Download citation
Download citation
link to html
The title compound, [Mg(C5H3N2O2)2(H2O)2]·2H2O, contains centrosymmetric neutral complex mol­ecules. The pyridazine-3-carboxyl­ate ligands bond in an N,O-bidentate mode and the octa­hedral Mg coordination is completed by two trans water mol­ecules. There are also two non-coordinated water mol­ecules. O—H...O and O—H...N hydrogen bonds are present, resulting in a three-dimensional network.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805041516/hb6299sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805041516/hb6299Isup2.hkl
Contains datablock I

CCDC reference: 296564

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.041
  • wR factor = 0.137
  • Data-to-parameter ratio = 15.8

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X) Mg1 - O1 .. 17.61 su PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X) Mg1 - O3 .. 13.81 su PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X) Mg1 - N2 .. 16.87 su
Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.28 PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ? PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature . 293 K PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C3 - C7 ... 1.53 Ang.
0 ALERT level A = In general: serious problem 3 ALERT level B = Potentially serious problem 6 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

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.

Experimental top

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.

Refinement top

H atoms were located in difference maps and freely refined with isotropic displacement parameters. The largest electron-density peak is 0.47 Å from Mg1 and the deepest hole is 0.62 Å from O3.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. A view of (I), showing 50% displacement ellipsoids (arbitrary spheres for the H atoms). Unlabelled atoms are generated by the symmetry operation (1 − x, 1 − y, 1 − z).
[Figure 2] Fig. 2. The unit-cell packing for (I), with dashed lines indicating hydrogen bonds.
trans-Diaquabis(pyridazine-3-carboxylato-κ2N,O)magnesium(II) dihydrate top
Crystal data top
[Mg(C5H3N2O2)2(H2O)2]·2H2OZ = 1
Mr = 342.56F(000) = 178
Triclinic, P1Dx = 1.586 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.3380 (11) ÅCell parameters from 25 reflections
b = 7.4680 (15) Åθ = 6–15°
c = 9.6410 (19) ŵ = 0.18 mm1
α = 79.23 (3)°T = 293 K
β = 88.91 (3)°Rod, colourless
γ = 71.93 (3)°0.40 × 0.09 × 0.07 mm
V = 358.63 (13) Å3
Data collection top
Kuma KM-4 four-circle
diffractometer
1463 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.023
Graphite monochromatorθmax = 30.1°, θmin = 2.2°
ω/2θ scansh = 70
Absorption correction: analytical
(Please give details)
k = 1010
Tmin = 0.978, Tmax = 0.986l = 1313
2327 measured reflections3 standard reflections every 200 reflections
2117 independent reflections intensity decay: 2.1%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: difference Fourier map
wR(F2) = 0.137All H-atom parameters refined
S = 1.06 w = 1/[σ2(Fo2) + (0.089P)2 + 0.0392P]
where P = (Fo2 + 2Fc2)/3
2117 reflections(Δ/σ)max < 0.001
134 parametersΔρmax = 0.60 e Å3
0 restraintsΔρmin = 0.27 e Å3
Crystal data top
[Mg(C5H3N2O2)2(H2O)2]·2H2Oγ = 71.93 (3)°
Mr = 342.56V = 358.63 (13) Å3
Triclinic, P1Z = 1
a = 5.3380 (11) ÅMo Kα radiation
b = 7.4680 (15) ŵ = 0.18 mm1
c = 9.6410 (19) ÅT = 293 K
α = 79.23 (3)°0.40 × 0.09 × 0.07 mm
β = 88.91 (3)°
Data collection top
Kuma KM-4 four-circle
diffractometer
1463 reflections with I > 2σ(I)
Absorption correction: analytical
(Please give details)
Rint = 0.023
Tmin = 0.978, Tmax = 0.9863 standard reflections every 200 reflections
2327 measured reflections intensity decay: 2.1%
2117 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.137All H-atom parameters refined
S = 1.06Δρmax = 0.60 e Å3
2117 reflectionsΔρmin = 0.27 e Å3
134 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
xyzUiso*/Ueq
Mg10.50000.50000.50000.01854 (18)
O30.3335 (2)0.32486 (19)0.41261 (15)0.0348 (3)
N20.2316 (2)0.75238 (18)0.36709 (14)0.0269 (3)
N10.0111 (3)0.8530 (2)0.39952 (15)0.0319 (3)
C40.2138 (4)0.9778 (3)0.1549 (2)0.0400 (4)
C60.1353 (3)1.0153 (3)0.3130 (2)0.0383 (4)
C30.3386 (3)0.8087 (2)0.24865 (16)0.0280 (3)
C50.0306 (4)1.0855 (3)0.1899 (2)0.0452 (5)
O20.7120 (3)0.71295 (19)0.11011 (13)0.0417 (3)
C70.6101 (3)0.6727 (2)0.22408 (17)0.0298 (3)
O10.7068 (2)0.53239 (17)0.32189 (12)0.0331 (3)
H320.298 (6)0.369 (4)0.322 (3)0.065 (8)*
H310.222 (7)0.285 (5)0.467 (4)0.089 (11)*
O40.2412 (3)0.4743 (3)0.12985 (16)0.0505 (4)
H50.128 (5)1.211 (4)0.130 (3)0.052 (7)*
H410.059 (7)0.568 (4)0.119 (3)0.069 (8)*
H420.290 (6)0.410 (4)0.048 (3)0.073 (9)*
H60.310 (5)1.092 (3)0.343 (2)0.040 (6)*
H40.309 (5)1.022 (4)0.069 (3)0.053 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mg10.0146 (3)0.0212 (3)0.0152 (3)0.0020 (2)0.0001 (2)0.0019 (2)
O30.0303 (6)0.0397 (6)0.0339 (7)0.0114 (5)0.0001 (5)0.0046 (5)
N20.0248 (6)0.0283 (6)0.0257 (6)0.0066 (5)0.0012 (5)0.0032 (5)
N10.0260 (6)0.0342 (7)0.0334 (7)0.0056 (5)0.0022 (5)0.0081 (5)
C40.0410 (9)0.0382 (9)0.0343 (8)0.0105 (7)0.0011 (7)0.0058 (7)
C60.0298 (8)0.0343 (8)0.0459 (10)0.0019 (6)0.0016 (7)0.0090 (7)
C30.0282 (7)0.0292 (7)0.0255 (7)0.0084 (6)0.0018 (6)0.0034 (6)
C50.0427 (10)0.0333 (9)0.0479 (11)0.0019 (7)0.0051 (8)0.0045 (8)
O20.0438 (7)0.0455 (7)0.0312 (6)0.0115 (6)0.0136 (5)0.0018 (5)
C70.0283 (7)0.0341 (8)0.0274 (7)0.0109 (6)0.0048 (6)0.0053 (6)
O10.0265 (5)0.0364 (6)0.0297 (6)0.0039 (5)0.0042 (4)0.0006 (4)
O40.0403 (8)0.0692 (10)0.0415 (8)0.0117 (7)0.0035 (6)0.0185 (7)
Geometric parameters (Å, º) top
Mg1—O12.0406 (13)C4—C51.377 (3)
Mg1—O1i2.0406 (13)C4—C31.389 (2)
Mg1—O32.0909 (14)C4—H41.02 (3)
Mg1—O3i2.0909 (14)C6—C51.385 (3)
Mg1—N22.1769 (16)C6—H61.00 (2)
Mg1—N2i2.1769 (16)C3—C71.534 (2)
O3—H320.88 (3)C5—H51.00 (2)
O3—H310.87 (4)O2—C71.245 (2)
N2—C31.324 (2)C7—O11.252 (2)
N2—N11.3451 (19)O4—H411.00 (3)
N1—C61.323 (2)O4—H420.99 (3)
O1—Mg1—O1i180.0N1—N2—Mg1126.30 (10)
O1—Mg1—O389.63 (6)C6—N1—N2118.08 (14)
O1i—Mg1—O390.37 (6)C5—C4—C3116.88 (17)
O1—Mg1—O3i90.37 (6)C5—C4—H4123.0 (15)
O1i—Mg1—O3i89.63 (6)C3—C4—H4120.0 (15)
O3—Mg1—O3i180.0N1—C6—C5123.55 (17)
O1—Mg1—N277.39 (5)N1—C6—H6116.3 (13)
O1i—Mg1—N2102.61 (5)C5—C6—H6120.1 (13)
O3—Mg1—N289.87 (5)N2—C3—C4122.34 (15)
O3i—Mg1—N290.13 (5)N2—C3—C7114.57 (13)
O1—Mg1—N2i102.61 (5)C4—C3—C7123.09 (15)
O1i—Mg1—N2i77.39 (5)C4—C5—C6117.90 (16)
O3—Mg1—N2i90.13 (5)C4—C5—H5121.1 (15)
O3i—Mg1—N2i89.87 (5)C6—C5—H5121.0 (15)
N2—Mg1—N2i180.0O2—C7—O1126.75 (15)
Mg1—O3—H32110.6 (19)O2—C7—C3117.09 (14)
Mg1—O3—H31113 (2)O1—C7—C3116.16 (13)
H32—O3—H31121 (3)C7—O1—Mg1119.08 (10)
C3—N2—N1121.16 (13)H41—O4—H42113 (3)
C3—N2—Mg1112.42 (10)
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H32···O40.88 (3)1.86 (3)2.737 (2)175 (3)
O3—H31···N1ii0.87 (4)2.04 (4)2.899 (2)170 (3)
O4—H41···O2iii1.00 (3)1.82 (3)2.822 (2)173 (3)
O4—H42···O2iv0.99 (3)1.92 (3)2.888 (2)165 (3)
Symmetry codes: (ii) x, y+1, z+1; (iii) x1, y, z; (iv) x+1, y+1, z.

