

Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807054864/hy2090sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536807054864/hy2090Isup2.hkl |
CCDC reference: 604089
A mixture of Cu(NO3)2.3H2O(0.120 g, 0.5 mmol), pyrazole-3,5-dicarboxylic acid (0.087 g, 0.5 mmol), 4,4'-bipyridine (0.122 g, 0.5 mmol), NaOH (0.04 g, 1 mmol) and water (10 ml) was sealed in a 23 ml Teflon-lined reactor and heated at 473 K for 6 d. After cooled to room temperature at a rate of 5 K h-1, black crystals of the title compound were obtained (yield 52%). Analysis calculated for C20H12Cu2N6O8: C 40.60, H 2.00, N 14.25%; found: C 40.62, H 2.05, N 14.21%.
H atoms were positioned geometrically and refined as riding, with C—H = 0.93 Å, N—H = 0.86 Å and Uiso(H) = 1.2Ueq(C,N).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (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).
(C10H10N2)[Cu2(C5HN2O4)2] | F(000) = 592 |
Mr = 591.44 | Dx = 2.070 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2356 reflections |
a = 8.1582 (18) Å | θ = 2.3–25.0° |
b = 6.3620 (12) Å | µ = 2.31 mm−1 |
c = 18.679 (3) Å | T = 293 K |
β = 101.862 (15)° | Block, black |
V = 948.8 (3) Å3 | 0.46 × 0.35 × 0.29 mm |
Z = 2 |
Bruker SMART APEX CCD area-detector diffractometer | 2187 independent reflections |
Radiation source: fine-focus sealed tube | 2032 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
ϕ and ω scan | θmax = 27.5°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→1 |
Tmin = 0.416, Tmax = 0.554 | k = −8→1 |
3105 measured reflections | l = −24→24 |
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)] = 0.025 | H-atom parameters constrained |
wR(F2) = 0.071 | w = 1/[σ2(Fo2) + (0.0338P)2 + 0.6043P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
2187 reflections | Δρmax = 0.38 e Å−3 |
164 parameters | Δρmin = −0.36 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0249 (13) |
(C10H10N2)[Cu2(C5HN2O4)2] | V = 948.8 (3) Å3 |
Mr = 591.44 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.1582 (18) Å | µ = 2.31 mm−1 |
b = 6.3620 (12) Å | T = 293 K |
c = 18.679 (3) Å | 0.46 × 0.35 × 0.29 mm |
β = 101.862 (15)° |
Bruker SMART APEX CCD area-detector diffractometer | 2187 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2032 reflections with I > 2σ(I) |
Tmin = 0.416, Tmax = 0.554 | Rint = 0.018 |
3105 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.071 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.38 e Å−3 |
2187 reflections | Δρmin = −0.36 e Å−3 |
164 parameters |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.11209 (3) | 0.72576 (4) | 0.501800 (11) | 0.02128 (11) | |
C1 | 0.3356 (2) | 0.7260 (3) | 0.63644 (10) | 0.0214 (4) | |
C2 | 0.2373 (2) | 0.9262 (3) | 0.63423 (9) | 0.0197 (3) | |
C3 | 0.2260 (2) | 1.1011 (3) | 0.67817 (9) | 0.0216 (4) | |
H3A | 0.2843 | 1.1266 | 0.7256 | 0.026* | |
C4 | 0.1067 (2) | 1.2288 (3) | 0.63437 (10) | 0.0201 (3) | |
C5 | 0.0225 (2) | 1.4354 (3) | 0.63753 (9) | 0.0207 (3) | |
C6 | 0.3833 (3) | 1.7140 (3) | 0.85036 (11) | 0.0309 (4) | |
H6A | 0.4011 | 1.8292 | 0.8223 | 0.037* | |
C7 | 0.4729 (3) | 1.6925 (3) | 0.92106 (11) | 0.0267 (4) | |
H7A | 0.5494 | 1.7956 | 0.9413 | 0.032* | |
C8 | 0.4491 (2) | 1.5165 (3) | 0.96242 (9) | 0.0202 (3) | |
C9 | 0.3284 (2) | 1.3702 (3) | 0.93080 (10) | 0.0271 (4) | |
H9A | 0.3078 | 1.2525 | 0.9571 | 0.033* | |
C10 | 0.2399 (3) | 1.4006 (4) | 0.86062 (10) | 0.0303 (4) | |
H10A | 0.1584 | 1.3043 | 0.8396 | 0.036* | |
N1 | 0.1315 (2) | 0.9517 (2) | 0.56971 (8) | 0.0244 (3) | |
N2 | 0.0535 (2) | 1.1346 (2) | 0.56948 (8) | 0.0248 (3) | |
N3 | 0.2707 (2) | 1.5681 (3) | 0.82268 (8) | 0.0301 (4) | |
H3B | 0.2158 | 1.5826 | 0.7785 | 0.036* | |
O1 | 0.29805 (16) | 0.6162 (2) | 0.57641 (7) | 0.0238 (3) | |
O2 | 0.44127 (18) | 0.6763 (3) | 0.69028 (8) | 0.0318 (3) | |
O3 | −0.07916 (17) | 1.4892 (2) | 0.57719 (7) | 0.0255 (3) | |
O4 | 0.04633 (18) | 1.5447 (2) | 0.69333 (7) | 0.0278 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.02635 (15) | 0.01578 (14) | 0.01696 (14) | 0.00340 (8) | −0.00663 (9) | −0.00196 (7) |
C1 | 0.0207 (8) | 0.0222 (9) | 0.0194 (8) | 0.0004 (7) | 0.0000 (7) | 0.0038 (7) |
C2 | 0.0210 (8) | 0.0208 (8) | 0.0147 (7) | −0.0008 (7) | −0.0027 (6) | 0.0023 (6) |
C3 | 0.0230 (8) | 0.0251 (9) | 0.0144 (7) | 0.0003 (7) | −0.0018 (6) | 0.0003 (7) |
C4 | 0.0233 (8) | 0.0193 (8) | 0.0155 (8) | −0.0017 (7) | −0.0009 (7) | −0.0013 (6) |
C5 | 0.0225 (8) | 0.0202 (8) | 0.0179 (7) | −0.0012 (7) | 0.0006 (6) | −0.0021 (7) |
C6 | 0.0363 (11) | 0.0330 (11) | 0.0225 (9) | 0.0010 (9) | 0.0040 (8) | 0.0058 (8) |
C7 | 0.0286 (9) | 0.0272 (10) | 0.0227 (9) | −0.0055 (8) | 0.0013 (7) | 0.0019 (8) |
C8 | 0.0197 (8) | 0.0250 (9) | 0.0157 (8) | −0.0004 (7) | 0.0029 (6) | −0.0009 (7) |
C9 | 0.0274 (9) | 0.0317 (10) | 0.0207 (8) | −0.0073 (8) | 0.0012 (7) | 0.0009 (8) |
C10 | 0.0287 (9) | 0.0371 (11) | 0.0225 (8) | −0.0053 (8) | −0.0010 (7) | −0.0052 (8) |
N1 | 0.0309 (8) | 0.0176 (7) | 0.0194 (7) | 0.0046 (6) | −0.0072 (6) | −0.0014 (6) |
N2 | 0.0324 (8) | 0.0170 (7) | 0.0194 (7) | 0.0051 (6) | −0.0079 (6) | −0.0018 (6) |
N3 | 0.0312 (8) | 0.0412 (10) | 0.0150 (7) | 0.0046 (8) | −0.0020 (6) | 0.0002 (7) |
O1 | 0.0253 (6) | 0.0223 (7) | 0.0205 (6) | 0.0054 (5) | −0.0029 (5) | −0.0010 (5) |
O2 | 0.0312 (7) | 0.0358 (8) | 0.0227 (6) | 0.0097 (6) | −0.0075 (6) | 0.0022 (6) |
O3 | 0.0297 (7) | 0.0214 (6) | 0.0206 (6) | 0.0056 (5) | −0.0062 (5) | −0.0051 (5) |
O4 | 0.0327 (7) | 0.0286 (7) | 0.0189 (6) | 0.0043 (6) | −0.0020 (5) | −0.0061 (5) |
Cu1—N1 | 1.9021 (16) | C6—N3 | 1.333 (3) |
Cu1—N2i | 1.9099 (15) | C6—C7 | 1.378 (3) |
Cu1—O1 | 1.9647 (13) | C6—H6A | 0.9300 |
Cu1—O3i | 1.9889 (13) | C7—C8 | 1.397 (3) |
Cu1—O3ii | 2.7543 (15) | C7—H7A | 0.9300 |
C1—O2 | 1.224 (2) | C8—C9 | 1.395 (3) |
C1—O1 | 1.303 (2) | C8—C8iii | 1.492 (3) |
C1—C2 | 1.501 (3) | C9—C10 | 1.374 (3) |
C2—N1 | 1.340 (2) | C9—H9A | 0.9300 |
C2—C3 | 1.397 (3) | C10—N3 | 1.332 (3) |
C3—C4 | 1.396 (3) | C10—H10A | 0.9300 |
C3—H3A | 0.9300 | N1—N2 | 1.326 (2) |
C4—N2 | 1.342 (2) | N2—Cu1i | 1.9099 (15) |
C4—C5 | 1.490 (2) | N3—H3B | 0.8600 |
C5—O4 | 1.235 (2) | O3—Cu1i | 1.9889 (13) |
C5—O3 | 1.300 (2) | ||
N1—Cu1—N2i | 93.64 (7) | N3—C6—H6A | 120.3 |
N1—Cu1—O1 | 81.29 (6) | C7—C6—H6A | 120.3 |
N2i—Cu1—O1 | 172.70 (6) | C6—C7—C8 | 120.20 (19) |
N1—Cu1—O3i | 173.89 (6) | C6—C7—H7A | 119.9 |
N2i—Cu1—O3i | 80.46 (6) | C8—C7—H7A | 119.9 |
O1—Cu1—O3i | 104.43 (6) | C9—C8—C7 | 117.83 (16) |
N1—Cu1—O3ii | 92.88 (6) | C9—C8—C8iii | 120.9 (2) |
N2i—Cu1—O3ii | 102.51 (6) | C7—C8—C8iii | 121.3 (2) |
O1—Cu1—O3ii | 83.08 (5) | C10—C9—C8 | 119.79 (19) |
O3i—Cu1—O3ii | 89.96 (5) | C10—C9—H9A | 120.1 |
O2—C1—O1 | 124.77 (18) | C8—C9—H9A | 120.1 |
O2—C1—C2 | 121.57 (17) | N3—C10—C9 | 120.04 (19) |
O1—C1—C2 | 113.66 (15) | N3—C10—H10A | 120.0 |
N1—C2—C3 | 108.88 (16) | C9—C10—H10A | 120.0 |
N1—C2—C1 | 111.66 (16) | N2—N1—C2 | 109.22 (15) |
C3—C2—C1 | 139.41 (16) | N2—N1—Cu1 | 133.39 (12) |
C4—C3—C2 | 103.99 (15) | C2—N1—Cu1 | 117.27 (13) |
C4—C3—H3A | 128.0 | N1—N2—C4 | 108.85 (15) |
C2—C3—H3A | 128.0 | N1—N2—Cu1i | 132.90 (12) |
N2—C4—C3 | 109.06 (16) | C4—N2—Cu1i | 118.24 (13) |
N2—C4—C5 | 111.32 (16) | C10—N3—C6 | 122.76 (17) |
C3—C4—C5 | 139.62 (17) | C10—N3—H3B | 118.6 |
O4—C5—O3 | 123.05 (17) | C6—N3—H3B | 118.6 |
O4—C5—C4 | 122.45 (16) | C1—O1—Cu1 | 115.54 (12) |
O3—C5—C4 | 114.50 (15) | C5—O3—Cu1i | 115.29 (12) |
N3—C6—C7 | 119.33 (19) | ||
O2—C1—C2—N1 | 178.59 (18) | O1—Cu1—N1—N2 | 177.5 (2) |
O1—C1—C2—N1 | −0.8 (2) | O3ii—Cu1—N1—N2 | −99.92 (19) |
O2—C1—C2—C3 | 1.8 (4) | N2i—Cu1—N1—C2 | 178.31 (15) |
O1—C1—C2—C3 | −177.5 (2) | O1—Cu1—N1—C2 | −6.97 (14) |
N1—C2—C3—C4 | −0.1 (2) | O3ii—Cu1—N1—C2 | 75.58 (15) |
C1—C2—C3—C4 | 176.7 (2) | C2—N1—N2—C4 | −0.7 (2) |
C2—C3—C4—N2 | −0.3 (2) | Cu1—N1—N2—C4 | 175.05 (15) |
C2—C3—C4—C5 | −179.8 (2) | C2—N1—N2—Cu1i | −179.60 (15) |
N2—C4—C5—O4 | 176.42 (18) | Cu1—N1—N2—Cu1i | −3.8 (3) |
C3—C4—C5—O4 | −4.0 (4) | C3—C4—N2—N1 | 0.6 (2) |
N2—C4—C5—O3 | −2.8 (2) | C5—C4—N2—N1 | −179.69 (16) |
C3—C4—C5—O3 | 176.8 (2) | C3—C4—N2—Cu1i | 179.69 (13) |
N3—C6—C7—C8 | 1.8 (3) | C5—C4—N2—Cu1i | −0.6 (2) |
C6—C7—C8—C9 | −2.5 (3) | C9—C10—N3—C6 | −1.5 (3) |
C6—C7—C8—C8iii | 176.7 (2) | C7—C6—N3—C10 | 0.3 (3) |
C7—C8—C9—C10 | 1.2 (3) | O2—C1—O1—Cu1 | 175.90 (16) |
C8iii—C8—C9—C10 | −178.0 (2) | C2—C1—O1—Cu1 | −4.8 (2) |
C8—C9—C10—N3 | 0.8 (3) | N1—Cu1—O1—C1 | 6.42 (14) |
C3—C2—N1—N2 | 0.5 (2) | O3i—Cu1—O1—C1 | −175.75 (13) |
C1—C2—N1—N2 | −177.25 (16) | O3ii—Cu1—O1—C1 | −87.58 (13) |
C3—C2—N1—Cu1 | −176.01 (12) | O4—C5—O3—Cu1i | −174.44 (14) |
C1—C2—N1—Cu1 | 6.2 (2) | C4—C5—O3—Cu1i | 4.7 (2) |
N2i—Cu1—N1—N2 | 2.8 (2) |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) x, y−1, z; (iii) −x+1, −y+3, −z+2. |
Experimental details
Crystal data | |
Chemical formula | (C10H10N2)[Cu2(C5HN2O4)2] |
