catena-Poly[bis(dimethylazanium) [[chloridocopper(II)]-di-μ-chlorido-[chloridocopper(II)]-di-μ-azido-κ4N:N]]

Zhang, W.-Y.; Yang, L.; Liu, J.

doi:10.1107/S1600536811050537

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Pages m1877-m1878

https://doi.org/10.1107/S1600536811050537

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catena-Poly[bis(dimethylazanium) [[chloridocopper(II)]-di-μ-chlorido-[chloridocopper(II)]-di-μ-azido-κ⁴N:N]]

Wei-Yi Zhang,^a Li Yang ^b and Jie Liu ^c ^*

^aDepartment of Obstetrics and Gynecology, The First Affiliated Hospital of Henan University, of Traditional Chinese Medicine, Zhengzhou, 450008, People's Republic of China, ^bHenan Medical College for Staff and Workers, Zhengzhou, 451191, People's Republic of China, and ^cDepartment of Urology, Henan Provincial People's Pospital, Zhengzhou, 450003, People's Republic of China
^*Correspondence e-mail: liu_jie1011@163.com

(Received 11 September 2011; accepted 24 November 2011; online 30 November 2011)

The crystal structure of the title complex, {(C₂H₈N)[CuCl₂(N₃)]}_n, exhibits inorganic chains consisting of Cu(II) cations as well azide and chloride anions. The chains, made up from Cu—Cl—Cu—N—Cu linkages, are aligned parallel to the c axis. This architecture is further stabilized by a number of N—H⋯Cl hydrogen bonds involving the protonated charge-compensating dimethylamine cations and chloride atoms.

Related literature

For background to polynuclear complexes, see Goher et al. (2000 ); Liu et al. (2008 ); Ribas et al. (1994 ); Saha et al. (2005 ); Vicente et al. (1993 ); Wang et al. (2008 ). For di- or polyalkylamines as templates, see: Cheetham et al. (1999 ); Hagrman et al. (1999 ). For related copper(II) complexes, see: Mautner et al. (1999 ).

Experimental

Crystal data

(C₂H₈N)[CuCl₂(N₃)]
M_r = 222.57
Monoclinic, C 2/c
a = 15.348 (5) Å
b = 11.089 (2) Å
c = 10.729 (2) Å
β = 119.73 (2)°
V = 1585.7 (7) Å³
Z = 8
Mo Kα radiation
μ = 3.35 mm⁻¹
T = 298 K
0.14 × 0.10 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.651, T_max = 0.775
3510 measured reflections
1811 independent reflections
1251 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.066
S = 0.94
1811 reflections
85 parameters
13 restraints
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—N1ⁱ	1.987 (2)
Cu1—N1	2.002 (2)
Cu1—Cl2	2.2527 (8)
Cu1—Cl1	2.2729 (9)
Cu1—Cl1ⁱⁱ	2.8860 (13)
Cu1—Cu1ⁱ	3.1460 (7)
Symmetry codes: (i) -x, -y+1, -z; (ii) $[-x, y, -z+{\script{1\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H1⋯Cl1ⁱⁱⁱ	0.99	2.41	3.331 (3)	154
N4—H2⋯Cl2ⁱⁱ	0.87	2.50	3.257 (3)	146
N4—H2⋯Cl1	0.87	2.82	3.270 (2)	114
N4—H2⋯Cl2	0.87	2.92	3.340 (3)	112
Symmetry codes: (ii) $[-x, y, -z+{\script{1\over 2}}]$ ; (iii) $[-x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811050537/zb2020sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811050537/zb2020Isup2.hkl