Experimental details

Crystal data
Chemical formula[Mg(C5H3N2O2)2(H2O)2]·2H2O
Mr342.56
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)5.3380 (11), 7.4680 (15), 9.6410 (19)
α, β, γ (°)79.23 (3), 88.91 (3), 71.93 (3)
V3)358.63 (13)
Z1
Radiation typeMo Kα
µ (mm1)0.18
Crystal size (mm)0.40 × 0.09 × 0.07
Data collection
DiffractometerKuma KM-4 four-circle
diffractometer
Absorption correctionAnalytical
(Please give details)
Tmin, Tmax0.978, 0.986
No. of measured, independent and
observed [I > 2σ(I)] reflections
2327, 2117, 1463
Rint0.023
(sin θ/λ)max1)0.705
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.137, 1.06
No. of reflections2117
No. of parameters134
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.60, 0.27

Computer programs: KM-4 Software (Kuma, 1996), KM-4 Software, DATAPROC (Kuma, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1992), SHELXL97.

Selected geometric parameters (Å, º) top
Mg1—O12.0406 (13)Mg1—N22.1769 (16)
Mg1—O32.0909 (14)
O1—Mg1—N277.39 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H32···O40.88 (3)1.86 (3)2.737 (2)175 (3)
O3—H31···N1i0.87 (4)2.04 (4)2.899 (2)170 (3)
O4—H41···O2ii1.00 (3)1.82 (3)2.822 (2)173 (3)
O4—H42···O2iii0.99 (3)1.92 (3)2.888 (2)165 (3)
Symmetry codes: (i) x, y+1, z+1; (ii) x1, y, z; (iii) x+1, y+1, z.
 

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds