A one-dimensional double-chain coordination polymer: [Mn(C₁₂H₁₃NO₆S)(C₁₀H₈N₂)]_n

In the title compound, poly­[[(2,2′-bi­pyridine-κ²N,N′)­manganese(II)]-μ₃-N-tosyl-L-glutamato-κ⁴O,O′:O′′:O′′′], [Mn(tsgluo)(bipy)]_n, where tsgluo is N-tosyl-L-glutamate (C₁₂H₁₃NO₆S) and bipy is 2,2′-bi­pyridine (C₁₀H₈N₂), the Mn atoms are octahedrally coordinated by two N atoms of one bipy ligand and by four O atoms of three tsgluo²⁻ anions. The γ-carboxyl group coordinates to the Mn^II atom in a chelating mode, while the α-carboxyl group coordinates in a bidentate–bridging mode. The complex displays a one-dimensional double-chain structure.

S1. Comment

In recent years, there has been considerable interest in the design and synthesis of manganese(II) complexes with carboxylate ligands (Yu et al., 1992; Zheng et al., 2002; Tangoulis et al., 1996; Zhang et al., 2003). The main reason may be that these complexes can be used for investigation of the exchange coupling interactions between metal ions, as well as for a new variety of molecular-based magnetic materials (Cano et al., 1994; Ma et al., 2003; Sain et al., 2003). Furthermore, polymanganese complexes have been used as models for the study of the photosynthetic oxygen-evolving complexes (OEC) of photosystem II in green plants (Wieghardt, 1989). On the other hand, N-protected amino acids, being biologically important compounds derived from naturally occurring amino acids, have been studied extensively in the coordination chemistry of metal ions (Bonamartini Corradi., 1992). However, N-p-tolysulfonyl-L-glutamic acid (H₂tsglu), which may act as a polydentate ligand and present a variety of coordination modes because of the presence of two carboxyl functions and a sulfonamide group, has been studied only in a limited number of systems (Bonamartini Corradi et al., 1999) so far, and the manganese complex of H₂tsglu has not yet been reported. We present here the crystal structure of a manganese complex with mixed ligands of bipy and H₂tsglu, [Mn(C₁₂H₁₅NO₆S)(C₁₀H₈N₂)]_n,(I). The complex has a one-dimensional double-chain structure.

The molecular structure of (I) and the symmetry dimeric [Mn(C₁₂H₁₅NO₆S) (C₁₀H₈N₂)]₂ unit are shown in Figs. 1 and 2, respectively. The crystal structure consists of an infinite one-dimensional double chain. Each Mn ion is six-coordinated by two N atoms of one 2,2'-bipyridine group, two O atoms of the γ-carboxyl group of one tsgluo²⁻ ligand, and two O atoms from two α-carboxyl groups of two other tsgluo²⁻ ligands. The two carboxylate groups display different coordination modes. The γ-carboxyl group coordinates to Mn(II) in a chelating mode, while the α-carboxyl group coordinates in bidentate-bridging mode. The bridging of the α-carboxyl O atoms of a ligand between every two adjacent manganese ions gives rise to an infinite chain. The alternate disposition of the α- and γ-carboxylate terminals of the ligands along the a axis results in a one-dimensional double-chain structure. The Mn site exhibits a distorted octahedral coordination sphere, with bond angles ranging from 163.10 (6) to 176.54 (6)° for trans angles and from 71.58 (6) to 137.25 (6)° for the other angles (Table 1). The Mn—O bond distances range from 2.1268 (13) to 2.3010 (16) Å. The Mn1—O6 bond length [2.3010 (16) Å] is slightly longer than those of the other Mn1—O bonds (Table 1), indicating a weaker interaction of the axial coordination O atom (O6) as a result of the instability of the four-membered ring formed by the chelating action of the γ-carboxyl group. The Mn—N bond distances change from 2.2397 (15) to 2.2910 (15) Å and the C—O bond lengths are in the range 1.235 (2)–1.273 (2) Å; these values are in good agreement with the corresponding bond lengths found in manganese–carboxylic acid–phen complexes (Shen, 2003).

S2. Experimental

An ethanol solution (10 ml) of 2,2'-bipyridine (0.156 g, 1 mmol) was added dropwise with continuous stirring to an aqueous solution (10 ml) of N-p-tolylsul-fonyl-L-glutamic acid (0.301 g, 1 mmol), NaOH (0.080 g, 2 mmol) and MnSO₄·H₂O (0.175 g, 1 mmol). The resulting yellow solution was stirred for 4 h at room temperature and then filtered. Crystals of the title complex suitable for X-ray analysis were obtained by slow evaporation from the filtrate after 20 d. Analysis calculated for C₂₂H₂₁MnN₃O₆S: C 51.72, H 4.11, N 8.22, S 6.27%; found: C 51.76, H 4.15, N 8.23, S 6.28%.

S3. Refinement

The H atoms on atom C14 were positioned geometrically, with C—H distances of 0.96 Å, and included in the refinement with U_iso(H) values of 1.5U_eq(C). All other H atoms? were placed at idealized positions and refined using a riding model, with C—H distances of 0.93–0.98 Å, an N—H distance of 0.86 Å, and U_iso(H) values of 1.2U_eq(C,N). The U(eq) values of atoms O5 and C21 [0.0657 (6) Ų and 0.0518 (7) Ų] are greater than those of atoms C22 and C20 [0.0372 (5) Ų and 0.0295 (4) Ų]; this difference can be ascribed to the slight disorders of atoms O5 and C21.

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The [Mn(bipy)(tsgluo)] molecule in (I). Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A projection showing the polymeric ribbon of (I).

poly[[(2,2'-bipyridine-κ²N,N')manganese(II)]-µ₃-N-tosyl-L-glutamato- κ⁴O,O':O'':O''']

Crystal data

[Mn(C12H13NO6S)(C10H8N2)]	F(000) = 1052
Mr = 510.42	Dx = 1.539 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 924 reflections
a = 5.3131 (6) Å	θ = 3.6–27.0°
b = 17.727 (2) Å	µ = 0.74 mm^−1
c = 23.382 (3) Å	T = 293 K
V = 2202.2 (4) Å^3	Block, yellow
Z = 4	0.43 × 0.40 × 0.40 mm

Data collection

Bruker SMART CCD area-detector diffractometer	4789 independent reflections
Radiation source: fine-focus sealed tube	4406 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
ϕ and ω scans	θmax = 27.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→5
Tmin = 0.742, Tmax = 0.756	k = −22→19
13798 measured reflections	l = −29→29

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.025	H-atom parameters constrained
wR(F^2) = 0.067	w = 1/[σ^2(Fo^2) + (0.0428P)^2 + 0.0383P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.002
4789 reflections	Δρmax = 0.32 e Å^−3
298 parameters	Δρmin = −0.40 e Å^−3
0 restraints	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.003 (12)

