Hexaaqua­manganese(II) dipicrate dihydrate

Changying Liu; Xiufang Shi; Bin Du; Chunli Wu; Mingjie Zhang

doi:10.1107/S1600536807064276

. 2008 Jan 4;64(Pt 2):m270–m271. doi: 10.1107/S1600536807064276

Hexaaquamanganese(II) dipicrate dihydrate

Changying Liu ^a, Xiufang Shi ^b,^*, Bin Du ^b, Chunli Wu ^b, Mingjie Zhang ^a

PMCID: PMC2960271 PMID: 21201254

Abstract

In the title compound, [Mn(H₂O)₆](C₆H₂N₃O₇)₂·2H₂O, the manganese cation, on an inversion centre, is coordinated by six water molecules, but the picrate anion has no coordinative interaction with the manganese cation. The anions in the stack are linked via short intermolecular O⋯C (3.013 and 2.973 Å) and C⋯C (3.089 and 3.065 Å) contacts and hydrogen bonds.

Related literature

For related literature, see: Bibal et al. (2003 ▶); García et al. (2004 ▶); Harrowfield et al. (1995a ▶,b ▶); Honda et al. (2003 ▶); Ji & Chen (1996 ▶); Maartmann-Moe (1969 ▶); Olsher et al. (1996 ▶); Yang et al. (2001 ▶); Zhang et al. (2003 ▶).

Experimental

Crystal data

[Mn(H₂O)₆](C₆H₂N₃O₇)₂·2H₂O
M _r = 655.28
Orthorhombic,
a = 25.344 (6) Å
b = 7.1625 (17) Å
c = 13.217 (3) Å
V = 2399.2 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.67 mm⁻¹
T = 294 (2) K
0.28 × 0.24 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.835, T _max = 0.878
11295 measured reflections
2122 independent reflections
1643 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.158
S = 1.11
2122 reflections
211 parameters
8 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.50 e Å⁻³
Δρ_min = −1.20 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: SHELXTL (Bruker, 1997 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807064276/ww2104sup1.cif

e-64-0m270-sup1.cif^{(17.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807064276/ww2104Isup2.hkl

e-64-0m270-Isup2.hkl^{(104.5KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Mn1—O1	2.120 (3)
Mn1—O3	2.136 (3)
Mn1—O2	2.190 (2)

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O1—Mn1—O3	91.52 (11)
O1—Mn1—O3ⁱ	88.48 (11)
O1—Mn1—O2ⁱ	93.02 (11)
O3ⁱ—Mn1—O2ⁱ	86.83 (11)
O1—Mn1—O2	86.98 (11)
O3ⁱ—Mn1—O2	93.17 (11)

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Symmetry code: (i) Inline graphic .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O11ⁱⁱ	0.846 (10)	1.938 (12)	2.780 (4)	173 (4)
O1—H1B⋯O10ⁱⁱⁱ	0.852 (10)	2.10 (2)	2.906 (4)	157 (4)
O2—H2A⋯O10^iv	0.848 (10)	2.048 (12)	2.889 (4)	172 (4)
O2—H2A⋯O9^iv	0.848 (10)	2.53 (4)	2.986 (4)	115 (3)
O3—H3A⋯O11^v	0.832 (10)	1.951 (12)	2.782 (4)	176 (5)
O3—H3B⋯O6^vi	0.841 (10)	2.047 (12)	2.884 (4)	174 (5)
O11—H11A⋯O2^vii	0.847 (10)	2.213 (19)	3.006 (4)	156 (4)
O11—H11B⋯O10^viii	0.846 (10)	2.17 (2)	2.938 (4)	151 (4)
O11—H11B⋯O4^viii	0.846 (10)	2.27 (3)	2.913 (4)	133 (4)
O2—H2B⋯O4^ix	0.841 (10)	2.143 (19)	2.930 (4)	156 (4)

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Symmetry codes: (ii) Inline graphic ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) ; (ix) .

Acknowledgments

We acknowledge financial support of this study by Zhengzhou University.

supplementary crystallographic information

Comment

Picrate is commonly used as an accompanying ion in many systems involving extraction and transport of metal ions to improve the extractability and selectivity (Zhang et al., 2003; Bibal et al., 2003; García et al., 2004). In many structures, picrate interacts as monodentate, bidentate and tridentate ligand (Olsher et al., 1996). Besides, picrate is a penta-dentate ligand when it coordinates with sodium or potassium cation by chelating pairs of oxygen atoms from p-nitro groups of adjacent picrates, and with successive cation linking the array into two or three-dimensional network (Harrowfield et al., 1995a; Maartmann-Moe, 1969). Furthermore, the picrate interacts as a heptadentate ligand through all its available oxygen donor atoms to coordinate with caesium (Harrowfield et al., 1995a).

Fig. 1 shows the structure and the atomic numbering schemes of the crystal structure of the title manganese picrate complex (I). This situation is similar to the crystal structure of iron (II) picrate (Honda et al., 2003) and Magnesium (II) picrate (Harrowfield et al., 1995b) and the picrate anion adopts a keto form with C6—O10 bond distance of 1.257 (4) Å, C1—C6 and C5—C6 bond distance of 1.447 (5) and 1.456 (5) Å, respectively, which is longer than the other C—C bond lengths (between 1.374 (5) to 1.460 (4) Å) in the benzene ring. The Mn—O distance ranges from 2.120 (2) to 2.190 (2) Å. The bond angle C1—C6—C5 is 111.9 (3)°, which is the case in some picrate complexes, while the corresponding bond angle of picric acid is 116.4 (5)° (Yang et al., 2001). Selected bond lengths and angles are given in Table 1.

In the case of planarity of picrate anion, the ortho nitro group are twisted relative to the plane of the benzene ring, (between 19.01 and 27.69°), while para-positioned nitro group is deviated 13.02° off the benzene ring. The picrate ions are stacked head-to-tail, presumably as a result of charge-transfer interactions. The anion in the stack are linked via short intermolecular O···C and C···C contacts of 3.013, 2.973, 3.089 and 3.065Å for O6···C1^x, O7···C5^xi, C2···C2^x and C4···C4^xi [symmetry codes: (x) 1/2 - x, 3/2 - y, z; (xi) 1/2 - x, 5/2 - y, z] respectively (Fig.2). The picrate anions are not parallel to one another, and the dihedral angles between neighbouring benzene planes are 25.01°, 25.25° and 3.48° respectively.

Experimental

The title compound (I) was obtained by the reaction of 3.20 g (13.96 mmol) picric acid with 0.80 g (6.98 mmol) manganese carbonate in water (350 ml), according to Ji et al., 1996. Heating has been continued for another 1 h and filtered while it was still hot. The filtrate was partially evaporated and left to stand in open atmosphere for a few days, during which time, yellow crystals suitable for X-Ray determination were obtained. Analysis, calculated for C₁₂H₂₀N₆O₂₂Mn: C 21.98, H 3.05, N 12.80, Mn 8.40%; Found: C 22.35, H 3.34, N 12.46, Mn 8.68%.