Chlorido[2,2′-[1,2-phenyl­enebis(nitrilo­methanylyl­idyne)]diphenolato-κ4O,N,N′,O′]manganese(III) methanol monosolvate

Lin, H.; Wang, J.-G.; Shi, H.-T.; Chen, Q.; Zhang, Q.-F.

doi:10.1107/S1600536813016450

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 7| July 2013| Page m404

https://doi.org/10.1107/S1600536813016450

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Chlorido[2,2′-[1,2-phenylenebis(nitrilomethanylylidyne)]diphenolato-κ⁴O,N,N′,O′]manganese(III) methanol monosolvate

Hui Lin,^a Jian-Gang Wang,^a Hua-Tian Shi,^a Qun Chen ^b and Qian-Feng Zhang ^a,^b ^*

^aInstitute of Molecular Engineering and Applied Chemsitry, Anhui University of Technology, Ma'anshan, Anhui 243002, People's Republic of China, and ^bDepartment of Applied Chemistry, School of Petrochemical Engineering, Changzhou University, Jiangsu 213164, People's Republic of China
^*Correspondence e-mail: zhangqf@ahut.edu.cn

(Received 31 May 2013; accepted 13 June 2013; online 19 June 2013)

In the title complex, [Mn(C₂₀H₁₄N₂O₂)Cl]·CH₃OH, the central Mn^III atom displays a distorted square-pyramidal coordination by two N and two O atoms from the tetradentate 2,2′-[1,2-phenylenebis(nitrilomethanylylidyne)]diphenolate ligand and one chloride ligand. The Mn^III atom is 0.525 (4) Å out of the square basal N₂O₂ least-squares plane. The complex molecule is hydrogen bonded to the methanol solvent molecule.

Related literature

For background to manganese and manganese–salen complexes, see: Law et al. (1998 ); Lenoble et al. (1998 ); Horner et al. (1999 ); Asada et al. (2000 ); Dubois et al. (2003 ); Gultneh et al. (2003 ); Mitra et al. (2006 ). For related structures, see: Pecoraro & Butler (1986 ); Dang et al. (2005 ); Martínez et al. (2002 ); Panja et al. (2003 ).

Experimental

Crystal data

[Mn(C₂₀H₁₄N₂O₂)Cl]·CH₄O
M_r = 436.76
Triclinic, $[P \overline 1]$
a = 7.4251 (2) Å
b = 9.8341 (2) Å
c = 13.3035 (3) Å
α = 78.803 (1)°
β = 83.305 (2)°
γ = 86.344 (2)°
V = 945.58 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.87 mm⁻¹
T = 296 K
0.24 × 0.17 × 0.13 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.819, T_max = 0.896
17011 measured reflections
4302 independent reflections
3311 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.086
S = 1.02
4302 reflections
255 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1S—H1S⋯O1ⁱ	0.87	2.19	2.999 (3)	154
Symmetry code: (i) x+1, y, z.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536813016450/vn2073sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813016450/vn2073Isup2.hkl

checkCIF report

Comment top

The coordination chemistry of manganese complexes has been the subject of extensive investigation in the past several decades. Most of the studies have aimed to understand the role of manganese in many metallo-enzymes in terms of structure- property relationships (Dubois et al., 2003; Horner et al., 1999). Studies of high oxidation state complexes are of special importance because of their potential uses as oxidizing agents, catalysts and electro-catalysts, for the oxidation of compounds such as alcohols, esters and water (Gultneh et al., 2003). Of particular interest is the Schiff base complexes of manganese(III) which have been considered to be the simplest models for the reactivity of oxygen-evolving center (OEC) active site of mangano-enzymes (Law et al., 1998). The typical [Mn^III(salen)X] (X = Cl, Br, I) complexes (salen = N,N'-bis(salicylideneiminato)ethylene) have been prepared and are soluble in aqueous and methanolic solutions (Mitra et al., 2006). Series of monochloro- and dichloro-manganese(IV) complexes along with acetatomanganese(III) complexes with the salen ligands have been previously synthesized from the mixed aqueous-ethanol or -acetonitrile solutions (Asada et al., 2000; Lenoble et al., 1998; Pecoraro & Butler, 1986). In this paper, we report the synthesis of the manganese(III) complex [Mn^III(salen)Cl].CH₃OH (salen = N,N'-bis(salicylideneiminato)benzene) in a mixed aqueous-methanol solution and its structural characterization involving an N₂O₂ Schiff base ligand.

