trans-Diaqua­bis(6-methoxycarbonyl­pyridazine-3-carboxyl­ato-κ2N,O)zinc(II) dihydrate

Starosta, W.; Leciejewicz, J.

doi:10.1107/S1600536809017115

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page m640

doi:10.1107/S1600536809017115

Open

access

trans-Diaquabis(6-methoxycarbonylpyridazine-3-carboxylato-κ²N,O)zinc(II) dihydrate

Wojciech Starosta ^a and Janusz Leciejewicz ^a ^*

^aInstitute of Nuclear Chemistry and Technology, ul. Dorodna 16, 03-195 Warszawa, Poland
^*Correspondence e-mail: jlec@ichtj.waw.pl

(Received 28 April 2009; accepted 6 May 2009; online 14 May 2009)

In the title centrosymmetric complex, [Zn(C₇H₅N₂O₄)₂(H₂O)₂]·2H₂O, the Zn^II ion is coordinated in a trans mode by two symmetry-related bis-chelating 6-methoxycarbonylpyridazine-3-carboxylate ligands via N and O atoms, and by two aqua ligand O atoms in axial positions, in a slightly distorted octahedral environment. In the crystal structure, complex molecules are linked by intermolecular O—H⋯O hydrogen bonds between coordinated and solvent water molecules and carboxylate O atoms, forming molecular ribbons propagating along the a axis.

Related literature

For the crystal structures of two zinc complexes with pyridazine-3-carboxylate and water ligands, see: Gryz et al. (2003 , 2004 ). For a centrosymmetric dimeric zinc(II) complex with pyridazine-3,6-dicarboxylate and water ligands, see: Gryz et al. (2006 ). For modifications of pyridazine-3,6-dicarboxylic acid, see: Starosta & Leciejewicz (2004 ); Sueur et al. (1987 ).

Experimental

Crystal data

[Zn(C₇H₅N₂O₄)₂(H₂O)₂]·2H₂O
M_r = 499.69
Triclinic, $[P \overline 1]$
a = 6.3678 (13) Å
b = 8.3178 (17) Å
c = 9.7717 (19) Å
α = 102.99 (3)°
β = 108.90 (3)°
γ = 94.97 (3)°
V = 469.93 (17) Å³
Z = 1
Mo Kα radiation
μ = 1.38 mm⁻¹
T = 293 K
0.31 × 0.25 × 0.05 mm

Data collection

Kuma KM4 four-circle diffractometer
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd., Abingdon, England.]$ ) T_min = 0.699, T_max = 0.942
2787 measured reflections
2595 independent reflections
2235 reflections with I > 2σ(I)
R_int = 0.022
3 standard reflections every 200 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.101
S = 1.07
2595 reflections
159 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.65 e Å⁻³
Δρ_min = −0.75 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H22⋯O11ⁱ	0.93 (4)	1.99 (4)	2.874 (3)	158 (4)
O2—H21⋯O21ⁱⁱ	0.72 (4)	2.23 (4)	2.940 (3)	168 (4)
O1—H12⋯O12ⁱ	0.84 (3)	1.86 (3)	2.695 (2)	174 (3)
O1—H11⋯O2	0.90 (4)	1.89 (4)	2.720 (2)	152 (3)
Symmetry codes: (i) x-1, y, z; (ii) -x, -y+1, -z+1.

