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Acta Crystallogr Sect E Struct Rep Online. 2010 January 1; 66(Pt 1): m99.
Published online 2009 December 24. doi:  10.1107/S1600536809054634
PMCID: PMC2980198

Diaqua­bis(5-carb­oxy-2-propyl-1H-imidazole-4-carboxyl­ato-κ2 N 3,O 4)manganese(II) N,N-dimethyl­formamide disolvate

Abstract

In the title complex, [Mn(C8H9N2O4)2(H2O)2]·2C3H7NO, the MnII atom, lying on an inversion centre, is six-coordinated by two N,O-bidentate 5-carb­oxy-2-propyl-1H-imidazole-4-carb­oxyl­ate ligands and two water mol­ecules in a distorted octa­hedral environment. In the crystal structure, the complex mol­ecules and dimethyl­formamide solvent mol­ecules are linked by N—H(...)O and O—H(...)O hydrogen bonds into a two-dimensional supra­molecular network parallel to (001).

Related literature

For the potential uses and diverse structural types of complexes containing metals and N-heterocyclic carboxylic acids, see: Liang et al. (2002 [triangle]); Net et al. (1989 [triangle]); Nie et al. (2007 [triangle]); Song et al. (2010 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-00m99-scheme1.jpg

Experimental

Crystal data

  • [Mn(C8H9N2O4)2(H2O)2]·2C3H7NO
  • M r = 631.51
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-00m99-efi1.jpg
  • a = 7.3992 (8) Å
  • b = 9.4429 (11) Å
  • c = 11.1978 (13) Å
  • α = 76.591 (1)°
  • β = 87.927 (1)°
  • γ = 68.863 (1)°
  • V = 708.89 (14) Å3
  • Z = 1
  • Mo Kα radiation
  • μ = 0.54 mm−1
  • T = 273 K
  • 0.32 × 0.25 × 0.21 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle])) T min = 0.847, T max = 0.896
  • 3653 measured reflections
  • 2508 independent reflections
  • 2131 reflections with I > 2σ(I)
  • R int = 0.025

Refinement

  • R[F 2 > 2σ(F 2)] = 0.041
  • wR(F 2) = 0.114
  • S = 1.05
  • 2508 reflections
  • 191 parameters
  • 27 restraints
  • H-atom parameters constrained
  • Δρmax = 0.34 e Å−3
  • Δρmin = −0.32 e Å−3

Data collection: APEX2 (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
Selected bond lengths (Å)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809054634/hy2265sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809054634/hy2265Isup2.hkl

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

Acknowledgments

The authors acknowledge Guang Dong Ocean University for supporting this work.

supplementary crystallographic information

Comment

Structures of complexes containing metals and N-heterocyclic carboxylic acids have attracted much attention. The N-heterocyclic carboxylic acids can function as multidentate ligands, exhibiting diverse structrual types, and their metal complexes can be potentially used as functional materials (Liang et al., 2002; Net et al., 1989; Nie et al., 2007). Recently, we have reported a new complex, poly[diaquabis(4-carboxy-2-propyl-1H-imidazole-5-carboxylato- κ3N3,O4:O5)calcium(II)] (Song et al., 2010). In this paper, we report the synthesis and structure of a MnII complex obtained under hydrothermal conditions.

As illustrated in Fig. 1, the title complex molecule contains one MnII atom, lying on an inversion centre, one mono-deprotonated 5-carboxy-2-propyl-1H-imidazole-4-carboxylate ligand, one coordinated water molecule and one dimethylformamide solvent molecule in the asymmetric unit. The MnII atom is six-coordinated by two N,O-bidentate ligands and two water molecules in a distorted octahedral environment (Table 1). In the crystal structure, a two-dimensional supramolecular network is formed by N—H···O and O—H···O hydrogen bonds (Table 2 and Fig. 2).

Experimental

A mixture of MnCl2 (0.5 mmol, 0.06 g) and 2-propyl-1H-imidazole-4,5-dicarboxylic acid (0.5 mmol, 0.99 g) in 15 ml of dimethylformamide solution was sealed in an autoclave equipped with a Teflon liner (20 ml) and then heated at 433 K for 4 d. Crystals of the title compound were obtained by slow evaporation of the solvent at room temperature.

