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Acta Cryst. (2009). E65, m1480    [ doi:10.1107/S1600536809044298 ]

catena-Poly[[[[3-(2-pyridyl)-1H-pyrazole]manganese(II)]-[mu]-oxalato] sesquihydrate]

Z. An and L. Zhu

Abstract top

In the title compound, {[Mn(C2O4)(C8H7N3)]·1.5H2O}n, the MnII ion is chelated by two O,O'-bidentate oxalate ions and an N,N'-bidentate 3-(2-pyridyl)pyrazole molecule, resulting in a distorted cis-MnN2O4 octahedral geometry for the metal ion. The bridging oxalate ions generate wave-like polymeric chains propagating in [001]. The packing is consolidated by N-H...O and O-H...O hydrogen bonds. One of the water O atoms lies on a crystallographic twofold axis.

Comment top

The tridentate ligand 3-(2-pyridyl)pyrazole and its derivatives have been used widely in the construction of supramolecular architectures by way of metal-organic coordination (Ward, Fleming et al. 1998; Ward, 2001).

As a continuation of these studies, we now report the crystal structure of the title complex, (I).

The Mn ion is hexcoordianted, chelated by two oxalate and one 3-(2-pyridyl)pyrazole ligand (Table 1). While each oxalate ligand acts as one bridige to chalate two Mn ions, forming one wave-like line with Mn···Mn distance being 5.652 /%A, shown in Figure 2. The structure is consolidated by N—H···O and O—H···O hydrogen bonds (Table 2, Figure 3).

Related literature top

For coordination compounds with pyridyl-pyrazolide ligands, see: Ward et al. (1998, 2001).

Experimental top

A mixture of Mn(CH3COO)2.4H2O (1 mmol), 3-(2-pyridyl)pyrazole (1 mmol), oxalic acid (1 mmol), sodium hydroxide (1 mmol) and H2O (10 ml) was stirred for 30 min in air. The mixture was then transferred to a 25 ml Teflon-lined hydrothermal bomb. The bomb was kept at 433 K for 72 h under autogenous pressure. Upon cooling, pink prisms of (I) were obtained from the reaction mixture.

Refinement top

The C-bound H atoms were geometrically planced (C—H = 0.93/%A) and refined as riding with Uiso = 1.2Ueq(C). The N– and O-bound H atoms were located in difference maps and refined with distance restraints: N—H = 0.97 (1)/%A, O—H = 0.82 (2)/%A, H···H = 1.38 (2)/%A.

Computing details top

Data collection: SMART (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A view of (I) with the unique-atom labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. A view of (I) showing the extended chain strcuture.
[Figure 3] Fig. 3. A view of (I) showing the packing.
catena-Poly[[[[3-(2-pyridyl)-1H-pyrazole]manganese(II)]- µ-oxalato] sesquihydrate] top
Crystal data top
[Mn(C2O4)(C8H7N3)]·1.5H2OF(000) = 1280
Mr = 315.15Dx = 1.597 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2634 reflections
a = 29.460 (8) Åθ = 2.8–25.4°
b = 9.236 (3) ŵ = 1.03 mm−1
c = 9.875 (3) ÅT = 296 K
β = 102.706 (5)°Block, pink
V = 2621.0 (13) Å30.43 × 0.28 × 0.22 mm
Z = 8
Data collection top
Bruker APEXII CCD
diffractometer		2438 independent reflections
Radiation source: fine-focus sealed tube2004 reflections with I > 2σ(I)
graphiteRint = 0.020
φ and ω scansθmax = 25.5°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Bruker, 2005)		h = −35→35
Tmin = 0.665, Tmax = 0.805k = −10→11
6809 measured reflectionsl = −9→11
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.027Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.078H atoms treated by a mixture of independent and constrained refinement
S = 1.00 w = 1/[σ2(Fo2) + (0.045P)2 + 0.7224P]
where P = (Fo2 + 2Fc2)/3
2438 reflections(Δ/σ)max = 0.001
186 parametersΔρmax = 0.22 e Å−3
0 restraintsΔρmin = −0.16 e Å−3
Crystal data top
[Mn(C2O4)(C8H7N3)]·1.5H2OV = 2621.0 (13) Å3
Mr = 315.15Z = 8
Monoclinic, C2/cMo Kα radiation
a = 29.460 (8) ŵ = 1.03 mm−1
b = 9.236 (3) ÅT = 296 K
c = 9.875 (3) Å0.43 × 0.28 × 0.22 mm
β = 102.706 (5)°
Data collection top
Bruker APEXII CCD
diffractometer		2438 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2005)		2004 reflections with I > 2σ(I)
Tmin = 0.665, Tmax = 0.805Rint = 0.020
6809 measured reflectionsθmax = 25.5°
Refinement top
R[F2 > 2σ(F2)] = 0.027H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.078Δρmax = 0.22 e Å−3
S = 1.00Δρmin = −0.16 e Å−3
2438 reflectionsAbsolute structure: ?
186 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
C10.2903 (2)0.3204 (7)0.3530 (6)0.0620 (16)
H10.27800.22840.35940.074*
C20.2697 (2)0.4365 (8)0.4029 (7)0.0732 (19)
H20.24410.42290.44230.088*
C30.2872 (2)0.5721 (8)0.3938 (7)0.077 (2)
H30.27400.65180.42790.092*
C40.3246 (2)0.5889 (7)0.3340 (7)0.0685 (17)
H40.33670.68060.32570.082*
C50.34421 (19)0.4681 (6)0.2858 (5)0.0483 (13)
C60.3844 (2)0.4772 (6)0.2209 (6)0.0506 (13)
C70.4082 (3)0.5950 (7)0.1822 (8)0.079 (2)
H70.40240.69260.19400.095*
C80.4416 (3)0.5372 (7)0.1235 (8)0.085 (2)
H80.46320.58860.08680.102*
C90.39499 (16)0.0253 (5)0.5065 (5)0.0374 (11)
C100.34569 (16)−0.0362 (5)0.4432 (5)0.0367 (11)
N10.32730 (15)0.3343 (5)0.2955 (5)0.0472 (11)
N20.40299 (15)0.3533 (4)0.1877 (5)0.0470 (11)
N30.43793 (17)0.3939 (6)0.1279 (5)0.0628 (13)
H3A0.45560.33460.09650.075*
Mn10.36805 (2)0.14892 (8)0.22637 (7)0.0395 (3)
O10.41292 (12)0.1050 (4)0.4304 (4)0.0476 (9)
O20.32916 (13)−0.0076 (4)0.3189 (4)0.0514 (9)
O30.41261 (12)−0.0083 (4)0.6295 (3)0.0477 (9)
O40.32667 (11)−0.1102 (4)0.5215 (3)0.0433 (8)
O1W0.49441 (17)0.2150 (6)0.0153 (6)0.0849 (14)
O2W0.50000.8860 (7)0.25000.0754 (19)
H1W0.5197 (14)0.181 (7)0.056 (5)0.080*
H2W0.485 (2)0.183 (7)−0.063 (4)0.080*
H3W0.4792 (17)0.944 (6)0.222 (7)0.080*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.055 (3)0.068 (4)0.070 (4)0.001 (3)0.027 (3)−0.007 (3)
C20.054 (4)0.092 (5)0.080 (5)0.015 (4)0.028 (3)−0.012 (4)
C30.074 (4)0.079 (5)0.078 (5)0.028 (4)0.019 (4)−0.021 (4)
C40.079 (4)0.049 (3)0.076 (4)0.008 (3)0.016 (4)−0.018 (3)
C50.054 (3)0.043 (3)0.046 (3)0.004 (2)0.007 (2)−0.007 (2)
C60.057 (3)0.040 (3)0.055 (3)−0.003 (2)0.012 (3)−0.002 (2)
C70.101 (5)0.041 (3)0.104 (6)−0.009 (3)0.039 (5)0.007 (3)
C80.091 (5)0.065 (4)0.112 (6)−0.022 (4)0.047 (5)0.013 (4)
C90.042 (3)0.035 (3)0.037 (3)−0.002 (2)0.013 (2)−0.003 (2)
C100.043 (3)0.032 (2)0.038 (3)−0.003 (2)0.013 (2)−0.004 (2)
N10.048 (2)0.046 (3)0.051 (3)0.0022 (19)0.017 (2)−0.0065 (19)
N20.051 (3)0.041 (2)0.053 (3)−0.0033 (19)0.021 (2)0.0016 (19)
N30.061 (3)0.063 (3)0.074 (3)−0.006 (2)0.035 (3)0.008 (3)
Mn10.0490 (5)0.0355 (5)0.0370 (5)0.0002 (3)0.0160 (3)−0.0001 (3)
O10.046 (2)0.055 (2)0.043 (2)−0.0140 (16)0.0116 (16)0.0073 (16)
O20.056 (2)0.059 (2)0.037 (2)−0.0187 (18)0.0051 (16)0.0048 (16)
O30.046 (2)0.057 (2)0.039 (2)−0.0124 (16)0.0069 (16)0.0062 (16)
O40.0449 (19)0.0467 (19)0.0401 (19)−0.0105 (15)0.0132 (16)0.0017 (15)
O1W0.060 (3)0.103 (4)0.097 (4)0.016 (3)0.027 (3)−0.002 (3)
O2W0.047 (4)0.069 (4)0.102 (5)0.000−0.002 (4)0.000
Geometric parameters (Å, °) top
C1—N11.342 (7)C9—O31.250 (6)
C1—C21.376 (8)C9—C101.557 (7)
C1—H10.9300C10—O21.245 (6)
C2—C31.365 (10)C10—O41.253 (5)
C2—H20.9300N2—N31.348 (6)
C3—C41.367 (9)N3—H3A0.8600
C3—H30.9300Mn1—N12.280 (4)
C4—C51.388 (8)Mn1—N22.223 (4)
C4—H40.9300Mn1—O4i2.150 (3)
C5—N11.344 (6)Mn1—O22.168 (3)
C5—C61.468 (8)Mn1—O12.191 (4)
C6—N21.339 (7)Mn1—O3i2.208 (3)
C6—C71.392 (8)O3—Mn1ii2.208 (3)
C7—C81.357 (10)O4—Mn1ii2.150 (3)
C7—H70.9300O1W—H1W0.83 (5)
C8—N31.329 (8)O1W—H2W0.82 (4)
C8—H80.9300O2W—H3W0.82 (5)
C9—O11.250 (6)
N1—C1—C2122.7 (6)C1—N1—C5117.8 (5)
N1—C1—H1118.7C1—N1—Mn1125.8 (4)
C2—C1—H1118.7C5—N1—Mn1116.2 (3)
C3—C2—C1119.2 (6)C6—N2—N3105.2 (4)
C3—C2—H2120.4C6—N2—Mn1117.0 (3)
C1—C2—H2120.4N3—N2—Mn1137.6 (4)
C2—C3—C4119.0 (6)C8—N3—N2111.5 (5)
C2—C3—H3120.5C8—N3—H3A124.2
C4—C3—H3120.5N2—N3—H3A124.2
C3—C4—C5119.5 (6)O4i—Mn1—O292.44 (13)
C3—C4—H4120.3O4i—Mn1—O1159.58 (14)
C5—C4—H4120.3O2—Mn1—O175.93 (13)
N1—C5—C4121.7 (5)O4i—Mn1—O3i76.27 (12)
N1—C5—C6115.5 (4)O2—Mn1—O3i102.10 (16)
C4—C5—C6122.8 (5)O1—Mn1—O3i89.63 (13)
N2—C6—C7110.1 (5)O4i—Mn1—N299.67 (15)
N2—C6—C5118.1 (4)O2—Mn1—N2161.17 (16)
C7—C6—C5131.8 (5)O1—Mn1—N296.12 (15)
C8—C7—C6105.4 (6)O3i—Mn1—N294.79 (14)
C8—C7—H7127.3O4i—Mn1—N1100.36 (14)
C6—C7—H7127.3O2—Mn1—N190.74 (16)
N3—C8—C7107.8 (6)O1—Mn1—N196.58 (15)
N3—C8—H8126.1O3i—Mn1—N1166.79 (15)
C7—C8—H8126.1N2—Mn1—N173.01 (16)
O1—C9—O3126.2 (4)C9—O1—Mn1114.4 (3)
O1—C9—C10117.0 (4)C10—O2—Mn1115.4 (3)
O3—C9—C10116.8 (4)C9—O3—Mn1ii114.0 (3)
O2—C10—O4126.4 (4)C10—O4—Mn1ii115.7 (3)
O2—C10—C9116.5 (4)H1W—O1W—H2W114 (4)
O4—C10—C9117.1 (4)
Symmetry codes: (i) x, −y, z−1/2; (ii) x, −y, z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···O1W0.861.892.748 (7)175
O1W—H1W···O1iii0.83 (5)2.08 (4)2.851 (6)155 (6)
O1W—H2W···O2Wiv0.82 (4)2.10 (5)2.819 (6)148 (6)
O2W—H3W···O3v0.82 (5)2.06 (4)2.823 (4)156 (6)
Symmetry codes: (iii) −x+1, y, −z+1/2; (iv) −x+1, −y+1, −z; (v) x, −y+1, z−1/2.
Table 1
Selected geometric parameters (Å, °) top
Mn1—N12.280 (4)Mn1—O22.168 (3)
Mn1—N22.223 (4)Mn1—O12.191 (4)
Mn1—O4i2.150 (3)Mn1—O3i2.208 (3)
N2—Mn1—N173.01 (16)
Symmetry codes: (i) x, −y, z−1/2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···O1W0.861.892.748 (7)175
O1W—H1W···O1ii0.83 (5)2.08 (4)2.851 (6)155 (6)
O1W—H2W···O2Wiii0.82 (4)2.10 (5)2.819 (6)148 (6)
O2W—H3W···O3iv0.82 (5)2.06 (4)2.823 (4)156 (6)
Symmetry codes: (ii) −x+1, y, −z+1/2; (iii) −x+1, −y+1, −z; (iv) x, −y+1, z−1/2.
Acknowledgements top

The authors acknowledge financial support from the program for talent introduction in Guangdong Higher Education Institutions and the scientific research start-up funds of talent introduction in Maoming University.

references
References top

Bruker (2005). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Ward, M. D., Fleming, J. S., Psillakis, E., Jeffery, J. C. & McCleverty, J. A. (1998). Acta Cryst. C54, 609–612.

Ward, M. D., McCleverty, J. A. & Jeffery, J. C. (2001). Coord. Chem. Rev. 222, 251–272.