Diaqua­bis­(nitrato-κO)bis­(pyridine-κN)manganese(II)

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

doi:10.1107/S1600536812049161

metal-organic compounds

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Volume 69| Part 1| January 2013| Page m9

https://doi.org/10.1107/S1600536812049161

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Diaquabis(nitrato-κO)bis(pyridine-κN)manganese(II)

Naveed Alam,^a Muhammad Shahid ^a ^* and M. Khawar Rauf ^a

^aDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan
^*Correspondence e-mail: mkhawarrauf@yahoo.co.uk, shahid_chme@yahoo.com

(Received 20 November 2012; accepted 29 November 2012; online 5 December 2012)

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.

Related literature

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

Experimental

Crystal data

[Mn(NO₃)₂(C₅H₅N)₂(H₂O)₂]
M_r = 373.19
Monoclinic, P 2₁ /c
a = 8.8988 (7) Å
b = 11.8668 (10) Å
c = 7.5950 (6) Å
β = 107.500 (1)°
V = 764.91 (11) Å³
Z = 2
Mo Kα radiation
μ = 0.91 mm⁻¹
T = 100 K
0.43 × 0.39 × 0.39 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ) T_min = 0.583, T_max = 0.701
6644 measured reflections
1897 independent reflections
1817 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.064
S = 1.08
1897 reflections
112 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1B⋯O4ⁱ	0.82 (1)	1.98 (1)	2.7805 (11)	163 (2)
O1—H1A⋯O2ⁱⁱ	0.84 (1)	2.63 (2)	3.2504 (11)	132 (1)
O1—H1A⋯O4ⁱⁱ	0.84 (1)	1.91 (1)	2.7495 (11)	174 (2)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812049161/br2215sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812049161/br2215Isup2.hkl

checkCIF report

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 Mn^II 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 Mn^II 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)%.

Structure description 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 Mn^II complexes, see: Saphu et al. (2012).

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

	Fig. 1. View of the molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level with atom labeling.
	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
M_r = 373.19	D_x = 1.620 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 373 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.8988 (7) Å	Cell parameters from 6452 reflections
b = 11.8668 (10) Å	θ = 2.4–30.5°
c = 7.5950 (6) Å	µ = 0.91 mm⁻¹
β = 107.500 (1)°	T = 100 K
V = 764.91 (11) Å³	Block, colourless
Z = 2	0.43 × 0.39 × 0.39 mm

Data collection top

Bruker SMART APEX CCD diffractometer	1897 independent reflections
Radiation source: fine-focus sealed tube	1817 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ω scans	θ_max = 28.3°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS in SAINT-Plus; Bruker, 2003)	h = −11→11
T_min = 0.583, T_max = 0.701	k = −13→15
6644 measured reflections	l = −10→10

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.064	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0364P)² + 0.2526P] where P = (F_o² + 2F_c²)/3
1897 reflections	(Δ/σ)_max < 0.001
112 parameters	Δρ_max = 0.34 e Å⁻³
2 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

[Mn(NO₃)₂(C₅H₅N)₂(H₂O)₂]	V = 764.91 (11) Å³
M_r = 373.19	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.8988 (7) Å	µ = 0.91 mm⁻¹
b = 11.8668 (10) Å	T = 100 K
c = 7.5950 (6) Å	0.43 × 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)
T_min = 0.583, T_max = 0.701	R_int = 0.016
6644 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	2 restraints
wR(F²) = 0.064	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.34 e Å⁻³
1897 reflections	Δρ_min = −0.30 e Å⁻³
112 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

	x	y	z	U_iso*/U_eq
C1	0.73516 (12)	0.28979 (9)	0.04145 (16)	0.0191 (2)
H1	0.6397	0.2500	−0.0121	0.023*
C2	0.87624 (13)	0.23034 (10)	0.08651 (17)	0.0225 (2)
H2	0.8768	0.1517	0.0636	0.027*
C3	1.01597 (13)	0.28769 (10)	0.16539 (17)	0.0217 (2)
H3	1.1140	0.2491	0.1975	0.026*
C4	1.01000 (13)	0.40250 (10)	0.19649 (16)	0.0209 (2)
H4	1.1038	0.4440	0.2507	0.025*
C5	0.86473 (13)	0.45545 (9)	0.14696 (15)	0.0185 (2)
H5	0.8614	0.5342	0.1681	0.022*
Mn1	0.5000	0.5000	0.0000	0.01221 (8)
N1	0.72797 (10)	0.40102 (8)	0.07038 (12)	0.01619 (18)
N2	0.62538 (9)	0.58526 (7)	0.40827 (11)	0.01339 (17)
O1	0.38723 (9)	0.37524 (6)	0.12260 (10)	0.01650 (16)
H1A	0.3806 (18)	0.3081 (12)	0.085 (2)	0.025*
H1B	0.3892 (18)	0.3773 (14)	0.2317 (19)	0.025*
O2	0.58830 (9)	0.61467 (7)	0.23972 (10)	0.01857 (17)
O3	0.64860 (10)	0.48619 (6)	0.45430 (12)	0.01931 (17)
O4	0.63944 (9)	0.66239 (6)	0.52668 (10)	0.01668 (16)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0167 (5)	0.0158 (5)	0.0234 (5)	−0.0013 (4)	0.0042 (4)	−0.0019 (4)
C2	0.0206 (5)	0.0153 (5)	0.0303 (6)	0.0011 (4)	0.0057 (4)	−0.0027 (4)
C3	0.0162 (5)	0.0206 (5)	0.0273 (6)	0.0029 (4)	0.0051 (4)	0.0010 (4)
C4	0.0161 (5)	0.0202 (5)	0.0242 (5)	−0.0024 (4)	0.0026 (4)	−0.0007 (4)
C5	0.0187 (5)	0.0141 (5)	0.0212 (5)	−0.0015 (4)	0.0039 (4)	−0.0013 (4)
Mn1	0.01386 (13)	0.01072 (13)	0.01179 (12)	−0.00029 (7)	0.00348 (9)	−0.00047 (7)
N1	0.0160 (4)	0.0152 (4)	0.0171 (4)	−0.0005 (3)	0.0046 (3)	−0.0003 (3)
N2	0.0134 (4)	0.0130 (4)	0.0136 (4)	−0.0001 (3)	0.0037 (3)	−0.0008 (3)
O1	0.0238 (4)	0.0131 (4)	0.0138 (3)	−0.0021 (3)	0.0075 (3)	−0.0013 (3)
O2	0.0277 (4)	0.0160 (4)	0.0107 (3)	−0.0003 (3)	0.0038 (3)	0.0001 (3)
O3	0.0250 (4)	0.0122 (4)	0.0199 (4)	0.0026 (3)	0.0055 (3)	0.0022 (3)
O4	0.0240 (4)	0.0134 (4)	0.0122 (3)	−0.0010 (3)	0.0049 (3)	−0.0025 (3)

Geometric parameters (Å, º) top

C1—N1	1.3428 (14)	Mn1—O1	2.1513 (8)
C1—C2	1.3902 (15)	Mn1—O1ⁱ	2.1514 (8)
C1—H1	0.9500	Mn1—O2ⁱ	2.2189 (7)
C2—C3	1.3856 (16)	Mn1—O2	2.2189 (7)
C2—H2	0.9500	Mn1—N1ⁱ	2.2646 (9)
C3—C4	1.3864 (16)	Mn1—N1	2.2646 (9)
C3—H3	0.9500	N2—O3	1.2262 (11)
C4—C5	1.3839 (15)	N2—O4	1.2627 (11)
C4—H4	0.9500	N2—O2	1.2710 (11)
C5—N1	1.3457 (13)	O1—H1A	0.843 (13)
C5—H5	0.9500	O1—H1B	0.824 (13)

N1—C1—C2	122.85 (10)	O2ⁱ—Mn1—O2	180.00 (3)
N1—C1—H1	118.6	O1—Mn1—N1ⁱ	87.58 (3)
C2—C1—H1	118.6	O1ⁱ—Mn1—N1ⁱ	92.42 (3)
C3—C2—C1	118.93 (10)	O2ⁱ—Mn1—N1ⁱ	93.06 (3)
C3—C2—H2	120.5	O2—Mn1—N1ⁱ	86.94 (3)
C1—C2—H2	120.5	O1—Mn1—N1	92.42 (3)
C2—C3—C4	118.74 (10)	O1ⁱ—Mn1—N1	87.58 (3)
C2—C3—H3	120.6	O2ⁱ—Mn1—N1	86.94 (3)
C4—C3—H3	120.6	O2—Mn1—N1	93.06 (3)
C5—C4—C3	118.71 (10)	N1ⁱ—Mn1—N1	180.0
C5—C4—H4	120.6	C1—N1—C5	117.46 (9)
C3—C4—H4	120.6	C1—N1—Mn1	123.68 (7)
N1—C5—C4	123.30 (10)	C5—N1—Mn1	118.85 (7)
N1—C5—H5	118.3	O3—N2—O4	121.32 (9)
C4—C5—H5	118.3	O3—N2—O2	121.39 (9)
O1—Mn1—O1ⁱ	180.0	O4—N2—O2	117.29 (8)
O1—Mn1—O2ⁱ	80.61 (3)	Mn1—O1—H1A	119.7 (11)
O1ⁱ—Mn1—O2ⁱ	99.39 (3)	Mn1—O1—H1B	122.9 (11)
O1—Mn1—O2	99.39 (3)	H1A—O1—H1B	110.5 (15)
O1ⁱ—Mn1—O2	80.61 (3)	N2—O2—Mn1	125.36 (6)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···O4ⁱⁱ	0.82 (1)	1.98 (1)	2.7805 (11)	163 (2)
O1—H1A···O2ⁱⁱⁱ	0.84 (1)	2.63 (2)	3.2504 (11)	132 (1)
O1—H1A···O4ⁱⁱⁱ	0.84 (1)	1.91 (1)	2.7495 (11)	174 (2)

Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) −x+1, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Mn(NO₃)₂(C₅H₅N)₂(H₂O)₂]
M_r	373.19
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	8.8988 (7), 11.8668 (10), 7.5950 (6)
β (°)	107.500 (1)
V (Å³)	764.91 (11)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.91
Crystal size (mm)	0.43 × 0.39 × 0.39

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS in SAINT-Plus; Bruker, 2003)
T_min, T_max	0.583, 0.701
No. of measured, independent and observed [I > 2σ(I)] reflections	6644, 1897, 1817
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.064, 1.08
No. of reflections	1897
No. of parameters	112
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.30

Computer programs: SMART (Bruker, 2002), SAINT-Plus (Bruker, 2002), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···O4ⁱ	0.824 (13)	1.984 (14)	2.7805 (11)	162.5 (16)
O1—H1A···O2ⁱⁱ	0.843 (13)	2.627 (15)	3.2504 (11)	131.8 (13)
O1—H1A···O4ⁱⁱ	0.843 (13)	1.910 (13)	2.7495 (11)	174.0 (15)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y−1/2, −z+1/2.

Acknowledgements

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

References

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