catena-Poly[4,4′-bipyridinium [bis­(μ₃-pyrazole-3,5-dicarboxyl­ato-κ⁵O⁵,N¹:N²,O³:O³)dicopper(II)]]

The title compound, {(C₁₀H₁₀N₂)[Cu₂(C₅HN₂O₄)₂]}_n, has been synthesized under hydro­thermal conditions. The self-assembly of the pyrazole-3,5-dicarboxyl­ate ligands and Cu^II atoms results in a one-dimensional anionic chain, in which the Cu^II atom is five-coordinate in a square-pyramidal geometry. The doubly protonated 4,4′-bipyridine (bpy) cation lies on an inversion center. A two-dimensional supra­molecular network is formed through N—H...O hydrogen bonds between the bpy cations and the uncoordinated carboxyl­ate O atoms of the polymeric anions. The dinuclear repeat unit with two bridging pyrazole rings is centrosymmetric.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.025
• wR factor = 0.071
• Data-to-parameter ratio = 13.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       2.00 Ratio
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.92
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.40

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.924
            Tmax scaled      0.511 Tmin scaled      0.384
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)       2.21

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   4 ALERT level G = General alerts; check

   5 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
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

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 Cu^II ion.

The asymmetric unit of the title compound contains one Cu^II atom, one pydc ligand and a half protonated bpy ligand. Two centrosymmetric Cu^II 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 Cu^II 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).

Related literature

For related literature, see: Chaudhuri (2003); Han et al. (2007); Koomen-Van Oudenniel et al. (1989); La Monica & Ardizzoia (1997); Sears & Wong (1999); Tanase et al. (2005); Thompson (2002).

S2. Experimental

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%.

S3. Refinement

H atoms were positioned geometrically and refined as riding, with C—H = 0.93 Å, N—H = 0.86 Å and U_iso(H) = 1.2U_eq(C,N).

Computing details

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).

Figures

	Fig. 1. One-dimensional chain structure in the title compound. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) -x, 2 - y, 1 - z; (ii) x, y - 1, z; (iii) -x, 1 - y, 1 - z.]
	Fig. 2. Three-dimensional network of the title compound, showing the hydrogen-bonding interactions (dotted lines).

catena-Poly[4,4'-bipyridinium [bis(µ₃-pyrazole-3,5-dicarboxylato- κ⁵O⁵,N¹:N²,O³:O³)dicopper(II)]]

Crystal data

(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) Å^3	0.46 × 0.35 × 0.29 mm
Z = 2

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.025	H-atom parameters constrained
wR(F^2) = 0.071	w = 1/[σ^2(Fo^2) + (0.0338P)^2 + 0.6043P] where P = (Fo^2 + 2Fc^2)/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+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0249 (13)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

Cu1—N1	1.9021 (16)	C6—N3	1.333 (3)
Cu1—N2^i	1.9099 (15)	C6—C7	1.378 (3)
Cu1—O1	1.9647 (13)	C6—H6A	0.9300
Cu1—O3^i	1.9889 (13)	C7—C8	1.397 (3)
Cu1—O3^ii	2.7543 (15)	C7—H7A	0.9300
C1—O2	1.224 (2)	C8—C9	1.395 (3)
C1—O1	1.303 (2)	C8—C8^iii	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—Cu1^i	1.9099 (15)
C4—C5	1.490 (2)	N3—H3B	0.8600
C5—O4	1.235 (2)	O3—Cu1^i	1.9889 (13)
C5—O3	1.300 (2)
N1—Cu1—N2^i	93.64 (7)	N3—C6—H6A	120.3
N1—Cu1—O1	81.29 (6)	C7—C6—H6A	120.3
N2^i—Cu1—O1	172.70 (6)	C6—C7—C8	120.20 (19)
N1—Cu1—O3^i	173.89 (6)	C6—C7—H7A	119.9
N2^i—Cu1—O3^i	80.46 (6)	C8—C7—H7A	119.9
O1—Cu1—O3^i	104.43 (6)	C9—C8—C7	117.83 (16)
N1—Cu1—O3^ii	92.88 (6)	C9—C8—C8^iii	120.9 (2)
N2^i—Cu1—O3^ii	102.51 (6)	C7—C8—C8^iii	121.3 (2)
O1—Cu1—O3^ii	83.08 (5)	C10—C9—C8	119.79 (19)
O3^i—Cu1—O3^ii	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—Cu1^i	132.90 (12)
N2—C4—C3	109.06 (16)	C4—N2—Cu1^i	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—Cu1^i	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)	O3^ii—Cu1—N1—N2	−99.92 (19)
O2—C1—C2—C3	1.8 (4)	N2^i—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)	O3^ii—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—Cu1^i	−179.60 (15)
N2—C4—C5—O4	176.42 (18)	Cu1—N1—N2—Cu1^i	−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—Cu1^i	179.69 (13)
N3—C6—C7—C8	1.8 (3)	C5—C4—N2—Cu1^i	−0.6 (2)
C6—C7—C8—C9	−2.5 (3)	C9—C10—N3—C6	−1.5 (3)
C6—C7—C8—C8^iii	176.7 (2)	C7—C6—N3—C10	0.3 (3)
C7—C8—C9—C10	1.2 (3)	O2—C1—O1—Cu1	175.90 (16)
C8^iii—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)	O3^i—Cu1—O1—C1	−175.75 (13)
C1—C2—N1—N2	−177.25 (16)	O3^ii—Cu1—O1—C1	−87.58 (13)
C3—C2—N1—Cu1	−176.01 (12)	O4—C5—O3—Cu1^i	−174.44 (14)
C1—C2—N1—Cu1	6.2 (2)	C4—C5—O3—Cu1^i	4.7 (2)
N2^i—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.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···O4	0.86	1.90	2.719 (2)	160