catena-Poly­[[[(1,10-phenanthroline-κ²N,N′)­manganese(II)]-μ-L-tartrato-κ⁴O¹,O²:O³,O⁴] hexahydrate]

The title compound, {[Mn(C₄H₄O₆)(C₁₂H₈N₂)]·6H₂O}_n, has a linear chain structure containing monomeric [Mn(C₄H₄O₆)(C₁₂H₈N₂)] repeat units. Each manganese ion is six-coordinate, with the two phenanthroline N atoms [Mn—N = 2.229 (2) and 2.235 (2) Å] and four O atoms from two tartrate anions [Mn—O_COO = 2.1252 (19) and 2.1310 (19) Å, and Mn—O_OH = 2.2404 (19) and 2.2424 (19) Å] forming a seriously distorted octahedral coordination environment. Six water mol­ecules exist outside every repeat unit as solvate mol­ecules. Extensive hydrogen-bonding interactions and π–π stacking of the phenanthroline moieties exist between the chains.

S1. Comment

The structures and properties of polymanganese complexes are currently of great interest on account of their promising applications in diverse areas of technology (Aubin et al., 1997; Manson et al., 1998) and model complexes for the study of the photosynthetic oxygen-evolving complexes (OEC) of photosystem II in green plants (Wieghardt, 1989). L-Tartaric acid, as a polydentate ligand, has been extensively studied in transition metal compounds. The coordination modes of L-tartrate in these reported compounds are shown as (a) and (b) in the Scheme below, in which mode (a)is seldom found. However, only two manganese–L-tartrate compounds have been reported (Ruiz-Perez et al., 1996; Soylu, 1983) up to now. We report here the synthesis and crystal structure of the first mixed-ligand Mn/L-tartrate complex, viz. {[Mn(C₄H₄O₆)(phen)]·6H₂O}_n, (I)), which has a polymeric linear chain structure. A similar copper complex has been reported (McCann et al., 1997).

The crystal structure of (I) consists of an infinite {[Mn(C₄H₄O₆)(C₁₂H₈N₂)]·6H₂O}_n chain and its asymmetric unit is shown in Fig. 1. The Mn ion locates in a seriously distorted octahedral environment with three trans angles ranging from 155.82 (7) to 157.17 (9)°. The Mn ion is coordinated by two phenanthroline N atoms [Mn—N = 2.229 (2) and 2.235 (2) Å] and four O atoms [Mn—O = 2.1252 (19)–2.2424 (19) Å] from opposite ends of two tartrate ligands, which are symmetry-related to form three chelating rings (symmetry code: x − 1, y, z). A tartrate anion links two neighboring Mn ions by a single ligand bridge to form two chelating rings [form (b) in Scheme]. Thus, manganese ions are bridged by tetradentate L-tartrate forming a linear chain along the a axis of the cell (Fig. 2). Six water molecules exist outside every repeat unit as solvate molecules.

The distortion of the coordination geometry is caused mainly by the three chelating five-membered rings. Bond lengths and angles for the L-tartrate ligand are usual and do not deviate significantly from those in other reported L-tartrate coordination compounds (Ortega et al., 1982; Ruiz-Perez et al., 1996). The average Mn—O_OH distance [2.2414 (19) Å] is longer than that of Mn—O_COO [2.1281 (19) Å], which indicated that the hydroxyl groups of the L-tartrate ligand do not deprotonate, analogous to the reaction of L-tartrate ligand with other metal ions such as Cu^II, Ni^II, Zn^II, Co^II and Cd^II. According to charge-balance requirements, the oxidation state of Mn is +2. In addition, the room-temperature magnetic moments of a powdered sample of (I) (5.89 BM) were in the range expected for manganese II) complexes where there is no significant exchange interaction between metal centres.

Extensive hydrogen-bonding interactions are observed to correlate these chains. The packing diagram of the complex along the a axis is presented in Fig. 3, showing three types of hydrogen-bonding interactions as follows: (i) O_coord to water [2.854 (3) and 2.889 (3) Å], (ii) O_uncoord to water [2.709 (3)–2.904 (3) Å] and (iii) water to water [2.775 (4)–2.832 (4) Å]. The other detailed hydrogen-bonding data are listed in Table 2. In addition, the phenanthroline groups of each polymeric chain are interwoven between the chains to form a π–π stacking along the a axis, with interplanar distances ranging from 3.22 to 3.35 Å.

S2. Experimental

A mixture of Mn(CH₃COO)₂·4H₂O (0.25 g, 1.02 mmol), phen (2.0 g, 1 mmol), NaOCH₃ (0.11 g, 2 mmol) and L(+)-tartaric acid (0.15 g, 1 mmol) in MeOH/H₂O (16 ml, v/v, 1:1) was sealed in a 25 ml stainless-steel reactor with a Teflon liner. The reaction system was heated at 453 K for 72 h. Slow cooling to room temperature yielded deep-red crystals, which were collected by filtration (yield: 34%). Analysis calculated (%): C 39.12, H 4.92, N 5.70%; found (%): C 39.24, H 4.96, N 5.72.

S3. Refinement

H atoms bonded to C atoms were placed at calculated idealized positions using a riding model (C—H = 0.93 Å for 1,10-phenanthroline and 0.98 Å for L-tartrate). H atoms bonded to O atoms were located in a difference Fourier synthesis and were subsequently refined with restrained O—H distances approximately equal to 0.85 Å.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1994a); data reduction: XPREP in SHELXTL (Siemens, 1994); program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL (Bruker, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).

Figures

	Fig. 1. Part of the structure of {[Mn(C4H4O6)(C12H8N2)]·6H2O}n, showing the bridging mode of the L-tartrate anion and one of the independent structural units with the atom-numbering scheme.
	Fig. 2. Packing diagram of the title compound.

catena-Poly[[[(1,10-phenanthroline-κ²N,N')manganese(II)]-µ-L-tartrato- κ²O¹:O⁴] hexahydrate]

Crystal data

[Mn(C4H4O6)(C12H8N2)]·6H2O	F(000) = 1020
Mr = 491.31	Dx = 1.569 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 146 reflections
a = 6.7093 (9) Å	θ = 1.7–25.1°
b = 15.336 (3) Å	µ = 0.70 mm^−1
c = 20.210 (3) Å	T = 293 K
V = 2079.4 (6) Å^3	Block, deep red
Z = 4	0.36 × 0.24 × 0.20 mm

Data collection

Siemens SMART CCD diffractometer	3372 independent reflections
Radiation source: fine-focus sealed tube	3183 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
ϕ and ω scans	θmax = 25.1°, θmin = 1.7°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −7→7
Tmin = 0.777, Tmax = 0.869	k = −16→18
6282 measured reflections	l = −24→10

