supplementary materials


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

dn2281 scheme

Acta Cryst. (2008). E64, m3-m4    [ doi:10.1107/S1600536807061314 ]

[mu]-4,4'-Diazenediyldiphthalato-[kappa]2O2:O2'-bis[pentaaquamanganese(II)] tetrahydrate

J.-W. Bai, J. Wang, Y. Hou, B.-Z. Zhao and Q. Fu

Abstract top

The dinuclear complex in the title compound, [Mn2(C16H6N2O8)(H2O)10]·4H2O, lies on an inversion center. Two delocalized carboxylate groups are each connected in a monodentate fashion to two similar pentaaquamanganese units, whereas the other two localized carboxylate groups are uncoordinated. The metal ion has octahedral coordination, with the O atom of a carboxylate group and three coordinated water molecules forming the equatorial plane [Mn-OCOO = 2.143 (4) Å] and two water molecules occupying the axial positions. The architecture is further consolidated by extensive hydrogen bonds for which coordinated water molecules serve as donors or acceptors.

Comment top

Transition metal complexes with bipyridine derivatives are suitable models for the study of excited state dynamics. In addition, they are of interest for the development of light-energy conversion devices and optical sensors (Gokel et al., 2004; Shan et al., 2001; Lassahn et al., 2004). Although a great number of metal carboxylate have been obtained to date, the rational design and synthesis of novel metal carboxylates by employing new synthetic tools or by varying the natures of the reactants and synthetic conditions are currently under active investigation (Liu & Xu, 2005). In this context, L ligand which can exhibit a variety of coordination abilities and has a tendency to form architectures with multi-dimensional frameworks (Wang et al., 2007). In this paper, we report the synthesis and crystal structure of the title complex,(I).

The title complex (I) is arranged around a crystallographic inversion center located in the middle of the N=N bond. The metal ion is octahedrally coordinated by the oxygen atom of the carboxylate group [Mn-Ocarboxylate =2.143 (4)° A]and five coordinated water molecules. Two delocalized carboxyl –CO2 groups are each connected via monodentate fashion to two similar pentaaquamanganese units whereas the other two localized carboxyl –CO2 are free. The architecture is further consolidated by extensive hydrogen bonds for which the water molecules serves as donors or acceptors (Table 1).

Related literature top

For related literature, see: Gokel et al. (2004); Lassahn et al. (2004); Liu & Xu (2005); Shan et al. (2001); Wang et al. (2007).

Experimental top

MnSO4(0.032 g, 0.017 mmol), L(0.029 g, 0.014 mmol) and NaOH(0.048 mmol,0.12 mmol), were added in a mixed solvent of acetonitrile, the mixture was heated for six hours under reflux. During the process stirring and influx were required. The resultant was then filtered to give a pure solution which was infiltrated by diethyl ether freely in a closed vessel, a weeks later some single crystals of the size suitable for X-Ray diffraction analysis.

Refinement top

All H atoms attached to C atoms were fixed geometrically and treated as riding with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). H atoms of water molecule were located in difference Fourier maps and included in the subsequent refinement using restraints (O—H= 0.84 (1)Å and H···H= 1.38 (2) Å) with Uiso(H) = 1.5Ueq(O). In the last stage of refinement, they were treated as riding on their parent O atoms.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. View of complex (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen bonds are shown as dashed lines. H atoms are represented as small spheres of arbitrary radii. [Symmetry code (i): 1 - x,1 - y,1 - z].
µ-4,4'-Diazenediyldiphthalato-κ2O2:O2'– bis[pentaaquamanganese(II)] tetrahydrate top
Crystal data top
[Mn2(C16H6N2O8)(H2O)10]·4H2OF000 = 740
Mr = 716.33Dx = 1.678 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2649 reflections
a = 6.9674 (10) Åθ = 2.0–25.5º
b = 15.186 (2) ŵ = 0.99 mm−1
c = 13.5576 (19) ÅT = 298 (2) K
β = 98.812 (2)ºBlock, yellow
V = 1417.5 (3) Å30.29 × 0.25 × 0.18 mm
Z = 2
Data collection top
Bruker APEX-II area-detector
diffractometer		2649 independent reflections
Radiation source: fine-focus sealed tube2349 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.019
T = 298(2) Kθmax = 25.5º
φ and ω scanθmin = 2.0º
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		h = −8→7
Tmin = 0.763, Tmax = 0.842k = −18→17
7535 measured reflectionsl = −16→16
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)] = 0.033H-atom parameters constrained
wR(F2) = 0.090  w = 1/[σ2(Fo2) + (0.0505P)2 + 0.4924P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
2649 reflectionsΔρmax = 0.64 e Å−3
184 parametersΔρmin = −0.30 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Mn2(C16H6N2O8)(H2O)10]·4H2OV = 1417.5 (3) Å3
Mr = 716.33Z = 2
Monoclinic, P21/cMo Kα
a = 6.9674 (10) ŵ = 0.99 mm−1
b = 15.186 (2) ÅT = 298 (2) K
c = 13.5576 (19) Å0.29 × 0.25 × 0.18 mm
β = 98.812 (2)º
Data collection top
Bruker APEX-II area-detector
diffractometer		2649 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		2349 reflections with I > 2σ(I)
Tmin = 0.763, Tmax = 0.842Rint = 0.019
7535 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.033184 parameters
wR(F2) = 0.090H-atom parameters constrained
S = 1.06Δρmax = 0.64 e Å−3
2649 reflectionsΔρmin = −0.30 e Å−3
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
Mn11.15210 (4)0.59508 (2)0.87665 (2)0.02864 (12)
O10.9887 (2)0.47791 (9)0.83401 (10)0.0337 (3)
O20.9981 (2)0.33199 (9)0.83063 (10)0.0333 (3)
O31.3292 (2)0.26635 (10)0.62459 (11)0.0367 (4)
O41.3672 (2)0.37832 (10)0.73190 (12)0.0388 (4)
O1W1.3818 (3)0.54312 (11)0.80243 (14)0.0528 (5)
H1WA1.46000.56800.77300.079*
H1WB1.37300.49300.77900.079*
O2W1.2906 (2)0.52547 (12)1.01240 (12)0.0484 (4)
H2WA1.23590.48301.03200.073*
H2WB1.38290.53501.05400.073*
O3W1.3327 (2)0.70714 (11)0.92397 (13)0.0479 (4)
H3WB1.35300.71490.98500.072*
H3WA1.42800.72790.90500.072*
O4W0.9230 (2)0.63843 (10)0.96205 (10)0.033
H4WA0.93700.64701.02200.050*
H4WB0.85000.67700.93700.050*
O5W0.9978 (2)0.66502 (10)0.74917 (10)0.0379 (4)
H5WA1.00610.71700.73300.057*
H5WB0.88410.65300.72800.057*
O6W1.3892 (3)0.71325 (14)1.13418 (13)0.0563 (5)
H6WA1.46200.68091.17800.085*
H6WB1.27200.70291.14500.085*
O7W1.6084 (3)0.63676 (12)0.68914 (14)0.0547 (5)
H7WB1.56800.60400.63400.082*
H7WA1.53800.68400.68000.082*
N10.5413 (2)0.47199 (12)0.47708 (12)0.0319 (4)
C10.9867 (3)0.40586 (12)0.78879 (14)0.0235 (4)
C20.9492 (3)0.40791 (12)0.67589 (14)0.0225 (4)
C41.2725 (3)0.33562 (13)0.66100 (14)0.0266 (4)
C70.7227 (3)0.44018 (14)0.52778 (14)0.0275 (4)
C60.8475 (3)0.40308 (13)0.46864 (15)0.0299 (5)
H60.81290.40120.39960.036*
C51.0234 (3)0.36904 (13)0.51324 (14)0.0284 (4)
H51.10740.34440.47370.034*
C31.0769 (3)0.37103 (13)0.61650 (14)0.0240 (4)
C80.7726 (3)0.44200 (13)0.63154 (14)0.0259 (4)
H80.68740.46610.67070.031*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0314 (2)0.02601 (19)0.02938 (19)−0.00248 (12)0.00726 (14)−0.00193 (12)
O10.0456 (9)0.0266 (8)0.0288 (7)−0.0029 (6)0.0055 (6)−0.0064 (6)
O20.0488 (9)0.0263 (8)0.0237 (7)0.0037 (6)0.0023 (6)0.0022 (6)
O30.0288 (8)0.0391 (9)0.0409 (9)0.0106 (6)0.0014 (7)−0.0095 (7)
O40.0311 (8)0.0381 (9)0.0432 (9)0.0052 (7)−0.0073 (7)−0.0100 (7)
O1W0.0564 (11)0.0408 (10)0.0688 (12)−0.0066 (8)0.0341 (9)−0.0147 (8)
O2W0.0398 (9)0.0596 (11)0.0423 (9)−0.0040 (8)−0.0046 (7)0.0144 (8)
O3W0.0429 (10)0.0472 (10)0.0571 (11)−0.0201 (8)0.0179 (8)−0.0139 (8)
O4W0.0390.0360.0250.0070.0050.002
O5W0.0456 (9)0.0326 (8)0.0347 (8)−0.0026 (7)0.0037 (7)0.0072 (7)
O6W0.0440 (10)0.0748 (13)0.0481 (10)0.0035 (9)0.0002 (8)0.0117 (9)
O7W0.0524 (11)0.0463 (11)0.0631 (12)−0.0002 (8)0.0013 (9)−0.0084 (9)
N10.0277 (9)0.0406 (10)0.0261 (8)0.0068 (7)−0.0006 (7)0.0023 (7)
C10.0198 (9)0.0282 (11)0.0222 (9)−0.0003 (7)0.0024 (8)−0.0009 (8)
C20.0238 (10)0.0211 (9)0.0220 (9)0.0001 (7)0.0019 (7)0.0007 (7)
C40.0232 (10)0.0298 (11)0.0272 (10)0.0027 (8)0.0051 (8)0.0024 (8)
C70.0243 (10)0.0309 (11)0.0256 (10)0.0041 (8)−0.0010 (8)0.0030 (8)
C60.0320 (11)0.0356 (12)0.0211 (9)0.0039 (9)0.0008 (8)0.0007 (8)
C50.0287 (11)0.0336 (11)0.0237 (10)0.0043 (9)0.0065 (8)−0.0023 (8)
C30.0236 (10)0.0219 (10)0.0262 (10)0.0022 (7)0.0033 (8)0.0017 (8)
C80.0243 (10)0.0282 (10)0.0258 (9)0.0057 (8)0.0055 (8)0.0005 (8)
Geometric parameters (Å, °) top
Mn1—O12.1435 (15)O5W—H5WB0.8207
Mn1—O3W2.1548 (16)O6W—H6WA0.8708
Mn1—O1W2.1657 (17)O6W—H6WB0.8656
Mn1—O5W2.1683 (15)O7W—H7WB0.9061
Mn1—O4W2.2108 (14)O7W—H7WA0.8666
Mn1—O2W2.2119 (16)N1—N1i1.245 (3)
O1—C11.253 (2)N1—C71.427 (3)
O2—C11.254 (2)C1—C21.513 (3)
O3—C41.251 (2)C2—C81.385 (3)
O4—C41.259 (2)C2—C31.405 (3)
O1W—H1WA0.8156C4—C31.503 (3)
O1W—H1WB0.8230C7—C61.389 (3)
O2W—H2WA0.8145C7—C81.397 (3)
O2W—H2WB0.8008C6—C51.382 (3)
O3W—H3WB0.8259C6—H60.9300
O3W—H3WA0.8120C5—C31.393 (3)
O4W—H4WA0.8148C5—H50.9300
O4W—H4WB0.8151C8—H80.9300
O5W—H5WA0.8240
O1—Mn1—O3W176.04 (7)Mn1—O5W—H5WB120.3
O1—Mn1—O1W88.39 (6)H5WA—O5W—H5WB102.9
O3W—Mn1—O1W89.24 (7)H6WA—O6W—H6WB104.4
O1—Mn1—O5W90.78 (6)H7WB—O7W—H7WA103.9
O3W—Mn1—O5W92.65 (7)N1i—N1—C7115.7 (2)
O1W—Mn1—O5W96.88 (7)O1—C1—O2124.37 (18)
O1—Mn1—O4W89.55 (6)O1—C1—C2117.65 (16)
O3W—Mn1—O4W92.55 (6)O2—C1—C2117.72 (16)
O1W—Mn1—O4W174.90 (6)C8—C2—C3119.93 (17)
O5W—Mn1—O4W87.82 (6)C8—C2—C1116.82 (17)
O1—Mn1—O2W88.49 (6)C3—C2—C1123.04 (17)
O3W—Mn1—O2W88.24 (7)O3—C4—O4125.04 (18)
O1W—Mn1—O2W87.31 (7)O3—C4—C3117.63 (17)
O5W—Mn1—O2W175.73 (6)O4—C4—C3117.32 (18)
O4W—Mn1—O2W87.97 (6)C6—C7—C8120.53 (18)
C1—O1—Mn1145.33 (14)C6—C7—N1116.47 (17)
Mn1—O1W—H1WA130.9C8—C7—N1122.95 (17)
Mn1—O1W—H1WB120.0C5—C6—C7119.41 (18)
H1WA—O1W—H1WB104.8C5—C6—H6120.3
Mn1—O2W—H2WA118.9C7—C6—H6120.3
Mn1—O2W—H2WB134.5C6—C5—C3120.97 (18)
H2WA—O2W—H2WB106.2C6—C5—H5119.5
Mn1—O3W—H3WB114.5C3—C5—H5119.5
Mn1—O3W—H3WA132.9C5—C3—C2119.30 (18)
H3WB—O3W—H3WA103.8C5—C3—C4118.84 (17)
Mn1—O4W—H4WA125.8C2—C3—C4121.84 (17)
Mn1—O4W—H4WB116.8C2—C8—C7119.84 (18)
H4WA—O4W—H4WB105.8C2—C8—H8120.1
Mn1—O5W—H5WA129.4C7—C8—H8120.1
Symmetry codes: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O7W0.821.952.760 (3)170
O1W—H1WB···O40.821.852.675 (2)176
O2W—H2WA···O4Wii0.812.162.948 (2)163
O2W—H2WA···O1ii0.812.643.061 (2)114
O2W—H2WB···O1Wiii0.802.633.293 (3)142
O3W—H3WB···O6W0.832.002.818 (2)171
O3W—H3WA···O3iv0.811.892.696 (2)172
O4W—H4WA···O2ii0.812.002.8162 (19)174
O4W—H4WB···O3v0.821.942.758 (2)178
O5W—H5WA···O2v0.821.952.759 (2)169
O5W—H5WB···O7Wvi0.821.932.744 (2)173
O6W—H6WA···O4iii0.871.812.677 (2)174
O6W—H6WB···O2ii0.872.032.894 (2)175
O7W—H7WB···N1vii0.911.962.859 (3)174
O7W—H7WA···O6Wviii0.871.922.780 (3)169
Symmetry codes: (ii) −x+2, −y+1, −z+2; (iii) −x+3, −y+1, −z+2; (iv) −x+3, y+1/2, −z+3/2; (v) −x+2, y+1/2, −z+3/2; (vi) x−1, y, z; (vii) −x+2, −y+1, −z+1; (viii) x, −y+3/2, z−1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O7W0.821.952.760 (3)170
O1W—H1WB···O40.821.852.675 (2)176
O2W—H2WA···O4Wi0.812.162.948 (2)163
O2W—H2WA···O1i0.812.643.061 (2)114
O2W—H2WB···O1Wii0.802.633.293 (3)142
O3W—H3WB···O6W0.832.002.818 (2)171
O3W—H3WA···O3iii0.811.892.696 (2)172
O4W—H4WA···O2i0.812.002.8162 (19)174
O4W—H4WB···O3iv0.821.942.758 (2)178
O5W—H5WA···O2iv0.821.952.759 (2)169
O5W—H5WB···O7Wv0.821.932.744 (2)173
O6W—H6WA···O4ii0.871.812.677 (2)174
O6W—H6WB···O2i0.872.032.894 (2)175
O7W—H7WB···N1vi0.911.962.859 (3)174
O7W—H7WA···O6Wvii0.871.922.780 (3)169
Symmetry codes: (i) −x+2, −y+1, −z+2; (ii) −x+3, −y+1, −z+2; (iii) −x+3, y+1/2, −z+3/2; (iv) −x+2, y+1/2, −z+3/2; (v) x−1, y, z; (vi) −x+2, −y+1, −z+1; (vii) x, −y+3/2, z−1/2.
Acknowledgements top

The authors are grateful to SiChuan University for financial support.

references
References top

Bruker (2004). APEX2 (Version 1.22), SAINT (Version 6.0) and SADABS (Version 2004/1). Bruker AXS Inc., Madison, Wisconsin, USA.

Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Oak Ridge, Tennessee, U.S.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?.

Gokel, G. W., Leevy, W. M. & Weber, W. E. (2004). Chem. Rev. 104, 2723–2750.

Lassahn, P.-G., Lozan, V., Timco, G. A., Christian, P., Janiak, C. & Winpenny, R. E. P. (2004). J. Catal. 222, 260–267.

Liu, -Q. Y. & Xu, L. (2005). Eur. J. Inorg. Chem. pp. 3458–3466.

Shan, B. Z., Zhao, O., Goswami, N., Eichhorn, D. M. & Rillema, D. P. (2001). Coord. Chem. Rev. 211, 117–144.

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

Wang, J., Lu, L., Bai, J.-W. & Zhong, B.-Z. (2007). Acta Cryst. E63, o4414–?.