trans Di­aqua­bis­(pyridazine 3 carboxyl­ato κ2N,O)magnesium(II) dihydrate

metal-organic papers

Acta Cryst.(2006). E62, m123–m124 doi:10.1107/S1600536805041516 Gryzet al. _[Mg(C

5H3N2O2)2(H2O)2]2H2O

m123

Acta Crystallographica Section E

Structure Reports

Online

ISSN 1600-5368

trans-Diaquabis(pyridazine-3-carboxylato-

j

N,O)-magnesium(II) dihydrate

Michał Gryz,aWojciech Starostab and Janusz Leciejewiczb*

a_{Office for Medicinal Products, Medical Devices}

and Biocides, Za˛bkowska 41, 03-736 Warszawa, Poland, andb_{Institute of Nuclear}

Chemistry and Technology, Dorodna 16, 03-195 Warszawa, Poland

Correspondence e-mail: jlec@orange.ichtj.waw.pl

Key indicators

Single-crystal X-ray study

T= 293 K

Mean(C–C) = 0.003 A˚

Rfactor = 0.041

wRfactor = 0.137

Data-to-parameter ratio = 15.8

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2006 International Union of Crystallography Printed in Great Britain – all rights reserved

The title compound, [Mg(C5H3N2O2)2(H2O)2]2H2O, contains

centrosymmetric neutral complex molecules. The pyridazine-3-carboxylate ligands bond in anN,O-bidentate mode and the octahedral Mg coordination is completed by twotranswater molecules. There are also two non-coordinated water mol-ecules. O—H O and O—H N hydrogen bonds are present, resulting in a three-dimensional network.

Comment

The title compound, (I), is isostructural with the analogous complexes of manganese (Ardivinata et al., 1989) and zinc (Gryzet al., 2003) with the same ligands.

The structure of (I) is triclinic and its unit cell contains one monomeric [Mg(C5H3N2O2)2(H2O)2] complex molecule and

two non-coordinated water molecules. The MgII cation is located on an inversion centre and is coordinated by two equatorial bidentate-N,Oligand molecules. Two axial water O atoms complete a slightly distorted octahedron around the metal ion (Fig. 1 and Table 1). The pyridazine ring is almost planar (r.m.s. deviation 0.0106 A˚ ) and the carboxylate group is rotated from the mean ring plane by 5.3 (3)_.

Fig. 2 shows a packing diagram for (I) and the hydrogen-bonding scheme. Hydrogen bonds link the water molecules to uncoordinated carboxylate O atoms and uncoordinated hetero-ring N atoms in adjacent monomers, forming a three-dimensional network (Table 2). Monomeric molecules with octahedral coordination around the MgII cation have been also reported for magnesium(II) picolinate (Deloume et al., 1973) and magnesium aminopyrazinate (Ptasiewicz-Ba˛ket al., 1997). In both these compounds, the ligand molecules chelate the metal ionviaanN,O-bonding mode. However, the ligand planes are in acisarrangement, with a dihedral angle between the planes of 95_{in the former complex and 67.3 (5) in the}

latter.

Experimental

A hot aqueous solution (50 ml) containing pyridazine-3-carboxylic acid (2 mmol) was added with constant stirring to a hot aqueous

solution (50 ml) containing magnesium acetate tetrahydrate (1 mmol). After boiling for 1 h, the solution was left to crystallize at room temperature. After several days, single crystals of (I) in the form of colourless blocks deposited in the mother liquid. These were washed with cold water and ethanol and dried in air.

Crystal data

[Mg(C5H3N2O2)2(H2O)2]2H2O

Mr= 342.56 Triclinic,P1 a= 5.338 (1) A˚ b= 7.468 (2) A˚ c= 9.641 (2) A˚ = 79.23 (3)

= 88.91 (3)

= 71.93 (3)

V= 358.63 (13) A˚3

Z= 1

Dx= 1.586 Mg m

3

MoKradiation Cell parameters from 25

reflections = 6–15

= 0.18 mm1

T= 293 (2) K Rod, colourless 0.400.090.07 mm

Data collection

Kuma KM-4 four-circle diffractometer !/2scans

Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2000) Tmin= 0.978,Tmax= 0.986

2327 measured reflections 2117 independent reflections

1463 reflections withI> 2(I) Rint= 0.023

max= 30.1

h=7!0 k=10!10 l=13!13 3 standard reflections

every 200 reflections intensity decay: 2.1%

Refinement

Refinement onF2

R[F2_{> 2(F}2_{)] = 0.041}

wR(F2_{) = 0.137}

S= 1.06 2117 reflections 134 parameters

All H-atom parameters refined

w= 1/[2_(F

o2) + (0.089P)2

+ 0.0392P]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001

max= 0.60 e A˚ 3

min=0.27 e A˚ 3

Table 1

Selected geometric parameters (A˚ ,_).

Mg1—O1 2.0406 (13) Mg1—O3 2.0909 (14)

Mg1—N2 2.1769 (16)

O1—Mg1—N2 77.39 (5)

Table 2

Hydrogen-bond geometry (A˚ ,_).

D—H A D—H H A D A D—H A

O3—H32 O4 0.88 (3) 1.86 (3) 2.737 (2) 175 (3) O3—H31 N1i

0.87 (4) 2.04 (4) 2.899 (2) 170 (3) O4—H41 O2ii

1.00 (3) 1.82 (3) 2.822 (2) 173 (3) O4—H42 O2iii 0.99 (3) 1.92 (3) 2.888 (2) 165 (3)

Symmetry codes: (i)x;yþ1;zþ1; (ii)x1;y;z; (iii)xþ1;yþ1;z.

H atoms were located in difference maps and freely refined with isotropic displacement parameters. Refined C—H distances are in the range 1.00 (2)–1.02 (3) A˚ .

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, 1997); program(s) used to refine structure:SHELXL97(Sheldrick, 1997); molecular graphics: XP(Siemens, 1992); software used to prepare material for publication:SHELXL97.

This work was supported by the Ministry of Scientific Research and Information Technology (grant No. 3 T09 078 28).

References

Ardivinata, E. S., Craig, D. C. & Philips, D. J. (1989).Inorg. Chim. Acta,166, 233–237.

Deloume, J.-P., Loiseleur, H. & Thomas, G. (1973).Acta Cryst.B29, 668–673. Gryz, M., Starosta, W., Ptasiewicz-Ba˛k, H & Leciejewicz, J (2003).J. Coord.

Chem.56, 1505–1511.

Kuma (1996).KM-4 Software. Kuma Diffraction, Wrocław, Poland. Kuma (2001). DATAPROC. Version 10.0.7. Kuma Diffraction, Wrocław,

Poland.

Oxford Diffraction (2000).CrysAlis RED. Version 1.69. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.

Ptasiewicz-Ba˛k, H. & Leciejewicz, J. (1997).Polish J. Chem.71, 1350–1358. Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of

Go¨ttingen, Germany.

Siemens (1992).XP.Version 4.3. Siemens Analytical X–ray Instruments Inc., Karlsruhe, Germany.

Figure 1

A view of (I), showing 50% displacement ellipsoids (arbitrary spheres for the H atoms). Unlabelled atoms are generated by the symmetry operation (1x, 1y, 1z).

Figure 2

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supporting information

Acta Cryst. (2006). E62, m123–m124 [doi:10.1107/S1600536805041516]

trans

-Diaquabis(pyridazine-3-carboxylato-

κ

N

,

O

)magnesium(II) dihydrate

Micha

ł

Gryz, Wojciech Starosta and Janusz Leciejewicz

S1. Comment

The title compound, (I), is isostructural with the analogous complexes of manganese (Ardivinata et al., 1989) and zinc (Gryz et al., 2003) with the same ligands.

The structure of (I) is triclinic and its unit cell contains one monomeric [Mg(C5H3N2O2)2(H2O)2] complex molecule and

two non-coordinated water molecules. The MgII _{cation is located on an inversion centre and is coordinated by two}

equatorial bidentate-N,O ligand molecules. Two axial water O atoms complete a slightly distorted octahedron around the metal ion (Fig. 1 and Table 1). The pyridazine ring is almost planar (r.m.s. deviation 0.0106 Å) and the carboxylate entity is rotated from the ring best plane by 5.3(x)° [Please complete s.u.].

Fig. 2 shows the unit-cell packing diagram for (I) and the hydrogen-bonding scheme. Hydrogen bonds link the water molecules to uncoordinated carboxylate O atoms and uncoordinated hetero-ring N atoms in adjacent monomers, forming a three-dimensional network (Table 2). Monomeric molecules with octahedral coordination around the MgII _{cation have}

been also reported for magnesium(II) picolinate (Deloume et al., 1973) and magnesium aminopyrazinate (Ptasiewicz-Bąk

et al., 1997). In both these compounds, the ligand molecules chelate the metal ion via an N,O-bonding mode. However, the ligand planes are in a cis arrangement, with a dihedral angle between the planes of 95° in the former complex and 67.3 (5)° in the latter.

S2. Experimental

A hot aqueous solution (50 ml) containing pyridazine-3-carboxylic acid (2 mmol) was added with constant stirring to a hot aqueous solution (50 ml) containing magnesium acetate tetrahydrate (1 mmol). After boiling for 1 h, the solution was left to crystallize at room temperature. After several days, single crystals of (I) in the form of colourless blocks deposited in the mother liquid. These were washed with cold water and ethanol and dried in air.

S3. Refinement

Figure 1

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Figure 2

The unit-cell packing for (I), with dashed lines indicating hydrogen bonds.

trans-Diaquabis(pyridazine-3-carboxylato-κ2_{N,O)magnesium(II) dihydrate}

Crystal data

[Mg(C5H3N2O2)2(H2O)2]·2H2O

Mr = 342.56

Triclinic, P1 Hall symbol: -P 1

a = 5.3380 (11) Å

b = 7.4680 (15) Å

c = 9.6410 (19) Å

α = 79.23 (3)°

β = 88.91 (3)°

γ = 71.93 (3)°

V = 358.63 (13) Å3

Z = 1

F(000) = 178

Dx = 1.586 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 25 reflections

θ = 6–15°

µ = 0.18 mm−1

T = 293 K Rod, colourless 0.40 × 0.09 × 0.07 mm

Data collection

Kuma KM-4 four-circle diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω/2θ scans

Absorption correction: analytical (Please give details)

2117 independent reflections 1463 reflections with I > 2σ(I)

Rint = 0.023

θmax = 30.1°, θmin = 2.2°

k = −10→10

l = −13→13

3 standard reflections every 200 reflections intensity decay: 2.1%

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.041}

wR(F2_{) = 0.137}

S = 1.06 2117 reflections 134 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: difference Fourier map All H-atom parameters refined

w = 1/[σ2_(F

o2) + (0.089P)2 + 0.0392P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.60 e Å−3

Δρmin = −0.27 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 F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

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Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

Mg1 0.0146 (3) 0.0212 (3) 0.0152 (3) −0.0020 (2) 0.0001 (2) 0.0019 (2) O3 0.0303 (6) 0.0397 (6) 0.0339 (7) −0.0114 (5) 0.0001 (5) −0.0046 (5) N2 0.0248 (6) 0.0283 (6) 0.0257 (6) −0.0066 (5) 0.0012 (5) −0.0032 (5) N1 0.0260 (6) 0.0342 (7) 0.0334 (7) −0.0056 (5) 0.0022 (5) −0.0081 (5) C4 0.0410 (9) 0.0382 (9) 0.0343 (8) −0.0105 (7) 0.0011 (7) 0.0058 (7) C6 0.0298 (8) 0.0343 (8) 0.0459 (10) −0.0019 (6) −0.0016 (7) −0.0090 (7) C3 0.0282 (7) 0.0292 (7) 0.0255 (7) −0.0084 (6) 0.0018 (6) −0.0034 (6) C5 0.0427 (10) 0.0333 (9) 0.0479 (11) −0.0019 (7) −0.0051 (8) 0.0045 (8) O2 0.0438 (7) 0.0455 (7) 0.0312 (6) −0.0115 (6) 0.0136 (5) −0.0018 (5) C7 0.0283 (7) 0.0341 (8) 0.0274 (7) −0.0109 (6) 0.0048 (6) −0.0053 (6) O1 0.0265 (5) 0.0364 (6) 0.0297 (6) −0.0039 (5) 0.0042 (4) −0.0006 (4) O4 0.0403 (8) 0.0692 (10) 0.0415 (8) −0.0117 (7) −0.0035 (6) −0.0185 (7)

Geometric parameters (Å, º)

Mg1—O1 2.0406 (13) C4—C5 1.377 (3)

Mg1—O1i _{2.0406 (13) C4—C3 1.389 (2)}

Mg1—O3 2.0909 (14) C4—H4 1.02 (3)

Mg1—O3i _{2.0909 (14) C6—C5 1.385 (3)}

Mg1—N2 2.1769 (16) C6—H6 1.00 (2)

Mg1—N2i _{2.1769 (16) C3—C7 1.534 (2)}

O3—H32 0.88 (3) C5—H5 1.00 (2)

O3—H31 0.87 (4) O2—C7 1.245 (2)

N2—C3 1.324 (2) C7—O1 1.252 (2)

N2—N1 1.3451 (19) O4—H41 1.00 (3)

N1—C6 1.323 (2) O4—H42 0.99 (3)

O1—Mg1—O1i _{180.0 N1—N2—Mg1 126.30 (10)}

O1—Mg1—O3 89.63 (6) C6—N1—N2 118.08 (14) O1i_{—Mg1—O3 90.37 (6) C5—C4—C3 116.88 (17)}

O1—Mg1—O3i _{90.37 (6) C5—C4—H4 123.0 (15)}

O1i_—Mg1—O3i _{89.63 (6) C3—C4—H4 120.0 (15)}

O3—Mg1—O3i _{180.0 N1—C6—C5 123.55 (17)}

O1—Mg1—N2 77.39 (5) N1—C6—H6 116.3 (13) O1i_{—Mg1—N2 102.61 (5) C5—C6—H6 120.1 (13)}

O3—Mg1—N2 89.87 (5) N2—C3—C4 122.34 (15) O3i_{—Mg1—N2 90.13 (5) N2—C3—C7 114.57 (13)}

O1—Mg1—N2i _{102.61 (5) C4—C3—C7 123.09 (15)}

O1i_—Mg1—N2i _{77.39 (5) C4—C5—C6 117.90 (16)}

O3—Mg1—N2i _{90.13 (5) C4—C5—H5 121.1 (15)}

O3i_—Mg1—N2i _{89.87 (5) C6—C5—H5 121.0 (15)}

N2—Mg1—N2i _{180.0 O2—C7—O1 126.75 (15)}

C3—N2—Mg1 112.42 (10)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

O3—H32···O4 0.88 (3) 1.86 (3) 2.737 (2) 175 (3) O3—H31···N1ii _{0.87 (4) 2.04 (4) 2.899 (2) 170 (3)}

O4—H41···O2iii _{1.00 (3) 1.82 (3) 2.822 (2) 173 (3)}

O4—H42···O2iv _{0.99 (3) 1.92 (3) 2.888 (2) 165 (3)}