trans-Bis(methanol-κO)bis-(quinoline-2-carboxyl-ato-κN,O)manganese(II).

The title compound, [Mn(C(10)H(6)NO(2))(2)(CH(4)O)(2)], was obtained unintentionally as the product of an attempt to synthesize a polynuclear carboxyl-ate bridged manganese(III/IV) complex, using methanol to reduce the permanganate ion. The mol-ecule is centrosymmetric; the pairs of equivalent ligands coordinate trans to each other in a distorted octa-hedral geometry. Intra-molecular C-H⋯O bonds lying in the equatorial plane stabilize the mol-ecule. In the crystal, mol-ecules are linked by O-H⋯O and C-H⋯O hydrogen bonds, creating a three-dimensional supra-molecular structure. π-π and C-H⋯π inter-actions are also observed. The dihedral angle and centroid-to-centroid distance between the pyridine ring (A) and the benzene ring (B(i)) of a symmetrically related mol-ecule [symmetry code: (i) -1 - x, -y, -z] are 1.27 (11)° and 3.974 (2) Å, respectively. For the C-H⋯π inter-actions, the relevant distances and angles are: C⋯Cg[A(ii)] = 3.643 (2) Å, H⋯Cg[A(ii)] = 2.750 (2) Å and C-H⋯Cg[A(ii)] = 155 (1)° [symmetry code: (ii) x, -1 + y, z].

Related literature

For previously reported MnII complexes with the quinoline-2 carboxyl­ate ligand, see: Okabe &Koizumi (1997 ▶); Goher & Mautner (1993 ▶); Haendler (1996 ▶); Dobrzyńska & Jerzykiewicz (2004 ▶); Dobrzyńska et al. (2005 ▶, 2006 ▶).

Experimental

Crystal data

[Mn(C10H6NO2)2(CH4O)2]

M = 463.34

Monoclinic,

a = 10.596 (5) Å

b = 7.243 (3) Å

c = 13.534 (3) Å

β = 106.59 (4)°

V = 995.5 (7) Å3

Z = 2

Mo Kα radiation

μ = 0.71 mm−1

T = 100 (1) K

0.43 × 0.12 × 0.09 mm

Data collection

Kuma KM-4 CCD κ-axis diffractometer

Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2006 ▶) T min = 0.873, T max = 0.902

5405 measured reflections

1924 independent reflections

1475 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.089

S = 0.98

1924 reflections

146 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.37 e Å−3

Δρmin = −0.31 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXTL-NT (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL-NT; molecular graphics: SHELXTL-NT; software used to prepare material for publication: SHELXTL-NT.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808031905/su2065sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808031905/su2065Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Mn(C10H6NO2)2(CH4O)2]	F(000) = 478
Mr = 463.34	Dx = 1.546 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3842 reflections
a = 10.596 (5) Å	θ = 3–26°
b = 7.243 (3) Å	µ = 0.71 mm−1
c = 13.534 (3) Å	T = 100 K
β = 106.59 (4)°	Block, yellow
V = 995.5 (7) Å3	0.43 × 0.12 × 0.09 mm
Z = 2

Kuma KM-4-CCD κ-axis diffractometer	1924 independent reflections
Radiation source: fine-focus sealed tube	1475 reflections with I > 2σ(I)
graphite	Rint = 0.031
ω scans	θmax = 26.0°, θmin = 3.2°
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2006)	h = −13→12
Tmin = 0.873, Tmax = 0.902	k = −8→6
5405 measured reflections	l = −16→16

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ2(Fo2) + (0.0573P)2] where P = (Fo2 + 2Fc2)/3
1924 reflections	(Δ/σ)max < 0.001
146 parameters	Δρmax = 0.37 e Å−3
0 restraints	Δρmin = −0.31 e Å−3

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.

	x	y	z	Uiso*/Ueq
Mn1	0.0000	0.0000	0.0000	0.01282 (16)
O1	−0.06256 (14)	0.0841 (2)	−0.15489 (11)	0.0151 (3)
O2	−0.21857 (15)	0.2157 (2)	−0.28166 (11)	0.0235 (4)
O3	−0.08755 (15)	−0.2745 (2)	−0.04702 (12)	0.0179 (4)
N1	−0.21067 (17)	0.1118 (2)	−0.02417 (13)	0.0126 (4)
C1	−0.2606 (2)	0.1766 (3)	−0.11886 (16)	0.0137 (5)
C2	−0.3844 (2)	0.2649 (3)	−0.15224 (16)	0.0166 (5)
H2A	−0.4157	0.3101	−0.2191	0.020*
C3	−0.4573 (2)	0.2825 (3)	−0.08415 (17)	0.0187 (5)
H3A	−0.5391	0.3400	−0.1047	0.022*
C4	−0.4091 (2)	0.2138 (3)	0.01703 (16)	0.0156 (5)
C5	−0.4793 (2)	0.2244 (3)	0.09220 (17)	0.0184 (5)
H5A	−0.5612	0.2818	0.0756	0.022*
C6	−0.4280 (2)	0.1518 (3)	0.18819 (17)	0.0196 (5)
H6A	−0.4751	0.1600	0.2364	0.024*
C7	−0.3044 (2)	0.0644 (3)	0.21473 (17)	0.0184 (5)
H7A	−0.2713	0.0136	0.2802	0.022*
C8	−0.2318 (2)	0.0528 (3)	0.14573 (16)	0.0153 (5)
H8A	−0.1494	−0.0031	0.1647	0.018*
C9	−0.2833 (2)	0.1269 (3)	0.04511 (16)	0.0132 (5)
C10	−0.1752 (2)	0.1571 (3)	−0.19219 (16)	0.0145 (5)
C11	−0.1393 (2)	−0.3854 (3)	0.02034 (17)	0.0207 (5)
H11A	−0.1730	−0.4990	−0.0136	0.031*
H11B	−0.2090	−0.3196	0.0373	0.031*
H11C	−0.0705	−0.4118	0.0823	0.031*
H3	−0.141 (3)	−0.280 (4)	−0.102 (2)	0.050 (10)*

	U11	U22	U33	U12	U13	U23
Mn1	0.0121 (2)	0.0150 (3)	0.0109 (2)	0.0008 (2)	0.00264 (18)	0.0002 (2)
O1	0.0141 (8)	0.0196 (8)	0.0121 (7)	0.0013 (6)	0.0045 (6)	0.0006 (6)
O2	0.0180 (8)	0.0358 (10)	0.0161 (8)	0.0018 (7)	0.0040 (7)	0.0060 (7)
O3	0.0188 (8)	0.0180 (8)	0.0143 (8)	−0.0024 (7)	0.0007 (7)	0.0003 (7)
N1	0.0132 (9)	0.0113 (9)	0.0131 (9)	−0.0014 (7)	0.0035 (7)	−0.0022 (7)
C1	0.0121 (10)	0.0118 (11)	0.0168 (11)	−0.0023 (8)	0.0035 (9)	−0.0017 (9)
C2	0.0149 (11)	0.0158 (11)	0.0179 (11)	0.0003 (9)	0.0027 (9)	0.0044 (9)
C3	0.0150 (11)	0.0148 (11)	0.0248 (12)	0.0041 (9)	0.0032 (10)	0.0033 (10)
C4	0.0154 (11)	0.0113 (10)	0.0200 (12)	−0.0015 (8)	0.0049 (9)	−0.0031 (9)
C5	0.0141 (11)	0.0157 (11)	0.0265 (13)	0.0004 (9)	0.0078 (10)	−0.0037 (10)
C6	0.0197 (12)	0.0205 (12)	0.0224 (12)	−0.0037 (10)	0.0120 (10)	−0.0067 (10)
C7	0.0206 (12)	0.0200 (11)	0.0148 (11)	−0.0023 (9)	0.0053 (10)	−0.0010 (9)
C8	0.0144 (11)	0.0153 (11)	0.0158 (11)	0.0013 (8)	0.0037 (9)	−0.0026 (8)
C9	0.0142 (11)	0.0095 (11)	0.0167 (11)	−0.0022 (8)	0.0056 (9)	−0.0018 (9)
C10	0.0144 (11)	0.0147 (11)	0.0119 (11)	−0.0028 (9)	−0.0001 (9)	0.0003 (9)
C11	0.0228 (12)	0.0167 (12)	0.0223 (12)	−0.0006 (10)	0.0058 (10)	0.0002 (10)

Mn1—O1	2.100 (2)	C4—C9	1.424 (3)
Mn1—O3	2.209 (2)	C4—C5	1.424 (3)
Mn1—N1	2.308 (2)	C5—C6	1.363 (3)
Mn1—O1i	2.100 (2)	C6—C7	1.406 (3)
Mn1—O3i	2.209 (2)	C7—C8	1.372 (3)
Mn1—N1i	2.308 (2)	C8—C9	1.420 (3)
O1—C10	1.271 (3)	C2—H2A	0.93
O2—C10	1.241 (3)	C3—H3A	0.93
O3—C11	1.436 (3)	C5—H5A	0.93
O3—H3	0.80 (3)	C6—H6A	0.93
N1—C1	1.325 (3)	C7—H7A	0.93
N1—C9	1.377 (3)	C8—H8A	0.93
C1—C10	1.529 (3)	C11—H11A	0.96
C1—C2	1.413 (3)	C11—H11B	0.96
C2—C3	1.367 (3)	C11—H11C	0.96
C3—C4	1.409 (3)
O1—Mn1—O3	89.23 (7)	C3—C4—C5	123.9 (2)
O1—Mn1—N1	74.93 (7)	C4—C5—C6	120.9 (2)
O1—Mn1—O1i	180.00	C5—C6—C7	120.4 (2)
O1—Mn1—O3i	90.77 (7)	C6—C7—C8	121.1 (2)
O1—Mn1—N1i	105.07 (7)	C7—C8—C9	119.6 (2)
O3—Mn1—N1	88.01 (7)	N1—C9—C8	119.1 (2)
O1i—Mn1—O3	90.77 (7)	C4—C9—C8	119.8 (2)
O3—Mn1—O3i	180.00	N1—C9—C4	121.06 (19)
O3—Mn1—N1i	91.99 (7)	O2—C10—C1	118.6 (2)
O1i—Mn1—N1	105.07 (7)	O1—C10—O2	125.0 (2)
O3i—Mn1—N1	91.99 (7)	O1—C10—C1	116.33 (18)
N1—Mn1—N1i	180.00	C1—C2—H2A	121.00
O1i—Mn1—O3i	89.23 (7)	C3—C2—H2A	121.00
O1i—Mn1—N1i	74.93 (7)	C2—C3—H3A	120.00
O3i—Mn1—N1i	88.01 (7)	C4—C3—H3A	120.00
Mn1—O1—C10	120.67 (14)	C4—C5—H5A	120.00
Mn1—O3—C11	121.70 (13)	C6—C5—H5A	120.00
C11—O3—H3	105 (2)	C5—C6—H6A	120.00
Mn1—O3—H3	116 (2)	C7—C6—H6A	120.00
Mn1—N1—C9	129.59 (14)	C6—C7—H7A	119.00
C1—N1—C9	118.96 (19)	C8—C7—H7A	119.00
Mn1—N1—C1	111.36 (15)	C7—C8—H8A	120.00
C2—C1—C10	120.13 (19)	C9—C8—H8A	120.00
N1—C1—C2	123.2 (2)	O3—C11—H11A	109.00
N1—C1—C10	116.64 (19)	O3—C11—H11B	109.00
C1—C2—C3	118.6 (2)	O3—C11—H11C	109.00
C2—C3—C4	120.3 (2)	H11A—C11—H11B	109.00
C3—C4—C9	117.9 (2)	H11A—C11—H11C	109.00
C5—C4—C9	118.26 (19)	H11B—C11—H11C	110.00
O3—Mn1—O1—C10	89.82 (16)	C1—N1—C9—C4	−1.3 (3)
N1—Mn1—O1—C10	1.67 (15)	Mn1—N1—C9—C4	174.99 (15)
O3i—Mn1—O1—C10	−90.18 (16)	Mn1—N1—C9—C8	−5.6 (3)
N1i—Mn1—O1—C10	−178.33 (15)	C10—C1—C2—C3	−179.0 (2)
O1—Mn1—O3—C11	−149.62 (16)	C2—C1—C10—O1	176.7 (2)
N1—Mn1—O3—C11	−74.68 (16)	N1—C1—C10—O1	−1.5 (3)
O1i—Mn1—O3—C11	30.38 (16)	N1—C1—C10—O2	179.83 (19)
N1i—Mn1—O3—C11	105.32 (16)	N1—C1—C2—C3	−0.9 (3)
O1—Mn1—N1—C1	−2.35 (14)	C2—C1—C10—O2	−1.9 (3)
O1—Mn1—N1—C9	−178.82 (18)	C1—C2—C3—C4	0.1 (3)
O3—Mn1—N1—C1	−92.09 (14)	C2—C3—C4—C9	0.1 (3)
O3—Mn1—N1—C9	91.44 (17)	C2—C3—C4—C5	−179.2 (2)
O1i—Mn1—N1—C1	177.65 (14)	C3—C4—C9—N1	0.5 (3)
O1i—Mn1—N1—C9	1.18 (18)	C3—C4—C5—C6	178.7 (2)
O3i—Mn1—N1—C1	87.91 (14)	C9—C4—C5—C6	−0.6 (3)
O3i—Mn1—N1—C9	−88.56 (17)	C5—C4—C9—C8	0.4 (3)
Mn1—O1—C10—C1	−0.8 (3)	C3—C4—C9—C8	−178.9 (2)
Mn1—O1—C10—O2	177.74 (17)	C5—C4—C9—N1	179.8 (2)
Mn1—N1—C1—C2	−175.44 (17)	C4—C5—C6—C7	−0.1 (3)
C9—N1—C1—C2	1.5 (3)	C5—C6—C7—C8	1.1 (3)
C9—N1—C1—C10	179.63 (18)	C6—C7—C8—C9	−1.3 (3)
Mn1—N1—C1—C10	2.7 (2)	C7—C8—C9—N1	−178.9 (2)
C1—N1—C9—C8	178.2 (2)	C7—C8—C9—C4	0.5 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2ii	0.80 (3)	1.83 (3)	2.623 (3)	172 (3)
C2—H2A···O1iii	0.93	2.58	3.411 (3)	148
C8—H8A···O1i	0.93	2.36	3.241 (3)	158

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O2i	0.80 (3)	1.83 (3)	2.623 (3)	172 (3)
C2—H2A⋯O1ii	0.93	2.58	3.411 (3)	148
C8—H8A⋯O1iii	0.93	2.36	3.241 (3)	158

Symmetry codes: (i) ; (ii) ; (iii) .