checkCIF report

Comment top

It is well known that the azide ion is a versatile ligand, and its versatility and efficiency lie in its functionality as a terminal monodentate and a bridging bi-, tri-, and tetradentate ligand. Because of this unique capability, azide attracts a lot of attention in the design of mono- or multidimensional metal-assembled azido complexes. (Vicente et al., 1993; Ribas et al., 1994; Goher et al., 2000; Saha et al., 2005; Liu et al., 2008). Having control over the molecular dimensions and geometry of the metal-ligand moiety in the compounds may lead to the control over their magnetic properties.(Wang et al., 2008). Di- or polyalkylamines, if protonated, could be conveniently used as cationic templates, and they have been widely employed in making metal oxalates, metal phosphates, and oxometalates.(Cheetham et al., 1999; Hagrman et al., 1999).In order to study the coordination behavior of the azide ion and templates, we synthesized herein the title complex [(NH₂(CH₃)₂)(CuN₃Cl₂)]_n. As shown in Figure 1, each asymmetric unit contains one Cu(II) atom, two chloride atoms, one azide atom and one dimethylamine cation. This architecture is further stabilized by a number of N—H···Cl hydrogen bonds involving the protonated charge-compensating dimethylamine cations and chloride atoms.(Figure 2). The bond distances for Cu—N are 1.984 (2) and 2.001 (2) Å, respectively. and the angles for N—Cu—Cl are between 92.86 (6) and 167.48 (6)°. The Cu—Cl bond lengths are 2.2526 (8) Å, 2.2725 (10) Å, respectively. and the bond angles for N—Cu—N and Cl—Cu—Cl are 75.74 (10) and 94.61 (2)°, respectively. These bond distances and bond angles are in agreement with those found in the reported copper compounds(Mautner et al., 1999).

Related literature top

For background to polynuclear complexes, see Goher et al. (2000); Liu et al. (2008); Ribas et al. (1994); Saha et al. (2005); Vicente et al. (1993); Wang et al. (2008). For di- or polyalkylamines as templates, see: Cheetham et al. (1999); Hagrman et al. (1999). For related copper(II) complexes, see: Mautner et al.(1999).)

Experimental top

A mixture of methanol and water (1:1, 2 ml) was gently layered on the top of a solution of Cu(ClO₄)₂.6H₂O (37.1 mg, 0.1 mmol) in water (3 ml). A solution of dimethylamine (18 mg, 0.4 mmol), NaN₃ (13 mg, 0.2 mmol) and hydrochloric acid (40.5 mg, 0.4 mmol, 36%) in methanol (10 ml) was added carefully as the third layer. Green crystals were obtained after 3 weeks, washed with ethanol and ether, and dried in air.

Structure description top

For background to polynuclear complexes, see Goher et al. (2000); Liu et al. (2008); Ribas et al. (1994); Saha et al. (2005); Vicente et al. (1993); Wang et al. (2008). For di- or polyalkylamines as templates, see: Cheetham et al. (1999); Hagrman et al. (1999). For related copper(II) complexes, see: Mautner et al.(1999).)

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. The molecular structure for title compound. Displacement ellipsoids at the 30% probability level. Symmetry codes: (i) -x,-y + 1,-z

catena-Poly[bis(dimethylazanium) [[chloridocopper(II)]-di-µ-chlorido-[chloridocopper(II)]-di-µ-azido- κ⁴N:N]] top

Crystal data top

(C₂H₈N)[CuCl₂(N₃)]	F(000) = 888
M_r = 222.57	D_x = 1.865 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.348 (5) Å	Cell parameters from 1037 reflections
b = 11.089 (2) Å	θ = 2.6–24.6°
c = 10.729 (2) Å	µ = 3.35 mm⁻¹
β = 119.73 (2)°	T = 298 K
V = 1585.7 (7) Å³	Block, green
Z = 8	0.14 × 0.10 × 0.08 mm

Data collection top

Bruker APEXII CCD diffractometer	1811 independent reflections
Radiation source: fine-focus sealed tube	1251 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
phi and ω scans	θ_max = 27.5°, θ_min = 3.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −19→19
T_min = 0.651, T_max = 0.775	k = −14→14
3510 measured reflections	l = −13→13

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.027	H-atom parameters constrained
wR(F²) = 0.066	w = 1/[σ²(F_o²) + (0.0361P)²] where P = (F_o² + 2F_c²)/3
S = 0.94	(Δ/σ)_max = 0.012
1811 reflections	Δρ_max = 0.41 e Å⁻³
85 parameters	Δρ_min = −0.38 e Å⁻³
13 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0036 (3)

