Dipyridinium diaqua­bis­(pyrazole-3,5-di­carboxyl­ato-κ2N,O)cuprate(II) dihydrate

Si, Y.

doi:10.1107/S1600536812046508

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Pages m1497-m1498

doi:10.1107/S1600536812046508

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Dipyridinium diaquabis(pyrazole-3,5-dicarboxylato-κ²N,O)cuprate(II) dihydrate

Youtao Si ^a,^b ^*

^aState Key Laboratory Breeding Base of Humid Subtropical Mountain Ecology, College of Geographical Sciences, Fujian Normal University, Fuzhou 350007, People's Republic of China, and ^bUniversité Européenne de Bretagne, Université de Bretagne Occidentale, CS 93837, 29238 Brest Cedex 3, France
^*Correspondence e-mail: siyoutao@hotmail.com

(Received 30 October 2012; accepted 10 November 2012; online 17 November 2012)

In the mononuclear title salt, (C₅H₆N)₂[Cu(C₅H₂N₂O₄)₂(H₂O)₂]·2H₂O, the Cu^II ion is located on an inversion centre and is coordinated by two chelating pyrazole-3,5-dicarboxylate anions and two water molecules, forming a Jahn–Teller-distorted CuN₂O₄ octahedron. O—H⋯O and N—H⋯O hydrogen bonds are formed between water molecules, complex anions and the pyridine counter-cations, leading to the formation of layers parallel to (100). The layers are held together by weak C—H⋯O hydrogen bonds.

Related literature

For more information on ligands derived from pyrazole-3,5-dicarboxylic acid, see: King et al. (2004 ). For the bond-valence method, see: Brown (2002 ).

Experimental

Crystal data

(C₅H₆N)₂[Cu(C₅H₂N₂O₄)₂(H₂O)₂]·2H₂O
M_r = 603.99
Monoclinic, P 2₁ /c
a = 9.3531 (4) Å
b = 7.3521 (1) Å
c = 17.9903 (7) Å
β = 95.600 (2)°
V = 1231.20 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.96 mm⁻¹
T = 273 K
0.34 × 0.18 × 0.06 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.735, T_max = 0.944
3386 measured reflections
2106 independent reflections
1802 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.075
wR(F²) = 0.154
S = 1.26
2106 reflections
193 parameters
5 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Cu1—O4	1.959 (4)
Cu1—N2	2.006 (4)
Cu1—O5	2.539 (5)

O4—Cu1—N2	81.99 (16)
O4—Cu1—O5	90.92 (17)
N2—Cu1—O5	86.97 (17)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O6ⁱ	0.86	1.99	2.783 (6)	154
O5—H3A⋯O3ⁱⁱ	0.81 (4)	1.95 (4)	2.764 (6)	175 (8)
O5—H3B⋯O2ⁱⁱⁱ	0.82 (2)	2.04 (3)	2.845 (6)	170 (7)
O6—H4A⋯O4	0.82 (5)	1.96 (5)	2.735 (7)	159 (7)
O6—H4B⋯O1ⁱⁱ	0.82 (6)	2.01 (6)	2.801 (6)	162 (7)
N3—H5⋯O1^iv	0.87 (6)	1.81 (6)	2.665 (7)	171 (6)
C6—H6⋯O5^v	0.93	2.55	3.247 (9)	132
C8—H8⋯O3^vi	0.93	2.36	3.211 (8)	151
C10—H10⋯O2^vii	0.93	2.58	3.231 (8)	128
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+1, -y+2, -z+1; (iii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iv) $[x+1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (v) x+1, y, z; (vi) x, y-1, z; (vii) $[x+1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: SMART (Siemens, 1998 ); cell refinement: SAINT (Siemens, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: WinGX (Farrugia, 2012 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812046508/wm2698sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812046508/wm2698Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812046508/wm2698Isup4.cdx

checkCIF report

Comment top

Pyrazole-3,5-dicarboxylic acid (H₃dcp) is a versatile ligand with six potential coordinating sites, namely two N atoms of the pyrazole ring and four O atoms of the carboxyl groups. Together with π—π interactions between neighbouring pyrazole rings, the coordination mode of H₃dcp can lead to different possibilities for creating supramolecular structures (King et al., 2004). When trying to synthesize a copper-containing coordination compound involving H₃dcp, the title compound, (C₅H₆N)⁺₂[Cu(C₅H₂N₂O₄)₂(H₂O)₂]^2-^.2H₂O, was obtained.

