (3)	N2—C5—H5A	110.1
C6—C3—H3A	109.2	N2—C5—H5B	110.1
C6—C3—H3B	109.2	H5A—C5—H5B	108.4
C1—N1—Cd1	109.9 (2)	C3—C6—H6A	110.4
C1—N1—C3	109.7 (3)	C3—C6—H6B	110.4
C1—N1—C4	108.9 (3)	N2—C6—C3	106.7 (3)
C3—N1—Cd1	110.70 (19)	N2—C6—H6A	110.4
C4—N1—Cd1	110.4 (2)	N2—C6—H6B	110.4
C4—N1—C3	107.2 (3)	H6A—C6—H6B	108.6
N1—C4—H4A	109.3

Cd1—N1—C4—C5	−176.4 (2)	C1—C2—N2—C5	63.5 (4)
Cl2—Cd1—Cl4—Cd1ⁱ	−93.35 (4)	C1—C2—N2—C6	−56.8 (4)
Cl2—Cd1—N1—C1	67.3 (2)	C3—N1—C4—C5	−55.7 (4)
Cl2—Cd1—N1—C3	−171.4 (2)	N1—Cd1—Cl4—Cd1ⁱ	175.92 (7)
Cl2—Cd1—N1—C4	−52.9 (2)	N1—C1—C2—N2	−5.9 (5)
Cl3—Cd1—Cl4—Cd1ⁱ	85.88 (4)	N1—C3—C6—N2	−5.6 (4)
Cl3—Cd1—N1—C1	−47.9 (2)	N1—C4—C5—N2	−6.1 (4)
Cl3—Cd1—N1—C3	73.4 (2)	C2—C1—N1—Cd1	−176.3 (3)
Cl3—Cd1—N1—C4	−168.1 (2)	C2—C1—N1—C3	61.8 (4)
Cl4ⁱ—Cd1—Cl4—Cd1ⁱ	0.0	C2—C1—N1—C4	−55.2 (4)
Cl4—Cd1—N1—C1	−173.0 (2)	C2—N2—C5—C4	−56.7 (4)
Cl4ⁱ—Cd1—N1—C1	−155.2 (3)	C2—N2—C6—C3	63.1 (4)
Cl4—Cd1—N1—C3	−51.7 (2)	C5—N2—C6—C3	−58.0 (4)
Cl4ⁱ—Cd1—N1—C3	−33.9 (4)	C6—C3—N1—Cd1	−176.8 (3)
Cl4—Cd1—N1—C4	66.8 (2)	C6—C3—N1—C1	−55.5 (4)
Cl4ⁱ—Cd1—N1—C4	84.7 (4)	C6—C3—N1—C4	62.7 (4)
C1—N1—C4—C5	62.9 (4)	C6—N2—C5—C4	65.1 (4)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Cl3ⁱⁱ	0.91	2.33	3.205 (3)	162

Symmetry code: (ii) −x+1, y+1/2, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Cl3ⁱ	0.91	2.33	3.205 (3)	161.9

Symmetry code: (i) −x+1, y+1/2, −z+3/2.

Acknowledgements

This work was financially supported by the NSF of Jiangsu Province (BK20131244) and the Qing Lan Project of Jiangsu Province.

References

Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2004). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cai, Y. (2011). Acta Cryst. C67, m13–m16. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Chen, L. Z., Huang, D. D., Pan, Q. J. & Zhang, L. (2014). J. Mol. Struct. 1078, 68–73. Web of Science CSD CrossRef CAS Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2056-9890

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https://doi.org/10.1107/S2056989015023361

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