Diaqua­bis(ethyl­enediamine-κ2N,N′)copper(II) bis­(4-phenyl­benzoate) 2.66-hydrate

Fernandes, J.A.; Ramos, A.I.; Silva, P.; Braga, S.S.; Ribeiro-Claro, P.; Rocha, J.; Almeida Paz, F.A.

doi:10.1107/S1600536810016223

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 6| June 2010| Pages m626-m627

https://doi.org/10.1107/S1600536810016223

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Diaquabis(ethylenediamine-κ²N,N′)copper(II) bis(4-phenylbenzoate) 2.66-hydrate

José A. Fernandes,^a Ana I. Ramos,^a Patrícia Silva,^a Susana S. Braga,^a Paulo Ribeiro-Claro,^a João Rocha ^a and Filipe A. Almeida Paz ^a ^*

^aDepartment of Chemistry, University of Aveiro, CICECO, 3810-193 Aveiro, Portugal
^*Correspondence e-mail: filipe.paz@ua.pt

(Received 27 April 2010; accepted 3 May 2010; online 8 May 2010)

In the title complex, [Cu(C₂H₈N₂)₂(H₂O)₂](C₁₃H₉O₂)₂·2.66H₂O, the Cu^II centre (located at an inversion centre) is coordinated by two bidentate ethylenediamine (en) ligands and two water O atoms in a typical Jahn–Teller distorted octahedral geometry. The amino groups and the water molecules are disordered over two distinct crystallographic positions with occupancies of 1/3 and 2/3. In the crystal, the cations and anions are disposed in alternating layers. One of the water molecules of crystallization is disordered and the other has a fractional occupation. In the 2/3 occupancy component, water molecules are organized into a chain composed of hexameric units interconnected by carboxylate bridges.

Related literature

For general background to reactions based on the copper cation, see: Graham et al. (2000 ); Majumder et al. (2006 ); Rao et al. (2004 ); Zhao et al. (2009 ). For examples of framework-type structures of hybrid materials comprising carboxylate anions, see: Eddaoudi et al. (2001 ). For general background to crystal engineering approaches from our research group, see: Paz & Khimyak et al. (2002 ); Paz & Bond et al. (2002 ); Paz & Klinowski (2003 ); Paz et al. (2005 ); Shi et al. (2008 ). For a description of the graph-set notation for hydrogen-bonded aggregates, see: Grell et al. (1999 ).

Experimental

Crystal data

[Cu(C₂H₈N₂)₂(H₂O)₂](C₁₃H₉O₂)₂·2.66H₂O
M_r = 662.20
Monoclinic, P 2₁ /n
a = 6.1466 (6) Å
b = 34.984 (3) Å
c = 7.3101 (7) Å
β = 95.819 (4)°
V = 1563.8 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.76 mm⁻¹
T = 150 K
0.13 × 0.10 × 0.06 mm

Data collection

Bruker X8 Kappa CCD APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ) T_min = 0.908, T_max = 0.956
26073 measured reflections
4736 independent reflections
3908 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.137
S = 1.10
4736 reflections
259 parameters
15 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.66 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—N1	2.019 (2)
Cu1—N1′	2.035 (4)
Cu1—N2	2.006 (2)
Cu1—N2′	2.008 (4)
Cu1—O1W	2.496 (4)
Cu1—O3W	2.605 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱⁱ	0.92	2.13	2.986 (3)	154
N1—H1B⋯O2Wⁱⁱⁱ	0.92	2.32	3.093 (3)	141
N2—H2A⋯O2ⁱⁱⁱ	0.92	2.16	3.037 (3)	158
N1′—H1E⋯O2Wⁱⁱⁱ	0.92	2.51	3.375 (4)	157
N1′—H1F⋯O1ⁱⁱⁱ	0.92	2.20	3.087 (5)	161
N2′—H2E⋯O4W^iv	0.92	2.33	3.181 (9)	154
N2′—H2F⋯O2W^v	0.92	2.21	3.055 (5)	152
O1W—H1M⋯O2ⁱⁱⁱ	0.95 (1)	1.92 (1)	2.844 (4)	163 (4)
O1W—H1N⋯O2^vi	0.95 (1)	1.88 (1)	2.814 (4)	169 (4)
O2W—H2M⋯O2^vii	0.95 (1)	1.73 (1)	2.668 (2)	168 (5)
O2W—H2N⋯O1^viii	0.95 (1)	1.87 (2)	2.765 (2)	156 (5)
O3W—H3M⋯O2W^v	0.95 (1)	2.01 (1)	2.932 (3)	163 (3)
O3W—H3N⋯O1^ix	0.95 (1)	1.82 (1)	2.721 (3)	158 (3)
O4W—H4M⋯O1^x	0.95 (1)	1.91	2.8562 (17)	178
Symmetry codes: (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iv) -x, -y+1, -z; (v) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (vi) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z-{\script{1\over 2}}]$ ; (vii) x+1, y, z+1; (viii) x, y, z+1; (ix) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (x) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT-Plus (Bruker, 2005 ); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810016223/tk2668sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810016223/tk2668Isup2.hkl

checkCIF report

Comment top

Carboxylate anions are widely used in the synthesis of coordination polymers (Eddaoudi et al., 2001). Our research group specialises on the design and preparation of these compounds (Paz & Khimyak et al., 2002; Paz et al., 2003; Paz et al., 2005; Shi et al., 2008) and following our previous interest in the biphenyldicarboxylate anion (bpdc^2-) as a bridging ligand (Paz & Bond et al., 2002), we have recently started to use 4-phenylbenzoate (pb^-). Given its ability to form stable coordination complexes, copper was chosen as metal centre for our preliminary studies (Graham et al., 2000; Majumder et al., 2006; Rao et al., 2004; Zhao et al., 2009). While reacting pb^- with [Cu(en)₂(H₂O)₂](NO₃)₂ we isolated as a secondary product, the title complex, (I), whose structure we wish to report now.

