Tetra-aqua-bis(1,10-phenanthroline)bis-[μ(2)-1H-pyrazole-3,5-dicarboxyl-ato(3-)]tricopper(II) dihydrate.

The title compound, [Cu(3)(C(5)HN(2)O(4))(2)(C(12)H(8)N(2))(2)(H(2)O)(4)]·2H(2)O, is a trinuclear copper(II) complex in which two centrosymmetrically related pyrazole-3,5-dicarboxyl-ate(3-) and 1,10-phenanthroline ligands bind three Cu(II) atoms, with one Cu(II) atom located on a center of symmetry. In each complex, there are four coordinated water mol-ecules and two solvent water mol-ecules, which participate in extensive hydrogen-bond patterns. These inter-actions, as well as π-π inter-actions between neighbouring 1,10-phenanthroline ligands [shortest atom-to-atom distance = 3.363 (3) Å], extend the crystal structure into a three-dimensional supra-molecular network.

Related literature

For the potential applications of novel coordination architectures as new classes of materials, see: Kitagawa et al. (2004 ▶). The potential coordination sites of 3,5-pyrazoledicarboxylate are highly accessible to metal ions, see: Li (2005 ▶). However, divalent copper ions have rarely been coordinated with 3,5-pyrazoledicarboxylic acid at ambient temperature, see: King et al. (2003 ▶).

Experimental

Crystal data

[Cu3(C5HN2O4)2(C12H8N2)2(H2O)4]·2H2O

M = 965.28

Triclinic,

a = 7.7326 (8) Å

b = 9.3332 (9) Å

c = 12.6848 (12) Å

α = 100.204 (2)°

β = 98.376 (2)°

γ = 103.641 (2)°

V = 858.59 (15) Å3

Z = 1

Mo Kα radiation

μ = 1.93 mm−1

T = 187 K

0.07 × 0.07 × 0.03 mm

Data collection

Bruker APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T min = 0.872, T max = 0.937

4550 measured reflections

3151 independent reflections

2361 reflections with I > 2σ(I)

R int = 0.039

Refinement

R[F 2 > 2σ(F 2)] = 0.071

wR(F 2) = 0.155

S = 1.10

3151 reflections

274 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.87 e Å−3

Δρmin = −0.58 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810012833/ez2198sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810012833/ez2198Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cu3(C5HN2O4)2(C12H8N2)2(H2O)4]·2H2O	Z = 1
Mr = 965.28	F(000) = 489
Triclinic, P1	Dx = 1.867 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7326 (8) Å	Cell parameters from 737 reflections
b = 9.3332 (9) Å	θ = 2.3–22.4°
c = 12.6848 (12) Å	µ = 1.93 mm−1
α = 100.204 (2)°	T = 187 K
β = 98.376 (2)°	Block, blue
γ = 103.641 (2)°	0.07 × 0.07 × 0.03 mm
V = 858.59 (15) Å3

Bruker APEX CCD area-detector diffractometer	3151 independent reflections
Radiation source: fine-focus sealed tube	2361 reflections with I > 2σ(I)
graphite	Rint = 0.039
φ and ω scans	θmax = 25.5°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −8→9
Tmin = 0.872, Tmax = 0.937	k = −11→9
4550 measured reflections	l = −9→15

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)] = 0.071	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.155	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ2(Fo2) + (0.0597P)2 + 0.8906P] where P = (Fo2 + 2Fc2)/3
3151 reflections	(Δ/σ)max = 0.027
274 parameters	Δρmax = 0.87 e Å−3
2 restraints	Δρmin = −0.58 e Å−3

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	0.5000	0.5000	0.5000	0.0217 (3)
Cu2	0.31791 (11)	0.03642 (9)	0.30349 (7)	0.0197 (3)
N1	0.5830 (7)	0.3127 (5)	0.4748 (4)	0.0162 (12)
N2	0.5312 (7)	0.1718 (6)	0.4112 (4)	0.0185 (12)
N3	0.3647 (7)	0.1167 (6)	0.1569 (4)	0.0200 (13)
N4	0.1358 (7)	−0.1271 (6)	0.1893 (5)	0.0223 (13)
O1	0.7315 (6)	0.5766 (5)	0.6067 (4)	0.0232 (11)
O2	0.9943 (6)	0.5210 (5)	0.6534 (4)	0.0256 (12)
O3	0.4855 (6)	−0.1054 (5)	0.3024 (4)	0.0190 (11)
O4	0.7632 (6)	−0.1122 (5)	0.3758 (4)	0.0228 (11)
O5	0.3188 (6)	0.4290 (5)	0.6487 (4)	0.0301 (12)
H5A	0.2105	0.4377	0.6272	0.036*
H5B	0.2736	0.3280	0.6305	0.036*
O6	0.1384 (8)	0.1048 (7)	0.3818 (5)	0.0413 (15)
H6A	0.025 (5)	0.049 (8)	0.365 (7)	0.050*
H6B	0.175 (11)	0.116 (10)	0.453 (2)	0.050*
O7	0.3725 (8)	0.5886 (6)	0.1884 (5)	0.0453 (16)
H7A	0.4402	0.5425	0.2201	0.054*
H7B	0.4142	0.6789	0.2299	0.054*
C1	0.8372 (9)	0.4887 (7)	0.6033 (5)	0.0168 (14)
C2	0.7527 (9)	0.3356 (7)	0.5299 (5)	0.0165 (14)
C3	0.8129 (8)	0.2092 (7)	0.5029 (5)	0.0159 (14)
H3	0.9272	0.1942	0.5296	0.019*
C4	0.6679 (8)	0.1085 (7)	0.4275 (5)	0.0147 (14)
C5	0.6392 (9)	−0.0491 (7)	0.3650 (5)	0.0144 (14)
C6	0.4736 (10)	0.2407 (8)	0.1428 (7)	0.0294 (18)
H6	0.5417	0.3154	0.2054	0.035*
C7	0.4934 (11)	0.2670 (8)	0.0375 (7)	0.0342 (19)
H7	0.5729	0.3576	0.0299	0.041*
C8	0.3963 (10)	0.1598 (9)	−0.0520 (6)	0.0305 (18)
H8	0.4087	0.1752	−0.1228	0.037*
C9	0.2791 (10)	0.0281 (8)	−0.0407 (6)	0.0253 (17)
C10	0.1717 (10)	−0.0923 (9)	−0.1297 (6)	0.0296 (18)
H10	0.1831	−0.0840	−0.2021	0.036*
C11	0.0548 (10)	−0.2173 (8)	−0.1152 (6)	0.0277 (18)
H11	−0.0148	−0.2939	−0.1763	0.033*
C12	0.0373 (9)	−0.2327 (8)	−0.0056 (6)	0.0223 (16)
C13	−0.0827 (10)	−0.3571 (8)	0.0162 (7)	0.0303 (19)
H13	−0.1585	−0.4353	−0.0420	0.036*
C14	−0.0892 (10)	−0.3643 (8)	0.1231 (6)	0.0309 (18)
H14	−0.1693	−0.4481	0.1393	0.037*
C15	0.0211 (9)	−0.2496 (8)	0.2065 (6)	0.0247 (16)
H15	0.0158	−0.2573	0.2797	0.030*
C16	0.1457 (9)	−0.1181 (8)	0.0838 (6)	0.0221 (16)
C17	0.2664 (9)	0.0116 (8)	0.0656 (6)	0.0217 (16)

