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The title compound, [Cu(C2H2N3)Cl]n, has been prepared by hydro­thermal reaction of CuCl2 and 1,2,4-triazole. It is isostructural with its MnII, CoII, NiII and ZnII analogs. The CuII atom is surrounded by three N atoms belonging to three different triazolate ligands and a Cl atom, and exhibits a slightly distorted tetra­hedral coordination geometry. The triply bridging nature of the 1,2,4-triazolate ligand gives rise to a polymeric layer containing both binuclear and tetra­nuclear macrocyclic units. In the binuclear unit, two CuII atoms are bridged by two nearly coplanar triazolate groups through the 1,2-positions, affording a six-membered ring around an inversion center. Each binuclear unit is further connected to four parallel units through the other four N atoms of the triazolate groups. Four adjacent units, which are pairwise parallel, afford 16-membered tetra­nuclear macrocyclic units in which the two nearest-neighbor CuII atoms are bridged by a single triazolate ligand through the 1,4-positions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807040007/bi2227sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807040007/bi2227Isup2.hkl
Contains datablock I

CCDC reference: 1283846

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](N-C) = 0.003 Å
  • R factor = 0.019
  • wR factor = 0.038
  • Data-to-parameter ratio = 16.9

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.96 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Cu1 PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.22 Ratio
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1 (2) 2.15
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

Comment top

The title compound, [Cu(C2H2N3)Cl]n, is isostructural with its MnII (Gao et al., 2007b), CoII (Wayne et al., 2006), NiII (Gao et al., 2007a) and ZnII (Jonas et al., 1995) analogues.

The coordination polyhedron of the CuII atom (Fig. 1) can be described as a distorted tetrahedron. The CuII atom is surrounded by three N atoms belonging to three different triazolate ligands, and a Cl atom. The Cu—N bond lengths are in the range 1.9585 (19)–2.2057 (19) Å, and the Cu—Cl bond length is 2.1955 (8) Å. The bond angles around the CuII atom are in the range 103.92 (8)–113.97 (6) °.

Polymeric layers (Fig. 2) are formed due to the triply bridging nature of the 1,2,4-triazolate ligand, which is bonded to three different CuII atoms through its three N atoms. A layer contains both binuclear and tetranuclear macrocyclic units. In the binuclear unit, two CuII atoms are bridged by two nearly coplanar triazolate groups through the 1,2-positions, affording a six-membered ring around an inversion center. The Cu···Cu separation within the binuclear unit is 3.722 (1) Å. Each binuclear unit is further connected to four parallel units through the other four N atoms of the triazolate groups. Four adjacent units, which are pairwise parallel, afford 16-membered tetranuclear macrocyclic units. In each of these, the two nearest-neighbor CuII atoms are bridged by a single triazolate ligand through the 1,4-positions. The Cu···Cu separations are 5.628 (1) and 6.026 (1) Å.

Related literature top

For the isostructural analogues, see: Gao et al. (2007b) (MnII); Wayne et al. (2006) (CoII); Gao et al. (2007a) (NiII); Jonas et al. (1995) (ZnII).

Experimental top

A mixture of CuCl2 (0.5 mmol), KOH (0.5 mmol), 1,2,4-triazole (0.5 mmol) and H2O (8 ml) was sealed in a 25 ml Teflon-lined stainless steel autoclave and kept at 413 K for 2 d. On cooling to room temperature, blue crystals of the title compound were obtained in a yield of 11%. Elemental analysis calculated: C 14.37, H 1.20, N 25.15%; found: C 14.32, H 1.24, N 25.12%.

Refinement top

H atoms were placed in calculated positions and allowed to ride with C—H = 0.93%A and with Uiso(H) = 1.2Ueq(C).

Structure description top

The title compound, [Cu(C2H2N3)Cl]n, is isostructural with its MnII (Gao et al., 2007b), CoII (Wayne et al., 2006), NiII (Gao et al., 2007a) and ZnII (Jonas et al., 1995) analogues.

The coordination polyhedron of the CuII atom (Fig. 1) can be described as a distorted tetrahedron. The CuII atom is surrounded by three N atoms belonging to three different triazolate ligands, and a Cl atom. The Cu—N bond lengths are in the range 1.9585 (19)–2.2057 (19) Å, and the Cu—Cl bond length is 2.1955 (8) Å. The bond angles around the CuII atom are in the range 103.92 (8)–113.97 (6) °.

Polymeric layers (Fig. 2) are formed due to the triply bridging nature of the 1,2,4-triazolate ligand, which is bonded to three different CuII atoms through its three N atoms. A layer contains both binuclear and tetranuclear macrocyclic units. In the binuclear unit, two CuII atoms are bridged by two nearly coplanar triazolate groups through the 1,2-positions, affording a six-membered ring around an inversion center. The Cu···Cu separation within the binuclear unit is 3.722 (1) Å. Each binuclear unit is further connected to four parallel units through the other four N atoms of the triazolate groups. Four adjacent units, which are pairwise parallel, afford 16-membered tetranuclear macrocyclic units. In each of these, the two nearest-neighbor CuII atoms are bridged by a single triazolate ligand through the 1,4-positions. The Cu···Cu separations are 5.628 (1) and 6.026 (1) Å.

