trans-Diaqua­bis(6-methoxycarbonyl­pyridazine-3-carboxyl­ato-κ² N,O)zinc(II) dihydrate

Abstract

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,

• 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) ų

• 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 ▶) 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[F ² > 2σ(F ²)] = 0.035

• wR(F ²) = 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

Data collection: KM-4 Software (Kuma, 1996 ▶); cell refinement: KM-4 Software; 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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

H atoms bonded to C atoms were placed in calculated positions with C—H = 0.93 and 0.96 Å and included in a riding-model approximation with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C) for methyl atoms. Water H atoms were located in difference Fourier maps and were refined isotropically.

Figures

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.

Crystal data

[Zn(C7H5N2O4)2(H2O)2]·2H2O	Z = 1
Mr = 499.69	F(000) = 256
Triclinic, P1	Dx = 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

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

Refinement

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(Fo2) + (0.0761P)2 + 0.0253P] where P = (Fo2 + 2Fc2)/3
2595 reflections	(Δ/σ)max = 0.002
159 parameters	Δρmax = 0.65 e Å−3
0 restraints	Δρmin = −0.75 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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 codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

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.