	U11	U22	U33	U12	U13	U23
Cu1	0.0237 (7)	0.0135 (6)	0.0264 (8)	0.0099 (5)	−0.0023 (5)	−0.0002 (5)
Cu2	0.0173 (5)	0.0231 (5)	0.0140 (5)	0.0037 (3)	0.0001 (3)	−0.0038 (4)
N1	0.019 (3)	0.007 (3)	0.016 (3)	−0.002 (2)	−0.003 (2)	−0.002 (2)
N2	0.019 (3)	0.020 (3)	0.018 (3)	0.008 (2)	0.002 (2)	0.005 (2)
N3	0.025 (3)	0.020 (3)	0.018 (3)	0.012 (2)	0.004 (2)	0.004 (2)
N4	0.019 (3)	0.025 (3)	0.019 (3)	0.006 (2)	0.002 (2)	−0.003 (3)
O1	0.024 (3)	0.016 (2)	0.028 (3)	0.010 (2)	−0.001 (2)	0.000 (2)
O2	0.023 (3)	0.021 (3)	0.029 (3)	0.009 (2)	−0.003 (2)	−0.001 (2)
O3	0.019 (2)	0.013 (2)	0.022 (3)	0.0055 (19)	−0.002 (2)	0.000 (2)
O4	0.023 (3)	0.021 (2)	0.023 (3)	0.009 (2)	0.003 (2)	0.000 (2)
O5	0.025 (3)	0.022 (3)	0.042 (3)	0.006 (2)	0.004 (2)	0.006 (2)
O6	0.032 (3)	0.047 (4)	0.040 (4)	0.006 (3)	0.004 (3)	0.006 (3)
O7	0.056 (4)	0.027 (3)	0.040 (4)	0.011 (3)	−0.016 (3)	−0.004 (3)
C1	0.020 (4)	0.018 (3)	0.009 (3)	0.004 (3)	−0.002 (3)	0.003 (3)
C2	0.025 (4)	0.010 (3)	0.012 (4)	0.002 (3)	0.003 (3)	0.001 (3)
C3	0.015 (3)	0.017 (3)	0.018 (4)	0.007 (3)	0.001 (3)	0.006 (3)
C4	0.021 (3)	0.015 (3)	0.013 (4)	0.009 (3)	0.010 (3)	0.005 (3)
C5	0.021 (4)	0.012 (3)	0.011 (3)	0.004 (3)	0.004 (3)	0.003 (3)
C6	0.031 (4)	0.023 (4)	0.032 (5)	0.009 (3)	0.003 (3)	0.001 (3)
C7	0.039 (5)	0.023 (4)	0.044 (5)	0.008 (3)	0.011 (4)	0.013 (4)
C8	0.028 (4)	0.046 (5)	0.026 (4)	0.018 (4)	0.013 (3)	0.015 (4)
C9	0.027 (4)	0.034 (4)	0.017 (4)	0.018 (3)	0.005 (3)	0.001 (3)
C10	0.034 (4)	0.049 (5)	0.012 (4)	0.024 (4)	0.005 (3)	0.004 (3)
C11	0.031 (4)	0.025 (4)	0.021 (4)	0.011 (3)	−0.004 (3)	−0.007 (3)
C12	0.025 (4)	0.026 (4)	0.015 (4)	0.016 (3)	−0.002 (3)	−0.005 (3)
C13	0.029 (4)	0.016 (4)	0.038 (5)	0.004 (3)	−0.002 (3)	−0.007 (3)
C14	0.027 (4)	0.028 (4)	0.029 (5)	−0.003 (3)	0.000 (3)	0.003 (3)
C15	0.023 (4)	0.023 (4)	0.027 (4)	0.006 (3)	0.005 (3)	0.003 (3)
C16	0.018 (4)	0.027 (4)	0.021 (4)	0.009 (3)	0.003 (3)	−0.002 (3)
C17	0.024 (4)	0.025 (4)	0.020 (4)	0.015 (3)	0.006 (3)	0.003 (3)

Cu1—O1	1.974 (5)	C1—C2	1.499 (8)
Cu1—O1i	1.974 (5)	C2—C3	1.374 (8)
Cu1—N1i	1.990 (5)	C3—C4	1.388 (8)
Cu1—N1	1.990 (5)	C3—H3	0.9500
Cu2—N2	1.983 (5)	C4—C5	1.491 (8)
Cu2—O6	1.979 (6)	C6—C7	1.423 (10)
Cu2—N4	2.005 (5)	C6—H6	0.9500
Cu2—O3	2.059 (4)	C7—C8	1.359 (10)
Cu2—N3	2.171 (6)	C7—H7	0.9500
N1—C2	1.343 (8)	C8—C9	1.388 (10)
N1—N2	1.350 (7)	C8—H8	0.9500
N2—C4	1.335 (8)	C9—C17	1.399 (9)
N3—C6	1.318 (9)	C9—C10	1.436 (10)
N3—C17	1.368 (8)	C10—C11	1.357 (10)
N4—C15	1.344 (9)	C10—H10	0.9500
N4—C16	1.368 (8)	C11—C12	1.445 (10)
O1—C1	1.287 (8)	C11—H11	0.9500
O2—C1	1.227 (7)	C12—C13	1.402 (10)
O3—C5	1.266 (7)	C12—C16	1.415 (9)
O4—C5	1.242 (7)	C13—C14	1.377 (10)
O5—H5A	0.8692	C13—H13	0.9500
O5—H5B	0.8987	C14—C15	1.378 (10)
O6—H6A	0.88 (2)	C14—H14	0.9500
O6—H6B	0.88 (2)	C15—H15	0.9500
O7—H7A	0.8526	C16—C17	1.421 (10)
O7—H7B	0.8695
O1—Cu1—O1i	180.000 (1)	C4—C3—H3	128.1
O1—Cu1—N1i	97.50 (19)	N2—C4—C3	110.0 (5)
O1i—Cu1—N1i	82.50 (19)	N2—C4—C5	117.1 (6)
O1—Cu1—N1	82.50 (19)	C3—C4—C5	132.9 (6)
O1i—Cu1—N1	97.50 (19)	O4—C5—O3	125.9 (6)
N1i—Cu1—N1	180.000 (1)	O4—C5—C4	119.6 (6)
N2—Cu2—O6	94.4 (2)	O3—C5—C4	114.5 (5)
N2—Cu2—N4	168.4 (2)	N3—C6—C7	122.6 (7)
O6—Cu2—N4	95.8 (2)	N3—C6—H6	118.7
N2—Cu2—O3	80.9 (2)	C7—C6—H6	118.7
O6—Cu2—O3	142.7 (2)	C8—C7—C6	118.6 (7)
N4—Cu2—O3	87.6 (2)	C8—C7—H7	120.7
N2—Cu2—N3	100.5 (2)	C6—C7—H7	120.7
O6—Cu2—N3	118.2 (2)	C7—C8—C9	120.6 (7)
N4—Cu2—N3	79.4 (2)	C7—C8—H8	119.7
O3—Cu2—N3	98.95 (19)	C9—C8—H8	119.7
C2—N1—N2	107.8 (5)	C8—C9—C17	117.2 (7)
C2—N1—Cu1	111.5 (4)	C8—C9—C10	125.0 (7)
N2—N1—Cu1	140.3 (4)	C17—C9—C10	117.9 (7)
C4—N2—N1	108.1 (5)	C11—C10—C9	123.0 (7)
C4—N2—Cu2	112.9 (4)	C11—C10—H10	118.5
N1—N2—Cu2	139.0 (4)	C9—C10—H10	118.5
C6—N3—C17	117.7 (6)	C10—C11—C12	119.3 (6)
C6—N3—Cu2	131.6 (5)	C10—C11—H11	120.4
C17—N3—Cu2	110.7 (4)	C12—C11—H11	120.4
C15—N4—C16	118.2 (6)	C13—C12—C16	118.4 (7)
C15—N4—Cu2	126.5 (5)	C13—C12—C11	122.7 (6)
C16—N4—Cu2	115.0 (4)	C16—C12—C11	118.9 (6)
C1—O1—Cu1	115.1 (4)	C14—C13—C12	119.1 (7)
C5—O3—Cu2	114.6 (4)	C14—C13—H13	120.5
H5A—O5—H5B	88.9	C12—C13—H13	120.5
Cu2—O6—H6A	119 (5)	C15—C14—C13	119.7 (7)
Cu2—O6—H6B	109 (6)	C15—C14—H14	120.1
H6A—O6—H6B	107 (8)	C13—C14—H14	120.1
H7A—O7—H7B	100.3	N4—C15—C14	123.2 (7)
O2—C1—O1	125.7 (6)	N4—C15—H15	118.4
O2—C1—C2	120.2 (6)	C14—C15—H15	118.4
O1—C1—C2	114.1 (5)	N4—C16—C12	121.5 (6)
N1—C2—C3	110.3 (5)	N4—C16—C17	118.2 (6)
N1—C2—C1	115.9 (5)	C12—C16—C17	120.3 (7)
C3—C2—C1	133.8 (6)	N3—C17—C9	123.3 (6)
C2—C3—C4	103.9 (5)	N3—C17—C16	116.1 (6)
C2—C3—H3	128.1	C9—C17—C16	120.5 (6)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O2ii	0.87	2.05	2.842 (7)	152
O5—H5B···O4iii	0.90	1.95	2.824 (7)	163
O6—H6A···O4ii	0.88 (5)	2.26 (6)	3.104 (8)	161 (7)
O6—H6B···O4iii	0.89 (3)	2.16 (3)	3.042 (8)	172 (10)
O7—H7A···O5i	0.85	2.24	2.977 (8)	145
O7—H7B···O3iv	0.87	1.97	2.829 (7)	170

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5A⋯O2i	0.87	2.05	2.842 (7)	152
O5—H5B⋯O4ii	0.90	1.95	2.824 (7)	163
O6—H6A⋯O4i	0.88 (5)	2.26 (6)	3.104 (8)	161 (7)
O6—H6B⋯O4ii	0.89 (3)	2.16 (3)	3.042 (8)	172 (10)
O7—H7A⋯O5iii	0.85	2.24	2.977 (8)	145
O7—H7B⋯O3iv	0.87	1.97	2.829 (7)	170

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .