trans-Tetra­aqua­bis­(pyridazine-4-car­box­yl­ato-κO)magnesium(II) dihydrate

Starosta, W.; Leciejewicz, J.

doi:10.1107/S1600536811004168

metal-organic compounds

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Volume 67| Part 3| March 2011| Page m316

doi:10.1107/S1600536811004168

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trans-Tetraaquabis(pyridazine-4-carboxylato-κO)magnesium(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: j.leciejewicz@ichtj.waw.pl

(Received 1 February 2011; accepted 3 February 2011; online 9 February 2011)

The crystal structure of the title compound, [Mg(C₅H₃N₂O₂)₂(H₂O)₄]·2H₂O, is composed of centrosymmetric monomers in which an Mg^II ion is coordinated by two carboxylate O atoms from the two pyridazine-4-carboxylate ligands. The monomers linked by O—H⋯O and O—H⋯N hydrogen bonds into layers which are held together by hydrogen bonds in which solvent water O atoms act as donors and acceptors, resulting in a three-dimensional network.

Related literature

For the crystal structure of a Pb(II) complex with pyridazine-4-carboxylate and water ligands, see: Starosta & Leciejewicz, (2009 ). The structure of pyridazine-4-carboxylic acid hydrochloride was determined earlier (Starosta & Leciejewicz, 2008 ). The structure of a Mg^II complex with pyridazine-3-carboxylate and water ligands has been also reported by Gryz et al. (2006 ).

Experimental

Crystal data

[Mg(C₅H₃N₂O₂)₂(H₂O)₄]·2H₂O
M_r = 378.59
Monoclinic, P 2₁ /c
a = 7.2571 (15) Å
b = 11.688 (2) Å
c = 10.550 (2) Å
β = 108.36 (3)°
V = 849.3 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.16 mm⁻¹
T = 293 K
0.24 × 0.22 × 0.08 mm

Data collection

Kuma KM-4 four-circle diffractometer
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008) $[Oxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ T_min = 0.968, T_max = 0.987
2007 measured reflections
1873 independent reflections
1136 reflections with I > 2σ(I)
R_int = 0.023
3 standard reflections every 200 reflections intensity decay: 1.3%

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.122
S = 1.04
1873 reflections
139 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H31⋯O5	0.83 (2)	1.97 (2)	2.775 (3)	164 (3)
O4—H42⋯N1ⁱ	0.81 (2)	2.01 (2)	2.817 (2)	172 (3)
O5—H51⋯N2ⁱⁱ	0.82 (2)	1.98 (2)	2.798 (3)	179 (3)
O3—H32⋯O2ⁱⁱⁱ	0.80 (2)	1.92 (2)	2.675 (2)	159 (3)
O5—H52⋯O2^iv	0.81 (2)	1.97 (2)	2.765 (3)	168 (3)
O4—H41⋯O5^v	0.80 (2)	1.97 (2)	2.766 (3)	175 (3)
Symmetry codes: (i) x, y, z+1; (ii) -x+1, -y+1, -z; (iii) -x+1, -y+1, -z+1; (iv) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) x-1, y, z.

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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811004168/kp2307sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811004168/kp2307Isup2.hkl

checkCIF report

Comment top

The structure of the title compound (I) is built of monomeric molecules in which the Mg⁺² located in an inversion centre is chelated by two carboxylate atoms each donated by one of symmetry ralated ligand molecules and by two pairs of aqua O atoms resulting in a slightly distorted octahedral geometry. The carboxylate O1, O1⁽ⁱ⁾ and aqua O3, O3⁽ⁱ⁾ atoms form an equatorial plane, aqua O4 and O4⁽ⁱ⁾ atoms are at the axial positions. The observed Mg—O bond lengths and bond angles are almost the same as reported for the complex with pyridazine-3-carboxylate and water ligands (Gryz et al., 2006). The pyridazine ring is planar with r.m.s. of 0.0046 (1) Å. The observed bond distances and angles are close to those reported for the parent acid (Starosta & Leciejewicz, 2008). The carboxylate group is rotated from the mean plane by 8.1 (1)°. Hydrogen bonds link the monomers to form molecular sheets. They operate between coordinated water O atoms as donors and uncoordinated carboxylate O atoms and pyridazine-N atoms in adjacent monomers as acceptors. The sheets are held together by hydrogen bonds in which crystal water molecules act as donors and acceptors resulting in a three-dimensional network. The coordination mode reported in the structure of a Mg^II complex with pyridazine-3-carboxylate and water ligands is also octahedral but the Mg^II ion is coordinated by a pair of symmetry related N,O-chelating groups of the ligands and a pair of water O atoms (Gryz et al., 2006). The Pb(II) complex with the title ligand shows entirely different coordination mode. Two symmetry related metal ions form a dimer in which they are bridged by hetero-ring N atoms of two symmetry related ligands amd two aqua-O atoms. Each Pb(II) ion is also coordinated by both carboxylate O atoms of another ligand whose hetero-ring N atoms do not coordinate to Pb(II). (Starosta & Leciejewicz, 2009).

