A new three-dimensional manganese(II) coordination polymer based on the 1,3,5-tris­[(1H-imidazol-1-yl)meth­yl]benzene ligand

The self-assembly of coordination polymers and the crystal engineering of metal-organic coordination frameworks have attracted great inter­est, but it is still a challenge to predict and control the compositions and structures of the complexes. Employing multidentate organic ligands and suitable metal ions to construct inorganic-organic hybrid materials through metal-ligand coordination and hydrogen-bonding inter­actions has become a major strategy. Recently, imidazole-containing multidentate ligands that contain an aromatic core have received much attention. A new three-dimensional Mn^II coordination polymer based on 1,3,5-tris­[(1H-imidazol-1-yl)meth­yl]benzene, namely poly[(ethane-1,2-diol-[kappa]O)([mu]-sulfato-[kappa]²O:O'){[mu]₃-1,3,5-tris­[(1H-imidazol-1-yl)meth­yl]benzene-[kappa]³N:N':N''}manganese(II)], [Mn(SO₄)(C₁₈H₁₈N₆)(C₂H₆O₂)]_n, was syn­thesized and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Crystal structural analysis shows that there are two kinds of crystallographically independent Mn^II centres, each lying on a centrosymmetric position and having a similar six-coordinated octa­hedral structure. One is coordinated by four N atoms from four 1,3,5-tris­[(1H-imidazol-1-yl)meth­yl]benzene (timb) ligands and two O atoms from two different bridging sulfate anions. The second is surrounded by two timb N atoms and four O atoms, two from sulfate anions and two from two ethane-1,2-diol ligands. The tripodal timb ligand bridges neighbouring Mn^II centres to generate a two-dimensional layered structure running parallel to the ab plane. Adjacent layers are further bridged by sulfate anions, resulting in a three-dimensional structure with 3,4,6-c topology. Thermogravimetric analysis of the title polymer shows that it is stable up to 533 K. The first weight loss between 533 and 573 K corresponds to the release of coordinated ethane-1,2-diol mol­ecules, and further decomposition occurred at 648 K.

Computing details

Data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Poly[(ethane-1,2-diol-κO)(µ-sulfato-κ²O:O'){µ₃-1,3,5-tris[(1H-imidazol-1-yl)methyl]benzene-κ³N:N':N''}manganese(II)]

Crystal data

[Mn(SO4)(C18H18N6)(C2H6O2)]	Z = 2
Mr = 531.45	F(000) = 550
Triclinic, P1	Dx = 1.569 Mg m^−3
a = 8.8547 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.9689 (7) Å	Cell parameters from 3024 reflections
c = 12.9721 (10) Å	θ = 2.3–28.1°
α = 97.005 (1)°	µ = 0.73 mm^−1
β = 97.885 (1)°	T = 223 K
γ = 90.929 (1)°	Block, yellow
V = 1125.14 (14) Å^3	0.32 × 0.20 × 0.15 mm

Data collection

Rigaku Mercury CCD diffractometer	5541 independent reflections
Radiation source: fine-focus sealed tube	4514 reflections with I > 2σ(I)
Detector resolution: 28.5714 pixels mm^-1	Rint = 0.018
ω scans	θmax = 28.3°, θmin = 1.6°
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	h = −11→7
Tmin = 0.839, Tmax = 0.896	k = −12→13
8239 measured reflections	l = −17→17

