Bis{2-meth­oxy-6-[tris­(hydroxy­meth­yl)methyl­imino­meth­yl]phenolato-κ3O,N,O′}manganese(II) dimethanol solvate hemihydrate

Zhang, X.; Wei, P.; Dou, J.; Li, B.; Hu, B.

doi:10.1107/S1600536809005364

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Pages m293-m294

doi:10.1107/S1600536809005364

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Bis{2-methoxy-6-[tris(hydroxymethyl)methyliminomethyl]phenolato-κ³O,N,O′}manganese(II) dimethanol solvate hemihydrate

Xiutang Zhang,^a,^b ^* Peihai Wei,^a Jianmin Dou,^b Bin Li ^a and Bo Hu ^c

^aAdvanced Material Institute of Research, Department of Chemistry and Chemical Engineering, Shandong Institute of Education, Jinan 250013, People's Republic of China, ^bCollege of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252059, People's Republic of China, and ^cDepartment of Chemistry and Chemical Engineering, Shandong Institute of Education, Jinan 250013, People's Republic of China
^*Correspondence e-mail: xiutangzhang@yahoo.com.cn

(Received 2 January 2009; accepted 15 February 2009; online 21 February 2009)

In the title complex, [Mn(C₁₂H₁₆NO₅)₂]·2CH₃OH·0.5H₂O, the Mn^II atom has a distorted octahedral coordination geometry in which two N atoms from two 6-methoxy-2-[tris(hydroxymethyl)methyliminomethyl]phenolate ligands adopt a trans arrangement. The Mn—O(H) bonds (mean length 2.134 Å) are significantly longer than the Mn—O and Mn—N bonds (mean length 2.011 and 2.027 Å, respectively), and the dihedral angle between the mean planes through the aromatic rings of the two ligands is 76.8 (1)°. A complex network of O—H⋯O hydrogen bonds is formed between the complexes and the uncoordinated methanol and water molecules. The C and O atoms of one C—OH group are disordered with equal occupancies.

Related literature

For Schiff-base complexes of transition metals, see: Ward (2007 ). For details of the synthesis and a related structure, see: Wang et al. (2007 ).

Experimental

Crystal data

[Mn(C₁₂H₁₆NO₅)₂]·2CH₄O·0.5H₂O
M_r = 636.55
Monoclinic, P 2₁ /n
a = 8.141 (2) Å
b = 18.130 (5) Å
c = 20.211 (6) Å
β = 93.590 (4)°
V = 2977.2 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.51 mm⁻¹
T = 293 K
0.12 × 0.10 × 0.09 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.941, T_max = 0.955
14576 measured reflections
5287 independent reflections
4036 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.148
S = 1.05
5287 reflections
416 parameters
16 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.93 e Å⁻³
Δρ_min = −0.65 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O8	0.86 (1)	1.885 (10)	2.706 (5)	160 (4)
O4—H4⋯O9	0.86 (1)	1.802 (12)	2.664 (5)	174 (5)
O5—H5⋯O2ⁱ	0.85 (1)	1.886 (13)	2.736 (4)	173 (6)
O6—H6⋯O3	0.86 (1)	1.886 (9)	2.737 (7)	172 (6)
O9—H9⋯O11	0.85 (1)	1.888 (10)	2.712 (5)	162 (4)
O10—H10⋯O1W	0.86 (1)	1.90 (4)	2.585 (6)	136 (5)
O11—H11⋯O6ⁱⁱ	0.85 (1)	1.897 (18)	2.739 (4)	169 (7)
O12—H12⋯O2	0.85	2.12	2.967 (7)	180
O12A—H12A⋯O5ⁱⁱⁱ	0.85	2.10	2.946 (7)	180
O1W—H1W⋯O5	0.85	1.81	2.657 (8)	180
O1W—H2W⋯O12A^iv	0.85	2.14	2.990 (9)	180
Symmetry codes: (i) x-1, y, z; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) x+1, y, z; (iv) -x+1, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT-Plus (Bruker, 2001 ); data reduction: SAINT-Plus; 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 global, I. DOI: 10.1107/S1600536809005364/bi2342sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809005364/bi2342Isup2.hkl

checkCIF report

Comment top

Transition metal Schiff-base complexes have been intensively studied owing to their interesting physical and chemical properties, including magnetic, optics and catalysis (Ward et al.). Herein, we report a crystal structure of an Mn^II complex incorporating the Schiff-base ligand, (E)-2-(2-hydroxy-3-methoxybenzylideneamino)-2-(hydroxymethyl)propane-1,3-diol.

The asymmetric unit (Fig. 1) comprises one [MnL₂] complex, two uncoordinated methanol molecules and one lattice water molecule. The coordination geometry of Mn^II is distorted octahedral, with the N atoms of the two ligands trans to each other. The Mn—O and Mn—N bond distances are in the normal range compared to similar reported complexes (for example, Wang et al., 2007). A complex network of O—H···O hydrogen bonds is formed between the complexes and the lattice methanol and water molecules.

Related literature top

For Schiff-base complexes of transition metals, see: Ward (2007). For synthesis details and a related structure, see: Wang et al. (2007).

Experimental top

The Schiff-base ligand (HL) was synthesized according to the reported literature procedure (Wang et al.). The title complex was then prepared by refluxing HL (0.050 g, 0.2 mmol) and MnSO₄.H₂O in the mixed solvent system CH₃OH:H₂O (4:1) until all solid was dissolved. The solution was then cooled to room temperature and filtered. Crystals for diffraction analysis were obtained by slow evaporation of the filtrate. Elemental analysis calculated: C 48.05, H 6.47, N 4.31%; found: C 49.89, H 6.39, N 4.28%.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); 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 molecular structure with displacement ellipsoids at 30% probability for non-H atoms.

Bis{2-methoxy-6-[tris(hydroxymethyl)methyliminomethyl]phenolato- κ³O,N,O'}manganese(II) dimethanol solvate hemihydrate top

Crystal data top

[Mn(C₁₂H₁₆NO₅)₂]·2CH₄O·0.5H₂O	F(000) = 1344
M_r = 636.55	D_x = 1.420 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5287 reflections
a = 8.141 (2) Å	θ = 2.0–25.3°
b = 18.130 (5) Å	µ = 0.51 mm⁻¹
c = 20.211 (6) Å	T = 293 K
β = 93.590 (4)°	Block, pink
V = 2977.2 (14) Å³	0.12 × 0.10 × 0.09 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	5287 independent reflections
Radiation source: fine-focus sealed tube	4036 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ϕ and ω scans	θ_max = 25.3°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −9→9
T_min = 0.941, T_max = 0.955	k = −21→17
14576 measured reflections	l = −22→24

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.148	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0796P)² + 1.8727P] where P = (F_o² + 2F_c²)/3
5287 reflections	(Δ/σ)_max = 0.001
416 parameters	Δρ_max = 0.93 e Å⁻³
16 restraints	Δρ_min = −0.65 e Å⁻³

Crystal data top

[Mn(C₁₂H₁₆NO₅)₂]·2CH₄O·0.5H₂O	V = 2977.2 (14) Å³
M_r = 636.55	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.141 (2) Å	µ = 0.51 mm⁻¹
b = 18.130 (5) Å	T = 293 K
c = 20.211 (6) Å	0.12 × 0.10 × 0.09 mm
β = 93.590 (4)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	5287 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	4036 reflections with I > 2σ(I)
T_min = 0.941, T_max = 0.955	R_int = 0.031
14576 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	16 restraints
wR(F²) = 0.148	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.93 e Å⁻³
5287 reflections	Δρ_min = −0.65 e Å⁻³
416 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	Occ. (<1)
C1	0.8762 (6)	0.5053 (3)	0.3266 (3)	0.0813 (14)
H1A	0.9812	0.5090	0.3509	0.122*
H1B	0.8876	0.5190	0.2813	0.122*
H1C	0.8368	0.4555	0.3285	0.122*
C2	0.6105 (4)	0.56122 (19)	0.32411 (18)	0.0476 (8)
C3	0.5514 (5)	0.5215 (2)	0.26979 (19)	0.0574 (10)
H3A	0.6184	0.4870	0.2506	0.069*
C4	0.3910 (6)	0.5330 (2)	0.24340 (18)	0.0604 (10)
H4A	0.3507	0.5059	0.2068	0.072*
C5	0.2934 (5)	0.5839 (2)	0.27131 (17)	0.0521 (9)
H5A	0.1873	0.5919	0.2530	0.062*
C6	0.3507 (4)	0.62479 (18)	0.32757 (16)	0.0440 (8)
C7	0.5118 (4)	0.61434 (18)	0.35482 (16)	0.0430 (8)
C8	0.2333 (4)	0.67685 (19)	0.35280 (17)	0.0450 (8)
H8A	0.1325	0.6813	0.3288	0.054*
C9	0.1240 (4)	0.76952 (19)	0.42168 (17)	0.0447 (8)
C10	0.1292 (4)	0.7749 (2)	0.49750 (18)	0.0524 (9)
H10A	0.0662	0.8172	0.5106	0.063*
H10B	0.0813	0.7309	0.5157	0.063*
C11	−0.0517 (4)	0.7489 (2)	0.3971 (2)	0.0596 (10)
H11A	−0.1283	0.7852	0.4124	0.071*
H11B	−0.0608	0.7486	0.3490	0.071*
C12	0.1665 (5)	0.8444 (2)	0.39232 (19)	0.0563 (9)
H12B	0.0816	0.8796	0.4021	0.068*
H12C	0.2694	0.8617	0.4137	0.068*
C13	0.5914 (9)	1.0165 (3)	0.3854 (3)	0.1014 (18)
H13A	0.5234	1.0219	0.3452	0.152*
H13B	0.7017	1.0315	0.3780	0.152*
H13C	0.5488	1.0467	0.4194	0.152*
C14	0.6726 (6)	0.9237 (2)	0.46473 (19)	0.0594 (10)
C15	0.7689 (7)	0.9712 (2)	0.5036 (2)	0.0746 (13)
H15A	0.7847	1.0194	0.4894	0.090*
C16	0.8427 (6)	0.9479 (2)	0.5637 (2)	0.0721 (12)
H16A	0.9086	0.9800	0.5895	0.087*
C17	0.8178 (5)	0.8778 (2)	0.58459 (19)	0.0547 (9)
H17A	0.8657	0.8629	0.6254	0.066*
C18	0.7211 (4)	0.82661 (19)	0.54598 (17)	0.0445 (8)
C19	0.6493 (4)	0.84878 (19)	0.48343 (16)	0.0428 (8)
C20	0.7043 (4)	0.75505 (19)	0.57352 (17)	0.0441 (8)
H20A	0.7661	0.7456	0.6129	0.053*
C21	0.6069 (5)	0.63052 (19)	0.5864 (2)	0.0567 (10)
C22	0.4262 (5)	0.6059 (2)	0.5794 (2)	0.0630 (11)
H22A	0.4184	0.5544	0.5918	0.076*
H22B	0.3624	0.6346	0.6090	0.076*
C23	0.6610 (6)	0.6332 (3)	0.6597 (2)	0.0782 (14)
H23A	0.6497	0.5844	0.6786	0.094*
H23B	0.7764	0.6468	0.6646	0.094*
C24	0.7115 (19)	0.5685 (9)	0.5636 (8)	0.076 (4)	0.50
H24A	0.8226	0.5871	0.5609	0.092*	0.50
H24B	0.7156	0.5308	0.5977	0.092*	0.50
O12	0.6698 (8)	0.5379 (3)	0.5091 (3)	0.0742 (17)	0.50
H12	0.6435	0.5701	0.4797	0.111*	0.50
C24A	0.7240 (16)	0.5822 (9)	0.5488 (10)	0.076 (4)	0.50
H24C	0.7127	0.5329	0.5666	0.092*	0.50
H24D	0.6770	0.5803	0.5035	0.092*	0.50
O12A	0.8824 (6)	0.5918 (3)	0.5439 (3)	0.0722 (16)	0.50
H12A	0.8899	0.6168	0.5087	0.108*	0.50
C25	0.5935 (11)	0.8441 (6)	0.2719 (4)	0.169 (4)
H25A	0.5563	0.8942	0.2672	0.254*
H25B	0.5871	0.8205	0.2293	0.254*
H25C	0.7054	0.8436	0.2900	0.254*
C26	0.2701 (11)	0.8216 (4)	0.7004 (3)	0.131 (3)
H26A	0.3613	0.8342	0.7307	0.197*
H26B	0.1866	0.7976	0.7241	0.197*
H26C	0.2256	0.8656	0.6799	0.197*
Mn1	0.45435 (5)	0.71273 (2)	0.46924 (2)	0.02874 (16)
N1	0.2550 (3)	0.71681 (14)	0.40435 (14)	0.0407 (6)
N2	0.6132 (3)	0.70187 (14)	0.55018 (14)	0.0433 (7)
O1	0.7639 (3)	0.55283 (16)	0.35476 (15)	0.0694 (8)
O2	0.5780 (3)	0.65014 (15)	0.40653 (13)	0.0586 (7)
O3	0.5054 (6)	0.8104 (4)	0.3093 (2)	0.159 (2)
H3	0.545 (8)	0.814 (5)	0.3492 (7)	0.239*
O4	0.2975 (3)	0.78214 (14)	0.52223 (12)	0.0496 (6)
H4	0.297 (6)	0.782 (2)	0.5650 (6)	0.074*
O5	−0.0915 (3)	0.67810 (19)	0.42156 (19)	0.0826 (10)
H5	−0.193 (2)	0.668 (3)	0.414 (3)	0.124*
O6	0.1812 (4)	0.84266 (19)	0.32360 (14)	0.0779 (9)
H6	0.279 (2)	0.829 (3)	0.316 (3)	0.117*
O7	0.5916 (5)	0.94260 (17)	0.40552 (15)	0.0847 (10)
O8	0.5665 (3)	0.80546 (13)	0.44233 (11)	0.0475 (6)
O9	0.3196 (7)	0.7771 (3)	0.65421 (19)	0.145 (2)
H9	0.383 (6)	0.7408 (19)	0.664 (5)	0.218*
O10	0.3606 (3)	0.61528 (15)	0.51303 (15)	0.0656 (8)
H10	0.294 (5)	0.590 (2)	0.488 (2)	0.098*
O11	0.5671 (5)	0.6847 (2)	0.69558 (16)	0.0911 (10)
H11	0.591 (8)	0.679 (4)	0.7369 (9)	0.137*
O1W	0.0648 (7)	0.5679 (4)	0.4852 (4)	0.0806 (18)	0.50
H1W	0.0147	0.6032	0.4650	0.121*	0.50
H2W	0.0795	0.5224	0.4770	0.121*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.068 (3)	0.080 (3)	0.097 (4)	0.026 (2)	0.023 (3)	−0.006 (3)
C2	0.048 (2)	0.0451 (19)	0.050 (2)	−0.0014 (16)	0.0098 (15)	−0.0001 (16)
C3	0.078 (3)	0.046 (2)	0.049 (2)	0.0068 (19)	0.0133 (19)	−0.0072 (16)
C4	0.090 (3)	0.052 (2)	0.038 (2)	0.002 (2)	−0.0006 (19)	−0.0120 (16)
C5	0.064 (2)	0.051 (2)	0.0411 (19)	−0.0031 (17)	−0.0026 (16)	−0.0061 (16)
C6	0.0481 (19)	0.0430 (18)	0.0411 (18)	−0.0053 (15)	0.0042 (14)	−0.0057 (14)
C7	0.0434 (18)	0.0434 (18)	0.0429 (18)	−0.0056 (14)	0.0078 (14)	−0.0078 (14)
C8	0.0393 (18)	0.050 (2)	0.0450 (19)	−0.0023 (15)	−0.0040 (14)	−0.0103 (16)
C9	0.0371 (17)	0.0474 (19)	0.049 (2)	0.0034 (14)	−0.0014 (14)	−0.0109 (15)
C10	0.0397 (18)	0.065 (2)	0.053 (2)	0.0014 (16)	0.0040 (15)	−0.0099 (17)
C11	0.0356 (19)	0.071 (3)	0.072 (3)	0.0055 (18)	−0.0029 (17)	−0.018 (2)
C12	0.062 (2)	0.049 (2)	0.056 (2)	0.0033 (18)	−0.0075 (18)	−0.0038 (17)
C13	0.143 (5)	0.072 (3)	0.091 (4)	0.009 (3)	0.019 (4)	0.032 (3)
C14	0.082 (3)	0.049 (2)	0.048 (2)	−0.010 (2)	0.0109 (19)	0.0011 (17)
C15	0.115 (4)	0.047 (2)	0.063 (3)	−0.026 (2)	0.009 (3)	−0.0032 (19)
C16	0.096 (3)	0.055 (2)	0.065 (3)	−0.032 (2)	0.002 (2)	−0.018 (2)
C17	0.063 (2)	0.053 (2)	0.048 (2)	−0.0133 (18)	−0.0015 (17)	−0.0143 (17)
C18	0.0418 (18)	0.047 (2)	0.0447 (19)	−0.0047 (15)	0.0031 (14)	−0.0075 (15)
C19	0.0405 (17)	0.0482 (19)	0.0404 (18)	−0.0071 (15)	0.0072 (14)	−0.0087 (15)
C20	0.0417 (18)	0.0465 (19)	0.0434 (18)	−0.0017 (15)	−0.0040 (14)	−0.0038 (15)
C21	0.053 (2)	0.0377 (19)	0.078 (3)	−0.0042 (16)	−0.0116 (19)	0.0085 (18)
C22	0.058 (2)	0.053 (2)	0.078 (3)	−0.0117 (19)	−0.007 (2)	0.013 (2)
C23	0.075 (3)	0.065 (3)	0.091 (3)	−0.010 (2)	−0.026 (3)	0.034 (3)
C24	0.055 (3)	0.036 (5)	0.140 (8)	−0.009 (3)	0.016 (4)	0.009 (6)
O12	0.086 (4)	0.059 (4)	0.077 (4)	0.007 (3)	0.000 (3)	−0.006 (3)
C24A	0.055 (3)	0.036 (5)	0.140 (8)	−0.009 (3)	0.016 (4)	0.009 (6)
O12A	0.053 (3)	0.066 (4)	0.096 (5)	0.003 (3)	−0.010 (3)	0.018 (3)
C25	0.160 (8)	0.275 (12)	0.074 (4)	−0.007 (8)	0.019 (5)	0.042 (6)
C26	0.208 (9)	0.096 (5)	0.090 (4)	0.016 (5)	0.006 (5)	0.001 (4)
Mn1	0.0227 (2)	0.0306 (3)	0.0325 (3)	−0.00272 (17)	−0.00254 (16)	−0.00772 (18)
N1	0.0329 (14)	0.0443 (15)	0.0449 (16)	−0.0037 (11)	0.0017 (11)	−0.0078 (12)
N2	0.0392 (15)	0.0403 (15)	0.0499 (16)	−0.0038 (12)	−0.0022 (12)	−0.0013 (12)
O1	0.0516 (16)	0.0741 (19)	0.083 (2)	0.0111 (14)	0.0072 (14)	−0.0217 (15)
O2	0.0378 (13)	0.0666 (16)	0.0705 (17)	−0.0002 (12)	−0.0023 (12)	−0.0337 (14)
O3	0.114 (3)	0.299 (7)	0.064 (3)	−0.080 (4)	−0.003 (2)	0.000 (4)
O4	0.0462 (13)	0.0615 (15)	0.0408 (13)	0.0030 (11)	−0.0002 (11)	−0.0082 (12)
O5	0.0400 (15)	0.088 (2)	0.119 (3)	−0.0172 (16)	−0.0023 (16)	−0.007 (2)
O6	0.089 (2)	0.092 (2)	0.0502 (17)	−0.0103 (19)	−0.0159 (16)	0.0114 (15)
O7	0.128 (3)	0.0641 (19)	0.0599 (19)	−0.0113 (19)	−0.0078 (18)	0.0153 (15)
O8	0.0468 (13)	0.0554 (14)	0.0400 (13)	−0.0114 (11)	0.0000 (10)	−0.0050 (10)
O9	0.159 (4)	0.228 (6)	0.047 (2)	0.108 (4)	−0.002 (2)	−0.008 (3)
O10	0.0547 (16)	0.0536 (17)	0.085 (2)	−0.0118 (13)	−0.0213 (14)	0.0063 (14)
O11	0.098 (3)	0.118 (3)	0.0554 (19)	0.015 (2)	−0.0102 (18)	0.020 (2)
O1W	0.050 (3)	0.067 (4)	0.123 (5)	−0.010 (3)	0.000 (3)	−0.010 (4)

Geometric parameters (Å, º) top

C1—O1	1.402 (5)	C19—O8	1.300 (4)
C1—H1A	0.960	C20—N2	1.288 (4)
C1—H1B	0.960	C20—H20A	0.930
C1—H1C	0.960	C21—N2	1.488 (4)
C2—O1	1.367 (5)	C21—C24	1.500 (10)
C2—C3	1.374 (5)	C21—C23	1.521 (6)
C2—C7	1.422 (5)	C21—C24A	1.531 (9)
C3—C4	1.395 (6)	C21—C22	1.535 (5)
C3—H3A	0.930	C22—O10	1.422 (5)
C4—C5	1.363 (5)	C22—H22A	0.970
C4—H4A	0.930	C22—H22B	0.970
C5—C6	1.412 (5)	C23—O11	1.432 (7)
C5—H5A	0.930	C23—H23A	0.970
C6—C7	1.403 (5)	C23—H23B	0.970
C6—C8	1.458 (5)	C24—O12	1.261 (13)
C7—O2	1.316 (4)	C24—H24A	0.970
C8—N1	1.272 (4)	C24—H24B	0.970
C8—H8A	0.930	O12—H12	0.850
C9—N1	1.490 (4)	C24A—O12A	1.311 (12)
C9—C12	1.530 (5)	C24A—H24C	0.970
C9—C11	1.531 (5)	C24A—H24D	0.970
C9—C10	1.533 (5)	O12A—H12A	0.850
C10—O4	1.435 (4)	C25—O3	1.234 (8)
C10—H10A	0.970	C25—H25A	0.960
C10—H10B	0.970	C25—H25B	0.960
C11—O5	1.421 (5)	C25—H25C	0.960
C11—H11A	0.970	C26—O9	1.316 (7)
C11—H11B	0.970	C26—H26A	0.960
C12—O6	1.402 (5)	C26—H26B	0.960
C12—H12B	0.970	C26—H26C	0.960
C12—H12C	0.970	Mn1—O8	2.005 (2)
C13—O7	1.400 (5)	Mn1—O2	2.017 (2)
C13—H13A	0.960	Mn1—N1	2.023 (3)
C13—H13B	0.960	Mn1—N2	2.030 (3)
C13—H13C	0.960	Mn1—O4	2.129 (2)
C14—O7	1.373 (5)	Mn1—O10	2.138 (3)
C14—C15	1.377 (6)	O3—H3	0.86 (1)
C14—C19	1.426 (5)	O4—H4	0.87 (1)
C15—C16	1.388 (6)	O5—H5	0.85 (1)
C15—H15A	0.930	O6—H6	0.86 (1)
C16—C17	1.358 (6)	O9—H9	0.85 (1)
C16—H16A	0.930	O10—H10	0.85 (1)
C17—C18	1.419 (5)	O11—H11	0.85 (1)
C17—H17A	0.930	O1W—H1W	0.850
C18—C19	1.417 (5)	O1W—H2W	0.850
C18—C20	1.422 (5)

