Bis(μ-pyridine-2,4-dicarboxyl­ato)-κ3N,O2:O2;κ3O2:N,O2-bis­[triaqua­magnesium(II)]

Zhang, Q.-F.; Han, D.-D.; Pang, J.-D.; Meng, N.-N.

doi:10.1107/S1600536810030722

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 9| September 2010| Page m1067

https://doi.org/10.1107/S1600536810030722

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Bis(μ-pyridine-2,4-dicarboxylato)-κ³N,O²:O²;κ³O²:N,O²-bis[triaquamagnesium(II)]

Qing-Fu Zhang,^a ^* Dan-Dan Han,^a Jian-Dong Pang ^a and Ning-Ning Meng ^a

^aCollege of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People's Republic of China
^*Correspondence e-mail: zhangqingfu@foxmail.com

(Received 29 July 2010; accepted 2 August 2010; online 11 August 2010)

In the title centrosymmetric Mg^II complex, [Mg₂(C₇H₃NO₄)₂(H₂O)₆], each Mg cation is N,O-chelated by a pyridine-2,4-dicarboxylate dianion and is coordinated by three water molecules. A carboxylate O atom from the neighboring pyridine-2,4-dicarboxylate dianion bridges the Mg cation to complete the MgNO₅ distorted octahedral coordination geometry. The dinuclear complex molecules are linked by intermolecular O—H⋯O hydrogen bonding, forming a three-dimensional supramolecular structure.

Related literature

For the applications of Mg complexes, see: Davies et al. (2007 ); Dinca & Long (2005 ).

Experimental

Crystal data

[Mg₂(C₇H₃NO₄)₂(H₂O)₆]
M_r = 486.92
Orthorhombic, P b c a
a = 7.9221 (8) Å
b = 12.0951 (12) Å
c = 20.2989 (18) Å
V = 1945.0 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 293 K
0.25 × 0.18 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.951, T_max = 0.970
8884 measured reflections
1719 independent reflections
1289 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.100
S = 1.06
1719 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Selected bond lengths (Å)

Mg1—N1	2.2202 (19)
Mg1—O1	2.1011 (19)
Mg1—O1ⁱ	2.0613 (16)
Mg1—O5	2.0953 (19)
Mg1—O6	2.017 (2)
Mg1—O7	2.033 (2)
Symmetry code: (i) -x, -y+1, -z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5A⋯O4ⁱⁱ	0.87	1.80	2.668 (3)	172
O5—H5B⋯O2ⁱⁱⁱ	0.86	2.12	2.834 (3)	140
O6—H6A⋯O3^iv	0.87	1.73	2.576 (3)	163
O6—H6B⋯O5^v	0.87	2.07	2.880 (2)	154
O7—H7A⋯O4^vi	0.86	1.89	2.745 (2)	174
O7—H7B⋯O4^vii	0.86	2.02	2.857 (3)	166
Symmetry codes: (ii) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (iii) $[-x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (iv) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ ; (vi) $[-x+{\script{1\over 2}}, -y+1, z-{\script{1\over 2}}]$ ; (vii) $[x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; 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: https://doi.org/10.1107/S1600536810030722/xu5007sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810030722/xu5007Isup2.hkl

checkCIF report

Comment top

Magnesium(II) complexes have been extensively studied in recent year due to their wide application in synthesis of inorganic materials, catalysis of organic reactions and storage of hydrogen (Dinca & Long, 2005). In order to explore the relationship between these applications and their structures, a series of magnesium(II) complexes have been prepared and structural characterized (Davies et al., 2007). To expand research in this area, here we report a dinuclear magnesium(II) complex.

As shown in Fig.1, each magnesium(II) ion in the title complex is coordinated by two carboxyl O atoms, one pyridyl N atom and three water molecules, forming a distorted octahedral geometry (axial angle, O7—Mg1—O5 = 173.33 (9)°). Interestingly, the two adjacent magnesium(II) ions are linked by two µ₂-carboxylate O atoms to form a dinuclear strucutre.

In the crystal strucutre, these dimeric molecules are linked by intermolecular O—H···O H-bonding interactions into a three-dimensional framework (Fig.2).

Related literature top

For the applications of Mg complexes, see: Davies et al. (2007); Dinca & Long (2005).

Experimental top

A mixture of pyridine-2,4-dicarboxylic acid (16.7 mg, 0.10 mmol) and magnesium chloride hexahydrate (20.3 mg, 0.10 mmol) in 5 ml dimethyl acetamide (DMA) was heated to 373 K in a sealed 10 ml Teflon-lined reactor for 72 h. The mixture was allowed to cool to room temperature and the resulting block-shaped colorless crystals filtered from the reaction mixture. Yield, 72%.

Structure description top

In the crystal strucutre, these dimeric molecules are linked by intermolecular O—H···O H-bonding interactions into a three-dimensional framework (Fig.2).

For the applications of Mg complexes, see: Davies et al. (2007); Dinca & Long (2005).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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. The molecular structure of the title compound, showing 30% probability displacement ellipsoids.
	Fig. 2. The packing diagram of the title complex.

Bis(µ-pyridine-2,4-dicarboxylato)- κ³N,O²:O²;κ³O²:N,O²- bis[triaquamagnesium(II)] top

Crystal data top

[Mg₂(C₇H₃NO₄)₂(H₂O)₆]	F(000) = 1008
M_r = 486.92	D_x = 1.663 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2705 reflections
a = 7.9221 (8) Å	θ = 3.2–26.8°
b = 12.0951 (12) Å	µ = 0.21 mm⁻¹
c = 20.2989 (18) Å	T = 293 K
V = 1945.0 (3) Å³	Block, colorless
Z = 4	0.25 × 0.18 × 0.15 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1719 independent reflections
Radiation source: fine-focus sealed tube	1289 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
φ and ω scans	θ_max = 25.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −5→9
T_min = 0.951, T_max = 0.970	k = −14→14
8884 measured reflections	l = −24→23

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.100	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0376P)² + 1.7679P] where P = (F_o² + 2F_c²)/3
1719 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.36 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

[Mg₂(C₇H₃NO₄)₂(H₂O)₆]	V = 1945.0 (3) Å³
M_r = 486.92	Z = 4
Orthorhombic, Pbca	Mo Kα radiation
a = 7.9221 (8) Å	µ = 0.21 mm⁻¹
b = 12.0951 (12) Å	T = 293 K
c = 20.2989 (18) Å	0.25 × 0.18 × 0.15 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1719 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1289 reflections with I > 2σ(I)
T_min = 0.951, T_max = 0.970	R_int = 0.042
8884 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.100	H-atom parameters constrained
S = 1.06	Δρ_max = 0.36 e Å⁻³
1719 reflections	Δρ_min = −0.30 e Å⁻³
145 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	0.07954 (11)	0.60169 (7)	0.04323 (3)	0.0240 (2)
O1	−0.0075 (2)	0.43818 (14)	0.05141 (7)	0.0272 (4)
O2	−0.0923 (4)	0.30663 (19)	0.12021 (10)	0.0760 (9)
O3	−0.0102 (4)	0.3649 (2)	0.35781 (9)	0.0875 (11)
H6A	0.1178	0.8068	0.0765	0.105*
H5B	−0.1892	0.7246	0.0848	0.105*
H5A	−0.2377	0.6193	0.0826	0.105*
H7A	0.3503	0.5401	−0.0194	0.105*
H7B	0.4054	0.5600	0.0457	0.105*
H6B	0.2174	0.8016	0.0211	0.105*
O4	0.1026 (2)	0.51899 (15)	0.39638 (8)	0.0364 (5)
O5	−0.1604 (2)	0.66298 (14)	0.06670 (8)	0.0323 (5)
O6	0.1539 (3)	0.76106 (16)	0.04659 (9)	0.0491 (6)
O7	0.3209 (2)	0.56088 (17)	0.01937 (8)	0.0430 (5)
N1	0.1126 (3)	0.56101 (17)	0.14911 (9)	0.0257 (5)
C1	−0.0232 (4)	0.3941 (2)	0.10852 (11)	0.0325 (6)
C2	0.0461 (3)	0.4620 (2)	0.16485 (11)	0.0261 (6)
C3	0.0314 (3)	0.4258 (2)	0.22895 (11)	0.0302 (6)
H3	−0.0135	0.3564	0.2378	0.036*
C4	0.0838 (3)	0.4934 (2)	0.28011 (11)	0.0281 (6)
C5	0.0576 (4)	0.4556 (2)	0.35037 (12)	0.0361 (7)
C6	0.1530 (4)	0.5952 (2)	0.26430 (11)	0.0318 (6)
H6	0.1902	0.6426	0.2973	0.038*
C7	0.1660 (4)	0.6255 (2)	0.19836 (11)	0.0325 (6)
H7	0.2139	0.6935	0.1881	0.039*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mg1	0.0328 (5)	0.0234 (5)	0.0157 (4)	−0.0004 (4)	0.0015 (3)	−0.0008 (3)
O1	0.0415 (11)	0.0250 (10)	0.0151 (8)	0.0001 (8)	−0.0028 (8)	0.0000 (7)
O2	0.151 (3)	0.0485 (15)	0.0289 (11)	−0.0543 (16)	−0.0205 (13)	0.0080 (10)
O3	0.176 (3)	0.0627 (17)	0.0241 (11)	−0.0682 (19)	0.0088 (14)	0.0028 (10)
O4	0.0497 (12)	0.0419 (12)	0.0176 (8)	−0.0064 (9)	−0.0043 (8)	−0.0016 (8)
O5	0.0379 (11)	0.0271 (10)	0.0320 (9)	0.0057 (8)	0.0049 (8)	−0.0031 (8)
O6	0.0683 (15)	0.0308 (11)	0.0482 (12)	−0.0158 (10)	0.0282 (11)	−0.0089 (9)
O7	0.0339 (11)	0.0693 (15)	0.0260 (9)	0.0104 (10)	−0.0014 (8)	−0.0103 (9)
N1	0.0348 (13)	0.0239 (12)	0.0185 (10)	−0.0021 (9)	−0.0003 (9)	0.0002 (8)
C1	0.0538 (18)	0.0229 (14)	0.0208 (13)	−0.0060 (13)	−0.0040 (12)	−0.0003 (11)
C2	0.0327 (15)	0.0238 (14)	0.0220 (12)	−0.0006 (11)	−0.0008 (11)	0.0010 (10)
C3	0.0445 (17)	0.0256 (14)	0.0205 (12)	−0.0074 (12)	−0.0023 (12)	0.0028 (10)
C4	0.0349 (15)	0.0301 (15)	0.0194 (12)	−0.0011 (12)	−0.0010 (11)	0.0007 (10)
C5	0.0526 (19)	0.0362 (17)	0.0193 (13)	−0.0074 (14)	−0.0014 (12)	0.0027 (12)
C6	0.0449 (16)	0.0308 (15)	0.0196 (12)	−0.0068 (13)	−0.0052 (12)	−0.0026 (10)
C7	0.0466 (17)	0.0275 (15)	0.0236 (13)	−0.0102 (13)	−0.0025 (12)	0.0009 (11)

Geometric parameters (Å, º) top

Mg1—N1	2.2202 (19)	O7—H7A	0.8581
Mg1—O1	2.1011 (19)	O7—H7B	0.8563
Mg1—O1ⁱ	2.0613 (16)	N1—C7	1.336 (3)
Mg1—O5	2.0953 (19)	N1—C2	1.347 (3)
Mg1—O6	2.017 (2)	C1—C2	1.511 (3)
Mg1—O7	2.033 (2)	C2—C3	1.378 (3)
O1—C1	1.282 (3)	C3—C4	1.385 (3)
O2—C1	1.215 (3)	C3—H3	0.9300
O3—C5	1.231 (3)	C4—C6	1.385 (4)
O4—C5	1.260 (3)	C4—C5	1.512 (3)
O5—H5B	0.8616	C6—C7	1.392 (3)
O5—H5A	0.8701	C6—H6	0.9300
O6—H6A	0.8688	C7—H7	0.9300
O6—H6B	0.8725

O6—Mg1—O7	88.02 (9)	H6A—O6—H6B	104.2
O6—Mg1—O1ⁱ	109.63 (8)	Mg1—O7—H7A	123.0
O7—Mg1—O1ⁱ	88.93 (7)	Mg1—O7—H7B	126.1
O6—Mg1—O5	85.36 (8)	H7A—O7—H7B	110.8
O7—Mg1—O5	173.33 (9)	C7—N1—C2	117.7 (2)
O1ⁱ—Mg1—O5	92.50 (7)	C7—N1—Mg1	129.22 (17)
O6—Mg1—O1	173.16 (8)	C2—N1—Mg1	112.37 (15)
O7—Mg1—O1	95.68 (8)	O2—C1—O1	125.6 (2)
O1ⁱ—Mg1—O1	76.26 (7)	O2—C1—C2	119.3 (2)
O5—Mg1—O1	90.98 (8)	O1—C1—C2	115.0 (2)
O6—Mg1—N1	98.32 (8)	N1—C2—C3	122.7 (2)
O7—Mg1—N1	93.77 (8)	N1—C2—C1	116.5 (2)
O1ⁱ—Mg1—N1	152.00 (8)	C3—C2—C1	120.7 (2)
O5—Mg1—N1	88.02 (8)	C2—C3—C4	119.7 (2)
O1—Mg1—N1	75.74 (7)	C2—C3—H3	120.2
O6—Mg1—Mg1ⁱ	148.06 (7)	C4—C3—H3	120.2
O7—Mg1—Mg1ⁱ	92.97 (6)	C6—C4—C3	118.0 (2)
O1ⁱ—Mg1—Mg1ⁱ	38.56 (5)	C6—C4—C5	122.8 (2)
O5—Mg1—Mg1ⁱ	92.20 (6)	C3—C4—C5	119.2 (2)
O1—Mg1—Mg1ⁱ	37.70 (4)	O3—C5—O4	125.1 (2)
N1—Mg1—Mg1ⁱ	113.44 (7)	O3—C5—C4	116.5 (2)
C1—O1—Mg1ⁱ	135.94 (16)	O4—C5—C4	118.4 (2)
C1—O1—Mg1	119.66 (15)	C4—C6—C7	119.1 (2)
Mg1ⁱ—O1—Mg1	103.74 (7)	C4—C6—H6	120.5
Mg1—O5—H5B	130.0	C7—C6—H6	120.5
Mg1—O5—H5A	120.5	N1—C7—C6	122.9 (2)
H5B—O5—H5A	100.5	N1—C7—H7	118.6
Mg1—O6—H6A	122.4	C6—C7—H7	118.6
Mg1—O6—H6B	133.3

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O4ⁱⁱ	0.87	1.80	2.668 (3)	172
O5—H5B···O2ⁱⁱⁱ	0.86	2.12	2.834 (3)	140
O6—H6A···O3^iv	0.87	1.73	2.576 (3)	163
O6—H6B···O5^v	0.87	2.07	2.880 (2)	154
O7—H7A···O4^vi	0.86	1.89	2.745 (2)	174
O7—H7B···O4^vii	0.86	2.02	2.857 (3)	166

Symmetry codes: (ii) x−1/2, y, −z+1/2; (iii) −x−1/2, y+1/2, z; (iv) −x, y+1/2, −z+1/2; (v) x+1/2, −y+3/2, −z; (vi) −x+1/2, −y+1, z−1/2; (vii) x+1/2, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Mg₂(C₇H₃NO₄)₂(H₂O)₆]
M_r	486.92
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	7.9221 (8), 12.0951 (12), 20.2989 (18)
V (Å³)	1945.0 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.21
Crystal size (mm)	0.25 × 0.18 × 0.15

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.951, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	8884, 1719, 1289
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.100, 1.06
No. of reflections	1719
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.30

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Mg1—N1	2.2202 (19)	Mg1—O5	2.0953 (19)
Mg1—O1	2.1011 (19)	Mg1—O6	2.017 (2)
Mg1—O1ⁱ	2.0613 (16)	Mg1—O7	2.033 (2)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O4ⁱⁱ	0.87	1.80	2.668 (3)	171.5
O5—H5B···O2ⁱⁱⁱ	0.86	2.12	2.834 (3)	139.9
O6—H6A···O3^iv	0.87	1.73	2.576 (3)	163.2
O6—H6B···O5^v	0.87	2.07	2.880 (2)	153.5
O7—H7A···O4^vi	0.86	1.89	2.745 (2)	173.5
O7—H7B···O4^vii	0.86	2.02	2.857 (3)	166.4

Symmetry codes: (ii) x−1/2, y, −z+1/2; (iii) −x−1/2, y+1/2, z; (iv) −x, y+1/2, −z+1/2; (v) x+1/2, −y+3/2, −z; (vi) −x+1/2, −y+1, z−1/2; (vii) x+1/2, y, −z+1/2.

Acknowledgements

We acknowledge the Scientific Research Startup Fund of Liaocheng University (31805) and the Students Science and Technology Innovation Fund of Liaocheng University, China (SRT10060HX2).

References

Davies, R. P., Less, R. J., Lickiss, P. D. & White, A. J. P. (2007). Dalton Trans. pp. 2528–2535. Web of Science CSD CrossRef Google Scholar
Dinca, M. & Long, J. R. (2005). J. Am. Chem. Soc. 127, 9376–9377. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens. (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar

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