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Acta Cryst. (2008). E64, m657-m658    [ doi:10.1107/S1600536808009549 ]

cis-Dichloridobis[2-(hydroxymethyl)tetrahydrofuran-[kappa]2O,O']manganese(II)

L. B. Jerzykiewcz, J. Utko and P. Sobota

Abstract top

The structure of the title compound, [MnCl2(C5H10O2)2], was solved from low-temperature data collected at 100 (2) K. The asymmetric unit contains one half-molecule with the MnII ion located on a twofold axis. A distorted octahedral environment around the Mn atom is formed by two ether and two hydroxyl O atoms of two 2-(hydroxymethyl)tetrahydrofuran ligands, and by two chloride ions. The chelating tetrahydrofuran ligands, which form five-membered rings, are cis oriented. The crystal structure is stabilized by hydrogen bonding between the coordinated OH groups and the chloride ions.

Comment top

The investigation presented in this work is a part of our research project concerning complexes with O,O'–bifunctional ligands (Jerzykiewicz et al., 1997; Janas et al., 1997; Sobota et al., 1998a; Sobota et al., 1998b; Janas et al., 1999; Sobota et al., 2000a; Sobota et al., 2000b; Utko et al., 2003, Jerzykiewicz et al., 2007a; Jerzykiewicz et al. 2007b). The use of chelating alkoxides can provide new compounds which are potential candidates for both sol-gel and metal-organic chemical vapour (MOCV) conversion of the precursor into the ceramic materials (Hubert-Pfalzgraf, 1998; Bradley, 1989). In this paper we describe the structure of a monomeric manganese(II) alkoxide complex: Mn(thffoH)2Cl2 (thffoH – tetrahydrofurfuryl alcohol) (Fig. 1). The MnII atom located at the special position (0, y, 1/4) on the two-fold axes displays a slightly distorted octahedral geometry (Table 1). The thffoH molecules bond to Mn atom as bidentate ligands through O11 hydroxyl group and O10 of ether group close two five-membered rings. The hydroxyl groups are cis arranged, whereas ether oxygen atoms of chelating ligands are situated trans. The coordination sphere of metal ion is completed by the Cl- ions, which are in cis-positions. In contrast to other structures with O,O'–functional ligand MnBr2(MeOH)(Hmepap) (where mepma = N–(2–methoxyethyl)–N–(pyridin–2–ylmethyl)amine) (Wu et al., 2004) and Mn4Cl4(OCH2CH2OCH3)4(EtOH)4 (Jerzykiewicz et al., 2007a) the lengths of Mn–O(ether) and Mn–O(hydroxyl) bonds do not differ significantly. The Mn–Cl bond length of 2.459 (1) Å is similar to corresponding bonds distances in other monomeric octahedral manganese (II) compounds with cis–Cl atoms Mn(2,2'-bpy)2(C1)2 (where 2,2'-bpy = 2,2'-bipyridine) (Lumme & Lindell, 1988), Mn(2,2'-bpy)2(C1)2.SC(NH2)2 (Choudhury et al., 2006), MnCl2(HL)2 (where HL = N–(3–chlorophenyl)pyridine–2–carboxamide) (Yang et al., 2003). The tetrahydrofouran ring adopts an envelope conformation. The whole structure is held together by intermolecular hydrogen bonds of O–H···Cl type (Table 2, Fig. 2).

Related literature top

For general background, see: Bradley (1989); Hubert-Pfalzgraf (1998); Jerzykiewicz et al. (1997, 2007a,b); Janas et al. (1997, 1999); Sobota et al. (1998a,b, 2000a,b); Utko et al. (2003).For related compounds, see: Wu et al. (2004); Lumme & Lindell (1988); Choudhury et al. (2006); Yang et al. (2003).

Experimental top

The air- and moisture-sensitive title compound was prepared under dried N2. A mixture of 1.26 g (10 mmol) MnC12 and 1.93 cm3 (20 mmol) tetrahydrofurfuryl alcohol (thffoH, Aldrich) in 15 mL of absolute ethanol was refluxed for 50 min, and the resulting precipitate was filtered, washed with ethanol, dried and recrystallized from ethanol.

Refinement top

Carbon bonded hydrogen atoms were included in calculated positions and refined in the riding mode using SHELXTL default parameters. The remaining H atoms were located in a difference map and refined freely.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2007); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), PLATON (Spek, 2003), enCIFer (Allen et al., 2004) and publCIF (Westrip, 2008).

