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In the title compound, [CuCl2(C3H5N7)2], the coordination polyhedron of the Cu atom is an elongated square bipyramid with \overline 1 site symmetry. The equatorial positions are occupied by the two Cl atoms with Cu—Cl distances of 2.288 (1) Å and two azido­ethyl­tetrazole ligands with Cu—N distances of 1.999 (2) Å. Two Cl atoms in axial positions are 2.956 (1) Å distant from the Cu atom. The Cl atoms play the role of non-symmetrical bridges responsible for formation of layers parallel to the bc plane.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801009965/ya6036sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801009965/ya6036Isup2.hkl
Contains datablock I

CCDC reference: 170862

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.033
  • wR factor = 0.097
  • Data-to-parameter ratio = 16.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
PLAT_731 Alert C Bond Calc 2.956(3), Rep 2.9560(10) .... 3.00 s.u-Ratio CU1 -CL1 1.555 2.545
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

It has been found in the past few years that the complexes of copper(II) chloride with 1-monosubstituted tetrazole of composition CuCl2L2, where L = 1-ethyl-, 1-hexyl, 1-vinyl and 1-allyltetrazole, undergo magnetic phase transition to ferromagnetic form at T = 10–12 K (Gaponik, 1998). X-ray investigations of the complexes with L = 1-ethyltetrazole (Virovets et al., 1995) and L = 1-allyltetrazole (Virovets et al., 1996) showed layered polymeric crystal structure of these compounds, which is known to be a necessary condition for ferromagnetic ordering for transition metal complexes (Ovcharenko & Sagdeev, 1999). In the present work, the crystal structure of a new complex, (I), of composition CuCl2L2 (L = 1-azidoethyltetrazole), is reported.

In the title compound, the coordination polyhedron of the Cu atom is an elongated square bipyramid with 1 site symmetry. The equatorial positions are occupied by the two Cl atoms with Cu—Cl distances of 2.288 (1) Å and two N4 atoms of azidoethyltetrazole molecules with Cu—N distances of 1.999 (2) Å. Two Cl atoms in axial position are at a distance of 2.956 (1) Å from the Cu atom.

The tetrazole ring is essentially planar, with a mean deviation of terazole ring atoms from their least-squares plane of 0.006 (2) Å. The tetrazole plane forms the dihedral angle of 50.9 (1)° with the equatorial plane of the coordination square pyramid of the Cu atom. In the azide fragment, the N5—N6 distance is 1.204 (4) Å and the N6—N7 distance is 1.123 (4) Å; the N5—N6—N7 and C7—N5—N6 bond angles are 173.1 (4) and 115.7 (3)°, respectively.

The analysis of the crystal packing of complex (I) reveals a couple of interesting features. The Cl atoms play the role of non-symmetrical bridges which are responsible for formation of layers parallel to the yz plane. They also act as acceptors of non-classic intermolecular hydrogen bonds C5—H5···Cl, with a Cl···C5 distance of 3.529 (3) Å (Steiner, 1996). Thus, the title compound has a layered polymeric crystal structure, and hence may be an object for magnetic properties investigations.

Experimental top

The synthesis of the title compound was carried out at 425–426 K by reaction of CuCl2·2H2O with 1-(2-azidoethyl)tetrazole (molar ratio 1:2) by a method proposed by Degtiarik et al. (1985). Recrystallization of (I) was performed from water solution. 1-(2-Azidoethyl)tetrazole was prepared by heterocyclization of 1-amino-2-azidoethan with ethyl orthoformate and sodium azide in acetic acid (Gaponik et al., 1985).

Refinement top

The H– toms were included in geometrically calculated positions and refined using a riding model with Uiso(H) = 1.2Ueq of the corresponding carrier atom.

