trans-Di­aqua­bis­(pyridazine-3-carboxyl­ato-κ2N2,O)copper(II)

Pache, A.; Iturrospe, A.; San Felices, L.; Reinoso, S.; Gutiérrez-Zorrilla, J.M.

doi:10.1107/S1600536814004334

metal-organic compounds

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ISSN: 2056-9890

Volume 70| Part 3| March 2014| Pages m114-m115

doi:10.1107/S1600536814004334

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trans-Diaquabis(pyridazine-3-carboxylato-κ²N²,O)copper(II)

Aroa Pache,^a Amaia Iturrospe,^a Leire San Felices,^a Santiago Reinoso ^a and Juan M. Gutiérrez-Zorrilla ^a ^*

^aDepartamento de Química Inorgánica, Facultad de Ciencia y Tecnología, Universidad de País Vasco (UPV/EHU), PO Box 644, E-48080 Bilbao, Spain
^*Correspondence e-mail: juanma.zorrilla@ehu.es

(Received 18 February 2014; accepted 25 February 2014; online 28 February 2014)

In the title compound, [Cu(C₅H₃N₂O₂)₂(H₂O)₂], the Cu^II ion, located on an inversion center, exhibits an octahedral coordination geometry. The equatorial plane is defined by two trans-related N,O-bidentate pyridazine-3-carboxylate ligands and the axial positions are occupied by two water molecules. In the crystal, molecules are connected by O—H⋯O hydrogen bonds between the water molecules and the noncoordinating carboxylate O atoms, forming layers parallel to the bc plane. The layers are stacked along the a axis by further O—H⋯O hydrogen bonds between the water molecules and the coordinating carboxylate O atoms. Weak C—H⋯O hydrogen bonds are also observed between the pyridazine rings and the water molecules and between the pyridazine rings and the non-coordinating carboxylate O atoms.

CCDC reference: 988680

Related literature

For the isotypic zinc complex, see: Gryz et al. (2004 ). For a related cobalt(II) complex which contains two non-coordinating water molecules, see: Artetxe et al. (2013 ).

Experimental

Crystal data

[Cu(C₅H₃N₂O₂)₂(H₂O)₂]
M_r = 345.76
Monoclinic, P 2₁ /c
a = 5.4014 (1) Å
b = 11.5633 (3) Å
c = 9.6283 (2) Å
β = 101.837 (3)°
V = 588.58 (2) Å³
Z = 2
Mo Kα radiation
μ = 1.89 mm⁻¹
T = 100 K
0.19 × 0.09 × 0.06 mm

Data collection

Agilent SuperNova diffractometer
Absorption correction: numerical (CrysAlis PRO; Agilent, 2012 ) T_min = 0.772, T_max = 0.898
2532 measured reflections
1216 independent reflections
1077 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.065
S = 1.06
1216 reflections
105 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—O1	1.9792 (15)
Cu1—N2	1.9822 (18)
Cu1—O1W	2.4207 (16)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O1ⁱ	0.87 (2)	1.99 (2)	2.865 (2)	175 (2)
O1W—H1WB⋯O2ⁱⁱ	0.87 (1)	2.03 (2)	2.878 (2)	165 (3)
C4—H4⋯O1Wⁱⁱⁱ	0.93	2.52	3.403 (3)	158
C6—H6⋯O2^iv	0.93	2.39	3.141 (3)	138
Symmetry codes: (i) x-1, y, z; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[x-1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Agilent, 2012); program(s) used to solve structure: OLEX2 (Dolomanov et al., 2009 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and DIAMOND (Brandenburg, 2010 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

CCDC reference: 988680

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536814004334/is5342sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814004334/is5342Isup2.hkl

checkCIF report

Comment top

The metal ion, the pyridazine ring and carboxylate atoms are coplanar. As expected, the Cu—O and Cu—N distances (Table 1) are similar to the Zn(II) and Co(II) analogue compounds (Gryz et al., 2004; Artetxe et al., 2013). Table 2 summarizes the geometrical parameters of the O—H···O and C—H···O hydrogen bonding interactions.

Related literature top

For an isotypic zinc(II) complex, see: Gryz et al. (2004). For a related cobalt(II) complex which contains two non-coordinating water molecules, see: Artetxe et al. (2013).

Experimental top

To a solution of CuCl₂.2H₂O (34 mg, 0.2 mmol) in water (10 mL) 3-pyridazine carboxylic acid (48 mg, 0.4 mmol) was dropwise added and the resulting solution was stirred for 1 h at 80 °C. Blue prismatic crystals suitable for single-crystal X-ray diffraction were obtained by slow evaporation of the resulting solution after six days.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis RED (Agilent, 2012); program(s) used to solve structure: OLEX2 (Dolomanov et al., 2009); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2010); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. Molecular structure of the title compound, showing atom labelling and 50% probability displacement ellipsoids. [Symmetry code: (i) 1 - x, 1 - y, 1 - z.]
	Fig. 2. Left: View of the crystal packing along the b axis. Right: Projection of a layer along the a axis (O—H···O hydrogen bonds represented as dotted red lines and weak C—H···O interactions as dotted green lines).

trans-Diaquabis(pyridazine-3-carboxylato-κ²N²,O)copper(II) top

Crystal data top

[Cu(C₅H₃N₂O₂)₂(H₂O)₂]	F(000) = 350
M_r = 345.76	D_x = 1.951 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1663 reflections
a = 5.4014 (1) Å	θ = 2.8–28.4°
b = 11.5633 (3) Å	µ = 1.89 mm⁻¹
c = 9.6283 (2) Å	T = 100 K
β = 101.837 (3)°	Prism, blue
V = 588.58 (2) Å³	0.19 × 0.09 × 0.06 mm
Z = 2

Data collection top

Agilent SuperNova diffractometer	1216 independent reflections
Radiation source: Nova (Mo) X-ray micro-source	1077 reflections with I > 2σ(I)
Multilayer optics monochromator	R_int = 0.022
Detector resolution: 16.2439 pixels mm^-1	θ_max = 26.5°, θ_min = 2.8°
ω scans	h = −6→6
Absorption correction: numerical (CrysAlis PRO; Agilent, 2012)	k = −13→14
T_min = 0.772, T_max = 0.898	l = −12→9
2532 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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.065	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0235P)² + 0.6643P] where P = (F_o² + 2F_c²)/3
1216 reflections	(Δ/σ)_max < 0.001
105 parameters	Δρ_max = 0.44 e Å⁻³
3 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

[Cu(C₅H₃N₂O₂)₂(H₂O)₂]	V = 588.58 (2) Å³
M_r = 345.76	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.4014 (1) Å	µ = 1.89 mm⁻¹
b = 11.5633 (3) Å	T = 100 K
c = 9.6283 (2) Å	0.19 × 0.09 × 0.06 mm
β = 101.837 (3)°

Data collection top

Agilent SuperNova diffractometer	1216 independent reflections
Absorption correction: numerical (CrysAlis PRO; Agilent, 2012)	1077 reflections with I > 2σ(I)
T_min = 0.772, T_max = 0.898	R_int = 0.022
2532 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	3 restraints
wR(F²) = 0.065	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.44 e Å⁻³
1216 reflections	Δρ_min = −0.45 e Å⁻³
105 parameters

Special details top

Experimental. IR (cm^-1): 3554(s), 3315(s), 3233(s), 1628(s), 1571(m), 1578(s), 1365(w), 1231(w), 1152(w), 1091(w), 1072(w), 1039(w), 978(m), 851(m), 785(m), 722(m), 669(w), 536(w), 440(w).

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
C3	0.4961 (4)	0.27046 (19)	0.4096 (2)	0.0083 (4)
C4	0.4421 (4)	0.15278 (19)	0.3920 (2)	0.0107 (4)
H4	0.5153	0.1071	0.3318	0.013*
C5	0.2754 (4)	0.10781 (19)	0.4680 (2)	0.0106 (5)
H5	0.2313	0.03	0.4606	0.013*
C6	0.1737 (4)	0.18136 (19)	0.5564 (2)	0.0111 (5)
H6	0.0632	0.1503	0.6089	0.013*
C7	0.6781 (4)	0.33471 (19)	0.3358 (2)	0.0097 (4)
Cu1	0.5	0.5	0.5	0.00820 (13)
N1	0.2267 (3)	0.29375 (16)	0.5696 (2)	0.0101 (4)
N2	0.3890 (3)	0.33637 (16)	0.49462 (18)	0.0084 (4)
O1	0.7022 (3)	0.44303 (13)	0.36438 (16)	0.0100 (3)
O2	0.7873 (3)	0.28108 (13)	0.25561 (17)	0.0135 (4)
O1W	0.1555 (3)	0.53934 (14)	0.30161 (17)	0.0121 (3)
H1WA	0.014 (3)	0.514 (2)	0.321 (3)	0.024 (8)*
H1WB	0.149 (6)	0.6143 (9)	0.292 (4)	0.051 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C3	0.0088 (10)	0.0095 (11)	0.0063 (10)	0.0001 (8)	0.0005 (8)	0.0003 (8)
C4	0.0128 (11)	0.0094 (11)	0.0094 (10)	0.0035 (9)	0.0014 (9)	−0.0004 (8)
C5	0.0107 (10)	0.0082 (11)	0.0117 (11)	−0.0007 (8)	−0.0007 (9)	0.0019 (8)
C6	0.0106 (10)	0.0125 (11)	0.0106 (11)	−0.0011 (9)	0.0028 (9)	0.0014 (9)
C7	0.0091 (10)	0.0120 (11)	0.0080 (10)	−0.0007 (8)	0.0018 (9)	0.0001 (9)
Cu1	0.0111 (2)	0.0052 (2)	0.0101 (2)	−0.00061 (14)	0.00618 (15)	−0.00061 (14)
N1	0.0107 (9)	0.0099 (9)	0.0104 (9)	−0.0019 (7)	0.0039 (8)	−0.0002 (7)
N2	0.0091 (9)	0.0092 (9)	0.0072 (9)	0.0007 (7)	0.0021 (7)	0.0013 (7)
O1	0.0112 (7)	0.0071 (8)	0.0128 (8)	−0.0012 (6)	0.0052 (6)	0.0004 (6)
O2	0.0158 (8)	0.0120 (8)	0.0152 (8)	−0.0009 (6)	0.0094 (7)	−0.0033 (6)
O1W	0.0101 (8)	0.0105 (8)	0.0161 (8)	0.0006 (6)	0.0037 (7)	0.0023 (7)

Geometric parameters (Å, º) top

C3—N2	1.334 (3)	C7—C3	1.520 (3)
C3—C4	1.395 (3)	Cu1—O1ⁱ	1.9792 (15)
C3—C7	1.520 (3)	Cu1—O1	1.9792 (15)
C4—C5	1.374 (3)	Cu1—N2	1.9822 (18)
C4—H4	0.93	Cu1—N2ⁱ	1.9822 (18)
C5—C6	1.393 (3)	Cu1—O1W	2.4207 (16)
C5—H5	0.93	Cu1—O1Wⁱ	2.4207 (16)
C6—N1	1.331 (3)	N1—N2	1.339 (3)
C6—H6	0.93	O1W—H1WA	0.872 (10)
C7—O2	1.231 (3)	O1W—H1WB	0.872 (10)
C7—O1	1.283 (3)

N2—C3—C4	121.7 (2)	O1ⁱ—Cu1—N2ⁱ	82.52 (7)
N2—C3—C7	114.28 (19)	N2—Cu1—N2ⁱ	180
C4—C3—C7	124.0 (2)	O1—Cu1—O1W	88.90 (6)
C5—C4—C3	116.6 (2)	O1ⁱ—Cu1—O1W	91.10 (6)
C5—C4—H4	121.7	N2—Cu1—O1W	88.82 (6)
C3—C4—H4	121.7	N2ⁱ—Cu1—O1W	91.18 (6)
C4—C5—C6	118.6 (2)	O1—Cu1—O1Wⁱ	91.10 (6)
C4—C5—H5	120.7	O1ⁱ—Cu1—O1Wⁱ	88.90 (6)
C6—C5—H5	120.7	N2—Cu1—O1Wⁱ	91.18 (6)
N1—C6—C5	123.4 (2)	N2ⁱ—Cu1—O1Wⁱ	88.82 (6)
N1—C6—H6	118.3	O1W—Cu1—O1Wⁱ	180
C5—C6—H6	118.3	C6—N1—N2	117.37 (19)
O2—C7—O1	125.8 (2)	C3—N2—N1	122.33 (19)
O2—C7—C3	119.1 (2)	C3—N2—Cu1	113.24 (15)
O1—C7—C3	115.06 (19)	N1—N2—Cu1	124.43 (14)
O1ⁱ—Cu1—O1	180	C7—O1—Cu1	114.89 (13)
O1—Cu1—N2	82.52 (7)	Cu1—O1W—H1WA	109.8 (19)
O1ⁱ—Cu1—N2	97.48 (7)	Cu1—O1W—H1WB	106 (2)
O1—Cu1—N2ⁱ	97.48 (7)	H1WA—O1W—H1WB	109 (2)

N2—C3—C4—C5	−0.8 (3)	O1W—Cu1—N2—C3	89.46 (15)
C7—C3—C4—C5	179.22 (19)	O1Wⁱ—Cu1—N2—C3	−90.54 (15)
C3—C4—C5—C6	−0.2 (3)	O1—Cu1—N2—N1	179.32 (17)
C4—C5—C6—N1	1.1 (3)	O1ⁱ—Cu1—N2—N1	−0.68 (17)
C5—C6—N1—N2	−0.9 (3)	O1W—Cu1—N2—N1	−91.63 (16)
C4—C3—N2—N1	1.0 (3)	O1Wⁱ—Cu1—N2—N1	88.37 (16)
C7—C3—N2—N1	−179.04 (18)	O2—C7—O1—Cu1	−179.34 (18)
C4—C3—N2—Cu1	179.92 (16)	C3—C7—O1—Cu1	0.8 (2)
C7—C3—N2—Cu1	−0.1 (2)	N2—Cu1—O1ⁱ—C7ⁱ	−179.30 (15)
C6—N1—N2—C3	−0.1 (3)	N2—Cu1—O1—C7	−0.70 (15)
C6—N1—N2—Cu1	−178.91 (15)	O1W—Cu1—O1—C7	−89.65 (15)
O1—Cu1—N2—C3	0.41 (14)	O1Wⁱ—Cu1—O1—C7	90.35 (15)
O1ⁱ—Cu1—N2—C3	−179.59 (14)

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
O1W—H1WA···O1ⁱⁱ	0.87 (2)	1.99 (2)	2.865 (2)	175 (2)
O1W—H1WB···O2ⁱⁱⁱ	0.87 (1)	2.03 (2)	2.878 (2)	165 (3)
C4—H4···O1W^iv	0.93	2.52	3.403 (3)	158
C6—H6···O2^v	0.93	2.39	3.141 (3)	138

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

Selected bond lengths (Å) top

Cu1—O1	1.9792 (15)	Cu1—O1W	2.4207 (16)
Cu1—N2	1.9822 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O1ⁱ	0.874 (19)	1.993 (19)	2.865 (2)	175 (2)
O1W—H1WB···O2ⁱⁱ	0.872 (11)	2.028 (15)	2.878 (2)	165 (3)
C4—H4···O1Wⁱⁱⁱ	0.930	2.52	3.403 (3)	158
C6—H6···O2^iv	0.930	2.39	3.141 (3)	138

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

Acknowledgements

This work was supported financially by Eusko Jaurlaritza/Gobierno Vasco (grant IT477–10). AP also thanks EJ/GV for predoctoral fellowships.

References

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