Figures top
[Figure 1] Fig. 1. A view of the title compound with the atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level. Mn(II) is located at the two-fold axes.
[Figure 2] Fig. 2. The packing of the title compound, viewed down the c axis, showing one layer of molecules connected by O—H···Cl hydrogen bonds (dashed lines).
cis-Dichloridobis[2-(hydroxymethyl)tetrahydrofuran- κ2O,O']manganese(II) top
Crystal data top
[MnCl2(C5H10O2)2]F000 = 684
Mr = 330.10Dx = 1.571 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 4812 reflections
a = 17.463 (3) Åθ = 3–29º
b = 6.171 (2) ŵ = 1.33 mm−1
c = 13.159 (3) ÅT = 100 (2) K
β = 100.24 (2)ºBlock, colorless
V = 1395.5 (6) Å30.33 × 0.21 × 0.18 mm
Z = 4
Data collection top
Kuma KM-4 CCD κ-axis
diffractometer		1757 independent reflections
Radiation source: fine-focus sealed tube1667 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.034
T = 100(2) Kθmax = 28.5º
ω scansθmin = 3.6º
Absorption correction: analytical
(CrysAlis CCD; Oxford Diffraction, 2006)		h = −23→23
Tmin = 0.721, Tmax = 0.818k = −8→8
7753 measured reflectionsl = −11→17
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)] = 0.025H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.057  w = 1/[σ2(Fo2) + (0.0255P)2 + 0.9537P]
where P = (Fo2 + 2Fc2)/3
S = 1.13(Δ/σ)max < 0.001
1757 reflectionsΔρmax = 0.36 e Å−3
91 parametersΔρmin = −0.32 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[MnCl2(C5H10O2)2]V = 1395.5 (6) Å3
Mr = 330.10Z = 4
Monoclinic, C2/cMo Kα
a = 17.463 (3) ŵ = 1.33 mm−1
b = 6.171 (2) ÅT = 100 (2) K
c = 13.159 (3) Å0.33 × 0.21 × 0.18 mm
β = 100.24 (2)º
Data collection top
Kuma KM-4 CCD κ-axis
diffractometer		1757 independent reflections
Absorption correction: analytical
(CrysAlis CCD; Oxford Diffraction, 2006)		1667 reflections with I > 2σ(I)
Tmin = 0.721, Tmax = 0.818Rint = 0.034
7753 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.02591 parameters
wR(F2) = 0.057H atoms treated by a mixture of
independent and constrained refinement
S = 1.13Δρmax = 0.36 e Å−3
1757 reflectionsΔρmin = −0.32 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
Mn0.00000.60449 (4)0.25000.01153 (8)
Cl10.097635 (19)0.86166 (5)0.33711 (2)0.01677 (9)
O100.05616 (5)0.56904 (15)0.11203 (7)0.01400 (19)
O110.08645 (6)0.33832 (17)0.28441 (8)0.0203 (2)
H110.0799 (13)0.215 (4)0.2945 (16)0.035 (6)*
C110.11816 (8)0.4088 (2)0.11569 (11)0.0158 (3)
H11A0.09720.27250.08010.017 (4)*
C120.17872 (8)0.5110 (2)0.05927 (11)0.0192 (3)
H12A0.23230.47680.09460.021 (4)*
H12B0.17190.4602−0.01320.028 (5)*
C130.16192 (8)0.7537 (2)0.06439 (12)0.0203 (3)
H13A0.18720.81660.13110.029 (5)*
H13B0.17940.83320.00730.033 (5)*
C140.07401 (8)0.7568 (2)0.05337 (11)0.0171 (3)
H14A0.05620.89210.08220.028 (5)*
H14B0.04900.7444−0.02000.024 (5)*
C150.14969 (8)0.3643 (2)0.22866 (11)0.0183 (3)
H15A0.18170.23100.23520.024 (4)*
H15B0.18320.48620.25840.017 (4)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn0.01366 (14)0.00883 (13)0.01296 (14)0.0000.00471 (10)0.000
Cl10.01853 (17)0.01165 (15)0.01927 (17)−0.00251 (11)0.00099 (12)−0.00065 (11)
O100.0142 (4)0.0143 (4)0.0147 (4)0.0012 (3)0.0060 (4)0.0023 (3)
O110.0236 (5)0.0134 (5)0.0276 (6)0.0050 (4)0.0145 (4)0.0082 (4)
C110.0138 (6)0.0133 (6)0.0211 (7)0.0007 (5)0.0055 (5)−0.0028 (5)
C120.0154 (6)0.0251 (7)0.0187 (7)0.0004 (5)0.0073 (5)0.0007 (5)
C130.0153 (6)0.0231 (7)0.0224 (7)−0.0042 (5)0.0027 (5)0.0073 (5)
C140.0166 (6)0.0183 (6)0.0167 (6)−0.0014 (5)0.0041 (5)0.0070 (5)
C150.0161 (6)0.0178 (6)0.0226 (7)0.0042 (5)0.0076 (5)0.0056 (5)
Geometric parameters (Å, °) top
Mn—Cl12.459 (1)C13—C141.516 (2)
Mn—O102.222 (2)O11—H110.78 (2)
Mn—O112.222 (2)C11—H11A1.00
Mn—Cl1i2.459 (1)C12—H12A0.99
Mn—O10i2.222 (2)C12—H12B0.99
Mn—O11i2.222 (2)C13—H13A0.99
O10—C111.461 (2)C13—H13B0.99
O10—C141.456 (2)C14—H14A0.99
O11—C151.439 (2)C14—H14B0.99
C11—C121.532 (2)C15—H15A0.99
C11—C151.516 (2)C15—H15B0.99
C12—C131.530 (2)
Cl1—Mn—O1094.26 (3)O10—C14—C13104.34 (10)
Cl1—Mn—O1189.57 (3)O11—C15—C11110.01 (11)
Cl1—Mn—Cl1i99.60 (2)O10—C11—H11A110
Cl1—Mn—O10i93.03 (3)C12—C11—H11A110
Cl1—Mn—O11i164.10 (3)C15—C11—H11A110
O10—Mn—O1173.22 (4)C11—C12—H12A111
Cl1i—Mn—O1093.03 (3)C11—C12—H12B111
O10—Mn—O10i168.70 (4)C13—C12—H12A111
O10—Mn—O11i98.24 (4)C13—C12—H12B111
Cl1i—Mn—O11164.10 (3)H12A—C12—H12B109
O10i—Mn—O1198.24 (4)C12—C13—H13A111
O11—Mn—O11i84.69 (4)C12—C13—H13B111
Cl1i—Mn—O10i94.26 (3)C14—C13—H13A111
Cl1i—Mn—O11i89.57 (3)C14—C13—H13B111
O10i—Mn—O11i73.22 (4)H13A—C13—H13B109
Mn—O10—C11118.15 (8)O10—C14—H14A111
Mn—O10—C14121.45 (8)O10—C14—H14B111
C11—O10—C14109.20 (10)C13—C14—H14A111
Mn—O11—C15111.64 (8)C13—C14—H14B111
Mn—O11—H11129.6 (17)H14A—C14—H14B109
C15—O11—H11110.0 (17)O11—C15—H15A110
C12—C11—C15112.84 (12)O11—C15—H15B110
O10—C11—C12106.07 (10)C11—C15—H15A110
O10—C11—C15107.03 (11)C11—C15—H15B110
C11—C12—C13103.14 (11)H15A—C15—H15B108
C12—C13—C14101.94 (11)
Cl1—Mn—O10—C1185.96 (8)Mn—O10—C11—C15−21.30 (12)
Cl1—Mn—O10—C14−53.90 (9)C14—O10—C11—C122.38 (14)
O11—Mn—O10—C11−2.30 (8)C14—O10—C11—C15123.09 (11)
O11—Mn—O10—C14−142.16 (10)Mn—O10—C14—C13117.39 (10)
Cl1i—Mn—O10—C11−174.18 (8)C11—O10—C14—C13−25.61 (13)
Cl1i—Mn—O10—C1445.96 (9)Mn—O11—C15—C11−48.82 (11)
O11i—Mn—O10—C11−84.18 (9)O10—C11—C12—C1321.45 (14)
O11i—Mn—O10—C14135.96 (9)C15—C11—C12—C13−95.43 (13)
Cl1—Mn—O11—C15−67.02 (8)O10—C11—C15—O1144.63 (13)
O10—Mn—O11—C1527.56 (8)C12—C11—C15—O11160.94 (10)
O10i—Mn—O11—C15−160.02 (8)C11—C12—C13—C14−36.08 (14)
O11i—Mn—O11—C15127.83 (9)C12—C13—C14—O1038.10 (13)
Mn—O10—C11—C12−142.01 (9)
Symmetry codes: (i) −x, y, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O11—H11···Cl1ii0.79 (2)2.26 (2)3.021 (2)164 (2)
Symmetry codes: (ii) x, y−1, z.
Table 1
Selected geometric parameters (Å, °) top
Mn—Cl12.459 (1)O10—C111.461 (2)
Mn—O102.222 (2)O10—C141.456 (2)
Mn—O112.222 (2)O11—C151.439 (2)
Cl1—Mn—O1094.26 (3)Mn—O10—C11118.15 (8)
Cl1—Mn—O1189.57 (3)Mn—O10—C14121.45 (8)
Cl1—Mn—Cl1i99.60 (2)C11—O10—C14109.20 (10)
Cl1—Mn—O10i93.03 (3)Mn—O11—C15111.64 (8)
Cl1—Mn—O11i164.10 (3)O10—C11—C12106.07 (10)
O10—Mn—O1173.22 (4)O10—C11—C15107.03 (11)
O10—Mn—O10i168.70 (4)O10—C14—C13104.34 (10)
O10—Mn—O11i98.24 (4)O11—C15—C11110.01 (11)
O11—Mn—O11i84.69 (4)
Symmetry codes: (i) −x, y, −z+1/2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O11—H11···Cl1ii0.79 (2)2.26 (2)3.021 (2)164 (2)
Symmetry codes: (ii) x, y−1, z.
Acknowledgements top

This work was supported by the Polish State Committee for Scientific Research [grant Nos. PBZ-KBN-118/T09/19 and N N2054036 33].

references
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