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.028	w = 1/[σ^2(Fo^2) + (0.0341P)^2 + 1.1316P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.074	(Δ/σ)max < 0.001
S = 1.02	Δρmax = 0.19 e Å^−3
3372 reflections	Δρmin = −0.33 e Å^−3
337 parameters	Extinction correction: SHELXTL (Bruker, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
13 restraints	Extinction coefficient: 0.0119 (8)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1242 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.01 (2)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Mn	−0.00979 (6)	0.39805 (2)	0.171244 (17)	0.02953 (12)
N1	−0.0230 (4)	0.42888 (14)	0.06355 (10)	0.0365 (5)
N2	−0.0065 (4)	0.26908 (13)	0.11978 (9)	0.0309 (4)
O1	0.1203 (3)	0.34887 (13)	0.25991 (9)	0.0393 (5)
O2	0.3221 (3)	0.38181 (14)	0.34320 (9)	0.0455 (5)
O3	0.3030 (3)	0.44880 (13)	0.17610 (9)	0.0347 (4)
H3B	0.355 (5)	0.4875 (18)	0.1520 (15)	0.061 (11)*
O4	0.6777 (3)	0.37675 (11)	0.20711 (9)	0.0319 (4)
H4A	0.650 (6)	0.3306 (17)	0.2274 (17)	0.062 (12)*
O5	0.8784 (3)	0.52225 (12)	0.19948 (11)	0.0416 (5)
O6	0.6459 (3)	0.59918 (14)	0.25045 (13)	0.0555 (6)
O7	−0.0165 (4)	0.19440 (15)	0.32786 (11)	0.0524 (5)
H7B	0.048 (5)	0.2368 (18)	0.3119 (17)	0.063 (13)*
H7C	0.039 (7)	0.1459 (18)	0.322 (2)	0.098 (17)*
O8	0.4147 (5)	0.2368 (2)	0.42085 (14)	0.0723 (9)
H8B	0.372 (9)	0.233 (4)	0.4604 (13)	0.12 (2)*
H8C	0.379 (8)	0.279 (3)	0.396 (3)	0.109 (19)*
O9	0.6220 (5)	0.22952 (18)	0.26598 (16)	0.0692 (8)
H9B	0.535 (5)	0.191 (2)	0.2634 (19)	0.071 (12)*
H9C	0.725 (5)	0.210 (3)	0.285 (2)	0.094 (17)*
O10	0.4547 (5)	0.56282 (18)	0.09144 (13)	0.0719 (9)
H10B	0.514 (7)	0.609 (2)	0.103 (2)	0.104 (17)*
H10C	0.424 (7)	0.566 (3)	0.0513 (11)	0.090 (16)*
O11	−0.1806 (6)	0.2555 (2)	0.44580 (14)	0.0717 (8)
H11B	−0.122 (7)	0.225 (3)	0.4159 (19)	0.092 (16)*
H11C	−0.306 (4)	0.256 (5)	0.436 (4)	0.17 (3)*
O12	0.0504 (5)	0.40839 (19)	0.45313 (14)	0.0691 (8)
H12B	−0.027 (8)	0.362 (3)	0.453 (2)	0.102 (17)*
H12C	0.124 (6)	0.398 (3)	0.4199 (16)	0.087 (15)*
C1	−0.0316 (5)	0.5074 (2)	0.03669 (16)	0.0498 (8)
H1A	−0.0379	0.5556	0.0645	0.060*
C2	−0.0315 (5)	0.5210 (2)	−0.03183 (16)	0.0562 (9)
H2A	−0.0384	0.5772	−0.0490	0.067*
C3	−0.0215 (5)	0.4516 (2)	−0.07266 (14)	0.0535 (8)
H3A	−0.0193	0.4599	−0.1182	0.064*
C4	−0.0144 (5)	0.3672 (2)	−0.04666 (12)	0.0427 (7)
C5	−0.0086 (5)	0.2895 (2)	−0.08624 (13)	0.0512 (8)
H5A	−0.0055	0.2944	−0.1321	0.061*
C6	−0.0074 (5)	0.2105 (2)	−0.05858 (14)	0.0492 (7)
H6A	−0.0068	0.1614	−0.0856	0.059*
C7	−0.0071 (5)	0.19955 (18)	0.01218 (12)	0.0386 (6)
C8	−0.0066 (5)	0.11834 (19)	0.04343 (15)	0.0468 (7)
H8A	−0.0085	0.0675	0.0184	0.056*
C9	−0.0034 (5)	0.11388 (18)	0.11094 (15)	0.0465 (7)
H9A	−0.0016	0.0601	0.1322	0.056*
C10	−0.0029 (5)	0.19077 (17)	0.14733 (13)	0.0394 (6)
H10A	0.0001	0.1870	0.1932	0.047*