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
Mn1	0.72871 (5)	0.609304 (14)	0.134143 (10)	0.02652 (8)
S1	0.35609 (8)	1.02332 (3)	0.044762 (19)	0.02931 (11)
C1	0.4396 (4)	0.46327 (12)	0.18564 (9)	0.0400 (5)
H1A	0.3425	0.4685	0.1528	0.048*
C2	0.3920 (5)	0.40278 (12)	0.22153 (10)	0.0468 (5)
H2A	0.2657	0.3682	0.2130	0.056*
C3	0.5364 (5)	0.39494 (13)	0.27025 (9)	0.0482 (5)
H3A	0.5111	0.3544	0.2948	0.058*
C4	0.7183 (5)	0.44806 (11)	0.28187 (8)	0.0439 (5)
H4A	0.8151	0.4442	0.3149	0.053*
C5	0.7565 (4)	0.50734 (10)	0.24413 (7)	0.0316 (4)
C6	0.9517 (4)	0.56641 (11)	0.25393 (8)	0.0309 (4)
C7	1.1166 (5)	0.56643 (12)	0.29969 (8)	0.0413 (5)
H7A	1.1052	0.5294	0.3278	0.050*
C8	1.2975 (4)	0.62155 (12)	0.30330 (9)	0.0470 (5)
H8A	1.4108	0.6220	0.3336	0.056*
C9	1.3095 (4)	0.67631 (13)	0.26149 (9)	0.0443 (5)
H9A	1.4312	0.7139	0.2629	0.053*
C10	1.1383 (4)	0.67400 (12)	0.21791 (8)	0.0395 (5)
H10A	1.1450	0.7114	0.1900	0.047*
C11	0.6614 (4)	1.13718 (11)	0.00700 (10)	0.0420 (5)
H11B	0.7522	1.1301	0.0406	0.050*
C12	0.7351 (5)	1.19097 (11)	−0.03214 (11)	0.0521 (6)
H12B	0.8773	1.2199	−0.0246	0.063*
C13	0.6035 (5)	1.20318 (12)	−0.08239 (11)	0.0484 (6)
C14	0.6867 (6)	1.26405 (15)	−0.12361 (12)	0.0694 (8)
H14D	0.8340	1.2886	−0.1089	0.104*
H14E	0.5541	1.3004	−0.1281	0.104*
H14F	0.7247	1.2418	−0.1600	0.104*
C15	0.3946 (5)	1.15857 (13)	−0.09320 (10)	0.0497 (6)
H15B	0.3049	1.1653	−0.1270	0.060*
C16	0.3171 (4)	1.10403 (12)	−0.05442 (9)	0.0456 (5)
H16B	0.1763	1.0745	−0.0621	0.055*
C17	0.4513 (4)	1.09393 (10)	−0.00420 (8)	0.0322 (4)
C18	0.6613 (3)	0.92065 (9)	0.00158 (7)	0.0244 (3)
H18B	0.7727	0.9537	0.0236	0.029*
C19	0.7280 (3)	0.93104 (8)	−0.06176 (7)	0.0245 (3)
C20	0.7148 (4)	0.83882 (9)	0.02092 (7)	0.0295 (4)
H20C	0.6050	0.8045	0.0004	0.035*
H20D	0.8875	0.8257	0.0118	0.035*
C21	0.6722 (5)	0.83030 (12)	0.08468 (8)	0.0518 (7)
H21C	0.7935	0.8614	0.1048	0.062*
H21D	0.5055	0.8490	0.0940	0.062*
C22	0.6951 (4)	0.75004 (11)	0.10572 (8)	0.0372 (5)
N1	0.6189 (3)	0.51462 (9)	0.19599 (6)	0.0323 (3)
N2	0.9621 (3)	0.62064 (9)	0.21345 (6)	0.0320 (3)
N3	0.4024 (3)	0.94276 (8)	0.01471 (6)	0.0256 (3)
H3B	0.2783	0.9135	0.0066	0.031*
O1	0.5201 (3)	1.02823 (9)	0.09317 (6)	0.0407 (3)
O2	0.0906 (3)	1.03016 (9)	0.05359 (7)	0.0431 (4)
O3	0.9627 (2)	0.92866 (8)	−0.07255 (5)	0.0347 (3)
O5	0.8317 (4)	0.70448 (9)	0.07940 (8)	0.0657 (6)
O6	0.5809 (3)	0.72964 (9)	0.14941 (6)	0.0504 (4)