Related literature top

For the crystal structure of a Pb(II) complex with pyridazine-4-carboxylate and water ligands, see: Starosta & Leciejewicz, (2009). The structure of pyridazine-4-carboxylic acid hydrochloride was determined earlier (Starosta & Leciejewicz, 2008). The structure of a Mg^II complex with pyridazine-3-carboxylate and water ligands has been also reported by Gryz et al. (2006).

Experimental top

The title compound was obtained by mixing boiling aqueous solutions, one containig 2 mmols of pyridazine-4-carboxylic acid (Aldrich), the other 1 mmol of magnesium diacetate tetrahydrate (Aldrich). The mixture was boiled under reflux for two h, then cooled to room temperature and left to crystallise. A few days latter, colourless crystalline plates were found after evaporation to dryness. They were recrystallised from water several times until well formed single crystals were obtained. Crystals were washed with cold ethanol and dried in the 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A structural unit of (I) with atom labelling scheme and the 50% probability displacement ellipsoids. Symmetry code: (i) -x + 1,-y + 1,-z + 1. (ii) x, y, z + 1.
	Fig. 2. Crystal packing of I.

trans-Tetraaquabis(pyridazine-4-carboxylato-κO)magnesium(II) dihydrate top

Crystal data top

[Mg(C₅H₃N₂O₂)₂(H2O)₄]·2H2O	F(000) = 396
M_r = 378.59	D_x = 1.480 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.2571 (15) Å	Cell parameters from 25 reflections
b = 11.688 (2) Å	θ = 6–15°
c = 10.550 (2) Å	µ = 0.16 mm⁻¹
β = 108.36 (3)°	T = 293 K
V = 849.3 (3) Å³	Plate, colourless
Z = 2	0.24 × 0.22 × 0.08 mm

Data collection top

Kuma KM-4 four-circle diffractometer	1136 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.023
Graphite monochromator	θ_max = 27.7°, θ_min = 2.7°
profile data from ω/2θ scans	h = −9→0
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008)	k = 0→15
T_min = 0.968, T_max = 0.987	l = −13→12
2007 measured reflections	3 standard reflections every 200 reflections
1873 independent reflections	intensity decay: 1.3%

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0628P)² + 0.293P] where P = (F_o² + 2F_c²)/3
1873 reflections	(Δ/σ)_max < 0.001
139 parameters	Δρ_max = 0.28 e Å⁻³
6 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

[Mg(C₅H₃N₂O₂)₂(H2O)₄]·2H2O	V = 849.3 (3) Å³
M_r = 378.59	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.2571 (15) Å	µ = 0.16 mm⁻¹
b = 11.688 (2) Å	T = 293 K
c = 10.550 (2) Å	0.24 × 0.22 × 0.08 mm
β = 108.36 (3)°

Data collection top

Kuma KM-4 four-circle diffractometer	1136 reflections with I > 2σ(I)
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008)	R_int = 0.023
T_min = 0.968, T_max = 0.987	3 standard reflections every 200 reflections
2007 measured reflections	intensity decay: 1.3%
1873 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	6 restraints
wR(F²) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.28 e Å⁻³
1873 reflections	Δρ_min = −0.21 e Å⁻³
139 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
Mg1	0.5000	0.5000	0.5000	0.0236 (3)
O1	0.3810 (2)	0.54000 (14)	0.29844 (14)	0.0318 (4)
O2	0.2156 (3)	0.38329 (15)	0.20927 (16)	0.0453 (5)
N1	0.2554 (3)	0.58217 (18)	−0.19230 (18)	0.0339 (5)
C7	0.2921 (3)	0.47760 (19)	0.2019 (2)	0.0284 (5)
N2	0.1945 (3)	0.47789 (17)	−0.16963 (18)	0.0336 (5)
C5	0.3386 (3)	0.62622 (19)	0.0395 (2)	0.0311 (5)
H5	0.3895	0.6782	0.1084	0.037*
C4	0.2765 (3)	0.52021 (19)	0.0639 (2)	0.0260 (5)
C3	0.2036 (3)	0.4491 (2)	−0.0472 (2)	0.0312 (5)
H3	0.1587	0.3770	−0.0338	0.037*
C6	0.3231 (4)	0.6534 (2)	−0.0916 (2)	0.0344 (5)
H6	0.3626	0.7257	−0.1092	0.041*
O4	0.2870 (2)	0.59132 (16)	0.54856 (16)	0.0347 (4)
O5	0.9316 (3)	0.67116 (16)	0.38743 (16)	0.0358 (4)
O3	0.6662 (3)	0.64863 (14)	0.52618 (17)	0.0338 (4)
H31	0.751 (4)	0.642 (3)	0.489 (3)	0.056 (10)*
H42	0.267 (5)	0.586 (3)	0.620 (2)	0.058 (10)*
H51	0.896 (4)	0.628 (2)	0.323 (2)	0.041 (8)*
H32	0.711 (5)	0.656 (3)	0.6052 (19)	0.062 (10)*
H52	0.905 (5)	0.7357 (18)	0.360 (3)	0.065 (11)*
H41	0.187 (3)	0.614 (2)	0.498 (3)	0.048 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mg1	0.0276 (5)	0.0249 (5)	0.0176 (5)	−0.0002 (4)	0.0061 (4)	0.0006 (4)
O1	0.0389 (9)	0.0329 (8)	0.0207 (7)	−0.0020 (7)	0.0052 (6)	−0.0005 (6)
O2	0.0681 (13)	0.0384 (10)	0.0276 (8)	−0.0184 (9)	0.0126 (8)	−0.0026 (7)
N1	0.0380 (11)	0.0409 (11)	0.0239 (9)	0.0057 (9)	0.0111 (8)	0.0042 (8)
C7	0.0290 (11)	0.0335 (12)	0.0221 (10)	0.0032 (9)	0.0073 (9)	−0.0013 (8)
N2	0.0374 (11)	0.0386 (11)	0.0221 (9)	0.0020 (8)	0.0056 (8)	−0.0031 (7)
C5	0.0363 (12)	0.0314 (12)	0.0242 (10)	0.0000 (9)	0.0077 (9)	−0.0046 (9)
C4	0.0223 (10)	0.0325 (12)	0.0221 (10)	0.0044 (8)	0.0052 (8)	−0.0014 (8)
C3	0.0353 (12)	0.0309 (12)	0.0252 (11)	0.0003 (10)	0.0063 (9)	−0.0028 (9)
C6	0.0408 (13)	0.0328 (12)	0.0305 (11)	0.0024 (10)	0.0125 (10)	0.0013 (10)
O4	0.0337 (9)	0.0476 (10)	0.0230 (8)	0.0114 (8)	0.0091 (7)	0.0051 (7)
O5	0.0403 (10)	0.0352 (10)	0.0269 (8)	0.0016 (8)	0.0035 (7)	−0.0006 (7)
O3	0.0407 (10)	0.0342 (9)	0.0276 (9)	−0.0055 (7)	0.0123 (8)	0.0010 (7)

Geometric parameters (Å, º) top

Mg1—O4ⁱ	2.0714 (17)	C5—C4	1.370 (3)
Mg1—O4	2.0714 (17)	C5—C6	1.389 (3)
Mg1—O1ⁱ	2.0807 (16)	C5—H5	0.9300
Mg1—O1	2.0807 (16)	C4—C3	1.398 (3)
Mg1—O3	2.0829 (17)	C3—H3	0.9300
Mg1—O3ⁱ	2.0829 (17)	C6—H6	0.9300
Mg1—H32	2.42 (3)	O4—H42	0.809 (18)
O1—C7	1.254 (3)	O4—H41	0.798 (18)
O2—C7	1.248 (3)	O5—H51	0.819 (17)
N1—C6	1.317 (3)	O5—H52	0.809 (18)
N1—N2	1.343 (3)	O3—H31	0.828 (18)
C7—C4	1.509 (3)	O3—H32	0.799 (18)
N2—C3	1.316 (3)

