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Acta Crystallogr Sect E Struct Rep Online. 2010 May 1; 66(Pt 5): m513.
Published online 2010 April 10. doi:  10.1107/S1600536810012638
PMCID: PMC2979258

Tetra­aqua­bis[4-(imidazol-1-yl-κN 3)benzoato]manganese(II)

Abstract

In the title compound, [Mn(C10H7N2O2)2(H2O)4], the MnII atom, lying on an inversion center, has an octa­hedral environment with four coordinated water mol­ecules in the equatorial plane and two N atoms from two 4-(imidazol-1-yl)benzoate ligands at the axial sites. The complex mol­ecules are connected into a three-dimensional network by extensive hydrogen bonds between the water mol­ecules and the carboxyl­ate O atoms.

Related literature

For the good coordination ability and diverse coordination modes of ligands containing imidazole and carboxyl­ate groups, see: Fan et al. (2004 [triangle]); Sun et al. (2005 [triangle]). For the construction of metal–organic frameworks using ligands based on imidazolyl and carboxyl­ate groups as building blocks, see: Carlucci et al. (2008 [triangle]); Zhang et al. (2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0m513-scheme1.jpg

Experimental

Crystal data

  • [Mn(C10H7N2O2)2(H2O)4]
  • M r = 501.36
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0m513-efi1.jpg
  • a = 12.278 (12) Å
  • b = 11.026 (11) Å
  • c = 7.978 (7) Å
  • β = 96.91 (2)°
  • V = 1072.2 (18) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.67 mm−1
  • T = 293 K
  • 0.28 × 0.14 × 0.10 mm

Data collection

  • Bruker SMART APEX CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.536, T max = 1.000
  • 7972 measured reflections
  • 2444 independent reflections
  • 2131 reflections with I > 2σ(I)
  • R int = 0.023

Refinement

  • R[F 2 > 2σ(F 2)] = 0.032
  • wR(F 2) = 0.113
  • S = 0.91
  • 2444 reflections
  • 195 parameters
  • All H-atom parameters refined
  • Δρmax = 0.36 e Å−3
  • Δρmin = −0.23 e Å−3

Data collection: SMART (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810012638/hy2292sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810012638/hy2292Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank the National Natural Science Foundation of China and the State Key Laboratory of Structural Chemistry for financial support.

supplementary crystallographic information

Comment

Over past few years, considerable effort was paied in the study of metal-organic frameworks (MOFs) owing to their intriguing structural diversity and potential application in adsorption, molecular recognition, catalysis and maganetism. The field of molecular magnets has attracted great interest from different horizons for many years. In this context, the ligand containing imidazole and carboxylate groups is of special interest due to its good coordination ability and diverse coordination modes (Fan et al., 2004; Sun et al., 2005). However, the reports of ligands based on imidazole and carboxylate groups as building blocks for the construction of MOFs (Carlucci et al., 2008; Zhang et al., 2007) are still rare. In this paper, we report the synthesis and structural characterzation of the title compound.

As shown in Fig. 1, the molecular structure of the title compound is a momonuclear MnII complex and the dihedral angle between the imidazolyl ring and the benzene ring of the 4-(imidazol-1-yl)benzoate is 6.3 (2)°. The MnII ion is coordinated by four water molecules and two N atoms from two different 4-(imidazol-1-yl)benzoate ligands, forming a distorted octahedral coordination environment. The Mn—N and Mn—O bond distances are 2.238 (2) Å and 2.149 (2) and 2.189 (3) Å, respectively. The related hydrogen-bonding geometry is given in Table 1. A l l values involved with hydrogen bonds fall in a normal range. The intermolecular O—H···O hydrogen-bonding interactions between the coordinated water molecules and carboxylate O atoms of 4-(imidazol-1-yl)benzoate ligands lead to the formation of a three-dimensional network structure as shown in Fig. 2.

Experimental

A 10 ml aqueous solution of 4-(imidazole-1-yl)benzoic acid (0.038 g, 0.20 mmol) was slowly added into the manganese(II) perchlorate (0.663 g, 0.30 mmol) solution in methanol (10 ml). The mixed solution was stirred for 20 min and then HClO4 solution was added dropwise with constant stirring until the mixed solution was clear. The resulting solution was filtered and the slow evaporation of filtrate in air gave rise to the desirable products, which were subsequently washed twice with Et2O (yield 38%).

Refinement

All H atoms were located in a difference Fourier map and refined isotropically.

Figures

Fig. 1.
The molecular structure of the title compound, with the 50% probability displacement ellipsoids. H atoms have been omitted for clarity. [Symmetry code: (i) -x, -y, -z.]
Fig. 2.
The crystal packing of the title compound, showing O—H···O hydrogen bonds (dashed lines). H atoms not involved in hydrogen bonding have been omitted.

Crystal data

[Mn(C10H7N2O2)2(H2O)4]F(000) = 518
Mr = 501.36Dx = 1.553 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3126 reflections
a = 12.278 (12) Åθ = 3.3–27.5°
b = 11.026 (11) ŵ = 0.67 mm1
c = 7.978 (7) ÅT = 293 K
β = 96.91 (2)°Prism, yellow
V = 1072.2 (18) Å30.28 × 0.14 × 0.10 mm
Z = 2

Data collection

Bruker SMART APEX CCD diffractometer2444 independent reflections
Radiation source: fine-focus sealed tube2131 reflections with I > 2σ(I)
graphiteRint = 0.023
[var phi] and ω scansθmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −15→15
Tmin = 0.536, Tmax = 1.000k = −14→13
7972 measured reflectionsl = −10→10

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113All H-atom parameters refined
S = 0.91w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3
2444 reflections(Δ/σ)max < 0.001
195 parametersΔρmax = 0.36 e Å3
0 restraintsΔρmin = −0.23 e Å3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Mn10.00000.00000.00000.02675 (15)
O1−0.85062 (8)0.13841 (11)−0.33828 (13)0.0376 (3)
O2−0.77609 (10)0.03929 (15)−0.53834 (16)0.0491 (3)
O30.02777 (12)0.01354 (13)0.27549 (16)0.0452 (3)
O4−0.07938 (14)−0.17041 (13)0.03407 (19)0.0636 (5)
N1−0.16150 (10)0.09039 (13)0.01711 (16)0.0364 (3)
N2−0.33890 (9)0.12493 (11)−0.04316 (14)0.0289 (3)
C1−0.25122 (12)0.06006 (16)−0.0792 (2)0.0383 (4)
C2−0.19202 (15)0.17902 (19)0.1215 (3)0.0523 (5)
C3−0.30063 (15)0.20096 (19)0.0867 (3)0.0550 (5)
C4−0.44787 (10)0.11462 (12)−0.12551 (16)0.0259 (3)
C5−0.52854 (12)0.19507 (14)−0.08855 (19)0.0325 (3)
C6−0.63403 (12)0.18533 (14)−0.1733 (2)0.0332 (3)
C7−0.65917 (11)0.09772 (13)−0.29617 (17)0.0265 (3)
C8−0.57766 (14)0.01717 (15)−0.3290 (2)0.0347 (4)
C9−0.47314 (14)0.02432 (16)−0.2445 (2)0.0372 (4)
C10−0.77070 (11)0.09005 (14)−0.39869 (17)0.0301 (3)
H1−0.254 (3)0.0002 (18)−0.158 (4)0.067 (8)*
H2−0.139 (2)0.212 (2)0.210 (3)0.068 (7)*
H3−0.347 (2)0.254 (2)0.135 (3)0.070 (7)*
H5−0.5108 (14)0.263 (2)−0.006 (2)0.047 (6)*
H6−0.6944 (15)0.2366 (18)−0.149 (2)0.039 (5)*
H8−0.5940 (17)−0.048 (2)−0.418 (3)0.052 (5)*
H9−0.4164 (18)−0.036 (2)−0.264 (2)0.048 (5)*
H11−0.0941 (19)−0.239 (2)−0.025 (3)0.065 (6)*
H12−0.1116 (17)−0.1765 (18)0.126 (3)0.047 (5)*
H13−0.016 (2)−0.035 (2)0.316 (3)0.050 (6)*
H140.086 (2)0.021 (2)0.330 (3)0.060 (7)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Mn10.0172 (2)0.0347 (2)0.0279 (2)−0.00251 (9)0.00068 (13)−0.00317 (10)
O10.0226 (5)0.0550 (7)0.0358 (6)0.0086 (4)0.0055 (4)0.0051 (5)
O20.0278 (6)0.0822 (9)0.0354 (6)0.0050 (6)−0.0040 (5)−0.0161 (6)
O30.0302 (7)0.0748 (9)0.0294 (7)−0.0122 (6)−0.0018 (5)−0.0016 (5)
O40.0892 (11)0.0500 (8)0.0604 (9)−0.0349 (8)0.0443 (9)−0.0225 (7)
N10.0238 (6)0.0475 (8)0.0367 (6)0.0026 (5)−0.0010 (5)−0.0049 (6)
N20.0225 (6)0.0352 (6)0.0286 (6)0.0042 (4)0.0020 (4)−0.0011 (5)
C10.0229 (7)0.0500 (10)0.0413 (8)0.0063 (6)0.0008 (6)−0.0125 (7)
C20.0345 (9)0.0640 (12)0.0547 (11)0.0065 (8)−0.0093 (8)−0.0253 (9)
C30.0340 (9)0.0664 (12)0.0613 (12)0.0119 (8)−0.0084 (8)−0.0349 (10)
C40.0208 (6)0.0311 (7)0.0258 (6)0.0010 (5)0.0021 (5)0.0016 (5)
C50.0268 (7)0.0338 (8)0.0365 (7)0.0020 (5)0.0028 (6)−0.0087 (6)
C60.0240 (6)0.0356 (8)0.0404 (8)0.0066 (5)0.0062 (6)−0.0035 (6)
C70.0216 (6)0.0308 (7)0.0274 (6)0.0006 (5)0.0045 (5)0.0040 (5)
C80.0274 (8)0.0400 (8)0.0355 (9)0.0045 (6)−0.0007 (7)−0.0098 (6)
C90.0268 (8)0.0413 (8)0.0425 (9)0.0105 (6)0.0004 (7)−0.0116 (7)
C100.0233 (6)0.0388 (8)0.0285 (7)0.0005 (5)0.0037 (5)0.0072 (6)

Geometric parameters (Å, °)

Mn1—O42.149 (2)C2—C31.351 (3)
Mn1—O32.188 (2)C2—H20.97 (2)
Mn1—N12.238 (2)C3—H30.93 (3)
O1—C101.2623 (19)C4—C91.385 (2)
O2—C101.242 (2)C4—C51.387 (2)
O3—H130.85 (2)C5—C61.391 (2)
O3—H140.79 (3)C5—H51.00 (2)
O4—H110.90 (2)C6—C71.385 (2)
O4—H120.87 (2)C6—H60.970 (19)
N1—C11.308 (2)C7—C81.387 (2)
N1—C21.366 (2)C7—C101.511 (2)
N2—C11.352 (2)C8—C91.378 (3)
N2—C31.371 (2)C8—H81.02 (2)
N2—C41.422 (2)C9—H90.99 (2)
C1—H10.91 (2)
O4—Mn1—O4i180.00 (9)N2—C1—H1125 (2)
O4—Mn1—O387.18 (6)C3—C2—N1109.84 (16)
O4i—Mn1—O392.82 (6)C3—C2—H2130.1 (14)
O4—Mn1—O3i92.82 (6)N1—C2—H2119.9 (14)
O4i—Mn1—O3i87.18 (6)C2—C3—N2106.62 (16)
O3—Mn1—O3i180.00 (8)C2—C3—H3131.2 (15)
O4—Mn1—N1i92.12 (9)N2—C3—H3122.2 (15)
O4i—Mn1—N1i87.88 (9)C9—C4—C5119.91 (14)
O3—Mn1—N1i93.41 (6)C9—C4—N2119.65 (12)
O3i—Mn1—N1i86.59 (6)C5—C4—N2120.44 (13)
O4—Mn1—N187.88 (9)C4—C5—C6119.61 (14)
O4i—Mn1—N192.12 (9)C4—C5—H5120.7 (10)
O3—Mn1—N186.59 (6)C6—C5—H5119.6 (10)
O3i—Mn1—N193.41 (6)C7—C6—C5120.87 (13)
N1i—Mn1—N1180.00 (9)C7—C6—H6115.9 (11)
Mn1—O3—H13108.2 (16)C5—C6—H6123.2 (11)
Mn1—O3—H14125.7 (18)C6—C7—C8118.45 (14)
H13—O3—H14115 (2)C6—C7—C10122.20 (13)
Mn1—O4—H11137.2 (15)C8—C7—C10119.32 (14)
Mn1—O4—H12115.5 (13)C9—C8—C7121.45 (15)
H11—O4—H12107.2 (18)C9—C8—H8118.5 (12)
C1—N1—C2105.52 (14)C7—C8—H8120.1 (12)
C1—N1—Mn1122.68 (12)C8—C9—C4119.67 (14)
C2—N1—Mn1131.77 (11)C8—C9—H9121.2 (13)
C1—N2—C3105.95 (14)C4—C9—H9119.1 (13)
C1—N2—C4126.05 (13)O2—C10—O1124.98 (13)
C3—N2—C4128.00 (13)O2—C10—C7117.26 (13)
N1—C1—N2112.07 (15)O1—C10—C7117.73 (14)
N1—C1—H1123 (2)

Symmetry codes: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O3—H13···O1ii0.85 (2)2.02 (2)2.837 (3)161 (2)
O3—H14···O2iii0.79 (3)1.90 (3)2.688 (3)179 (2)
O4—H11···O1iv0.90 (2)1.82 (2)2.702 (3)168 (2)
O4—H12···O1ii0.87 (2)1.86 (2)2.694 (3)158.9 (19)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HY2292).

References

  • Bruker (2007). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Carlucci, L., Ciani, G., Maggini, S. & Proserpio, D. M. (2008). Cryst. Growth Des.8, 162–165.
  • Fan, J., Sun, W.-Y., Okamura, T., Zheng, Y.-Q., Sui, B., Tang, W.-X. & Ueyama, N. (2004). Cryst. Growth Des.4, 579–584.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Sun, C.-Y., Zheng, X.-J., Gao, S., Li, L.-C. & Jin, L.-P. (2005). Eur. J. Inorg. Chem. pp. 4150–4159.
  • Zhang, J.-Z., Cao, W.-R., Pan, J.-X. & Chen, Q.-W. (2007). Inorg. Chem. Commun.10, 1360–1364.

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