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While bis(1-methyl-1H-tetra­zol-5-yl)diazene, C4H6N10, (I), has no crystallographically imposed symmetry, in the two title chloro­copper(I) complexes, [Cu2Cl2(C4H6N10)]n, (II), and [CuCl(C4H6N10)]n, (III), the organic ligands lie across centres of inversion; in (III), the Cu and Cl atoms additionally lie about a twofold rotation axis in the space group P2/c. Complex (II) forms a two-dimensional coordination polymer containing tetra­hedrally coordinated CuI atoms, and complex (III) forms a one-dimensional coordination polymer containing five-coordinate square-pyramidal CuI atoms.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106013199/gd3013sup1.cif
Contains datablocks global, I, II, III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106013199/gd3013Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106013199/gd3013IIsup3.hkl
Contains datablock absg

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106013199/gd3013IIIsup4.hkl
Contains datablock l02

CCDC references: 612427; 612428; 612429

Comment top

N-Substituted bistetrazoles are of considerable interest for coordination and supramolecular chemistry owing to their attractiveness as chelating agents and initial compounds for synthesis of one-, two- and three-dimensional coordination polymers (Voitekhovich et al., 2002; Ivashkevich et al., 2003; Grunert et al., 2004; Bronisz, 2004; Lyakhov et al., 2004). Recently, we investigated the molecular and crystal structures of the coordination compounds of bistetrazoles in which two N-substiuted tetrazole rings are connected via their C atoms by –CH2—CH2– (Ivashkevich et al., 2003), –CH2—CH2—O—CH2—CH2– (Voitekhovich et al., 2002) and –NN—NH– (Lyakhov et al., 2004) bridges. Compounds with a –CH(CN)- bridge were also investigated (Saalfrank et al., 1995). Complexes of N-substituted bistetrazoles with a diazene bridge, –N N–, have not been described, although these ligands are attractive because of possible participation of bridge N atoms in metal coordination. To date, only one bistetrazole, viz. bis(2-methyl-1H-tetrazol-5-yl)diazene, and a series of salts of the anionic form of bis(tetrazol-5-yl)diazene with alkali, alkaline earth and several trivalent metal cations have been synthesized and structurally characterized (Hammerl et al., 2002).

We report here both a new synthesis and the structure of a bistetrazole containing a diazene bridge, namely bis(1-methyl-1H-tetrazol-5-yl)diazene, (I), and two related copper(I)–chloro complexes, Cu2Cl2L, catena-poly[[µ-1,2-bis(1-methyl-tetrazol-5-yl-κ2N4:N4')diazene- κ2N1:N2]-dicopper(I)-di-µ-chloro], (II), and CuClL, catena-poly[[µ-1,2-bis(1-methyl-tetrazol-5-yl-κ2N4:N4')diazene- κ2N1:N2]chlorocopper(I)], (III).

The present investigation showed that compound (I) did not form any complexes with copper(II) chloride under the usual conditions for the preparation of N-substiuted bistetrazoles (Voitekhovich et al., 2002; Ivashkevich et al., 2003; Grunert et al., 2004; Bronisz 2004; Lyakhov et al., 2004). Rather unusual conditions were needed to prepare complexes (II) and (III), which were obtained under reflux followed by slow evaporation of a solution containing compound (I) and excess of copper(II) chloride dihydrate in ethanol–triethyl orthoformate at room temperature. Because (II) and (III) are CuI complexes, reduction of CuII by ethanol has occurred under the reaction conditions. Attempts to prepare any chloride complexes of Co and Ni with (I) have failed. Thus compound (I) shows low coordination ability in spite of the presence of N atoms of different types as potential donor atoms.

The molecules of (I) (Fig. 1) exhibit no symmetry, despite the trans orientation of the tetrazole rings relative to the diazene bridge. The tetrazole rings A and B are planar to within 0.0009 (10) and 0.0035 (10) Å, respectively. The dihedral angle between the least-squares planes of the rings is 22.87 (7)°. In the fragment C5A—N7A N7B—C5B, the mean deviation of the atoms from the least-squares plane is 0.0113 (6) Å. The bond length of the NN bridge is 1.2530 (17) Å. The N4AC5A—N7AN7B and N4BC5B—N7BN7A torsion angles are 10.7 (2) and 14.4 (2)°, respectively. The non-planarity of the molecule does not permit significant conjugation. The tetrazole ring geometry in (I) (Table 1) is typical of that of 1,5-disubstituted tetrazoles. Only van der Waals interactions exist in the crystal structure of (I).

In complex (II), the organic ligands lie across centres of inversion in space group Pbca. The coordination geometry around the CuI atom is best described as distorted tetrahedral (Fig. 2). The Cu—N and Cu—Cl bond lengths lie in a narrow range 2.025 (3)–2.2696 (10) Å (Table 2). The distortion of the tetrahedron is related to the rather small value of the bite angle [N4—Cu1—N7 = 75.90 (10)°]. The remaining bond angles of atom Cu1 lie in the range 107.24 (7)–119.01 (9)°. The tetrazole rings are essentially planar, with an r.m.s. deviation from the least squares plane of 0.0001 (19) Å. Atom C6 of the methyl group and atom N7 of the diazene group lie 0.052 (6) and 0.055 (5) Å, respectively, out of the tetrazole ring plane. The ligand molecule is planar within to 0.013 (3) Å (without taking into account the methyl group atoms).

Complex (II) forms a two-dimensional coordination polymer with layers parallel to the ab plane (Fig. 3). The nearest Cu atoms, separated by ca 3.440 Å, are linked by Cl atoms to form polymeric chains running along the b axis. These chains are connected through the ligand molecules via atoms N4 and N7 to give a polymeric sheet. No hydrogen bonds exist in complex (II).

In complex (III), the CuI atom, lying on a twofold axis, is surrounded by five atoms forming a distorted square pyramid, with a τ value of 0.22 (extreme forms are 1 for a trigonal bipyramid and 0 for a square pyramid; Addison et al., 1984). The Cl atom, also on the twofold axis, lies in the apical position of the pyramid, whereas the basal sites are occupied by two N4 and two N7 atoms from two ligand molecules. Atom Cu1 is displaced 1.0325 (16) Å above the least-squaares basal plane of four N atoms [their r.m.s deviation from the least-squares plane is 0.0835 (15) Å]. Two significantly different sets of Cu—N bond lengths characterize the equatorial asymmetry, two Cu1—N4 bonds [2.004 (2) Å] and two Cu1—N7 bonds [2.594 (2) Å]. A similar geometry of the atomic environment of five-coordinate CuI atoms has been observed in complexes with rigid macrocyclic ligands (Cambridge Structural Database; Version 5.27 of November 2005; Allen, 2002).

The tetrazole ligand in (III) lies across an inversion centre at the mid-point of the NN bond (Fig. 4). The tetrazole rings are planar to within 0.002 (2) Å. Atom C6 of the methyl group and atom N7 of the diazene group are displaced from the tetrazole ring plane by 0.130 (6) and 0.038 (4) Å, respectively. By excluding the methyl group atoms, the ligand molecule is planar to within 0.009 (2) Å. In complex (III), the Cu ions are linked together by ligand molecules giving polymeric chains running along the c axis, with van der Waals interaction between the chains (Fig. 5).

In both investigated complexes, ligand molecules are linked in a bidentate fashion with two Cu atoms and show chelating and bridging properties. Comparison of the bond lengths of ligand molecules in (I), (II) and (III) shows that the corresponding values are rather close, although some elongation of the NN bond and shortening of the C5—N7 bond in the complexes relative to (I) is observed. The participation of the ligand molecule in complexation gives rise to essential deformation of the molecule. In both complexes, an increase of the N1—C5—N7 angle and a decrease of N4 C5—N7 and C5—N7N7 in comparison with (I) are observed (Tables 1–3). Moreover, torsion angles in the bridge of molecules correspond to more flattened molecular geometry in (II) and (III) than in (I). Probably, the coordination of diazene N atoms by Cu atoms is responsible for the change in ligand molecule conformation. Complexation and chelation in (II) and (III) make it possible to stabilize the flattened ligand conformation and to form an extended conjugation system. NN bond enlongation, as well as C5—N7 bond shortening, may be considered as a confirmation of the conjugation.

Experimental top

For the synthesis of (I), a mixture of 5-amino-1-methyltetrazole (0.99 g, 10 mmol), N-bromosuccinimide (3.56 g, 20 mmol) and 2,2'-azobisisobutyronitrile (17 mg, 0.1 mmol) in acetonitile (25 ml) was stirred for 5 h under reflux. The solvent was removed in vacuo. Recrystallization of a residue from water and then from ethyl acetate gave an orange solid of (I) (0.61 g, yield 63%). M.p. 455–457 K [in agreement with data published by Williams et al. (1957)]. Single crystals of (I) were prepared by slow evaporation of an ethyl acetate solution. For the synthesis of (II) and (III), a solution of bis-(1-methyl-1H-tetrazol-5-yl)diazene (0.097 g, 0.5 mmol) and copper(II) chloride dihydrate (0.51 g, 3 mmol) in ethanol and triethylorthoformate (75 ml, volume ratio 3:1) was heated for 1 h at 343–353 K. The solution was kept at room temperature for several (10–15) days, and black crystals of complexes (II) and (III) suitable for X-ray analysis were formed.

Refinement top

For all compounds, H atoms of the methyl group were included in geometrically calculated positions, with C—H distances of 0.96 Å, and refined using a riding model, with Uiso(H) equal to 1.5Ueq(C).

Computing details top

For all 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 and PLATON.

Figures top
[Figure 1] Fig. 1. An ORTEP-3 plot (Farrugia, 1997) of the asymmetric unit of (I). Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as spheres of arbitrary radii.
[Figure 2] Fig. 2. The environment of the CuI atom in the structure of (II). Displacement ellipsoids are drawn at the 30% probability level. Symmetry codes (i) and (ii) correspond to those in Table 2.
[Figure 3] Fig. 3. The atomic arrangement of a layer in (II), viewed along the c axis.
[Figure 4] Fig. 4. The environment of the CuI atom in the structure of (III). Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) 2 − x, −y, 1 − z; (ii) 2 − x, y, 1.5 − z; (iii) x, −y, 1/2 + z.]
[Figure 5] Fig. 5. Polymeric chains in the structure of (III), viewed along the a axis.
(I) Bis(1-methyl-1H-tetrazol-5-yl)diazene top
Crystal data top
C4H6N10F(000) = 400
Mr = 194.19Dx = 1.520 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 25 reflections
a = 6.889 (2) Åθ = 12.0–20.3°
b = 9.684 (3) ŵ = 0.12 mm1
c = 12.719 (4) ÅT = 294 K
V = 848.5 (4) Å3Prism, orange
Z = 40.4 × 0.3 × 0.2 mm
Data collection top
Nicolet R3m four-circle
diffractometer
Rint = 0.023
Radiation source: fine-focus sealed tubeθmax = 30.1°, θmin = 2.6°
Graphite monochromatorh = 09
ω/2θ scansk = 013
1569 measured reflectionsl = 117
1455 independent reflections3 standard reflections every 100 reflections
1297 reflections with I > 2σ(I) intensity decay: none
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.031H-atom parameters constrained
wR(F2) = 0.092 w = 1/[σ2(Fo2) + (0.060P)2 + 0.0346P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
1455 reflectionsΔρmax = 0.15 e Å3
130 parametersΔρmin = 0.15 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.107 (9)
Crystal data top
C4H6N10V = 848.5 (4) Å3
Mr = 194.19Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 6.889 (2) ŵ = 0.12 mm1
b = 9.684 (3) ÅT = 294 K
c = 12.719 (4) Å0.4 × 0.3 × 0.2 mm
Data collection top
Nicolet R3m four-circle
diffractometer
Rint = 0.023
1569 measured reflections3 standard reflections every 100 reflections
1455 independent reflections intensity decay: none
1297 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0310 restraints
wR(F2) = 0.092H-atom parameters constrained
S = 1.04Δρmax = 0.15 e Å3
1455 reflectionsΔρmin = 0.15 e Å3
130 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
N1A0.79400 (18)0.06129 (12)0.56928 (9)0.0399 (3)
N2A0.6281 (2)0.02324 (14)0.61500 (11)0.0503 (3)
N3A0.4915 (2)0.04009 (16)0.54499 (12)0.0559 (4)
N4A0.5644 (2)0.08806 (15)0.45388 (12)0.0515 (3)
C5A0.7526 (2)0.10045 (14)0.47082 (11)0.0381 (3)
C6A0.9783 (2)0.0581 (2)0.62527 (13)0.0579 (4)