Computing details top

Data collection: R3m Software (Nicolet, 1980); cell refinement: R3m software; data reduction: R3m software; program(s) used to solve structure: SIR97 (Altomare et al., 1999); 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 top
[Figure 1] Fig. 1. ORTEP-3 (Farrugia, 1997) drawing of the molecule of (I). Long intermolecular Cu···Cl interactions are shown as dashed lines. Displacement ellipsoids are plotted at the 50% probability level.
[Figure 2] Fig. 2. The packing diagram of (I) viewed along the x axis (H atoms have been omitted for clarity).
catena-poly[[bis(1-(2-azidoethyl)tetrazole-N4)-copper(II)]-di-µ-chloro] top
Crystal data top
[CuCl2(C3H5N7)2]F(000) = 414
Mr = 412.72Dx = 1.818 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 15.616 (2) ÅCell parameters from 25 reflections
b = 6.702 (2) Åθ = 17.2–24.2°
c = 7.208 (6) ŵ = 1.83 mm1
β = 91.87 (3)°T = 293 K
V = 754.0 (7) Å3Plate, blue
Z = 20.80 × 0.46 × 0.02 mm
Data collection top
Nicolet R3m four-circle
diffractometer
1529 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.018
Graphite monochromatorθmax = 27.5°, θmin = 1.3°
ω/2θ scansh = 2020
Absorption correction: ψ scan
(North et al., 1968)
k = 80
Tmin = 0.323, Tmax = 0.964l = 09
1880 measured reflections3 standard reflections every 100 reflections
1734 independent reflections intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.069P)2 + 0.223P]
where P = (Fo2 + 2Fc2)/3
1734 reflections(Δ/σ)max < 0.001
106 parametersΔρmax = 0.47 e Å3
0 restraintsΔρmin = 0.34 e Å3
Crystal data top
[CuCl2(C3H5N7)2]V = 754.0 (7) Å3
Mr = 412.72Z = 2
Monoclinic, P21/cMo Kα radiation
a = 15.616 (2) ŵ = 1.83 mm1
b = 6.702 (2) ÅT = 293 K
c = 7.208 (6) Å0.80 × 0.46 × 0.02 mm
β = 91.87 (3)°
Data collection top
Nicolet R3m four-circle
diffractometer
1529 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.018
Tmin = 0.323, Tmax = 0.9643 standard reflections every 100 reflections
1880 measured reflections intensity decay: none
1734 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0330 restraints
wR(F2) = 0.097H-atom parameters constrained
S = 1.04Δρmax = 0.47 e Å3
1734 reflectionsΔρmin = 0.34 e Å3
106 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
xyzUiso*/Ueq
Cu10.00000.50000.50000.02654 (15)
Cl10.05746 (3)0.71706 (7)0.28493 (7)0.02841 (16)
N10.20604 (11)0.8732 (3)0.4690 (3)0.0315 (4)
N20.24478 (14)0.6972 (3)0.4424 (4)0.0463 (6)
N30.18738 (13)0.5609 (3)0.4586 (4)0.0427 (5)
N40.11123 (10)0.6469 (3)0.4928 (2)0.0259 (4)
C50.12436 (13)0.8398 (3)0.4984 (3)0.0301 (4)
H50.08320.93670.51960.036*
C60.25272 (17)1.0620 (4)0.4532 (5)0.0462 (6)
H6A0.21651.17090.49200.055*
H6B0.26641.08410.32450.055*
C70.33252 (18)1.0609 (5)0.5685 (5)0.0493 (7)
H7A0.36920.95160.53270.059*
H7B0.31981.04590.69860.059*
N50.37491 (16)1.2541 (4)0.5364 (5)0.0634 (8)
N60.44506 (17)1.2736 (4)0.6084 (4)0.0605 (7)
N70.5109 (2)1.3094 (7)0.6666 (6)0.1060 (14)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0247 (2)0.0269 (2)0.0280 (2)0.00358 (12)0.00057 (14)0.00865 (13)
Cl10.0346 (3)0.0283 (3)0.0223 (3)0.00035 (17)0.00029 (19)0.00461 (18)
N10.0296 (9)0.0286 (9)0.0364 (11)0.0046 (7)0.0016 (7)0.0013 (7)
N20.0326 (10)0.0355 (10)0.0718 (17)0.0034 (8)0.0140 (10)0.0078 (10)
N30.0303 (9)0.0305 (9)0.0679 (16)0.0010 (8)0.0093 (9)0.0085 (10)
N40.0263 (8)0.0268 (8)0.0248 (9)0.0013 (6)0.0034 (6)0.0033 (7)
C50.0285 (10)0.0282 (9)0.0337 (12)0.0016 (8)0.0008 (8)0.0018 (8)
C60.0394 (13)0.0352 (12)0.0635 (18)0.0136 (11)0.0071 (12)0.0120 (12)
C70.0439 (14)0.0448 (13)0.0585 (18)0.0159 (12)0.0088 (13)0.0069 (13)
N50.0509 (15)0.0575 (14)0.081 (2)0.0275 (12)0.0146 (14)0.0163 (13)
N60.0510 (14)0.0704 (17)0.0600 (17)0.0302 (13)0.0016 (12)0.0021 (13)
N70.064 (2)0.141 (4)0.111 (3)0.052 (2)0.024 (2)0.010 (3)
Geometric parameters (Å, º) top
Cu1—Cl12.288 (1)C5—H50.9300
Cu1—Cl1i2.956 (1)C6—C71.475 (4)
Cu1—N41.999 (2)C6—H6A0.9700
N1—N21.342 (3)C6—H6B0.9700
N1—C51.319 (3)C7—N51.476 (3)
N1—C61.467 (3)C7—H7A0.9700
N2—N31.288 (3)C7—H7B0.9700
N3—N41.351 (3)N5—N61.204 (4)
N4—C51.309 (3)N6—N71.123 (4)
N4—Cu1—Cl189.49 (5)N1—C6—C7111.4 (2)
N4ii—Cu1—Cl1i89.18 (6)N1—C6—H6A109.3
Cl1—Cu1—Cl1i93.35 (5)C7—C6—H6A109.3
C5—N1—N2108.5 (2)N1—C6—H6B109.3
C5—N1—C6130.1 (2)C7—C6—H6B109.3
N2—N1—C6121.3 (2)H6A—C6—H6B108.0
N3—N2—N1107.0 (2)C6—C7—N5106.4 (2)
N2—N3—N4109.5 (2)C6—C7—H7A110.4
C5—N4—N3106.8 (2)N5—C7—H7A110.4
C5—N4—Cu1128.4 (1)C6—C7—H7B110.4
N3—N4—Cu1124.4 (1)N5—C7—H7B110.4
N4—C5—N1108.3 (2)H7A—C7—H7B108.6
N4—C5—H5125.9N6—N5—C7115.7 (3)
N1—C5—H5125.9N7—N6—N5173.1 (4)
C5—N1—N2—N30.9 (3)Cl1i—Cu1—N4—N332.29 (18)
C6—N1—N2—N3177.7 (2)N3—N4—C5—N10.1 (3)
N1—N2—N3—N40.9 (3)Cu1—N4—C5—N1172.95 (15)
N2—N3—N4—C50.5 (3)N2—N1—C5—N40.6 (3)
N2—N3—N4—Cu1172.71 (18)C6—N1—C5—N4177.0 (2)
Cl1—Cu1—N4—C546.07 (19)C5—N1—C6—C7132.1 (3)
Cl1ii—Cu1—N4—C5133.93 (19)N2—N1—C6—C751.9 (4)
Cl1i—Cu1—N4—C5139.41 (18)N1—C6—C7—N5178.1 (3)
Cl1—Cu1—N4—N3125.63 (19)C6—C7—N5—N6174.3 (3)
Cl1ii—Cu1—N4—N354.37 (19)
Symmetry codes: (i) x, y1/2, z+1/2; (ii) x, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5···Cl1iii0.932.753.529 (3)142
Symmetry code: (iii) x, y+2, z+1.