The Cu^II ion sits on an inversion center. One fully deprotonated pyrazole-3,5-dicarboxylic acid, one coordinating water molecule, one lattice water molecule and one pyridinium cation are also present in the asymmetric unit. The other half of the metal-containing moiety is generated by the inversion centre. Each pyrazole-3,5-dicarboxylate anion chelates the metal by one N atom and one O atom in the equatorial plane of an octahedron whereas the axial ligands are provided from water molecules at considerably longer distances (Fig. 1), in agreement with the tetragonal Jahn-Teller distortion (Table 1).

The BVS calculation (Brown, 2002) of the Cu ion gave a value of 1.88 valence units, which indicates that the Cu ion is divalent. Because pyrazole-3,5-dicarboxylic acid is a rather strong acid, the terminal non-coordinating carboxyl group also loses its proton to make the solvent pyridine molecules protonated. Besides four protonated pyridine molecules, four lattice water molecules are present in one unit cell as solvent molecules.

Classical O—H···O and N—H···O hydrogen bonding occurs between water molecules, pyridinium cations and complex anions to form a layer in (100), in which N1, N3, O5, O6 act as donor atoms, and O1, O2, O3, O4, O6 are acceptors (Table 2). The packing of adjacent layers along [100] is accomplished through non-classical weak C—H···O contacts, with the donor belonging to pyridine and acceptor being O atoms of the non-coordinating carboxylate groups.

Related literature top

For more information on ligands derived from pyrazole-3,5-dicarboxylic acid, see: King et al. (2004). For the bond-valence method, see: Brown (2002).

Experimental top

0.5 mmol H₃dcp and 0.05 mmol CuCl were mixted in 10 ml H₂O to give a suspension. After addition of 0.5 ml pyridine, the suspension turned to solution, which was then stirred for 4 h and filtered. After standing in ambient conditions for about 3 days, the filtrate yielded blue crystals suitable for X-ray diffraction.

Computing details top

Data collection: SMART (Siemens, 1998); cell refinement: SAINT (Siemens, 1998); data reduction: SAINT (Siemens, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: WinGX (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom labels and 20% probability displacement ellipsoids for all non-H atoms. [Symmetry code A: -x+1, -y+1, -z+1.]
	Fig. 2. The packing diagram of the title compound, viewed down the b axis. Hydrogen bonding interactions are gived as dashed lines.

Dipyridinium diaquabis(pyrazole-3,5-dicarboxylato-κ²N,O)cuprate(II) dihydrate top

Crystal data top

(C₅H₆N)₂[Cu(C₅H₂N₂O₄)₂(H₂O)₂]·2H₂O	F(000) = 622
M_r = 603.99	D_x = 1.629 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1917 reflections
a = 9.3531 (4) Å	θ = 2.2–25.0°
b = 7.3521 (1) Å	µ = 0.96 mm⁻¹
c = 17.9903 (7) Å	T = 273 K
β = 95.600 (2)°	Prism, blue
V = 1231.20 (7) Å³	0.34 × 0.18 × 0.06 mm
Z = 2

Data collection top

Bruker SMART CCD diffractometer	2106 independent reflections
Radiation source: fine-focus sealed tube	1802 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
phi and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→9
T_min = 0.735, T_max = 0.944	k = −8→7
3386 measured reflections	l = −21→10

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)] = 0.075	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.154	H atoms treated by a mixture of independent and constrained refinement
S = 1.26	w = 1/[σ²(F_o²) + (0.0117P)² + 6.7689P] where P = (F_o² + 2F_c²)/3
2106 reflections	(Δ/σ)_max < 0.001
193 parameters	Δρ_max = 0.50 e Å⁻³
5 restraints	Δρ_min = −0.41 e Å⁻³

Crystal data top

(C₅H₆N)₂[Cu(C₅H₂N₂O₄)₂(H₂O)₂]·2H₂O	V = 1231.20 (7) Å³
M_r = 603.99	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.3531 (4) Å	µ = 0.96 mm⁻¹
b = 7.3521 (1) Å	T = 273 K
c = 17.9903 (7) Å	0.34 × 0.18 × 0.06 mm
β = 95.600 (2)°

Data collection top

Bruker SMART CCD diffractometer	2106 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1802 reflections with I > 2σ(I)
T_min = 0.735, T_max = 0.944	R_int = 0.038
3386 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.075	5 restraints
wR(F²) = 0.154	H atoms treated by a mixture of independent and constrained refinement
S = 1.26	Δρ_max = 0.50 e Å⁻³
2106 reflections	Δρ_min = −0.41 e Å⁻³
193 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
Cu1	0.5000	0.5000	0.5000	0.0307 (3)
O1	0.3159 (5)	1.0520 (5)	0.7574 (2)	0.0340 (10)
O3	0.7070 (4)	0.9725 (6)	0.5173 (2)	0.0334 (10)
N1	0.3911 (5)	0.6681 (6)	0.6461 (2)	0.0253 (11)
H1	0.3367	0.5826	0.6599	0.030*
O4	0.6331 (4)	0.6957 (5)	0.4799 (2)	0.0303 (10)
N2	0.4725 (5)	0.6559 (6)	0.5890 (2)	0.0250 (10)
C2	0.4060 (6)	0.8331 (8)	0.6791 (3)	0.0238 (12)
O2	0.2622 (5)	0.7604 (6)	0.7754 (2)	0.0405 (11)
C1	0.3205 (6)	0.8838 (8)	0.7425 (3)	0.0265 (13)
C4	0.5402 (6)	0.8162 (7)	0.5856 (3)	0.0220 (12)
O5	0.2915 (6)	0.6726 (6)	0.4319 (3)	0.0425 (11)
H3A	0.290 (8)	0.779 (4)	0.444 (4)	0.051*
H3B	0.287 (8)	0.679 (10)	0.3864 (12)	0.051*
C5	0.6349 (6)	0.8345 (7)	0.5240 (3)	0.0221 (12)
C3	0.5020 (6)	0.9310 (8)	0.6420 (3)	0.0270 (13)
H2	0.5345	1.0487	0.6523	0.032*
O6	0.7456 (6)	0.6665 (6)	0.3457 (3)	0.0482 (13)
H4A	0.719 (8)	0.703 (10)	0.385 (2)	0.058*
H4B	0.709 (8)	0.739 (9)	0.315 (3)	0.058*
N3	1.1229 (6)	0.2882 (8)	0.3354 (3)	0.0381 (13)
H5	1.185 (6)	0.350 (8)	0.313 (3)	0.046*
C9	1.0145 (7)	0.0054 (11)	0.3514 (4)	0.0479 (17)
H9	1.0028	−0.1166	0.3385	0.057*
C10	1.1080 (7)	0.1140 (9)	0.3174 (4)	0.0408 (16)
H10	1.1615	0.0649	0.2814	0.049*
C7	0.9545 (8)	0.2621 (13)	0.4227 (4)	0.056 (2)
H7	0.9016	0.3144	0.4583	0.067*
C8	0.9389 (7)	0.0817 (11)	0.4047 (4)	0.0496 (19)
H8	0.8760	0.0102	0.4291	0.059*
C6	1.0501 (8)	0.3639 (11)	0.3870 (4)	0.0512 (19)
H6	1.0637	0.4862	0.3989	0.061*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0437 (6)	0.0249 (5)	0.0268 (5)	−0.0106 (5)	0.0198 (4)	−0.0103 (5)
O1	0.042 (3)	0.029 (2)	0.033 (2)	0.0026 (19)	0.018 (2)	−0.0069 (18)
O3	0.038 (2)	0.031 (2)	0.034 (2)	−0.009 (2)	0.0175 (19)	−0.0081 (19)
N1	0.030 (3)	0.024 (2)	0.024 (2)	−0.001 (2)	0.013 (2)	−0.002 (2)
O4	0.040 (2)	0.027 (2)	0.027 (2)	−0.0115 (18)	0.0212 (19)	−0.0082 (17)
N2	0.031 (3)	0.024 (2)	0.021 (2)	−0.001 (2)	0.012 (2)	−0.001 (2)
C2	0.027 (3)	0.027 (3)	0.018 (3)	0.002 (2)	0.004 (2)	−0.003 (2)
O2	0.059 (3)	0.034 (2)	0.032 (2)	−0.004 (2)	0.024 (2)	0.002 (2)
C1	0.027 (3)	0.034 (3)	0.020 (3)	0.008 (3)	0.004 (2)	−0.007 (3)
C4	0.026 (3)	0.021 (3)	0.019 (3)	−0.004 (2)	0.004 (2)	−0.005 (2)
O5	0.068 (3)	0.030 (2)	0.030 (2)	−0.004 (2)	0.006 (2)	−0.002 (2)
C5	0.021 (3)	0.025 (3)	0.021 (3)	−0.001 (2)	0.003 (2)	−0.001 (2)
C3	0.028 (3)	0.025 (3)	0.029 (3)	−0.004 (2)	0.009 (3)	−0.004 (2)
O6	0.078 (4)	0.030 (3)	0.042 (3)	−0.004 (2)	0.037 (3)	−0.005 (2)
N3	0.037 (3)	0.046 (3)	0.033 (3)	−0.009 (3)	0.012 (2)	0.009 (3)
C9	0.045 (4)	0.049 (4)	0.050 (4)	−0.009 (4)	0.002 (3)	0.012 (4)
C10	0.042 (4)	0.046 (4)	0.035 (4)	0.000 (3)	0.008 (3)	0.001 (3)
C7	0.039 (4)	0.092 (6)	0.040 (4)	−0.002 (4)	0.019 (3)	−0.016 (4)
C8	0.037 (4)	0.076 (5)	0.035 (4)	−0.020 (4)	0.000 (3)	0.018 (4)
C6	0.051 (4)	0.051 (4)	0.054 (4)	−0.006 (4)	0.018 (4)	−0.013 (4)

