Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807030528/hb2444sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807030528/hb2444Isup2.hkl |
CCDC reference: 1212036
A mixture of copper dichloride hexahydrate (0.5 mmol), potassium hydroxide (0.5 mmol), 2-pyrazine caboxylic acid (0.5 mmol), EtOH (8 ml) and H2O (8 ml) in a 25 ml Teflon-lined stainless steel autoclave was heated to at 413 K for 2 d, and then cooled to room temperature. Red block-shaped crystals of (I) were obtained in a yield of 36%. Anal. Calc. for C10H8CuN4O5: C 36.62, H 2.44, N 17.09%; Found: C 36.59, H 2.47, N 17.01%.
All H atoms on C atoms were generated geometrically (C—H = 0.93 Å) and refined as riding with Uiso(H) = 1.2Ueq(C). The H atoms of the water molecule were located from difference density maps and were refined with distance restraints of O—H = 0.82 (1) Å and H···H = 1.38 (2) Å and a fixed Uiso(H) of 0.08 Å2.
The title compound, (I), is isostructural with its FeII, CoII, and NiII analogues [Hao & Liu, (2007); Hao, Mu & Liu, (2007); Gao et al. (2007)]. The CuII atom in (I) is coordinated in a bidentate fashion by two O and two N atoms from two independent pyrazine-2-carboxylate anions. The distorted octhedral coordiantion is completed by another N atom from a third pyrazine-2-carboxylate ligand, and by the O atom of a water molecule (Fig. 1, Table 1). One pyrazine-2-carboxylate ligand coordinates to a neighboring Cu atom via its second N atom, leading to a polymeic structure with zigzag chains extending parallel to the b axis (Fig. 2). Hydrogen bonding involving the water molecules (Table 2) stablizes the structure.
For the isostructural FeII, CoII, and NiII analogues, see: Hao & Liu (2007); Hao et al. (2007); Gao et al. (2007).
[Prep section states red block crystals were formed, but CIF data tables state blue cube - which is correct?]
Data collection: SMART (Bruker, 2001) [Or APEX2?]; cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; 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.
[Cu(C5H3N2O2)2(H2O)] | F(000) = 660 |
Mr = 327.74 | Dx = 1.894 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 2460 reflections |
a = 7.7379 (5) Å | θ = 2.5–27.0° |
b = 9.9021 (5) Å | µ = 1.93 mm−1 |
c = 15.002 (1) Å | T = 298 K |
V = 1149.48 (12) Å3 | Cube, blue |
Z = 4 | 0.10 × 0.10 × 0.10 mm |
Bruker APEXII CCD area-detector diffractometer | 2219 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.032 |
Graphite monochromator | θmax = 27.0°, θmin = 2.5° |
φ and ω scans | h = −8→9 |
6840 measured reflections | k = −12→12 |
2460 independent reflections | l = −15→19 |