The title complex crystallizes in the triclinic P-1 space group. The asymmetric unit of the crystal structure consists of the neutral mononuclear complex [Mn^III(salen)Cl] and one methanol molecule in the lattice. A view of the complex is shown in Fig. 1. In this monomeric complex, the central manganese atom is coordinated by two nitrogen and two oxygen atoms from the salen ligand and one chloride atom. Owing to the presence of the chloride atom, the manganese atom is 0.525 (4) Å above the square basal N₂O₂ plane and the geometry around the metal centre may be better described as distorted square-pyramidal. The average Mn—N and Mn—O bond lengths in the title complex are 2.0992 (16) and 1.8942 (14) Å, respectively, which are compared with those in [Mn(salen)Cl(H₂O)].H₂O (salen = N,N'- bis(salicylideneiminato)ethylene) [av. Mn—N = 1.984 (17) Å and av. Mn—O = 1.883 (14) Å] (Panja et al., 2003), [MnCl(salen)(H₂O)] (salen = 2,2'-[1,2-ethanediylbis- (nitrilomethylidyne)]-diphenolato) [av. Mn—N = 1.980 (5) Å and av. Mn—O = 1.890 (4) Å] (Martínez et al., 2002), and [Mn(L)Cl] (L = N,N'-bis{4-(diethylamino)- salicylideneiminato}-cyclohexane) [av. Mn—N = 1.986 (12) Å and av. Mn—O = 1.872 (12) Å] (Dang et al., 2005). The Mn—Cl bond length of 2.2276 (7) %A in the title complex is obviously shorter than those in [Mn(salen)Cl(H₂O)].H₂O (salen = N,N'-bis(salicylideneiminato)ethylene) (2.584 (12) %A) (Panja et al., 2003), [MnCl(salen)(H₂O)] (salen = 2,2'-[1,2-ethanediylbis-(nitrilomethylidyne)]-diphenolato) (2.468 (2) Å) (Martínez et al., 2002), and [Mn(L)Cl] (L = N,N'-bis{4-(diethylamino)salicylideneiminato}cyclohexane) (2.386 (2) Å) (Dang et al., 2005). The basal bond angles are all approximately close to 90° [O(1)—Mn(1)—O(2), O(1)—Mn(1)—N(1) and O(2)—Mn(1)—N(2) are 91.48 (6)°, 87.99 (6)° and 87.68 (6)°, respectively] except N(1)-Mn(1)-N(2) (76.74 (6)°) which is large smaller than expected (Pecoraro & Butler, 1986). The methanol molecule takes part in one hydrogen-bond involving in H1S with the phenoxo-oxygen O1a from the next unit-cell and the distance O1a···H1S (a: x + 1, y, z) is 2.19 (2) Å (see Fig. 2).

Related literature top

For background to manganese and manganese–salen complexes, see: Law et al. (1998); Lenoble et al. (1998); Horner et al. (1999); Asada et al. (2000); Dubois et al. (2003); Gultneh et al. (2003); Mitra et al. (2006); For related structures, see: Pecoraro & Butler (1986); Dang et al. (2005); Martínez et al. (2002); Panja et al. (2003).

Experimental top

To a solution of the Schiff base ligand (H₂salen) (158 mg, 0.5 mmol) in methanol (10 mL) was added Et₃N (101 mg, 1.0 mmol), and then a solution of MnCl₂.6H₂O (117 mg, 0.5 mmol) in distilled water (5 mL) was dropwise added to the above methanol solution. The resulting solution was refluxed for 4 h, and then the mixture was filtered and the filtrate was allowed to evaporate slowly, which led to deposition of a brown solid. The solid was collected by filtration, washed with Et₂O and recrystallized from CH₃OH-Et₂O mixture (1:1). Yield: 111 mg, 58 %. Analysis for C₂₁H₁₈N₂O₃ClMn: calcd C 57.75, H 4.15, N 6.41 %; found C 57.63, H 4.12, N 6.37 %.

