Diaqua­bis(2-methyl-1H-imidazol-3-ium-4,5-dicarboxyl­ato-κ2O,O′)magnesium

Li, Y.L.; Guo, X.; Wang, J.X.; Wang, Y.C.

doi:10.1107/S160053680902176X

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page m772

doi:10.1107/S160053680902176X

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Diaquabis(2-methyl-1H-imidazol-3-ium-4,5-dicarboxylato-κ²O,O′)magnesium

Yi Liang Li,^a Xin Guo,^a Ju Xian Wang ^a and Yu Cheng Wang ^a ^*

^aInstitute of Medicinal Biotechnology, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing 100050, People's Republic of China
^*Correspondence e-mail: hongzhaoupr@yahoo.com

(Received 31 May 2009; accepted 9 June 2009; online 13 June 2009)

The title compound, [Mg(C₆H₅N₂O₄)₂(H₂O)₂], was prepared by reaction of Mg(NO₃)₂ and 2-methyl-1H-imidazole-4,5-dicarboxylic acid under hydrothermal conditions. The Mg^II atom lies on an inversion centre and displays a distorted octahedral coordination geometry. An extended three-dimensional network of intermolecular O—H⋯O and N—H⋯O hydrogen bonds stabilizes the crystal structure.

Related literature

For the crystal structures of metal complexes with N-heterocyclic carboxylic acids, see: Nie et al. (2007 ); Liang et al. (2002 ); Net et al. (1989 ); Zeng et al. (2008 ).

Experimental

Crystal data

[Mg(C₆H₅N₂O₄)₂(H₂O)₂]
M_r = 398.58
Triclinic, $[P \overline 1]$
a = 4.943 (2) Å
b = 8.750 (6) Å
c = 9.621 (6) Å
α = 109.18 (3)°
β = 95.142 (17)°
γ = 93.14 (2)°
V = 389.9 (4) Å³
Z = 1
Mo Kα radiation
μ = 0.18 mm⁻¹
T = 292 K
0.30 × 0.25 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.948, T_max = 0.967
4002 measured reflections
1767 independent reflections
1308 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.061
wR(F²) = 0.213
S = 1.19
1767 reflections
125 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O4ⁱ	0.95	1.78	2.696 (4)	161
N2—H2⋯O2ⁱⁱ	0.95	1.81	2.727 (4)	162
O5—H5B⋯O2ⁱⁱⁱ	0.93	2.23	3.155 (4)	172
O5—H5B⋯O1ⁱⁱⁱ	0.93	2.36	2.961 (4)	122
O5—H5A⋯O3^iv	0.87	1.98	2.841 (4)	170
Symmetry codes: (i) -x, -y+1, -z+1; (ii) -x+2, -y+2, -z+1; (iii) x-1, y, z; (iv) -x, -y+2, -z+2.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXTL/PC.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680902176X/rz2332sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680902176X/rz2332Isup2.hkl

checkCIF report

Comment top

Recently, the study of metal complexes with N-heterocyclic carboxylic acids has been given considerable attention (Nie et al., 2007; Liang et al., 2002; Net et al., 1989; Zeng et al., 2008). In this paper, we report on the synthesis and crystal structure of the title compound, which was obtained by the hydrothermal reaction of Mg(NO₃)₂ with 2-methyl-1H-imidazole-4,5-dicarboxylic acid.

As shown in Fig. 1, the magnesium(II) atom, which lies on an inversion centre, adopts a distorted octahedral coordination, with the equatorial plane provided by four O atoms from two organic ligands [Mg1–O1 = 2.011 (2) Å; Mg1–O3 = 2.036 (2) Å] and the axial sites occupied by the O atoms of two water molecules [Mg1–O5 = 2.110 (3) Å]. The seven-membered chelate ring assumes an envelope-like conformation, with atom Mg1 displaced by 0.4353 (4) Å from the mean plane of the remaining atoms of the ring. The crystal structure is stabilized by intermolecular O—H···O and N—H···O hydrogen bonds (Table 1), forming an extended three-dimensional network (Fig. 2).

Related literature top

For the crystal structures of metal complexes with N-heterocyclic carboxylic acids, see: Nie et al. (2007); Liang et al. (2002); Net et al. (1989); Zeng et al. (2008).

Experimental top

Colourless single crystals of title compound were obtained by hydrothermal treatment of Mg(NO₃)₂ (1 mmol), 2-methyl-1H-imidazole-4,5-dicarboxylic acid (1 mmol) and water (5 ml) over 4 days at 368 K. Yield: 67% (based on Mg(NO₃)₂.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXTL/PC (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Atoms with suffix A are related to atoms with no suffix by 1-x, 2-y, 2-z.
	Fig. 2. Packing diagram of the title compound viewed along the b axis. Intermolecular hydrogen bonds are shown as dashed lines.

Diaquabis(2-methyl-1H-imidazol-3-ium-4,5-dicarboxylato- κ²O,O')magnesium top

Crystal data top

[Mg(C₆H₅N₂O₄)₂(H₂O)₂]	Z = 1
M_r = 398.58	F(000) = 206
Triclinic, P1	D_x = 1.698 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.943 (2) Å	Cell parameters from 1023 reflections
b = 8.750 (6) Å	θ = 3.9–27.4°
c = 9.621 (6) Å	µ = 0.18 mm⁻¹
α = 109.18 (3)°	T = 292 K
β = 95.142 (17)°	Block, colourless
γ = 93.14 (2)°	0.30 × 0.25 × 0.20 mm
V = 389.9 (4) Å³

Data collection top

Rigaku SCXmini diffractometer	1767 independent reflections
Radiation source: fine-focus sealed tube	1308 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.4°, θ_min = 2.7°
ω scans	h = −6→6
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −11→11
T_min = 0.948, T_max = 0.967	l = −12→12
4002 measured reflections

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.213	H-atom parameters constrained
S = 1.19	w = 1/[σ²(F_o²) + (0.1078P)² + 0.1465P] where P = (F_o² + 2F_c²)/3
1767 reflections	(Δ/σ)_max < 0.001
125 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

[Mg(C₆H₅N₂O₄)₂(H₂O)₂]	γ = 93.14 (2)°
M_r = 398.58	V = 389.9 (4) Å³
Triclinic, P1	Z = 1
a = 4.943 (2) Å	Mo Kα radiation
b = 8.750 (6) Å	µ = 0.18 mm⁻¹
c = 9.621 (6) Å	T = 292 K
α = 109.18 (3)°	0.30 × 0.25 × 0.20 mm
β = 95.142 (17)°

