Diaqua­dichloridobis(pyridine-κN)manganese(II)

Karthikeyan, M.; Karthikeyan, S.; Manimaran, B.

doi:10.1107/S160053681103546X

metal-organic compounds

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Volume 67| Part 10| October 2011| Page m1367

https://doi.org/10.1107/S160053681103546X

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Diaquadichloridobis(pyridine-κN)manganese(II)

M. Karthikeyan,^a S. Karthikeyan ^a and Bala. Manimaran ^a ^*

^aDepartment of Chemistry, Pondicherry University, Puducherry 605 014, India
^*Correspondence e-mail: manimaran.che@pondiuni.edu.in

(Received 16 August 2011; accepted 31 August 2011; online 14 September 2011)

The molecular title compound, [MnCl₂(C₅H₅N)₂(H₂O)₂], lies about an inversion centre. The Mn^II atom is in an all-trans octahedral environment defined by two water molecules, two chloride anions and two pyridine ligands. An intermolecular hydrogen-bonding interaction between a water molecule and a chloride anion bonded to an adjacent Mn^II atom generates an eight-membered ring. The crystal packing exhibits two intermolecular π–π stacking interactions between the aromatic rings, with centroid–centroid distances of 3.485 (12) and 3.532 (12) Å.

Related literature

For hydrogen-bond motifs, see: Frost et al. (2006 ). For related structures, see: Cotton et al. (1995 ); Kruszynski et al. (2001 ).

Experimental

Crystal data

[MnCl₂(C₅H₅N)₂(H₂O)₂]
M_r = 320.07
Triclinic, $[P \overline 1]$
a = 6.2290 (5) Å
b = 6.6327 (5) Å
c = 8.6831 (7) Å
α = 108.931 (7)°
β = 103.499 (7)°
γ = 96.969 (6)°
V = 322.30 (4) Å³
Z = 1
Mo Kα radiation
μ = 1.43 mm⁻¹
T = 150 K
0.26 × 0.14 × 0.07 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.733, T_max = 1.000
1951 measured reflections
1137 independent reflections
1031 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.022
wR(F²) = 0.056
S = 1.05
1137 reflections
87 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1B⋯Cl1ⁱ	0.86 (1)	2.38 (1)	3.2301 (13)	170 (2)
Symmetry code: (i) x, y-1, z.

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: PLATON.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S160053681103546X/ng5215sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681103546X/ng5215Isup2.hkl

checkCIF report

Comment top

The molecular structure of the title compound C₁₀H₁₄Cl₂MnN₂O₂ is isostructural with Cr (Cotton et al., 1995) compound. The title compound is shown in Fig. 1. The bond length of Mn—N, Mn—O, and Mn—Cl is comparable to those observed in a related crystal structure namely that diaqua-dichloro-bis(1-((2-(2,4-dichlorophenyl)-1,3-dioxalan-2-yl)methyl)-4H-1,2,4-triazol-4-yl)-manganese(II) (Kruszynski et al., 2001). The molecule exibits two intermolecular hydrogen bonding (O—H···Cl) between water molecule coordinated to manganese and a chloride bonded to adjacent manganese center with a distance of 2.281 (15) Å (Fig. 2) and 2.377 (16) Å (Fig. 3) which leads to layered structure (Frost et al.., 2006). The crystal packing exhibits two intermolecular π–π stacking interaction between the aromatic rings with the centroid to centroid distance of 3.485 (12) and 3.532 (12) Å (Fig. 4).

Related literature top

For hydrogen-bond motifs, see: Frost et al. (2006). For related structures, see: Cotton et al. (1995); Kruszynski et al. (2001).

Experimental top

A solution of manganese(II) chloride tetrahydrate (692 mg, 3.5 mmol) in distilled water (2 ml) was added a solution of pyridine (0.28 ml, 3.5 mmol) in a 1:1 ethanol-water mixture (2 ml) slowly. Colorless white crystals began to form at ambient temperature after a week.

Structure description top

For hydrogen-bond motifs, see: Frost et al. (2006). For related structures, see: Cotton et al. (1995); Kruszynski et al. (2001).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. : The molecular structure of title compound, showing displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. : A view of the intermolecular (O1—H1A···Cl1) hydrogen bonding interaction shown as dashed line.
	Fig. 3. : A view of the intermolecular (O1—H1B···Cl1) hydrogen bonding interaction shown as dashed line.
	Fig. 4. : A view of the crystal packing showing intermolecular π···π stacking interaction.

Diaquadichloridobis(pyridine-κN)manganese(II) top

Crystal data top

[MnCl₂(C₅H₅N)₂(H₂O)₂]	Z = 1
M_r = 320.07	F(000) = 163
Triclinic, P1	D_x = 1.649 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.2290 (5) Å	Cell parameters from 1883 reflections
b = 6.6327 (5) Å	θ = 2.6–28.8°
c = 8.6831 (7) Å	µ = 1.43 mm⁻¹
α = 108.931 (7)°	T = 150 K
β = 103.499 (7)°	Block, colorless
γ = 96.969 (6)°	0.26 × 0.14 × 0.07 mm
V = 322.30 (4) Å³

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	1137 independent reflections
Radiation source: fine-focus sealed tube	1031 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
Detector resolution: 15.9821 pixels mm^-1	θ_max = 25.0°, θ_min = 2.6°
ω scans	h = −7→5
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −7→7
T_min = 0.733, T_max = 1.000	l = −10→10
1951 measured reflections

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)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.056	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0294P)² + 0.1426P] where P = (F_o² + 2F_c²)/3
1137 reflections	(Δ/σ)_max = 0.011
87 parameters	Δρ_max = 0.27 e Å⁻³
2 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

[MnCl₂(C₅H₅N)₂(H₂O)₂]	γ = 96.969 (6)°
M_r = 320.07	V = 322.30 (4) Å³
Triclinic, P1	Z = 1
a = 6.2290 (5) Å	Mo Kα radiation
b = 6.6327 (5) Å	µ = 1.43 mm⁻¹
c = 8.6831 (7) Å	T = 150 K
α = 108.931 (7)°	0.26 × 0.14 × 0.07 mm
β = 103.499 (7)°

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	1137 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	1031 reflections with I > 2σ(I)
T_min = 0.733, T_max = 1.000	R_int = 0.022
1951 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.022	2 restraints
wR(F²) = 0.056	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.27 e Å⁻³
1137 reflections	Δρ_min = −0.22 e Å⁻³
87 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
H1A	0.097 (2)	−0.252 (4)	0.484 (3)	0.038 (7)*
H1B	0.237 (5)	−0.3957 (19)	0.455 (3)	0.045 (8)*
Mn1	0.5000	0.0000	0.5000	0.00900 (13)
Cl1	0.22317 (7)	0.23567 (7)	0.43191 (5)	0.01375 (13)
N1	0.4713 (2)	−0.1480 (2)	0.22133 (17)	0.0115 (3)
O1	0.2181 (2)	−0.2694 (2)	0.45397 (16)	0.0150 (3)
C3	0.6365 (3)	−0.2269 (3)	−0.0085 (2)	0.0169 (4)
H3	0.7657	−0.2195	−0.0444	0.020*
C2	0.4261 (3)	−0.3200 (3)	−0.1260 (2)	0.0186 (4)
H2	0.4112	−0.3782	−0.2419	0.022*
C4	0.6529 (3)	−0.1449 (3)	0.1626 (2)	0.0139 (4)
H4	0.7956	−0.0850	0.2407	0.017*
C5	0.2673 (3)	−0.2372 (3)	0.1057 (2)	0.0147 (4)
H5	0.1398	−0.2401	0.1440	0.018*
C1	0.2383 (3)	−0.3246 (3)	−0.0671 (2)	0.0188 (4)
H1	0.0943	−0.3857	−0.1429	0.023*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0090 (2)	0.0087 (2)	0.0082 (2)	0.00120 (14)	0.00223 (14)	0.00214 (15)
Cl1	0.0119 (2)	0.0125 (2)	0.0175 (2)	0.00426 (17)	0.00427 (18)	0.00570 (18)
N1	0.0138 (8)	0.0098 (7)	0.0107 (7)	0.0030 (6)	0.0030 (6)	0.0037 (6)
O1	0.0135 (7)	0.0115 (7)	0.0213 (7)	0.0018 (5)	0.0070 (5)	0.0066 (6)
C3	0.0228 (10)	0.0162 (10)	0.0186 (9)	0.0092 (8)	0.0120 (8)	0.0092 (8)
C2	0.0336 (11)	0.0135 (9)	0.0102 (8)	0.0087 (8)	0.0064 (8)	0.0051 (7)
C4	0.0144 (9)	0.0114 (9)	0.0151 (9)	0.0038 (7)	0.0030 (7)	0.0043 (7)
C5	0.0139 (9)	0.0140 (9)	0.0154 (9)	0.0011 (7)	0.0028 (7)	0.0060 (7)
C1	0.0207 (10)	0.0148 (10)	0.0138 (9)	0.0010 (8)	−0.0030 (8)	0.0031 (8)

Geometric parameters (Å, º) top

Mn1—O1ⁱ	2.2100 (13)	C3—C2	1.382 (3)
Mn1—O1	2.2100 (13)	C3—C4	1.381 (2)
Mn1—N1	2.2505 (14)	C3—H3	0.9300
Mn1—N1ⁱ	2.2505 (14)	C2—C1	1.383 (3)
Mn1—Cl1	2.5582 (4)	C2—H2	0.9300
Mn1—Cl1ⁱ	2.5582 (4)	C4—H4	0.9300
N1—C4	1.346 (2)	C5—C1	1.379 (3)
N1—C5	1.345 (2)	C5—H5	0.9300
O1—H1A	0.8629 (10)	C1—H1	0.9300
O1—H1B	0.8630 (10)

O1ⁱ—Mn1—O1	180.00 (5)	Mn1—O1—H1A	124.5 (16)
O1ⁱ—Mn1—N1	92.86 (5)	Mn1—O1—H1B	123.3 (18)
O1—Mn1—N1	87.14 (5)	H1A—O1—H1B	105 (2)
O1ⁱ—Mn1—N1ⁱ	87.14 (5)	C2—C3—C4	119.36 (17)
O1—Mn1—N1ⁱ	92.86 (5)	C2—C3—H3	120.3
N1—Mn1—N1ⁱ	180.00 (3)	C4—C3—H3	120.3
O1ⁱ—Mn1—Cl1	88.86 (3)	C3—C2—C1	118.34 (17)
O1—Mn1—Cl1	91.14 (3)	C3—C2—H2	120.8
N1—Mn1—Cl1	89.26 (4)	C1—C2—H2	120.8
N1ⁱ—Mn1—Cl1	90.74 (4)	N1—C4—C3	122.77 (17)
O1ⁱ—Mn1—Cl1ⁱ	91.14 (3)	N1—C4—H4	118.6
O1—Mn1—Cl1ⁱ	88.86 (3)	C3—C4—H4	118.6
N1—Mn1—Cl1ⁱ	90.74 (4)	N1—C5—C1	123.08 (17)
N1ⁱ—Mn1—Cl1ⁱ	89.26 (4)	N1—C5—H5	118.5
Cl1—Mn1—Cl1ⁱ	180.0	C1—C5—H5	118.5
C4—N1—C5	117.32 (15)	C5—C1—C2	119.12 (17)
C4—N1—Mn1	122.28 (11)	C5—C1—H1	120.4
C5—N1—Mn1	120.36 (12)	C2—C1—H1	120.4

O1ⁱ—Mn1—N1—C4	35.44 (13)	Cl1ⁱ—Mn1—N1—C5	126.61 (12)
O1—Mn1—N1—C4	−144.56 (13)	C4—C3—C2—C1	0.9 (3)
N1ⁱ—Mn1—N1—C4	174 (7)	C5—N1—C4—C3	0.5 (2)
Cl1—Mn1—N1—C4	124.26 (13)	Mn1—N1—C4—C3	−177.19 (13)
Cl1ⁱ—Mn1—N1—C4	−55.74 (13)	C2—C3—C4—N1	−1.2 (3)
O1ⁱ—Mn1—N1—C5	−142.21 (13)	C4—N1—C5—C1	0.3 (3)
O1—Mn1—N1—C5	37.79 (13)	Mn1—N1—C5—C1	178.05 (14)
N1ⁱ—Mn1—N1—C5	−4 (7)	N1—C5—C1—C2	−0.5 (3)
Cl1—Mn1—N1—C5	−53.39 (12)	C3—C2—C1—C5	−0.2 (3)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···Cl1ⁱⁱ	0.86 (1)	2.38 (1)	3.2301 (13)	170 (2)

Symmetry code: (ii) x, y−1, z.

Experimental details

Crystal data
Chemical formula	[MnCl₂(C₅H₅N)₂(H₂O)₂]
M_r	320.07
Crystal system, space group	Triclinic, P1
Temperature (K)	150
a, b, c (Å)	6.2290 (5), 6.6327 (5), 8.6831 (7)
α, β, γ (°)	108.931 (7), 103.499 (7), 96.969 (6)
V (Å³)	322.30 (4)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.43
Crystal size (mm)	0.26 × 0.14 × 0.07

Data collection
Diffractometer	Oxford Diffraction Xcalibur Eos
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.733, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	1951, 1137, 1031
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.056, 1.05
No. of reflections	1137
No. of parameters	87
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)	0.27, −0.22

Computer programs: CrysAlis CCD (Oxford Diffraction, 2009), CrysAlis RED (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···Cl1ⁱ	0.8630 (10)	2.376 (5)	3.2301 (13)	170 (2)

Symmetry code: (i) x, y−1, z.

Acknowledgements

BM thanks the Council of Science and Industrial Research (CSIR), Government of India, for financial support. We are thankful to the Department of Science and Technology (DST), Government of India, for providing the single crystal X-ray diffractometer facility at the Department of Chemistry, Pondicherry University, under the DST–FIST program.

References

Cotton, F. A., Daniels, L. M., Feng, X., Maloney, D. J., Murillo, C. A. & Zuniga, L. A. (1995). Inorg. Chim. Acta, 235, 21–28. CSD CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Frost, B. J., Bautista, C. M., Huang, R. & Shearer, J. (2006). Inorg. Chem. 45, 3481–3483. Web of Science CrossRef PubMed CAS Google Scholar
Kruszynski, R., Bartczak, T. J., Adamczyk, A., Czakis-Sulikowska, D. & Kałużna, J. (2001). Acta Cryst. E57, m183–m185. Web of Science CSD CrossRef IUCr Journals Google Scholar
Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar