catena-Poly[[bis(cis-1-tert-butyltetrazole-[kappa]N⁴)copper(II)]-di-[mu]-chloro]

The title polymeric compound, [CuCl₂(C₅H₁₀N₄)₂]_n, is the first structurally characterized complex with a bulky 1-alkyl­tetrazole ligand. The coordination polyhedron of the Cu atom is an elongated octahedron. The equatorial positions of the octahedron are occupied by the two Cl atoms, with Cu-Cl distances of 2.2920 (8) and 2.2796 (9) Å, and by the two N-4 atoms of the tetrazole ligands, with Cu-N distances of 2.023 (2) and 2.039 (2) Å. Two symmetry-related Cl atoms occupy the axial positions, at distances of 2.8244 (8) and 3.0174 (8) Å from the Cu atom. The [CuCl₂(C₅H₁₀N₄)₂] units form infinite chains extended along the b axis, linked together only by van der Waals interactions. The skeleton of each chain consists of Cu and Cl atoms.

S1. Comment

It has been found that the complexes of copper(II) chloride with 1-substituted tetrazoles, of the composition CuCl₂L₂, undergo magnetic phase transition to a ferromagnetic form at T = 10–12 K (Gaponik, 1998). X-ray investigations of such complexes are important to obtain the correlation between their structures and their magnetic properties. The present work is concerned with a crystal structure investigation of a new complex of the composition CuCl₂L₂, namely the title complex, (I) (Fig. 1). \sch

There are two ligand molecules in the asymmetric unit of (I), and these are denoted A and B. The tetrazole rings of molecules A and B have very similar geometries, close to those previously observed for these rings (Cambridge Structural Database; Version?; Allen & Kennard, 1993). The rings are essentially planar, with mean deviations of the tetrazole ring atoms from the least-squares plane of 0.0084 (3) and 0.0041 (3) Å for molecules A and B, respectively.

In (I), the coordination polyhedron of the Cu atom is an elongated octahedron (Table 1). The equatorial positions of the octahedron are occupied by the two Cl atoms, with Cu—Cl1 2.2920 (8) Å and Cu—Cl2 2.2796 (9) Å, and by the two N4 atoms of the 1-tert-butyltetrazole ligands, with Cu—N4A 2.023 (2) Å and Cu—N4B 2.039 (2) Å. The dihedral angle between the planes of the tetrazole rings of molecules A and B is 81.88 (14)°. The Cu—Cl distances for the axial bridging Cl atoms are 2.8244 (8) Å for Cl1ⁱ and 3.0174 (8) Å for Cl2ⁱⁱ [symmetry codes: (i) -x, 1 - y, -z; (ii) -x, -y, -z].

With regard to the packing structure of (I), the following may be noted. The [CuCl₂(C₅H₁₀N₄)₂] units form infinite chains extended along the b axis, linked together only by van der Waals interactions. The skeleton of each chain consists of Cu and Cl atoms. There are no classical hydrogen bonds in the structure of (I), but the following intermolecular contacts may be indicated: C5B—H5B···Cl2ⁱ 3.369 (3) Å, C5A—H5A···Cl1ⁱⁱ 3.369 (3) Å and C5A—H5A···Cl2ⁱⁱ 3.343 (3) Å (Steiner, 1996). These long contacts are additional interactions in the polymeric chains.

S2. Experimental

1-tert-Butyltetrazole was prepared by heterocyclization of tert-butylamine with triethyl orthoformate and trimethylsilylazide (Grigoriev et al., 1997). Single crystals of (I) were grown by slow crytallization from a solution in methanol-2-propanol-butanol (molar ratio 2:1.5:1) of a mixture containing CuCl₂·2H₂O and 1-tert-butyltetrazole in a 1:2.1 molar ratio over one week at 288–291 K.

S3. Refinement

The positions of atoms H5A and H5B, on atoms C5A and C5B, respectively, were refined, and these H atoms were subsequently treated as riding, with U_iso(H) = 1.2U_eq(C). The remaining H atoms were included in their idealized positions, with C—H = 0.96 Å, and refined using a riding model, with U_iso(H) = 1.5U_eq(C). Please check added text.