The asymmetric unit of (I) contains one 4-phenylbenzoate anion, 1.33 water molecules of crystallisation, and 1/2 of the [Cu(en)₂(H₂O)₂]²⁺ cation; the latter is situated about a centre of inversion. The species are distributed in alternating layers along the b axis (Fig. 1a). An ordered hydrophobic layer is composed by the aromatic rings from pb^- and occupies the unit cell regions located between ca. 0.1 < b < 0.4 and 0.6 < b < 0.9 (Fig. 1a). Along the c axis, these moieties are distributed in two alternating layers, from which the aromatic rings of a specific layer are off-set from those of the layers directly above and below, avoiding efficient π-π stacking (Fig. 1b). The two average planes containing the phenyl rings are mutually rotated by ca. 40°, which increases the distance between hydrogen atoms of neighbouring pb^- anions.

The hydrophilic layer, which is formed by the carboxylate groups, the [Cu(en)₂(H₂O)₂]²⁺ cations and the water molecules of crystallisation, exhibits extensive crystallographic disorder. On the one hand, the centrosymmetric cation has two possible mutually-tilted crystallographic positions (rates of occupancy of 1/3 and 2/3; see Fig. 2), which have in common the two carbon atoms and the Cu centre. For each possibility the Cu centre exhibits a typical octahedral coordination environment with a strong Jahn-Teller distortion: the Cu—N bonds (equatorial planes) range from 2.006 (2) to 2.035 (4) Å, and the Cu—O_water (apical positions) are either 2.601 (2) Å (2/3 occupancy) or 2.495 (4) Å (1/3 occupancy); however, the cis octahedral angles fall within a rather short range around the ideal value: 84.65 (15) – 95.35 (15) ° (Table 1).

The crystal structure is rich with a variety of hydrogen bonds due to the presence of amines, carboxylates and water molecules (both coordinated and uncoordinated). The formed hydrogen bonding sub-network is strongly affected by the aforementioned crystal disorder plus some additional disorder associated with the two uncoordinated water molecules (O2W and O4W). The coordinated O3W and uncoordinated O2W water molecules, plus the O1 oxygen atom of the carboxylate group are engaged in a series of strong [O···O distances ranging from 2.668 (2) to 2.932 (3) Å; Table 2] and rather directional [angles in the range 156 (5) – 168 (5) °; Table 2] O—H···O hydrogen bonds, forming an almost planar supramolecular hexagon (longest distance to the average plane of ca. 0.17 Å) with a graph set motif R₆⁴(12) (Grell et al., 1999) (Fig. 3). Remarkably, the carboxylate group further establishes bridges between adjacent supramolecular hexagons [O2W—H2M···O2 at 1.731 (10) Å; Fig. 3], leading to a 1-D hydrogen bonded chain running parallel the a axis (Fig. 3). The amino groups also participate in the hydrogen bonding network with rather directional interactions [angles are in the range 141 – 174 °; Table 2], even though the N···O distances with the O2 carboxylate atom and the water molecules are relatively long [N1···O2 2.986 (3) Å, N2···O2 3.037 (3) Å and N1···O2W 3.093 (3) Å].

Related literature top

For general background to reactions based on the copper cation, see: Graham et al. (2000); Majumder et al. (2006); Rao et al. (2004); Zhao et al. (2009). For examples of framework-type structures of hybrid materials comprising carboxylate anions, see: Eddaoudi et al. (2001). For general background to crystal engineering approaches from our research group, see: Paz & Khimyak et al. (2002); Paz & Bond et al. (2002); Paz et al. (2003); Paz et al. (2005); Shi et al. (2008). For a description of the graph-set notation for hydrogen-bonded aggregates, see: Grell et al. (1999).

Experimental top

All chemicals were purchased from commercial sources and were used as received without any further purification. An aqueous solution of Cu(NO₃)₂^.3H₂O (Sigma-Aldrich, 0.80 g, 3.3 mmol, 5 ml) was added to a solution of ethylenediamine (Riedel-de Haën, 0.5 ml, 7.3 mmol) in water (5 ml). After 1 min, a deep-violet solution was formed. Slow evaporation of the aqueous solution yielded crystalline plates of [Cu(en)₂(H₂O)₂](NO₃)₂ after 15 days.

An aqueous solution of KOH (Eka, 0.106 g, 1.89 mmol, 10 ml) was added to a suspension of 4-phenylbenzoic acid (Hpb, Sigma-Aldrich, 0.375 g, 0.945 mmol) in water (40 ml). The resulting solution was filtered and added to an aqueous solution of [Cu(en)₂(H₂O)₂](NO₃)₂ (0.228 g, 0.945 mmol, 10 ml). The precipitation of a blue-violet powder was immediate. The slow evaporation of the aqueous solution yielded crystalline needles of the title complex after 60 days.

Selected FT—IR (KBr, cm^-1): ν(NH₂) = 3363s, 3307s, 3216s and 3138m; ν_asym(—COO^-) = 1596vs, 1541vs and 1577vs; 1447m; ν_sym(—COO^-) = 1395vs; 1101m; 1045s; γ(-CH, di-subs. Ph) = 838m and 800m; γ(-CH, mono-subs. Ph) = 751s; 694m; 525m; 461m.

Structure description top

For general background to reactions based on the copper cation, see: Graham et al. (2000); Majumder et al. (2006); Rao et al. (2004); Zhao et al. (2009). For examples of framework-type structures of hybrid materials comprising carboxylate anions, see: Eddaoudi et al. (2001). For general background to crystal engineering approaches from our research group, see: Paz & Khimyak et al. (2002); Paz & Bond et al. (2002); Paz et al. (2003); Paz et al. (2005); Shi et al. (2008). For a description of the graph-set notation for hydrogen-bonded aggregates, see: Grell et al. (1999).

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT-Plus (Bruker, 2005); data reduction: SAINT-Plus (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Perspective views along the (a) [001] and (b) [100] directions of the unit cell of the crystal packing of the title compound. Only the major contribution for the cation and water molecules of crystallisation are represented.
	Fig. 2. Octahedral coordination environments of the Cu centres. Symmetry transformations used to generate equivalent atoms: (i) 1-x, -y, -z.
	Fig. 3. Hydrogen bonding network solely composed by the major component of the title complex. The O—H···O bonds are depicted in violet, and N—H···O bonds are depicted in blue. The organic part of the pb^- ligand has been omitted for clarity. Symmetry operations used to generate equivalent atoms have been omitted for simplicity.

Diaquabis(1,2-ethylenediamine-κ²N,N')copper(II) bis(4-phenylbenzoate) 2.66-hydrate top

Crystal data top

[Cu(C₂H₈N₂)₂(H₂O)₂](C₁₃H₉O₂)₂·2.66H₂O	F(000) = 699
M_r = 662.20	D_x = 1.406 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9591 reflections
a = 6.1466 (6) Å	θ = 3.3–30.5°
b = 34.984 (3) Å	µ = 0.76 mm⁻¹
c = 7.3101 (7) Å	T = 150 K
β = 95.819 (4)°	Needle, violet
V = 1563.8 (3) Å³	0.13 × 0.10 × 0.06 mm
Z = 2

Data collection top

Bruker X8 Kappa CCD APEXII diffractometer	4736 independent reflections
Radiation source: fine-focus sealed tube	3908 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ω/φ scans	θ_max = 30.5°, θ_min = 3.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −8→8
T_min = 0.908, T_max = 0.956	k = −47→49
26073 measured reflections	l = −10→9

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ²(F_o²) + (0.0755P)² + 0.5782P] where P = (F_o² + 2F_c²)/3
4736 reflections	(Δ/σ)_max < 0.001
259 parameters	Δρ_max = 0.52 e Å⁻³
15 restraints	Δρ_min = −0.66 e Å⁻³

Crystal data top

[Cu(C₂H₈N₂)₂(H₂O)₂](C₁₃H₉O₂)₂·2.66H₂O	V = 1563.8 (3) Å³
M_r = 662.20	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.1466 (6) Å	µ = 0.76 mm⁻¹
b = 34.984 (3) Å	T = 150 K
c = 7.3101 (7) Å	0.13 × 0.10 × 0.06 mm
β = 95.819 (4)°

Data collection top

Bruker X8 Kappa CCD APEXII diffractometer	4736 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	3908 reflections with I > 2σ(I)
T_min = 0.908, T_max = 0.956	R_int = 0.034
26073 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	15 restraints
wR(F²) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.52 e Å⁻³
4736 reflections	Δρ_min = −0.66 e Å⁻³
259 parameters

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 > 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	Occ. (<1)
Cu1	0.5000	0.0000	0.0000	0.02840 (11)
N1	0.6260 (4)	0.04498 (6)	0.1479 (3)	0.0285 (4)	0.67
H1A	0.5747	0.0453	0.2618	0.034*	0.67
H1B	0.7761	0.0434	0.1639	0.034*	0.67
N2	0.3249 (4)	0.03936 (6)	−0.1506 (3)	0.0326 (5)	0.67
H2A	0.3829	0.0428	−0.2607	0.039*	0.67
H2B	0.1831	0.0310	−0.1755	0.039*	0.67
C1	0.5555 (4)	0.08119 (5)	0.0418 (3)	0.0337 (4)	0.67
H1C	0.5564	0.1032	0.1272	0.040*	0.67
H1D	0.6583	0.0867	−0.0506	0.040*	0.67
C2	0.3274 (3)	0.07512 (5)	−0.0527 (3)	0.0336 (4)	0.67
H2C	0.2201	0.0744	0.0395	0.040*	0.67
H2D	0.2878	0.0963	−0.1393	0.040*	0.67
N1'	0.6818 (6)	0.04865 (12)	0.0030 (6)	0.0247 (8)	0.33
H1E	0.7995	0.0465	0.0907	0.030*	0.33
H1F	0.7345	0.0518	−0.1095	0.030*	0.33
N2'	0.2445 (6)	0.03581 (11)	−0.0017 (6)	0.0237 (8)	0.33
H2E	0.1326	0.0280	−0.0866	0.028*	0.33
H2F	0.1935	0.0365	0.1123	0.028*	0.33
C1'	0.5555 (4)	0.08119 (5)	0.0418 (3)	0.0337 (4)	0.33
H1G	0.6207	0.1047	−0.0051	0.040*	0.33
H1H	0.5507	0.0839	0.1762	0.040*	0.33
C2'	0.3274 (3)	0.07512 (5)	−0.0527 (3)	0.0336 (4)	0.33
H2G	0.3299	0.0769	−0.1876	0.040*	0.33
H2H	0.2282	0.0952	−0.0139	0.040*	0.33
O1W	0.4441 (9)	−0.00131 (10)	−0.3429 (6)	0.0369 (10)	0.33
H1M	0.467 (14)	0.0206 (7)	−0.415 (6)	0.055*	0.33
H1N	0.473 (14)	−0.0236 (7)	−0.410 (7)	0.055*	0.33
O1	0.3256 (2)	0.42163 (4)	0.1362 (2)	0.0358 (3)
O2	−0.0141 (2)	0.42725 (4)	0.00400 (19)	0.0357 (3)
C3	0.1443 (3)	0.40764 (5)	0.0747 (2)	0.0281 (3)
C4	0.1163 (3)	0.36494 (5)	0.0880 (2)	0.0246 (3)
C5	0.2925 (3)	0.34223 (5)	0.1570 (2)	0.0279 (3)
H5	0.4286	0.3538	0.1973	0.034*
C6	0.2705 (3)	0.30293 (5)	0.1670 (2)	0.0281 (3)
H6	0.3920	0.2879	0.2144	0.034*
C7	0.0717 (3)	0.28509 (4)	0.1083 (2)	0.0236 (3)
C8	−0.1055 (3)	0.30806 (5)	0.0421 (2)	0.0265 (3)
H8	−0.2425	0.2965	0.0035	0.032*
C9	−0.0835 (3)	0.34750 (5)	0.0321 (2)	0.0272 (3)
H9	−0.2052	0.3627	−0.0132	0.033*
C10	0.0507 (3)	0.24284 (4)	0.1143 (2)	0.0245 (3)
C11	0.2192 (3)	0.21931 (5)	0.0648 (3)	0.0288 (3)
H11	0.3483	0.2304	0.0270	0.035*
C12	0.1993 (3)	0.17987 (5)	0.0705 (3)	0.0343 (4)
H12	0.3136	0.1642	0.0343	0.041*
C13	0.0136 (3)	0.16311 (5)	0.1287 (3)	0.0353 (4)
H13	0.0019	0.1361	0.1346	0.042*
C14	−0.1549 (3)	0.18613 (5)	0.1784 (3)	0.0325 (4)
H14	−0.2825	0.1748	0.2182	0.039*
C15	−0.1371 (3)	0.22569 (5)	0.1697 (2)	0.0283 (3)
H15	−0.2541	0.2412	0.2019	0.034*
O2W	0.5759 (3)	0.43249 (6)	0.8469 (2)	0.0544 (5)
H2M	0.716 (3)	0.4273 (15)	0.908 (4)	0.082*	0.67
H2N	0.474 (4)	0.4355 (17)	0.935 (3)	0.082*	0.67
H2O	0.563 (15)	0.4550 (11)	0.918 (8)	0.082*	0.33
H2P	0.510 (14)	0.4117 (13)	0.904 (9)	0.082*	0.33
O3W	0.1809 (3)	−0.00801 (6)	0.2058 (3)	0.0345 (4)	0.67
H3M	0.124 (6)	0.0139 (5)	0.261 (4)	0.052*	0.67
H3N	0.184 (6)	−0.0289 (5)	0.289 (3)	0.052*	0.67
O4W	0.0081 (8)	0.99783 (6)	0.3679 (12)	0.067 (2)	0.33
H4M	0.0656	0.9728	0.3644	0.101*	0.33
H4N	0.1242 (18)	1.01587 (19)	0.377 (17)	0.101*	0.33

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.03755 (18)	0.01744 (15)	0.02768 (18)	0.00265 (10)	−0.00905 (12)	−0.00195 (10)
N1	0.0365 (11)	0.0218 (9)	0.0259 (10)	−0.0002 (8)	−0.0038 (8)	−0.0054 (8)
N2	0.0453 (13)	0.0211 (10)	0.0288 (11)	0.0044 (9)	−0.0085 (9)	−0.0006 (8)
C1	0.0507 (10)	0.0214 (8)	0.0297 (8)	−0.0054 (7)	0.0080 (7)	−0.0036 (6)
C2	0.0462 (10)	0.0230 (8)	0.0325 (9)	0.0091 (7)	0.0081 (8)	0.0035 (7)
N1'	0.0226 (17)	0.027 (2)	0.0234 (19)	−0.0036 (14)	−0.0015 (14)	0.0001 (15)
N2'	0.0203 (17)	0.0252 (18)	0.0253 (19)	−0.0006 (14)	0.0018 (14)	−0.0003 (15)
C1'	0.0507 (10)	0.0214 (8)	0.0297 (8)	−0.0054 (7)	0.0080 (7)	−0.0036 (6)
C2'	0.0462 (10)	0.0230 (8)	0.0325 (9)	0.0091 (7)	0.0081 (8)	0.0035 (7)
O1W	0.065 (3)	0.0230 (18)	0.0216 (18)	−0.0027 (16)	−0.0006 (18)	0.0007 (13)
O1	0.0410 (7)	0.0305 (6)	0.0368 (7)	−0.0123 (5)	0.0081 (6)	−0.0007 (5)
O2	0.0386 (7)	0.0244 (6)	0.0462 (9)	0.0002 (5)	0.0140 (6)	0.0015 (5)
C3	0.0374 (8)	0.0246 (7)	0.0247 (8)	−0.0056 (6)	0.0143 (6)	−0.0024 (6)
C4	0.0303 (7)	0.0227 (7)	0.0219 (7)	−0.0030 (6)	0.0076 (6)	−0.0022 (6)
C5	0.0277 (7)	0.0292 (8)	0.0267 (8)	−0.0051 (6)	0.0015 (6)	−0.0020 (6)
C6	0.0259 (7)	0.0298 (8)	0.0277 (8)	0.0004 (6)	−0.0014 (6)	−0.0001 (6)
C7	0.0263 (7)	0.0232 (7)	0.0211 (7)	−0.0008 (5)	0.0020 (5)	−0.0001 (6)
C8	0.0256 (7)	0.0236 (7)	0.0297 (8)	−0.0031 (6)	0.0004 (6)	0.0004 (6)
C9	0.0278 (7)	0.0245 (7)	0.0293 (8)	0.0001 (6)	0.0036 (6)	0.0009 (6)
C10	0.0291 (7)	0.0233 (7)	0.0203 (7)	−0.0007 (5)	−0.0016 (5)	0.0013 (5)
C11	0.0287 (7)	0.0263 (8)	0.0307 (8)	0.0026 (6)	−0.0006 (6)	0.0022 (6)
C12	0.0352 (9)	0.0266 (8)	0.0392 (10)	0.0074 (6)	−0.0048 (7)	−0.0010 (7)
C13	0.0442 (10)	0.0226 (8)	0.0368 (10)	−0.0002 (7)	−0.0076 (8)	0.0028 (7)
C14	0.0390 (9)	0.0274 (8)	0.0304 (9)	−0.0064 (7)	0.0002 (7)	0.0028 (7)
C15	0.0319 (8)	0.0268 (8)	0.0260 (8)	−0.0016 (6)	0.0028 (6)	−0.0008 (6)
O2W	0.0487 (9)	0.0846 (13)	0.0313 (8)	−0.0280 (9)	0.0115 (6)	−0.0046 (8)
O3W	0.0367 (10)	0.0221 (8)	0.0430 (12)	0.0042 (7)	−0.0037 (9)	−0.0011 (8)
O4W	0.040 (3)	0.028 (2)	0.129 (7)	−0.0058 (17)	−0.009 (3)	0.004 (3)

Geometric parameters (Å, º) top

Cu1—N1	2.019 (2)	C3—C4	1.508 (2)
Cu1—N1'	2.035 (4)	C4—C9	1.395 (2)
Cu1—N2	2.006 (2)	C4—C5	1.395 (2)
Cu1—N2'	2.008 (4)	C5—C6	1.384 (2)
Cu1—O1W	2.496 (4)	C5—H5	0.9500
Cu1—O3W	2.605 (2)	C6—C7	1.400 (2)
Cu1—N2ⁱ	2.006 (2)	C6—H6	0.9500
Cu1—N2'ⁱ	2.008 (4)	C7—C8	1.400 (2)
Cu1—N1ⁱ	2.019 (2)	C7—C10	1.485 (2)
Cu1—N1'ⁱ	2.035 (4)	C8—C9	1.389 (2)
Cu1—O1Wⁱ	2.496 (4)	C8—H8	0.9500
Cu1—O3Wⁱ	2.605 (2)	C9—H9	0.9500
N1—C1	1.525 (3)	C10—C15	1.397 (2)
N1—H1A	0.9200	C10—C11	1.399 (2)
N1—H1B	0.9200	C11—C12	1.386 (2)
N2—C2	1.441 (3)	C11—H11	0.9500
N2—H2A	0.9200	C12—C13	1.388 (3)
N2—H2B	0.9200	C12—H12	0.9500
C1—C2	1.514 (3)	C13—C14	1.389 (3)
C1—H1C	0.9900	C13—H13	0.9500
C1—H1D	0.9900	C14—C15	1.390 (2)
C2—H2C	0.9900	C14—H14	0.9500
C2—H2D	0.9900	C15—H15	0.9500
N1'—H1E	0.9200	O2W—H2M	0.9500 (11)
N1'—H1F	0.9200	O2W—H2N	0.9500 (10)
N2'—H2E	0.9200	O2W—H2O	0.9500 (11)
N2'—H2F	0.9200	O2W—H2P	0.9500 (12)
O1W—H1M	0.9500 (10)	O3W—H3M	0.9499 (10)
O1W—H1N	0.9500 (10)	O3W—H3N	0.9500 (10)
O1—C3	1.258 (2)	O4W—H4M	0.9457
O2—C3	1.258 (2)	O4W—H4N	0.950 (2)

N2—Cu1—N1	85.08 (9)	H2A—N2—H2B	108.1
N2—Cu1—N1ⁱ	94.92 (9)	C2—C1—N1	108.52 (15)
N2'—Cu1—N1'	84.65 (15)	C2—C1—Cu1	73.63 (9)
N2'—Cu1—N1'ⁱ	95.35 (15)	C2—C1—H1C	110.0
N1'—Cu1—O1W	92.62 (15)	N1—C1—H1C	110.0
N1'—Cu1—O1Wⁱ	87.38 (15)	Cu1—C1—H1C	145.9
N2ⁱ—Cu1—N2	180.00 (9)	C2—C1—H1D	110.0
N2ⁱ—Cu1—N2'ⁱ	36.18 (14)	N1—C1—H1D	110.0
N2—Cu1—N2'ⁱ	143.82 (14)	Cu1—C1—H1D	101.4
N2ⁱ—Cu1—N2'	143.82 (14)	H1C—C1—H1D	108.4
N2—Cu1—N2'	36.18 (14)	N2—C2—C1	108.13 (16)
N2'ⁱ—Cu1—N2'	180.0 (3)	C1—C2—Cu1	75.67 (9)
N2ⁱ—Cu1—N1ⁱ	85.08 (9)	N2—C2—H2C	110.1
N2'ⁱ—Cu1—N1ⁱ	76.97 (13)	C1—C2—H2C	110.1
N2'—Cu1—N1ⁱ	103.03 (13)	Cu1—C2—H2C	98.7
N2ⁱ—Cu1—N1	94.92 (9)	N2—C2—H2D	110.1
N2'ⁱ—Cu1—N1	103.03 (13)	C1—C2—H2D	110.1
N2'—Cu1—N1	76.97 (13)	Cu1—C2—H2D	147.5
N1ⁱ—Cu1—N1	180.00 (14)	H2C—C2—H2D	108.4
N2ⁱ—Cu1—N1'ⁱ	72.26 (13)	Cu1—N1'—H1E	109.4
N2—Cu1—N1'ⁱ	107.74 (13)	Cu1—N1'—H1F	109.4
N2'ⁱ—Cu1—N1'ⁱ	84.65 (15)	H1E—N1'—H1F	108.0
N1ⁱ—Cu1—N1'ⁱ	33.06 (14)	Cu1—N2'—H2E	110.4
N1—Cu1—N1'ⁱ	146.94 (14)	Cu1—N2'—H2F	110.4
N2ⁱ—Cu1—N1'	107.74 (13)	H2E—N2'—H2F	108.6
N2—Cu1—N1'	72.26 (13)	Cu1—O1W—H1M	122 (3)
N2'ⁱ—Cu1—N1'	95.35 (15)	Cu1—O1W—H1N	121 (4)
N1ⁱ—Cu1—N1'	146.94 (14)	H1M—O1W—H1N	109.34 (16)
N1—Cu1—N1'	33.06 (14)	O2—C3—O1	123.74 (16)
N1'ⁱ—Cu1—N1'	180.00 (13)	O2—C3—C4	118.56 (15)
N2ⁱ—Cu1—O1Wⁱ	56.63 (12)	O1—C3—C4	117.70 (16)
N2—Cu1—O1Wⁱ	123.37 (12)	C9—C4—C5	119.00 (15)
N2'ⁱ—Cu1—O1Wⁱ	88.69 (17)	C9—C4—C3	121.13 (15)
N2'—Cu1—O1Wⁱ	91.31 (17)	C5—C4—C3	119.86 (15)
N1ⁱ—Cu1—O1Wⁱ	123.96 (11)	C6—C5—C4	120.56 (15)
N1—Cu1—O1Wⁱ	56.04 (11)	C6—C5—H5	119.7
N1'ⁱ—Cu1—O1Wⁱ	92.62 (15)	C4—C5—H5	119.7
N2ⁱ—Cu1—O1W	123.37 (12)	C5—C6—C7	120.87 (15)
N2—Cu1—O1W	56.63 (12)	C5—C6—H6	119.6
N2'ⁱ—Cu1—O1W	91.31 (17)	C7—C6—H6	119.6
N2'—Cu1—O1W	88.69 (17)	C8—C7—C6	118.33 (15)
N1ⁱ—Cu1—O1W	56.04 (11)	C8—C7—C10	120.99 (14)
N1—Cu1—O1W	123.96 (11)	C6—C7—C10	120.68 (14)
N1'ⁱ—Cu1—O1W	87.38 (15)	C9—C8—C7	120.77 (15)
O1Wⁱ—Cu1—O1W	180.0	C9—C8—H8	119.6
N2ⁱ—Cu1—O3W	90.15 (9)	C7—C8—H8	119.6
N2—Cu1—O3W	89.85 (9)	C8—C9—C4	120.45 (15)
N2'ⁱ—Cu1—O3W	124.30 (13)	C8—C9—H9	119.8
N2'—Cu1—O3W	55.70 (13)	C4—C9—H9	119.8
N1ⁱ—Cu1—O3W	87.42 (8)	C15—C10—C11	118.51 (15)
N1—Cu1—O3W	92.58 (8)	C15—C10—C7	120.86 (15)
N1'ⁱ—Cu1—O3W	58.09 (13)	C11—C10—C7	120.64 (15)
N1'—Cu1—O3W	121.91 (13)	C12—C11—C10	120.55 (17)
O1Wⁱ—Cu1—O3W	57.13 (13)	C12—C11—H11	119.7
O1W—Cu1—O3W	122.87 (13)	C10—C11—H11	119.7
N2ⁱ—Cu1—O3Wⁱ	89.85 (9)	C11—C12—C13	120.49 (17)
N2—Cu1—O3Wⁱ	90.15 (9)	C11—C12—H12	119.8
N2'ⁱ—Cu1—O3Wⁱ	55.70 (13)	C13—C12—H12	119.8
N2'—Cu1—O3Wⁱ	124.30 (13)	C12—C13—C14	119.58 (16)
N1ⁱ—Cu1—O3Wⁱ	92.58 (8)	C12—C13—H13	120.2
N1—Cu1—O3Wⁱ	87.42 (8)	C14—C13—H13	120.2
N1'ⁱ—Cu1—O3Wⁱ	121.91 (13)	C13—C14—C15	120.06 (17)
N1'—Cu1—O3Wⁱ	58.09 (13)	C13—C14—H14	120.0
O1Wⁱ—Cu1—O3Wⁱ	122.87 (13)	C15—C14—H14	120.0
O1W—Cu1—O3Wⁱ	57.13 (13)	C14—C15—C10	120.80 (16)
O3W—Cu1—O3Wⁱ	180.00 (5)	C14—C15—H15	119.6
C1—N1—Cu1	107.53 (14)	C10—C15—H15	119.6
C1—N1—H1A	110.2	H2M—O2W—H2N	109.33 (16)
Cu1—N1—H1A	110.2	H2M—O2W—H2O	91 (6)
C1—N1—H1B	110.2	H2N—O2W—H2O	56 (4)
Cu1—N1—H1B	110.2	H2M—O2W—H2P	93 (6)
H1A—N1—H1B	108.5	H2N—O2W—H2P	56 (4)
C2—N2—Cu1	110.19 (15)	H2O—O2W—H2P	109.33 (17)
C2—N2—H2A	109.6	Cu1—O3W—H3M	119 (2)
Cu1—N2—H2A	109.6	Cu1—O3W—H3N	119 (2)
C2—N2—H2B	109.6	H3M—O3W—H3N	109.33 (16)
Cu1—N2—H2B	109.6	H4M—O4W—H4N	109.7

N2ⁱ—Cu1—N1—C1	168.87 (15)	N2'ⁱ—Cu1—C2—N2	102.4 (3)
N2—Cu1—N1—C1	−11.13 (15)	N2'—Cu1—C2—N2	−77.6 (3)
N2'ⁱ—Cu1—N1—C1	133.12 (18)	N1ⁱ—Cu1—C2—N2	−19.2 (2)
N2'—Cu1—N1—C1	−46.88 (18)	N1—Cu1—C2—N2	160.8 (2)
N1'ⁱ—Cu1—N1—C1	−126.5 (2)	N1'ⁱ—Cu1—C2—N2	−59.0 (2)
N1'—Cu1—N1—C1	53.5 (2)	N1'—Cu1—C2—N2	121.0 (2)
O1Wⁱ—Cu1—N1—C1	−147.5 (2)	O1Wⁱ—Cu1—C2—N2	−157.5 (2)
O1W—Cu1—N1—C1	32.5 (2)	O1W—Cu1—C2—N2	22.5 (2)
O3W—Cu1—N1—C1	−100.76 (15)	O3W—Cu1—C2—N2	−102.02 (19)
O3Wⁱ—Cu1—N1—C1	79.24 (15)	O3Wⁱ—Cu1—C2—N2	77.98 (19)
N2'ⁱ—Cu1—N2—C2	−121.7 (2)	N2ⁱ—Cu1—C2—C1	39.2 (2)
N2'—Cu1—N2—C2	58.3 (2)	N2—Cu1—C2—C1	−140.8 (2)
N1ⁱ—Cu1—N2—C2	163.71 (18)	N2'ⁱ—Cu1—C2—C1	−38.4 (3)
N1—Cu1—N2—C2	−16.29 (18)	N2'—Cu1—C2—C1	141.6 (3)
N1'ⁱ—Cu1—N2—C2	132.5 (2)	N1ⁱ—Cu1—C2—C1	−160.01 (12)
N1'—Cu1—N2—C2	−47.5 (2)	N1—Cu1—C2—C1	19.99 (12)
O1Wⁱ—Cu1—N2—C2	27.0 (3)	N1'ⁱ—Cu1—C2—C1	160.24 (18)
O1W—Cu1—N2—C2	−153.0 (3)	N1'—Cu1—C2—C1	−19.76 (18)
O3W—Cu1—N2—C2	76.31 (18)	O1Wⁱ—Cu1—C2—C1	61.70 (16)
O3Wⁱ—Cu1—N2—C2	−103.69 (18)	O1W—Cu1—C2—C1	−118.30 (16)
Cu1—N1—C1—C2	35.43 (19)	O3W—Cu1—C2—C1	117.21 (12)
N2ⁱ—Cu1—C1—C2	−158.57 (13)	O3Wⁱ—Cu1—C2—C1	−62.79 (12)
N2—Cu1—C1—C2	21.43 (13)	O2—C3—C4—C9	−3.1 (2)
N2'ⁱ—Cu1—C1—C2	157.87 (17)	O1—C3—C4—C9	176.50 (16)
N2'—Cu1—C1—C2	−22.13 (17)	O2—C3—C4—C5	176.68 (16)
N1ⁱ—Cu1—C1—C2	35.0 (2)	O1—C3—C4—C5	−3.7 (2)
N1—Cu1—C1—C2	−145.0 (2)	C9—C4—C5—C6	1.0 (3)
N1'ⁱ—Cu1—C1—C2	−36.8 (3)	C3—C4—C5—C6	−178.83 (15)
N1'—Cu1—C1—C2	143.2 (3)	C4—C5—C6—C7	0.0 (3)
O1Wⁱ—Cu1—C1—C2	−118.33 (16)	C5—C6—C7—C8	−1.1 (3)
O1W—Cu1—C1—C2	61.67 (16)	C5—C6—C7—C10	178.21 (16)
O3W—Cu1—C1—C2	−63.05 (12)	C6—C7—C8—C9	1.0 (3)
O3Wⁱ—Cu1—C1—C2	116.95 (12)	C10—C7—C8—C9	−178.23 (16)
N2ⁱ—Cu1—C1—N1	−13.52 (19)	C7—C8—C9—C4	0.0 (3)
N2—Cu1—C1—N1	166.48 (19)	C5—C4—C9—C8	−1.0 (3)
N2'ⁱ—Cu1—C1—N1	−57.1 (2)	C3—C4—C9—C8	178.81 (16)
N2'—Cu1—C1—N1	122.9 (2)	C8—C7—C10—C15	−41.2 (2)
N1ⁱ—Cu1—C1—N1	180.0	C6—C7—C10—C15	139.60 (17)
N1'ⁱ—Cu1—C1—N1	108.2 (3)	C8—C7—C10—C11	138.95 (17)
N1'—Cu1—C1—N1	−71.8 (3)	C6—C7—C10—C11	−40.3 (2)
O1Wⁱ—Cu1—C1—N1	26.7 (2)	C15—C10—C11—C12	0.1 (2)
O1W—Cu1—C1—N1	−153.3 (2)	C7—C10—C11—C12	−179.99 (16)
O3W—Cu1—C1—N1	81.99 (16)	C10—C11—C12—C13	−1.2 (3)
O3Wⁱ—Cu1—C1—N1	−98.01 (16)	C11—C12—C13—C14	1.2 (3)
Cu1—N2—C2—C1	40.1 (2)	C12—C13—C14—C15	0.0 (3)
N1—C1—C2—N2	−50.0 (2)	C13—C14—C15—C10	−1.1 (3)
Cu1—C1—C2—N2	−26.13 (15)	C11—C10—C15—C14	1.0 (2)
N1—C1—C2—Cu1	−23.88 (13)	C7—C10—C15—C14	−178.88 (16)
N2ⁱ—Cu1—C2—N2	180.0

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱⁱ	0.92	2.13	2.986 (3)	154
N1—H1B···O2Wⁱⁱⁱ	0.92	2.32	3.093 (3)	141
N2—H2A···O2ⁱⁱⁱ	0.92	2.16	3.037 (3)	158
N1′—H1E···O2Wⁱⁱⁱ	0.92	2.51	3.375 (4)	157
N1′—H1F···O1ⁱⁱⁱ	0.92	2.20	3.087 (5)	161
N2′—H2E···O4W^iv	0.92	2.33	3.181 (9)	154
N2′—H2F···O2W^v	0.92	2.21	3.055 (5)	152
O1W—H1M···O2ⁱⁱⁱ	0.95 (1)	1.92 (1)	2.844 (4)	163 (4)
O1W—H1N···O2^vi	0.95 (1)	1.88 (1)	2.814 (4)	169 (4)
O2W—H2M···O2^vii	0.95 (1)	1.73 (1)	2.668 (2)	168 (5)
O2W—H2N···O1^viii	0.95 (1)	1.87 (2)	2.765 (2)	156 (5)
O3W—H3M···O2W^v	0.95 (1)	2.01 (1)	2.932 (3)	163 (3)
O3W—H3N···O1^ix	0.95 (1)	1.82 (1)	2.721 (3)	158 (3)
O4W—H4M···O1^x	0.95 (1)	1.91	2.8562 (17)	178

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

Experimental details

Crystal data
Chemical formula	[Cu(C₂H₈N₂)₂(H₂O)₂](C₁₃H₉O₂)₂·2.66H₂O
M_r	662.20
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	150
a, b, c (Å)	6.1466 (6), 34.984 (3), 7.3101 (7)
β (°)	95.819 (4)
V (Å³)	1563.8 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.76
Crystal size (mm)	0.13 × 0.10 × 0.06

Data collection
Diffractometer	Bruker X8 Kappa CCD APEXII
Absorption correction	Multi-scan (SADABS; Sheldrick, 1997)
T_min, T_max	0.908, 0.956
No. of measured, independent and observed [I > 2σ(I)] reflections	26073, 4736, 3908
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.714

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.137, 1.10
No. of reflections	4736
No. of parameters	259
No. of restraints	15
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.66

Computer programs: APEX2 (Bruker, 2006), SAINT-Plus (Bruker, 2005), SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 2006).

Selected geometric parameters (Å, º) top

Cu1—N1	2.019 (2)	Cu1—N2'	2.008 (4)
Cu1—N1'	2.035 (4)	Cu1—O1W	2.496 (4)
Cu1—N2	2.006 (2)	Cu1—O3W	2.605 (2)

N2—Cu1—N1	85.08 (9)	N1'—Cu1—O1Wⁱ	87.38 (15)
N2—Cu1—N1ⁱ	94.92 (9)	N2'ⁱ—Cu1—O1Wⁱ	88.69 (17)
N2'—Cu1—N1'	84.65 (15)	N2—Cu1—O3W	89.85 (9)
N2'—Cu1—N1'ⁱ	95.35 (15)	N1ⁱ—Cu1—O3W	87.42 (8)

C6—C7—C10—C11	−40.3 (2)

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱⁱ	0.92	2.13	2.986 (3)	154
N1—H1B···O2Wⁱⁱⁱ	0.92	2.32	3.093 (3)	141
N2—H2A···O2ⁱⁱⁱ	0.92	2.16	3.037 (3)	158
N1'—H1E···O2Wⁱⁱⁱ	0.92	2.51	3.375 (4)	157
N1'—H1F···O1ⁱⁱⁱ	0.92	2.20	3.087 (5)	161
N2'—H2E···O4W^iv	0.92	2.33	3.181 (9)	154
N2'—H2F···O2W^v	0.92	2.21	3.055 (5)	152
O1W—H1M···O2ⁱⁱⁱ	0.95 (1)	1.924 (13)	2.844 (4)	163 (4)
O1W—H1N···O2^vi	0.95 (1)	1.876 (9)	2.814 (4)	169 (4)
O2W—H2M···O2^vii	0.95 (1)	1.731 (10)	2.668 (2)	168 (5)
O2W—H2N···O1^viii	0.95 (1)	1.87 (2)	2.765 (2)	156 (5)
O3W—H3M···O2W^v	0.95 (1)	2.009 (10)	2.932 (3)	163 (3)
O3W—H3N···O1^ix	0.95 (1)	1.818 (12)	2.721 (3)	158 (3)
O4W—H4M···O1^x	0.95 (1)	1.91	2.8562 (17)	178

Acknowledgements

We are grateful to the Fundação para a Ciência e a Tecnologia (FCT, Portugal) for their general financial support (R&D projects PTDC/QUI/65805/2006 and PDTC/QUI/69302/2006), for a post-doctoral research grant (under the former project), for the PhD grant SFRH/BD46601/2008, and also for specific funding toward the purchase of the single-crystal diffractometer.

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