C11	−0.0102 (5)	0.27405 (17)	0.05233 (11)	0.0310 (5)
C12	−0.0150 (4)	0.35877 (17)	0.02287 (11)	0.0329 (5)
C13	0.2654 (4)	0.38954 (18)	0.28493 (12)	0.0313 (6)
C14	0.3759 (4)	0.45574 (19)	0.24209 (13)	0.0287 (6)
H14A	0.3415	0.5140	0.2584	0.034*
C15	0.6027 (4)	0.44594 (18)	0.24681 (13)	0.0275 (6)
H15A	0.6340	0.4316	0.2929	0.033*
C16	0.7158 (4)	0.52992 (17)	0.22992 (14)	0.0344 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn	0.0285 (2)	0.0348 (2)	0.02522 (18)	0.0001 (2)	0.00010 (19)	−0.00161 (15)
N1	0.0354 (13)	0.0411 (12)	0.0329 (11)	−0.0011 (11)	−0.0014 (11)	0.0057 (9)
N2	0.0298 (11)	0.0365 (11)	0.0263 (9)	0.0028 (12)	0.0004 (11)	0.0004 (8)
O1	0.0364 (12)	0.0505 (12)	0.0309 (9)	−0.0131 (9)	−0.0058 (9)	0.0091 (9)
O2	0.0470 (11)	0.0656 (14)	0.0239 (9)	−0.0087 (11)	−0.0034 (8)	0.0060 (9)
O3	0.0292 (9)	0.0483 (11)	0.0267 (9)	−0.0073 (9)	−0.0028 (8)	0.0088 (9)
O4	0.0308 (10)	0.0271 (10)	0.0377 (10)	−0.0002 (8)	0.0050 (8)	−0.0023 (8)
O5	0.0362 (11)	0.0324 (10)	0.0562 (12)	−0.0045 (8)	0.0125 (10)	−0.0023 (9)
O6	0.0457 (13)	0.0321 (11)	0.0888 (17)	0.0016 (11)	0.0031 (12)	−0.0177 (12)
O7	0.0563 (14)	0.0483 (13)	0.0526 (12)	0.0064 (13)	0.0094 (15)	0.0032 (11)
O8	0.100 (2)	0.0688 (18)	0.0486 (15)	0.0245 (16)	0.0025 (14)	0.0099 (14)
O9	0.0667 (19)	0.0491 (15)	0.092 (2)	−0.0167 (14)	−0.0171 (17)	0.0233 (15)
O10	0.102 (3)	0.0667 (16)	0.0467 (14)	−0.0328 (16)	−0.0071 (15)	0.0170 (12)
O11	0.084 (2)	0.0811 (19)	0.0503 (15)	−0.0186 (18)	0.0110 (15)	−0.0146 (14)
O12	0.084 (2)	0.0581 (16)	0.0650 (16)	−0.0126 (15)	0.0233 (14)	−0.0120 (13)
C1	0.052 (2)	0.0484 (17)	0.0488 (16)	−0.0006 (17)	−0.0007 (16)	0.0109 (14)
C2	0.050 (2)	0.065 (2)	0.0538 (18)	−0.0021 (18)	−0.0019 (17)	0.0293 (16)
C3	0.0414 (18)	0.087 (2)	0.0322 (14)	−0.005 (2)	0.0009 (15)	0.0218 (15)
C4	0.0264 (14)	0.0735 (19)	0.0282 (12)	−0.0033 (16)	0.0002 (14)	0.0063 (13)
C5	0.0344 (16)	0.094 (2)	0.0247 (12)	−0.002 (2)	0.0026 (15)	−0.0061 (14)
C6	0.0330 (15)	0.078 (2)	0.0371 (14)	−0.003 (2)	0.0000 (16)	−0.0260 (15)
C7	0.0247 (13)	0.0527 (15)	0.0384 (13)	0.0006 (16)	0.0002 (15)	−0.0121 (12)
C8	0.0343 (15)	0.0491 (16)	0.0571 (17)	0.0002 (17)	0.0005 (16)	−0.0204 (13)
C9	0.0436 (16)	0.0361 (14)	0.0598 (17)	0.0047 (18)	0.0008 (17)	0.0007 (12)
C10	0.0383 (14)	0.0427 (14)	0.0374 (12)	0.0021 (16)	0.0020 (15)	0.0036 (11)
C11	0.0207 (12)	0.0461 (14)	0.0261 (11)	0.0019 (15)	0.0028 (13)	−0.0038 (10)
C12	0.0222 (13)	0.0506 (15)	0.0260 (11)	−0.0034 (14)	0.0003 (13)	0.0018 (10)
C13	0.0304 (14)	0.0383 (14)	0.0253 (12)	0.0042 (12)	0.0007 (11)	−0.0008 (11)
C14	0.0267 (14)	0.0333 (15)	0.0260 (13)	0.0004 (11)	−0.0014 (11)	−0.0037 (12)
C15	0.0297 (13)	0.0308 (14)	0.0220 (13)	0.0004 (11)	−0.0009 (11)	−0.0031 (11)
C16	0.0353 (16)	0.0307 (14)	0.0371 (14)	0.0010 (12)	−0.0055 (12)	−0.0052 (12)