Data collection: KM-4 Software (Kuma, 1996 $[Kuma (1996). KM-4 Software. Kuma Diffraction Ltd. Wrocław, Poland.]$ ); cell refinement: KM-4 Software; data reduction: DATAPROC (Kuma, 2001 $[Kuma (2001). DATAPROC. Kuma Diffraction Ltd. Wrocław, Poland.]$ ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809017115/lh2816sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809017115/lh2816Isup2.hkl

checkCIF report

Comment top

In the molecluar structure of the title compound (I) (Fig.1) the Zn^II ion, which is located on a center of symmetry, is coordinated in trans mode by two, symmetry related, bis chelating ligand molecules through their N,O bonding atoms. Two water O atoms in axial positions complete the number of coordinated atoms to six. The coordination geometry is slightly distorted octahedral. Bond distances and bond angles are close to those reported for two zinc complexes with pyridazine-3-carboxylate and water ligands (Gryz et al., 2003, 2004), a complex with pyridazine-3,6-dicarboxylate and water ligands (Gryz et al., 2006) and for both modifications of pyridazine-3,6-dicarboxylic acid (Sueur et al., 1987; Starosta & Leciejewicz, 2004). The ligand molecules and the Zn^II ion are almost coplanar [r.m.s. 0.0074 Å]. The carboxylic C12/O11/O12 and the carboxymethyl C18/O21/O22/C19 groups make dihedral angles with the pyridazine ring of 3.0 (2) and 6.8 (1)°, respectively. In the crystal structure complex molecules are linked by hydrogen bonds to form molecular ribbons (Fig. 2). The relevant hydrogen-bond parameters are listed in Table 1.

Related literature top

For the crystal structures of two zinc complexes with pyridazine-3-carboxylate and water ligands, see: Gryz et al. (2003, 2004). For a centrosymmetric dimeric zinc(II) complex with pyridazine-3,6-dicarboxylate and water ligands, see: Gryz et al. (2006). For modifications of pyridazine-3,6-dicarboxylic acid, see: Starosta & Leciejewicz (2004); Sueur et al. (1987).

Experimental top

Hot aqueous solutions containing 2 mmol of 6-carboxymethylpyridazine-3-carboxylic acid and 1 mmol of zinc(II) acetate tetrahydrate, respectively, were mixed and boiled for two hours with constant stirring and then left to crystallize at room temperature. After few days, well formed colorless single crystals were found in the mother liquid in the mass of polycrystalline material. The crystals were washed with cold ethanol and dried in air.

Computing details top

Data collection: KM-4 Software (Kuma, 1996); cell refinement: KM-4 Software (Kuma, 1996); data reduction: DATAPROC (Kuma, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I) with atom labelling scheme and 50% probability displacement ellipsoids. Symmetry code:(i) -x + 1, -y + 1, -z + 1. The symmetry related solvent water molecule is not shown.
	Fig. 2. Part of the crystal structure with hydrogen bonds shown as dashed lines.

trans-Diaquabis(6-methoxycarbonylpyridazine-3-carboxylato- κ²N,O)zinc(II) dihydrate top

Crystal data top

[Zn(C₇H₅N₂O₄)₂(H₂O)₂]·2H₂O	Z = 1
M_r = 499.69	F(000) = 256
Triclinic, P1	D_x = 1.766 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.3678 (13) Å	Cell parameters from 25 reflections
b = 8.3178 (17) Å	θ = 6–15°
c = 9.7717 (19) Å	µ = 1.38 mm⁻¹
α = 102.99 (3)°	T = 293 K
β = 108.90 (3)°	Plate, colourless
γ = 94.97 (3)°	0.31 × 0.25 × 0.05 mm
V = 469.93 (17) Å³

Data collection top

Kuma KM4 four-circle diffractometer	2235 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.022
Graphite monochromator	θ_max = 30.1°, θ_min = 2.3°
profile data from ω/2θ scans	h = 0→8
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008)	k = −8→11
T_min = 0.699, T_max = 0.942	l = −13→13
2787 measured reflections	3 standard reflections every 200 reflections
2595 independent reflections	intensity decay: 0.0%

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0761P)² + 0.0253P] where P = (F_o² + 2F_c²)/3
2595 reflections	(Δ/σ)_max = 0.002
159 parameters	Δρ_max = 0.65 e Å⁻³
0 restraints	Δρ_min = −0.75 e Å⁻³

Crystal data top

[Zn(C₇H₅N₂O₄)₂(H₂O)₂]·2H₂O	γ = 94.97 (3)°
M_r = 499.69	V = 469.93 (17) Å³
Triclinic, P1	Z = 1
a = 6.3678 (13) Å	Mo Kα radiation
b = 8.3178 (17) Å	µ = 1.38 mm⁻¹
c = 9.7717 (19) Å	T = 293 K
α = 102.99 (3)°	0.31 × 0.25 × 0.05 mm
β = 108.90 (3)°

Data collection top

Kuma KM4 four-circle diffractometer	2235 reflections with I > 2σ(I)
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008)	R_int = 0.022
T_min = 0.699, T_max = 0.942	3 standard reflections every 200 reflections
2787 measured reflections	intensity decay: 0.0%
2595 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.65 e Å⁻³
2595 reflections	Δρ_min = −0.75 e Å⁻³
159 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
Zn1	0.5000	0.5000	0.5000	0.02700 (11)
O11	0.8125 (2)	0.43757 (16)	0.58939 (15)	0.0313 (3)
O12	1.0055 (2)	0.22915 (17)	0.57098 (18)	0.0371 (3)
N11	0.2403 (2)	0.15325 (19)	0.29574 (15)	0.0255 (3)
N12	0.4382 (2)	0.24189 (17)	0.39017 (15)	0.0235 (3)
C17	0.8332 (3)	0.2900 (2)	0.53776 (18)	0.0253 (3)
C13	0.6217 (3)	0.1734 (2)	0.42383 (17)	0.0226 (3)
C14	0.6202 (3)	0.0068 (2)	0.36089 (19)	0.0278 (3)
H14	0.7511	−0.0393	0.3832	0.033*
O1	0.4013 (2)	0.44171 (18)	0.67752 (15)	0.0326 (3)
H11	0.382 (6)	0.535 (5)	0.738 (4)	0.060 (9)*
O21	−0.1599 (2)	−0.0300 (2)	0.10069 (19)	0.0436 (3)
C16	0.2308 (3)	−0.0079 (2)	0.23612 (17)	0.0242 (3)
C18	−0.0011 (3)	−0.0981 (2)	0.13509 (17)	0.0272 (3)
C15	0.4172 (3)	−0.0876 (2)	0.26422 (19)	0.0297 (3)
H15	0.4048	−0.2008	0.2191	0.036*
O22	−0.0035 (2)	−0.25921 (17)	0.09206 (16)	0.0378 (3)
C19	−0.2178 (4)	−0.3623 (3)	−0.0046 (3)	0.0479 (5)
H191	−0.3354	−0.2966	−0.0089	0.072*
H192	−0.2459	−0.4546	0.0346	0.072*
H193	−0.2146	−0.4041	−0.1036	0.072*
O2	0.1965 (3)	0.6755 (3)	0.8035 (2)	0.0493 (4)
H12	0.274 (5)	0.379 (4)	0.639 (3)	0.043 (7)*
H21	0.207 (6)	0.765 (5)	0.830 (4)	0.061 (11)*
H22	0.054 (7)	0.622 (6)	0.738 (4)	0.074 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.01928 (14)	0.01626 (16)	0.03827 (16)	0.00521 (9)	0.00402 (10)	0.00167 (10)
O11	0.0207 (5)	0.0216 (6)	0.0435 (6)	0.0055 (4)	0.0047 (5)	0.0023 (5)
O12	0.0205 (5)	0.0257 (7)	0.0593 (8)	0.0086 (5)	0.0064 (5)	0.0095 (6)
N11	0.0200 (6)	0.0217 (6)	0.0317 (6)	0.0038 (5)	0.0065 (5)	0.0048 (5)
N12	0.0199 (6)	0.0177 (6)	0.0308 (6)	0.0042 (5)	0.0073 (5)	0.0045 (5)
C17	0.0190 (6)	0.0219 (7)	0.0346 (7)	0.0040 (5)	0.0080 (5)	0.0088 (6)
C13	0.0206 (6)	0.0193 (7)	0.0288 (6)	0.0045 (5)	0.0092 (5)	0.0071 (5)
C14	0.0230 (7)	0.0223 (8)	0.0373 (8)	0.0080 (6)	0.0098 (6)	0.0065 (6)
O1	0.0249 (6)	0.0286 (6)	0.0404 (6)	0.0026 (5)	0.0095 (5)	0.0053 (5)
O21	0.0268 (6)	0.0339 (8)	0.0563 (8)	0.0047 (5)	0.0021 (6)	0.0040 (6)
C16	0.0237 (7)	0.0200 (7)	0.0265 (6)	0.0024 (5)	0.0072 (5)	0.0043 (5)
C18	0.0271 (7)	0.0233 (8)	0.0271 (6)	0.0004 (6)	0.0072 (6)	0.0038 (5)
C15	0.0312 (8)	0.0181 (7)	0.0369 (8)	0.0060 (6)	0.0113 (6)	0.0022 (6)
O22	0.0329 (6)	0.0231 (6)	0.0429 (7)	−0.0004 (5)	0.0017 (5)	−0.0002 (5)
C19	0.0403 (10)	0.0297 (10)	0.0535 (11)	−0.0072 (9)	0.0010 (9)	−0.0003 (8)
O2	0.0391 (8)	0.0403 (10)	0.0611 (10)	0.0129 (7)	0.0139 (7)	0.0023 (8)

Geometric parameters (Å, º) top

Zn1—O11	2.0617 (13)	C14—H14	0.9300
Zn1—O11ⁱ	2.0617 (13)	O1—H11	0.90 (4)
Zn1—N12ⁱ	2.1118 (15)	O1—H12	0.84 (3)
Zn1—N12	2.1118 (15)	O21—C18	1.192 (2)
Zn1—O1ⁱ	2.1612 (14)	C16—C15	1.390 (2)
Zn1—O1	2.1612 (14)	C16—C18	1.500 (2)
O11—C17	1.253 (2)	C18—O22	1.309 (2)
O12—C17	1.227 (2)	C15—H15	0.9300
N11—C16	1.324 (2)	O22—C19	1.445 (2)
N11—N12	1.3277 (19)	C19—H191	0.9600
N12—C13	1.323 (2)	C19—H192	0.9600
C17—C13	1.520 (2)	C19—H193	0.9600
C13—C14	1.382 (2)	O2—H21	0.72 (4)
C14—C15	1.371 (2)	O2—H22	0.93 (4)

O11—Zn1—O11ⁱ	180.0	C14—C13—C17	122.46 (14)
O11—Zn1—N12ⁱ	101.21 (6)	C15—C14—C13	117.11 (16)
O11ⁱ—Zn1—N12ⁱ	78.79 (6)	C15—C14—H14	121.4
O11—Zn1—N12	78.79 (6)	C13—C14—H14	121.4
O11ⁱ—Zn1—N12	101.21 (6)	Zn1—O1—H11	111 (2)
N12ⁱ—Zn1—N12	180.0	Zn1—O1—H12	108.5 (18)
O11—Zn1—O1ⁱ	89.08 (6)	H11—O1—H12	106 (3)
O11ⁱ—Zn1—O1ⁱ	90.91 (6)	N11—C16—C15	123.58 (15)
N12ⁱ—Zn1—O1ⁱ	89.79 (6)	N11—C16—C18	113.77 (15)
N12—Zn1—O1ⁱ	90.20 (6)	C15—C16—C18	122.66 (15)
O11—Zn1—O1	90.92 (6)	O21—C18—O22	125.50 (16)
O11ⁱ—Zn1—O1	89.08 (6)	O21—C18—C16	123.73 (16)
N12ⁱ—Zn1—O1	90.21 (6)	O22—C18—C16	110.77 (15)
N12—Zn1—O1	89.80 (6)	C14—C15—C16	117.52 (16)
O1ⁱ—Zn1—O1	180.00 (6)	C14—C15—H15	121.2
C17—O11—Zn1	116.33 (11)	C16—C15—H15	121.2
C16—N11—N12	117.85 (14)	C18—O22—C19	116.76 (16)
C13—N12—N11	121.74 (14)	O22—C19—H191	109.5
C13—N12—Zn1	112.69 (11)	O22—C19—H192	109.5
N11—N12—Zn1	125.56 (11)	H191—C19—H192	109.5
O12—C17—O11	126.85 (16)	O22—C19—H193	109.5
O12—C17—C13	116.54 (15)	H191—C19—H193	109.5
O11—C17—C13	116.61 (14)	H192—C19—H193	109.5
N12—C13—C14	122.16 (15)	H21—O2—H22	114 (4)
N12—C13—C17	115.37 (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
O2—H22···O11ⁱⁱ	0.93 (4)	1.99 (4)	2.874 (3)	158 (4)
O2—H21···O21ⁱⁱⁱ	0.72 (4)	2.23 (4)	2.940 (3)	168 (4)
O1—H12···O12ⁱⁱ	0.84 (3)	1.86 (3)	2.695 (2)	174 (3)
O1—H11···O2	0.90 (4)	1.89 (4)	2.720 (2)	152 (3)

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

Experimental details

Crystal data
Chemical formula	[Zn(C₇H₅N₂O₄)₂(H₂O)₂]·2H₂O
M_r	499.69
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	6.3678 (13), 8.3178 (17), 9.7717 (19)
α, β, γ (°)	102.99 (3), 108.90 (3), 94.97 (3)
V (Å³)	469.93 (17)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.38
Crystal size (mm)	0.31 × 0.25 × 0.05

Data collection
Diffractometer	Kuma KM4 four-circle diffractometer
Absorption correction	Analytical (CrysAlis RED; Oxford Diffraction, 2008)
T_min, T_max	0.699, 0.942
No. of measured, independent and observed [I > 2σ(I)] reflections	2787, 2595, 2235
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.705

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.101, 1.07
No. of reflections	2595
No. of parameters	159
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.65, −0.75

Computer programs: KM-4 Software (Kuma, 1996), DATAPROC (Kuma, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H22···O11ⁱ	0.93 (4)	1.99 (4)	2.874 (3)	158 (4)
O2—H21···O21ⁱⁱ	0.72 (4)	2.23 (4)	2.940 (3)	168 (4)
O1—H12···O12ⁱ	0.84 (3)	1.86 (3)	2.695 (2)	174 (3)
O1—H11···O2	0.90 (4)	1.89 (4)	2.720 (2)	152 (3)

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

References

Gryz, M., Starosta, W. & Leciejewicz, J. (2004). Acta Cryst. E60, m1481–m1483. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Gryz, M., Starosta, W. & Leciejewicz, J. (2006). Acta Cryst. E62, m3470–m3472. Web of Science CSD CrossRef IUCr Journals Google Scholar
Gryz, M., Starosta, W., Ptasiewicz-Bąk, H. & Leciejewicz, J. (2003). J. Coord. Chem. 56, 1505–1511. Web of Science CSD CrossRef CAS Google Scholar
Kuma (1996). KM-4 Software. Kuma Diffraction Ltd. Wrocław, Poland. Google Scholar
Kuma (2001). DATAPROC. Kuma Diffraction Ltd. Wrocław, Poland. Google Scholar
Oxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd., Abingdon, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Starosta, W. & Leciejewicz, J. (2004). Acta Cryst. E60, o2219–o2220. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sueur, S., Lagrenee, M., Abraham, F. & Bremard, C. (1987). J. Heterocycl. Chem. 24, 1285–1289. CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.