Crystal data top

(C₂H₈N)[CuCl₂(N₃)]	V = 1585.7 (7) Å³
M_r = 222.57	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 15.348 (5) Å	µ = 3.35 mm⁻¹
b = 11.089 (2) Å	T = 298 K
c = 10.729 (2) Å	0.14 × 0.10 × 0.08 mm
β = 119.73 (2)°

Data collection top

Bruker APEXII CCD diffractometer	1811 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1251 reflections with I > 2σ(I)
T_min = 0.651, T_max = 0.775	R_int = 0.025
3510 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	13 restraints
wR(F²) = 0.066	H-atom parameters constrained
S = 0.94	Δρ_max = 0.41 e Å⁻³
1811 reflections	Δρ_min = −0.38 e Å⁻³
85 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	−0.03408 (2)	0.39407 (3)	0.06367 (3)	0.03133 (14)
Cl1	−0.14064 (5)	0.39423 (5)	0.15347 (8)	0.03677 (18)
Cl2	−0.03672 (5)	0.19228 (5)	0.03779 (7)	0.0404 (2)
N1	−0.04383 (19)	0.57303 (19)	0.0352 (3)	0.0409 (6)
N2	−0.08322 (18)	0.64469 (19)	0.0760 (3)	0.0388 (6)
N3	−0.1205 (2)	0.7121 (2)	0.1134 (3)	0.0659 (9)
N4	−0.1737 (2)	0.1071 (2)	0.1860 (3)	0.0492 (6)
H1	−0.2164	0.1291	0.0834	0.059*
H2	−0.1180	0.1479	0.2287	0.059*
C1	−0.1482 (3)	−0.0211 (3)	0.1877 (4)	0.0631 (9)
H1A	−0.1133	−0.0496	0.2850	0.095*
H1B	−0.1062	−0.0303	0.1455	0.095*
H1C	−0.2087	−0.0669	0.1337	0.095*
C2	−0.2303 (3)	0.1339 (3)	0.2608 (4)	0.0579 (8)
H2A	−0.2921	0.0894	0.2167	0.087*
H2B	−0.2446	0.2186	0.2544	0.087*
H2C	−0.1911	0.1110	0.3598	0.087*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0392 (2)	0.02505 (19)	0.0368 (2)	0.00100 (14)	0.02419 (17)	0.00218 (13)
Cl1	0.0405 (4)	0.0355 (4)	0.0434 (4)	0.0016 (3)	0.0277 (3)	0.0042 (3)
Cl2	0.0520 (5)	0.0270 (3)	0.0459 (5)	−0.0020 (3)	0.0271 (4)	−0.0012 (3)
N1	0.0609 (17)	0.0280 (11)	0.0535 (16)	0.0035 (10)	0.0433 (14)	0.0048 (10)
N2	0.0495 (15)	0.0285 (12)	0.0501 (16)	0.0050 (10)	0.0336 (13)	0.0062 (10)
N3	0.087 (2)	0.0483 (17)	0.092 (2)	0.0157 (15)	0.067 (2)	0.0034 (14)
N4	0.0569 (14)	0.0425 (11)	0.0524 (14)	−0.0084 (10)	0.0303 (11)	−0.0003 (9)
C1	0.0676 (17)	0.0421 (14)	0.0641 (17)	−0.0036 (14)	0.0208 (15)	0.0025 (13)
C2	0.0592 (17)	0.0641 (15)	0.0575 (17)	−0.0108 (14)	0.0342 (14)	0.0001 (13)

Geometric parameters (Å, º) top

Cu1—N1ⁱ	1.987 (2)	N4—C1	1.471 (4)
Cu1—N1	2.002 (2)	N4—C2	1.477 (4)
Cu1—Cl2	2.2527 (8)	N4—H1	0.9931
Cu1—Cl1	2.2729 (9)	N4—H2	0.8693
Cu1—Cl1ⁱⁱ	2.8860 (13)	C1—H1A	0.9600
Cu1—Cu1ⁱ	3.1460 (7)	C1—H1B	0.9600
Cl1—Cu1ⁱⁱ	2.8860 (13)	C1—H1C	0.9600
N1—N2	1.205 (3)	C2—H2A	0.9600
N1—Cu1ⁱ	1.987 (2)	C2—H2B	0.9600
N2—N3	1.129 (3)	C2—H2C	0.9600

N1ⁱ—Cu1—N1	75.87 (10)	N3—N2—N1	179.6 (3)
N1ⁱ—Cu1—Cl2	95.48 (7)	C1—N4—C2	114.3 (2)
N1—Cu1—Cl2	166.02 (7)	C1—N4—H1	106.0
N1ⁱ—Cu1—Cl1	167.54 (7)	C2—N4—H1	108.0
N1—Cu1—Cl1	92.79 (7)	C1—N4—H2	108.1
Cl2—Cu1—Cl1	94.60 (3)	C2—N4—H2	107.4
N1ⁱ—Cu1—Cl1ⁱⁱ	94.01 (8)	H1—N4—H2	113.1
N1—Cu1—Cl1ⁱⁱ	96.89 (7)	N4—C1—H1A	109.5
Cl2—Cu1—Cl1ⁱⁱ	94.63 (2)	N4—C1—H1B	109.5
Cl1—Cu1—Cl1ⁱⁱ	92.46 (3)	H1A—C1—H1B	109.5
N1ⁱ—Cu1—Cu1ⁱ	38.11 (6)	N4—C1—H1C	109.5
N1—Cu1—Cu1ⁱ	37.76 (7)	H1A—C1—H1C	109.5
Cl2—Cu1—Cu1ⁱ	132.67 (3)	H1B—C1—H1C	109.5
Cl1—Cu1—Cu1ⁱ	130.36 (2)	N4—C2—H2A	109.5
Cl1ⁱⁱ—Cu1—Cu1ⁱ	96.92 (2)	N4—C2—H2B	109.5
Cu1—Cl1—Cu1ⁱⁱ	87.54 (3)	H2A—C2—H2B	109.5
N2—N1—Cu1ⁱ	128.05 (19)	N4—C2—H2C	109.5
N2—N1—Cu1	127.70 (19)	H2A—C2—H2C	109.5
Cu1ⁱ—N1—Cu1	104.13 (10)	H2B—C2—H2C	109.5

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H1···Cl1ⁱⁱⁱ	0.99	2.41	3.331 (3)	154
N4—H2···Cl2ⁱⁱ	0.87	2.50	3.257 (3)	146
N4—H2···Cl1	0.87	2.82	3.270 (2)	114
N4—H2···Cl2	0.87	2.92	3.340 (3)	112

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

Experimental details

Crystal data
Chemical formula	(C₂H₈N)[CuCl₂(N₃)]
M_r	222.57
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	15.348 (5), 11.089 (2), 10.729 (2)
β (°)	119.73 (2)
V (Å³)	1585.7 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	3.35
Crystal size (mm)	0.14 × 0.10 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.651, 0.775
No. of measured, independent and observed [I > 2σ(I)] reflections	3510, 1811, 1251
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.066, 0.94
No. of reflections	1811
No. of parameters	85
No. of restraints	13
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.38

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010).

Selected bond lengths (Å) top

Cu1—N1ⁱ	1.987 (2)	Cu1—Cl1	2.2729 (9)
Cu1—N1	2.002 (2)	Cu1—Cl1ⁱⁱ	2.8860 (13)
Cu1—Cl2	2.2527 (8)	Cu1—Cu1ⁱ	3.1460 (7)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H1···Cl1ⁱⁱⁱ	0.99	2.41	3.331 (3)	154.0
N4—H2···Cl2ⁱⁱ	0.87	2.50	3.257 (3)	145.7
N4—H2···Cl1	0.87	2.82	3.270 (2)	113.9
N4—H2···Cl2	0.87	2.92	3.340 (3)	111.6

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

Acknowledgements

This study was supported by the Doctoral Research Fund of Henan Chinese Medicine (BSJJ2009–42).

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