For the isostructural analogues, see: Gao et al. (2007b) (MnII); Wayne et al. (2006) (CoII); Gao et al. (2007a) (NiII); Jonas et al. (1995) (ZnII).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids for non-H atoms. The subscript I denotes the the symmetry operation -x + 1/2, y - 1/2, -z + 3/2).
[Figure 2] Fig. 2. View of a layer showing both the binuclear units and the tetranuclear cavities.
Poly[chlorido(µ3-1,2,4-triazolato)copper(II)] top
Crystal data top
[Cu(C2H2N3)Cl]F(000) = 324
Mr = 167.06Dx = 2.170 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1096 reflections
a = 6.0213 (10) Åθ = 3.1–26.9°
b = 9.960 (2) ŵ = 4.65 mm1
c = 8.6869 (10) ÅT = 293 K
β = 101.021 (10)°Block, blue
V = 511.38 (15) Å30.12 × 0.10 × 0.10 mm
Z = 4
Data collection top
Bruker APEX II CCD
diffractometer
1096 independent reflections
Radiation source: fine-focus sealed tube917 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
φ and ω scansθmax = 26.9°, θmin = 3.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = 77
Tmin = 0.606, Tmax = 0.654k = 1212
4256 measured reflectionsl = 1010
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)] = 0.019H-atom parameters constrained
wR(F2) = 0.038 w = 1/[σ2(Fo2) + 0.65P]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
1096 reflectionsΔρmax = 0.32 e Å3
65 parametersΔρmin = 0.32 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0269 (11)
Crystal data top
[Cu(C2H2N3)Cl]V = 511.38 (15) Å3
Mr = 167.06Z = 4
Monoclinic, P21/nMo Kα radiation
a = 6.0213 (10) ŵ = 4.65 mm1
b = 9.960 (2) ÅT = 293 K
c = 8.6869 (10) Å0.12 × 0.10 × 0.10 mm
β = 101.021 (10)°
Data collection top
Bruker APEX II CCD
diffractometer
1096 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
917 reflections with I > 2σ(I)
Tmin = 0.606, Tmax = 0.654Rint = 0.026
4256 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0190 restraints
wR(F2) = 0.038H-atom parameters constrained
S = 1.00Δρmax = 0.32 e Å3
1096 reflectionsΔρmin = 0.32 e Å3
65 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
C10.2402 (4)0.6685 (2)1.2710 (3)0.0277 (5)
H10.24950.65371.37780.033*
C20.2874 (4)0.7543 (3)1.0620 (3)0.0315 (6)
H20.33310.81000.98800.038*
Cl10.30626 (12)0.55329 (7)0.67333 (8)0.04266 (19)
Cu10.04412 (4)0.58056 (3)0.81490 (3)0.01897 (11)
N10.1593 (3)0.6475 (2)1.0271 (2)0.0274 (5)
N20.3427 (3)0.77240 (19)1.2138 (2)0.0259 (4)
N30.1277 (3)0.59126 (19)1.1642 (2)0.0247 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0344 (13)0.0305 (13)0.0168 (11)0.0032 (11)0.0013 (9)0.0008 (9)
C20.0417 (14)0.0305 (13)0.0202 (11)0.0118 (11)0.0010 (10)0.0022 (10)
Cl10.0394 (4)0.0548 (5)0.0376 (4)0.0036 (3)0.0168 (3)0.0020 (3)
Cu10.02207 (16)0.02000 (17)0.01356 (15)0.00051 (11)0.00020 (9)0.00153 (10)
N10.0347 (11)0.0280 (11)0.0173 (9)0.0051 (9)0.0007 (8)0.0027 (8)
N20.0292 (10)0.0255 (10)0.0213 (10)0.0034 (8)0.0002 (8)0.0016 (8)
N30.0295 (10)0.0266 (10)0.0169 (9)0.0025 (9)0.0015 (7)0.0029 (8)
Geometric parameters (Å, º) top
C1—N31.293 (3)Cu1—N11.9585 (19)
C1—N21.348 (3)Cu1—N2i1.9950 (19)
C1—H10.930Cu1—N3ii2.0257 (19)
C2—N21.309 (3)N1—N31.362 (3)
C2—N11.315 (3)N2—Cu1iii1.9950 (19)
C2—H20.930N3—Cu1ii2.0257 (19)
Cl1—Cu12.1955 (8)
N3—C1—N2114.0 (2)N3ii—Cu1—Cl1112.32 (6)
N3—C1—H1123.0C2—N1—N3107.76 (18)
N2—C1—H1123.0C2—N1—Cu1125.38 (16)
N2—C2—N1111.6 (2)N3—N1—Cu1126.84 (15)
N2—C2—H2124.2C2—N2—C1102.67 (19)
N1—C2—H2124.2C2—N2—Cu1iii124.10 (17)
N1—Cu1—N2i103.92 (8)C1—N2—Cu1iii133.17 (15)
N1—Cu1—N3ii107.36 (8)C1—N3—N1103.95 (18)
N2i—Cu1—N3ii112.44 (8)C1—N3—Cu1ii130.17 (16)
N1—Cu1—Cl1113.97 (6)N1—N3—Cu1ii125.79 (14)
N2i—Cu1—Cl1106.62 (6)
Symmetry codes: (i) x1/2, y+3/2, z1/2; (ii) x, y+1, z+2; (iii) x+1/2, y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula[Cu(C2H2N3)Cl]
Mr167.06
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)6.0213 (10), 9.960 (2), 8.6869 (10)
β (°) 101.021 (10)
V3)511.38 (15)
Z4
Radiation typeMo Kα
µ (mm1)4.65
Crystal size (mm)0.12 × 0.10 × 0.10
Data collection
DiffractometerBruker APEX II CCD
Absorption correctionMulti-scan
(SADABS; Bruker, 2001)
Tmin, Tmax0.606, 0.654
No. of measured, independent and
observed [I > 2σ(I)] reflections
4256, 1096, 917
Rint0.026
(sin θ/λ)max1)0.637
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.019, 0.038, 1.00
No. of reflections1096
No. of parameters65
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.32, 0.32

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001).

 

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