Data collection top

Rigaku SCXmini diffractometer	1767 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1308 reflections with I > 2σ(I)
T_min = 0.948, T_max = 0.967	R_int = 0.046
4002 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.061	0 restraints
wR(F²) = 0.213	H-atom parameters constrained
S = 1.19	Δρ_max = 0.39 e Å⁻³
1767 reflections	Δρ_min = −0.42 e Å⁻³
125 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	1.0000	1.0000	0.0250 (4)
C1	0.3793 (6)	0.7562 (4)	0.6015 (3)	0.0229 (7)
C2	0.5912 (6)	0.8628 (4)	0.6010 (3)	0.0223 (7)
C3	0.5089 (7)	0.6811 (4)	0.3730 (4)	0.0267 (7)
C4	0.5167 (9)	0.5941 (5)	0.2137 (4)	0.0385 (9)
H4A	0.4178	0.6492	0.1569	0.058*
H4B	0.4347	0.4851	0.1885	0.058*
H4C	0.7026	0.5915	0.1922	0.058*
C5	0.1991 (7)	0.7356 (4)	0.7122 (3)	0.0240 (7)
C6	0.7466 (6)	1.0094 (4)	0.7140 (3)	0.0233 (7)
N1	0.3343 (6)	0.6454 (3)	0.4585 (3)	0.0268 (6)
H1	0.2007	0.5554	0.4365	0.040*
N2	0.6676 (6)	0.8120 (3)	0.4581 (3)	0.0258 (6)
H2	0.7914	0.8719	0.4213	0.039*
O1	0.6722 (5)	1.0584 (3)	0.8405 (2)	0.0319 (6)
O2	0.9380 (5)	1.0749 (3)	0.6734 (3)	0.0380 (7)
O3	0.2358 (5)	0.8310 (3)	0.8427 (2)	0.0312 (6)
O4	0.0166 (6)	0.6225 (3)	0.6638 (3)	0.0410 (7)
O5	0.2236 (5)	1.1757 (3)	1.0012 (3)	0.0336 (6)
H5B	0.1354	1.1572	0.9070	0.050*
H5A	0.0940	1.1836	1.0574	0.050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mg1	0.0230 (8)	0.0287 (8)	0.0195 (8)	−0.0077 (6)	0.0050 (6)	0.0042 (6)
C1	0.0240 (15)	0.0222 (15)	0.0209 (15)	−0.0021 (12)	0.0033 (12)	0.0055 (12)
C2	0.0213 (14)	0.0243 (15)	0.0216 (15)	−0.0001 (12)	0.0050 (12)	0.0078 (12)
C3	0.0294 (17)	0.0240 (16)	0.0261 (16)	−0.0019 (13)	0.0057 (13)	0.0076 (13)
C4	0.054 (2)	0.0332 (19)	0.0227 (18)	−0.0042 (17)	0.0105 (16)	0.0014 (15)
C5	0.0232 (15)	0.0254 (15)	0.0224 (15)	−0.0035 (12)	0.0057 (12)	0.0067 (12)
C6	0.0230 (15)	0.0259 (16)	0.0206 (15)	−0.0033 (12)	0.0031 (12)	0.0081 (13)
N1	0.0277 (14)	0.0253 (14)	0.0248 (14)	−0.0064 (11)	0.0068 (11)	0.0052 (11)
N2	0.0284 (14)	0.0268 (14)	0.0228 (14)	−0.0031 (11)	0.0060 (11)	0.0092 (11)
O1	0.0353 (13)	0.0336 (14)	0.0227 (12)	−0.0103 (11)	0.0076 (10)	0.0049 (10)
O2	0.0346 (14)	0.0432 (16)	0.0330 (14)	−0.0165 (12)	0.0112 (11)	0.0098 (12)
O3	0.0319 (13)	0.0347 (14)	0.0208 (12)	−0.0114 (10)	0.0069 (10)	0.0022 (10)
O4	0.0408 (15)	0.0392 (15)	0.0323 (14)	−0.0239 (12)	0.0092 (12)	0.0008 (11)
O5	0.0280 (13)	0.0385 (14)	0.0326 (13)	−0.0015 (10)	0.0091 (10)	0.0090 (11)

Geometric parameters (Å, º) top

Mg1—O1ⁱ	2.010 (2)	C3—C4	1.475 (5)
Mg1—O1	2.010 (2)	C4—H4A	0.9600
Mg1—O3ⁱ	2.036 (2)	C4—H4B	0.9600
Mg1—O3	2.036 (2)	C4—H4C	0.9600
Mg1—O5ⁱ	2.110 (3)	C5—O4	1.238 (4)
Mg1—O5	2.110 (3)	C5—O3	1.249 (4)
C1—C2	1.365 (4)	C6—O2	1.237 (4)
C1—N1	1.388 (4)	C6—O1	1.247 (4)
C1—C5	1.496 (4)	N1—H1	0.9534
C2—N2	1.393 (4)	N2—H2	0.9489
C2—C6	1.498 (5)	O5—H5B	0.9297
C3—N2	1.330 (4)	O5—H5A	0.8656
C3—N1	1.336 (4)

O1ⁱ—Mg1—O1	180.000 (1)	C3—C4—H4A	109.5
O1ⁱ—Mg1—O3ⁱ	89.92 (10)	C3—C4—H4B	109.5
O1—Mg1—O3ⁱ	90.08 (10)	H4A—C4—H4B	109.5
O1ⁱ—Mg1—O3	90.08 (10)	C3—C4—H4C	109.5
O1—Mg1—O3	89.92 (10)	H4A—C4—H4C	109.5
O3ⁱ—Mg1—O3	180.000 (1)	H4B—C4—H4C	109.5
O1ⁱ—Mg1—O5ⁱ	87.90 (11)	O4—C5—O3	124.6 (3)
O1—Mg1—O5ⁱ	92.10 (11)	O4—C5—C1	115.5 (3)
O3ⁱ—Mg1—O5ⁱ	88.95 (11)	O3—C5—C1	119.9 (3)
O3—Mg1—O5ⁱ	91.05 (11)	O2—C6—O1	124.7 (3)
O1ⁱ—Mg1—O5	92.10 (11)	O2—C6—C2	117.0 (3)
O1—Mg1—O5	87.90 (11)	O1—C6—C2	118.3 (3)
O3ⁱ—Mg1—O5	91.05 (11)	C3—N1—C1	110.7 (3)
O3—Mg1—O5	88.95 (11)	C3—N1—H1	129.8
O5ⁱ—Mg1—O5	180.000 (1)	C1—N1—H1	119.3
C2—C1—N1	105.8 (3)	C3—N2—C2	110.1 (3)
C2—C1—C5	136.3 (3)	C3—N2—H2	123.8
N1—C1—C5	117.9 (3)	C2—N2—H2	125.2
C1—C2—N2	106.6 (3)	C6—O1—Mg1	147.0 (2)
C1—C2—C6	135.2 (3)	C5—O3—Mg1	145.7 (2)
N2—C2—C6	118.2 (3)	Mg1—O5—H5B	111.2
N2—C3—N1	106.8 (3)	Mg1—O5—H5A	117.4
N2—C3—C4	127.0 (3)	H5B—O5—H5A	104.9
N1—C3—C4	126.2 (3)