Mr | 591.44 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 8.1582 (18), 6.3620 (12), 18.679 (3) |
β (°) | 101.862 (15) |
V (Å3) | 948.8 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.31 |
Crystal size (mm) | 0.46 × 0.35 × 0.29 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.416, 0.554 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3105, 2187, 2032 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.071, 1.05 |
No. of reflections | 2187 |
No. of parameters | 164 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.38, −0.36 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001).
Cu1—N1 | 1.9021 (16) | Cu1—O3i | 1.9889 (13) |
Cu1—N2i | 1.9099 (15) | Cu1—O3ii | 2.7543 (15) |
Cu1—O1 | 1.9647 (13) | ||
N1—Cu1—N2i | 93.64 (7) | O1—Cu1—O3i | 104.43 (6) |
N1—Cu1—O1 | 81.29 (6) | N1—Cu1—O3ii | 92.88 (6) |
N2i—Cu1—O1 | 172.70 (6) | N2i—Cu1—O3ii | 102.51 (6) |
N1—Cu1—O3i | 173.89 (6) | O1—Cu1—O3ii | 83.08 (5) |
N2i—Cu1—O3i | 80.46 (6) | O3i—Cu1—O3ii | 89.96 (5) |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) x, y−1, z. |
Coordination chemistry of copper(II) complexes is a subject of continuing importance in connection with the structures and their magnetic properties (Tanase et al., 2005). Particular interest has been directed towards the investigation of the copper(II) complexes, which have been intensively studied as a result of the efforts to understand the factors that are responsible for the magnetic-exchange interactions between uncoupled metal centers (Sears & Wong, 1999; Thompson, 2002; Chaudhuri, 2003; La Monica & Ardizzoia, 1997). We report here the synthesis and structure of a coordination polymer assembled by pyrazole-3,5-dicarboxylic acid (H3pydc), 4,4'-bipyridine (bpy) and CuII ion.
The asymmetric unit of the title compound contains one CuII atom, one pydc ligand and a half protonated bpy ligand. Two centrosymmetric CuII atoms are bridged by a pair of anionic pydc ligands, forming a binuclear unit. The binuclear units are further connected by O3 atoms of adjacent units to form a one-dimensional zigzag chain (Han et al., 2007). Each CuII atom is five-coordinated by three O atoms and two N atoms from three individual pydc ligands in a square-pyramidal coordination geometry (Fig. 1; Table 1). One intriguing feature of the structure is that there exist two bimetallic rings. One is a six-membered Cu2N4 ring with a Cu···Cu separation of 3.934 (3) Å. The other is a four-membered Cu2O2 ring with a Cu···Cu separation of 3.399 (3) Å. This short Cu···Cu separation is very similar to the distance observed in a structurally related copper complex recently reported (Koomen-Van Oudenniel et al., 1989). Another interesting feature is that the zigzag chains are further extended into a three-dimensional supramolecular network (Fig. 2) though N—H···O hydrogen bonds between the carboxylate O atoms of the anionic [Cu2(pydc)2] units and the protonated bpy molecules (Table 2).