O4ⁱ—Mg1—O4	180.00 (6)	O2—C7—O1	126.0 (2)
O4ⁱ—Mg1—O1ⁱ	92.02 (7)	O2—C7—C4	116.88 (19)
O4—Mg1—O1ⁱ	87.99 (7)	O1—C7—C4	117.1 (2)
O4ⁱ—Mg1—O1	87.98 (7)	C3—N2—N1	119.28 (19)
O4—Mg1—O1	92.02 (7)	C4—C5—C6	117.8 (2)
O1ⁱ—Mg1—O1	180.0	C4—C5—H5	121.1
O4ⁱ—Mg1—O3	90.95 (7)	C6—C5—H5	121.1
O4—Mg1—O3	89.05 (7)	C5—C4—C3	116.1 (2)
O1ⁱ—Mg1—O3	90.88 (7)	C5—C4—C7	123.40 (19)
O1—Mg1—O3	89.12 (7)	C3—C4—C7	120.4 (2)
O4ⁱ—Mg1—O3ⁱ	89.05 (7)	N2—C3—C4	124.0 (2)
O4—Mg1—O3ⁱ	90.95 (7)	N2—C3—H3	118.0
O1ⁱ—Mg1—O3ⁱ	89.12 (7)	C4—C3—H3	118.0
O1—Mg1—O3ⁱ	90.88 (7)	N1—C6—C5	123.5 (2)
O3—Mg1—O3ⁱ	180.000 (1)	N1—C6—H6	118.3
O4ⁱ—Mg1—H32	95.0 (8)	C5—C6—H6	118.3
O4—Mg1—H32	85.0 (8)	Mg1—O4—H42	123 (2)
O1ⁱ—Mg1—H32	72.6 (6)	Mg1—O4—H41	127 (2)
O1—Mg1—H32	107.4 (6)	H42—O4—H41	105 (3)
O3—Mg1—H32	18.6 (6)	H51—O5—H52	108 (3)
O3ⁱ—Mg1—H32	161.4 (6)	Mg1—O3—H31	110 (2)
C7—O1—Mg1	129.89 (15)	Mg1—O3—H32	105 (2)
C6—N1—N2	119.35 (19)	H31—O3—H32	112 (3)

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
O3—H31···O5	0.83 (2)	1.97 (2)	2.775 (3)	164 (3)
O4—H42···N1ⁱⁱ	0.81 (2)	2.01 (2)	2.817 (2)	172 (3)
O5—H51···N2ⁱⁱⁱ	0.82 (2)	1.98 (2)	2.798 (3)	179 (3)
O3—H32···O2ⁱ	0.80 (2)	1.92 (2)	2.675 (2)	159 (3)
O5—H52···O2^iv	0.81 (2)	1.97 (2)	2.765 (3)	168 (3)
O4—H41···O5^v	0.80 (2)	1.97 (2)	2.766 (3)	175 (3)

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

Experimental details

Crystal data
Chemical formula	[Mg(C₅H₃N₂O₂)₂(H2O)₄]·2H2O
M_r	378.59
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	7.2571 (15), 11.688 (2), 10.550 (2)
β (°)	108.36 (3)
V (Å³)	849.3 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.16
Crystal size (mm)	0.24 × 0.22 × 0.08

Data collection
Diffractometer	Kuma KM-4 four-circle diffractometer
Absorption correction	Analytical (CrysAlis RED; Oxford Diffraction, 2008)
T_min, T_max	0.968, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	2007, 1873, 1136
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.654

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.122, 1.04
No. of reflections	1873
No. of parameters	139
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.21

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
O3—H31···O5	0.828 (18)	1.97 (2)	2.775 (3)	164 (3)
O4—H42···N1ⁱ	0.809 (18)	2.013 (19)	2.817 (2)	172 (3)
O5—H51···N2ⁱⁱ	0.819 (17)	1.979 (18)	2.798 (3)	179 (3)
O3—H32···O2ⁱⁱⁱ	0.799 (18)	1.92 (2)	2.675 (2)	159 (3)
O5—H52···O2^iv	0.809 (18)	1.968 (19)	2.765 (3)	168 (3)
O4—H41···O5^v	0.798 (18)	1.970 (18)	2.766 (3)	175 (3)

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

References

Gryz, M., Starosta, W. & Leciejewicz, J. (2006). Acta Cryst. E62, m123–m124. Web of Science CSD CrossRef IUCr Journals 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. (2008). Acta Cryst. E64, o461. Web of Science CSD CrossRef IUCr Journals Google Scholar
Starosta, W. & Leciejewicz, J. (2009). Acta Cryst. E65, m1291. Web of Science CrossRef IUCr Journals Google Scholar

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