Diaqua­bis(5-carb­oxy-2-methyl-1H-imidazole-4-carboxyl­ato-κ2N3,O4)manganese(II)

Zeng, J.-Z.; Yi, X.-G.; Lin, J.-Y.; Ying, S.-M.; Huang, G.-S.

doi:10.1107/S160053680800411X

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 3| March 2008| Page m476

doi:10.1107/S160053680800411X

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Diaquabis(5-carboxy-2-methyl-1H-imidazole-4-carboxylato-κ²N³,O⁴)manganese(II)

Jian-Zhong Zeng,^a Xiu-Guang Yi,^b ^* Jun-Yue Lin,^b Shao-Ming Ying ^b and Gan-Sheng Huang ^b

^aCollege of Life Sciences, Jinggangshan University, Ji'an, Jiangxi 343009, People's Republic of China, and ^bCollege of Chemistry and Chemical Engineering, Jinggangshan University, Ji'an, Jiangxi 343009, People's Republic of China
^*Correspondence e-mail: yingshaoming@hotmail.com

(Received 9 January 2008; accepted 9 February 2008; online 15 February 2008)

The title complex, [Mn(C₆H₅N₂O₄)₂(H₂O)₂], was obtained by hydrothermal synthesis. The Mn^II atom, which lies on an inversion centre, displays a slightly distorted octahedral geometry. In the crystal packing, complex molecules are linked by intermolecular O—H⋯O and N—H⋯O hydrogen bonds to form a three-dimensional supramolecular structure. The title complex is isostructural with the corresponding cadmium(II) complex [Nie, Wen, Wu, Liu & Liu (2007 ). Acta Cryst. E63, m753–m755].

Related literature

For related literature, see: Liang et al. (2002 ); Net et al. (1989 ); Nie et al. (2007); Ying & Mao (2006 ).

Experimental

Crystal data

[Mn(C₆H₅N₂O₄)₂(H₂O)₂]
M_r = 429.21
Monoclinic, P 2₁ /c
a = 12.2047 (12) Å
b = 9.1607 (9) Å
c = 7.3860 (7) Å
β = 101.355 (2)°
V = 809.62 (14) Å³
Z = 2
Mo Kα radiation
μ = 0.88 mm⁻¹
T = 293 (2) K
0.30 × 0.21 × 0.12 mm

Data collection

Bruker APEX area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ) T_min = 0.778, T_max = 0.902
5936 measured reflections
1931 independent reflections
1387 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.096
S = 0.96
1931 reflections
132 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5B⋯O3ⁱ	0.77 (3)	2.01 (3)	2.763 (2)	168 (3)
O5—H5A⋯O4ⁱⁱ	0.78 (3)	1.98 (3)	2.760 (2)	174 (3)
N2—H2A⋯O1ⁱⁱⁱ	0.86	2.06	2.841 (2)	151
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) -x+1, -y+1, -z+1.

Data collection: SMART (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Version 5.1; Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680800411X/rz2194sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680800411X/rz2194Isup2.hkl

checkCIF report

Comment top

The use of multifunctional ligands to construct coordination polymers is of current interest due to their potential ability to generate new solid materials with novel network topologies by deliberate design (Ying & Mao, 2006). In these studies, much attention has been put into coordination polymers containing metals and N-heterocyclic carboxylic acids because they can exhibit abundant structural type and can be potentially used as functional materials (Nie et al., 2007; Liang et al., 2002; Net et al., 1989). In this paper, we report the synthesis and structure of a new manganese(II) complex obtained from 2-methyl-1H-imidazole-4,5-dicarboxylic acid (H₃MIA).

The title mononuclear complex molecule contains one manganese(II) ion, two mono-deprotonated H₂MIA ligands and two water molecules. The manganese(II) ion lies on an inversion centre and is six-coordinated by two carboxylate oxygen atoms and two nitrogen atoms of the H₂MIA ligands, and by the oxygen atoms of two water molecules forming a slightly distorted octahedral geometry (Fig. 1). The Mn—O distances are 2.1433 (19) and 2.2103 (13) Å and the Mn—N distance is 2.2700 (16) Å. In the crystal packing, complex molecules are linked by intermolecular O—H···O and N—H···O hydrogen bonds to form a three-dimensional supermolecular structure (Fig. 2). The complex is isostructural with the corresponding cadmium(II) complex which has been reported recently (Nie et al., 2007).

Related literature top

For related literature, see: Liang et al. (2002); Net et al. (1989); Nie et al. (2007); Ying & Mao (2006)

Experimental top

A mixture of manganese(II) acetate (0.5 mmol, 0.120 g) and 2-methyl-1H-imidazole-4,5-dicarboxylic acid in 10 ml of distilled water was sealed in an autoclave equipped with a Teflon liner (20 ml) and then heated at 150°C for 3 days. Crystals of the title compound were obtained by slow evaporation of the solvent at room temperature.

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Version 5.1; Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Version 5.1; Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level. Symmetry code: (A) -x, -y + 1, -z.
	Fig. 2. Packing diagram of the title compound viewed along the c axis. Hydrogen atoms are omitted for clarity. The hydrogen bonds are drawn as dotted lines.

Diaquabis(5-carboxy-2-methyl-1H-imidazole-4-carboxylato- κ²N³,O⁴)manganese(II) top

Crystal data top

[Mn(C₆H₅N₂O₄)₂(H₂O)₂]	F(000) = 438
M_r = 429.21	D_x = 1.761 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3147 reflections
a = 12.2047 (12) Å	θ = 2.8–28.2°
b = 9.1607 (9) Å	µ = 0.88 mm⁻¹
c = 7.3860 (7) Å	T = 293 K
β = 101.355 (2)°	Plate, colourless
V = 809.62 (14) Å³	0.30 × 0.21 × 0.12 mm
Z = 2

Data collection top

Bruker APEX area-detector diffractometer	1931 independent reflections
Radiation source: fine-focus sealed tube	1387 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ϕ and ω scans	θ_max = 28.3°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −16→16
T_min = 0.778, T_max = 0.902	k = −12→12
5936 measured reflections	l = −9→9

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 0.96	w = 1/[σ²(F_o²) + (0.0578P)²] where P = (F_o² + 2F_c²)/3
1931 reflections	(Δ/σ)_max < 0.001
132 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

[Mn(C₆H₅N₂O₄)₂(H₂O)₂]	V = 809.62 (14) Å³
M_r = 429.21	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.2047 (12) Å	µ = 0.88 mm⁻¹
b = 9.1607 (9) Å	T = 293 K
c = 7.3860 (7) Å	0.30 × 0.21 × 0.12 mm
β = 101.355 (2)°

Data collection top

Bruker APEX area-detector diffractometer	1931 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	1387 reflections with I > 2σ(I)
T_min = 0.778, T_max = 0.902	R_int = 0.033
5936 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 0.96	Δρ_max = 0.35 e Å⁻³
1931 reflections	Δρ_min = −0.35 e Å⁻³
132 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
Mn1	0.0000	0.5000	0.0000	0.02937 (16)
N1	0.18504 (13)	0.50974 (16)	0.1269 (2)	0.0293 (4)
N2	0.35369 (14)	0.52117 (17)	0.2952 (3)	0.0363 (4)
H2A	0.4143	0.5577	0.3581	0.044*
O1	0.50357 (12)	0.30235 (19)	0.4426 (3)	0.0559 (5)
O2	0.39335 (12)	0.12886 (16)	0.3029 (2)	0.0484 (4)
H2B	0.3298	0.1226	0.2415	0.073*
O3	0.19549 (11)	0.11771 (14)	0.1132 (2)	0.0352 (4)
O4	0.06082 (11)	0.27347 (14)	−0.01036 (19)	0.0330 (3)
O5	−0.02904 (16)	0.4590 (2)	0.2723 (3)	0.0459 (5)
C1	0.2586 (2)	0.7599 (2)	0.2185 (4)	0.0549 (7)
H1A	0.1875	0.7922	0.1503	0.082*
H1B	0.3172	0.8005	0.1645	0.082*
H1C	0.2675	0.7915	0.3444	0.082*
C2	0.26397 (16)	0.5981 (2)	0.2124 (3)	0.0339 (5)
C3	0.41682 (17)	0.2662 (2)	0.3431 (3)	0.0370 (5)
C4	0.33359 (15)	0.3766 (2)	0.2638 (3)	0.0309 (5)
C5	0.22732 (15)	0.3710 (2)	0.1569 (3)	0.0273 (4)
C6	0.15691 (15)	0.2449 (2)	0.0818 (3)	0.0277 (4)
H5B	−0.071 (2)	0.499 (2)	0.319 (4)	0.041 (8)*
H5A	0.001 (2)	0.397 (3)	0.336 (4)	0.065 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0254 (2)	0.0274 (2)	0.0312 (3)	0.00137 (17)	−0.00438 (17)	0.00092 (17)
N1	0.0265 (9)	0.0253 (8)	0.0328 (10)	−0.0015 (6)	−0.0023 (7)	−0.0002 (7)
N2	0.0232 (8)	0.0327 (10)	0.0468 (12)	−0.0040 (7)	−0.0081 (7)	−0.0053 (8)
O1	0.0338 (9)	0.0507 (10)	0.0697 (12)	0.0059 (7)	−0.0231 (8)	−0.0116 (9)
O2	0.0350 (8)	0.0358 (9)	0.0650 (11)	0.0064 (7)	−0.0127 (7)	−0.0026 (7)
O3	0.0305 (7)	0.0248 (7)	0.0466 (9)	−0.0008 (6)	−0.0011 (6)	−0.0008 (6)
O4	0.0275 (7)	0.0276 (7)	0.0379 (9)	−0.0018 (6)	−0.0080 (6)	−0.0034 (6)
O5	0.0493 (11)	0.0499 (10)	0.0391 (10)	0.0240 (9)	0.0099 (8)	0.0137 (8)
C1	0.0500 (15)	0.0375 (13)	0.071 (2)	0.0001 (11)	−0.0042 (13)	−0.0063 (12)
C2	0.0283 (10)	0.0309 (10)	0.0388 (13)	−0.0037 (8)	−0.0029 (9)	−0.0022 (9)
C3	0.0276 (10)	0.0376 (12)	0.0415 (14)	0.0043 (8)	−0.0037 (9)	−0.0016 (10)
C4	0.0244 (10)	0.0317 (11)	0.0335 (12)	−0.0012 (8)	−0.0022 (8)	−0.0025 (8)
C5	0.0230 (9)	0.0293 (10)	0.0275 (11)	−0.0010 (7)	−0.0003 (7)	−0.0006 (8)
C6	0.0255 (10)	0.0276 (10)	0.0286 (11)	−0.0023 (8)	0.0015 (8)	−0.0010 (8)

Geometric parameters (Å, º) top

Mn1—O5ⁱ	2.1433 (19)	O2—H2B	0.8200
Mn1—O5	2.1433 (19)	O3—C6	1.261 (2)
Mn1—O4	2.2103 (13)	O4—C6	1.262 (2)
Mn1—O4ⁱ	2.2103 (13)	O5—H5B	0.77 (3)
Mn1—N1	2.2700 (16)	O5—H5A	0.78 (3)
Mn1—N1ⁱ	2.2700 (16)	C1—C2	1.485 (3)
N1—C2	1.320 (2)	C1—H1A	0.9600
N1—C5	1.373 (2)	C1—H1B	0.9600
N2—C2	1.344 (3)	C1—H1C	0.9600
N2—C4	1.358 (2)	C3—C4	1.471 (3)
N2—H2A	0.8600	C4—C5	1.380 (3)
O1—C3	1.210 (2)	C5—C6	1.481 (3)
O2—C3	1.311 (2)

O5ⁱ—Mn1—O5	180.00 (10)	Mn1—O5—H5A	124 (2)
O5ⁱ—Mn1—O4	90.77 (6)	H5B—O5—H5A	110 (3)
O5—Mn1—O4	89.23 (6)	C2—C1—H1A	109.5
O5ⁱ—Mn1—O4ⁱ	89.23 (6)	C2—C1—H1B	109.5
O5—Mn1—O4ⁱ	90.77 (6)	H1A—C1—H1B	109.5
O4—Mn1—O4ⁱ	180.00 (10)	C2—C1—H1C	109.5
O5ⁱ—Mn1—N1	92.62 (7)	H1A—C1—H1C	109.5
O5—Mn1—N1	87.38 (7)	H1B—C1—H1C	109.5
O4—Mn1—N1	74.79 (5)	N1—C2—N2	110.42 (18)
O4ⁱ—Mn1—N1	105.21 (5)	N1—C2—C1	126.44 (19)
O5ⁱ—Mn1—N1ⁱ	87.38 (7)	N2—C2—C1	123.14 (18)
O5—Mn1—N1ⁱ	92.62 (7)	O1—C3—O2	121.74 (19)
O4—Mn1—N1ⁱ	105.21 (5)	O1—C3—C4	120.44 (19)
O4ⁱ—Mn1—N1ⁱ	74.79 (5)	O2—C3—C4	117.82 (17)
N1—Mn1—N1ⁱ	180.00 (8)	N2—C4—C5	104.59 (16)
C2—N1—C5	105.93 (16)	N2—C4—C3	121.00 (17)
C2—N1—Mn1	142.63 (14)	C5—C4—C3	134.39 (18)
C5—N1—Mn1	110.00 (11)	N1—C5—C4	109.80 (15)
C2—N2—C4	109.25 (16)	N1—C5—C6	119.32 (16)
C2—N2—H2A	125.4	C4—C5—C6	130.84 (17)
C4—N2—H2A	125.4	O4—C6—O3	124.39 (16)
C3—O2—H2B	109.5	O4—C6—C5	116.68 (16)
C6—O4—Mn1	117.32 (11)	O3—C6—C5	118.93 (16)
Mn1—O5—H5B	126 (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—H5B···O3ⁱⁱ	0.77 (3)	2.01 (3)	2.763 (2)	168 (3)
O5—H5A···O4ⁱⁱⁱ	0.78 (3)	1.98 (3)	2.760 (2)	174 (3)
N2—H2A···O1^iv	0.86	2.06	2.841 (2)	151

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

Experimental details

Crystal data
Chemical formula	[Mn(C₆H₅N₂O₄)₂(H₂O)₂]
M_r	429.21
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	12.2047 (12), 9.1607 (9), 7.3860 (7)
β (°)	101.355 (2)
V (Å³)	809.62 (14)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.88
Crystal size (mm)	0.30 × 0.21 × 0.12

Data collection
Diffractometer	Bruker APEX area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2002)
T_min, T_max	0.778, 0.902
No. of measured, independent and observed [I > 2σ(I)] reflections	5936, 1931, 1387
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.096, 0.96
No. of reflections	1931
No. of parameters	132
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.35

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Version 5.1; Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5B···O3ⁱ	0.77 (3)	2.01 (3)	2.763 (2)	168 (3)
O5—H5A···O4ⁱⁱ	0.78 (3)	1.98 (3)	2.760 (2)	174 (3)
N2—H2A···O1ⁱⁱⁱ	0.86	2.06	2.841 (2)	151.1

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

References

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