Geometric parameters (Å, º)

Mn—O5^i	2.1252 (19)	O11—H11C	0.86 (3)
Mn—O1	2.1310 (19)	O12—H12B	0.88 (5)
Mn—N1	2.229 (2)	O12—H12C	0.85 (4)
Mn—N2	2.235 (2)	C1—C2	1.400 (4)
Mn—O3	2.2404 (19)	C1—H1A	0.9300
Mn—O4^i	2.2424 (19)	C2—C3	1.348 (5)
N1—C1	1.322 (4)	C2—H2A	0.9300
N1—C12	1.354 (3)	C3—C4	1.398 (5)
N2—C10	1.324 (3)	C3—H3A	0.9300
N2—C11	1.366 (3)	C4—C12	1.411 (3)
O1—C13	1.262 (3)	C4—C5	1.436 (4)
O2—C13	1.243 (3)	C5—C6	1.335 (5)
O3—C14	1.425 (3)	C5—H5A	0.9300
O3—H3B	0.844 (19)	C6—C7	1.440 (4)
O4—C15	1.422 (3)	C6—H6A	0.9300
O4—Mn^ii	2.2424 (19)	C7—C8	1.396 (4)
O4—H4A	0.838 (19)	C7—C11	1.401 (4)
O5—C16	1.258 (3)	C8—C9	1.366 (4)
O5—Mn^ii	2.1252 (19)	C8—H8A	0.9300
O6—C16	1.233 (3)	C9—C10	1.390 (4)
O7—H7B	0.846 (19)	C9—H9A	0.9300
O7—H7C	0.841 (19)	C10—H10A	0.9300
O8—H8B	0.85 (3)	C11—C12	1.430 (4)
O8—H8C	0.85 (5)	C13—C14	1.526 (4)
O9—H9B	0.832 (19)	C14—C15	1.532 (3)
O9—H9C	0.84 (2)	C14—H14A	0.9800
O10—H10B	0.85 (2)	C15—C16	1.533 (4)
O10—H10C	0.838 (19)	C15—H15A	0.9800
O11—H11B	0.86 (4)
O5^i—Mn—O1	103.65 (8)	C3—C4—C5	124.1 (3)
O5^i—Mn—N1	93.33 (8)	C12—C4—C5	118.6 (3)
O1—Mn—N1	155.84 (9)	C6—C5—C4	121.4 (2)
O5^i—Mn—N2	157.17 (9)	C6—C5—H5A	119.3
O1—Mn—N2	94.25 (8)	C4—C5—H5A	119.3
N1—Mn—N2	74.56 (8)	C5—C6—C7	121.4 (3)
O5^i—Mn—O3	90.44 (8)	C5—C6—H6A	119.3
O1—Mn—O3	72.69 (7)	C7—C6—H6A	119.3
N1—Mn—O3	90.36 (8)	C8—C7—C11	117.7 (2)
N2—Mn—O3	108.58 (8)	C8—C7—C6	123.6 (3)
O5^i—Mn—O4^i	73.36 (7)	C11—C7—C6	118.7 (3)
O1—Mn—O4^i	93.42 (7)	C9—C8—C7	119.8 (2)
N1—Mn—O4^i	108.02 (8)	C9—C8—H8A	120.1
N2—Mn—O4^i	91.76 (8)	C7—C8—H8A	120.1
O3—Mn—O4^i	155.82 (7)	C8—C9—C10	119.1 (3)
C1—N1—C12	118.4 (2)	C8—C9—H9A	120.5
C1—N1—Mn	126.6 (2)	C10—C9—H9A	120.5
C12—N1—Mn	115.00 (16)	N2—C10—C9	123.2 (2)
C10—N2—C11	118.1 (2)	N2—C10—H10A	118.4
C10—N2—Mn	127.40 (16)	C9—C10—H10A	118.4
C11—N2—Mn	114.52 (16)	N2—C11—C7	122.2 (2)
C13—O1—Mn	118.56 (17)	N2—C11—C12	117.8 (2)
