catena-Poly­[[aqua(2,2′-bi­pyridine-κ²N,N′)­manganese(II)]-μ-terephthalato-κ³O,O′:O′′]

The title complex, [Mn(C₈H₄O₄)(C₁₀H₈N₂)(H₂O)]_n, takes the form of a zigzag chain, with the terephthalate dianion (tp) acting as a tridentate ligand. The Mn^II center is surrounded by two tp ligands, one water mol­ecule and one 2,2′-bi­pyridine (bipy) ligand and exhibits a severely distorted octahedral coordination environment, with cis angles ranging from 57.31 (8) to 123.97 (11)°. The complete solid-state structure can be described as a three-dimensional supramolecular framework stabilized by hydrogen-bonding interactions involving the coordinated water mol­ecule and the carboxy O atoms of the tp ligands, and by π–π stacking interactions involving the bipy rings and the benzene ring of the tp ligand.

S1. Comment

Owing to the great variety of intriguing structural topologies (Zaworotko, 1994) and potential applications in such fields as catalysis (Fujita et al., 1994) and molecular magnetism (Miller & Epstein, 1994), the crystal engineering of supramolecular architectures organized by coordinate covalent bonds and/or supramolecular contacts, such as hydrogen bonds and π–π interactions, has been investigated actively. A commonly used strategy for obtaining such systems is to select appropriate bridging ligands with versatile bonding modes, in order to bind more than one metal ion, and with the ability to form hydrogen bonds. Aromatic chelating ligands, such as 2,2'-bipyridine and 1,10-phenanthroline, are often introduced as ancillary ligands, with the hope of providing potential supramolecular recognition sites for π–π stacking interactions.

Terephthalate has been proved to be an appropriate bridging ligand for mediating magnetic exchange interactions between paramagnetic metal centers over a limited distance (about 11 Å; Bürger et al., 1995). Its versatile binding ability has been manifested by the formation of one mononuclear (Xiang et al., 1998), one dinuclear (Cano et al., 1997), three one-dimensional (Hong & Do, 1997; Li et al., 2002; Yang et al., 2003) and four three-dimensional (Hong & Do, 1997; Sun et al., 2001; Kaduk, 2002; Cano et al., 1994; Ma et al., 2003a) manganese(II) terephthalate complexes, and various bonding modes, including unidentate, bidentate and tetradentate for the tp ligands, were observed in these complexes. In this paper, we report the single-crystal structure of a new polymeric Mn^II terephthalate complex, (I), in which the tp dianion acts as a tridentate bridging ligand, a rare coordination mode that has not been reported previously in manganese terephthalate complexes.

Compound (I) consists of infinite one-dimensional chains, in which successive Mn^II atoms are bridged by one tp ligand, as shown in Fig. 1. Each Mn^II atom has a severely distorted six-coordinate geometry (Table 1), with three trans angles [147.16 (10), 158.43 (11) and 143.66 (10)°] deviating significantly from the ideal value of 180°. The Mn atom is coordinated by three carboxy O atoms [Mn—O = 2.098 (2)–2.281 (2) Å] from two tp ligands, one water O atom [Mn—O5 = 2.160 (3) Å] and two pyridyl N atoms [Mn—N = 2.235 (3) and 2.260 (3) Å] from the chelating bipy ligand. The Mn—N and Mn—O(carboxyl) bond lengths are similar to those found for another ternary Mn—tp—bipy polymeric complex, [Mn₂(tp)(bipy)₂]_n(ClO₄)_2n (Cano et al., 1994). The Mn—O5(water) distance is comparable to those in other Mn^II–water complexes (Okabe & Koizumi, 1997; Hao et al., 2000; Ma et al., 2002; Schlueter & Geiser, 2003; Ma, et al., 2003b). The main distortion from ideal octahedral geometry is caused by the double chelation by the rigid bipy ligand and the chelating carboxylate group of the tp ligand. The N1—Mn—N2 bipy chelate angle of 72.56 (11)° is in agreement with other bipy-containing Mn^II complexes (Shen, 2003; Zhang et al., 2002; Baumeister & Hartung, 1997). The O1—Mn—O2 carboxy chelate angle of 57.31 (8)° is very close to that in [Mn(tp)(4,4'-bipy)]_n [57.07 (11)°; Ma et al., 2003a], but significantly larger than that in [Mn₂(tp)(dca)₂(terpy)₂(MeOH)₂]_n [52.94 (10)°; Escuer et al., 2002].

