Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807040007/bi2227sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807040007/bi2227Isup2.hkl |
CCDC reference: 1283846
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%.
H atoms were placed in calculated positions and allowed to ride with C—H = 0.93%A and with Uiso(H) = 1.2Ueq(C).
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).
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).
[Cu(C2H2N3)Cl] | F(000) = 324 |
Mr = 167.06 | Dx = 2.170 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 1096 reflections |
a = 6.0213 (10) Å | θ = 3.1–26.9° |
b = 9.960 (2) Å | µ = 4.65 mm−1 |
c = 8.6869 (10) Å | T = 293 K |
β = 101.021 (10)° | Block, blue |
V = 511.38 (15) Å3 | 0.12 × 0.10 × 0.10 mm |
Z = 4 |
Bruker APEX II CCD diffractometer | 1096 independent reflections |
Radiation source: fine-focus sealed tube | 917 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
φ and ω scans | θmax = 26.9°, θmin = 3.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −7→7 |
Tmin = 0.606, Tmax = 0.654 | k = −12→12 |
4256 measured reflections | l = −10→10 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.019 | H-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 reflections | Δρmax = 0.32 e Å−3 |
65 parameters | Δρmin = −0.32 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0269 (11) |
[Cu(C2H2N3)Cl] | V = 511.38 (15) Å3 |
Mr = 167.06 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.0213 (10) Å | µ = 4.65 mm−1 |
b = 9.960 (2) Å | T = 293 K |
c = 8.6869 (10) Å | 0.12 × 0.10 × 0.10 mm |
β = 101.021 (10)° |
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 = 0.654 | Rint = 0.026 |
4256 measured reflections |
R[F2 > 2σ(F2)] = 0.019 | 0 restraints |
wR(F2) = 0.038 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.32 e Å−3 |
1096 reflections | Δρmin = −0.32 e Å−3 |
65 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.2402 (4) | 0.6685 (2) | 1.2710 (3) | 0.0277 (5) | |
H1 | 0.2495 | 0.6537 | 1.3778 | 0.033* | |
C2 | 0.2874 (4) | 0.7543 (3) | 1.0620 (3) | 0.0315 (6) | |
H2 | 0.3331 | 0.8100 | 0.9880 | 0.038* | |
Cl1 | 0.30626 (12) | 0.55329 (7) | 0.67333 (8) | 0.04266 (19) | |
Cu1 | 0.04412 (4) | 0.58056 (3) | 0.81490 (3) | 0.01897 (11) | |
N1 | 0.1593 (3) | 0.6475 (2) | 1.0271 (2) | 0.0274 (5) | |
N2 | 0.3427 (3) | 0.77240 (19) | 1.2138 (2) | 0.0259 (4) | |
N3 | 0.1277 (3) | 0.59126 (19) | 1.1642 (2) | 0.0247 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0344 (13) | 0.0305 (13) | 0.0168 (11) | −0.0032 (11) | 0.0013 (9) | −0.0008 (9) |
C2 | 0.0417 (14) | 0.0305 (13) | 0.0202 (11) | −0.0118 (11) | 0.0010 (10) | 0.0022 (10) |
Cl1 | 0.0394 (4) | 0.0548 (5) | 0.0376 (4) | 0.0036 (3) | 0.0168 (3) | −0.0020 (3) |
Cu1 | 0.02207 (16) | 0.02000 (17) | 0.01356 (15) | −0.00051 (11) | 0.00020 (9) | 0.00153 (10) |
N1 | 0.0347 (11) | 0.0280 (11) | 0.0173 (9) | −0.0051 (9) | −0.0007 (8) | 0.0027 (8) |
N2 | 0.0292 (10) | 0.0255 (10) | 0.0213 (10) | −0.0034 (8) | 0.0002 (8) | −0.0016 (8) |
N3 | 0.0295 (10) | 0.0266 (10) | 0.0169 (9) | −0.0025 (9) | 0.0015 (7) | 0.0029 (8) |
C1—N3 | 1.293 (3) | Cu1—N1 | 1.9585 (19) |
C1—N2 | 1.348 (3) | Cu1—N2i | 1.9950 (19) |
C1—H1 | 0.930 | Cu1—N3ii | 2.0257 (19) |
C2—N2 | 1.309 (3) | N1—N3 | 1.362 (3) |
C2—N1 | 1.315 (3) | N2—Cu1iii | 1.9950 (19) |
C2—H2 | 0.930 | N3—Cu1ii | 2.0257 (19) |
Cl1—Cu1 | 2.1955 (8) | ||
N3—C1—N2 | 114.0 (2) | N3ii—Cu1—Cl1 | 112.32 (6) |
N3—C1—H1 | 123.0 | C2—N1—N3 | 107.76 (18) |
N2—C1—H1 | 123.0 | C2—N1—Cu1 | 125.38 (16) |
N2—C2—N1 | 111.6 (2) | N3—N1—Cu1 | 126.84 (15) |
N2—C2—H2 | 124.2 | C2—N2—C1 | 102.67 (19) |
N1—C2—H2 | 124.2 | C2—N2—Cu1iii | 124.10 (17) |
N1—Cu1—N2i | 103.92 (8) | C1—N2—Cu1iii | 133.17 (15) |
N1—Cu1—N3ii | 107.36 (8) | C1—N3—N1 | 103.95 (18) |
N2i—Cu1—N3ii | 112.44 (8) | C1—N3—Cu1ii | 130.17 (16) |
N1—Cu1—Cl1 | 113.97 (6) | N1—N3—Cu1ii | 125.79 (14) |
N2i—Cu1—Cl1 | 106.62 (6) |
Symmetry codes: (i) x−1/2, −y+3/2, z−1/2; (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] |
Mr | 167.06 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 6.0213 (10), 9.960 (2), 8.6869 (10) |
β (°) | 101.021 (10) |
V (Å3) | 511.38 (15) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 4.65 |
Crystal size (mm) | 0.12 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Bruker APEX II CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.606, 0.654 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4256, 1096, 917 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.637 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.019, 0.038, 1.00 |
No. of reflections | 1096 |
No. of parameters | 65 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.32 |
Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001).
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.