Computing details

Data collection: R3m Software (Nicolet, 1980); cell refinement: R3m Software; data reduction: R3m Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A view of the structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are plotted at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A fragment of the structure of (I) showing the chlorine-bridged chain.

catena-Poly-[[bis(cis-1-tert-butyltetrazole-κN⁴)copper(II)]-di-µ-chloro]

Crystal data

[CuCl2(C5H10N4)2]	F(000) = 796
Mr = 386.78	Dx = 1.455 Mg m^−3
Monoclinic, P21/n	Melting point: 413 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71069 Å
a = 13.389 (3) Å	Cell parameters from 25 reflections
b = 7.146 (1) Å	θ = 12.9–23.5°
c = 19.473 (4) Å	µ = 1.55 mm^−1
β = 108.57 (3)°	T = 293 K
V = 1766.1 (6) Å^3	Prism, green
Z = 4	0.64 × 0.42 × 0.30 mm

Data collection

Nicolet R3m four-circle diffractometer	4063 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.039
Graphite monochromator	θmax = 30.1°, θmin = 1.6°
ω/2θ scans	h = 0→18
Absorption correction: ψ-scan (North et al., 1968)	k = 0→10
Tmin = 0.438, Tmax = 0.654	l = −27→26
5383 measured reflections	3 standard reflections every 100 reflections
5183 independent reflections	intensity decay: none