Geometric parameters (Å, º) top

Cu1—O4	1.959 (4)	O5—H3A	0.82 (2)
Cu1—O4ⁱ	1.959 (4)	O5—H3B	0.82 (2)
Cu1—N2	2.006 (4)	C3—H2	0.9300
Cu1—N2ⁱ	2.006 (4)	O6—H4A	0.82 (2)
Cu1—O5	2.539 (5)	O6—H4B	0.82 (2)
Cu1—O5ⁱ	2.539 (5)	N3—C10	1.325 (9)
O1—C1	1.267 (7)	N3—C6	1.325 (8)
O3—C5	1.230 (6)	N3—H5	0.87 (2)
N1—N2	1.341 (6)	C9—C8	1.367 (10)
N1—C2	1.351 (7)	C9—C10	1.371 (9)
N1—H1	0.8600	C9—H9	0.9300
O4—C5	1.292 (6)	C10—H10	0.9300
N2—C4	1.342 (7)	C7—C8	1.369 (11)
C2—C3	1.374 (8)	C7—C6	1.373 (10)
C2—C1	1.502 (7)	C7—H7	0.9300
O2—C1	1.239 (7)	C8—H8	0.9300
C4—C3	1.393 (7)	C6—H6	0.9300
C4—C5	1.491 (7)

O4—Cu1—O4ⁱ	179.999 (1)	H3A—O5—H3B	102 (7)
O4—Cu1—N2	81.99 (16)	O3—C5—O4	124.5 (5)
O4ⁱ—Cu1—N2	98.01 (16)	O3—C5—C4	121.2 (5)
O4—Cu1—N2ⁱ	98.01 (16)	O4—C5—C4	114.3 (5)
O4ⁱ—Cu1—N2ⁱ	81.99 (16)	C2—C3—C4	105.2 (5)
N2—Cu1—N2ⁱ	179.999 (1)	C2—C3—H2	127.4
O4—Cu1—O5	90.92 (17)	C4—C3—H2	127.4
O4ⁱ—Cu1—O5	89.08 (17)	H4A—O6—H4B	103 (7)
N2—Cu1—O5	86.97 (17)	C10—N3—C6	121.9 (6)
N2ⁱ—Cu1—O5	93.03 (17)	C10—N3—H5	117 (5)
N2—N1—C2	110.8 (4)	C6—N3—H5	121 (5)
N2—N1—H1	124.6	C8—C9—C10	118.0 (7)
C2—N1—H1	124.6	C8—C9—H9	121.0
C5—O4—Cu1	116.0 (3)	C10—C9—H9	121.0
N1—N2—C4	106.3 (4)	N3—C10—C9	120.7 (7)
N1—N2—Cu1	141.0 (4)	N3—C10—H10	119.6
C4—N2—Cu1	111.6 (3)	C9—C10—H10	119.6
N1—C2—C3	107.6 (5)	C8—C7—C6	118.5 (7)
N1—C2—C1	121.1 (5)	C8—C7—H7	120.8
C3—C2—C1	131.3 (5)	C6—C7—H7	120.8
O2—C1—O1	126.0 (5)	C9—C8—C7	120.8 (7)
O2—C1—C2	118.2 (5)	C9—C8—H8	119.6
O1—C1—C2	115.8 (5)	C7—C8—H8	119.6
N2—C4—C3	110.1 (5)	N3—C6—C7	120.1 (7)
N2—C4—C5	115.5 (4)	N3—C6—H6	120.0
C3—C4—C5	134.4 (5)	C7—C6—H6	120.0

