Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101014639/fr1345sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101014639/fr1345Isup2.hkl |
CCDC reference: 179250
For related literature, see: Dong et al. (2000); Goher et al. (1998); Klein et al. (1982); Zheng et al. (2000).
The title compound was prepared by the hydrothermal reaction of CuII(pyrazine-2-carboxylate)2 (0.0276 g, 0.1 mmol) with CuCl2·2H2O (0.0275 g, 0.2 mmol) in water (0.8 ml) in an evacuated sealed Pyrex tube. The reaction was heated to 403 K at 1 K min-1 and held at 403 K for 24 h before cooling slowly (0.5 K min-1) to room temperature. The reaction yielded abundant dark blue-green crystals of (I).
All H atoms could be located in the Fourier difference maps. Those bound to C atoms were placed in calculated positions (C—H = 0.930 Å) and given Uiso values 1.2 times those of the parent C atom. Water H atoms were refined isotropically, subject to a distance restraint of O—H = 0.8 Å.
Data collection: SMART NT (Bruker, 1999); cell refinement: SAINT+ NT (Bruker, 1999); data reduction: SAINT+ NT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
[CuCl(C5H3N2O2)(H2O)] | F(000) = 952 |
Mr = 240.10 | Dx = 2.111 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 18.8435 (17) Å | Cell parameters from 3228 reflections |
b = 6.2038 (6) Å | θ = 3.2–26.3° |
c = 13.4129 (12) Å | µ = 3.21 mm−1 |
β = 105.534 (2)° | T = 293 K |
V = 1510.7 (2) Å3 | Fragment, blue green |
Z = 8 | 0.30 × 0.22 × 0.16 mm |
Bruker SMART APEX CCD area-detector diffractometer | 1547 independent reflections |
Radiation source: sealed tube | 1323 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
ω scans | θmax = 26.4°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −23→22 |
Tmin = 0.449, Tmax = 0.599 | k = −7→7 |
4831 measured reflections | l = −16→16 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.025 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.063 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0358P)2] where P = (Fo2 + 2Fc2)/3 |
1547 reflections | (Δ/σ)max < 0.001 |
117 parameters | Δρmax = 0.42 e Å−3 |
2 restraints | Δρmin = −0.41 e Å−3 |
[CuCl(C5H3N2O2)(H2O)] | V = 1510.7 (2) Å3 |
Mr = 240.10 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 18.8435 (17) Å | µ = 3.21 mm−1 |
b = 6.2038 (6) Å | T = 293 K |
c = 13.4129 (12) Å | 0.30 × 0.22 × 0.16 mm |
β = 105.534 (2)° |
Bruker SMART APEX CCD area-detector diffractometer | 1547 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | 1323 reflections with I > 2σ(I) |
Tmin = 0.449, Tmax = 0.599 | Rint = 0.025 |
4831 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 2 restraints |
wR(F2) = 0.063 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.42 e Å−3 |
1547 reflections | Δρmin = −0.41 e Å−3 |
117 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 | ||
Cu | 0.384384 (17) | 0.56823 (5) | 0.35749 (2) | 0.02374 (12) | |
Cl | 0.46448 (4) | 0.83711 (12) | 0.37073 (5) | 0.03774 (19) | |
C1 | 0.36240 (13) | 0.3766 (4) | 0.53576 (18) | 0.0221 (5) | |
C2 | 0.36048 (14) | 0.3388 (4) | 0.63671 (18) | 0.0256 (5) | |
H2 | 0.3427 | 0.2081 | 0.6540 | 0.031* | |
C3 | 0.40963 (14) | 0.6744 (4) | 0.68166 (18) | 0.0280 (6) | |
H3 | 0.4243 | 0.7834 | 0.7305 | 0.034* | |
C4 | 0.41481 (14) | 0.7076 (4) | 0.58210 (18) | 0.0267 (5) | |
H4 | 0.4355 | 0.8344 | 0.5657 | 0.032* | |
C5 | 0.33198 (14) | 0.2205 (4) | 0.44837 (18) | 0.0244 (5) | |
N1 | 0.39020 (11) | 0.5583 (3) | 0.50923 (14) | 0.0225 (4) | |
N2 | 0.38405 (11) | 0.4895 (4) | 0.70953 (14) | 0.0244 (4) | |
O1 | 0.33849 (10) | 0.2827 (3) | 0.36047 (12) | 0.0293 (4) | |
O2 | 0.30234 (10) | 0.0545 (3) | 0.46599 (13) | 0.0313 (4) | |
O3 | 0.27682 (13) | 0.7284 (4) | 0.32162 (17) | 0.0456 (5) | |
H3WA | 0.2815 (18) | 0.835 (3) | 0.355 (2) | 0.042 (9)* | |
H3WB | 0.2433 (12) | 0.734 (5) | 0.2713 (16) | 0.045 (10)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu | 0.0309 (2) | 0.02735 (18) | 0.01294 (17) | −0.00202 (13) | 0.00588 (12) | −0.00023 (11) |
Cl | 0.0434 (4) | 0.0426 (4) | 0.0289 (4) | −0.0150 (3) | 0.0126 (3) | −0.0038 (3) |
C1 | 0.0256 (13) | 0.0242 (12) | 0.0164 (11) | 0.0018 (10) | 0.0055 (10) | 0.0009 (9) |
C2 | 0.0316 (14) | 0.0249 (13) | 0.0207 (12) | 0.0009 (11) | 0.0078 (11) | 0.0004 (10) |
C3 | 0.0327 (15) | 0.0308 (14) | 0.0190 (12) | −0.0014 (11) | 0.0043 (11) | −0.0047 (10) |
C4 | 0.0325 (15) | 0.0259 (13) | 0.0202 (13) | −0.0052 (11) | 0.0045 (11) | −0.0009 (10) |
C5 | 0.0268 (14) | 0.0244 (13) | 0.0212 (13) | 0.0031 (10) | 0.0052 (10) | −0.0022 (10) |
N1 | 0.0252 (11) | 0.0262 (11) | 0.0154 (10) | 0.0012 (9) | 0.0043 (8) | 0.0004 (8) |
N2 | 0.0288 (12) | 0.0300 (11) | 0.0144 (10) | 0.0012 (9) | 0.0058 (9) | 0.0005 (8) |
O1 | 0.0460 (12) | 0.0270 (9) | 0.0142 (8) | −0.0060 (8) | 0.0071 (8) | −0.0034 (7) |
O2 | 0.0451 (12) | 0.0256 (10) | 0.0244 (10) | −0.0066 (8) | 0.0114 (9) | −0.0024 (7) |
O3 | 0.0445 (13) | 0.0473 (13) | 0.0344 (12) | 0.0165 (11) | −0.0079 (10) | −0.0171 (11) |
Cu—O1 | 1.9762 (17) | C3—N2 | 1.336 (3) |
Cu—N1 | 2.0095 (19) | C3—C4 | 1.380 (3) |
Cu—N2i | 2.0151 (19) | C3—H3 | 0.9300 |
Cu—Cl | 2.2245 (7) | C4—N1 | 1.336 (3) |
Cu—O3 | 2.192 (2) | C4—H4 | 0.9300 |
C1—N1 | 1.331 (3) | C5—O2 | 1.224 (3) |
C1—C2 | 1.384 (3) | C5—O1 | 1.277 (3) |
C1—C5 | 1.510 (3) | N2—Cuii | 2.0151 (19) |
C2—N2 | 1.339 (3) | O3—H3WA | 0.788 (10) |
C2—H2 | 0.9300 | O3—H3WB | 0.792 (10) |
O1—Cu—N1 | 81.81 (7) | C4—C3—H3 | 119.2 |
O1—Cu—N2i | 88.54 (8) | N1—C4—C3 | 120.2 (2) |
N1—Cu—N2i | 167.67 (9) | N1—C4—H4 | 119.9 |
O1—Cu—O3 | 91.54 (9) | C3—C4—H4 | 119.9 |
N1—Cu—O3 | 91.87 (8) | O2—C5—O1 | 126.4 (2) |
N2i—Cu—O3 | 96.06 (8) | O2—C5—C1 | 119.2 (2) |
O1—Cu—Cl | 164.09 (6) | O1—C5—C1 | 114.3 (2) |
N1—Cu—Cl | 95.19 (6) | C1—N1—C4 | 118.4 (2) |
N2i—Cu—Cl | 92.00 (6) | C1—N1—Cu | 112.23 (15) |
O3—Cu—Cl | 104.20 (7) | C4—N1—Cu | 129.31 (17) |
N1—C1—C2 | 121.4 (2) | C3—N2—C2 | 118.0 (2) |
N1—C1—C5 | 115.5 (2) | C3—N2—Cuii | 121.47 (16) |
C2—C1—C5 | 123.1 (2) | C2—N2—Cuii | 120.48 (17) |
N2—C2—C1 | 120.3 (2) | C5—O1—Cu | 116.12 (15) |
N2—C2—H2 | 119.8 | Cu—O3—H3WA | 107 (2) |
C1—C2—H2 | 119.8 | Cu—O3—H3WB | 133 (2) |
N2—C3—C4 | 121.5 (2) | H3WA—O3—H3WB | 113 (3) |
N2—C3—H3 | 119.2 |
Symmetry codes: (i) x, −y+1, z−1/2; (ii) x, −y+1, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3WA···O2iii | 0.79 (2) | 1.98 (2) | 2.752 (3) | 166 (3) |
O3—H3WB···O1iv | 0.79 (2) | 2.03 (2) | 2.821 (3) | 174 (3) |
Symmetry codes: (iii) x, y+1, z; (iv) −x+1/2, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [CuCl(C5H3N2O2)(H2O)] |
Mr | 240.10 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 18.8435 (17), 6.2038 (6), 13.4129 (12) |
β (°) | 105.534 (2) |
V (Å3) | 1510.7 (2) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 3.21 |
Crystal size (mm) | 0.30 × 0.22 × 0.16 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1999) |
Tmin, Tmax | 0.449, 0.599 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4831, 1547, 1323 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.063, 1.00 |
No. of reflections | 1547 |
No. of parameters | 117 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.42, −0.41 |
Computer programs: SMART NT (Bruker, 1999), SAINT+ NT (Bruker, 1999), SAINT+ NT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
Cu—O1 | 1.9762 (17) | Cu—Cl | 2.2245 (7) |
Cu—N1 | 2.0095 (19) | Cu—O3 | 2.192 (2) |
Cu—N2i | 2.0151 (19) | ||
O1—Cu—N1 | 81.81 (7) | N2i—Cu—O3 | 96.06 (8) |
O1—Cu—N2i | 88.54 (8) | O1—Cu—Cl | 164.09 (6) |
N1—Cu—N2i | 167.67 (9) | N1—Cu—Cl | 95.19 (6) |
O1—Cu—O3 | 91.54 (9) | N2i—Cu—Cl | 92.00 (6) |
N1—Cu—O3 | 91.87 (8) | O3—Cu—Cl | 104.20 (7) |
Symmetry code: (i) x, −y+1, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3WA···O2ii | 0.79 (2) | 1.98 (2) | 2.752 (3) | 166 (3) |
O3—H3WB···O1iii | 0.79 (2) | 2.03 (2) | 2.821 (3) | 174 (3) |
Symmetry codes: (ii) x, y+1, z; (iii) −x+1/2, y+1/2, −z+1/2. |
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Pyrazine-2-carboxylato (hereinafter pyzca) complexes of copper(II) (Klein et al., 1982) have recently been used to construct several novel mixed-metal and mixed-valent coordination polymers (Dong et al., 2000; Zheng et al., 2000). The attractiveness of this complex as a `metal-containing building block' for the construction of novel framework materials of varying dimensionality lies in its donor-acceptor versatility. Chelation of the CuII center by two pyrazine-2-carboxylato ligands leaves two para N donors and two free carboxylate O atoms available for intermolecular bonding and supramolecular interactions. Since this complex often forms as a bis(aqua) complex, structural diversity through hydrogen-bonding interactions is also possible. Investigation of the hydrothermal reactivity of [Cu(pyzca)2] with various metal salts has led to the formation of a new polymorph of [CuCl(pyzca)(H2O)], (I), reported here. \sch
The structure of (I) consists of one-dimensional chains of CuII centers connected through pyzca ligands (Fig. 1). The Cu2+ ion resides in a pseudo-square-pyramidal coordination environment. An O atom and an N atom from the chelating end of a pyzca ligand, a para N atom from a symmetry-equivalent pyzca ligand [symmetry code: (vi) x, -y, z - 1/2] and a Cl ligand form the base of the pyramid. A water molecule occupies the apical site. The distortion from ideal square-pyramidal geometry is due primarily to the larger size of the Cl ligand (Table I).
Compound (I) is a polymorph of the structure reported by Goher et al. (1998). The central structural unit of both, the one-dimensional chains, is virtually identical. The two structures differ in the pattern of hydrogen bonding linking the chains. In (I), the chains assemble into bilayers parallel to the crystallographic bc plane. The water ligands in (I) point toward the bilayer interior and form a hydrogen-bonding network involving an unchelated carboxylate O atom (O3—H3WA···O2) and a carboxylate O atom bound to Cu (O3—H3WB···O1). Each water molecule is linked to two neighboring chains in this fashion. The Cl ligands protrude outward from the bilayers, which then stack in a centrosymmetric fashion along [001] (Fig. 2).
The structure reported by Goher et al. (1998) was crystallized in low (15%) yield by the ambient temperature evaporation of a 2:1 ethanol-water solution. Due to the noncentrosymmetic stacking of individual chains, each water ligand forms hydrogen bonds to two neighboring chains through a Cl ligand and an unchelated carboxylate O atom of a pyzca ligand, rather than through an exclusively O—H···O network as in (I). Interestingly, although much harsher hydrothermal reaction conditions in pure water produced (I) rather than the previous structure, (I) is in fact isostructural with the azido analog [CuII(N3)(pyrazine-2-carboxylato)(H2O)], also obtained by Goher et al. by evaporation at room temperature.