Experimental details

Crystal data
Chemical formula[CuCl2(C3H5N7)2]
Mr412.72
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)15.616 (2), 6.702 (2), 7.208 (6)
β (°) 91.87 (3)
V3)754.0 (7)
Z2
Radiation typeMo Kα
µ (mm1)1.83
Crystal size (mm)0.80 × 0.46 × 0.02
Data collection
DiffractometerNicolet R3m four-circle
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.323, 0.964
No. of measured, independent and
observed [I > 2σ(I)] reflections
1880, 1734, 1529
Rint0.018
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.033, 0.097, 1.04
No. of reflections1734
No. of parameters106
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.47, 0.34

Computer programs: R3m Software (Nicolet, 1980), R3m software, SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97.

Selected geometric parameters (Å, º) top
Cu1—Cl12.288 (1)N3—N41.351 (3)
Cu1—Cl1i2.956 (1)N4—C51.309 (3)
Cu1—N41.999 (2)C6—C71.475 (4)
N1—N21.342 (3)C7—N51.476 (3)
N1—C51.319 (3)N5—N61.204 (4)
N1—C61.467 (3)N6—N71.123 (4)
N2—N31.288 (3)
N4—Cu1—Cl189.49 (5)C5—N4—N3106.8 (2)
N4ii—Cu1—Cl1i89.18 (6)C5—N4—Cu1128.4 (1)
Cl1—Cu1—Cl1i93.35 (5)N3—N4—Cu1124.4 (1)
C5—N1—N2108.5 (2)N4—C5—N1108.3 (2)
C5—N1—C6130.1 (2)N1—C6—C7111.4 (2)
N2—N1—C6121.3 (2)C6—C7—N5106.4 (2)
N3—N2—N1107.0 (2)N6—N5—C7115.7 (3)
N2—N3—N4109.5 (2)N7—N6—N5173.1 (4)
Symmetry codes: (i) x, y1/2, z+1/2; (ii) x, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5···Cl1iii0.932.753.529 (3)141.8
Symmetry code: (iii) x, y+2, z+1.
 

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