cyclo-Tetra-kis(μ-3-acetyl-4-methyl-1H-pyrazole-5-carboxyl-ato-κN,O:N,O)tetra-kis[aqua-copper(II)] tetra-deca-hydrate.

The title compound, [Cu(4)(C(7)H(6)N(2)O(3))(4)(H(2)O)(4)]·14H(2)O, a tetra-nuclear [2 × 2] grid-type complex with S4 symmetry, contains four Cu(II) atoms which are bridged by four pyrazole-carboxyl-ate ligand anions and are additionally bonded to a water molecule. Each Cu(II) atom is coordinated by two O atoms of the carboxyl-ate and acetyl groups, two pyrazole N atoms of doubly deprotonated 3-acetyl-4-methyl-1H-pyrazole-5-carb-oxy-lic acid and one O atom of a water mol-ecule. The geometry at each Cu(II) atom is distorted square-pyramidal, with the two N and two O atoms in the equatorial plane and O atoms in the axial positions. O-H⋯O hydrogen-bonding interactions additionally stabilize the structure. One of the uncoordinated water molecules shows half-occupancy.

Related literature

For the use of pyrazolate ligands in the preparation of polynuclear supra­molecular compounds, see: Piguet et al. (1997 ▶); Krämer et al. (2002 ▶); Zhang et al. (1996 ▶); Van der Vlugt et al. (2008 ▶); Klingele et al. (2007 ▶); Kovbasyuk et al. (2004 ▶); Pons et al. (2003 ▶). For the use of asymmetric ligands in the preparation of heterometallic complexes, see: Moroz et al. (2010 ▶). For related structures, see: Mokhir et al. (2002 ▶); Sliva et al. (1997 ▶); Wörl et al. (2005a ▶,b ▶); Świątek-Kozłowska et al. (2000 ▶). For the preparation of related ligands, see: Sachse et al. (2008 ▶).

Experimental

Crystal data

[Cu4(C7H6N2O3)4(H2O)4]·14H2O

M = 1243.00

Tetragonal,

a = 13.8502 (7) Å

c = 26.280 (3) Å

V = 5041.1 (6) Å3

Z = 4

Mo Kα radiation

μ = 1.76 mm−1

T = 100 K

0.35 × 0.25 × 0.15 mm

Data collection

Bruker SMART APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.578, T max = 0.778

37816 measured reflections

3993 independent reflections

3254 reflections with I > 2σ(I)

R int = 0.037

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.097

S = 1.06

3993 reflections

165 parameters

H-atom parameters constrained

Δρmax = 1.20 e Å−3

Δρmin = −0.58 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2009 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811030832/jh2318sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811030832/jh2318Isup2.hkl

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

[Cu4(C7H6N2O3)4(H2O)4]·14H2O	Dx = 1.638 Mg m−3
Mr = 1243.00	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/a	Cell parameters from 9905 reflections
Hall symbol: -I 4ad	θ = 2.6–30.3°
a = 13.8502 (7) Å	µ = 1.76 mm−1
c = 26.280 (3) Å	T = 100 K
V = 5041.1 (6) Å3	Block, blue
Z = 4	0.35 × 0.25 × 0.15 mm
F(000) = 2560

Bruker SMART APEXII CCD diffractometer	3993 independent reflections
Radiation source: fine-focus sealed tube	3254 reflections with I > 2σ(I)
flat graphite crystal	Rint = 0.037
Detector resolution: 16 pixels mm-1	θmax = 30.9°, θmin = 1.7°
φ scans and ω scans	h = −19→19
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	k = −19→19
Tmin = 0.578, Tmax = 0.778	l = −37→38
37816 measured reflections

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0463P)2 + 11.3899P] where P = (Fo2 + 2Fc2)/3
3993 reflections	(Δ/σ)max < 0.001
165 parameters	Δρmax = 1.20 e Å−3
0 restraints	Δρmin = −0.58 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	Occ. (<1)
Cu1	0.164669 (16)	0.330841 (17)	0.089037 (8)	0.01628 (8)
O1	0.19490 (11)	0.47600 (11)	0.13584 (6)	0.0220 (3)
O2	0.18857 (10)	0.33808 (11)	0.01594 (5)	0.0191 (3)
O3	0.11824 (11)	0.36118 (11)	−0.05924 (5)	0.0207 (3)
O4	0.30114 (11)	0.29660 (13)	0.09939 (6)	0.0290 (4)
H4O	0.3390	0.2983	0.0745	0.044*
H4P	0.3283	0.3161	0.1259	0.044*
O5	0.42451 (14)	0.31765 (18)	0.02160 (7)	0.0496 (6)
H5O	0.4877	0.3162	0.0229	0.074*
H5P	0.3994	0.3042	−0.0049	0.074*
O6	0.34700 (12)	0.60006 (12)	0.10161 (6)	0.0300 (3)
H6O	0.3363	0.6619	0.0904	0.045*
H6P	0.2916	0.5694	0.1089	0.045*
O7	0.32202 (12)	0.28601 (12)	−0.06718 (6)	0.0275 (3)
H7O	0.3430	0.3107	−0.0939	0.041*
H7P	0.2651	0.2997	−0.0606	0.041*
O8	0.4789 (2)	0.4970 (4)	0.04080 (17)	0.0610 (16)	0.50
H8O	0.4561	0.4429	0.0310	0.092*	0.50
H8P	0.4390	0.5278	0.0564	0.092*	0.50
N1	0.13450 (12)	0.30012 (11)	0.16041 (6)	0.0161 (3)
N2	0.03441 (11)	0.36571 (11)	0.06776 (6)	0.0152 (3)
C1	0.17729 (14)	0.46349 (14)	0.18133 (8)	0.0191 (4)
C2	0.18659 (19)	0.54292 (15)	0.21907 (9)	0.0284 (5)
H2A	0.2408	0.5293	0.2419	0.043*
H2B	0.1269	0.5478	0.2389	0.043*
H2C	0.1982	0.6040	0.2012	0.043*
C3	0.14765 (13)	0.36668 (13)	0.19793 (7)	0.0159 (3)
C4	−0.07281 (13)	0.38673 (13)	0.00422 (7)	0.0161 (3)
C5	−0.11564 (15)	0.39273 (16)	−0.04787 (7)	0.0218 (4)
H5A	−0.0653	0.3807	−0.0733	0.033*
H5B	−0.1430	0.4572	−0.0531	0.033*
H5C	−0.1667	0.3442	−0.0513	0.033*
C6	0.02326 (13)	0.36773 (13)	0.01655 (7)	0.0145 (3)
C7	0.11406 (13)	0.35477 (13)	−0.01228 (7)	0.0159 (3)

	U11	U22	U33	U12	U13	U23
Cu1	0.01545 (12)	0.02178 (13)	0.01160 (11)	−0.00004 (8)	−0.00341 (8)	0.00135 (8)
O1	0.0244 (7)	0.0211 (7)	0.0207 (7)	−0.0033 (5)	−0.0084 (5)	0.0037 (5)
O2	0.0159 (6)	0.0270 (7)	0.0145 (6)	−0.0023 (5)	−0.0004 (5)	0.0028 (5)
O3	0.0246 (7)	0.0253 (7)	0.0122 (6)	−0.0018 (6)	0.0017 (5)	0.0031 (5)
O4	0.0222 (7)	0.0459 (10)	0.0190 (7)	0.0079 (7)	−0.0080 (6)	−0.0070 (7)
O5	0.0298 (9)	0.0881 (17)	0.0307 (9)	0.0203 (10)	−0.0046 (8)	−0.0200 (10)
O6	0.0302 (8)	0.0300 (8)	0.0297 (8)	−0.0047 (7)	−0.0066 (7)	0.0033 (7)
O7	0.0244 (7)	0.0294 (8)	0.0288 (8)	−0.0005 (6)	0.0089 (6)	0.0036 (6)
O8	0.0102 (14)	0.102 (4)	0.071 (3)	0.0179 (18)	−0.0138 (16)	−0.068 (3)
N1	0.0212 (8)	0.0149 (7)	0.0121 (7)	0.0011 (6)	−0.0041 (6)	−0.0001 (5)
N2	0.0158 (7)	0.0197 (7)	0.0102 (6)	−0.0028 (5)	−0.0003 (5)	0.0028 (5)
C1	0.0199 (8)	0.0157 (8)	0.0216 (9)	0.0016 (6)	−0.0083 (7)	−0.0002 (7)
C2	0.0416 (13)	0.0164 (9)	0.0270 (10)	−0.0008 (8)	−0.0070 (9)	−0.0035 (8)
C3	0.0188 (8)	0.0150 (8)	0.0138 (8)	0.0031 (6)	−0.0046 (6)	−0.0008 (6)
C4	0.0172 (8)	0.0170 (8)	0.0140 (8)	−0.0046 (6)	−0.0030 (6)	0.0045 (6)
C5	0.0218 (9)	0.0284 (10)	0.0152 (8)	−0.0034 (8)	−0.0070 (7)	0.0038 (7)
C6	0.0164 (8)	0.0158 (8)	0.0112 (7)	−0.0037 (6)	−0.0017 (6)	0.0029 (6)
C7	0.0184 (8)	0.0155 (8)	0.0138 (8)	−0.0037 (6)	0.0009 (6)	0.0025 (6)

Cu1—N2	1.9495 (16)	O8—H8O	0.8529
Cu1—O2	1.9519 (14)	O8—H8P	0.8080
Cu1—O4	1.9676 (15)	N1—N2i	1.329 (2)
Cu1—N1	1.9682 (16)	N1—C3	1.362 (2)
Cu1—O1	2.3938 (15)	N2—N1ii	1.329 (2)
Cu1—Cu1i	4.0600 (4)	N2—C6	1.355 (2)
Cu1—Cu1ii	4.0600 (4)	C1—C3	1.469 (3)
Cu1—Cu1iii	5.0814 (5)	C1—C2	1.487 (3)
O1—C1	1.232 (3)	C2—H2A	0.9800
O2—C7	1.292 (2)	C2—H2B	0.9800
O3—C7	1.239 (2)	C2—H2C	0.9800
O4—H4O	0.8400	C3—C4i	1.405 (3)
O4—H4P	0.8355	C4—C6	1.394 (2)
O5—H5O	0.8760	C4—C3ii	1.405 (3)
O5—H5P	0.7998	C4—C5	1.494 (3)
O6—H6O	0.9174	C5—H5A	0.9800
O6—H6P	0.8985	C5—H5B	0.9800
O7—H7O	0.8324	C5—H5C	0.9800
O7—H7P	0.8289	C6—C7	1.479 (3)
N2—Cu1—O2	82.06 (6)	H7O—O7—H7P	114.5
N2—Cu1—O4	171.24 (6)	H8O—O8—H8P	111.3
O2—Cu1—O4	89.18 (6)	N2i—N1—C3	108.05 (15)
N2—Cu1—N1	97.49 (7)	N2i—N1—Cu1	130.03 (12)
O2—Cu1—N1	170.07 (6)	C3—N1—Cu1	121.00 (13)
O4—Cu1—N1	91.15 (7)	N1ii—N2—C6	108.91 (15)
N2—Cu1—O1	95.81 (6)	N1ii—N2—Cu1	137.70 (12)
O2—Cu1—O1	115.65 (6)	C6—N2—Cu1	113.30 (12)
O4—Cu1—O1	87.90 (6)	O1—C1—C3	118.16 (17)
N1—Cu1—O1	74.28 (6)	O1—C1—C2	121.73 (18)
N2—Cu1—Cu1i	94.38 (5)	C3—C1—C2	120.11 (18)
O2—Cu1—Cu1i	123.35 (4)	C1—C2—H2A	109.5
O4—Cu1—Cu1i	90.48 (5)	C1—C2—H2B	109.5
N1—Cu1—Cu1i	46.73 (5)	H2A—C2—H2B	109.5
O1—Cu1—Cu1i	120.95 (4)	C1—C2—H2C	109.5
N2—Cu1—Cu1ii	44.57 (5)	H2A—C2—H2C	109.5
O2—Cu1—Cu1ii	125.84 (4)	H2B—C2—H2C	109.5
O4—Cu1—Cu1ii	144.00 (5)	N1—C3—C4i	109.93 (16)
N1—Cu1—Cu1ii	55.97 (5)	N1—C3—C1	116.13 (16)
O1—Cu1—Cu1ii	70.56 (4)	C4i—C3—C1	133.70 (17)
Cu1i—Cu1—Cu1ii	77.482 (5)	C6—C4—C3ii	103.01 (15)
N2—Cu1—Cu1iii	43.82 (5)	C6—C4—C5	127.02 (18)
O2—Cu1—Cu1iii	100.07 (4)	C3ii—C4—C5	129.97 (17)
O4—Cu1—Cu1iii	139.12 (6)	C4—C5—H5A	109.5
N1—Cu1—Cu1iii	73.39 (5)	C4—C5—H5B	109.5
O1—Cu1—Cu1iii	121.81 (4)	H5A—C5—H5B	109.5
Cu1i—Cu1—Cu1iii	51.259 (3)	C4—C5—H5C	109.5
Cu1ii—Cu1—Cu1iii	51.259 (3)	H5A—C5—H5C	109.5
C1—O1—Cu1	110.22 (12)	H5B—C5—H5C	109.5
C7—O2—Cu1	116.03 (12)	N2—C6—C4	110.08 (16)
Cu1—O4—H4O	119.0	N2—C6—C7	114.16 (15)
Cu1—O4—H4P	118.0	C4—C6—C7	135.66 (17)
H4O—O4—H4P	111.1	O3—C7—O2	123.20 (17)
H5O—O5—H5P	117.6	O3—C7—C6	122.78 (17)
H6O—O6—H6P	111.8	O2—C7—C6	114.02 (15)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4O···O5	0.84	1.84	2.680 (3)	173.
O4—H4P···O3iv	0.84	2.03	2.868 (2)	177.
O5—H5O···O5v	0.88	2.22	2.808 (4)	124.
O5—H5P···O7	0.80	1.97	2.766 (3)	171.
O6—H6O···O7vi	0.92	1.84	2.752 (2)	177.
O6—H6P···O1	0.90	1.99	2.863 (2)	163.
O7—H7O···O6vii	0.83	1.92	2.707 (2)	157.
O7—H7P···O3	0.83	2.21	3.016 (2)	166.
O7—H7P···O2	0.83	2.33	2.951 (2)	132.
O8—H8O···O5	0.85	1.81	2.644 (5)	167.
O8—H8P···O6	0.81	2.01	2.815 (4)	174.

Cu1—N2	1.9495 (16)
Cu1—O2	1.9519 (14)
Cu1—O4	1.9676 (15)
Cu1—N1	1.9682 (16)
Cu1—O1	2.3938 (15)

N2—Cu1—O2	82.06 (6)
O2—Cu1—O4	89.18 (6)
N2—Cu1—N1	97.49 (7)
O4—Cu1—N1	91.15 (7)
N1—Cu1—O1	74.28 (6)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4O⋯O5	0.84	1.84	2.680 (3)	173
O4—H4P⋯O3iv	0.84	2.03	2.868 (2)	177
O5—H5O⋯O5v	0.88	2.22	2.808 (4)	124
O5—H5P⋯O7	0.80	1.97	2.766 (3)	171
O6—H6O⋯O7vi	0.92	1.84	2.752 (2)	177
O6—H6P⋯O1	0.90	1.99	2.863 (2)	163
O7—H7O⋯O6vii	0.83	1.92	2.707 (2)	157
O7—H7P⋯O3	0.83	2.21	3.016 (2)	166
O7—H7P⋯O2	0.83	2.33	2.951 (2)	132
O8—H8O⋯O5	0.85	1.81	2.644 (5)	167
O8—H8P⋯O6	0.81	2.01	2.815 (4)	174

Symmetry codes: (iv) ; (v) ; (vi) ; (vii) .