Structure description top

For background to manganese and manganese–salen complexes, see: Law et al. (1998); Lenoble et al. (1998); Horner et al. (1999); Asada et al. (2000); Dubois et al. (2003); Gultneh et al. (2003); Mitra et al. (2006); For related structures, see: Pecoraro & Butler (1986); Dang et al. (2005); Martínez et al. (2002); Panja et al. (2003).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of [Mn^III(salen)Cl] (salen = N,N'-bis(salicylideneiminato)- benzene); displacement ellipsoids at the 50% probability level.
	Fig. 2. Packing diagram of the title complex in a unit cell. Dash lines denote the intermolecular (CH₃)O—H···O(salen) hydrogen bonds.

Chlorido[2,2'-[1,2-phenylenebis(nitrilomethanylylidyne)]diphenolato-κ⁴O,N,N',O']manganese(III) methanol monosolvate top

Crystal data top

[Mn(C₂₀H₁₄N₂O₂)Cl]·CH₄O	Z = 2
M_r = 436.76	F(000) = 448
Triclinic, P1	D_x = 1.534 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4251 (2) Å	Cell parameters from 5729 reflections
b = 9.8341 (2) Å	θ = 2.4–26.8°
c = 13.3035 (3) Å	µ = 0.87 mm⁻¹
α = 78.803 (1)°	T = 296 K
β = 83.305 (2)°	Block, pink
γ = 86.344 (2)°	0.24 × 0.17 × 0.13 mm
V = 945.58 (4) Å³

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	4302 independent reflections
Radiation source: fine-focus sealed tube	3311 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
phi and ω scans	θ_max = 27.5°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −9→9
T_min = 0.819, T_max = 0.896	k = −12→12
17011 measured reflections	l = −17→17

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.086	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0419P)² + 0.2015P] where P = (F_o² + 2F_c²)/3
4302 reflections	(Δ/σ)_max = 0.001
255 parameters	Δρ_max = 0.33 e Å⁻³
1 restraint	Δρ_min = −0.40 e Å⁻³

Crystal data top

[Mn(C₂₀H₁₄N₂O₂)Cl]·CH₄O	γ = 86.344 (2)°
M_r = 436.76	V = 945.58 (4) Å³
Triclinic, P1	Z = 2
a = 7.4251 (2) Å	Mo Kα radiation
b = 9.8341 (2) Å	µ = 0.87 mm⁻¹
c = 13.3035 (3) Å	T = 296 K
α = 78.803 (1)°	0.24 × 0.17 × 0.13 mm
β = 83.305 (2)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	4302 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	3311 reflections with I > 2σ(I)
T_min = 0.819, T_max = 0.896	R_int = 0.032
17011 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	1 restraint
wR(F²) = 0.086	H-atom parameters constrained
S = 1.02	Δρ_max = 0.33 e Å⁻³
4302 reflections	Δρ_min = −0.40 e Å⁻³
255 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Mn1	0.06050 (4)	0.87475 (3)	0.26112 (2)	0.03227 (10)
Cl1	0.30457 (9)	0.81214 (7)	0.34473 (5)	0.06368 (18)
N1	0.1304 (2)	1.06118 (16)	0.16224 (12)	0.0368 (4)
N2	−0.0670 (2)	1.02686 (16)	0.33991 (11)	0.0345 (4)
O1	0.0801 (2)	0.79008 (14)	0.14311 (10)	0.0475 (4)
O2	−0.1221 (2)	0.75440 (15)	0.32907 (11)	0.0522 (4)
C1	0.1710 (3)	0.8242 (2)	0.05065 (14)	0.0388 (4)
C2	0.2021 (3)	0.7250 (2)	−0.01285 (16)	0.0479 (5)
H2	0.1588	0.6364	0.0104	0.057*
C3	0.2960 (3)	0.7574 (3)	−0.10922 (17)	0.0535 (6)
H3	0.3169	0.6897	−0.1498	0.064*
C4	0.3601 (3)	0.8889 (3)	−0.14702 (17)	0.0537 (6)
H4	0.4250	0.9092	−0.2119	0.064*
C5	0.3266 (3)	0.9881 (2)	−0.08765 (16)	0.0477 (5)
H5	0.3662	1.0772	−0.1136	0.057*
C6	0.2334 (3)	0.9589 (2)	0.01207 (14)	0.0383 (4)
C7	0.2019 (3)	1.0706 (2)	0.06718 (15)	0.0394 (4)
H7	0.2356	1.1580	0.0320	0.047*
C8	0.1020 (3)	1.18087 (19)	0.20795 (14)	0.0358 (4)
C9	0.1713 (3)	1.3105 (2)	0.16491 (16)	0.0453 (5)
H9	0.2440	1.3228	0.1023	0.054*
C10	0.1317 (3)	1.4201 (2)	0.21548 (17)	0.0485 (5)
H10	0.1778	1.5064	0.1867	0.058*
C11	0.0245 (3)	1.4028 (2)	0.30831 (18)	0.0482 (5)
H11	−0.0018	1.4779	0.3414	0.058*
C12	−0.0441 (3)	1.2757 (2)	0.35271 (16)	0.0433 (5)
H12	−0.1157	1.2648	0.4157	0.052*
C13	−0.0057 (3)	1.16326 (19)	0.30263 (14)	0.0344 (4)
C14	−0.1822 (3)	1.0000 (2)	0.42216 (14)	0.0369 (4)
H14	−0.2217	1.0734	0.4551	0.044*
C15	−0.2531 (3)	0.8672 (2)	0.46599 (14)	0.0367 (4)
C16	−0.3650 (3)	0.8553 (2)	0.56071 (15)	0.0427 (5)
H16	−0.3912	0.9332	0.5906	0.051*
C17	−0.4353 (3)	0.7316 (2)	0.60900 (16)	0.0486 (5)
H17	−0.5095	0.7254	0.6709	0.058*
C18	−0.3944 (3)	0.6145 (2)	0.56445 (17)	0.0507 (6)
H18	−0.4384	0.5293	0.5982	0.061*
C19	−0.2902 (3)	0.6237 (2)	0.47166 (17)	0.0501 (5)
H19	−0.2670	0.5449	0.4425	0.060*
C20	−0.2181 (3)	0.7492 (2)	0.41977 (15)	0.0395 (5)
C1S	0.6113 (4)	0.6064 (3)	0.1772 (3)	0.0922 (10)
H1S1	0.6377	0.5284	0.2298	0.138*
H1S2	0.5154	0.5847	0.1411	0.138*
H1S3	0.5742	0.6855	0.2081	0.138*
O1S	0.7639 (3)	0.6357 (2)	0.10906 (15)	0.0848 (6)
H1S	0.8457 (10)	0.6671 (4)	0.1397 (4)	0.127*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.04290 (19)	0.02961 (15)	0.02400 (15)	−0.00218 (12)	0.00435 (11)	−0.00877 (11)
Cl1	0.0695 (4)	0.0623 (4)	0.0640 (4)	0.0191 (3)	−0.0223 (3)	−0.0216 (3)
N1	0.0434 (9)	0.0363 (8)	0.0313 (8)	−0.0010 (7)	−0.0008 (7)	−0.0095 (7)
N2	0.0406 (9)	0.0335 (8)	0.0296 (8)	0.0000 (7)	−0.0012 (7)	−0.0082 (7)
O1	0.0711 (10)	0.0413 (8)	0.0303 (7)	−0.0094 (7)	0.0070 (7)	−0.0124 (6)
O2	0.0673 (10)	0.0460 (8)	0.0445 (8)	−0.0185 (7)	0.0193 (7)	−0.0215 (7)
C1	0.0462 (12)	0.0448 (11)	0.0256 (9)	0.0027 (9)	−0.0009 (8)	−0.0105 (8)
C2	0.0654 (15)	0.0439 (12)	0.0346 (11)	0.0005 (10)	0.0002 (10)	−0.0125 (9)
C3	0.0662 (15)	0.0590 (14)	0.0373 (11)	0.0093 (12)	0.0022 (10)	−0.0224 (11)
C4	0.0579 (14)	0.0696 (16)	0.0329 (11)	−0.0013 (12)	0.0084 (10)	−0.0159 (11)
C5	0.0521 (13)	0.0557 (13)	0.0346 (11)	−0.0075 (10)	0.0048 (9)	−0.0105 (10)
C6	0.0409 (11)	0.0442 (11)	0.0302 (10)	−0.0005 (9)	−0.0001 (8)	−0.0104 (8)
C7	0.0453 (12)	0.0397 (10)	0.0319 (10)	−0.0054 (9)	0.0019 (8)	−0.0062 (8)
C8	0.0445 (11)	0.0316 (9)	0.0318 (10)	0.0000 (8)	−0.0047 (8)	−0.0074 (8)
C9	0.0592 (14)	0.0397 (11)	0.0355 (11)	−0.0066 (10)	0.0010 (10)	−0.0056 (9)
C10	0.0626 (14)	0.0335 (10)	0.0486 (13)	−0.0058 (10)	−0.0052 (11)	−0.0046 (9)
C11	0.0559 (14)	0.0359 (11)	0.0550 (13)	0.0026 (10)	−0.0020 (11)	−0.0175 (10)
C12	0.0477 (12)	0.0402 (11)	0.0426 (12)	0.0033 (9)	0.0008 (9)	−0.0144 (9)
C13	0.0387 (11)	0.0314 (9)	0.0333 (10)	0.0018 (8)	−0.0039 (8)	−0.0080 (8)
C14	0.0405 (11)	0.0390 (10)	0.0318 (10)	0.0024 (8)	0.0004 (8)	−0.0121 (8)
C15	0.0368 (11)	0.0409 (10)	0.0331 (10)	−0.0011 (8)	−0.0009 (8)	−0.0107 (8)
C16	0.0448 (12)	0.0473 (12)	0.0353 (10)	−0.0006 (9)	0.0057 (9)	−0.0131 (9)
C17	0.0493 (13)	0.0600 (14)	0.0351 (11)	−0.0083 (11)	0.0084 (9)	−0.0113 (10)
C18	0.0568 (14)	0.0497 (13)	0.0438 (12)	−0.0178 (11)	0.0059 (10)	−0.0060 (10)
C19	0.0570 (14)	0.0461 (12)	0.0493 (13)	−0.0142 (10)	0.0095 (11)	−0.0192 (10)
C20	0.0409 (11)	0.0437 (11)	0.0345 (10)	−0.0069 (9)	0.0039 (8)	−0.0117 (9)
C1S	0.093 (2)	0.077 (2)	0.100 (2)	−0.0166 (18)	0.029 (2)	−0.0218 (18)
O1S	0.0820 (14)	0.1037 (16)	0.0640 (12)	−0.0195 (12)	0.0008 (11)	−0.0039 (11)

Geometric parameters (Å, º) top

Mn1—O2	1.8868 (14)	C9—C10	1.377 (3)
Mn1—O1	1.9022 (13)	C9—H9	0.9300
Mn1—N1	2.0944 (16)	C10—C11	1.376 (3)
Mn1—N2	2.1047 (15)	C10—H10	0.9300
Mn1—Cl1	2.2277 (7)	C11—C12	1.377 (3)
N1—C7	1.302 (2)	C11—H11	0.9300
N1—C8	1.420 (2)	C12—C13	1.396 (3)
N2—C14	1.303 (2)	C12—H12	0.9300
N2—C13	1.421 (2)	C14—C15	1.429 (3)
O1—C1	1.325 (2)	C14—H14	0.9300
O2—C20	1.321 (2)	C15—C20	1.412 (3)
C1—C2	1.402 (3)	C15—C16	1.415 (3)
C1—C6	1.411 (3)	C16—C17	1.365 (3)
C2—C3	1.376 (3)	C16—H16	0.9300
C2—H2	0.9300	C17—C18	1.395 (3)
C3—C4	1.387 (3)	C17—H17	0.9300
C3—H3	0.9300	C18—C19	1.369 (3)
C4—C5	1.364 (3)	C18—H18	0.9300
C4—H4	0.9300	C19—C20	1.398 (3)
C5—C6	1.409 (3)	C19—H19	0.9300
C5—H5	0.9300	C1S—O1S	1.374 (3)
C6—C7	1.428 (3)	C1S—H1S1	0.9600
C7—H7	0.9300	C1S—H1S2	0.9600
C8—C9	1.396 (3)	C1S—H1S3	0.9600
C8—C13	1.398 (3)	O1S—H1S	0.8725

O2—Mn1—O1	91.47 (6)	C10—C9—H9	120.1
O2—Mn1—N1	148.62 (7)	C8—C9—H9	120.1
O1—Mn1—N1	87.98 (6)	C11—C10—C9	120.50 (19)
O2—Mn1—N2	87.70 (6)	C11—C10—H10	119.8
O1—Mn1—N2	148.11 (7)	C9—C10—H10	119.8
N1—Mn1—N2	76.74 (6)	C10—C11—C12	120.75 (19)
O2—Mn1—Cl1	105.95 (6)	C10—C11—H11	119.6
O1—Mn1—Cl1	108.96 (5)	C12—C11—H11	119.6
N1—Mn1—Cl1	103.86 (5)	C11—C12—C13	119.64 (19)
N2—Mn1—Cl1	101.87 (5)	C11—C12—H12	120.2
C7—N1—C8	120.67 (16)	C13—C12—H12	120.2
C7—N1—Mn1	124.46 (13)	C12—C13—C8	119.69 (17)
C8—N1—Mn1	114.81 (12)	C12—C13—N2	125.41 (18)
C14—N2—C13	120.85 (16)	C8—C13—N2	114.90 (16)
C14—N2—Mn1	124.04 (13)	N2—C14—C15	125.47 (18)
C13—N2—Mn1	114.86 (12)	N2—C14—H14	117.3
C1—O1—Mn1	131.49 (12)	C15—C14—H14	117.3
C20—O2—Mn1	130.62 (12)	C20—C15—C16	118.96 (18)
O1—C1—C2	119.31 (18)	C20—C15—C14	123.61 (17)
O1—C1—C6	122.27 (17)	C16—C15—C14	117.43 (17)
C2—C1—C6	118.39 (18)	C17—C16—C15	121.27 (19)
C3—C2—C1	120.6 (2)	C17—C16—H16	119.4
C3—C2—H2	119.7	C15—C16—H16	119.4
C1—C2—H2	119.7	C16—C17—C18	119.27 (19)
C2—C3—C4	121.3 (2)	C16—C17—H17	120.4
C2—C3—H3	119.4	C18—C17—H17	120.4
C4—C3—H3	119.4	C19—C18—C17	120.7 (2)
C5—C4—C3	119.0 (2)	C19—C18—H18	119.6
C5—C4—H4	120.5	C17—C18—H18	119.6
C3—C4—H4	120.5	C18—C19—C20	121.3 (2)
C4—C5—C6	121.6 (2)	C18—C19—H19	119.3
C4—C5—H5	119.2	C20—C19—H19	119.3
C6—C5—H5	119.2	O2—C20—C19	119.40 (18)
C5—C6—C1	119.06 (18)	O2—C20—C15	122.20 (17)
C5—C6—C7	117.27 (18)	C19—C20—C15	118.39 (18)
C1—C6—C7	123.63 (17)	O1S—C1S—H1S1	109.5
N1—C7—C6	125.92 (18)	O1S—C1S—H1S2	109.5
N1—C7—H7	117.0	H1S1—C1S—H1S2	109.5
C6—C7—H7	117.0	O1S—C1S—H1S3	109.5
C9—C8—C13	119.60 (17)	H1S1—C1S—H1S3	109.5
C9—C8—N1	124.94 (18)	H1S2—C1S—H1S3	109.5
C13—C8—N1	115.45 (16)	C1S—O1S—H1S	109.5
C10—C9—C8	119.82 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1S—H1S···O1ⁱ	0.87	2.19	2.999 (3)	154

Symmetry code: (i) x+1, y, z.

Experimental details

Crystal data
Chemical formula	[Mn(C₂₀H₁₄N₂O₂)Cl]·CH₄O
M_r	436.76
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	7.4251 (2), 9.8341 (2), 13.3035 (3)
α, β, γ (°)	78.803 (1), 83.305 (2), 86.344 (2)
V (Å³)	945.58 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.87
Crystal size (mm)	0.24 × 0.17 × 0.13

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.819, 0.896
No. of measured, independent and observed [I > 2σ(I)] reflections	17011, 4302, 3311
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.086, 1.02
No. of reflections	4302
No. of parameters	255
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.40

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1S—H1S···O1ⁱ	0.87	2.19	2.999 (3)	153.7

Symmetry code: (i) x+1, y, z.

Acknowledgements

This project was supported by the Natural Science Foundation of China (90922008).

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