trans-Diaqua­bis(ethyl­enediamine-κ2N,N′)copper(II) bis[3-(3-pyrid­yl)propionate] dihydrate

Moncol, J.; Segľa, P.; Mikloš, D.; Fischer, A.; Marian, K.

doi:10.1107/S1600536808005400

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 4| April 2008| Pages m509-m510

doi:10.1107/S1600536808005400

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trans-Diaquabis(ethylenediamine-κ²N,N′)copper(II) bis[3-(3-pyridyl)propionate] dihydrate

Jan Moncol,^a ^* Peter Segľa,^a Dušan Mikloš,^a Andreas Fischer ^b and Koman Marian ^a

^aDepartment of Inorganic Chemistry, Slovak Technical University, Radlinského 9, SK-812 37 Bratislava, Slovakia, and ^bInorganic Chemistry, Royal Institute of Technology, 100 44 Stockholm, Sweden
^*Correspondence e-mail: jan.moncol@stuba.sk

(Received 11 February 2008; accepted 26 February 2008; online 5 March 2008)

The asymmetric unit of the title complex, [Cu(C₂H₈N₂)₂(H₂O)₂](C₈H₈NO₂)₂·2H₂O, contains one anion, one half-cation and one water molecule. The Cu^II atom in the [Cu(en)₂(H₂O)₂]²⁺ cation (en is ethylenediamine) lies on an inversion centre. The four N atoms of the en ligands in the equatorial plane around the Cu^II atom form a slightly distorted square-planar arrangement, while the slightly distorted Jahn–Teller octahedral coordination is completed by two water O atoms in axial positions. In the crystal structure, intra- and intermolecular N—H⋯O and O—H⋯O hydrogen bonds form a three-dimensional network.

Related literature

For general background, see: Hathaway & Hodgson (1973 ); Bernstein et al. (1995 ); Janiak (2000 ); Jeffrey (1997 ). For similar structures, see: Jašková et al. (2007 ); Miminoshvili et al. (2005 ); Carballo et al. (2005 ); Segla et al. (2000 ); Liu et al. (2004 ); Sharma et al. (2005 ); Anacona et al. (2002 ); Emsley et al. (1988 , 1990 ); Li et al. (2005 ); Gonzalez-Alvarez et al. (2003 ); Lee et al. (2005 ); Mahadevan et al. (1986 ); Kovbasyuk et al. (1997 ); Harrison et al. (2007 ).

Experimental

Crystal data

[Cu(C₂H₈N₂)₂(H₂O)₂](C₈H₈NO₂)₂·2H₂O
M_r = 556.13
Triclinic, $[P \overline 1]$
a = 6.2620 (1) Å
b = 8.5660 (2) Å
c = 13.3550 (4) Å
α = 75.271 (1)°
β = 83.809 (1)°
γ = 70.863 (1)°
V = 654.30 (3) Å³
Z = 1
Ag Kα radiation
μ = 0.47 mm⁻¹
T = 153 (2) K
0.45 × 0.25 × 0.20 mm

Data collection

Bruker–Nonius KappaCCD diffractometer
Absorption correction: numerical (HABITUS; Herrendorf & Bärnighausen, 1997 ) T_min = 0.808, T_max = 0.915
15039 measured reflections
2989 independent reflections
2644 reflections with I > 2σ(I)
R_int = 0.079

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.086
S = 1.07
2989 reflections
160 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱ	0.92	2.32	3.130 (3)	147
N1—H1A⋯O1ⁱ	0.92	2.41	3.247 (2)	152
N1—H1B⋯O2W	0.92	2.11	2.944 (3)	151
N2—H2A⋯O1ⁱⁱ	0.92	2.29	3.150 (3)	155
N2—H2B⋯O1	0.92	2.12	3.019 (2)	164
O1W—H1W⋯O2ⁱ	0.84	2.06	2.873 (3)	164
O1W—H2W⋯O1	0.84	2.00	2.814 (2)	164
O2W—H3W⋯N3ⁱⁱⁱ	0.84	2.08	2.899 (3)	163
O2W—H4W⋯O2^iv	0.84	2.03	2.859 (3)	169
Symmetry codes: (i) x+1, y, z; (ii) -x, -y+1, -z+1; (iii) x+1, y, z-1; (iv) -x, -y+2, -z+1.

Data collection: KappaCCD Software (Nonius, 1997 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: enCIFer (Allen et al., 2004 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808005400/hk2427sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808005400/hk2427Isup2.hkl

checkCIF report

Comment top

It is well known that copper(II) complexes having ethylenediamine (en) ligands show flexible coordination environment and adopt semi-coordation with tetragonal distortion. As part of our efforts to investigate metal(II) complexes based on pyridyl-carboxylic acids, we report herein the crystal structure of the title compound, (I).

The asymmetric unit of (I), (Fig. 1), contains one anion, one half-cation and one water molecule. The Cu^II atom in the centrosymmetric [Cu(en)₂(H₂O)₂]²⁺ cation lies on the inversion centre. The four N atoms of the ethylenediamine ligands in the equatorial plane around the Cu^II atom form a slightly distorted square-planar arrangement, while the slightly distorted Jahn-Teller octahedral coordination is completed by the two O atoms of water molecules in the axial positions (Table 1 and Fig. 1).

The Cu—N1 [2.015 (2) Å] and Cu—N2 [2.022 (2) Å] bond lengths and N1—Cu—N2 [84.91 (7)°] bond angle agree with those found in other [Cu(en)₂(H₂O)₂]²⁺ complexes (Table 1). The Cu—O1W [2.503 (2) Å] bond is much longer than Cu—N bonds, as a result of the Jahn-Teller distortion. The Cu—OW bonds in other [Cu(en)₂(H₂O)₂]²⁺ complexes are in the range of 2.416 (3)–2.693 (9) Å (Table 1). The value of the T parameter (Hathaway & Hodgson, 1973), which indicates the degree of tetragonal distortion about the Cu^II atom, is 0.81 and it agrees with the reported values, in the range of 0.76–0.84, for other [Cu(en)₂(H₂O)₂]²⁺ complexes (Table 1).

In the crystal structure, the [Cu(en)₂(H₂O)₂]²⁺ coordination cations and 3-(3-pyridyl)propionate anions are linked by O—H···O and N—H···O hydrogen-bonds (Table 2, Fig. 2) in parallel to the a axis. The amine H atom is linked to both carboxylate O atoms of 3-(3-pyridyl)propionate by three-centered/bifurcated N—H···O hydrogen-bonds (Jeffrey, 1997) and both of them form the R₁²(4) ring motif (Bernstein et al., 1995). The similar R₁²(4) ring motifs with sulfonate or carboxylate groups are reported in[Cu(en)₂(H₂O)₂](4-amino- naphthalene-1-sulfonate)₂.2 H₂O (Li et al., 2005)and [Cu(en)₂(H₂O)₂]- (N-carboxyglycinate).H₂O (Kovbasyuk et al., 1997).

The O—H···O hydrogen bonds between the coordinated water molecules and the carboxylate O atoms of 3-(3-pyridyl)propionate anions and N—H···O hydrogen bonds of amine H atoms form the R₂¹(6) and R₂²(8) ring motifs (Bernstein et al., 1995). These ring motifs are also reported for other [Cu(en)₂(H₂O)₂]X₂ complexes, while only the R₂²(8) ring motifs are present in [Cu(en)₂(H₂O)₂]X₂ complexes, [where X = 4-chlorobenzoate (Lee et al., 2005); X = 4-fluorobenzoate (Liu et al., 2004), X = isonicotinate (Segla et al., 2000) and X = 4-nitrobenzoate (Harrison et al., 2007)]. On the other hand, the R₂¹(6) ring motifs are reported for [Cu(en)₂(H₂O)₂]X₂ complexes, [where X = naphthalene-2-sulfonate (Sharma et al., 2005) and X = 2,6-dimethoxynicotinate (Jašková et al., 2007)]. To the best of our knowledge, only [Cu(en)₂(H₂O)₂](2-aminobenzoate)₂ complex (Miminoshvili et al., 2005), exhibits both R₂¹(6) and R₂²(8) ring motifs, in the crystal structure.

The additional N—H···O hydrogen bonds form further R₂¹(6) ring motifs. Finally, two [Cu(en)₂(H₂O)₂]²⁺ cations and two 3-(3-pyridyl)propionate anions are joined through R₄²(8) ring motifs to form a layer parallel to the a axis. The layers of [Cu(en)₂(H₂O)₂]²⁺ cations and 3-(3-pyridyl)- propionate anions are linked to form a three-dimensional network through uncoordinated water molecules by O—H···O and O—H···N hydrogen-bonds (Fig. 3).

The additional interactions between the 3-(3-pyridyl)propionate anions of (I) are the π-π stacking interactions (Janiak, 2000) between the two adjacent pyridine rings, (N3/C6—C10), with the centroid to centroid distances of C_g···C_g^v = 3.66 Å [symmetry code: (v) -x,-y + 2,-z + 2]. The distance between parallel planes of the stacked pyridine rings is 3.33 Å.

Related literature top

For general background, see: Hathaway & Hodgson (1973); Bernstein et al. (1995); Janiak (2000); Jeffrey (1997). For similar structures, see: Jašková et al. (2007); Miminoshvili et al. (2005); Carballo et al. (2005); Segla et al. (2000); Liu et al. (2004); Sharma et al. (2005); Anacona et al. (2002); Emsley et al. (1988, 1990); Li et al. (2005); Gonzalez-Alvarez et al. (2003); Lee et al. (2005); Mahadevan et al. (1986); Kovbasyuk et al. (1997); Harrison et al. (2007).

Experimental top

The violet [Cu(en)₂(H₂O)₂](3-pypr)₂.2H₂O was formed in a methanolic solution of [Cu(3-pypr)₂(H₂O)₂] (1.25 mmol) by adding ethylenediamine in the molar ratio of 1:2. The resulting solution was left to slowly evaporate at room temperature. In isolating the complex, it was necessary to add acetone to the concentrated solution. Well shaped violet crystals, suitable for X-ray structure analysis were collected after a few hours by filtration and finally dried in vacuo (yield; 90%). Anal. Calc. for C₂₀H₄₀N₆O₈; C, 43.20; H, 7.25; N, 15.11; Cu, 11.43. Found: C, 43.45; H, 7.47; N, 15.30; Cu, 11.21%. Selected IR data (cm^-1): 1592 versus,br (ν_a(COO^-) + ν(C?N)); 1392 versus (ν_s(COO^-)); 605 s (δ(py), pyridine ring in-plane bending); 405 m (γ(py), pyridine ring out-of-plane bending). Electronic data (cm^-1): 18 400 br.

Computing details top

Data collection: KappaCCD Software (Nonius, 1997); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: enCIFer (Allen et al., 2004).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Part of the crystal structure of (I), showing the formation of R²₁(4), R¹₂(6), R²₄(8) and R²₂(8) motifs [symmetry codes: (i) x + 1, y, z; (ii) -x, -y + 1, -z + 1].
	Fig. 3. A packing diagram of (I), showing hydrogen bonds and π-π stacking interactions, as dashed lines [symmetry codes: (iii) x + 1, y, z - 1; (iv) -x, -y + 2, -z + 1].

trans-Diaquabis(ethylenediamine-κ²N,N')copper(II) bis[3-(3-pyridyl)propionate] dihydrate top

Crystal data top

[Cu(C₂H₈N₂)₂(H₂O)₂](C₈H₈NO₂)₂·2H₂O	Z = 1
M_r = 556.13	F(000) = 295
Triclinic, P1	D_x = 1.411 Mg m⁻³
Hall symbol: -P 1	Ag Kα radiation, λ = 0.56085 Å
a = 6.2620 (1) Å	Cell parameters from 2489 reflections
b = 8.5660 (2) Å	θ = 3.3–21.4°
c = 13.3550 (4) Å	µ = 0.47 mm⁻¹
α = 75.271 (1)°	T = 153 K
β = 83.809 (1)°	Prism, violet
γ = 70.863 (1)°	0.45 × 0.25 × 0.20 mm
V = 654.30 (3) Å³

Data collection top

Bruker–Nonius KappaCCD diffractometer	2989 independent reflections
Radiation source: fine-focus sealed tube	2644 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.079
ω and ϕ scans	θ_max = 21.4°, θ_min = 3.3°
Absorption correction: numerical (HABITUS; Herrendorf & Bärnighausen, 1997)	h = −8→8
T_min = 0.808, T_max = 0.915	k = −11→11
15039 measured reflections	l = −17→17

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) = 0.086	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0215P)² + 0.3896P] where P = (F_o² + 2F_c²)/3
2989 reflections	(Δ/σ)_max < 0.001
160 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

[Cu(C₂H₈N₂)₂(H₂O)₂](C₈H₈NO₂)₂·2H₂O	γ = 70.863 (1)°
M_r = 556.13	V = 654.30 (3) Å³
Triclinic, P1	Z = 1
a = 6.2620 (1) Å	Ag Kα radiation, λ = 0.56085 Å
b = 8.5660 (2) Å	µ = 0.47 mm⁻¹
c = 13.3550 (4) Å	T = 153 K
α = 75.271 (1)°	0.45 × 0.25 × 0.20 mm
β = 83.809 (1)°

Data collection top

Bruker–Nonius KappaCCD diffractometer	2989 independent reflections
Absorption correction: numerical (HABITUS; Herrendorf & Bärnighausen, 1997)	2644 reflections with I > 2σ(I)
T_min = 0.808, T_max = 0.915	R_int = 0.079
15039 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.086	H-atom parameters constrained
S = 1.07	Δρ_max = 0.38 e Å⁻³
2989 reflections	Δρ_min = −0.31 e Å⁻³
160 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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

2.3086 (0.0059) x + 8.2273 (0.0023) y - 0.2376 (0.0130) z = 6.3254 (0.0154)

* 0.0032 (0.0016) N3

* -0.0044 (0.0016) C6

* 0.0010 (0.0017) C7

* -0.0039 (0.0017) C8

* 0.0003 (0.0018) C9

* 0.0038 (0.0017) C10

3.3255 (0.0028) N3_$6

3.3331 (0.0028) C6_$6

3.3277 (0.0030) C7_$6

3.3326 (0.0031) C8_$6

3.3285 (0.0029) C9_$6

3.3249 (0.0030) C10_$6

Rms deviation of fitted atoms = 0.0032

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
Cu	0.5000	0.5000	0.5000	0.02500 (12)
N1	0.5413 (3)	0.7274 (2)	0.48893 (14)	0.0328 (4)
H1A	0.6147	0.7242	0.5459	0.039*
H1B	0.6270	0.7540	0.4306	0.039*
N2	0.1813 (3)	0.6372 (2)	0.45504 (14)	0.0307 (4)
H2A	0.1410	0.5969	0.4047	0.037*
H2B	0.0813	0.6297	0.5104	0.037*
N3	−0.0294 (4)	0.8099 (3)	1.12361 (17)	0.0520 (6)
O1	−0.0720 (3)	0.6040 (3)	0.66095 (13)	0.0493 (5)
O2	−0.4121 (3)	0.7310 (2)	0.71927 (15)	0.0518 (5)
O1W	0.3984 (3)	0.4843 (2)	0.68797 (15)	0.0515 (5)
H1W	0.4422	0.5531	0.7088	0.063*
H2W	0.2570	0.5084	0.6916	0.063*
O2W	0.6770 (4)	0.9227 (3)	0.29173 (16)	0.0682 (6)
H3W	0.7363	0.8948	0.2368	0.063*
H4W	0.6086	1.0274	0.2809	0.063*
C1	0.1767 (4)	0.8158 (3)	0.41381 (19)	0.0399 (5)
H1C	0.0192	0.8928	0.4130	0.048*
H1D	0.2402	0.8312	0.3421	0.048*
C2	0.3163 (4)	0.8558 (3)	0.4831 (2)	0.0399 (5)
H2C	0.3294	0.9709	0.4542	0.048*
H2D	0.2442	0.8520	0.5530	0.048*
C3	−0.2033 (4)	0.6638 (3)	0.72904 (17)	0.0339 (5)
C4	−0.1063 (4)	0.6478 (3)	0.83208 (19)	0.0418 (5)
H4A	−0.2050	0.6083	0.8890	0.050*
H4B	0.0448	0.5608	0.8387	0.050*
C5	−0.0846 (6)	0.8114 (3)	0.8436 (2)	0.0575 (8)
H5A	−0.2360	0.8978	0.8392	0.069*
H5B	0.0113	0.8527	0.7860	0.069*
C6	0.0179 (4)	0.7906 (3)	0.94565 (19)	0.0389 (5)
C7	−0.1118 (4)	0.8301 (3)	1.0313 (2)	0.0458 (6)
H7	−0.2711	0.8749	1.0242	0.055*
C8	0.1937 (5)	0.7467 (3)	1.1312 (2)	0.0507 (7)
H8	0.2567	0.7298	1.1962	0.061*
C9	0.3376 (4)	0.7045 (3)	1.0513 (2)	0.0460 (6)
H9	0.4963	0.6603	1.0606	0.055*
C10	0.2489 (4)	0.7271 (3)	0.95738 (19)	0.0417 (5)
H10	0.3462	0.6992	0.9005	0.050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu	0.02142 (18)	0.02502 (19)	0.0296 (2)	−0.00597 (13)	−0.00336 (13)	−0.00873 (14)
N1	0.0370 (10)	0.0319 (10)	0.0332 (10)	−0.0132 (8)	−0.0058 (8)	−0.0086 (8)
N2	0.0266 (8)	0.0378 (10)	0.0292 (9)	−0.0082 (7)	−0.0023 (7)	−0.0121 (8)
N3	0.0777 (16)	0.0397 (12)	0.0397 (13)	−0.0190 (11)	0.0090 (11)	−0.0145 (10)
O1	0.0421 (9)	0.0819 (14)	0.0342 (9)	−0.0235 (9)	0.0035 (7)	−0.0280 (9)
O2	0.0401 (9)	0.0620 (12)	0.0555 (12)	−0.0036 (8)	−0.0106 (8)	−0.0300 (9)
O1W	0.0399 (9)	0.0668 (12)	0.0526 (11)	−0.0158 (8)	0.0015 (8)	−0.0243 (9)
O2W	0.0781 (14)	0.0525 (12)	0.0540 (13)	−0.0063 (10)	0.0207 (11)	−0.0053 (10)
C1	0.0364 (12)	0.0340 (12)	0.0404 (13)	0.0026 (9)	−0.0085 (10)	−0.0078 (10)
C2	0.0478 (13)	0.0284 (11)	0.0425 (14)	−0.0068 (10)	−0.0010 (10)	−0.0129 (10)
C3	0.0380 (12)	0.0386 (12)	0.0311 (12)	−0.0163 (9)	−0.0034 (9)	−0.0119 (9)
C4	0.0532 (14)	0.0418 (13)	0.0336 (13)	−0.0141 (11)	−0.0079 (10)	−0.0126 (10)
C5	0.089 (2)	0.0386 (14)	0.0508 (17)	−0.0225 (14)	−0.0349 (15)	−0.0035 (12)
C6	0.0540 (14)	0.0294 (11)	0.0378 (13)	−0.0159 (10)	−0.0144 (11)	−0.0068 (10)
C7	0.0436 (13)	0.0338 (12)	0.0636 (18)	−0.0142 (10)	−0.0036 (12)	−0.0137 (12)
C8	0.083 (2)	0.0384 (14)	0.0338 (14)	−0.0169 (13)	−0.0209 (13)	−0.0078 (11)
C9	0.0479 (14)	0.0426 (14)	0.0516 (16)	−0.0146 (11)	−0.0149 (12)	−0.0121 (12)
C10	0.0519 (14)	0.0419 (13)	0.0353 (13)	−0.0169 (11)	−0.0005 (10)	−0.0132 (10)

Geometric parameters (Å, º) top

Cu—O1Wⁱ	2.503 (2)	C1—C2	1.506 (3)
Cu—O1W	2.503 (2)	C1—H1C	0.9900
Cu—N1ⁱ	2.015 (2)	C1—H1D	0.9900
Cu—N1	2.015 (2)	C2—H2C	0.9900
Cu—N2ⁱ	2.022 (2)	C2—H2D	0.9900
Cu—N2	2.022 (2)	C3—C4	1.521 (3)
O1—C3	1.251 (3)	C4—C5	1.498 (3)
O2—C3	1.250 (3)	C4—H4A	0.9900
O1W—H1W	0.84	C4—H4B	0.9900
O1W—H2W	0.84	C5—C6	1.513 (3)
O2W—H3W	0.84	C5—H5A	0.9900
O2W—H4W	0.84	C5—H5B	0.9900
N1—C2	1.472 (3)	C6—C7	1.378 (4)
N1—H1A	0.9200	C6—C10	1.379 (3)
N1—H1B	0.9200	C7—H7	0.9500
N2—C1	1.480 (3)	C8—C9	1.363 (4)
N2—H2A	0.9200	C8—H8	0.9500
N2—H2B	0.9200	C9—C10	1.370 (3)
N3—C8	1.327 (4)	C9—H9	0.9500
N3—C7	1.337 (4)	C10—H10	0.9500

O1Wⁱ—Cu—O1W	180.0	H1C—C1—H1D	108.5
N1ⁱ—Cu—O1Wⁱ	88.72 (7)	N1—C2—C1	107.48 (18)
N1—Cu—O1Wⁱ	91.28 (7)	N1—C2—H2C	110.2
N2ⁱ—Cu—O1Wⁱ	93.19 (6)	C1—C2—H2C	110.2
N2—Cu—O1Wⁱ	86.81 (6)	N1—C2—H2D	110.2
N1ⁱ—Cu—O1W	91.28 (7)	C1—C2—H2D	110.2
N1—Cu—O1W	88.72 (7)	H2C—C2—H2D	108.5
N2ⁱ—Cu—O1W	86.81 (6)	O2—C3—O1	124.1 (2)
N2—Cu—O1W	93.19 (6)	O2—C3—C4	117.4 (2)
N1ⁱ—Cu—N1	180.00 (11)	O1—C3—C4	118.4 (2)
N1ⁱ—Cu—N2ⁱ	84.91 (7)	C5—C4—C3	113.0 (2)
N1—Cu—N2ⁱ	95.09 (7)	C5—C4—H4A	109.0
N1ⁱ—Cu—N2	95.09 (7)	C3—C4—H4A	109.0
N1—Cu—N2	84.91 (7)	C5—C4—H4B	109.0
N2ⁱ—Cu—N2	180.0	C3—C4—H4B	109.0
C2—N1—Cu	108.14 (13)	H4A—C4—H4B	107.8
C2—N1—H1A	110.1	C4—C5—C6	111.8 (2)
Cu—N1—H1A	110.1	C4—C5—H5A	109.2
C2—N1—H1B	110.1	C6—C5—H5A	109.2
Cu—N1—H1B	110.1	C4—C5—H5B	109.2
H1A—N1—H1B	108.4	C6—C5—H5B	109.2
C1—N2—Cu	107.44 (13)	H5A—C5—H5B	107.9
C1—N2—H2A	110.2	C7—C6—C10	116.7 (2)
Cu—N2—H2A	110.2	C7—C6—C5	122.5 (2)
C1—N2—H2B	110.2	C10—C6—C5	120.8 (2)
Cu—N2—H2B	110.2	N3—C7—C6	124.6 (2)
H2A—N2—H2B	108.5	N3—C7—H7	117.7
C8—N3—C7	116.3 (2)	C6—C7—H7	117.7
Cu—O1W—H1W	110.3	N3—C8—C9	123.8 (2)
Cu—O1W—H2W	104.9	N3—C8—H8	118.1
H1W—O1W—H2W	111.9	C9—C8—H8	118.1
H3W—O2W—H4W	111.2	C8—C9—C10	118.7 (2)
N2—C1—C2	107.81 (18)	C8—C9—H9	120.7
N2—C1—H1C	110.1	C10—C9—H9	120.7
C2—C1—H1C	110.1	C9—C10—C6	119.8 (2)
N2—C1—H1D	110.1	C9—C10—H10	120.1
C2—C1—H1D	110.1	C6—C10—H10	120.1

N2ⁱ—Cu—N1—C2	−165.34 (14)	O1—C3—C4—C5	104.8 (3)
N2—Cu—N1—C2	14.66 (14)	C3—C4—C5—C6	−178.5 (2)
O1Wⁱ—Cu—N1—C2	101.34 (14)	C4—C5—C6—C7	−96.9 (3)
O1W—Cu—N1—C2	−78.66 (14)	C4—C5—C6—C10	81.8 (3)
N1ⁱ—Cu—N2—C1	−165.31 (14)	C8—N3—C7—C6	−0.2 (4)
N1—Cu—N2—C1	14.70 (14)	C10—C6—C7—N3	−0.5 (4)
O1Wⁱ—Cu—N2—C1	−76.88 (14)	C5—C6—C7—N3	178.2 (2)
O1W—Cu—N2—C1	103.12 (14)	C7—N3—C8—C9	0.7 (4)
Cu—N2—C1—C2	−40.8 (2)	N3—C8—C9—C10	−0.4 (4)
Cu—N1—C2—C1	−40.7 (2)	C8—C9—C10—C6	−0.4 (4)
N2—C1—C2—N1	54.5 (2)	C7—C6—C10—C9	0.8 (3)
O2—C3—C4—C5	−77.7 (3)	C5—C6—C10—C9	−178.0 (2)

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—H1A···O2ⁱⁱ	0.92	2.32	3.130 (3)	147
N1—H1A···O1ⁱⁱ	0.92	2.41	3.247 (2)	152
N1—H1B···O2W	0.92	2.11	2.944 (3)	151
N2—H2A···O1ⁱⁱⁱ	0.92	2.29	3.150 (3)	155
N2—H2B···O1	0.92	2.12	3.019 (2)	164
O1W—H1W···O2ⁱⁱ	0.84	2.06	2.873 (3)	164
O1W—H2W···O1	0.84	2.00	2.814 (2)	164
O2W—H3W···N3^iv	0.84	2.08	2.899 (3)	163
O2W—H4W···O2^v	0.84	2.03	2.859 (3)	169

Symmetry codes: (ii) x+1, y, z; (iii) −x, −y+1, −z+1; (iv) x+1, y, z−1; (v) −x, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	[Cu(C₂H₈N₂)₂(H₂O)₂](C₈H₈NO₂)₂·2H₂O
M_r	556.13
Crystal system, space group	Triclinic, P1
Temperature (K)	153
a, b, c (Å)	6.2620 (1), 8.5660 (2), 13.3550 (4)
α, β, γ (°)	75.271 (1), 83.809 (1), 70.863 (1)
V (Å³)	654.30 (3)
Z	1
Radiation type	Ag Kα, λ = 0.56085 Å
µ (mm⁻¹)	0.47
Crystal size (mm)	0.45 × 0.25 × 0.20

Data collection
Diffractometer	Bruker–Nonius KappaCCD diffractometer
Absorption correction	Numerical (HABITUS; Herrendorf & Bärnighausen, 1997)
T_min, T_max	0.808, 0.915
No. of measured, independent and observed [I > 2σ(I)] reflections	15039, 2989, 2644
R_int	0.079
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.086, 1.07
No. of reflections	2989
No. of parameters	160
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.31

Computer programs: KappaCCD Software (Nonius, 1997), SCALEPACK (Otwinowski & Minor, 1997), SCALEPACK and DENZO (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), enCIFer (Allen et al., 2004).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.92	2.32	3.130 (3)	147.0
N1—H1A···O1ⁱ	0.92	2.41	3.247 (2)	151.9
N1—H1B···O2W	0.92	2.11	2.944 (3)	150.9
N2—H2A···O1ⁱⁱ	0.92	2.29	3.150 (3)	155.0
N2—H2B···O1	0.92	2.12	3.019 (2)	164.4
O1W—H1W···O2ⁱ	0.84	2.06	2.873 (3)	164.2
O1W—H2W···O1	0.84	2.00	2.814 (2)	164.1
O2W—H3W···N3ⁱⁱⁱ	0.84	2.08	2.899 (3)	163.0
O2W—H4W···O2^iv	0.84	2.03	2.859 (3)	169.0

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

Comparative geometrical parameters (Å, °) and T parameter for selected trans-[Cu(en)₂(H₂O)₂] X₂ complexes top

X₂	Cu–N1	Cu–N2	Cu–OW	T^a	N1–Cu–N2
(3-pypr)₂.2H₂O	2.015 (2)	2.022 (2)	2.503 (2)	0.81	84.91 (7)
(2,6-(MeO)₂nic)₂^b	2.018 (2)	2.020 (2)	2.467 (2)	0.82	83.96 (8)
(4-O₂Nbz)₂^c	2.015 (2)	2.027 (2)	2.537 (2)	0.80	84.92 (7)
(2-NH₂bz)₂^d	2.012 (4)	2.020 (5)	2.503 (4)	0.81	84.52 (9)
(benz)₂^e	2.009 (4)	2.017 (4)	2.653 (5)	0.76	84.8 (2)
(isonic)₂^f	2.021 (2)	2.018 (2)	2.598 (2)	0.78	84.98 (6)
(4-Fbz)₂^g	2.018 (4)	2.021 (4)	2.579 (4)	0.78	85.0 (2)
(naphs)₂^h	2.020 (2)	2.018 (2)	2.513 (1)	0.80	84.63 (7)
(stz)₂.2H₂Oⁱ	2.042 (3)	2.033 (3)	2.484 (3)	0.82	84.1 (1)
F₂.4H₂O^j	2.019 (5)	2.023 (5)	2.571 (6)	0.78	84.6 (2)
(NH₂naphs)₂.2H₂O^k	2.023 (2)	2.012 (2)	2.437 (2)	0.83	84.30 (9)
(Clbtts)₂^l	2.019 (4)	2.049 (3)	2.416 (3)	0.84	84.2 (2)
(Cl-Fbz)₂^m	2.009 (2)	2.016 (2)	2.618 (1)	0.77	84.30 (6)
(BPh₄)₂.2DMSOⁿ	2.022 (10)	2.055 (8)	2.693 (9)	0.76	84.9 (4)
(edcarb).2H₂O^o	1.996 (2)	2.022 (2)	2.556 (2)	0.79	84.78 (7)

(a) The value of the T parameter (T = R_S/R_L), indicating the degree of tetragonal distortion about the Cu^II atom (Hathaway & Hodgson, 1973); (b) Jašková et al. (2007) [2,6-(MeO)₂nic is 2,6-dimethoxynicotinate]; (c) Harrison et al. (2007) [4-O₂Nbz is 4-nitrobenzoate]; (d) Miminoshvili et al. (2005) [2-NH₂bz^c is 2-aminobenzoate]; (e) Carballo et al. (2005) [benz is benzilate]; (f) Segla et al. (2000) [isonic is isonicotinate]; (g) Liu et al. (2004) [4-Fbz is 4-fluorobenzoate]; (h) Sharma et al. (2005) [naphs is naphthalene-2-sulfonate]; (i) Anacona et al. (2002) [stz is sulfathiazole]; (j) Emsley et al. (1988; 1990); (k) Li et al. (2005) [NH₂naphs is 4-aminonaphthalene-1-sulfonate]; (l) Gonzalez-Alvarez et al. (2003) [Clbtts is N-2-(6-chlorobenzothiazole)toluenesulfonamide]; (m) Lee et al. (2005); (n) Mahadevan et al. (1986); (o) Kovbasyuk et al. (1997) [edcarb is ethylene-1,2-dicarbonate].

Acknowledgements

We thank the Scientific Grant Agency of the Ministry of Education of the Slovak Republic and the Slovak Academy of Sciences (grant Nos. 1/4454/07 and 1/0353/08).

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