O4	0.5623 (2)	0.94300 (8)	−0.09768 (5)	0.0320 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.02640 (14)	0.03232 (13)	0.02084 (12)	0.00071 (11)	−0.00146 (10)	0.00545 (10)
S1	0.0257 (2)	0.0326 (2)	0.0296 (2)	−0.00001 (18)	0.00221 (18)	−0.00644 (18)
C1	0.0434 (12)	0.0411 (11)	0.0354 (10)	−0.0052 (9)	−0.0020 (9)	0.0044 (9)
C2	0.0548 (14)	0.0389 (12)	0.0466 (12)	−0.0097 (10)	0.0048 (11)	0.0023 (9)
C3	0.0684 (15)	0.0382 (11)	0.0381 (11)	−0.0047 (11)	0.0076 (11)	0.0133 (9)
C4	0.0613 (14)	0.0413 (10)	0.0290 (9)	−0.0004 (11)	−0.0027 (10)	0.0104 (8)
C5	0.0387 (10)	0.0339 (9)	0.0221 (8)	0.0057 (9)	0.0029 (8)	0.0029 (6)
C6	0.0354 (10)	0.0344 (10)	0.0228 (8)	0.0066 (8)	0.0029 (8)	0.0028 (7)
C7	0.0548 (14)	0.0416 (11)	0.0275 (10)	0.0018 (10)	−0.0053 (9)	0.0085 (8)
C8	0.0532 (14)	0.0553 (13)	0.0324 (10)	−0.0009 (11)	−0.0168 (10)	0.0028 (9)
C9	0.0441 (13)	0.0504 (12)	0.0384 (10)	−0.0076 (10)	−0.0074 (9)	0.0037 (9)
C10	0.0416 (11)	0.0460 (11)	0.0310 (9)	−0.0059 (10)	−0.0029 (9)	0.0101 (8)
C11	0.0344 (11)	0.0348 (10)	0.0566 (13)	−0.0002 (8)	−0.0088 (10)	0.0011 (9)
C12	0.0409 (12)	0.0354 (11)	0.0800 (16)	−0.0044 (10)	−0.0013 (13)	0.0052 (10)
C13	0.0488 (13)	0.0350 (11)	0.0614 (15)	0.0025 (10)	0.0099 (11)	0.0048 (10)
C14	0.082 (2)	0.0509 (14)	0.0752 (18)	−0.0046 (13)	0.0137 (16)	0.0176 (13)
C15	0.0552 (15)	0.0475 (13)	0.0463 (12)	−0.0028 (11)	−0.0053 (11)	0.0071 (10)
C16	0.0448 (12)	0.0432 (11)	0.0487 (12)	−0.0089 (10)	−0.0072 (10)	0.0007 (9)
C17	0.0296 (9)	0.0261 (10)	0.0409 (10)	0.0014 (7)	0.0017 (8)	−0.0027 (7)
C18	0.0245 (9)	0.0245 (8)	0.0241 (8)	−0.0023 (7)	0.0028 (7)	0.0008 (6)
C19	0.0260 (9)	0.0219 (7)	0.0256 (8)	−0.0033 (7)	0.0024 (7)	0.0007 (6)
C20	0.0388 (11)	0.0252 (8)	0.0245 (8)	0.0030 (8)	0.0013 (8)	0.0031 (6)
C21	0.089 (2)	0.0367 (11)	0.0299 (10)	0.0140 (12)	0.0129 (11)	0.0085 (8)
C22	0.0466 (13)	0.0342 (10)	0.0308 (9)	0.0037 (9)	0.0015 (9)	0.0088 (8)
N1	0.0361 (9)	0.0339 (8)	0.0267 (8)	−0.0003 (7)	0.0004 (6)	0.0038 (6)
N2	0.0343 (8)	0.0403 (9)	0.0214 (7)	0.0021 (7)	−0.0011 (6)	0.0055 (6)
N3	0.0234 (7)	0.0264 (7)	0.0269 (7)	−0.0053 (6)	0.0024 (6)	−0.0022 (6)
O1	0.0435 (8)	0.0513 (9)	0.0273 (7)	−0.0013 (7)	−0.0029 (6)	−0.0109 (6)
O2	0.0280 (7)	0.0491 (9)	0.0521 (9)	−0.0003 (6)	0.0079 (6)	−0.0115 (7)
O3	0.0264 (7)	0.0490 (8)	0.0287 (7)	−0.0010 (6)	0.0057 (5)	0.0021 (6)
O5	0.0842 (14)	0.0430 (9)	0.0699 (11)	0.0263 (9)	0.0423 (10)	0.0242 (8)
O6	0.0657 (11)	0.0457 (9)	0.0397 (8)	0.0083 (8)	0.0181 (7)	0.0137 (7)
O4	0.0309 (7)	0.0403 (7)	0.0247 (6)	−0.0061 (6)	−0.0033 (5)	0.0061 (5)

Geometric parameters (Å, º)

Mn1—O3^i	2.1268 (13)	C11—C12	1.378 (3)
Mn1—O4^ii	2.1745 (13)	C11—C17	1.379 (3)
Mn1—O5	2.1874 (15)	C11—H11B	0.9300
Mn1—N2	2.2397 (15)	C12—C13	1.384 (3)
Mn1—N1	2.2910 (15)	C12—H12B	0.9300
Mn1—O6	2.3010 (16)	C13—C15	1.386 (3)
S1—O2	1.4308 (15)	C13—C14	1.513 (3)
S1—O1	1.4311 (14)	C14—H14D	0.9600
S1—N3	1.6104 (15)	C14—H14E	0.9600
S1—C17	1.770 (2)	C14—H14F	0.9600
C1—N1	1.340 (3)	C15—C16	1.388 (3)
C1—C2	1.385 (3)	C15—H15B	0.9300
C1—H1A	0.9300	C16—C17	1.386 (3)
C2—C3	1.380 (3)	C16—H16B	0.9300
C2—H2A	0.9300	C18—N3	1.463 (2)
C3—C4	1.376 (3)	C18—C19	1.534 (2)
C3—H3A	0.9300	C18—C20	1.546 (2)
C4—C5	1.387 (2)	C18—H18B	0.9800
C4—H4A	0.9300	C19—O4	1.235 (2)
C5—N1	1.348 (2)	C19—O3	1.273 (2)
C5—C6	1.491 (3)	C20—C21	1.515 (2)
C6—N2	1.350 (2)	C20—H20C	0.9700
C6—C7	1.383 (3)	C20—H20D	0.9700
C7—C8	1.373 (3)	C21—C22	1.510 (3)
C7—H7A	0.9300	C21—H21C	0.9700
C8—C9	1.379 (3)	C21—H21D	0.9700
C8—H8A	0.9300	C22—O6	1.242 (2)
C9—C10	1.366 (3)	C22—O5	1.248 (3)
C9—H9A	0.9300	N3—H3B	0.8600
C10—N2	1.335 (3)	O3—Mn1^ii	2.1268 (13)
C10—H10A	0.9300	O4—Mn1^i	2.1745 (13)
O3^i—Mn1—O4^ii	98.12 (5)	C13—C12—H12B	119.1
O3^i—Mn1—O5	90.80 (7)	C12—C13—C15	118.0 (2)
O4^ii—Mn1—O5	84.00 (6)	C12—C13—C14	120.3 (2)
O3^i—Mn1—N2	163.10 (6)	C15—C13—C14	121.6 (2)
O4^ii—Mn1—N2	84.93 (5)	C13—C14—H14D	109.5
O5—Mn1—N2	106.07 (7)	C13—C14—H14E	109.5
O3^i—Mn1—N1	91.52 (5)	H14D—C14—H14E	109.5
O4^ii—Mn1—N1	98.21 (6)	C13—C14—H14F	109.5
O5—Mn1—N1	176.54 (6)	H14D—C14—H14F	109.5
N2—Mn1—N1	71.58 (6)	H14E—C14—H14F	109.5
O3^i—Mn1—O6	99.88 (6)	C13—C15—C16	121.1 (2)
O4^ii—Mn1—O6	137.25 (6)	C13—C15—H15B	119.5
O5—Mn1—O6	57.40 (5)	C16—C15—H15B	119.5
N2—Mn1—O6	88.70 (6)	C17—C16—C15	119.4 (2)
N1—Mn1—O6	119.62 (5)	C17—C16—H16B	120.3
O2—S1—O1	118.75 (9)	C15—C16—H16B	120.3
O2—S1—N3	106.78 (9)	C11—C17—C16	120.38 (19)
O1—S1—N3	107.82 (8)	C11—C17—S1	120.11 (16)
O2—S1—C17	108.37 (10)	C16—C17—S1	119.49 (15)
O1—S1—C17	107.13 (9)	N3—C18—C19	112.81 (14)
N3—S1—C17	107.53 (8)	N3—C18—C20	111.28 (14)
N1—C1—C2	123.1 (2)	C19—C18—C20	110.65 (13)
N1—C1—H1A	118.4	N3—C18—H18B	107.3
C2—C1—H1A	118.4	C19—C18—H18B	107.3
C3—C2—C1	118.5 (2)	C20—C18—H18B	107.3
C3—C2—H2A	120.8	O4—C19—O3	124.68 (16)
C1—C2—H2A	120.8	O4—C19—C18	120.85 (16)
C4—C3—C2	118.96 (19)	O3—C19—C18	114.43 (15)
C4—C3—H3A	120.5	C21—C20—C18	110.72 (15)
C2—C3—H3A	120.5	C21—C20—H20C	109.5
C3—C4—C5	119.7 (2)	C18—C20—H20C	109.5
C3—C4—H4A	120.2	C21—C20—H20D	109.5
C5—C4—H4A	120.2	C18—C20—H20D	109.5
N1—C5—C4	121.61 (19)	H20C—C20—H20D	108.1
N1—C5—C6	115.99 (15)	C22—C21—C20	113.73 (17)
C4—C5—C6	122.40 (17)	C22—C21—H21C	108.8
N2—C6—C7	121.08 (18)	C20—C21—H21C	108.8
N2—C6—C5	114.87 (16)	C22—C21—H21D	108.8
C7—C6—C5	124.03 (17)	C20—C21—H21D	108.8
C8—C7—C6	119.43 (18)	H21C—C21—H21D	107.7
C8—C7—H7A	120.3	O6—C22—O5	120.08 (18)
C6—C7—H7A	120.3	O6—C22—C21	120.19 (19)
C7—C8—C9	119.31 (19)	O5—C22—C21	119.72 (18)
C7—C8—H8A	120.3	C1—N1—C5	118.12 (16)
C9—C8—H8A	120.3	C1—N1—Mn1	124.39 (13)
C10—C9—C8	118.5 (2)	C5—N1—Mn1	117.32 (13)
C10—C9—H9A	120.8	C10—N2—C6	118.57 (17)
C8—C9—H9A	120.8	C10—N2—Mn1	121.10 (12)
N2—C10—C9	123.11 (18)	C6—N2—Mn1	119.60 (13)
N2—C10—H10A	118.4	C18—N3—S1	118.22 (12)
C9—C10—H10A	118.4	C18—N3—H3B	120.9
C12—C11—C17	119.2 (2)	S1—N3—H3B	120.9
C12—C11—H11B	120.4	C19—O3—Mn1^ii	142.71 (12)
C17—C11—H11B	120.4	C22—O5—Mn1	93.73 (12)
C11—C12—C13	121.9 (2)	C22—O6—Mn1	88.60 (12)
C11—C12—H12B	119.1	C19—O4—Mn1^i	140.76 (11)
N1—C1—C2—C3	−0.1 (3)	O4^ii—Mn1—N1—C1	−99.76 (16)
C1—C2—C3—C4	1.2 (3)	N2—Mn1—N1—C1	178.41 (18)
C2—C3—C4—C5	−1.2 (3)	O6—Mn1—N1—C1	100.94 (17)
C3—C4—C5—N1	0.2 (3)	O3^i—Mn1—N1—C5	173.87 (14)
C3—C4—C5—C6	−179.5 (2)	O4^ii—Mn1—N1—C5	75.44 (14)
N1—C5—C6—N2	1.1 (2)	N2—Mn1—N1—C5	−6.39 (13)
C4—C5—C6—N2	−179.19 (18)	O6—Mn1—N1—C5	−83.86 (15)
N1—C5—C6—C7	−177.33 (18)	C9—C10—N2—C6	0.1 (3)
C4—C5—C6—C7	2.4 (3)	C9—C10—N2—Mn1	−170.05 (17)
N2—C6—C7—C8	−1.5 (3)	C7—C6—N2—C10	1.1 (3)
C5—C6—C7—C8	176.9 (2)	C5—C6—N2—C10	−177.42 (17)
C6—C7—C8—C9	0.7 (3)	C7—C6—N2—Mn1	171.41 (14)
C7—C8—C9—C10	0.5 (3)	C5—C6—N2—Mn1	−7.1 (2)
C8—C9—C10—N2	−0.9 (3)	O3^i—Mn1—N2—C10	178.17 (18)
C17—C11—C12—C13	0.3 (3)	O4^ii—Mn1—N2—C10	76.89 (16)
C11—C12—C13—C15	−1.0 (4)	O5—Mn1—N2—C10	−5.37 (17)
C11—C12—C13—C14	178.5 (2)	N1—Mn1—N2—C10	177.29 (17)
C12—C13—C15—C16	1.0 (4)	O6—Mn1—N2—C10	−60.80 (16)
C14—C13—C15—C16	−178.6 (2)	O3^i—Mn1—N2—C6	8.1 (3)
C13—C15—C16—C17	−0.2 (4)	O4^ii—Mn1—N2—C6	−93.19 (14)
C12—C11—C17—C16	0.5 (3)	O5—Mn1—N2—C6	−175.45 (14)
C12—C11—C17—S1	178.86 (17)	N1—Mn1—N2—C6	7.21 (13)
C15—C16—C17—C11	−0.5 (3)	O6—Mn1—N2—C6	129.12 (14)
C15—C16—C17—S1	−178.92 (18)	C19—C18—N3—S1	−101.84 (15)
O2—S1—C17—C11	133.51 (17)	C20—C18—N3—S1	133.10 (12)
O1—S1—C17—C11	4.26 (19)	O2—S1—N3—C18	−179.05 (13)
N3—S1—C17—C11	−111.41 (17)	O1—S1—N3—C18	−50.39 (14)
O2—S1—C17—C16	−48.11 (19)	C17—S1—N3—C18	64.82 (14)
O1—S1—C17—C16	−177.36 (16)	O4—C19—O3—Mn1^ii	−39.3 (3)
N3—S1—C17—C16	66.97 (18)	C18—C19—O3—Mn1^ii	142.93 (15)
N3—C18—C19—O4	−12.7 (2)	O6—C22—O5—Mn1	4.5 (2)
C20—C18—C19—O4	112.71 (18)	C21—C22—O5—Mn1	−176.31 (19)
N3—C18—C19—O3	165.17 (14)	O3^i—Mn1—O5—C22	98.72 (15)
C20—C18—C19—O3	−69.44 (19)	O4^ii—Mn1—O5—C22	−163.20 (15)
N3—C18—C20—C21	−59.0 (2)	N2—Mn1—O5—C22	−80.25 (15)
C19—C18—C20—C21	174.73 (18)	O6—Mn1—O5—C22	−2.50 (13)
C18—C20—C21—C22	174.12 (19)	O5—C22—O6—Mn1	−4.3 (2)
C20—C21—C22—O6	−153.6 (2)	C21—C22—O6—Mn1	176.5 (2)
C20—C21—C22—O5	27.2 (3)	O3^i—Mn1—O6—C22	−82.07 (13)
C2—C1—N1—C5	−1.0 (3)	O4^ii—Mn1—O6—C22	31.48 (16)
C2—C1—N1—Mn1	174.20 (17)	O5—Mn1—O6—C22	2.51 (13)
C4—C5—N1—C1	0.9 (3)	N2—Mn1—O6—C22	112.58 (13)
C6—C5—N1—C1	−179.38 (18)	N1—Mn1—O6—C22	−179.53 (12)
C4—C5—N1—Mn1	−174.58 (15)	O3—C19—O4—Mn1^i	120.75 (18)
C6—C5—N1—Mn1	5.1 (2)	C18—C19—O4—Mn1^i	−61.6 (2)
O3^i—Mn1—N1—C1	−1.33 (17)

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