N1—C1—C2—N2	−0.3 (4)	N1—C3—N2—C2	−0.7 (4)
C5—C1—C2—N2	−179.6 (4)	C4—C3—N2—C2	177.5 (4)
N1—C1—C2—C6	−179.5 (3)	C1—C2—N2—C3	0.7 (4)
C5—C1—C2—C6	1.2 (7)	C6—C2—N2—C3	−180.0 (3)
C2—C1—C5—O4	176.8 (4)	O2—C6—O1—Mg1	−150.7 (3)
N1—C1—C5—O4	−2.4 (5)	C2—C6—O1—Mg1	30.6 (6)
C2—C1—C5—O3	−2.0 (6)	O3ⁱ—Mg1—O1—C6	142.4 (4)
N1—C1—C5—O3	178.8 (3)	O3—Mg1—O1—C6	−37.6 (4)
C1—C2—C6—O2	177.8 (4)	O5ⁱ—Mg1—O1—C6	53.4 (4)
N2—C2—C6—O2	−1.3 (5)	O5—Mg1—O1—C6	−126.6 (4)
C1—C2—C6—O1	−3.4 (6)	O4—C5—O3—Mg1	163.9 (3)
N2—C2—C6—O1	177.5 (3)	C1—C5—O3—Mg1	−17.4 (6)
N2—C3—N1—C1	0.5 (4)	O1ⁱ—Mg1—O3—C5	−151.8 (4)
C4—C3—N1—C1	−177.8 (3)	O1—Mg1—O3—C5	28.2 (4)
C2—C1—N1—C3	−0.1 (4)	O5ⁱ—Mg1—O3—C5	−63.9 (4)
C5—C1—N1—C3	179.3 (3)	O5—Mg1—O3—C5	116.1 (4)

Symmetry code: (i) −x+1, −y+2, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4ⁱⁱ	0.95	1.78	2.696 (4)	161
N2—H2···O2ⁱⁱⁱ	0.95	1.81	2.727 (4)	162
O5—H5B···O2^iv	0.93	2.23	3.155 (4)	172
O5—H5B···O1^iv	0.93	2.36	2.961 (4)	122
O5—H5A···O3^v	0.87	1.98	2.841 (4)	170

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

Experimental details

Crystal data
Chemical formula	[Mg(C₆H₅N₂O₄)₂(H₂O)₂]
M_r	398.58
Crystal system, space group	Triclinic, P1
Temperature (K)	292
a, b, c (Å)	4.943 (2), 8.750 (6), 9.621 (6)
α, β, γ (°)	109.18 (3), 95.142 (17), 93.14 (2)
V (Å³)	389.9 (4)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.18
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.948, 0.967
No. of measured, independent and observed [I > 2σ(I)] reflections	4002, 1767, 1308
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.647

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.213, 1.19
No. of reflections	1767
No. of parameters	125
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.42

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL/PC (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4ⁱ	0.95	1.78	2.696 (4)	161.1
N2—H2···O2ⁱⁱ	0.95	1.81	2.727 (4)	162.4
O5—H5B···O2ⁱⁱⁱ	0.93	2.23	3.155 (4)	171.5
O5—H5B···O1ⁱⁱⁱ	0.93	2.36	2.961 (4)	122.4
O5—H5A···O3^iv	0.87	1.98	2.841 (4)	170.0

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

Acknowledgements

The work was supported by the National Basic Public Welfare Research Program of China (IMBF-20060403).

References

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