H6A1.08050.03450.57720.087*
H6B0.97230.00950.68030.087*
H6C1.00370.14730.65520.087*
N7A0.90285 (17)0.14002 (12)0.40341 (9)0.0407 (3)
N1B0.95089 (18)0.29795 (11)0.16327 (9)0.0397 (3)
N2B1.1157 (2)0.31476 (14)0.11018 (11)0.0514 (3)
N3B1.2501 (2)0.25004 (16)0.16302 (13)0.0569 (4)
N4B1.17711 (19)0.19178 (15)0.25032 (11)0.0494 (3)
C5B0.9908 (2)0.22379 (14)0.24915 (11)0.0379 (3)
C6B0.7676 (2)0.35671 (19)0.12722 (14)0.0530 (4)
H6D0.75340.44840.15490.080*
H6E0.66210.30020.15120.080*
H6F0.76680.36020.05180.080*
N7B0.84077 (18)0.18825 (13)0.31840 (9)0.0412 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N1A0.0434 (6)0.0387 (5)0.0377 (5)0.0017 (5)0.0030 (4)0.0006 (4)
N2A0.0526 (7)0.0469 (6)0.0513 (7)0.0088 (6)0.0107 (6)0.0005 (6)
N3A0.0456 (7)0.0573 (7)0.0647 (8)0.0110 (6)0.0065 (7)0.0023 (7)
N4A0.0408 (6)0.0560 (7)0.0577 (7)0.0053 (6)0.0015 (6)0.0044 (6)
C5A0.0388 (6)0.0359 (6)0.0395 (6)0.0000 (5)0.0008 (6)0.0011 (5)
C6A0.0496 (8)0.0772 (11)0.0467 (7)0.0029 (8)0.0070 (7)0.0076 (8)
N7A0.0385 (5)0.0446 (6)0.0390 (5)0.0009 (5)0.0012 (5)0.0027 (5)
N1B0.0443 (6)0.0381 (5)0.0367 (5)0.0021 (5)0.0017 (5)0.0003 (5)
N2B0.0527 (7)0.0499 (7)0.0516 (7)0.0037 (6)0.0121 (6)0.0043 (6)
N3B0.0468 (7)0.0578 (7)0.0662 (9)0.0005 (7)0.0132 (7)0.0033 (7)
N4B0.0402 (6)0.0541 (7)0.0539 (7)0.0025 (6)0.0016 (6)0.0034 (6)
C5B0.0396 (6)0.0378 (6)0.0362 (5)0.0017 (5)0.0016 (5)0.0013 (5)
C6B0.0505 (8)0.0601 (9)0.0486 (7)0.0039 (7)0.0067 (7)0.0086 (7)
N7B0.0404 (5)0.0448 (5)0.0384 (5)0.0004 (5)0.0007 (5)0.0015 (5)
Geometric parameters (Å, º) top
N1A—N2A1.3340 (17)N1B—N2B1.3309 (17)
N1A—C5A1.3392 (18)N1B—C5B1.3359 (18)
N1A—C6A1.456 (2)N1B—C6B1.459 (2)
N2A—N3A1.306 (2)N2B—N3B1.305 (2)
N3A—N4A1.346 (2)N3B—N4B1.343 (2)
N4A—C5A1.3195 (19)N4B—C5B1.320 (2)
C5A—N7A1.3978 (18)C5B—N7B1.4009 (19)
C6A—H6A0.9600C6B—H6D0.9600
C6A—H6B0.9600C6B—H6E0.9600
C6A—H6C0.9600C6B—H6F0.9600
N7A—N7B1.2530 (17)
N2A—N1A—C5A107.66 (12)N2B—N1B—C5B107.76 (12)
N2A—N1A—C6A121.86 (12)N2B—N1B—C6B122.07 (12)
C5A—N1A—C6A130.47 (13)C5B—N1B—C6B130.16 (13)
N3A—N2A—N1A106.59 (12)N3B—N2B—N1B106.58 (12)
N2A—N3A—N4A111.19 (13)N2B—N3B—N4B111.22 (13)
C5A—N4A—N3A104.92 (14)C5B—N4B—N3B104.84 (14)
N4A—C5A—N1A109.65 (13)N4B—C5B—N1B109.60 (14)
N4A—C5A—N7A130.72 (14)N4B—C5B—N7B130.73 (14)
N1A—C5A—N7A119.57 (13)N1B—C5B—N7B119.62 (13)
N1A—C6A—H6A109.5N1B—C6B—H6D109.5
N1A—C6A—H6B109.5N1B—C6B—H6E109.5
H6A—C6A—H6B109.5H6D—C6B—H6E109.5
N1A—C6A—H6C109.5N1B—C6B—H6F109.5
H6A—C6A—H6C109.5H6D—C6B—H6F109.5
H6B—C6A—H6C109.5H6E—C6B—H6F109.5
N7B—N7A—C5A112.26 (12)N7A—N7B—C5B112.47 (12)
C5A—N1A—N2A—N3A0.21 (16)C6B—N1B—N2B—N3B179.96 (14)
C6A—N1A—N2A—N3A179.01 (15)N1B—N2B—N3B—N4B0.45 (19)
N1A—N2A—N3A—N4A0.23 (18)N2B—N3B—N4B—C5B0.12 (19)
N2A—N3A—N4A—C5A0.15 (18)N3B—N4B—C5B—N1B0.66 (17)
N3A—N4A—C5A—N1A0.01 (17)N3B—N4B—C5B—N7B177.95 (14)
N3A—N4A—C5A—N7A177.00 (15)N2B—N1B—C5B—N4B0.95 (16)
N2A—N1A—C5A—N4A0.13 (16)C6B—N1B—C5B—N4B179.93 (15)
C6A—N1A—C5A—N4A179.01 (17)N2B—N1B—C5B—N7B178.60 (12)
N2A—N1A—C5A—N7A177.25 (13)C6B—N1B—C5B—N7B2.3 (2)
C6A—N1A—C5A—N7A3.6 (2)C5A—N7A—N7B—C5B178.00 (11)
N4A—C5A—N7A—N7B10.7 (2)N4B—C5B—N7B—N7A14.4 (2)
N1A—C5A—N7A—N7B172.60 (11)N1B—C5B—N7B—N7A168.54 (12)
C5B—N1B—N2B—N3B0.84 (16)
(II) poly[[[µ-1,2-bis(1-methyl-1H-tetrazol-5-yl)diazene- κ4N',N4:N,N4']dicopper(I)]-di-µ-chloro] top
Crystal data top
[Cu2Cl2(C4H6N10)]F(000) = 768
Mr = 392.16Dx = 2.202 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 25 reflections
a = 9.943 (2) Åθ = 12.4–20.6°
b = 6.4899 (18) ŵ = 4.05 mm1
c = 18.330 (4) ÅT = 292 K
V = 1182.8 (5) Å3Plate, black
Z = 40.28 × 0.28 × 0.08 mm
Data collection top
Nicolet R3m four-circle
diffractometer
1199 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.012
Graphite monochromatorθmax = 27.6°, θmin = 2.2°
ω/2θ scansh = 012
Absorption correction: gaussian
(Coppens et al., 1965)
k = 08
Tmin = 0.331, Tmax = 0.760l = 231
1517 measured reflections3 standard reflections every 100 reflections
1370 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)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.093H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0349P)2 + 3.5322P]
where P = (Fo2 + 2Fc2)/3
1370 reflections(Δ/σ)max = 0.001
83 parametersΔρmax = 0.94 e Å3
0 restraintsΔρmin = 1.48 e Å3
Crystal data top
[Cu2Cl2(C4H6N10)]V = 1182.8 (5) Å3
Mr = 392.16Z = 4
Orthorhombic, PbcaMo Kα radiation
a = 9.943 (2) ŵ = 4.05 mm1
b = 6.4899 (18) ÅT = 292 K
c = 18.330 (4) Å0.28 × 0.28 × 0.08 mm
Data collection top
Nicolet R3m four-circle
diffractometer
1199 reflections with I > 2σ(I)
Absorption correction: gaussian
(Coppens et al., 1965)
Rint = 0.012
Tmin = 0.331, Tmax = 0.7603 standard reflections every 100 reflections
1517 measured reflections intensity decay: none
1370 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.093H-atom parameters constrained
S = 1.06Δρmax = 0.94 e Å3
1370 reflectionsΔρmin = 1.48 e Å3
83 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
Cu10.19252 (6)0.21487 (8)0.55183 (3)0.04538 (19)
Cl10.14775 (9)0.51919 (13)0.60682 (5)0.0364 (2)
N10.0629 (3)0.0935 (4)0.65208 (14)0.0237 (5)
N20.1653 (3)0.2075 (4)0.67683 (16)0.0314 (6)
N30.2315 (3)0.2728 (5)0.61994 (15)0.0348 (6)
N40.1739 (3)0.2031 (4)0.55808 (14)0.0268 (6)
C50.0692 (3)0.0920 (4)0.57934 (16)0.0210 (5)
C60.0284 (4)0.0097 (6)0.70186 (18)0.0387 (8)
H6A0.04430.14780.68520.058*
H6B0.01070.01350.74970.058*
H6C0.11210.06400.70360.058*
N70.0158 (2)0.0159 (4)0.53384 (13)0.0219 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0625 (3)0.0404 (3)0.0332 (3)0.0111 (2)0.0165 (2)0.00999 (19)
Cl10.0397 (4)0.0283 (4)0.0411 (4)0.0007 (3)0.0107 (4)0.0038 (3)
N10.0275 (12)0.0223 (11)0.0213 (11)0.0013 (10)0.0000 (10)0.0003 (10)
N20.0346 (14)0.0324 (14)0.0271 (13)0.0079 (11)0.0008 (11)0.0053 (11)
N30.0389 (16)0.0362 (15)0.0292 (14)0.0138 (13)0.0013 (12)0.0032 (12)
N40.0299 (14)0.0260 (13)0.0243 (13)0.0075 (10)0.0005 (10)0.0008 (10)
C50.0230 (13)0.0183 (12)0.0218 (13)0.0010 (11)0.0006 (11)0.0011 (11)
C60.046 (2)0.045 (2)0.0252 (16)0.0140 (17)0.0031 (14)0.0037 (14)
N70.0214 (11)0.0232 (11)0.0212 (11)0.0015 (10)0.0014 (9)0.0018 (9)
Geometric parameters (Å, º) top
Cu1—N4i2.025 (3)N3—N41.348 (4)
Cu1—N72.206 (2)N4—C51.325 (4)
Cu1—Cl12.2617 (11)C5—N71.378 (4)
Cu1—Cl1ii2.2696 (10)C6—H6A0.9600
N1—C51.335 (4)C6—H6B0.9600
N1—N21.337 (4)C6—H6C0.9600
N1—C61.451 (4)N7—N7i1.296 (5)
N2—N31.304 (4)
N4i—Cu1—N775.90 (10)N3—N4—Cu1i141.7 (2)
N4i—Cu1—Cl1117.28 (9)N4—C5—N1109.0 (3)
N7—Cu1—Cl1114.90 (7)N4—C5—N7125.5 (3)
N4i—Cu1—Cl1ii119.01 (9)N1—C5—N7125.4 (3)
N7—Cu1—Cl1ii107.24 (7)N1—C6—H6A109.5
Cl1—Cu1—Cl1ii115.37 (4)N1—C6—H6B109.5
Cu1—Cl1—Cu1iii98.80 (4)H6A—C6—H6B109.5
C5—N1—N2107.9 (2)N1—C6—H6C109.5
C5—N1—C6130.8 (3)H6A—C6—H6C109.5
N2—N1—C6121.2 (3)H6B—C6—H6C109.5
N3—N2—N1107.0 (3)N7i—N7—C5110.5 (3)
N2—N3—N4110.4 (3)N7i—N7—Cu1115.4 (2)
C5—N4—N3105.6 (2)C5—N7—Cu1134.06 (19)
C5—N4—Cu1i112.6 (2)
N4i—Cu1—Cl1—Cu1iii60.91 (9)C6—N1—C5—N4177.3 (3)
N7—Cu1—Cl1—Cu1iii147.31 (7)N2—N1—C5—N7177.2 (3)
Cl1ii—Cu1—Cl1—Cu1iii87.12 (7)C6—N1—C5—N70.1 (5)
C5—N1—N2—N30.0 (3)N4—C5—N7—N7i3.9 (5)
C6—N1—N2—N3177.6 (3)N1—C5—N7—N7i179.4 (3)
N1—N2—N3—N40.0 (4)N4—C5—N7—Cu1178.8 (2)
N2—N3—N4—C50.0 (4)N1—C5—N7—Cu12.1 (5)
N2—N3—N4—Cu1i179.0 (3)N4i—Cu1—N7—N7i0.5 (3)
N3—N4—C5—N10.0 (3)Cl1—Cu1—N7—N7i114.3 (3)
Cu1i—N4—C5—N1179.33 (19)Cl1ii—Cu1—N7—N7i116.0 (3)
N3—N4—C5—N7177.2 (3)N4i—Cu1—N7—C5177.7 (3)
Cu1i—N4—C5—N73.5 (4)Cl1—Cu1—N7—C568.4 (3)
N2—N1—C5—N40.0 (3)Cl1ii—Cu1—N7—C561.2 (3)
Symmetry codes: (i) x, y, z+1; (ii) x1/2, y1/2, z; (iii) x1/2, y+1/2, z.
(III) catena-poly[[chlorocopper(I)]-µ-1,2-bis(1-methyl-1H-tetrazol-5-yl)diazene- κ4N',N4:N,N4']] top
Crystal data top
[CuCl(C4H6N10)]F(000) = 292
Mr = 293.18Dx = 1.886 Mg m3
Monoclinic, P2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ycCell parameters from 25 reflections
a = 8.528 (2) Åθ = 15.0–18.9°
b = 6.2456 (13) ŵ = 2.36 mm1
c = 10.059 (2) ÅT = 292 K
β = 105.462 (19)°Prism, black
V = 516.38 (19) Å30.34 × 0.24 × 0.18 mm
Z = 2
Data collection top
Nicolet R3m four-circle
diffractometer
1191 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.013
Graphite monochromatorθmax = 30.1°, θmin = 2.5°
ω/2θ scansh = 012
Absorption correction: ψ scan
(North et al., 1968)
k = 08
Tmin = 0.485, Tmax = 0.655l = 1413
1607 measured reflections3 standard reflections every 100 reflections
1517 independent reflections intensity decay: none
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046H-atom parameters constrained
wR(F2) = 0.127 w = 1/[σ2(Fo2) + (0.0532P)2 + 0.4842P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.001
1517 reflectionsΔρmax = 0.85 e Å3
76 parametersΔρmin = 0.75 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.014 (3)
Crystal data top
[CuCl(C4H6N10)]V = 516.38 (19) Å3
Mr = 293.18Z = 2
Monoclinic, P2/cMo Kα radiation
a = 8.528 (2) ŵ = 2.36 mm1
b = 6.2456 (13) ÅT = 292 K
c = 10.059 (2) Å0.34 × 0.24 × 0.18 mm
β = 105.462 (19)°
Data collection top
Nicolet R3m four-circle
diffractometer
1191 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.013
Tmin = 0.485, Tmax = 0.6553 standard reflections every 100 reflections
1607 measured reflections intensity decay: none
1517 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.127H-atom parameters constrained
S = 1.07Δρmax = 0.85 e Å3
1517 reflectionsΔρmin = 0.75 e Å3
76 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
Cu11.00000.22216 (9)0.75000.0869 (4)
Cl11.00000.56720 (16)0.75000.0695 (4)
N10.7046 (3)0.2175 (4)0.5122 (2)0.0488 (5)
N20.6129 (3)0.1853 (5)0.5996 (3)0.0643 (7)
N30.6772 (3)0.0283 (5)0.6807 (3)0.0616 (7)
N40.8116 (3)0.0435 (4)0.6468 (2)0.0442 (5)
C50.8261 (3)0.0766 (4)0.5430 (2)0.0384 (5)
C60.6765 (5)0.3960 (6)0.4155 (4)0.0717 (10)
H6A0.70080.35240.33170.108*
H6B0.56470.43970.39580.108*
H6C0.74550.51370.45550.108*
N70.9468 (2)0.0702 (3)0.47406 (19)0.0372 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0819 (5)0.0302 (3)0.1157 (6)0.0000.0310 (4)0.000
Cl10.1066 (10)0.0303 (4)0.0620 (6)0.0000.0058 (6)0.000
N10.0475 (11)0.0527 (13)0.0458 (11)0.0192 (10)0.0118 (9)0.0022 (9)
N20.0523 (14)0.0793 (19)0.0663 (16)0.0237 (14)0.0244 (12)0.0083 (14)
N30.0554 (14)0.0680 (17)0.0685 (16)0.0120 (13)0.0290 (12)0.0096 (14)
N40.0437 (11)0.0427 (11)0.0470 (11)0.0043 (9)0.0133 (8)0.0014 (9)
C50.0402 (11)0.0364 (11)0.0367 (10)0.0090 (9)0.0069 (8)0.0026 (8)
C60.081 (2)0.070 (2)0.0648 (19)0.0423 (19)0.0201 (17)0.0218 (16)
N70.0425 (10)0.0338 (9)0.0335 (8)0.0100 (8)0.0071 (7)0.0004 (7)
Geometric parameters (Å, º) top
Cu1—N4i2.004 (2)N2—N31.299 (4)
Cu1—N42.004 (2)N3—N41.356 (3)
Cu1—Cl12.1550 (12)N4—C51.318 (3)
Cu1—N7ii2.594 (2)C5—N71.387 (3)
Cu1—N7iii2.594 (2)C6—H6A0.9600
N1—C51.331 (3)C6—H6B0.9600
N1—N21.339 (4)C6—H6C0.9600
N1—C61.457 (4)N7—N7ii1.270 (4)
N4i—Cu1—N4112.31 (14)N2—N3—N4109.6 (2)
N4i—Cu1—Cl1123.85 (7)C5—N4—N3106.0 (2)
N4—Cu1—Cl1123.85 (7)C5—N4—Cu1119.73 (17)
N4i—Cu1—N7ii86.82 (8)N3—N4—Cu1131.96 (18)
N4—Cu1—N7ii69.39 (7)N4—C5—N1109.2 (2)
Cl1—Cu1—N7ii111.45 (4)N4—C5—N7128.2 (2)
N4i—Cu1—N7iii69.39 (8)N1—C5—N7122.5 (2)
N4—Cu1—N7iii86.82 (8)N1—C6—H6A109.5
Cl1—Cu1—N7iii111.45 (4)N1—C6—H6B109.5
N7ii—Cu1—N7iii137.09 (9)H6A—C6—H6B109.5
C5—N1—N2107.6 (2)N1—C6—H6C109.5
C5—N1—C6129.9 (2)H6A—C6—H6C109.5
N2—N1—C6122.2 (2)H6B—C6—H6C109.5
N3—N2—N1107.6 (2)N7ii—N7—C5111.0 (2)
C5—N1—N2—N30.3 (4)N7iii—Cu1—N4—N327.7 (3)
C6—N1—N2—N3173.8 (3)N3—N4—C5—N10.4 (3)
N1—N2—N3—N40.0 (4)Cu1—N4—C5—N1165.05 (18)
N2—N3—N4—C50.2 (4)N3—N4—C5—N7178.1 (2)
N2—N3—N4—Cu1162.2 (2)Cu1—N4—C5—N713.5 (4)
N4i—Cu1—N4—C566.03 (19)N2—N1—C5—N40.5 (3)
Cl1—Cu1—N4—C5113.97 (19)C6—N1—C5—N4173.3 (3)
N7ii—Cu1—N4—C511.36 (18)N2—N1—C5—N7178.2 (2)
N7iii—Cu1—N4—C5132.2 (2)C6—N1—C5—N75.3 (5)
N4i—Cu1—N4—N393.9 (3)N4—C5—N7—N7ii1.5 (4)
Cl1—Cu1—N4—N386.1 (3)N1—C5—N7—N7ii176.8 (3)
N7ii—Cu1—N4—N3171.3 (3)
Symmetry codes: (i) x+2, y, z+3/2; (ii) x+2, y, z+1; (iii) x, y, z+1/2.

Experimental details

(I)(II)(III)
Crystal data
Chemical formulaC4H6N10[Cu2Cl2(C4H6N10)][CuCl(C4H6N10)]
Mr194.19392.16293.18
Crystal system, space groupOrthorhombic, P212121Orthorhombic, PbcaMonoclinic, P2/c
Temperature (K)294292292
a, b, c (Å)6.889 (2), 9.684 (3), 12.719 (4)9.943 (2), 6.4899 (18), 18.330 (4)8.528 (2), 6.2456 (13), 10.059 (2)
α, β, γ (°)90, 90, 9090, 90, 9090, 105.462 (19), 90
V3)848.5 (4)1182.8 (5)516.38 (19)
Z442
Radiation typeMo KαMo KαMo Kα
µ (mm1)0.124.052.36
Crystal size (mm)0.4 × 0.3 × 0.20.28 × 0.28 × 0.080.34 × 0.24 × 0.18
Data collection
DiffractometerNicolet R3m four-circle
diffractometer
Nicolet R3m four-circle
diffractometer
Nicolet R3m four-circle
diffractometer
Absorption correctionGaussian
(Coppens et al., 1965)
ψ scan
(North et al., 1968)
Tmin, Tmax0.331, 0.7600.485, 0.655
No. of measured, independent and
observed [I > 2σ(I)] reflections
1569, 1455, 1297 1517, 1370, 1199 1607, 1517, 1191
Rint0.0230.0120.013
(sin θ/λ)max1)0.7050.6510.705
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.031, 0.092, 1.04 0.037, 0.093, 1.06 0.046, 0.127, 1.07
No. of reflections145513701517
No. of parameters1308376
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.15, 0.150.94, 1.480.85, 0.75

Computer programs: R3m Software (Nicolet, 1980), R3m Software, SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003), SHELXL97 and PLATON.

Selected geometric parameters (Å, º) for (I) top
N1A—N2A1.3340 (17)N1B—N2B1.3309 (17)
N1A—C5A1.3392 (18)N1B—C5B1.3359 (18)
N2A—N3A1.306 (2)N2B—N3B1.305 (2)
N3A—N4A1.346 (2)N3B—N4B1.343 (2)
N4A—C5A1.3195 (19)N4B—C5B1.320 (2)
C5A—N7A1.3978 (18)C5B—N7B1.4009 (19)
N7A—N7B1.2530 (17)
N4A—C5A—N7A130.72 (14)N4B—C5B—N7B130.73 (14)
N1A—C5A—N7A119.57 (13)N1B—C5B—N7B119.62 (13)
N7B—N7A—C5A112.26 (12)N7A—N7B—C5B112.47 (12)
Selected geometric parameters (Å, º) for (II) top
Cu1—N4i2.025 (3)N2—N31.304 (4)
Cu1—N72.206 (2)N3—N41.348 (4)
Cu1—Cl12.2617 (11)N4—C51.325 (4)
Cu1—Cl1ii2.2696 (10)C5—N71.378 (4)
N1—C51.335 (4)N7—N7i1.296 (5)
N1—N21.337 (4)
N4—C5—N7125.5 (3)N7i—N7—C5110.5 (3)
N1—C5—N7125.4 (3)
Symmetry codes: (i) x, y, z+1; (ii) x1/2, y1/2, z.
Selected geometric parameters (Å, º) for (III) top
Cu1—N42.004 (2)N2—N31.299 (4)
Cu1—Cl12.1550 (12)N3—N41.356 (3)
Cu1—N7i2.594 (2)N4—C51.318 (3)
N1—C51.331 (3)C5—N71.387 (3)
N1—N21.339 (4)N7—N7i1.270 (4)
N4—C5—N7128.2 (2)N7i—N7—C5111.0 (2)
N1—C5—N7122.5 (2)
Symmetry code: (i) x+2, y, z+1.
 

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