O1—C1—H1A	109.5	N2—C21—C24A	102.2 (8)
O1—C1—H1B	109.5	C23—C21—C24A	110.5 (9)
H1A—C1—H1B	109.5	N2—C21—C22	105.7 (3)
O1—C1—H1C	109.5	C24—C21—C22	108.2 (7)
H1A—C1—H1C	109.5	C23—C21—C22	108.5 (4)
H1B—C1—H1C	109.5	C24A—C21—C22	114.2 (7)
O1—C2—C3	124.6 (3)	O10—C22—C21	110.7 (3)
O1—C2—C7	113.8 (3)	O10—C22—H22A	109.5
C3—C2—C7	121.6 (3)	C21—C22—H22A	109.5
C2—C3—C4	120.0 (3)	O10—C22—H22B	109.5
C2—C3—H3A	120.0	C21—C22—H22B	109.5
C4—C3—H3A	120.0	H22A—C22—H22B	108.1
C5—C4—C3	119.9 (3)	O11—C23—C21	112.5 (3)
C5—C4—H4A	120.0	O11—C23—H23A	109.1
C3—C4—H4A	120.0	C21—C23—H23A	109.1
C4—C5—C6	121.1 (4)	O11—C23—H23B	109.1
C4—C5—H5A	119.4	C21—C23—H23B	109.1
C6—C5—H5A	119.4	H23A—C23—H23B	107.8
C7—C6—C5	119.9 (3)	O12—C24—C21	118.1 (12)
C7—C6—C8	124.6 (3)	O12—C24—H24A	107.8
C5—C6—C8	115.5 (3)	C21—C24—H24A	107.8
O2—C7—C6	124.8 (3)	O12—C24—H24B	107.8
O2—C7—C2	117.8 (3)	C21—C24—H24B	107.8
C6—C7—C2	117.4 (3)	H24A—C24—H24B	107.1
N1—C8—C6	126.5 (3)	C24—O12—H12	110.5
N1—C8—H8A	116.8	O12A—C24A—C21	127.4 (11)
C6—C8—H8A	116.8	O12A—C24A—H24C	105.5
N1—C9—C12	107.2 (3)	C21—C24A—H24C	105.5
N1—C9—C11	115.8 (3)	O12A—C24A—H24D	105.5
C12—C9—C11	108.7 (3)	C21—C24A—H24D	105.5
N1—C9—C10	107.5 (3)	H24C—C24A—H24D	106.0
C12—C9—C10	109.8 (3)	C24A—O12A—H12A	104.8
C11—C9—C10	107.8 (3)	O3—C25—H25A	109.7
O4—C10—C9	108.7 (3)	O3—C25—H25B	109.1
O4—C10—H10A	110.0	H25A—C25—H25B	109.5
C9—C10—H10A	110.0	O3—C25—H25C	109.7
O4—C10—H10B	110.0	H25A—C25—H25C	109.5
C9—C10—H10B	110.0	H25B—C25—H25C	109.5
H10A—C10—H10B	108.3	O9—C26—H26A	109.8
O5—C11—C9	109.7 (3)	O9—C26—H26B	109.5
O5—C11—H11A	109.7	H26A—C26—H26B	109.5
C9—C11—H11A	109.7	O9—C26—H26C	109.1
O5—C11—H11B	109.7	H26A—C26—H26C	109.5
C9—C11—H11B	109.7	H26B—C26—H26C	109.5
H11A—C11—H11B	108.2	O8—Mn1—O2	92.73 (11)
O6—C12—C9	113.5 (3)	O8—Mn1—N1	98.86 (10)
O6—C12—H12B	108.9	O2—Mn1—N1	91.42 (10)
C9—C12—H12B	108.9	O8—Mn1—N2	91.25 (10)
O6—C12—H12C	108.9	O2—Mn1—N2	97.70 (11)
C9—C12—H12C	108.9	N1—Mn1—N2	166.06 (11)
H12B—C12—H12C	107.7	O8—Mn1—O4	86.48 (10)
O7—C13—H13A	109.5	O2—Mn1—O4	170.91 (10)
O7—C13—H13B	109.5	N1—Mn1—O4	79.77 (10)
H13A—C13—H13B	109.5	N2—Mn1—O4	91.37 (11)
O7—C13—H13C	109.5	O8—Mn1—O10	170.32 (10)
H13A—C13—H13C	109.5	O2—Mn1—O10	90.02 (12)
H13B—C13—H13C	109.5	N1—Mn1—O10	90.34 (10)
O7—C14—C15	124.5 (4)	N2—Mn1—O10	79.18 (10)
O7—C14—C19	113.8 (3)	O4—Mn1—O10	92.25 (11)
C15—C14—C19	121.7 (4)	C8—N1—C9	119.5 (3)
C14—C15—C16	120.6 (4)	C8—N1—Mn1	125.1 (2)
C14—C15—H15A	119.7	C9—N1—Mn1	115.3 (2)
C16—C15—H15A	119.7	C20—N2—C21	120.5 (3)
C17—C16—C15	119.5 (4)	C20—N2—Mn1	123.1 (2)
C17—C16—H16A	120.2	C21—N2—Mn1	116.1 (2)
C15—C16—H16A	120.2	C2—O1—C1	119.0 (3)
C16—C17—C18	121.9 (4)	C7—O2—Mn1	125.5 (2)
C16—C17—H17A	119.0	C25—O3—H3	110 (3)
C18—C17—H17A	119.0	C10—O4—Mn1	111.1 (2)
C19—C18—C17	119.3 (3)	C10—O4—H4	107 (3)
C19—C18—C20	124.3 (3)	Mn1—O4—H4	123 (3)
C17—C18—C20	116.4 (3)	C11—O5—H5	112 (4)
O8—C19—C18	124.5 (3)	C12—O6—H6	109 (4)
O8—C19—C14	118.6 (3)	C14—O7—C13	118.9 (4)
C18—C19—C14	116.9 (3)	C19—O8—Mn1	124.0 (2)
N2—C20—C18	127.4 (3)	C26—O9—H9	121 (7)
N2—C20—H20A	116.3	C22—O10—Mn1	111.5 (2)
C18—C20—H20A	116.3	C22—O10—H10	133 (4)
N2—C21—C24	117.6 (8)	Mn1—O10—H10	115 (4)
N2—C21—C23	115.8 (3)	C23—O11—H11	109 (5)
C24—C21—C23	100.8 (7)	H1W—O1W—H2W	135.0

O1—C2—C3—C4	178.2 (4)	C12—C9—N1—Mn1	87.7 (3)
C7—C2—C3—C4	0.1 (6)	C11—C9—N1—Mn1	−150.8 (3)
C2—C3—C4—C5	0.4 (6)	C10—C9—N1—Mn1	−30.2 (3)
C3—C4—C5—C6	−1.1 (6)	O8—Mn1—N1—C8	105.0 (3)
C4—C5—C6—C7	1.3 (6)	O2—Mn1—N1—C8	12.0 (3)
C4—C5—C6—C8	−179.4 (3)	N2—Mn1—N1—C8	−119.0 (5)
C5—C6—C7—O2	179.1 (3)	O4—Mn1—N1—C8	−170.3 (3)
C8—C6—C7—O2	−0.1 (6)	O10—Mn1—N1—C8	−78.0 (3)
C5—C6—C7—C2	−0.8 (5)	O8—Mn1—N1—C9	−77.4 (2)
C8—C6—C7—C2	180.0 (3)	O2—Mn1—N1—C9	−170.4 (2)
O1—C2—C7—O2	1.9 (5)	N2—Mn1—N1—C9	58.6 (5)
C3—C2—C7—O2	−179.8 (3)	O4—Mn1—N1—C9	7.4 (2)
O1—C2—C7—C6	−178.2 (3)	O10—Mn1—N1—C9	99.6 (2)
C3—C2—C7—C6	0.1 (5)	C18—C20—N2—C21	−178.5 (3)
C7—C6—C8—N1	−4.2 (6)	C18—C20—N2—Mn1	−5.1 (5)
C5—C6—C8—N1	176.6 (3)	C24—C21—N2—C20	−98.6 (8)
N1—C9—C10—O4	45.2 (4)	C23—C21—N2—C20	20.6 (5)
C12—C9—C10—O4	−71.1 (4)	C24A—C21—N2—C20	−99.6 (8)
C11—C9—C10—O4	170.7 (3)	C22—C21—N2—C20	140.6 (3)
N1—C9—C11—O5	56.9 (4)	C24—C21—N2—Mn1	87.6 (8)
C12—C9—C11—O5	177.6 (3)	C23—C21—N2—Mn1	−153.2 (3)
C10—C9—C11—O5	−63.4 (4)	C24A—C21—N2—Mn1	86.6 (7)
N1—C9—C12—O6	57.4 (4)	C22—C21—N2—Mn1	−33.2 (4)
C11—C9—C12—O6	−68.5 (4)	O8—Mn1—N2—C20	16.8 (3)
C10—C9—C12—O6	173.8 (3)	O2—Mn1—N2—C20	109.7 (3)
O7—C14—C15—C16	178.2 (5)	N1—Mn1—N2—C20	−119.9 (4)
C19—C14—C15—C16	−2.1 (7)	O4—Mn1—N2—C20	−69.7 (3)
C14—C15—C16—C17	−0.7 (8)	O10—Mn1—N2—C20	−161.8 (3)
C15—C16—C17—C18	1.4 (7)	O8—Mn1—N2—C21	−169.6 (3)
C16—C17—C18—C19	0.6 (6)	O2—Mn1—N2—C21	−76.7 (3)
C16—C17—C18—C20	−179.8 (4)	N1—Mn1—N2—C21	53.8 (6)
C17—C18—C19—O8	175.9 (3)	O4—Mn1—N2—C21	103.9 (3)
C20—C18—C19—O8	−3.6 (5)	O10—Mn1—N2—C21	11.9 (3)
C17—C18—C19—C14	−3.2 (5)	C3—C2—O1—C1	5.7 (6)
C20—C18—C19—C14	177.3 (3)	C7—C2—O1—C1	−176.1 (4)
O7—C14—C19—O8	4.6 (5)	C6—C7—O2—Mn1	12.7 (5)
C15—C14—C19—O8	−175.2 (4)	C2—C7—O2—Mn1	−167.4 (2)
O7—C14—C19—C18	−176.3 (3)	O8—Mn1—O2—C7	−114.8 (3)
C15—C14—C19—C18	4.0 (6)	N1—Mn1—O2—C7	−15.9 (3)
C19—C18—C20—N2	−6.2 (6)	N2—Mn1—O2—C7	153.6 (3)
C17—C18—C20—N2	174.2 (3)	O10—Mn1—O2—C7	74.5 (3)
N2—C21—C22—O10	44.7 (4)	C9—C10—O4—Mn1	−40.2 (3)
C24—C21—C22—O10	−82.1 (8)	O8—Mn1—O4—C10	118.6 (2)
C23—C21—C22—O10	169.4 (3)	N1—Mn1—O4—C10	19.0 (2)
C24A—C21—C22—O10	−66.9 (10)	N2—Mn1—O4—C10	−150.2 (2)
N2—C21—C23—O11	57.4 (5)	O10—Mn1—O4—C10	−71.0 (2)
C24—C21—C23—O11	−174.6 (8)	C15—C14—O7—C13	−6.8 (7)
C24A—C21—C23—O11	173.0 (7)	C19—C14—O7—C13	173.5 (4)
C22—C21—C23—O11	−61.1 (4)	C18—C19—O8—Mn1	23.1 (5)
N2—C21—C24—O12	−71.5 (16)	C14—C19—O8—Mn1	−157.7 (3)
C23—C21—C24—O12	161.8 (13)	O2—Mn1—O8—C19	−123.4 (3)
C22—C21—C24—O12	48.1 (16)	N1—Mn1—O8—C19	144.7 (3)
N2—C21—C24A—O12A	64 (2)	N2—Mn1—O8—C19	−25.6 (3)
C23—C21—C24A—O12A	−60 (2)	O4—Mn1—O8—C19	65.7 (3)
C22—C21—C24A—O12A	177.2 (15)	C21—C22—O10—Mn1	−36.8 (4)
C6—C8—N1—C9	177.6 (3)	O2—Mn1—O10—C22	112.2 (3)
C6—C8—N1—Mn1	−4.9 (5)	N1—Mn1—O10—C22	−156.3 (3)
C12—C9—N1—C8	−94.5 (4)	N2—Mn1—O10—C22	14.4 (3)
C11—C9—N1—C8	26.9 (5)	O4—Mn1—O10—C22	−76.6 (3)
C10—C9—N1—C8	147.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O8	0.86 (1)	1.89 (1)	2.706 (5)	160 (4)
O4—H4···O9	0.86 (1)	1.80 (1)	2.664 (5)	174 (5)
O5—H5···O2ⁱ	0.85 (1)	1.89 (1)	2.736 (4)	173 (6)
O6—H6···O3	0.86 (1)	1.89 (1)	2.737 (7)	172 (6)
O9—H9···O11	0.85 (1)	1.89 (1)	2.712 (5)	162 (4)
O10—H10···O1W	0.86 (1)	1.90 (4)	2.585 (6)	136 (5)
O11—H11···O6ⁱⁱ	0.85 (1)	1.90 (2)	2.739 (4)	169 (7)
O12—H12···O2	0.85	2.12	2.967 (7)	180
O12A—H12A···O5ⁱⁱⁱ	0.85	2.10	2.946 (7)	180
O1W—H1W···O5	0.85	1.81	2.657 (8)	180
O1W—H2W···O12A^iv	0.85	2.14	2.990 (9)	180

Symmetry codes: (i) x−1, y, z; (ii) x+1/2, −y+3/2, z+1/2; (iii) x+1, y, z; (iv) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Mn(C₁₂H₁₆NO₅)₂]·2CH₄O·0.5H₂O
M_r	636.55
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	8.141 (2), 18.130 (5), 20.211 (6)
β (°)	93.590 (4)
V (Å³)	2977.2 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.51
Crystal size (mm)	0.12 × 0.10 × 0.09

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.941, 0.955
No. of measured, independent and observed [I > 2σ(I)] reflections	14576, 5287, 4036
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.148, 1.05
No. of reflections	5287
No. of parameters	416
No. of restraints	16
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.93, −0.65

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), 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
O3—H3···O8	0.86 (1)	1.885 (10)	2.706 (5)	160 (4)
O4—H4···O9	0.86 (1)	1.802 (12)	2.664 (5)	174 (5)
O5—H5···O2ⁱ	0.85 (1)	1.886 (13)	2.736 (4)	173 (6)
O6—H6···O3	0.86 (1)	1.886 (9)	2.737 (7)	172 (6)
O9—H9···O11	0.85 (1)	1.888 (10)	2.712 (5)	162 (4)
O10—H10···O1W	0.86 (1)	1.90 (4)	2.585 (6)	136 (5)
O11—H11···O6ⁱⁱ	0.85 (1)	1.897 (18)	2.739 (4)	169 (7)
O12—H12···O2	0.85	2.12	2.967 (7)	180.0
O12A—H12A···O5ⁱⁱⁱ	0.85	2.10	2.946 (7)	179.8
O1W—H1W···O5	0.85	1.81	2.657 (8)	179.6
O1W—H2W···O12A^iv	0.85	2.14	2.990 (9)	179.6

Symmetry codes: (i) x−1, y, z; (ii) x+1/2, −y+3/2, z+1/2; (iii) x+1, y, z; (iv) −x+1, −y+1, −z+1.

Acknowledgements

Financial support from the Natural Science Foundation of China (grant Nos. 20171028 and 20325105), the National Ministry of Science and Technology of China (grant No. 2001CB6105-07), and the Ministry of Education of China, Shandong University, is gratefully acknowledged.

References

Bruker (2001). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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