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.127	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.061P)^2 + 1.2623P] where P = (Fo^2 + 2Fc^2)/3
5183 reflections	(Δ/σ)max < 0.001
196 parameters	Δρmax = 0.74 e Å^−3
0 restraints	Δρmin = −0.66 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
Cu	0.05749 (2)	0.25642 (4)	−0.002988 (16)	0.03863 (11)
Cl1	−0.02626 (5)	0.38933 (8)	0.07084 (3)	0.03891 (14)
Cl2	−0.09005 (5)	0.11279 (8)	−0.07628 (3)	0.04031 (14)
N1A	0.24472 (18)	−0.0206 (3)	−0.10037 (12)	0.0442 (5)
N2A	0.2401 (3)	0.1468 (5)	−0.1318 (2)	0.0862 (11)
N3A	0.1767 (3)	0.2503 (4)	−0.1106 (2)	0.0823 (11)
N4A	0.14145 (17)	0.1527 (3)	−0.06431 (12)	0.0428 (5)
C5A	0.1820 (2)	−0.0130 (4)	−0.06019 (15)	0.0453 (6)
H5A	0.171 (2)	−0.109 (4)	−0.0339 (17)	0.050*
C6A	0.3108 (3)	−0.1769 (5)	−0.11317 (18)	0.0588 (7)
C7A	0.2430 (5)	−0.2853 (8)	−0.1790 (3)	0.126 (2)
H7A1	0.2278	−0.2079	−0.2214	0.189*
H7A2	0.1783	−0.3219	−0.1715	0.189*
H7A3	0.2805	−0.3948	−0.1855	0.189*
C8A	0.3320 (5)	−0.3109 (8)	−0.0510 (3)	0.1151 (19)
H8A1	0.3742	−0.4124	−0.0586	0.173*
H8A2	0.2666	−0.3590	−0.0480	0.173*
H8A3	0.3690	−0.2478	−0.0066	0.173*
C9A	0.4039 (5)	−0.0997 (8)	−0.1233 (6)	0.202 (5)
H9A1	0.3852	−0.0089	−0.1616	0.303*
H9A2	0.4433	−0.1991	−0.1356	0.303*
H9A3	0.4461	−0.0410	−0.0792	0.303*
N1B	0.32155 (16)	0.4826 (3)	0.14838 (11)	0.0431 (5)
N2B	0.3659 (2)	0.3454 (6)	0.1223 (2)	0.0936 (13)
N3B	0.2924 (2)	0.2610 (5)	0.0730 (2)	0.0929 (14)
N4B	0.19883 (15)	0.3401 (3)	0.06717 (11)	0.0411 (4)
C5B	0.21956 (19)	0.4765 (4)	0.11367 (13)	0.0398 (5)
H5B	0.170 (2)	0.561 (4)	0.1207 (16)	0.050*
C6B	0.3849 (2)	0.6152 (5)	0.20485 (15)	0.0527 (7)
C7B	0.3153 (3)	0.6863 (6)	0.24776 (18)	0.0723 (10)
H7B1	0.2547	0.7483	0.2157	0.108*
H7B2	0.3547	0.7729	0.2840	0.108*
H7B3	0.2929	0.5830	0.2707	0.108*
C8B	0.4181 (5)	0.7741 (8)	0.1665 (3)	0.118 (2)
H8B1	0.4609	0.7265	0.1392	0.177*
H8B2	0.4581	0.8627	0.2017	0.177*
H8B3	0.3570	0.8346	0.1344	0.177*
C9B	0.4769 (3)	0.5074 (7)	0.2558 (2)	0.0846 (13)
H9B1	0.4502	0.4048	0.2766	0.127*
H9B2	0.5175	0.5887	0.2936	0.127*
H9B3	0.5207	0.4602	0.2291	0.127*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.03170 (15)	0.04672 (19)	0.03872 (17)	−0.00179 (12)	0.01300 (12)	−0.01274 (12)
Cl1	0.0385 (3)	0.0399 (3)	0.0424 (3)	0.0010 (2)	0.0186 (2)	−0.0038 (2)
Cl2	0.0397 (3)	0.0401 (3)	0.0378 (3)	−0.0028 (2)	0.0077 (2)	−0.0025 (2)
N1A	0.0462 (11)	0.0473 (12)	0.0462 (11)	0.0017 (10)	0.0245 (9)	−0.0052 (9)
N2A	0.128 (3)	0.0658 (19)	0.104 (2)	0.0296 (19)	0.092 (2)	0.0259 (18)
N3A	0.121 (3)	0.0594 (18)	0.100 (3)	0.0262 (17)	0.082 (2)	0.0212 (16)
N4A	0.0458 (11)	0.0449 (11)	0.0436 (11)	−0.0031 (9)	0.0224 (9)	−0.0097 (9)
C5A	0.0450 (13)	0.0463 (14)	0.0524 (14)	−0.0069 (11)	0.0266 (11)	−0.0065 (12)
C6A	0.0569 (17)	0.0629 (18)	0.0645 (18)	0.0155 (15)	0.0304 (15)	−0.0023 (16)
C7A	0.143 (5)	0.121 (4)	0.102 (4)	0.052 (4)	0.021 (3)	−0.049 (3)
C8A	0.137 (5)	0.097 (3)	0.132 (4)	0.064 (3)	0.072 (4)	0.036 (3)
C9A	0.133 (5)	0.090 (4)	0.468 (14)	0.019 (4)	0.215 (8)	0.016 (6)
N1B	0.0332 (9)	0.0517 (12)	0.0406 (10)	0.0004 (9)	0.0065 (8)	−0.0064 (9)
N2B	0.0348 (13)	0.116 (3)	0.113 (3)	0.0135 (16)	0.0003 (15)	−0.064 (2)
N3B	0.0362 (13)	0.111 (3)	0.116 (3)	0.0168 (15)	0.0026 (15)	−0.067 (2)
N4B	0.0328 (9)	0.0454 (11)	0.0435 (11)	0.0042 (8)	0.0099 (8)	−0.0087 (9)
C5B	0.0331 (11)	0.0408 (12)	0.0416 (12)	0.0033 (10)	0.0066 (9)	−0.0034 (10)
C6B	0.0447 (14)	0.0630 (18)	0.0423 (13)	−0.0124 (13)	0.0021 (11)	−0.0075 (12)
C7B	0.067 (2)	0.078 (2)	0.062 (2)	0.0009 (18)	0.0072 (17)	−0.0268 (18)
C8B	0.153 (5)	0.120 (4)	0.077 (3)	−0.087 (4)	0.029 (3)	−0.008 (3)
C9B	0.0538 (19)	0.120 (4)	0.061 (2)	0.014 (2)	−0.0078 (15)	−0.021 (2)

Geometric parameters (Å, º)

Cu—N4A	2.023 (2)	C9A—H9A1	0.9600
Cu—N4B	2.039 (2)	C9A—H9A2	0.9600
Cu—Cl2	2.2796 (9)	C9A—H9A3	0.9600
Cu—Cl1	2.2920 (8)	N1B—C5B	1.317 (3)
Cu—Cl1^i	2.8244 (8)	N1B—N2B	1.328 (4)
Cu—Cl2^ii	3.0174 (8)	N1B—C6B	1.494 (3)
N1A—C5A	1.318 (3)	N2B—N3B	1.285 (4)
N1A—N2A	1.336 (4)	N3B—N4B	1.345 (3)
N1A—C6A	1.494 (4)	N4B—C5B	1.299 (3)
N2A—N3A	1.288 (4)	C5B—H5B	0.94 (3)
N3A—N4A	1.339 (4)	C6B—C8B	1.502 (5)
N4A—C5A	1.295 (4)	C6B—C9B	1.522 (5)
C5A—H5A	0.89 (3)	C6B—C7B	1.523 (5)
C6A—C9A	1.433 (6)	C7B—H7B1	0.9601
C6A—C8A	1.498 (6)	C7B—H7B2	0.9600
C6A—C7A	1.525 (6)	C7B—H7B3	0.9601
C7A—H7A1	0.9599	C8B—H8B1	0.9601
C7A—H7A2	0.9600	C8B—H8B2	0.9600
C7A—H7A3	0.9600	C8B—H8B3	0.9600
C8A—H8A1	0.9599	C9B—H9B1	0.9601
C8A—H8A2	0.9600	C9B—H9B2	0.9600
C8A—H8A3	0.9601	C9B—H9B3	0.9599
N4A—Cu—N4B	86.07 (9)	H8A2—C8A—H8A3	109.5
N4A—Cu—Cl2	89.95 (7)	C6A—C9A—H9A1	110.1
N4B—Cu—Cl2	170.30 (7)	C6A—C9A—H9A2	108.7
N4A—Cu—Cl1	175.38 (6)	H9A1—C9A—H9A2	109.5
N4B—Cu—Cl1	89.61 (6)	C6A—C9A—H9A3	109.6
Cl2—Cu—Cl1	94.57 (3)	H9A1—C9A—H9A3	109.5
N4A—Cu—Cl1^i	94.57 (7)	H9A2—C9A—H9A3	109.5
N4B—Cu—Cl1^i	91.03 (7)	C5B—N1B—N2B	107.2 (2)
Cl2—Cu—Cl1^i	98.10 (3)	C5B—N1B—C6B	130.6 (2)
Cl1—Cu—Cl1^i	83.85 (2)	N2B—N1B—C6B	122.1 (2)
N4A—Cu—Cl2^ii	87.98 (7)	N3B—N2B—N1B	107.6 (2)
N4B—Cu—Cl2^ii	87.81 (7)	N2B—N3B—N4B	109.7 (3)
Cl2—Cu—Cl2^ii	83.21 (3)	C5B—N4B—N3B	105.6 (2)
Cl1—Cu—Cl2^ii	93.51 (2)	C5B—N4B—Cu	129.34 (17)
Cl1^i—Cu—Cl2^ii	177.130 (18)	N3B—N4B—Cu	125.00 (18)
C5A—N1A—N2A	106.8 (2)	N4B—C5B—N1B	109.8 (2)
C5A—N1A—C6A	130.7 (3)	N4B—C5B—H5B	125.6 (19)
N2A—N1A—C6A	122.5 (2)	N1B—C5B—H5B	124.6 (19)
N3A—N2A—N1A	107.9 (2)	N1B—C6B—C8B	107.6 (3)
N2A—N3A—N4A	109.0 (3)	N1B—C6B—C9B	108.1 (3)
C5A—N4A—N3A	106.7 (2)	C8B—C6B—C9B	113.6 (4)
C5A—N4A—Cu	126.85 (19)	N1B—C6B—C7B	108.2 (2)
N3A—N4A—Cu	125.99 (19)	C8B—C6B—C7B	110.5 (4)
N4A—C5A—N1A	109.6 (3)	C9B—C6B—C7B	108.7 (3)
N4A—C5A—H5A	126 (2)	C6B—C7B—H7B1	109.5
N1A—C5A—H5A	124 (2)	C6B—C7B—H7B2	109.3
C9A—C6A—N1A	108.8 (3)	H7B1—C7B—H7B2	109.5
C9A—C6A—C8A	114.1 (5)	C6B—C7B—H7B3	109.6
N1A—C6A—C8A	108.2 (3)	H7B1—C7B—H7B3	109.5
C9A—C6A—C7A	113.0 (5)	H7B2—C7B—H7B3	109.5
N1A—C6A—C7A	107.1 (3)	C6B—C8B—H8B1	109.3
C8A—C6A—C7A	105.3 (4)	C6B—C8B—H8B2	109.3
C6A—C7A—H7A1	109.7	H8B1—C8B—H8B2	109.5
C6A—C7A—H7A2	109.5	C6B—C8B—H8B3	109.8
H7A1—C7A—H7A2	109.5	H8B1—C8B—H8B3	109.5
C6A—C7A—H7A3	109.2	H8B2—C8B—H8B3	109.5
H7A1—C7A—H7A3	109.5	C6B—C9B—H9B1	109.2
H7A2—C7A—H7A3	109.5	C6B—C9B—H9B2	109.7
C6A—C8A—H8A1	109.0	H9B1—C9B—H9B2	109.5
C6A—C8A—H8A2	109.7	C6B—C9B—H9B3	109.5
H8A1—C8A—H8A2	109.5	H9B1—C9B—H9B3	109.5
C6A—C8A—H8A3	109.7	H9B2—C9B—H9B3	109.5
H8A1—C8A—H8A3	109.5
C5A—N1A—N2A—N3A	0.2 (5)	C5B—N1B—N2B—N3B	0.5 (5)
C6A—N1A—N2A—N3A	179.7 (3)	C6B—N1B—N2B—N3B	−177.5 (3)
N1A—N2A—N3A—N4A	1.2 (5)	N1B—N2B—N3B—N4B	−1.0 (5)
N2A—N3A—N4A—C5A	−2.1 (5)	N2B—N3B—N4B—C5B	1.1 (5)
N2A—N3A—N4A—Cu	170.3 (3)	N2B—N3B—N4B—Cu	−179.7 (3)
N4B—Cu—N4A—C5A	89.0 (2)	N4A—Cu—N4B—C5B	154.2 (3)
Cl2—Cu—N4A—C5A	−82.1 (2)	Cl1—Cu—N4B—C5B	−24.2 (2)
Cl1^i—Cu—N4A—C5A	179.7 (2)	Cl1^i—Cu—N4B—C5B	59.6 (2)
Cl2^ii—Cu—N4A—C5A	1.1 (2)	Cl2^ii—Cu—N4B—C5B	−117.7 (2)
N4B—Cu—N4A—N3A	−82.0 (3)	N4A—Cu—N4B—N3B	−24.8 (3)
Cl2—Cu—N4A—N3A	106.9 (3)	Cl1—Cu—N4B—N3B	156.8 (3)
Cl1^i—Cu—N4A—N3A	8.8 (3)	Cl1^i—Cu—N4B—N3B	−119.3 (3)
Cl2^ii—Cu—N4A—N3A	−169.9 (3)	Cl2^ii—Cu—N4B—N3B	63.3 (3)
N3A—N4A—C5A—N1A	2.2 (4)	N3B—N4B—C5B—N1B	−0.8 (4)
Cu—N4A—C5A—N1A	−170.15 (18)	Cu—N4B—C5B—N1B	−179.95 (18)
N2A—N1A—C5A—N4A	−1.5 (4)	N2B—N1B—C5B—N4B	0.2 (4)
C6A—N1A—C5A—N4A	179.0 (3)	C6B—N1B—C5B—N4B	178.0 (3)
C5A—N1A—C6A—C9A	−147.0 (5)	C5B—N1B—C6B—C8B	−89.7 (4)
N2A—N1A—C6A—C9A	33.7 (6)	N2B—N1B—C6B—C8B	87.7 (4)
C5A—N1A—C6A—C8A	−22.5 (5)	C5B—N1B—C6B—C9B	147.3 (3)
N2A—N1A—C6A—C8A	158.1 (4)	N2B—N1B—C6B—C9B	−35.3 (4)
C5A—N1A—C6A—C7A	90.6 (4)	C5B—N1B—C6B—C7B	29.7 (4)
N2A—N1A—C6A—C7A	−88.8 (5)	N2B—N1B—C6B—C7B	−152.9 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5B—H5B···Cl2^i	0.94 (3)	2.59 (3)	3.369 (3)	140 (2)
C5A—H5A···Cl1^ii	0.89 (3)	2.72 (3)	3.369 (3)	130 (2)
C5A—H5A···Cl2^ii	0.89 (3)	2.70 (3)	3.343 (3)	130 (2)

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