Each tp dianion acts as a tridentate bridging ligand, joining two Mn atoms in a head-to-tail fashion; one of the carboxylate groups chelates one Mn atom, while the other binds the second Mn atom in a monodentate fashion. The present work is the first time that this tridentate µ₂ bridging mode has been observed for the tp ligand in Mn complexes, and to date it has been encountered in just one five-coordinate copper(II) complex (Yang et al., 2003). The two tp ligands coordinated to a given Mn center are cis to one another, resulting in a one-dimensional zigzag chain. The Mn···Mn···Mn angle formed by three successive Mn ions is 104.01 (2)° and successive bipy moieties are oriented at an angle of 89.5 (8)° to one another. The intrachain Mn···Mn separation is 11.132 (2) Å; the closest interchain contact is 5.642 (2) Å. Neighboring chains are arranged in an antiparallel fashion (Fig. 2a).

The neighboring zigzag chains are cross-linked by O5—H5B···O1(-x, −y, −z) hydrogen bonds, formed by the coordinated water molecule with one of the chelating carboxy O atoms of a symmetry-related chain (Table 2), thus resulting in the formation of a two-dimensional hydrogen-bonded pleated sheet, as shown in Fig. 2 b. The second water H atom is donated to form an intrachain O5—H5C···O4(x + 1/2, −y + 1/2, z − 1/2) hydrogen bond with the uncoordinated carboxy O atom. These two-dimensional hydrogen-bonded sheets are further packed into a three-dimensional herringbone-like supramolecular network via two kinds of π–π stacking interactions, namely between the bipy ligands and between the phenyl ring of the tp ligand and the bipy ligand, with perpendicular ring separations of 3.459 (8) and 3.542 (9) Å, respectively. A view along the a axis is shown in Fig. 3.

S2. Experimental

A mixture of Mn(NO₃)₂·6H₂O (1 mmol, 0.28 g), dipotassium terephthalate (1 mmol, 0.24 g) and 2,2'-bipyridine (1 mmol, 0.16 g) in mixed methanol–water solvent (1:2, v/v, 15 ml) was heated at 413 K for 4 d under autogenous pressure in a 25 ml sealed Teflon-lined stainless steel vessel, and then cooled to room temperature over a period of 5 h, yielding yellow crystals of (I). Analysis calculated for C₁₈H₁₄MnN₂O₅: C 54.98, H 3.59, N 7.12%; found: C 54.92, H 3.61, N 7.08%. FT–IR (KBr, N, cm⁻¹): 3205 (br, s), 1605 (s), 1577 (versus), 1531 (m), 1505 (m), 1475 (m), 1439 (s), 1379 (versus), 1313 (m), 1247 (w), 1151 (m), 1089 (w), 1050 (m), 1019 (m), 882 (w), 864 (w), 806 (m), 760 (s), 750 (s), 670 (m), 650 (m), 628 (m), 569 (w), 525 (m), 413 (m).

S3. Refinement

The water H atoms were located from difference maps and included in the refinement with a DFIX restraint of 0.85 (2) Å applied to the two O—H distances. Aromatic H atoms were placed in calculated positions and treated as riding atoms (C–H = 0.93 Å).