C14—O3—Mn	112.86 (15)	C7—C11—C12	120.0 (2)
C14—O3—H3B	110 (3)	N1—C12—C4	122.1 (3)
Mn—O3—H3B	128 (3)	N1—C12—C11	118.0 (2)
C15—O4—Mn^ii	113.86 (15)	C4—C12—C11	119.9 (2)
C15—O4—H4A	106 (3)	O2—C13—O1	124.6 (3)
Mn^ii—O4—H4A	119 (3)	O2—C13—C14	116.9 (2)
C16—O5—Mn^ii	121.42 (17)	O1—C13—C14	118.4 (2)
H7B—O7—H7C	113 (4)	O3—C14—C13	108.4 (2)
H8B—O8—H8C	121 (5)	O3—C14—C15	113.1 (2)
H9B—O9—H9C	110 (4)	C13—C14—C15	112.4 (2)
H10B—O10—H10C	109 (4)	O3—C14—H14A	107.6
H11B—O11—H11C	107 (6)	C13—C14—H14A	107.6
H12B—O12—H12C	101 (4)	C15—C14—H14A	107.6
N1—C1—C2	122.8 (3)	O4—C15—C14	112.9 (2)
N1—C1—H1A	118.6	O4—C15—C16	109.0 (2)
C2—C1—H1A	118.6	C14—C15—C16	113.3 (2)
C3—C2—C1	119.2 (3)	O4—C15—H15A	107.1
C3—C2—H2A	120.4	C14—C15—H15A	107.1
C1—C2—H2A	120.4	C16—C15—H15A	107.1
C2—C3—C4	120.1 (3)	O6—C16—O5	125.1 (3)
C2—C3—H3A	119.9	O6—C16—C15	117.4 (2)
C4—C3—H3A	119.9	O5—C16—C15	117.4 (2)
C3—C4—C12	117.3 (3)
O5^i—Mn—N1—C1	19.4 (3)	C11—N2—C10—C9	−0.2 (5)
O1—Mn—N1—C1	−115.6 (3)	Mn—N2—C10—C9	179.2 (3)
N2—Mn—N1—C1	179.8 (3)	C8—C9—C10—N2	0.4 (5)
O3—Mn—N1—C1	−71.0 (3)	C10—N2—C11—C7	−1.0 (5)
O4^i—Mn—N1—C1	93.0 (3)	Mn—N2—C11—C7	179.4 (2)
O5^i—Mn—N1—C12	−162.7 (2)	C10—N2—C11—C12	179.7 (3)
O1—Mn—N1—C12	62.3 (3)	Mn—N2—C11—C12	0.2 (4)
N2—Mn—N1—C12	−2.3 (2)	C8—C7—C11—N2	2.1 (5)
O3—Mn—N1—C12	106.9 (2)	C6—C7—C11—N2	−178.8 (3)
O4^i—Mn—N1—C12	−89.1 (2)	C8—C7—C11—C12	−178.7 (3)
O5^i—Mn—N2—C10	−118.4 (3)	C6—C7—C11—C12	0.5 (5)
O1—Mn—N2—C10	23.4 (3)	C1—N1—C12—C4	0.4 (5)
N1—Mn—N2—C10	−178.4 (3)	Mn—N1—C12—C4	−177.6 (2)
O3—Mn—N2—C10	96.6 (3)	C1—N1—C12—C11	−178.7 (3)
O4^i—Mn—N2—C10	−70.2 (3)	Mn—N1—C12—C11	3.3 (4)
O5^i—Mn—N2—C11	61.1 (3)	C3—C4—C12—N1	0.2 (5)
O1—Mn—N2—C11	−157.1 (2)	C5—C4—C12—N1	−179.1 (3)
N1—Mn—N2—C11	1.1 (2)	C3—C4—C12—C11	179.3 (3)
O3—Mn—N2—C11	−83.9 (2)	C5—C4—C12—C11	−0.1 (5)
O4^i—Mn—N2—C11	109.3 (2)	N2—C11—C12—N1	−2.4 (4)
O5^i—Mn—O1—C13	−62.7 (2)	C7—C11—C12—N1	178.4 (3)
N1—Mn—O1—C13	70.7 (3)	N2—C11—C12—C4	178.6 (3)
N2—Mn—O1—C13	131.5 (2)	C7—C11—C12—C4	−0.7 (5)
O3—Mn—O1—C13	23.39 (19)	Mn—O1—C13—O2	161.1 (2)
O4^i—Mn—O1—C13	−136.4 (2)	Mn—O1—C13—C14	−16.4 (3)
O5^i—Mn—O3—C14	77.46 (18)	Mn—O3—C14—C13	26.4 (2)
O1—Mn—O3—C14	−26.71 (17)	Mn—O3—C14—C15	151.7 (2)
N1—Mn—O3—C14	170.79 (18)	O2—C13—C14—O3	174.3 (2)
N2—Mn—O3—C14	−115.40 (17)	O1—C13—C14—O3	−7.9 (3)
O4^i—Mn—O3—C14	30.5 (3)	O2—C13—C14—C15	48.6 (3)
C12—N1—C1—C2	−0.4 (5)	O1—C13—C14—C15	−133.7 (3)
Mn—N1—C1—C2	177.4 (3)	Mn^ii—O4—C15—C14	151.00 (19)
N1—C1—C2—C3	−0.3 (6)	Mn^ii—O4—C15—C16	24.2 (2)
C1—C2—C3—C4	1.0 (5)	O3—C14—C15—O4	−43.5 (3)
C2—C3—C4—C12	−0.9 (5)	C13—C14—C15—O4	79.6 (3)
C2—C3—C4—C5	178.4 (3)	O3—C14—C15—C16	81.1 (3)
C3—C4—C5—C6	−178.1 (4)	C13—C14—C15—C16	−155.8 (2)
C12—C4—C5—C6	1.2 (5)	Mn^ii—O5—C16—O6	176.6 (2)
C4—C5—C6—C7	−1.5 (5)	Mn^ii—O5—C16—C15	0.9 (3)
C5—C6—C7—C8	179.8 (3)	O4—C15—C16—O6	166.8 (2)
C5—C6—C7—C11	0.7 (5)	C14—C15—C16—O6	40.1 (4)
C11—C7—C8—C9	−1.9 (5)	O4—C15—C16—O5	−17.2 (3)
C6—C7—C8—C9	179.0 (3)	C14—C15—C16—O5	−143.8 (3)
C7—C8—C9—C10	0.7 (6)

Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8B···O11^iii	0.85 (3)	1.92 (6)	2.775 (4)	168 (6)
O9—H9B···O6^iv	0.83 (2)	1.88 (2)	2.709 (3)	173 (4)
O10—H10B···O8^v	0.85 (2)	2.07 (3)	2.820 (4)	147 (4)
O9—H9C···O7^ii	0.85 (2)	1.95 (2)	2.782 (4)	168 (5)
O10—H10C···O12^vi	0.84 (2)	2.03 (2)	2.832 (4)	160 (4)
O11—H11C···O8^i	0.86 (3)	1.92 (3)	2.775 (5)	169 (6)
O7—H7C···O5^iv	0.84 (2)	2.02 (2)	2.854 (3)	170 (5)
O11—H11B···O7	0.86 (4)	1.96 (5)	2.790 (4)	159 (4)
O7—H7B···O1	0.85 (2)	2.07 (2)	2.889 (3)	163 (4)
O12—H12B···O11	0.88 (5)	1.94 (5)	2.817 (4)	174 (5)
O8—H8C···O2	0.86 (6)	1.94 (6)	2.794 (4)	173 (6)
O12—H12C···O2	0.85 (4)	2.06 (2)	2.904 (3)	173 (4)

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