Coordination polymers formed by bridging 2-substituted tetra­zole ligands: poly[[dichloro­copper(II)]-di-μ₂-2-prop­yl-2H-tetra­zole-κ²N¹:N⁴] and poly[[dichloro­copper(II)]-di-μ₂-2-all­yl-2H-tetra­zole-κ²N¹:N⁴]

Two polymeric complexes, [CuCl₂L₂]_n, where L is 2-propyl­tetra­zole (C₄H₈N₄) or 2-allyl­tetra­zole (C₄H₆N₄), are the first coordination polymers of 2-substituted tetra­zoles in which only the tetra­zole rings bridge neighbouring Cu atoms. In both complexes, the Cu atoms lie on inversion centres and are six-coordinated in tetra­gonally distorted octa­hedral geometries, CuCl₂N₄, with two N¹ tetra­zole ring atoms in the axial positions and two Cl atoms and two N⁴ tetra­zole ring atoms in the equatorial sites. The Cl atoms do not participate in the polymeric layer formation.

S1. Comment

We have recently reported the crystal structures of a number of copper(II) chloride complexes with 2-substituted tetrazoles (Lyakhov et al., 2005, and references cited therein). Some of them present chain coordination polymers with only Cl atoms as bridges between the neighbouring Cu atoms (Lyakhov et al., 2003a; Lyakhov et al., 2005). In other compounds, either chain coordination polymers (Lyakhov, Gaponik, Degtyarik, Matulis et al., 2003) or layered ones (Lyakhov et al., 2003b), polymeric structures are formed through both Cl bridges and tetrazole ring coordination. Here, we report two complexes of copper(II) chloride with 2-substituted tetrazoles, which are coordination polymers due only to the bridging coordination of the tetrazole rings. They are of the composition [CuCl₂L₂], where L is 2-propyltetrazole in (I) (Fig. 1) and 2-allyltetrazole in (II) (Fig. 2).

The tetrazole rings of the ligand molecules of complexes (I) and (II) are essentially planar, with mean deviations of the tetrazole ring atoms from their least-squares plane being 0.0007 (14) and 0.0010 (14) Å for (I) and (II), respectively. The ring geometries (Tables 1 and 3) are similar to those found previously for complexes of 2-substituted tetrazoles. For both compounds, the shortest ring bond is the formal N2—N3 single bond of 1.308 (2) and 1.305 (2) Å for (I) and (II), respectively. The remaining ring bonds lie within the ranges 1.324 (2)–1.337 (3) Å for (I) and 1.318 (3)–1.345 (3) Å for (II).

In both compounds, the Cu1 atoms lie on inversion centres and have tetragonally distorted octahedral coordination (Tables 1 and 3). In both complexes, the equatorial positions of the octahedra are occupied by two N4 and two Cl1 atoms, while two N1 atoms lie in the axial sites. The Cu1—N4 distances are similar in (I) and (II), as are the Cu1—Cl1 bond lengths, while the Cu1—N1 bond in (I) is 0.175 (2) Å longer than that in (II).

Both compounds are layered coordination polymers, in which only the ligand molecules act as bridges between neighbouring Cu atoms, through tetrazole ring atoms N4 and N1. The Cl atoms do not participate in the formation of polymeric layers. Figs. 3 and 4 show that the atomic arrangement of the polymeric layers is similar in both compounds. There are also differences within the layers of (I) and (II) with respect to the tetrazole ring orientations. The Cl1—Cu1—N4—C5 dihedral angle is −151.34 (19)° for (I) and 178.28 (19)° for (II), so that in the latter the tetrazole ring lies almost in the equatorial plane of the Cu octahedron.

In 2-substituted tetrazoles, N¹ ring atoms may be the preferred metal binding site compared with N³ atoms, based on the observed Cu—N¹ bond lengths of 2.7739 (17) Å in (I), 2.5987 (18) Å in (II) and 2.851 (2) Å in the related complex [CuCl₂L₂], where L is 2-ethyltetrazole (Lyakhov et al., 2003b), and the Cu—N³ bond length of 2.926 (3) Å in the complex [Cu₃L₄Cl₆], where L is 2-allyltetrazole (Lyakhov, Gaponik, Degtyarik, Matulis et al., 2003). Reliable conclusions about the electron-donating properties of the N¹ and N³ tetrazole ring atoms requires further experimental study, as well as verification by quantum-chemical calculations.

In the structures of (I) and (II), there are weak C5—H5···Cl hydrogen bonds (Tables 2 and 4), implemented inside the polymeric layers. In complex (II), there are also interlayer hydrogen bonds between the methylene H atom of the allyl substituent and a Cl atom of a neighbouring layer (Table 4). Because the propyl and allyl substituents at the N2 tetrazole ring atom of the ligand molecules are similar in size, it was expected that complexes (I) and (II) would be isostructural. However, the obtained data show a similarity only in the atomic arrangement inside the polymeric layers.

S2. Experimental

2-Propyltetrazole and 2-allyltetrazole were prepared by the method described by Gaponik et al. (1980). For the synthesis of (I), 2-propyltetrazole (1.23 g, 0.011 mol) was added to a solution of CuCl₂·2H₂O (0.85 g, 0.005 mol) in methanol (10 ml). The mixture was stirred for 1 h at room temperature and then kept for about 20 d at room temperature in air. Green–blue crystals of (I) were obtained (yield 1.20 g, 67%). Analysis for (I), found: Cu 17.9, Cl 19.5%; C₈H₁₆Cl₂CuN₈ requires: Cu 17.7, Cl 19.8. For the synthesis of (II), CuCl₂·2H₂O (0.85 g, 0.005 mol) was added to a solution containing 2-allylterazole (1.21 g, 0.011 mol) in a methanol–diethyl ether mixture (50 ml, molar ratio 1:4). The resulting mixture was stirred for 1 h at room temperature. After removing about 35 ml of solvent by heating the mixture at 353 K (water bath) for 30 min in air, it was cooled to room temperature and filtered. From the filtrate, 10 d later, green–blue crystals of (II) were obtained (yield 0.91 g, 51%). Analysis for (II), found: Cu 17.6, Cl 19.5%; C₈H₁₂Cl₂CuN₈ requires: Cu 17.9, Cl 20.0%.

S3. Refinement

The H atoms were included in geometrically calculated positions, with C—H = 0.93–0.97 Å, and refined using a riding model, with U_iso(H) equal to 1.5U_eq(C) for the methyl group and 1.2U_eq(C) for other H atoms.

Computing details

For both compounds, 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) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A plot of the asymmetric unit of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A plot of the asymmetric unit of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 3. The atomic arrangement of the polymeric layer, viewed parallel to the ab plane, in complex (I).
	Fig. 4. The atomic arrangement of the polymeric layer, viewed parallel to the bc plane, in complex (II).

(I) poly[[dichlorocopper(II)]-di-µ₂-2-propyl-2H-tetrazole-κ²N¹:N⁴]

Crystal data

[CuCl2(C4H8N4)2]	F(000) = 732
Mr = 358.73	Dx = 1.590 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 24 reflections
a = 9.885 (3) Å	θ = 16.6–22.0°
b = 8.867 (2) Å	µ = 1.81 mm^−1
c = 17.092 (4) Å	T = 292 K
V = 1498.1 (7) Å^3	Prism, green-blue
Z = 4	0.58 × 0.54 × 0.40 mm

Data collection

Nicolet R3m four-circle diffractometer	2024 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.027
Graphite monochromator	θmax = 30.1°, θmin = 2.4°
ω/2θ scans	h = 0→13
Absorption correction: ψ scan (North et al., 1968)	k = 0→12
Tmin = 0.379, Tmax = 0.483	l = −24→2
2477 measured reflections	3 standard reflections every 100 reflections
2201 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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.124	H-atom parameters constrained
S = 1.13	w = 1/[σ^2(Fo^2) + (0.0762P)^2 + 0.5691P] where P = (Fo^2 + 2Fc^2)/3
2201 reflections	(Δ/σ)max < 0.001
89 parameters	Δρmax = 0.67 e Å^−3
0 restraints	Δρmin = −0.80 e Å^−3

Special details

Experimental. Because of instability on the air, single-crystal was mounted in glass capillary.

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
Cu1	0.5000	0.5000	0.5000	0.03073 (14)
Cl1	0.60885 (5)	0.47837 (6)	0.61608 (3)	0.03696 (15)
N1	0.15612 (18)	0.2420 (2)	0.54928 (10)	0.0406 (4)
N2	0.19012 (16)	0.30519 (19)	0.61691 (9)	0.0351 (3)
N3	0.29953 (17)	0.3880 (2)	0.61424 (9)	0.0375 (4)
N4	0.34130 (16)	0.37998 (18)	0.54076 (9)	0.0336 (3)
C5	0.2534 (2)	0.2918 (3)	0.50275 (11)	0.0394 (4)
H5	0.2599	0.2683	0.4499	0.047*
C6	0.1067 (2)	0.2940 (3)	0.68746 (12)	0.0448 (5)
H6A	0.1588	0.3275	0.7323	0.054*
H6B	0.0817	0.1895	0.6960	0.054*
C7	−0.0195 (3)	0.3884 (4)	0.68043 (16)	0.0552 (6)
H7A	−0.0790	0.3425	0.6421	0.066*
H7B	−0.0662	0.3880	0.7303	0.066*
C8	0.0068 (4)	0.5486 (5)	0.6569 (3)	0.0806 (11)
H8A	0.0745	0.5913	0.6905	0.121*
H8B	−0.0753	0.6059	0.6614	0.121*
H8C	0.0380	0.5513	0.6037	0.121*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0298 (2)	0.0310 (2)	0.0315 (2)	−0.00562 (10)	0.00078 (10)	0.00283 (10)
Cl1	0.0375 (3)	0.0381 (3)	0.0353 (2)	−0.00010 (17)	−0.00241 (16)	0.00357 (16)
N1	0.0444 (9)	0.0355 (8)	0.0417 (8)	−0.0127 (7)	0.0074 (7)	−0.0051 (6)
N2	0.0369 (8)	0.0325 (7)	0.0358 (7)	−0.0057 (6)	0.0049 (6)	0.0006 (6)
N3	0.0370 (8)	0.0415 (8)	0.0339 (7)	−0.0089 (7)	0.0036 (6)	0.0004 (6)
N4	0.0350 (7)	0.0320 (7)	0.0339 (7)	−0.0063 (6)	0.0040 (6)	0.0008 (6)
C5	0.0445 (11)	0.0360 (9)	0.0377 (9)	−0.0121 (8)	0.0071 (7)	−0.0052 (7)
C6	0.0484 (11)	0.0494 (11)	0.0368 (9)	−0.0105 (9)	0.0106 (8)	0.0009 (8)
C7	0.0423 (11)	0.0690 (17)	0.0543 (13)	−0.0038 (11)	0.0093 (10)	−0.0136 (12)
C8	0.096 (3)	0.066 (2)	0.079 (2)	0.0259 (17)	0.0224 (18)	−0.001 (2)

Geometric parameters (Å, º)

Cu1—N4	2.0196 (15)	N4—C5	1.337 (3)
Cu1—N4^i	2.0197 (16)	C5—H5	0.9300
Cu1—Cl1	2.2652 (6)	C6—C7	1.507 (4)
Cu1—Cl1^i	2.2652 (6)	C6—H6A	0.9700
Cu1—N1^ii	2.7739 (17)	C6—H6B	0.9700
Cu1—N1^iii	2.7739 (17)	C7—C8	1.499 (5)
Cu1—Cu1^iii	6.6396 (13)	C7—H7A	0.9700
N1—C5	1.324 (2)	C7—H7B	0.9700
N1—N2	1.328 (2)	C8—H8A	0.9600
N2—N3	1.308 (2)	C8—H8B	0.9600
N2—C6	1.464 (2)	C8—H8C	0.9600
N3—N4	1.324 (2)
N4—Cu1—N4^i	180.0	N2—N3—N4	105.13 (15)
N4—Cu1—Cl1	91.27 (5)	N3—N4—C5	106.84 (15)
N4^i—Cu1—Cl1	88.73 (5)	N3—N4—Cu1	122.77 (12)
N4—Cu1—Cl1^i	88.73 (5)	C5—N4—Cu1	130.17 (12)
N4^i—Cu1—Cl1^i	91.27 (5)	N1—C5—N4	112.04 (16)
Cl1—Cu1—Cl1^i	180.0	N1—C5—H5	124.0
N4—Cu1—N1^ii	82.57 (6)	N4—C5—H5	124.0
N4^i—Cu1—N1^ii	97.43 (6)	N2—C6—C7	111.27 (19)
Cl1—Cu1—N1^ii	93.66 (4)	N2—C6—H6A	109.4
Cl1^i—Cu1—N1^ii	86.34 (4)	C7—C6—H6A	109.4
N4—Cu1—N1^iii	97.43 (6)	N2—C6—H6B	109.4
N4^i—Cu1—N1^iii	82.57 (6)	C7—C6—H6B	109.4
Cl1—Cu1—N1^iii	86.34 (4)	H6A—C6—H6B	108.0
Cl1^i—Cu1—N1^iii	93.66 (4)	C8—C7—C6	113.8 (2)
N1^ii—Cu1—N1^iii	180.00 (7)	C8—C7—H7A	108.8
N4—Cu1—Cu1^iii	103.08 (5)	C6—C7—H7A	108.8
N4^i—Cu1—Cu1^iii	76.92 (5)	C8—C7—H7B	108.8
Cl1—Cu1—Cu1^iii	65.788 (16)	C6—C7—H7B	108.8
Cl1^i—Cu1—Cu1^iii	114.212 (16)	H7A—C7—H7B	107.7
N1^ii—Cu1—Cu1^iii	158.53 (3)	C7—C8—H8A	109.5
N1^iii—Cu1—Cu1^iii	21.47 (3)	C7—C8—H8B	109.5
C5—N1—N2	101.42 (16)	H8A—C8—H8B	109.5
N3—N2—N1	114.57 (15)	C7—C8—H8C	109.5
N3—N2—C6	122.16 (16)	H8A—C8—H8C	109.5
N1—N2—C6	123.09 (16)	H8B—C8—H8C	109.5
C5—N1—N2—N3	−0.1 (2)	Cl1—Cu1—N4—C5	−151.34 (19)
C5—N1—N2—C6	175.1 (2)	Cl1^i—Cu1—N4—C5	28.66 (19)
N1—N2—N3—N4	0.0 (2)	N1^ii—Cu1—N4—C5	115.1 (2)
C6—N2—N3—N4	−175.24 (18)	N1^iii—Cu1—N4—C5	−64.9 (2)
N2—N3—N4—C5	0.1 (2)	Cu1^iii—Cu1—N4—C5	−85.92 (19)
N2—N3—N4—Cu1	175.18 (13)	N2—N1—C5—N4	0.2 (3)
Cl1—Cu1—N4—N3	34.81 (15)	N3—N4—C5—N1	−0.2 (3)
Cl1^i—Cu1—N4—N3	−145.19 (15)	Cu1—N4—C5—N1	−174.77 (15)
N1^ii—Cu1—N4—N3	−58.71 (15)	N3—N2—C6—C7	102.9 (2)
N1^iii—Cu1—N4—N3	121.29 (15)	N1—N2—C6—C7	−71.9 (3)
Cu1^iii—Cu1—N4—N3	100.23 (15)	N2—C6—C7—C8	−51.6 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···Cl1^i	0.93	2.83	3.183 (2)	104

Symmetry code: (i) −x+1, −y+1, −z+1.

(II) poly[[dichlorocopper(II)]-di-µ₂-2-allyl-2H-tetrazole-κ²N¹:N⁴]

Crystal data

[CuCl2(C4H6N4)2]	F(000) = 358
Mr = 354.70	Dx = 1.688 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 8.524 (3) Å	θ = 17.9–23.6°
b = 8.855 (3) Å	µ = 1.95 mm^−1
c = 9.593 (2) Å	T = 292 K
β = 105.51 (2)°	Prism, green-blue
V = 697.7 (4) Å^3	0.40 × 0.38 × 0.26 mm
Z = 2

Data collection

Nicolet R3m four-circle diffractometer	1824 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.062
Graphite monochromator	θmax = 29.6°, θmin = 2.5°
ω/2θ scans	h = 0→11
Absorption correction: ψ scan (North et al., 1968)	k = 0→12
Tmin = 0.484, Tmax = 0.600	l = −13→12
2066 measured reflections	3 standard reflections every 100 reflections
1949 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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.109	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0721P)^2 + 0.3127P] where P = (Fo^2 + 2Fc^2)/3
1949 reflections	(Δ/σ)max < 0.001
88 parameters	Δρmax = 0.69 e Å^−3
0 restraints	Δρmin = −0.95 e Å^−3

Special details

Experimental. Because of instability on the air, single-crystal was mounted in glass capillary.

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
Cu1	1.0000	0.5000	0.5000	0.02679 (13)
Cl1	0.75801 (6)	0.38044 (6)	0.46359 (5)	0.03523 (15)
N1	0.9006 (2)	0.7743 (2)	0.1272 (2)	0.0371 (4)
N2	0.7622 (2)	0.70125 (19)	0.11737 (18)	0.0300 (3)
N3	0.7682 (2)	0.6046 (2)	0.22137 (18)	0.0333 (4)
N4	0.9182 (2)	0.61315 (18)	0.30631 (18)	0.0296 (3)
C5	0.9958 (3)	0.7167 (3)	0.2467 (2)	0.0371 (4)
H5	1.1040	0.7443	0.2853	0.044*
C6	0.6133 (3)	0.7260 (3)	0.0005 (2)	0.0386 (4)
H6A	0.6116	0.8297	−0.0323	0.046*
H6B	0.5196	0.7114	0.0383	0.046*
C7	0.5992 (3)	0.6231 (3)	−0.1253 (3)	0.0490 (6)
H7	0.5045	0.6314	−0.2005	0.059*
C8	0.7047 (6)	0.5230 (4)	−0.1416 (4)	0.0665 (9)
H8A	0.8015	0.5101	−0.0697	0.080*
H8B	0.6834	0.4645	−0.2250	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.02700 (19)	0.02710 (19)	0.02549 (19)	−0.00584 (10)	0.00565 (13)	0.00328 (10)
Cl1	0.0297 (2)	0.0370 (3)	0.0372 (3)	−0.00925 (17)	0.00589 (18)	0.00577 (18)
N1	0.0320 (8)	0.0404 (9)	0.0387 (9)	−0.0012 (7)	0.0091 (7)	0.0138 (7)
N2	0.0292 (7)	0.0324 (8)	0.0291 (7)	0.0013 (6)	0.0092 (6)	0.0045 (6)
N3	0.0328 (8)	0.0357 (8)	0.0302 (7)	−0.0032 (6)	0.0062 (6)	0.0071 (6)
N4	0.0298 (7)	0.0299 (7)	0.0293 (7)	−0.0023 (6)	0.0083 (6)	0.0035 (6)
C5	0.0323 (9)	0.0409 (10)	0.0366 (10)	−0.0039 (8)	0.0068 (8)	0.0123 (8)
C6	0.0311 (9)	0.0442 (11)	0.0376 (10)	0.0035 (8)	0.0042 (8)	0.0098 (9)
C7	0.0528 (14)	0.0496 (13)	0.0377 (11)	−0.0132 (11)	0.0002 (10)	0.0052 (10)
C8	0.094 (3)	0.0516 (15)	0.0532 (17)	−0.0029 (16)	0.0182 (17)	−0.0106 (13)

Geometric parameters (Å, º)

Cu1—N4	2.0615 (16)	N3—N4	1.322 (2)
Cu1—N4^i	2.0615 (16)	N4—C5	1.345 (3)
Cu1—Cl1	2.2611 (8)	C5—H5	0.9300
Cu1—Cl1^i	2.2611 (8)	C6—C7	1.491 (4)
Cu1—N1^ii	2.5987 (18)	C6—H6A	0.9700
Cu1—Cu1^ii	6.5276 (13)	C6—H6B	0.9700
N1—C5	1.318 (3)	C7—C8	1.302 (5)
N1—N2	1.326 (2)	C7—H7	0.9300
N2—N3	1.305 (2)	C8—H8A	0.9300
N2—C6	1.468 (3)	C8—H8B	0.9300
N4—Cu1—N4^i	180.00 (8)	N2—N3—N4	105.48 (16)
N4—Cu1—Cl1	90.77 (5)	N3—N4—C5	106.39 (16)
N4^i—Cu1—Cl1	89.23 (5)	N3—N4—Cu1	124.47 (13)
N4—Cu1—Cl1^i	89.23 (5)	C5—N4—Cu1	128.92 (14)
N4^i—Cu1—Cl1^i	90.77 (5)	N1—C5—N4	112.03 (19)
Cl1—Cu1—Cl1^i	180.00 (3)	N1—C5—H5	124.0
N4—Cu1—N1^ii	91.42 (7)	N4—C5—H5	124.0
N4^i—Cu1—N1^ii	88.58 (7)	N2—C6—C7	113.16 (19)
Cl1—Cu1—N1^ii	88.06 (5)	N2—C6—H6A	108.9
Cl1^i—Cu1—N1^ii	91.94 (5)	C7—C6—H6A	108.9
N4—Cu1—Cu1^ii	74.57 (5)	N2—C6—H6B	108.9
N4^i—Cu1—Cu1^ii	105.43 (5)	C7—C6—H6B	108.9
Cl1—Cu1—Cu1^ii	75.41 (2)	H6A—C6—H6B	107.8
Cl1^i—Cu1—Cu1^ii	104.59 (2)	C8—C7—C6	127.2 (3)
N1^ii—Cu1—Cu1^ii	21.46 (4)	C8—C7—H7	116.4
C5—N1—N2	101.67 (16)	C6—C7—H7	116.4
N3—N2—N1	114.43 (16)	C7—C8—H8A	120.0
N3—N2—C6	122.05 (17)	C7—C8—H8B	120.0
N1—N2—C6	123.52 (17)	H8A—C8—H8B	120.0
C5—N1—N2—N3	−0.2 (2)	Cl1—Cu1—N4—C5	178.28 (19)
C5—N1—N2—C6	179.5 (2)	Cl1^i—Cu1—N4—C5	−1.72 (19)
N1—N2—N3—N4	0.3 (2)	N1^ii—Cu1—N4—C5	−93.7 (2)
C6—N2—N3—N4	−179.45 (18)	Cu1^ii—Cu1—N4—C5	−107.09 (19)
N2—N3—N4—C5	−0.2 (2)	N2—N1—C5—N4	0.0 (3)
N2—N3—N4—Cu1	174.81 (13)	N3—N4—C5—N1	0.1 (3)
Cl1—Cu1—N4—N3	4.39 (16)	Cu1—N4—C5—N1	−174.62 (15)
Cl1^i—Cu1—N4—N3	−175.61 (16)	N3—N2—C6—C7	−89.1 (3)
N1^ii—Cu1—N4—N3	92.47 (16)	N1—N2—C6—C7	91.2 (2)
Cu1^ii—Cu1—N4—N3	79.02 (16)	N2—C6—C7—C8	−2.7 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···Cl1^i	0.93	2.63	3.122 (2)	114
C6—H6B···Cl1^iii	0.97	2.80	3.548 (2)	135

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