Computing details

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

Figures

	Fig. 1. A view of part of the polymeric chain of (I), showing the atom-labelling scheme and displacement ellipsoids at the 30% probability level. Atoms with the suffixes A and B are at the symmetry positions (1 − x, 1/2 − y, z − 1/2) and (x − 1/2, 1/2 − y, 1/2 + z), respectively. Intrachain hydrogen bonds are depicted as double dashed lines.
	Fig. 2. The crystal packing of (I), showing (a) the antiparallel relationship of neighboring chains and the interchain hydrogen-bonding cross-linkage, and (b) part of the two-dimensional hydrogen-bonded network. bipy ligands and H atoms have been omitted for clarity. Atoms labelled with an ampersand (&) or dollar sign () are at the symmetry positions (-x, −y, −z) and (x + 1/2, −y + 1/2, z − 1/2), respectively.
	Fig. 3. A partial packing diagram of (I), viewed along the a axis.

catena-Poly[[aqua(2,2'-bipyridine-κ²N,N')manganese(II)]-µ-terephthalato- κ³O,O':O'']

Crystal data

[Mn(C8H4O4)(C10H8N2)(H2O)]	F(000) = 804
Mr = 393.25	Dx = 1.543 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2431 reflections
a = 9.8637 (2) Å	θ = 2.3–25.0°
b = 16.3316 (5) Å	µ = 0.81 mm^−1
c = 11.3110 (1) Å	T = 293 K
β = 111.726 (2)°	Block, pale yellow
V = 1692.66 (6) Å^3	0.54 × 0.53 × 0.30 mm
Z = 4

Data collection

Siemens SMART CCD area-detector diffractometer	2973 independent reflections
Radiation source: fine-focus sealed tube	2230 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ϕ and ω scans	θmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan SADABS (Sheldrick, 1996)	h = −9→11
Tmin = 0.626, Tmax = 0.784	k = −12→19
5399 measured reflections	l = −13→9

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.150	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.1P)^2] where P = (Fo^2 + 2Fc^2)/3
2973 reflections	(Δ/σ)max < 0.001
243 parameters	Δρmax = 0.40 e Å^−3
2 restraints	Δρmin = −0.30 e Å^−3

