cyclo-Tetra­kis(μ-3-acetyl-4-methyl-1H-pyrazole-5-carboxyl­ato-κ4N2,O3:N1,O5)tetra­kis[aqua­copper(II)] tetra­deca­hydrate

Malinkin, S.; Golenya, I.A.; Pavlenko, V.A.; Haukka, M.; Iskenderov, T.S.

doi:10.1107/S1600536811030832

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Pages m1260-m1261

doi:10.1107/S1600536811030832

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cyclo-Tetrakis(μ-3-acetyl-4-methyl-1H-pyrazole-5-carboxylato-κ⁴N²,O³:N¹,O⁵)tetrakis[aquacopper(II)] tetradecahydrate

Sergey Malinkin,^a ^* Irina A. Golenya,^a Vadim A. Pavlenko,^a Matti Haukka ^b and Turganbay S. Iskenderov ^a

^aKiev National Taras Shevchenko University, Department of Chemistry, Volodymyrska Str. 64, 01601 Kiev, Ukraine, and ^bUniversity of Joensuu, Department of Chemistry, PO Box 111, FI-80101 Joensuu, Finland
^*Correspondence e-mail: malinachem@mail.ru

(Received 26 July 2011; accepted 1 August 2011; online 17 August 2011)

The title compound, [Cu₄(C₇H₆N₂O₃)₄(H₂O)₄]·14H₂O, a tetranuclear [2 × 2] grid-type complex with S4 symmetry, contains four Cu^II atoms which are bridged by four pyrazolecarboxylate ligand anions and are additionally bonded to a water molecule. Each Cu^II atom is coordinated by two O atoms of the carboxylate and acetyl groups, two pyrazole N atoms of doubly deprotonated 3-acetyl-4-methyl-1H-pyrazole-5-carboxylic acid and one O atom of a water molecule. 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_r = 1243.00
Tetragonal, I 4₁ /a
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[F² > 2σ(F²)] = 0.034
wR(F²) = 0.097
S = 1.06
3993 reflections
165 parameters
H-atom parameters constrained
Δρ_max = 1.20 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

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⋯O3^iv	0.84	2.03	2.868 (2)	177
O5—H5O⋯O5^v	0.88	2.22	2.808 (4)	124
O5—H5P⋯O7	0.80	1.97	2.766 (3)	171
O6—H6O⋯O7^vi	0.92	1.84	2.752 (2)	177
O6—H6P⋯O1	0.90	1.99	2.863 (2)	163
O7—H7O⋯O6^vii	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) $[-y+{\script{3\over 4}}, x+{\script{1\over 4}}, z+{\script{1\over 4}}]$ ; (v) $[-x+1, -y+{\script{1\over 2}}, z]$ ; (vi) $[x, y+{\script{1\over 2}}, -z]$ ; (vii) $[y-{\script{1\over 4}}, -x+{\script{3\over 4}}, z-{\script{1\over 4}}]$ .

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811030832/jh2318sup1.cif

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

checkCIF report

Comment top

Substituted pyrazolate ligands have found widespread use as building blocks for the formation of self-assembled supramolecular coordination complexes with an array of transition metal ions and a variety of different structures, e.g., helical polymers (Piguet et al., 1997; Krämer et al., 2002), so-called [2 × 2] grids (Zhang et al., 1996; Van der Vlugt et al., 2008; Klingele et al., 2007) and other polynuclear structures (Kovbasyuk et al., 2004; Pons et al., 2003). Introduction of different donor substituents in 3- and 5-positions of the pyrazole ring is still rare, and such ligands can be successully used for the obtaining of oligonuclear heterometallic species (Moroz et al., 2010). Reported here is a new copper(II) complex with [2 × 2] grid-structure based on a novel asymmetric pyrazolate ligand having different substituents (the carboxylic and acetyl gropus) in 3- and 5-positions.

In the title compound, (I), the tetranuclear [2 × 2] grid-type complex with S4 symmetry are composed of four Cu^II ions, four ligands and four metal-bound water molecules (Fig. 1).

Each copper ion is nested in a square-pyramidal environment that is composed of the pyrazolate-N2, deprotonated carboxyl-O2 from a compartment of one ligand molecule and acetyl-O1 atoms, the pyrazolate-N1 from another ligand and one water-O4.

The intermetallic separations pyrazolate-bridged Cu^II ions is 4.0600 (4) Å which is similar to that seen in the structures reported by Zhang et al., 1996 (4.098 – 4.115 Å), while the distance between diagonal copper atoms is 5.0814 (5) Å, which is more longer to that observed in the structures reported by Klingele et al., 2007 (4.7091 (5) Å) and Van der Vlugt et al., 2008 (4.2308 (6) Å).

The coordinated pyrazolate ligand exhibits C—C, C—N, N—N bond lengths which are normal for bridging pyrazolate rings (Sliva et al., 1997; Świątek-Kozłowska et al., 2000; Mokhir et al., 2002). The C—O bond lengths in the deprotonated carboxylic groups differs significantly (1.239 (2) and 1.292 (2) ) which is typical for monodentately coordinated carboxylates (Wörl et al., 2005a,b).

A part of the crystal packing of (I) is presented in Fig.2. In the crystal packing the complex molecules are associated via intermolecular hydrogen bonds that involve the O—H interactions between the coordinated and the solvate water molecules and the non-coordinating carboxylate-O atoms. Thus, the tetranuclear molecules are stacked along the crystallographic x and y axises, forming the columns. The columns bisect one another at right angles to give a layer-like structure.

Related literature top

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 top

The ligand 5-acetyl-4-methyl-1H-pyrazole-3-carboxylic acid (Sachse et al., 2008) (0.25 g, 1.5 mmol) was added to a solution of Cu(Ac)₂.H₂O (0.30 g, 1.5 mmol) in H₂O–CH₃OH (50 mL) [80:20 v/v]. The reaction mixture was heated for 30 min with constant stirring at 80 °C until completedissolution of the ligand occurred. The resulting deep blue solution was filtered to remove any undissolved ligand and left at room temperature. Square block dark blue crystals suitable for X-ray diffraction were isolated after standing for several days (yield 0.32 g, 80%). Elemental analysis calc. (%) for C₂₈H₄₀Cu₄N₈O₂₀: C 31.64; H 3.79; N 10.54; found: C 31.22; H 3.47; N 10.34.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound. H atoms are omitted for clarity.
	Fig. 2. A packing diagram for the title compound, showing the columns along the y-axis direction. Copper atoms and water molecules are depicted as the big and the small balls, respectively.

cyclo-Tetrakis(µ-3-acetyl-4-methyl-1H-pyrazole-5-carboxylato- κ⁴N²,O³:N¹,O⁵)tetrakis[aquacopper(II)] tetradecahydrate top

Crystal data top

[Cu₄(C₇H₆N₂O₃)₄(H₂O)₄]·14H₂O	D_x = 1.638 Mg m⁻³
M_r = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0463P)² + 11.3899P] where P = (F_o² + 2F_c²)/3
3993 reflections	(Δ/σ)_max < 0.001
165 parameters	Δρ_max = 1.20 e Å⁻³
0 restraints	Δρ_min = −0.58 e Å⁻³

Crystal data top

[Cu₄(C₇H₆N₂O₃)₄(H₂O)₄]·14H₂O	Z = 4
M_r = 1243.00	Mo Kα radiation
Tetragonal, I4₁/a	µ = 1.76 mm⁻¹
a = 13.8502 (7) Å	T = 100 K
c = 26.280 (3) Å	0.35 × 0.25 × 0.15 mm
V = 5041.1 (6) Å³

Data collection top

Bruker SMART APEXII CCD diffractometer	3993 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	3254 reflections with I > 2σ(I)
T_min = 0.578, T_max = 0.778	R_int = 0.037
37816 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.097	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0463P)² + 11.3899P] where P = (F_o² + 2F_c²)/3
3993 reflections	Δρ_max = 1.20 e Å⁻³
165 parameters	Δρ_min = −0.58 e Å⁻³

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Symmetry codes: (i) y−1/4, −x+1/4, −z+1/4; (ii) −y+1/4, x+1/4, −z+1/4; (iii) −x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

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···O3^iv	0.84	2.03	2.868 (2)	177
O5—H5O···O5^v	0.88	2.22	2.808 (4)	124
O5—H5P···O7	0.80	1.97	2.766 (3)	171
O6—H6O···O7^vi	0.92	1.84	2.752 (2)	177
O6—H6P···O1	0.90	1.99	2.863 (2)	163
O7—H7O···O6^vii	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) −y+3/4, x+1/4, z+1/4; (v) −x+1, −y+1/2, z; (vi) x, y+1/2, −z; (vii) y−1/4, −x+3/4, z−1/4.

Experimental details

Crystal data
Chemical formula	[Cu₄(C₇H₆N₂O₃)₄(H₂O)₄]·14H₂O
M_r	1243.00
Crystal system, space group	Tetragonal, I4₁/a
Temperature (K)	100
a, c (Å)	13.8502 (7), 26.280 (3)
V (Å³)	5041.1 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.76
Crystal size (mm)	0.35 × 0.25 × 0.15

Data collection
Diffractometer	Bruker SMART APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2008)
T_min, T_max	0.578, 0.778
No. of measured, independent and observed [I > 2σ(I)] reflections	37816, 3993, 3254
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.723

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.097, 1.06
No. of reflections	3993
No. of parameters	165
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0463P)² + 11.3899P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.20, −0.58

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2009).

Selected geometric parameters (Å, º) top

Cu1—N2	1.9495 (16)	Cu1—O1	2.3938 (15)
Cu1—O2	1.9519 (14)	Cu1—Cu1ⁱ	4.0600 (4)
Cu1—O4	1.9676 (15)	Cu1—Cu1ⁱⁱ	4.0600 (4)
Cu1—N1	1.9682 (16)	Cu1—Cu1ⁱⁱⁱ	5.0814 (5)

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

Symmetry codes: (i) y−1/4, −x+1/4, −z+1/4; (ii) −y+1/4, x+1/4, −z+1/4; (iii) −x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4O···O5	0.84	1.84	2.680 (3)	173.0
O4—H4P···O3^iv	0.84	2.03	2.868 (2)	177.2
O5—H5O···O5^v	0.88	2.22	2.808 (4)	124.4
O5—H5P···O7	0.80	1.97	2.766 (3)	171.1
O6—H6O···O7^vi	0.92	1.84	2.752 (2)	176.8
O6—H6P···O1	0.90	1.99	2.863 (2)	163.3
O7—H7O···O6^vii	0.83	1.92	2.707 (2)	156.7
O7—H7P···O3	0.83	2.21	3.016 (2)	165.5
O7—H7P···O2	0.83	2.33	2.951 (2)	131.6
O8—H8O···O5	0.85	1.81	2.644 (5)	167.1
O8—H8P···O6	0.81	2.01	2.815 (4)	174.1

Symmetry codes: (iv) −y+3/4, x+1/4, z+1/4; (v) −x+1, −y+1/2, z; (vi) x, y+1/2, −z; (vii) y−1/4, −x+3/4, z−1/4.

Acknowledgements

Financial support from the State Fund for Fundamental Research of Ukraine (grant No. F40.3/041) and the Swedish Institute (Visby Program) is gratefully acknowledged.

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