supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

ww2104 scheme

Acta Cryst. (2008). E64, m270-m271    [ doi:10.1107/S1600536807064276 ]

Hexaaquamanganese(II) dipicrate dihydrate

C. Liu, X. Shi, B. Du, C. Wu and M. Zhang

Abstract top

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.

Comment top

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···C1x, O7···C5xi, C2···C2x and C4···C4xi [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.

Related literature top

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 top

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%.

Refinement top

All H atoms of water were located from difference map and then refined with O—H distances restrained to 0.85 (1) Å. All other H atoms were positioned geometrically and refined using a riding mode with the C—H bond lengths of 0.93 Å and Uiso(H)=1.2Ueq(carrier atom).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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 (Bruker, 1997).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with displacement ellipsoids at the 50% probability level and the atomic labeling scheme.
[Figure 2] Fig. 2. The crystal structure of (I), projected along the c axis. The dashed lines indicate short intermolecular contacts with N···O, C···C and O···C distances less than 3.0, 3.2 and 3.0 Å, respectively. [Symmetry mode: (x) 1/2 - x, 3/2 - y, z; (xi) 1/2 - x, 5/2 - y, z]
Hexaaquamanganese(II) dipicrate dihydrate top
Crystal data top
[Mn(H2O)6](C6H2N3O7)2·2H2OF000 = 1340
Mr = 655.28Dx = 1.814 Mg m−3
Orthorhombic, PccnMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ab 2acCell parameters from 3819 reflections
a = 25.344 (6) Åθ = 3.0–26.9º
b = 7.1625 (17) ŵ = 0.67 mm−1
c = 13.217 (3) ÅT = 294 (2) K
V = 2399.2 (9) Å3Prism, yellow
Z = 40.28 × 0.24 × 0.20 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		2122 independent reflections
Radiation source: fine-focus sealed tube1643 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.033
T = 294(2) Kθmax = 25.0º
φ and ω scansθmin = 3.0º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −30→20
Tmin = 0.835, Tmax = 0.878k = −6→8
11295 measured reflectionsl = −14→15
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.047H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.158  w = 1/[σ2(Fo2) + (0.1031P)2 + 1.8926P]
where P = (Fo2 + 2Fc2)/3
S = 1.11(Δ/σ)max = 0.002
2122 reflectionsΔρmax = 0.50 e Å−3
211 parametersΔρmin = −1.20 e Å−3
8 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Mn(H2O)6](C6H2N3O7)2·2H2OV = 2399.2 (9) Å3
Mr = 655.28Z = 4
Orthorhombic, PccnMo Kα
a = 25.344 (6) ŵ = 0.67 mm−1
b = 7.1625 (17) ÅT = 294 (2) K
c = 13.217 (3) Å0.28 × 0.24 × 0.20 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		2122 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1643 reflections with I > 2σ(I)
Tmin = 0.835, Tmax = 0.878Rint = 0.033
11295 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0478 restraints
wR(F2) = 0.158H atoms treated by a mixture of
independent and constrained refinement
S = 1.11Δρmax = 0.50 e Å−3
2122 reflectionsΔρmin = −1.20 e Å−3
211 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
xyzUiso*/Ueq
Mn10.50000.00000.50000.0324 (3)
O10.46126 (10)0.2424 (4)0.4457 (2)0.0421 (7)
H1A0.4744 (16)0.322 (5)0.406 (3)0.051*
H1B0.4352 (12)0.300 (6)0.472 (3)0.051*
O20.55826 (9)0.1880 (4)0.56780 (19)0.0330 (6)
H2A0.5744 (14)0.275 (4)0.537 (3)0.040*
H2B0.5784 (12)0.128 (5)0.606 (2)0.040*
O30.45862 (10)0.0148 (5)0.6406 (2)0.0445 (8)
H3A0.4722 (18)0.009 (6)0.6979 (17)0.053*
H3B0.4257 (5)0.002 (6)0.637 (4)0.053*
O40.38727 (10)0.9511 (5)0.2517 (2)0.0513 (8)
O50.31431 (10)0.8379 (4)0.30495 (17)0.0370 (6)
O60.15343 (9)0.9452 (4)0.1363 (2)0.0377 (7)
O70.15241 (9)1.0752 (4)−0.0108 (2)0.0394 (7)
O80.31310 (10)1.1774 (4)−0.18909 (18)0.0380 (6)
O90.38129 (10)1.0114 (4)−0.15080 (19)0.0366 (7)
O100.39594 (9)0.9860 (4)0.05051 (18)0.0341 (6)
N10.34078 (10)0.9135 (4)0.2395 (2)0.0283 (7)
N20.17602 (11)1.0079 (4)0.0613 (2)0.0251 (7)
N30.33772 (10)1.0754 (4)−0.1311 (2)0.0258 (6)
C10.31536 (13)0.9605 (5)0.1440 (2)0.0242 (7)
C20.26072 (13)0.9623 (5)0.1463 (3)0.0251 (7)
H20.24280.93700.20620.030*
C30.23318 (13)1.0019 (4)0.0588 (2)0.0235 (7)
C40.25917 (13)1.0386 (4)−0.0315 (3)0.0245 (7)
H40.24021.0684−0.08950.029*
C50.31330 (13)1.0304 (4)−0.0340 (2)0.0229 (7)
C60.34639 (13)0.9917 (4)0.0536 (3)0.0246 (7)
O110.50741 (10)0.9801 (4)0.8282 (2)0.0377 (7)
H11A0.4971 (15)0.878 (3)0.854 (3)0.045*
H11B0.5400 (6)0.982 (6)0.842 (3)0.045*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0302 (5)0.0345 (5)0.0324 (5)−0.0018 (3)−0.0020 (3)0.0010 (3)
O10.0328 (14)0.0450 (17)0.0486 (17)0.0143 (12)0.0079 (12)0.0177 (13)
O20.0237 (12)0.0355 (14)0.0398 (15)−0.0053 (10)−0.0081 (10)0.0038 (11)
O30.0233 (14)0.080 (2)0.0299 (15)−0.0049 (13)0.0010 (11)0.0035 (14)
O40.0246 (14)0.098 (2)0.0312 (15)−0.0061 (14)−0.0079 (11)0.0097 (15)
O50.0351 (13)0.0514 (17)0.0247 (13)0.0044 (12)0.0019 (10)0.0052 (12)
O60.0214 (13)0.0518 (17)0.0399 (15)0.0010 (11)0.0062 (11)0.0082 (13)
O70.0202 (13)0.0538 (18)0.0443 (16)0.0023 (12)−0.0087 (11)0.0137 (13)
O80.0415 (14)0.0462 (16)0.0263 (13)0.0089 (12)−0.0015 (11)0.0059 (12)
O90.0194 (13)0.0578 (18)0.0325 (14)0.0028 (11)0.0030 (10)−0.0004 (12)
O100.0160 (12)0.0588 (18)0.0274 (14)0.0035 (10)−0.0005 (9)0.0030 (11)
N10.0224 (15)0.0361 (17)0.0265 (15)0.0045 (12)−0.0018 (12)−0.0022 (13)
N20.0187 (14)0.0231 (15)0.0334 (17)−0.0001 (11)−0.0012 (12)−0.0012 (12)
N30.0235 (14)0.0308 (15)0.0231 (14)−0.0023 (12)−0.0018 (11)−0.0031 (12)
C10.0208 (16)0.0291 (18)0.0226 (16)0.0028 (13)−0.0026 (13)−0.0010 (14)
C20.0218 (17)0.0265 (18)0.0269 (17)0.0002 (13)0.0015 (13)−0.0006 (14)
C30.0180 (16)0.0232 (16)0.0294 (18)0.0012 (12)−0.0011 (13)−0.0019 (13)
C40.0204 (17)0.0259 (17)0.0271 (17)0.0018 (13)−0.0060 (13)−0.0009 (14)
C50.0200 (16)0.0263 (18)0.0224 (16)−0.0011 (13)0.0000 (13)−0.0007 (13)
C60.0208 (17)0.0265 (18)0.0265 (19)0.0016 (13)−0.0029 (13)−0.0023 (13)
O110.0303 (15)0.0455 (17)0.0374 (16)−0.0029 (12)−0.0032 (12)0.0069 (12)
Geometric parameters (Å, °) top
Mn1—O12.120 (3)C1—C21.385 (5)
Mn1—O1i2.120 (3)C1—C61.447 (5)
Mn1—O32.136 (3)C2—C31.380 (5)
Mn1—O3i2.136 (3)C3—C41.389 (5)
Mn1—O22.190 (2)C4—C51.374 (5)
Mn1—O22.190 (2)C5—C61.456 (5)
O4—N11.219 (4)C2—H20.931
O5—N11.222 (4)C4—H40.931
O6—N21.229 (4)O1—H1A0.846 (10)
O7—N21.225 (4)O1—H1B0.852 (10)
O8—N31.229 (4)O2—H2A0.848 (10)
O9—N31.224 (4)O2—H2B0.841 (10)
O10—C61.257 (4)O3—H3A0.832 (10)
N1—C11.456 (4)O3—H3B0.841 (10)
N2—C31.450 (4)O11—H11A0.847 (10)
N3—C51.460 (4)O11—H11B0.846 (10)
O1—Mn1—O1i180.0O9—N3—O8123.2 (3)
O1—Mn1—O391.52 (11)O9—N3—C5119.1 (3)
O1i—Mn1—O388.48 (11)O8—N3—C5117.7 (3)
O1—Mn1—O3i88.48 (11)C2—C1—C6124.1 (3)
O1i—Mn1—O3i91.52 (11)C2—C1—N1115.1 (3)
O3—Mn1—O3i180.0C6—C1—N1120.7 (3)
O1—Mn1—O2i93.02 (11)C3—C2—C1119.3 (3)
O1i—Mn1—O2i86.98 (11)C2—C3—C4121.3 (3)
O3—Mn1—O2i93.18 (11)C2—C3—N2119.5 (3)
O3i—Mn1—O2i86.83 (11)C4—C3—N2119.2 (3)
O1—Mn1—O286.98 (11)C5—C4—C3119.1 (3)
O1i—Mn1—O293.02 (11)C4—C5—C6124.4 (3)
O3—Mn1—O286.83 (11)C4—C5—N3115.8 (3)
O3i—Mn1—O293.17 (11)C6—C5—N3119.8 (3)
O2i—Mn1—O2180.0O10—C6—C1124.4 (3)
O4—N1—O5122.3 (3)O10—C6—C5123.8 (3)
O4—N1—C1119.5 (3)C1—C6—C5111.9 (3)
O5—N1—C1118.3 (3)C3—C2—H2120.36
O7—N2—O6123.0 (3)C1—C2—H2120.37
O7—N2—C3118.8 (3)C3—C4—H4120.43
O6—N2—C3118.2 (3)C5—C4—H4120.41
O4—N1—C1—C2−162.6 (3)C3—C4—C5—C6−2.3 (5)
O5—N1—C1—C217.1 (4)C3—C4—C5—N3−178.5 (3)
O4—N1—C1—C620.8 (5)O9—N3—C5—C4−154.6 (3)
O5—N1—C1—C6−159.6 (3)O8—N3—C5—C425.5 (4)
C6—C1—C2—C3−2.2 (5)O9—N3—C5—C629.0 (4)
N1—C1—C2—C3−178.8 (3)O8—N3—C5—C6−150.8 (3)
C1—C2—C3—C40.5 (5)C2—C1—C6—O10−178.3 (3)
C1—C2—C3—N2−178.7 (3)N1—C1—C6—O10−1.9 (5)
O7—N2—C3—C2167.0 (3)C2—C1—C6—C51.6 (5)
O6—N2—C3—C2−12.8 (4)N1—C1—C6—C5178.0 (3)
O7—N2—C3—C4−12.2 (4)C4—C5—C6—O10−179.4 (3)
O6—N2—C3—C4168.0 (3)N3—C5—C6—O10−3.4 (5)
C2—C3—C4—C51.7 (5)C4—C5—C6—C10.7 (4)
N2—C3—C4—C5−179.1 (3)N3—C5—C6—C1176.7 (3)
Symmetry codes: (i) −x+1, −y, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O11ii0.846 (10)1.938 (12)2.780 (4)173 (4)
O1—H1B···O10iii0.852 (10)2.10 (2)2.906 (4)157 (4)
O2—H2A···O10iv0.848 (10)2.048 (12)2.889 (4)172 (4)
O2—H2A···O9iv0.848 (10)2.53 (4)2.986 (4)115 (3)
O3—H3A···O11v0.832 (10)1.951 (12)2.782 (4)176 (5)
O3—H3B···O6vi0.841 (10)2.047 (12)2.884 (4)174 (5)
O11—H11A···O2vii0.847 (10)2.213 (19)3.006 (4)156 (4)
O11—H11B···O10viii0.846 (10)2.17 (2)2.938 (4)151 (4)
O11—H11B···O4viii0.846 (10)2.27 (3)2.913 (4)133 (4)
O2—H2B···O4ix0.841 (10)2.143 (19)2.930 (4)156 (4)
Symmetry codes: (ii) x, −y+3/2, z−1/2; (iii) x, −y+3/2, z+1/2; (iv) −x+1, y−1/2, −z+1/2; (v) x, y−1, z; (vi) −x+1/2, y−1, z+1/2; (vii) −x+1, y+1/2, −z+3/2; (viii) −x+1, −y+2, −z+1; (ix) −x+1, −y+1, −z+1.
Table 1
Selected geometric parameters (Å, °) top
Mn1—O12.120 (3)C1—C21.385 (5)
Mn1—O32.136 (3)C1—C61.447 (5)
Mn1—O22.190 (2)C2—C31.380 (5)
O10—C61.257 (4)C3—C41.389 (5)
N1—C11.456 (4)C4—C51.374 (5)
N2—C31.450 (4)C5—C61.456 (5)
N3—C51.460 (4)
O1—Mn1—O391.52 (11)C2—C3—C4121.3 (3)
O1—Mn1—O3i88.48 (11)C2—C3—N2119.5 (3)
O1—Mn1—O2i93.02 (11)C4—C3—N2119.2 (3)
O3i—Mn1—O2i86.83 (11)C5—C4—C3119.1 (3)
O1—Mn1—O286.98 (11)C4—C5—C6124.4 (3)
O3i—Mn1—O293.17 (11)C4—C5—N3115.8 (3)
C2—C1—C6124.1 (3)C6—C5—N3119.8 (3)
C2—C1—N1115.1 (3)O10—C6—C1124.4 (3)
C6—C1—N1120.7 (3)O10—C6—C5123.8 (3)
C3—C2—C1119.3 (3)C1—C6—C5111.9 (3)
Symmetry codes: (i) −x+1, −y, −z+1.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O11ii0.846 (10)1.938 (12)2.780 (4)173 (4)
O1—H1B···O10iii0.852 (10)2.10 (2)2.906 (4)157 (4)
O2—H2A···O10iv0.848 (10)2.048 (12)2.889 (4)172 (4)
O2—H2A···O9iv0.848 (10)2.53 (4)2.986 (4)115 (3)
O3—H3A···O11v0.832 (10)1.951 (12)2.782 (4)176 (5)
O3—H3B···O6vi0.841 (10)2.047 (12)2.884 (4)174 (5)
O11—H11A···O2vii0.847 (10)2.213 (19)3.006 (4)156 (4)
O11—H11B···O10viii0.846 (10)2.17 (2)2.938 (4)151 (4)
O11—H11B···O4viii0.846 (10)2.27 (3)2.913 (4)133 (4)
O2—H2B···O4ix0.841 (10)2.143 (19)2.930 (4)156 (4)
Symmetry codes: (ii) x, −y+3/2, z−1/2; (iii) x, −y+3/2, z+1/2; (iv) −x+1, y−1/2, −z+1/2; (v) x, y−1, z; (vi) −x+1/2, y−1, z+1/2; (vii) −x+1, y+1/2, −z+3/2; (viii) −x+1, −y+2, −z+1; (ix) −x+1, −y+1, −z+1.
Acknowledgements top

We acknowledge financial support of this study by Zhengzhou University.

references
References top

Bibal, B., Declercq, J. P., Dutasta, J. P., Tinant, B. & Valade, A. G. (2003). Tetrahedron, 59, 5849–5854.

Bruker (1997). SMART, SAINT and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.

García, M. M. R., Verboom, W., Reinhoudt, D. N., Malinowska, E., Pietrzak, M. & Wojciechowska, D. (2004). Tetrahedron, 60, 11299–11306.

Harrowfield, J. M., Skelton, B. W. & White, A. H. (1995a). Aust. J. Chem. 48, 1311–1331.

Harrowfield, J. M., Skelton, B. W. & White, A. H. (1995b). Aust. J. Chem. 48, 1333–1347.

Honda, K., Yamawaki, H., Matsukawa, M., Goto, M., Matsunaga, T., Aoki, K., Yoshida, M. & Fujiwara, S. (2003). Acta Cryst. C59, m319–m321.

Ji, B. M. & Chen, H. T. (1996). J. Luoyang Teach. Coll. 15, 44–48.

Maartmann-Moe, K. (1969). Acta Cryst. B25, 1452–1460.

Olsher, U., Feinberg, H., Frolow, F. & Shoham, G. (1996). Pure Appl. Chem. 68, 1195–1199.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Yang, L., Zhang, T. L., Feng, C. G., Zhang, J. G. & Yu, K. B. (2001). Energ. Mater. 9, 37–39.

Zhang, Y. L., Jiang, W. H., Liu, W. S., Wen, Y. H. & Yu, K. B. (2003). Polyhedron, 22, 1695–1699.