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	0.29665 (5)	0.04021 (3)	0.12849 (5)	0.0325 (2)
O1	0.0809 (2)	0.09837 (15)	0.1140 (2)	0.0420 (6)
O2	0.2808 (2)	0.13618 (15)	0.2681 (2)	0.0390 (6)
O3	−0.1197 (3)	0.38453 (16)	0.5214 (2)	0.0452 (6)
O4	−0.3006 (3)	0.38864 (19)	0.3321 (3)	0.0605 (8)
O5	0.1858 (3)	−0.02654 (17)	−0.0456 (3)	0.0434 (6)
H5B	0.105 (3)	−0.054 (3)	−0.067 (5)	0.085 (18)*
H5C	0.172 (5)	0.011 (2)	−0.101 (4)	0.088 (19)*
N1	0.2832 (3)	−0.06673 (18)	0.2505 (3)	0.0395 (7)
N2	0.5235 (3)	0.01268 (19)	0.2626 (3)	0.0391 (7)
C1	0.0596 (3)	0.1985 (2)	0.2614 (3)	0.0304 (7)
C2	0.1288 (4)	0.2408 (2)	0.3730 (3)	0.0453 (10)
H2A	0.2284	0.2338	0.4172	0.054*
C3	0.0514 (4)	0.2933 (2)	0.4196 (3)	0.0471 (10)
H3A	0.0993	0.3209	0.4956	0.057*
C4	−0.0965 (3)	0.3057 (2)	0.3552 (3)	0.0330 (8)
C5	−0.1640 (4)	0.2656 (2)	0.2410 (3)	0.0395 (9)
H5A	−0.2623	0.2752	0.1943	0.047*
C6	−0.0877 (4)	0.2115 (2)	0.1951 (3)	0.0386 (8)
H6A	−0.1356	0.1836	0.1194	0.046*
C7	0.1469 (4)	0.1414 (2)	0.2124 (3)	0.0324 (8)
C8	−0.1799 (4)	0.3642 (2)	0.4064 (3)	0.0359 (8)
C9	0.1606 (4)	−0.1075 (3)	0.2371 (4)	0.0530 (10)
H9A	0.0757	−0.0945	0.1688	0.064*
C10	0.1548 (5)	−0.1676 (3)	0.3197 (5)	0.0604 (12)
H10A	0.0679	−0.1951	0.3069	0.072*
C11	0.2787 (5)	−0.1866 (3)	0.4209 (4)	0.0628 (12)
H11A	0.2769	−0.2269	0.4783	0.075*
C12	0.4063 (5)	−0.1456 (2)	0.4373 (4)	0.0507 (10)
H12A	0.4914	−0.1576	0.5060	0.061*
C13	0.4058 (4)	−0.0861 (2)	0.3494 (3)	0.0378 (8)
C14	0.5393 (4)	−0.0403 (2)	0.3574 (3)	0.0377 (8)
C15	0.6717 (4)	−0.0510 (2)	0.4556 (4)	0.0473 (10)
H15A	0.6807	−0.0880	0.5206	0.057*
C16	0.7904 (5)	−0.0066 (3)	0.4568 (4)	0.0601 (12)
H16A	0.8802	−0.0129	0.5230	0.072*
C17	0.7753 (5)	0.0475 (3)	0.3589 (4)	0.0597 (12)
H17A	0.8544	0.0779	0.3572	0.072*
C18	0.6407 (4)	0.0552 (3)	0.2645 (4)	0.0507 (11)