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)] = 0.038 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.099 | w = 1/[σ2(Fo2) + (0.0666P)2 + 0.3756P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.014 |
2460 reflections | Δρmax = 1.20 e Å−3 |
182 parameters | Δρmin = −0.36 e Å−3 |
3 restraints | Absolute structure: Flack (1983), with 1004 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.49 (2) |
[Cu(C5H3N2O2)2(H2O)] | V = 1149.48 (12) Å3 |
Mr = 327.74 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.7379 (5) Å | µ = 1.93 mm−1 |
b = 9.9021 (5) Å | T = 298 K |
c = 15.002 (1) Å | 0.10 × 0.10 × 0.10 mm |
Bruker APEXII CCD area-detector diffractometer | 2219 reflections with I > 2σ(I) |
6840 measured reflections | Rint = 0.032 |
2460 independent reflections |
R[F2 > 2σ(F2)] = 0.038 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.099 | Δρmax = 1.20 e Å−3 |
S = 1.01 | Δρmin = −0.36 e Å−3 |
2460 reflections | Absolute structure: Flack (1983), with 1004 Friedel pairs |
182 parameters | Absolute structure parameter: 0.49 (2) |
3 restraints |
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 | ||
Cu1 | 0.42685 (6) | 0.63422 (4) | 0.59076 (3) | 0.01911 (14) | |
C1 | 0.1940 (5) | 0.8096 (4) | 0.6830 (3) | 0.0259 (5) | |
C2 | 0.3720 (5) | 0.8540 (4) | 0.7110 (2) | 0.0174 (7) | |
C3 | 0.3948 (5) | 0.9581 (4) | 0.7733 (3) | 0.0214 (8) | |
H3 | 0.2981 | 1.0026 | 0.7955 | 0.026* | |
C4 | 0.6843 (6) | 0.9334 (4) | 0.7638 (3) | 0.0243 (9) | |
H4 | 0.7954 | 0.9589 | 0.7804 | 0.029* | |
C5 | 0.6628 (5) | 0.8307 (4) | 0.6996 (3) | 0.0226 (9) | |
H5 | 0.7594 | 0.7905 | 0.6740 | 0.027* | |
C6 | 0.6424 (6) | 0.4713 (4) | 0.4810 (3) | 0.0228 (9) | |
C7 | 0.4616 (5) | 0.4269 (4) | 0.4590 (3) | 0.0232 (9) | |
C8 | 0.4259 (6) | 0.3353 (4) | 0.3918 (3) | 0.0323 (10) | |
H8 | 0.5175 | 0.2988 | 0.3597 | 0.039* | |
C9 | 0.1408 (6) | 0.3514 (4) | 0.4213 (3) | 0.0307 (9) | |
H9 | 0.0268 | 0.3269 | 0.4101 | 0.037* | |
C10 | 0.1755 (6) | 0.4432 (4) | 0.4894 (3) | 0.0271 (9) | |
H10 | 0.0847 | 0.4779 | 0.5230 | 0.033* | |
N1 | 0.5062 (4) | 0.7910 (3) | 0.6756 (2) | 0.0195 (7) | |
N2 | 0.5494 (4) | 0.9948 (3) | 0.8012 (2) | 0.0191 (7) | |
N3 | 0.3352 (4) | 0.4817 (3) | 0.5070 (2) | 0.0197 (7) | |
N4 | 0.2667 (5) | 0.2974 (4) | 0.3713 (3) | 0.0383 (10) | |
O1 | 0.1945 (3) | 0.7028 (3) | 0.63112 (18) | 0.0201 (6) | |
O2 | 0.0686 (3) | 0.8697 (3) | 0.70894 (18) | 0.0259 (5) | |
O3 | 0.6530 (4) | 0.5644 (3) | 0.54124 (19) | 0.0218 (6) | |
O4 | 0.7633 (4) | 0.4208 (4) | 0.4411 (3) | 0.0434 (9) | |
O5 | 0.4184 (4) | 0.7653 (3) | 0.48314 (19) | 0.0274 (6) | |
H1W | 0.509 (5) | 0.793 (6) | 0.462 (5) | 0.080* | |
H2W | 0.335 (5) | 0.815 (6) | 0.475 (5) | 0.080* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0166 (2) | 0.0202 (2) | 0.0205 (2) | −0.00007 (19) | −0.00077 (19) | −0.00039 (19) |
C1 | 0.0155 (10) | 0.0306 (12) | 0.0314 (12) | 0.0031 (11) | −0.0021 (9) | −0.0043 (10) |
C2 | 0.0168 (17) | 0.0186 (17) | 0.0168 (17) | 0.0012 (14) | −0.0034 (13) | 0.0012 (15) |
C3 | 0.021 (2) | 0.0237 (18) | 0.0189 (18) | 0.0014 (15) | 0.0012 (16) | −0.0043 (15) |
C4 | 0.019 (2) | 0.0229 (19) | 0.031 (2) | −0.0010 (17) | −0.0004 (17) | −0.0052 (17) |
C5 | 0.0156 (19) | 0.024 (2) | 0.029 (2) | 0.0018 (16) | 0.0015 (16) | −0.0003 (16) |
C6 | 0.0189 (19) | 0.024 (2) | 0.025 (2) | −0.0033 (16) | 0.0005 (16) | 0.0005 (16) |
C7 | 0.024 (2) | 0.0222 (19) | 0.023 (2) | 0.0035 (16) | 0.0005 (16) | 0.0005 (16) |
C8 | 0.023 (2) | 0.037 (2) | 0.038 (3) | 0.003 (2) | 0.002 (2) | −0.0162 (17) |
C9 | 0.0215 (19) | 0.033 (2) | 0.038 (2) | −0.0013 (18) | −0.0046 (18) | −0.007 (2) |
C10 | 0.022 (2) | 0.027 (2) | 0.032 (2) | 0.0010 (17) | 0.0026 (18) | −0.0019 (17) |
N1 | 0.0169 (15) | 0.0205 (16) | 0.0211 (17) | 0.0013 (13) | −0.0001 (13) | 0.0009 (13) |
N2 | 0.0184 (17) | 0.0182 (14) | 0.0206 (15) | 0.0002 (14) | 0.0006 (13) | −0.0037 (12) |
N3 | 0.0185 (16) | 0.0182 (16) | 0.0223 (16) | 0.0007 (13) | −0.0003 (14) | −0.0014 (13) |
N4 | 0.031 (2) | 0.041 (2) | 0.043 (2) | −0.0074 (18) | −0.0033 (18) | −0.0200 (19) |
O1 | 0.0146 (13) | 0.0238 (13) | 0.0219 (14) | 0.0003 (11) | −0.0022 (11) | −0.0039 (11) |
O2 | 0.0155 (10) | 0.0306 (12) | 0.0314 (12) | 0.0031 (11) | −0.0021 (9) | −0.0043 (10) |
O3 | 0.0135 (13) | 0.0233 (14) | 0.0286 (15) | −0.0016 (11) | 0.0001 (11) | −0.0007 (12) |
O4 | 0.0217 (17) | 0.054 (2) | 0.054 (2) | 0.0074 (16) | 0.0067 (15) | −0.0191 (17) |
O5 | 0.0234 (15) | 0.0304 (15) | 0.0285 (14) | 0.0089 (15) | 0.0052 (14) | 0.0127 (12) |
Cu1—O1 | 2.015 (3) | C5—H5 | 0.9300 |
Cu1—O3 | 2.023 (3) | C6—O4 | 1.218 (5) |
Cu1—O5 | 2.073 (3) | C6—O3 | 1.293 (5) |
Cu1—N3 | 2.089 (3) | C6—C7 | 1.503 (6) |
Cu1—N1 | 2.099 (3) | C7—N3 | 1.331 (5) |
Cu1—N2i | 2.137 (3) | C7—C8 | 1.384 (6) |
C1—O2 | 1.203 (5) | C8—N4 | 1.324 (6) |
C1—O1 | 1.313 (5) | C8—H8 | 0.9300 |
C1—C2 | 1.506 (5) | C9—N4 | 1.341 (6) |
C2—N1 | 1.323 (5) | C9—C10 | 1.394 (6) |
C2—C3 | 1.402 (5) | C9—H9 | 0.9300 |
C3—N2 | 1.319 (5) | C10—N3 | 1.320 (6) |
C3—H3 | 0.9300 | C10—H10 | 0.9300 |
C4—N2 | 1.332 (5) | N2—Cu1ii | 2.137 (3) |
C4—C5 | 1.410 (6) | O5—H1W | 0.82 (5) |
C4—H4 | 0.9300 | O5—H2W | 0.82 (5) |
C5—N1 | 1.324 (5) | ||
O1—Cu1—O3 | 175.85 (12) | O4—C6—O3 | 126.0 (4) |
O1—Cu1—O5 | 89.69 (12) | O4—C6—C7 | 119.1 (4) |
O3—Cu1—O5 | 87.45 (12) | O3—C6—C7 | 114.9 (3) |
O1—Cu1—N3 | 96.98 (12) | N3—C7—C8 | 121.0 (4) |
O3—Cu1—N3 | 79.95 (12) | N3—C7—C6 | 116.5 (3) |
O5—Cu1—N3 | 88.47 (13) | C8—C7—C6 | 122.6 (4) |
O1—Cu1—N1 | 80.18 (12) | N4—C8—C7 | 122.8 (4) |
O3—Cu1—N1 | 102.86 (13) | N4—C8—H8 | 118.6 |
O5—Cu1—N1 | 91.06 (13) | C7—C8—H8 | 118.6 |
N3—Cu1—N1 | 177.12 (14) | N4—C9—C10 | 122.0 (4) |
O1—Cu1—N2i | 93.83 (12) | N4—C9—H9 | 119.0 |
O3—Cu1—N2i | 89.04 (12) | C10—C9—H9 | 119.0 |
O5—Cu1—N2i | 176.48 (14) | N3—C10—C9 | 121.0 (4) |
N3—Cu1—N2i | 91.07 (13) | N3—C10—H10 | 119.5 |
N1—Cu1—N2i | 89.57 (12) | C9—C10—H10 | 119.5 |
O2—C1—O1 | 126.3 (4) | C2—N1—C5 | 118.0 (3) |
O2—C1—C2 | 120.2 (4) | C2—N1—Cu1 | 111.3 (3) |
O1—C1—C2 | 113.5 (3) | C5—N1—Cu1 | 130.7 (3) |
N1—C2—C3 | 121.0 (3) | C3—N2—C4 | 116.8 (3) |
N1—C2—C1 | 117.9 (3) | C3—N2—Cu1ii | 119.8 (3) |
C3—C2—C1 | 121.1 (3) | C4—N2—Cu1ii | 123.2 (3) |
N2—C3—C2 | 121.9 (4) | C10—N3—C7 | 117.5 (3) |
N2—C3—H3 | 119.1 | C10—N3—Cu1 | 130.3 (3) |
C2—C3—H3 | 119.1 | C7—N3—Cu1 | 111.8 (3) |
N2—C4—C5 | 121.6 (4) | C9—N4—C8 | 115.7 (4) |
N2—C4—H4 | 119.2 | C1—O1—Cu1 | 116.9 (2) |
C5—C4—H4 | 119.2 | C6—O3—Cu1 | 116.5 (3) |
N1—C5—C4 | 120.5 (4) | Cu1—O5—H1W | 119 (5) |
N1—C5—H5 | 119.8 | Cu1—O5—H2W | 121 (5) |
C4—C5—H5 | 119.8 | H1W—O5—H2W | 114 (3) |
O2—C1—C2—N1 | −175.2 (4) | C5—C4—N2—Cu1ii | 172.6 (3) |
O1—C1—C2—N1 | 5.7 (5) | C9—C10—N3—C7 | −1.8 (6) |
O2—C1—C2—C3 | 5.3 (6) | C9—C10—N3—Cu1 | 170.6 (3) |
O1—C1—C2—C3 | −173.8 (3) | C8—C7—N3—C10 | 1.5 (6) |
N1—C2—C3—N2 | −2.1 (6) | C6—C7—N3—C10 | −179.4 (4) |
C1—C2—C3—N2 | 177.3 (4) | C8—C7—N3—Cu1 | −172.3 (3) |
N2—C4—C5—N1 | −1.0 (6) | C6—C7—N3—Cu1 | 6.8 (4) |
O4—C6—C7—N3 | 177.6 (4) | O1—Cu1—N3—C10 | −1.5 (4) |
O3—C6—C7—N3 | −3.8 (5) | O3—Cu1—N3—C10 | −178.6 (4) |
O4—C6—C7—C8 | −3.3 (6) | O5—Cu1—N3—C10 | −91.0 (4) |
O3—C6—C7—C8 | 175.3 (4) | N2i—Cu1—N3—C10 | 92.5 (4) |
N3—C7—C8—N4 | 0.1 (7) | O1—Cu1—N3—C7 | 171.3 (3) |
C6—C7—C8—N4 | −179.0 (4) | O3—Cu1—N3—C7 | −5.9 (2) |
N4—C9—C10—N3 | 0.6 (7) | O5—Cu1—N3—C7 | 81.8 (3) |
C3—C2—N1—C5 | −1.1 (6) | N2i—Cu1—N3—C7 | −94.7 (3) |
C1—C2—N1—C5 | 179.4 (4) | C10—C9—N4—C8 | 1.0 (7) |
C3—C2—N1—Cu1 | 176.9 (3) | C7—C8—N4—C9 | −1.3 (7) |
C1—C2—N1—Cu1 | −2.6 (4) | O2—C1—O1—Cu1 | 175.0 (4) |
C4—C5—N1—C2 | 2.6 (6) | C2—C1—O1—Cu1 | −6.0 (5) |
C4—C5—N1—Cu1 | −175.0 (3) | O3—Cu1—O1—C1 | −133.6 (16) |
O1—Cu1—N1—C2 | −0.4 (2) | O5—Cu1—O1—C1 | −87.4 (3) |
O3—Cu1—N1—C2 | 176.7 (3) | N3—Cu1—O1—C1 | −175.8 (3) |
O5—Cu1—N1—C2 | 89.1 (3) | N1—Cu1—O1—C1 | 3.8 (3) |
N2i—Cu1—N1—C2 | −94.4 (3) | N2i—Cu1—O1—C1 | 92.7 (3) |
O1—Cu1—N1—C5 | 177.3 (4) | O4—C6—O3—Cu1 | 177.0 (4) |
O3—Cu1—N1—C5 | −5.6 (4) | C7—C6—O3—Cu1 | −1.6 (4) |
O5—Cu1—N1—C5 | −93.2 (4) | O1—Cu1—O3—C6 | −38.5 (18) |
N2i—Cu1—N1—C5 | 83.3 (4) | O5—Cu1—O3—C6 | −84.9 (3) |
C2—C3—N2—C4 | 3.7 (6) | N3—Cu1—O3—C6 | 4.0 (3) |
C2—C3—N2—Cu1ii | −171.3 (3) | N1—Cu1—O3—C6 | −175.4 (3) |
C5—C4—N2—C3 | −2.2 (6) | N2i—Cu1—O3—C6 | 95.3 (3) |
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+1, y+1/2, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H2W···O3iii | 0.82 (5) | 1.86 (5) | 2.682 (4) | 177 (7) |
O5—H1W···O1iv | 0.82 (5) | 2.01 (4) | 2.757 (4) | 153 (7) |
Symmetry codes: (iii) x−1/2, −y+3/2, −z+1; (iv) x+1/2, −y+3/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C5H3N2O2)2(H2O)] |
Mr | 327.74 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 298 |
a, b, c (Å) | 7.7379 (5), 9.9021 (5), 15.002 (1) |
V (Å3) | 1149.48 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.93 |
Crystal size (mm) | 0.10 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6840, 2460, 2219 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.099, 1.01 |
No. of reflections | 2460 |
No. of parameters | 182 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.20, −0.36 |
Absolute structure | Flack (1983), with 1004 Friedel pairs |
Absolute structure parameter | 0.49 (2) |
Computer programs: SMART (Bruker, 2001) [Or APEX2?], SAINT-Plus (Bruker, 2001), SAINT-Plus, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001), SHELXTL.
Cu1—O1 | 2.015 (3) | Cu1—N3 | 2.089 (3) |
Cu1—O3 | 2.023 (3) | Cu1—N1 | 2.099 (3) |
Cu1—O5 | 2.073 (3) | Cu1—N2i | 2.137 (3) |
Symmetry code: (i) −x+1, y−1/2, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H2W···O3ii | 0.82 (5) | 1.86 (5) | 2.682 (4) | 177 (7) |
O5—H1W···O1iii | 0.82 (5) | 2.01 (4) | 2.757 (4) | 153 (7) |
Symmetry codes: (ii) x−1/2, −y+3/2, −z+1; (iii) x+1/2, −y+3/2, −z+1. |
The title compound, (I), is isostructural with its FeII, CoII, and NiII analogues [Hao & Liu, (2007); Hao, Mu & Liu, (2007); Gao et al. (2007)]. The CuII atom in (I) is coordinated in a bidentate fashion by two O and two N atoms from two independent pyrazine-2-carboxylate anions. The distorted octhedral coordiantion is completed by another N atom from a third pyrazine-2-carboxylate ligand, and by the O atom of a water molecule (Fig. 1, Table 1). One pyrazine-2-carboxylate ligand coordinates to a neighboring Cu atom via its second N atom, leading to a polymeic structure with zigzag chains extending parallel to the b axis (Fig. 2). Hydrogen bonding involving the water molecules (Table 2) stablizes the structure.