Refinement

C– and N-bound H atoms were placed at calculated positions and refined as riding atoms, with C—H = 0.93 (CH), 0.97 (CH2) and 0.96 (CH3) Å and N—H = 0.86 Å and with Uiso(H) = 1.2(1.5 for methyl)Ueq(C, N). H atoms of water and carboxyl group were located in a difference Fourier map and refined as riding atoms, with Uiso(H) = 1.5Ueq(O).

Figures

Fig. 1.
Molecular structure of the title compound. Displacement ellipsoids are shown at the 30% probability level. [Symmetry code: (i) -x, 2 - y, -z.]
Fig. 2.
A view of the two-dimensional network constructed by O—H···O and N—H···O hydrogen bonds (dashed lines).

Crystal data

[Mn(C8H9N2O4)2H2O)2]·2C3H7NOZ = 1
Mr = 631.51F(000) = 331
Triclinic, P1Dx = 1.479 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.3992 (8) ÅCell parameters from 3600 reflections
b = 9.4429 (11) Åθ = 1.4–28°
c = 11.1978 (13) ŵ = 0.54 mm1
α = 76.591 (1)°T = 273 K
β = 87.927 (1)°Block, colourless
γ = 68.863 (1)°0.32 × 0.25 × 0.21 mm
V = 708.89 (14) Å3

Data collection

Bruker APEXII CCD diffractometer2131 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.025
[var phi] and ω scanθmax = 25.2°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996))h = −8→8
Tmin = 0.847, Tmax = 0.896k = −9→11
3653 measured reflectionsl = −13→12
2508 independent reflections

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)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.114H-atom parameters constrained
S = 1.05w = 1/[σ2(Fo2) + (0.0549P)2 + 0.120P] where P = (Fo2 + 2Fc2)/3
2508 reflections(Δ/σ)max < 0.001
191 parametersΔρmax = 0.34 e Å3
27 restraintsΔρmin = −0.32 e Å3

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

xyzUiso*/Ueq
Mn10.00001.00000.00000.03110 (18)
O1−0.0548 (3)0.92199 (19)−0.16620 (15)0.0379 (4)
O1W−0.2795 (2)0.9893 (2)0.06711 (17)0.0434 (4)
H1W−0.29330.91130.04840.065*
H2W−0.36721.07430.03290.065*
O20.0012 (3)0.7160 (2)−0.24509 (15)0.0424 (4)
O30.1886 (3)0.4324 (2)−0.18355 (17)0.0469 (5)
H30.12940.5271−0.20210.070*
O40.3630 (3)0.25664 (19)−0.02155 (18)0.0456 (5)
N10.1434 (3)0.7447 (2)0.04969 (16)0.0279 (4)
N20.3073 (3)0.4924 (2)0.10599 (17)0.0312 (4)
H20.37820.40300.15040.037*
C10.1335 (3)0.6770 (2)−0.0454 (2)0.0261 (5)
C20.2340 (3)0.5196 (3)−0.0111 (2)0.0285 (5)
C30.2498 (3)0.6292 (3)0.1400 (2)0.0303 (5)
C40.0194 (3)0.7798 (3)−0.1592 (2)0.0306 (5)
C50.2661 (3)0.3927 (3)−0.0755 (2)0.0337 (5)
C60.2933 (4)0.6449 (3)0.2642 (2)0.0410 (6)
H6A0.25840.75480.26250.049*
H6B0.43170.59390.28400.049*
C70.1855 (5)0.5745 (4)0.3637 (3)0.0616 (8)
H7A0.04770.62060.34090.074*
H7B0.22680.46330.36880.074*
C80.2178 (5)0.5986 (4)0.4887 (3)0.0648 (9)
H8A0.34570.53070.52170.097*
H8B0.12340.57530.54270.097*
H8C0.20490.70520.48110.097*
O90.4607 (3)−0.2429 (2)0.7294 (2)0.0626 (6)
N50.3789 (3)0.0120 (3)0.6354 (2)0.0470 (6)
C170.4889 (4)−0.1190 (4)0.7092 (3)0.0501 (7)
H170.5962−0.11810.74920.060*
C180.2038 (5)0.0185 (4)0.5761 (3)0.0702 (10)
H18A0.09370.06410.62120.105*
H18B0.2138−0.08520.57450.105*
H18C0.18800.08100.49360.105*
C190.4104 (7)0.1561 (4)0.6248 (4)0.0879 (12)
H19A0.53090.13530.66730.132*
H19B0.30610.22590.66040.132*
H19C0.41510.20330.53960.132*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Mn10.0369 (3)0.0180 (3)0.0364 (3)−0.0063 (2)−0.0014 (2)−0.0080 (2)
O10.0483 (10)0.0222 (9)0.0367 (9)−0.0057 (8)−0.0087 (7)−0.0043 (7)
O1W0.0411 (10)0.0287 (9)0.0616 (12)−0.0120 (8)0.0038 (8)−0.0142 (8)
O20.0568 (11)0.0346 (10)0.0329 (9)−0.0101 (9)−0.0099 (8)−0.0112 (8)
O30.0609 (12)0.0307 (10)0.0473 (11)−0.0079 (9)−0.0035 (9)−0.0189 (8)
O40.0465 (10)0.0218 (9)0.0645 (12)−0.0044 (8)−0.0026 (9)−0.0145 (8)
N10.0344 (10)0.0210 (10)0.0277 (10)−0.0092 (8)−0.0017 (8)−0.0055 (8)
N20.0332 (10)0.0188 (9)0.0351 (11)−0.0048 (8)−0.0052 (8)−0.0002 (8)
C10.0279 (11)0.0210 (11)0.0294 (11)−0.0085 (9)0.0007 (9)−0.0064 (9)
C20.0288 (11)0.0228 (12)0.0341 (12)−0.0087 (9)0.0016 (9)−0.0083 (9)
C30.0340 (12)0.0234 (12)0.0328 (12)−0.0106 (10)−0.0036 (9)−0.0040 (9)
C40.0330 (12)0.0272 (12)0.0295 (12)−0.0087 (10)−0.0024 (9)−0.0055 (10)
C50.0326 (12)0.0267 (13)0.0440 (14)−0.0105 (10)0.0066 (10)−0.0138 (11)
C60.0512 (15)0.0365 (14)0.0354 (13)−0.0164 (12)−0.0098 (11)−0.0062 (11)
C70.072 (2)0.076 (2)0.0455 (16)−0.0325 (18)0.0089 (15)−0.0238 (15)
C80.069 (2)0.077 (2)0.0424 (16)−0.0168 (19)0.0026 (15)−0.0191 (16)
O90.0712 (14)0.0298 (11)0.0699 (14)−0.0062 (10)−0.0216 (11)0.0047 (10)
N50.0535 (13)0.0309 (12)0.0502 (13)−0.0098 (11)0.0019 (11)−0.0065 (10)
C170.0472 (15)0.0471 (18)0.0500 (16)−0.0084 (14)−0.0051 (13)−0.0129 (13)
C180.0575 (19)0.058 (2)0.073 (2)−0.0073 (16)−0.0120 (16)0.0061 (17)
C190.134 (4)0.050 (2)0.089 (3)−0.044 (2)0.019 (3)−0.0182 (19)

Geometric parameters (Å, °)

Mn1—N12.1960 (18)C6—H6A0.9700
Mn1—O1W2.2036 (17)C6—H6B0.9700
Mn1—O12.2530 (17)C7—C81.509 (4)
O1—C41.238 (3)C7—H7A0.9700
O1W—H1W0.8509C7—H7B0.9700
O1W—H2W0.8436C8—H8A0.9600
O2—C41.282 (3)C8—H8B0.9600
O3—C51.272 (3)C8—H8C0.9600
O3—H30.8200O9—C171.229 (4)
O4—C51.240 (3)N5—C171.313 (4)
N1—C31.326 (3)N5—C191.440 (4)
N1—C11.379 (3)N5—C181.452 (4)
N2—C31.347 (3)C17—H170.9300
N2—C21.369 (3)C18—H18A0.9600
N2—H20.8600C18—H18B0.9600
C1—C21.367 (3)C18—H18C0.9600
C1—C41.480 (3)C19—H19A0.9600
C2—C51.481 (3)C19—H19B0.9600
C3—C61.491 (3)C19—H19C0.9600
C6—C71.516 (4)
N1i—Mn1—N1180.0O4—C5—C2118.9 (2)
N1i—Mn1—O1W87.40 (7)O3—C5—C2116.6 (2)
N1—Mn1—O1W92.60 (6)C3—C6—C7112.7 (2)
N1i—Mn1—O1Wi92.60 (6)C3—C6—H6A109.1
N1—Mn1—O1Wi87.40 (7)C7—C6—H6A109.1
O1W—Mn1—O1Wi180.0C3—C6—H6B109.1
N1i—Mn1—O1i75.41 (6)C7—C6—H6B109.1
N1—Mn1—O1i104.59 (6)H6A—C6—H6B107.8
O1W—Mn1—O1i91.40 (6)C8—C7—C6113.4 (3)
O1Wi—Mn1—O1i88.60 (6)C8—C7—H7A108.9
N1i—Mn1—O1104.59 (6)C6—C7—H7A108.9
N1—Mn1—O175.41 (6)C8—C7—H7B108.9
O1W—Mn1—O188.60 (6)C6—C7—H7B108.9
O1Wi—Mn1—O191.40 (6)H7A—C7—H7B107.7
O1i—Mn1—O1180.0C7—C8—H8A109.5
C4—O1—Mn1115.45 (14)C7—C8—H8B109.5
Mn1—O1W—H1W107.7H8A—C8—H8B109.5
Mn1—O1W—H2W107.5C7—C8—H8C109.5
H1W—O1W—H2W112.0H8A—C8—H8C109.5
C5—O3—H3109.5H8B—C8—H8C109.5
C3—N1—C1105.96 (18)C17—N5—C19121.9 (3)
C3—N1—Mn1141.35 (15)C17—N5—C18119.5 (3)
C1—N1—Mn1112.53 (13)C19—N5—C18118.0 (3)
C3—N2—C2108.51 (18)O9—C17—N5125.0 (3)
C3—N2—H2125.7O9—C17—H17117.5
C2—N2—H2125.7N5—C17—H17117.5
C2—C1—N1109.72 (19)N5—C18—H18A109.5
C2—C1—C4132.5 (2)N5—C18—H18B109.5
N1—C1—C4117.81 (19)H18A—C18—H18B109.5
C1—C2—N2105.37 (19)N5—C18—H18C109.5
C1—C2—C5132.1 (2)H18A—C18—H18C109.5
N2—C2—C5122.5 (2)H18B—C18—H18C109.5
N1—C3—N2110.44 (19)N5—C19—H19A109.5
N1—C3—C6125.5 (2)N5—C19—H19B109.5
N2—C3—C6124.0 (2)H19A—C19—H19B109.5
O1—C4—O2123.4 (2)N5—C19—H19C109.5
O1—C4—C1118.6 (2)H19A—C19—H19C109.5
O2—C4—C1117.9 (2)H19B—C19—H19C109.5
O4—C5—O3124.4 (2)

Symmetry codes: (i) −x, −y+2, −z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2···O9ii0.861.842.682 (3)165
O3—H3···O20.821.652.471 (2)176
O1W—H1W···O4iii0.851.922.764 (2)170
O1W—H2W···O4iv0.842.112.927 (2)164

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HY2265).

References

  • Bruker (2007). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Liang, Y. C., Cao, R. & Hong, M. C. (2002). Inorg. Chem. Commun.5, 366–368.
  • Net, G., Bayon, J. C., Butler, W. M. & Rasmussen, P. (1989). J. Chem. Soc. Chem. Commun. pp. 1022–1023.
  • Nie, X.-L., Wen, H.-L., Wu, Z.-S., Liu, D.-B. & Liu, C.-B. (2007). Acta Cryst. E63, m753–m755.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Song, W.-D., Yan, J.-B., Li, S.-J., Miao, D.-L. & Li, X.-F. (2010). Acta Cryst. E66, m53. [PMC free article] [PubMed]

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