H18A	0.6298	0.0917	0.1985	0.061*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn	0.0343 (3)	0.0301 (3)	0.0347 (3)	0.0015 (2)	0.0148 (2)	0.0019 (2)
O1	0.0390 (13)	0.0423 (15)	0.0456 (15)	−0.0017 (11)	0.0168 (12)	−0.0144 (12)
O2	0.0342 (14)	0.0414 (15)	0.0397 (14)	0.0070 (11)	0.0117 (11)	−0.0030 (11)
O3	0.0473 (15)	0.0525 (16)	0.0358 (14)	0.0105 (13)	0.0154 (12)	−0.0077 (12)
O4	0.0434 (16)	0.074 (2)	0.0537 (17)	0.0192 (14)	0.0052 (13)	−0.0207 (15)
O5	0.0475 (17)	0.0363 (15)	0.0471 (16)	−0.0104 (13)	0.0182 (13)	−0.0071 (12)
N1	0.0415 (18)	0.0333 (16)	0.0464 (18)	0.0014 (14)	0.0194 (15)	0.0035 (13)
N2	0.0383 (17)	0.0412 (18)	0.0414 (17)	0.0052 (14)	0.0189 (14)	0.0070 (14)
C1	0.0339 (18)	0.0280 (18)	0.0312 (18)	0.0021 (14)	0.0144 (14)	0.0022 (14)
C2	0.034 (2)	0.054 (2)	0.042 (2)	0.0106 (18)	0.0059 (17)	−0.0085 (18)
C3	0.041 (2)	0.054 (2)	0.036 (2)	0.0084 (19)	0.0035 (17)	−0.0135 (18)
C4	0.0343 (19)	0.0334 (19)	0.0341 (19)	0.0002 (15)	0.0157 (15)	−0.0022 (15)
C5	0.0290 (18)	0.040 (2)	0.045 (2)	0.0018 (15)	0.0086 (16)	−0.0076 (16)
C6	0.0353 (19)	0.041 (2)	0.038 (2)	−0.0033 (16)	0.0123 (16)	−0.0139 (16)
C7	0.039 (2)	0.0279 (18)	0.0331 (18)	0.0010 (15)	0.0162 (16)	0.0035 (14)
C8	0.0316 (19)	0.0344 (19)	0.043 (2)	0.0017 (15)	0.0150 (16)	−0.0057 (16)
C9	0.046 (2)	0.046 (2)	0.067 (3)	−0.0056 (19)	0.021 (2)	0.004 (2)
C10	0.060 (3)	0.046 (3)	0.084 (3)	−0.011 (2)	0.037 (3)	0.008 (2)
C11	0.085 (3)	0.039 (2)	0.078 (3)	−0.002 (2)	0.046 (3)	0.013 (2)
C12	0.060 (2)	0.040 (2)	0.058 (3)	0.007 (2)	0.028 (2)	0.0095 (19)
C13	0.045 (2)	0.032 (2)	0.040 (2)	0.0065 (16)	0.0212 (18)	0.0006 (16)
C14	0.049 (2)	0.0309 (19)	0.0371 (19)	0.0106 (16)	0.0207 (17)	0.0033 (15)
C15	0.047 (2)	0.051 (2)	0.041 (2)	0.0074 (19)	0.0129 (19)	0.0110 (17)
C16	0.038 (2)	0.081 (3)	0.055 (3)	0.009 (2)	0.0095 (19)	0.009 (2)
C17	0.037 (2)	0.078 (3)	0.062 (3)	−0.004 (2)	0.015 (2)	0.007 (2)
C18	0.040 (2)	0.062 (3)	0.053 (2)	0.0032 (19)	0.021 (2)	0.018 (2)

Geometric parameters (Å, º)

Mn—O3^i	2.098 (2)	C3—H3A	0.9300
Mn—O5	2.160 (3)	C4—C5	1.379 (5)
Mn—N2	2.235 (3)	C4—C8	1.509 (4)
Mn—N1	2.260 (3)	C5—C6	1.380 (5)
Mn—O2	2.271 (2)	C5—H5A	0.9300
Mn—O1	2.281 (2)	C6—H6A	0.9300
Mn—C7	2.617 (3)	C9—C10	1.371 (6)
O1—C7	1.272 (4)	C9—H9A	0.9300
O2—C7	1.238 (4)	C10—C11	1.365 (6)
O3—C8	1.259 (4)	C10—H10A	0.9300
O3—Mn^ii	2.098 (2)	C11—C12	1.375 (6)
O4—C8	1.241 (4)	C11—H11A	0.9300
O5—H5B	0.861 (19)	C12—C13	1.389 (5)
O5—H5C	0.847 (19)	C12—H12A	0.9300
N1—C9	1.340 (5)	C13—C14	1.487 (5)
N1—C13	1.346 (5)	C14—C15	1.377 (5)
N2—C18	1.341 (5)	C15—C16	1.373 (6)
N2—C14	1.341 (4)	C15—H15A	0.9300
C1—C2	1.378 (5)	C16—C17	1.381 (6)
C1—C6	1.382 (4)	C16—H16A	0.9300
C1—C7	1.508 (4)	C17—C18	1.367 (6)
C2—C3	1.376 (5)	C17—H17A	0.9300
C2—H2A	0.9300	C18—H18A	0.9300
C3—C4	1.383 (5)
O3^i—Mn—O5	86.79 (10)	C4—C5—C6	121.0 (3)
O3^i—Mn—N2	90.04 (10)	C4—C5—H5A	119.5
O5—Mn—N2	123.97 (11)	C6—C5—H5A	119.5
O3^i—Mn—N1	158.43 (11)	C5—C6—C1	120.3 (3)
O5—Mn—N1	92.42 (11)	C5—C6—H6A	119.9
N2—Mn—N1	72.56 (11)	C1—C6—H6A	119.9
O3^i—Mn—O2	98.05 (10)	O2—C7—O1	120.8 (3)
O5—Mn—O2	147.16 (10)	O2—C7—C1	120.2 (3)
N2—Mn—O2	88.63 (10)	O1—C7—C1	119.1 (3)
N1—Mn—O2	94.26 (10)	O2—C7—Mn	60.14 (17)
O3^i—Mn—O1	105.72 (9)	O1—C7—Mn	60.62 (17)
O5—Mn—O1	90.04 (10)	C1—C7—Mn	179.0 (2)
N2—Mn—O1	143.66 (10)	O4—C8—O3	125.6 (3)
N1—Mn—O1	95.83 (10)	O4—C8—C4	117.8 (3)
O2—Mn—O1	57.31 (8)	O3—C8—C4	116.6 (3)
O3^i—Mn—C7	103.58 (10)	N1—C9—C10	122.9 (4)
O5—Mn—C7	119.07 (11)	N1—C9—H9A	118.6
N2—Mn—C7	116.00 (11)	C10—C9—H9A	118.6
N1—Mn—C7	95.64 (10)	C11—C10—C9	118.9 (4)
O2—Mn—C7	28.22 (9)	C11—C10—H10A	120.5
O1—Mn—C7	29.09 (9)	C9—C10—H10A	120.5
C7—O1—Mn	90.30 (19)	C10—C11—C12	119.5 (4)
C7—O2—Mn	91.6 (2)	C10—C11—H11A	120.2
C8—O3—Mn^ii	128.0 (2)	C12—C11—H11A	120.2
Mn—O5—H5B	128 (3)	C11—C12—C13	118.9 (4)
Mn—O5—H5C	102 (4)	C11—C12—H12A	120.5
H5B—O5—H5C	106 (5)	C13—C12—H12A	120.5
C9—N1—C13	118.2 (3)	N1—C13—C12	121.5 (3)
C9—N1—Mn	124.7 (3)	N1—C13—C14	115.8 (3)
C13—N1—Mn	116.8 (2)	C12—C13—C14	122.7 (3)
C18—N2—C14	118.5 (3)	N2—C14—C15	121.4 (4)
C18—N2—Mn	123.1 (2)	N2—C14—C13	115.9 (3)
C14—N2—Mn	117.6 (2)	C15—C14—C13	122.6 (3)
C2—C1—C6	119.0 (3)	C16—C15—C14	119.4 (4)
C2—C1—C7	119.4 (3)	C16—C15—H15A	120.3
C6—C1—C7	121.6 (3)	C14—C15—H15A	120.3
C3—C2—C1	120.4 (3)	C15—C16—C17	119.5 (4)
C3—C2—H2A	119.8	C15—C16—H16A	120.3
C1—C2—H2A	119.8	C17—C16—H16A	120.3
C2—C3—C4	121.0 (3)	C18—C17—C16	118.0 (4)
C2—C3—H3A	119.5	C18—C17—H17A	121.0
C4—C3—H3A	119.5	C16—C17—H17A	121.0
