Diaqua­bis­(1H-imidazole-4-carboxyl­ato-κ2N3,O4)manganese(II)

Xiong, Z.-Y.; Li, L.; Zhao, X.-J.; Chen, H.-M.

doi:10.1107/S1600536813004091

metal-organic compounds

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Volume 69| Part 3| March 2013| Page m172

doi:10.1107/S1600536813004091

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Diaquabis(1H-imidazole-4-carboxylato-κ²N³,O⁴)manganese(II)

Zhi-Yong Xiong,^a,^b,^c Lin Li,^a ^* Xiang-Jie Zhao ^a and Hai-Ming Chen ^a

^aCollege of Light Industry and Food Sciences, South China University of Technology, Guangzhou 510641, People's Republic of China, ^bEngineering Research Center of Starch and Vegetable Protein Processing, Ministry of Education, South China University of Technology, Guangzhou 510640, People's Republic of China, and ^cSchool of Chemical Engineering and Materials Science, Beijing Institute of Technology, Zhuhai 519088, People's Republic of China
^*Correspondence e-mail: adamscutzhbit@yahoo.com.cn

(Received 31 January 2013; accepted 11 February 2013; online 28 February 2013)

In the title compound, [Mn(C₄H₃N₂O₂)₂(H₂O)₂], the Mn^II ion is located on a twofold rotation axis and displays a distorted octahedral coordination environment, defined by two N,O-bidentate 1H-imidazole-4-carboxylate ligands in the equatorial plane and two water molecules in axial positions. In the crystal, O—H⋯O and N—H⋯O hydrogen bonds link the molecules into a three-dimensional supramolecular network. π–π stacking interactions between the imidazole rings [centroid–centroid distances = 3.5188 (15) and 3.6687 (15) Å] further stabilize the structure.

Related literature

For related structures, see: Cai et al. (2012 ); Chen (2012 ); Gryz et al. (2007 ); Haggag (2005 ); Shuai et al. (2011 ); Starosta & Leciejewicz (2006 ); Yin et al. (2009 ); Zheng et al. (2011 ).

Experimental

Crystal data

[Mn(C₄H₃N₂O₂)₂(H₂O)₂]
M_r = 313.14
Orthorhombic, P c c n
a = 7.3052 (10) Å
b = 11.7997 (17) Å
c = 13.5156 (19) Å
V = 1165.0 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.16 mm⁻¹
T = 298 K
0.36 × 0.32 × 0.30 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.679, T_max = 0.721
5775 measured reflections
1145 independent reflections
972 reflections with I > 2σ(I)
R_int = 0.067

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.109
S = 1.07
1145 reflections
87 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.57 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O2ⁱ	0.86	1.95	2.811 (3)	173
O1W—H1WA⋯O2ⁱⁱ	0.87	1.96	2.818 (2)	167
O1W—H1WB⋯O2ⁱⁱⁱ	0.73	2.02	2.751 (2)	176
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y, z-{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813004091/hy2616sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813004091/hy2616Isup2.hkl

checkCIF report

Comment top

In the past few years, structures containing metals and N-heterocyclic carboxylic acids have attracted much attention due to their fascinating structures and potential applications in many fields. 1H-Imidazole-4-carboxylic acid (H₂imc), which contains two N atoms of an imidazole group and one carboxylate group, has been widely used to prepare a variety of coordination polymers with different structures and exceptional properties (Cai et al., 2012; Gryz et al., 2007; Haggag, 2005; Starosta & Leciejewicz, 2006; Zheng et al., 2011). For instance, three mononuclear complexes, [Cd(Himc)₂(H₂O)₂] (Yin et al., 2009), [Zn(Himc)₂(H₂O)₂] (Shuai et al., 2011) and [Co(Himc)₂(H₂O)₂] (Chen, 2012), have been reported. In this paper, we report the synthesis and structure of a new Mn(II) coordination polymer, [Mn(Himc)₂(H₂O)₂], which is isomorphous with the Cd(II), Zn(II) and Co(II) analogs.

The asymmetric unit of the title compound contains a half of [Mn(Himc)₂(H₂O)₂] formula unit. The Mn^II ion, lying on a twofold rotation axis, is six-coordinated by two N and two O atoms from two cis-oriented N,O-bidentate Himc ligands in the equatorial plane, and two water molecules in the axial positions, forming a slightly distorted octahedral geometry (Fig. 1). The bond lengths and angles around the Mn atom are normal. In the crystal structure, intermolecular O—H···O and N—H···O hydrogen bonds (Table 1) involving the coordinated water O atoms, carboxylate O atoms and imidazole N atoms link the molecules into a three-dimensional supramolecular network, as presented in Fig. 2. π–π stacking interactions between the imidazole rings [centroid–centroid distances = 3.5188 (15) and 3.6687 (15) Å] further stabilize the crystal structure.

Related literature top

For related structures, see: Cai et al. (2012); Chen (2012); Gryz et al. (2007); Haggag (2005); Shuai et al. (2011); Starosta & Leciejewicz (2006); Yin et al. (2009); Zheng et al. (2011).

Experimental top

A mixture of H₂imc (0.30 mmol), MnCl₂.6H₂O (0.30 mmol) and 6 ml EtOH/H₂O (v/v 1:1) was sealed into a 10 ml sample bottle reactor and heated at 373 k for 72 h under autogenous pressure, and then slowly cooled to room temperature at a rate of 5 K/h. Colorless block crystals of the title compound were obtained, washed with distilled water and dried in air (yield: 30%).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (i) -x+3/2, -y+3/2, z.]
	Fig. 2. The crystal packing of the title compound, showing the three-dimensional supramolecular network. Hydrogen bonds are shown as dashed lines.

Diaquabis(1H-imidazole-4-carboxylato-κ²N³,O⁴)manganese(II) top

Crystal data top

[Mn(C₄H₃N₂O₂)₂(H₂O)₂]	F(000) = 636
M_r = 313.14	D_x = 1.785 Mg m⁻³
Orthorhombic, Pccn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2ac	Cell parameters from 1516 reflections
a = 7.3052 (10) Å	θ = 3.3–24.9°
b = 11.7997 (17) Å	µ = 1.16 mm⁻¹
c = 13.5156 (19) Å	T = 298 K
V = 1165.0 (3) Å³	Block, colourless
Z = 4	0.36 × 0.32 × 0.30 mm

Data collection top

Bruker APEXII CCD diffractometer	1145 independent reflections
Radiation source: fine-focus sealed tube	972 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.067
ϕ and ω scans	θ_max = 26.0°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −8→9
T_min = 0.679, T_max = 0.721	k = −14→10
5775 measured reflections	l = −16→15

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.109	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0489P)² + 0.3284P] where P = (F_o² + 2F_c²)/3
1145 reflections	(Δ/σ)_max = 0.001
87 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.57 e Å⁻³

Crystal data top

[Mn(C₄H₃N₂O₂)₂(H₂O)₂]	V = 1165.0 (3) Å³
M_r = 313.14	Z = 4
Orthorhombic, Pccn	Mo Kα radiation
a = 7.3052 (10) Å	µ = 1.16 mm⁻¹
b = 11.7997 (17) Å	T = 298 K
c = 13.5156 (19) Å	0.36 × 0.32 × 0.30 mm

Data collection top

Bruker APEXII CCD diffractometer	1145 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	972 reflections with I > 2σ(I)
T_min = 0.679, T_max = 0.721	R_int = 0.067
5775 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.109	H-atom parameters constrained
S = 1.07	Δρ_max = 0.34 e Å⁻³
1145 reflections	Δρ_min = −0.57 e Å⁻³
87 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	0.7500	0.7500	0.63202 (3)	0.0256 (2)
N1	0.5501 (2)	0.81048 (17)	0.52125 (14)	0.0282 (5)
N2	0.3599 (3)	0.87066 (19)	0.40742 (14)	0.0342 (5)
H2	0.3136	0.8835	0.3500	0.041*
C1	0.4022 (3)	0.87462 (18)	0.67505 (16)	0.0238 (5)
C2	0.4063 (3)	0.86601 (18)	0.56583 (16)	0.0241 (5)
C4	0.5155 (3)	0.8144 (2)	0.42597 (17)	0.0350 (6)
H4	0.5895	0.7822	0.3775	0.042*
C3	0.2882 (4)	0.9039 (2)	0.49557 (18)	0.0312 (5)
H3	0.1804	0.9442	0.5057	0.037*
O1	0.5374 (2)	0.83532 (14)	0.72111 (11)	0.0310 (4)
O2	0.2642 (2)	0.91985 (15)	0.71532 (12)	0.0302 (4)
O1W	0.5981 (2)	0.59207 (14)	0.66084 (14)	0.0392 (5)
H1WA	0.6528	0.5466	0.7024	0.059*
H1WB	0.5022	0.5856	0.6758	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0235 (4)	0.0344 (4)	0.0189 (3)	0.00646 (18)	0.000	0.000
N1	0.0272 (11)	0.0389 (12)	0.0184 (10)	0.0068 (8)	−0.0009 (8)	−0.0021 (8)
N2	0.0348 (13)	0.0490 (13)	0.0186 (10)	0.0037 (9)	−0.0074 (8)	0.0014 (8)
C1	0.0247 (12)	0.0233 (11)	0.0233 (12)	−0.0029 (9)	0.0020 (9)	−0.0011 (8)
C2	0.0243 (12)	0.0288 (12)	0.0192 (12)	0.0008 (9)	0.0002 (9)	−0.0007 (8)
C4	0.0359 (15)	0.0506 (16)	0.0186 (12)	0.0067 (11)	0.0000 (10)	−0.0031 (10)
C3	0.0289 (12)	0.0391 (13)	0.0256 (13)	0.0037 (10)	−0.0008 (10)	0.0009 (10)
O1	0.0287 (10)	0.0457 (10)	0.0186 (8)	0.0087 (7)	−0.0010 (7)	−0.0002 (7)
O2	0.0243 (10)	0.0432 (11)	0.0232 (10)	0.0047 (6)	0.0048 (6)	−0.0051 (7)
O1W	0.0279 (10)	0.0429 (11)	0.0467 (12)	0.0036 (7)	0.0039 (8)	0.0133 (8)

Geometric parameters (Å, º) top

Mn1—O1W	2.2037 (17)	N2—H2	0.8600
Mn1—O1Wⁱ	2.2038 (17)	C1—O1	1.257 (3)
Mn1—O1ⁱ	2.2079 (16)	C1—O2	1.264 (3)
Mn1—O1	2.2079 (16)	C1—C2	1.480 (3)
Mn1—N1	2.2097 (19)	C2—C3	1.359 (3)
Mn1—N1ⁱ	2.2097 (19)	C4—H4	0.9300
N1—C4	1.313 (3)	C3—H3	0.9300
N1—C2	1.377 (3)	O1W—H1WA	0.87
N2—C4	1.340 (3)	O1W—H1WB	0.73
N2—C3	1.359 (3)

O1W—Mn1—O1Wⁱ	159.64 (10)	C4—N2—H2	126.1
O1W—Mn1—O1ⁱ	82.66 (6)	C3—N2—H2	126.1
O1Wⁱ—Mn1—O1ⁱ	86.27 (6)	O1—C1—O2	124.7 (2)
O1W—Mn1—O1	86.27 (6)	O1—C1—C2	116.93 (18)
O1Wⁱ—Mn1—O1	82.66 (6)	O2—C1—C2	118.34 (19)
O1ⁱ—Mn1—O1	113.90 (8)	C3—C2—N1	109.6 (2)
O1W—Mn1—N1	93.44 (7)	C3—C2—C1	131.4 (2)
O1Wⁱ—Mn1—N1	100.34 (7)	N1—C2—C1	118.98 (18)
O1ⁱ—Mn1—N1	168.96 (6)	N1—C4—N2	111.4 (2)
O1—Mn1—N1	75.97 (7)	N1—C4—H4	124.3
O1W—Mn1—N1ⁱ	100.34 (7)	N2—C4—H4	124.3
O1Wⁱ—Mn1—N1ⁱ	93.44 (7)	C2—C3—N2	105.9 (2)
O1ⁱ—Mn1—N1ⁱ	75.96 (7)	C2—C3—H3	127.1
O1—Mn1—N1ⁱ	168.97 (6)	N2—C3—H3	127.1
N1—Mn1—N1ⁱ	94.70 (10)	C1—O1—Mn1	116.82 (14)
C4—N1—C2	105.38 (19)	Mn1—O1W—H1WA	113.7
C4—N1—Mn1	143.43 (17)	Mn1—O1W—H1WB	128.2
C2—N1—Mn1	111.19 (14)	H1WA—O1W—H1WB	101.3
C4—N2—C3	107.8 (2)

O1W—Mn1—N1—C4	−95.6 (3)	O1—C1—C2—N1	3.7 (3)
O1Wⁱ—Mn1—N1—C4	99.5 (3)	O2—C1—C2—N1	−175.9 (2)
O1ⁱ—Mn1—N1—C4	−26.7 (5)	C2—N1—C4—N2	1.0 (3)
O1—Mn1—N1—C4	179.1 (3)	Mn1—N1—C4—N2	−178.4 (2)
N1ⁱ—Mn1—N1—C4	5.1 (3)	C3—N2—C4—N1	−0.8 (3)
O1W—Mn1—N1—C2	85.01 (16)	N1—C2—C3—N2	0.3 (3)
O1Wⁱ—Mn1—N1—C2	−79.94 (16)	C1—C2—C3—N2	−179.3 (2)
O1ⁱ—Mn1—N1—C2	153.9 (3)	C4—N2—C3—C2	0.3 (3)
O1—Mn1—N1—C2	−0.28 (15)	O2—C1—O1—Mn1	175.69 (16)
N1ⁱ—Mn1—N1—C2	−174.31 (19)	C2—C1—O1—Mn1	−3.9 (2)
C4—N1—C2—C3	−0.8 (3)	O1W—Mn1—O1—C1	−92.12 (16)
Mn1—N1—C2—C3	178.83 (16)	O1Wⁱ—Mn1—O1—C1	105.01 (16)
C4—N1—C2—C1	178.8 (2)	O1ⁱ—Mn1—O1—C1	−172.39 (18)
Mn1—N1—C2—C1	−1.5 (2)	N1—Mn1—O1—C1	2.38 (16)
O1—C1—C2—C3	−176.7 (2)	N1ⁱ—Mn1—O1—C1	35.2 (4)
O2—C1—C2—C3	3.7 (3)

Symmetry code: (i) −x+3/2, −y+3/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2ⁱⁱ	0.86	1.95	2.811 (3)	173
O1W—H1WA···O2ⁱⁱⁱ	0.87	1.96	2.818 (2)	167
O1W—H1WB···O2^iv	0.73	2.02	2.751 (2)	176

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

Experimental details

Crystal data
Chemical formula	[Mn(C₄H₃N₂O₂)₂(H₂O)₂]
M_r	313.14
Crystal system, space group	Orthorhombic, Pccn
Temperature (K)	298
a, b, c (Å)	7.3052 (10), 11.7997 (17), 13.5156 (19)
V (Å³)	1165.0 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.16
Crystal size (mm)	0.36 × 0.32 × 0.30

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.679, 0.721
No. of measured, independent and observed [I > 2σ(I)] reflections	5775, 1145, 972
R_int	0.067
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.109, 1.07
No. of reflections	1145
No. of parameters	87
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.57

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2ⁱ	0.86	1.95	2.811 (3)	173
O1W—H1WA···O2ⁱⁱ	0.87	1.96	2.818 (2)	167
O1W—H1WB···O2ⁱⁱⁱ	0.73	2.02	2.751 (2)	176

Symmetry codes: (i) −x+1/2, y, z−1/2; (ii) −x+1, y−1/2, −z+3/2; (iii) −x+1/2, −y+3/2, z.

Acknowledgements

The authors acknowledge the Engineering Research Center of Starch and Vegetable Protein Processing, Ministry of Education, South China University of Technology for supporting this work.

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