N2—Cu1—O4—C5	−5.9 (4)	Cu1—N2—C4—C5	−7.8 (6)
N2ⁱ—Cu1—O4—C5	174.1 (4)	Cu1—O4—C5—O3	−176.5 (4)
C2—N1—N2—C4	−0.1 (6)	Cu1—O4—C5—C4	3.3 (6)
C2—N1—N2—Cu1	−166.3 (5)	N2—C4—C5—O3	−176.9 (5)
O4—Cu1—N2—N1	173.2 (6)	C3—C4—C5—O3	4.2 (10)
O4ⁱ—Cu1—N2—N1	−6.8 (6)	N2—C4—C5—O4	3.3 (7)
O4—Cu1—N2—C4	7.4 (4)	C3—C4—C5—O4	−175.6 (6)
O4ⁱ—Cu1—N2—C4	−172.6 (4)	N1—C2—C3—C4	0.8 (6)
N2—N1—C2—C3	−0.5 (6)	C1—C2—C3—C4	−176.5 (6)
N2—N1—C2—C1	177.2 (5)	N2—C4—C3—C2	−0.9 (7)
N1—C2—C1—O2	16.6 (8)	C5—C4—C3—C2	178.0 (6)
C3—C2—C1—O2	−166.4 (6)	C6—N3—C10—C9	0.7 (11)
N1—C2—C1—O1	−163.7 (5)	C8—C9—C10—N3	−0.8 (10)
C3—C2—C1—O1	13.3 (9)	C10—C9—C8—C7	1.1 (11)
N1—N2—C4—C3	0.6 (6)	C6—C7—C8—C9	−1.3 (11)
Cu1—N2—C4—C3	171.3 (4)	C10—N3—C6—C7	−0.9 (11)
N1—N2—C4—C5	−178.5 (5)	C8—C7—C6—N3	1.1 (12)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O6ⁱ	0.86	1.99	2.783 (6)	154
O5—H3A···O3ⁱⁱ	0.81 (4)	1.95 (4)	2.764 (6)	175 (8)
O5—H3B···O2ⁱⁱⁱ	0.82 (2)	2.04 (3)	2.845 (6)	170 (7)
O6—H4A···O4	0.82 (5)	1.96 (5)	2.735 (7)	159 (7)
O6—H4B···O1ⁱⁱ	0.82 (6)	2.01 (6)	2.801 (6)	162 (7)
N3—H5···O1^iv	0.87 (6)	1.81 (6)	2.665 (7)	171 (6)
C6—H6···O5^v	0.93	2.55	3.247 (9)	132
C8—H8···O3^vi	0.93	2.36	3.211 (8)	151
C10—H10···O2^vii	0.93	2.58	3.231 (8)	128

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

Experimental details

Crystal data
Chemical formula	(C₅H₆N)₂[Cu(C₅H₂N₂O₄)₂(H₂O)₂]·2H₂O
M_r	603.99
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	273
a, b, c (Å)	9.3531 (4), 7.3521 (1), 17.9903 (7)
β (°)	95.600 (2)
V (Å³)	1231.20 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.96
Crystal size (mm)	0.34 × 0.18 × 0.06

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.735, 0.944
No. of measured, independent and observed [I > 2σ(I)] reflections	3386, 2106, 1802
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.075, 0.154, 1.26
No. of reflections	2106
No. of parameters	193
No. of restraints	5
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.41

Computer programs: SMART (Siemens, 1998), SAINT (Siemens, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), WinGX (Farrugia, 2012), publCIF (Westrip, 2010).

Selected geometric parameters (Å, º) top

Cu1—O4	1.959 (4)	Cu1—O5	2.539 (5)
Cu1—N2	2.006 (4)

O4—Cu1—N2	81.99 (16)	N2—Cu1—O5	86.97 (17)
O4—Cu1—O5	90.92 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O6ⁱ	0.860	1.986	2.783 (6)	154
O5—H3A···O3ⁱⁱ	0.81 (4)	1.95 (4)	2.764 (6)	175 (8)
O5—H3B···O2ⁱⁱⁱ	0.82 (2)	2.04 (3)	2.845 (6)	170 (7)
O6—H4A···O4	0.82 (5)	1.96 (5)	2.735 (7)	159 (7)
O6—H4B···O1ⁱⁱ	0.82 (6)	2.01 (6)	2.801 (6)	162 (7)
N3—H5···O1^iv	0.87 (6)	1.81 (6)	2.665 (7)	171 (6)
C6—H6···O5^v	0.93	2.55	3.247 (9)	132
C8—H8···O3^vi	0.93	2.36	3.211 (8)	151
C10—H10···O2^vii	0.93	2.58	3.231 (8)	128

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

Acknowledgements

The author thanks the Centre Nationale de la Recherche Scientique (CNRS) for financial support.

References

Brown, I. D. (2002). In The Chemical Bond in Inorganic Chemistry: The Bond Valence Model. Oxford University Press. Google Scholar
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King, P., Clérac, R., Anson, C. E. & Powell, A. K. (2004). Dalton Trans. pp. 852–861. Web of Science CSD CrossRef Google Scholar
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Siemens (1998). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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