C5—C4—C3	118.3 (3)	N2—C18—C17	123.2 (4)
C5—C4—C8	121.1 (3)	N2—C18—H18A	118.4
C3—C4—C8	120.6 (3)	C17—C18—H18A	118.4
O3^i—Mn—O1—C7	−89.8 (2)	Mn—O1—C7—C1	−179.0 (3)
O5—Mn—O1—C7	−176.4 (2)	C2—C1—C7—O2	−4.1 (5)
N2—Mn—O1—C7	22.8 (3)	C6—C1—C7—O2	173.9 (3)
N1—Mn—O1—C7	91.1 (2)	C2—C1—C7—O1	175.3 (3)
O2—Mn—O1—C7	−0.21 (18)	C6—C1—C7—O1	−6.7 (5)
O3^i—Mn—O2—C7	103.8 (2)	O3^i—Mn—C7—O2	−81.6 (2)
O5—Mn—O2—C7	7.2 (3)	O5—Mn—C7—O2	−175.55 (18)
N2—Mn—O2—C7	−166.4 (2)	N2—Mn—C7—O2	15.2 (2)
N1—Mn—O2—C7	−94.0 (2)	N1—Mn—C7—O2	88.5 (2)
O1—Mn—O2—C7	0.21 (18)	O1—Mn—C7—O2	−179.6 (3)
O3^i—Mn—N1—C9	−139.0 (3)	O3^i—Mn—C7—O1	97.99 (19)
O5—Mn—N1—C9	−51.7 (3)	O5—Mn—C7—O1	4.1 (2)
N2—Mn—N1—C9	−176.6 (3)	N2—Mn—C7—O1	−165.20 (19)
O2—Mn—N1—C9	96.2 (3)	N1—Mn—C7—O1	−91.9 (2)
O1—Mn—N1—C9	38.6 (3)	O2—Mn—C7—O1	179.6 (3)
C7—Mn—N1—C9	67.9 (3)	Mn^ii—O3—C8—O4	3.5 (5)
O3^i—Mn—N1—C13	46.3 (4)	Mn^ii—O3—C8—C4	−177.2 (2)
O5—Mn—N1—C13	133.7 (3)	C5—C4—C8—O4	−15.1 (5)
N2—Mn—N1—C13	8.8 (2)	C3—C4—C8—O4	162.5 (4)
O2—Mn—N1—C13	−78.5 (2)	C5—C4—C8—O3	165.5 (3)
O1—Mn—N1—C13	−136.0 (2)	C3—C4—C8—O3	−16.9 (5)
C7—Mn—N1—C13	−106.8 (2)	C13—N1—C9—C10	0.2 (6)
O3^i—Mn—N2—C18	13.2 (3)	Mn—N1—C9—C10	−174.4 (3)
O5—Mn—N2—C18	99.4 (3)	N1—C9—C10—C11	0.6 (7)
N1—Mn—N2—C18	−179.7 (3)	C9—C10—C11—C12	−0.5 (7)
O2—Mn—N2—C18	−84.8 (3)	C10—C11—C12—C13	−0.4 (6)
O1—Mn—N2—C18	−104.1 (3)	C9—N1—C13—C12	−1.1 (5)
C7—Mn—N2—C18	−92.0 (3)	Mn—N1—C13—C12	173.9 (3)
O3^i—Mn—N2—C14	−177.3 (3)	C9—N1—C13—C14	178.4 (3)
O5—Mn—N2—C14	−91.1 (3)	Mn—N1—C13—C14	−6.6 (4)
N1—Mn—N2—C14	−10.2 (3)	C11—C12—C13—N1	1.2 (6)
O2—Mn—N2—C14	84.7 (3)	C11—C12—C13—C14	−178.3 (3)
O1—Mn—N2—C14	65.5 (3)	C18—N2—C14—C15	0.5 (5)
C7—Mn—N2—C14	77.6 (3)	Mn—N2—C14—C15	−169.5 (3)
C6—C1—C2—C3	1.8 (6)	C18—N2—C14—C13	−179.6 (3)
C7—C1—C2—C3	179.9 (3)	Mn—N2—C14—C13	10.4 (4)
C1—C2—C3—C4	−0.8 (6)	N1—C13—C14—N2	−2.4 (5)
C2—C3—C4—C5	−1.7 (6)	C12—C13—C14—N2	177.1 (3)
C2—C3—C4—C8	−179.3 (3)	N1—C13—C14—C15	177.5 (3)
C3—C4—C5—C6	3.1 (6)	C12—C13—C14—C15	−3.0 (6)
C8—C4—C5—C6	−179.3 (3)	N2—C14—C15—C16	0.0 (6)
C4—C5—C6—C1	−2.1 (6)	C13—C14—C15—C16	−180.0 (4)
C2—C1—C6—C5	−0.4 (5)	C14—C15—C16—C17	−0.6 (7)
C7—C1—C6—C5	−178.5 (3)	C15—C16—C17—C18	0.7 (7)
Mn—O2—C7—O1	−0.4 (3)	C14—N2—C18—C17	−0.4 (6)
Mn—O2—C7—C1	179.0 (3)	Mn—N2—C18—C17	169.0 (3)
Mn—O1—C7—O2	0.4 (3)	C16—C17—C18—N2	−0.2 (7)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5B···O1^iii	0.86 (2)	1.86 (2)	2.718 (4)	172 (5)
O5—H5C···O4^i	0.85 (2)	1.87 (3)	2.672 (4)	157 (5)

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