supplementary materials


br2215 scheme

Acta Cryst. (2013). E69, m9    [ doi:10.1107/S1600536812049161 ]

Diaquabis(nitrato-[kappa]O)bis(pyridine-[kappa]N)manganese(II)

N. Alam, M. Shahid and M. K. Rauf

Abstract top

The structure of the title manganese complex, [Mn(NO3)2(C5H5N)2(H2O)2], consists of discrete monomeric entities with Mn2+ ions located on centres of inversion. The metal cation is octahedrally coordinated by a trans-N2O4 donor set with the pyridine N atoms located in the apical positions. Discrete molecules are linked by O-H...O hydrogen bonds into one-dimensional supramolecular infinite chains along the b and c axes.

Comment top

In relation to our previous work on the structural chemistry of transition metal complexes (Shahid et al., 2010) as potential precursors for ceramic oxides of the type MO(M = Cu, Zn, Mn, Ni etc), the title compound was prepared as the unintented product of the recation of Mn(NO3)2.4H2O with potassium O-n-butyl xanthate in acetone and pyridine. The asymmetric unit of the title compound contains one pyridine, one nitrate and one water molecule coordinated with one Mn(II) atom. Fig. 1 shows a perspective view of the monomeric unit with the atomic numbering scheme. The Mn(II) atom is in a octahedral environment surrounded by two nitrate, two water and two pyridines ligands. As illustrated in Fig. 1, the Mn(II) atom is six-coordinated observing octahedral geometry with pyridine ligands located at apical positions. The Mn—O distance of nitrate are in good agreement with those reported in similar MnII complexes (Saphu et al., 2012). In the crystal structure, molecules are assembled into one dimensional supramolecular infinite chains along bc axis through O—H···O intermolecular hydrogen bonds (Table1, Fig. 2).

Related literature top

For our previous work on the structural chemistry of transition metal complexes, see: Shahid et al. (2010). For details concerning the geometric parameters of MnII complexes, see: Saphu et al. (2012).

Experimental top

Mn(NO3)2.4H2O (0.47 g, 0.27 mmol) was added to a stirred solution of potassium O-n-butyl xanthate(1.0 g,0.53 mmol) in acetone (30 ml). The contents were stirred until complete dissolution of the salt to which about 30 ml of pyridine was added and stirred for 1hr. Filtrate was kept under slow evaporation at room temperature to give the title compound as colourless crystals. Yield 60% (0.42 g), m.p. 373 K. Elemental analysis: calculated (found): C 32.18(31.78), H 3.78(3.35), N 15.01(15.35)%.

Refinement top

Water hydrogen atoms were tentatively found in the difference density Fourier map and were refined with an isotropic displacement parameter 1.5 that of the adjacent oxygen atom. The O—H distances were restrained to be 0.84Å within a standard deviation of 0.02 with Uiso(H) =1.5 Ueq(O). All other Hydrogen atoms were placed in calculated positions with C—H distances of 0.95Å for aromatic H atoms with Uiso(H) =1.2 Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT-Plus (Bruker, 2002); data reduction: SAINT-Plus (Bruker, 2002); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. View of the molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level with atom labeling.
[Figure 2] Fig. 2. Packing diagram of the title compound. Hydrogen bonds are indicated by dashed lines.
Diaquabis(nitrato-κO)bis(pyridine-κN)manganese(II) top
Crystal data top
[Mn(NO3)2(C5H5N)2(H2O)2]F(000) = 382
Mr = 373.19Dx = 1.620 Mg m3
Monoclinic, P21/cMelting point: 373 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 8.8988 (7) ÅCell parameters from 6452 reflections
b = 11.8668 (10) Åθ = 2.4–30.5°
c = 7.5950 (6) ŵ = 0.91 mm1
β = 107.500 (1)°T = 100 K
V = 764.91 (11) Å3Block, colourless
Z = 20.43 × 0.39 × 0.39 mm
Data collection top
Bruker SMART APEX CCD
diffractometer
1897 independent reflections
Radiation source: fine-focus sealed tube1817 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.016
ω scansθmax = 28.3°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS in SAINT-Plus; Bruker, 2003)
h = 1111
Tmin = 0.583, Tmax = 0.701k = 1315
6644 measured reflectionsl = 1010
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)] = 0.023Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.064H atoms treated by a mixture of independent and constrained refinement
S = 1.08 w = 1/[σ2(Fo2) + (0.0364P)2 + 0.2526P]
where P = (Fo2 + 2Fc2)/3
1897 reflections(Δ/σ)max < 0.001
112 parametersΔρmax = 0.34 e Å3
2 restraintsΔρmin = 0.30 e Å3
Crystal data top
[Mn(NO3)2(C5H5N)2(H2O)2]V = 764.91 (11) Å3
Mr = 373.19Z = 2
Monoclinic, P21/cMo Kα radiation
a = 8.8988 (7) ŵ = 0.91 mm1
b = 11.8668 (10) ÅT = 100 K
c = 7.5950 (6) Å0.43 × 0.39 × 0.39 mm
β = 107.500 (1)°
Data collection top
Bruker SMART APEX CCD
diffractometer
1897 independent reflections
Absorption correction: multi-scan
(SADABS in SAINT-Plus; Bruker, 2003)
1817 reflections with I > 2σ(I)
Tmin = 0.583, Tmax = 0.701Rint = 0.016
6644 measured reflectionsθmax = 28.3°
Refinement top
R[F2 > 2σ(F2)] = 0.023H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.064Δρmax = 0.34 e Å3
S = 1.08Δρmin = 0.30 e Å3
1897 reflectionsAbsolute structure: ?
112 parametersFlack parameter: ?
2 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
C10.73516 (12)0.28979 (9)0.04145 (16)0.0191 (2)
H10.63970.25000.01210.023*
C20.87624 (13)0.23034 (10)0.08651 (17)0.0225 (2)
H20.87680.15170.06360.027*
C31.01597 (13)0.28769 (10)0.16539 (17)0.0217 (2)
H31.11400.24910.19750.026*
C41.01000 (13)0.40250 (10)0.19649 (16)0.0209 (2)
H41.10380.44400.25070.025*
C50.86473 (13)0.45545 (9)0.14696 (15)0.0185 (2)
H50.86140.53420.16810.022*
Mn10.50000.50000.00000.01221 (8)
N10.72797 (10)0.40102 (8)0.07038 (12)0.01619 (18)
N20.62538 (9)0.58526 (7)0.40827 (11)0.01339 (17)
O10.38723 (9)0.37524 (6)0.12260 (10)0.01650 (16)
H1A0.3806 (18)0.3081 (12)0.085 (2)0.025*
H1B0.3892 (18)0.3773 (14)0.2317 (19)0.025*
O20.58830 (9)0.61467 (7)0.23972 (10)0.01857 (17)
O30.64860 (10)0.48619 (6)0.45430 (12)0.01931 (17)
O40.63944 (9)0.66239 (6)0.52668 (10)0.01668 (16)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0167 (5)0.0158 (5)0.0234 (5)0.0013 (4)0.0042 (4)0.0019 (4)
C20.0206 (5)0.0153 (5)0.0303 (6)0.0011 (4)0.0057 (4)0.0027 (4)
C30.0162 (5)0.0206 (5)0.0273 (6)0.0029 (4)0.0051 (4)0.0010 (4)
C40.0161 (5)0.0202 (5)0.0242 (5)0.0024 (4)0.0026 (4)0.0007 (4)
C50.0187 (5)0.0141 (5)0.0212 (5)0.0015 (4)0.0039 (4)0.0013 (4)
Mn10.01386 (13)0.01072 (13)0.01179 (12)0.00029 (7)0.00348 (9)0.00047 (7)
N10.0160 (4)0.0152 (4)0.0171 (4)0.0005 (3)0.0046 (3)0.0003 (3)
N20.0134 (4)0.0130 (4)0.0136 (4)0.0001 (3)0.0037 (3)0.0008 (3)
O10.0238 (4)0.0131 (4)0.0138 (3)0.0021 (3)0.0075 (3)0.0013 (3)
O20.0277 (4)0.0160 (4)0.0107 (3)0.0003 (3)0.0038 (3)0.0001 (3)
O30.0250 (4)0.0122 (4)0.0199 (4)0.0026 (3)0.0055 (3)0.0022 (3)
O40.0240 (4)0.0134 (4)0.0122 (3)0.0010 (3)0.0049 (3)0.0025 (3)
Geometric parameters (Å, º) top
C1—N11.3428 (14)Mn1—O12.1513 (8)
C1—C21.3902 (15)Mn1—O1i2.1514 (8)
C1—H10.9500Mn1—O2i2.2189 (7)
C2—C31.3856 (16)Mn1—O22.2189 (7)
C2—H20.9500Mn1—N1i2.2646 (9)
C3—C41.3864 (16)Mn1—N12.2646 (9)
C3—H30.9500N2—O31.2262 (11)
C4—C51.3839 (15)N2—O41.2627 (11)
C4—H40.9500N2—O21.2710 (11)
C5—N11.3457 (13)O1—H1A0.843 (13)
C5—H50.9500O1—H1B0.824 (13)
N1—C1—C2122.85 (10)O2i—Mn1—O2180.00 (3)
N1—C1—H1118.6O1—Mn1—N1i87.58 (3)
C2—C1—H1118.6O1i—Mn1—N1i92.42 (3)
C3—C2—C1118.93 (10)O2i—Mn1—N1i93.06 (3)
C3—C2—H2120.5O2—Mn1—N1i86.94 (3)
C1—C2—H2120.5O1—Mn1—N192.42 (3)
C2—C3—C4118.74 (10)O1i—Mn1—N187.58 (3)
C2—C3—H3120.6O2i—Mn1—N186.94 (3)
C4—C3—H3120.6O2—Mn1—N193.06 (3)
C5—C4—C3118.71 (10)N1i—Mn1—N1180.0
C5—C4—H4120.6C1—N1—C5117.46 (9)
C3—C4—H4120.6C1—N1—Mn1123.68 (7)
N1—C5—C4123.30 (10)C5—N1—Mn1118.85 (7)
N1—C5—H5118.3O3—N2—O4121.32 (9)
C4—C5—H5118.3O3—N2—O2121.39 (9)
O1—Mn1—O1i180.0O4—N2—O2117.29 (8)
O1—Mn1—O2i80.61 (3)Mn1—O1—H1A119.7 (11)
O1i—Mn1—O2i99.39 (3)Mn1—O1—H1B122.9 (11)
O1—Mn1—O299.39 (3)H1A—O1—H1B110.5 (15)
O1i—Mn1—O280.61 (3)N2—O2—Mn1125.36 (6)
Symmetry code: (i) x+1, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1B···O4ii0.82 (1)1.98 (1)2.7805 (11)163 (2)
O1—H1A···O2iii0.84 (1)2.63 (2)3.2504 (11)132 (1)
O1—H1A···O4iii0.84 (1)1.91 (1)2.7495 (11)174 (2)
Symmetry codes: (ii) x+1, y+1, z+1; (iii) x+1, y1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1B···O4i0.824 (13)1.984 (14)2.7805 (11)162.5 (16)
O1—H1A···O2ii0.843 (13)2.627 (15)3.2504 (11)131.8 (13)
O1—H1A···O4ii0.843 (13)1.910 (13)2.7495 (11)174.0 (15)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y1/2, z+1/2.
Acknowledgements top

MKR is grateful to Quaid-i-Azam University, Islamabad, for financial support through a Postdoctoral Fellowship.

references
References top

Bruker (2002). SMART and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2003). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Saphu, W., Chanthee, S., Chainok, K., Harding, D. J. & Pakawatchai, C. (2012). Acta Cryst. E68, m1026.

Shahid, M., Mazhar, M., Hamid, M., 'O Brien, P., Malik, M. A., Helliwell, M. & Raftery, J. (2010). Appl. Organomet. Chem. 24, 714–720.

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

Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.