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.096	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0449P)^2 + 0.3728P] where P = (Fo^2 + 2Fc^2)/3
5541 reflections	(Δ/σ)max = 0.008
340 parameters	Δρmax = 0.39 e Å^−3
40 restraints	Δρmin = −0.35 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Mn1	0.0000	1.0000	1.0000	0.02196 (10)
Mn2	0.0000	1.0000	0.5000	0.02554 (11)
S1	−0.06771 (5)	1.10138 (5)	0.74667 (3)	0.02478 (11)
O1	0.01176 (18)	1.04605 (15)	0.83903 (11)	0.0377 (4)
O2	0.03052 (16)	1.08503 (14)	0.66267 (10)	0.0321 (3)
O3	−0.21174 (18)	1.02169 (17)	0.70940 (12)	0.0429 (4)
O4	−0.09813 (18)	1.24321 (15)	0.77319 (12)	0.0382 (4)
O5	0.24625 (18)	1.05849 (17)	0.49149 (12)	0.0437 (4)
H5A	0.2595	1.0321	0.4311	0.066*
O6	0.4896 (15)	1.1931 (12)	0.4058 (6)	0.113 (5)	0.468 (3)
H6B	0.4928	1.1123	0.3848	0.169*	0.468 (3)
O6'	0.5072 (16)	1.0929 (15)	0.6390 (11)	0.077 (4)	0.157 (3)
H6'	0.4464	1.0284	0.6322	0.115*	0.157 (3)
O6"	0.5223 (12)	1.1536 (12)	0.4203 (6)	0.056 (2)	0.375 (3)
H6"A	0.5043	1.0718	0.4113	0.084*	0.375 (3)
N1	0.09987 (19)	1.20592 (16)	1.07083 (13)	0.0291 (4)
N2	0.21868 (18)	1.38017 (16)	1.17216 (13)	0.0270 (3)
N3	0.23886 (19)	0.91907 (17)	1.00046 (14)	0.0302 (4)
N4	0.46679 (19)	0.85378 (17)	1.06180 (14)	0.0310 (4)
N5	0.0784 (2)	0.80422 (17)	0.54590 (14)	0.0334 (4)
N6	0.12064 (19)	0.63507 (17)	0.63905 (14)	0.0302 (4)
C1	0.4517 (2)	1.52098 (19)	1.24236 (15)	0.0261 (4)
C2	0.4543 (2)	1.6423 (2)	1.19962 (17)	0.0315 (4)
H2A	0.3639	1.6867	1.1842	0.038*
C3	0.5909 (2)	1.6977 (2)	1.17973 (17)	0.0312 (4)
C4	0.7252 (2)	1.63167 (19)	1.20523 (16)	0.0285 (4)
H4A	0.8172	1.6688	1.1931	0.034*
C5	0.7244 (2)	1.51111 (19)	1.24858 (15)	0.0260 (4)
C6	0.5874 (2)	1.45535 (19)	1.26609 (15)	0.0272 (4)
H6A	0.5859	1.3737	1.2938	0.033*
C7	0.3027 (2)	1.4623 (2)	1.26397 (16)	0.0300 (4)
H7A	0.3231	1.4069	1.3205	0.036*
H7B	0.2396	1.5355	1.2871	0.036*
C8	0.5990 (2)	0.8327 (2)	1.1378 (2)	0.0432 (6)
H8A	0.6067	0.9047	1.1959	0.052*
H8B	0.6905	0.8377	1.1048	0.052*
C9	0.1243 (2)	0.5544 (2)	0.72605 (18)	0.0335 (5)
H9A	0.0443	0.4844	0.7087	0.040*
H9B	0.1030	0.6120	0.7879	0.040*
C10	0.1553 (3)	1.4263 (2)	1.08107 (18)	0.0385 (5)
H10A	0.1606	1.5145	1.0649	0.046*
C11	0.0835 (2)	1.3183 (2)	1.01938 (17)	0.0359 (5)
H11A	0.0311	1.3199	0.9523	0.043*
C12	0.1819 (2)	1.24667 (19)	1.16208 (16)	0.0274 (4)
H12A	0.2109	1.1907	1.2132	0.033*
C13	0.4396 (3)	0.8017 (3)	0.9588 (2)	0.0465 (6)
H13A	0.5040	0.7484	0.9214	0.056*
C14	0.3003 (3)	0.8430 (2)	0.92168 (19)	0.0439 (5)
H14A	0.2528	0.8229	0.8528	0.053*
C15	0.3435 (2)	0.9231 (2)	1.08285 (16)	0.0304 (4)
H15A	0.3335	0.9687	1.1484	0.036*
C16	0.1536 (3)	0.5920 (2)	0.54021 (18)	0.0381 (5)
H16A	0.1876	0.5075	0.5166	0.046*
C17	0.1268 (3)	0.6968 (2)	0.48396 (17)	0.0370 (5)
H17A	0.1392	0.6961	0.4139	0.044*
C18	0.0770 (2)	0.7629 (2)	0.63876 (17)	0.0332 (4)
H18A	0.0492	0.8161	0.6967	0.040*
C19	0.3079 (3)	1.1928 (3)	0.5203 (3)	0.0624 (8)
H19A	0.2910	1.2228	0.5917	0.075*
H19B	0.2522	1.2514	0.4752	0.075*
C20	0.4726 (6)	1.2096 (5)	0.5138 (4)	0.0694 (12)	0.468 (3)
H20A	0.5103	1.2987	0.5466	0.083*	0.468 (3)
H20B	0.5296	1.1423	0.5495	0.083*	0.468 (3)
C20'	0.471 (3)	1.170 (2)	0.5558 (15)	0.052 (5)	0.157 (3)
H20C	0.5143	1.1269	0.4960	0.063*	0.157 (3)
H20D	0.5223	1.2580	0.5760	0.063*	0.157 (3)
C20"	0.4726 (6)	1.2096 (5)	0.5138 (4)	0.0694 (12)	0.375 (3)
H20E	0.4989	1.3055	0.5246	0.083*	0.375 (3)
H20F	0.5291	1.1696	0.5713	0.083*	0.375 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0221 (2)	0.02152 (19)	0.0215 (2)	0.00093 (14)	−0.00086 (15)	0.00388 (15)
Mn2	0.0317 (2)	0.0247 (2)	0.0220 (2)	0.00689 (16)	0.00537 (16)	0.00740 (16)
S1	0.0296 (2)	0.0271 (2)	0.0179 (2)	0.00167 (18)	0.00301 (17)	0.00406 (17)
O1	0.0464 (9)	0.0459 (9)	0.0230 (7)	0.0097 (7)	0.0036 (6)	0.0136 (6)
O2	0.0362 (8)	0.0391 (8)	0.0221 (7)	0.0021 (6)	0.0081 (6)	0.0030 (6)
O3	0.0412 (9)	0.0556 (10)	0.0300 (8)	−0.0160 (7)	0.0063 (7)	−0.0012 (7)
O4	0.0451 (9)	0.0316 (8)	0.0380 (8)	0.0094 (6)	0.0068 (7)	0.0029 (6)
O5	0.0443 (9)	0.0524 (10)	0.0327 (8)	−0.0091 (8)	0.0090 (7)	−0.0045 (7)
O6	0.150 (10)	0.085 (7)	0.111 (7)	−0.045 (6)	0.060 (6)	0.002 (4)
O6'	0.067 (8)	0.078 (9)	0.081 (9)	0.009 (7)	0.003 (7)	0.003 (7)
O6"	0.045 (3)	0.064 (6)	0.057 (4)	−0.016 (3)	0.018 (3)	−0.007 (3)
N1	0.0305 (9)	0.0244 (8)	0.0314 (9)	−0.0008 (6)	0.0023 (7)	0.0022 (7)
N2	0.0250 (8)	0.0257 (8)	0.0299 (9)	−0.0030 (6)	0.0025 (7)	0.0037 (7)
N3	0.0273 (9)	0.0310 (9)	0.0323 (9)	0.0050 (7)	0.0013 (7)	0.0073 (7)
N4	0.0250 (8)	0.0293 (8)	0.0411 (10)	0.0053 (7)	0.0037 (7)	0.0148 (7)
N5	0.0436 (10)	0.0291 (9)	0.0289 (9)	0.0108 (7)	0.0045 (8)	0.0085 (7)
N6	0.0292 (9)	0.0280 (8)	0.0351 (9)	0.0068 (7)	0.0021 (7)	0.0130 (7)
C1	0.0248 (9)	0.0247 (9)	0.0276 (10)	−0.0031 (7)	0.0020 (7)	0.0010 (7)
C2	0.0212 (9)	0.0283 (10)	0.0447 (12)	0.0022 (7)	−0.0005 (8)	0.0092 (9)
C3	0.0258 (10)	0.0277 (10)	0.0411 (12)	0.0006 (8)	−0.0009 (8)	0.0145 (9)
C4	0.0221 (9)	0.0293 (10)	0.0355 (11)	−0.0008 (7)	0.0015 (8)	0.0131 (8)
C5	0.0236 (9)	0.0273 (9)	0.0279 (10)	0.0037 (7)	0.0016 (7)	0.0082 (8)
C6	0.0276 (10)	0.0237 (9)	0.0312 (10)	−0.0007 (7)	0.0032 (8)	0.0089 (8)
C7	0.0278 (10)	0.0324 (10)	0.0289 (10)	−0.0057 (8)	0.0054 (8)	0.0000 (8)
C8	0.0272 (11)	0.0362 (12)	0.0680 (17)	0.0000 (9)	−0.0057 (10)	0.0281 (11)
C9	0.0265 (10)	0.0354 (11)	0.0434 (12)	0.0078 (8)	0.0060 (9)	0.0214 (9)
C10	0.0473 (13)	0.0278 (10)	0.0391 (12)	−0.0042 (9)	−0.0062 (10)	0.0136 (9)
C11	0.0403 (12)	0.0325 (11)	0.0333 (11)	−0.0012 (9)	−0.0042 (9)	0.0089 (9)
C12	0.0279 (10)	0.0248 (9)	0.0299 (10)	−0.0006 (7)	0.0032 (8)	0.0056 (8)
C13	0.0437 (14)	0.0489 (14)	0.0477 (14)	0.0144 (11)	0.0146 (11)	−0.0016 (11)
C14	0.0445 (13)	0.0492 (14)	0.0348 (12)	0.0061 (11)	0.0016 (10)	−0.0041 (10)
C15	0.0293 (10)	0.0328 (10)	0.0304 (10)	0.0075 (8)	0.0042 (8)	0.0083 (8)
C16	0.0495 (13)	0.0279 (10)	0.0374 (12)	0.0113 (9)	0.0065 (10)	0.0049 (9)
C17	0.0483 (13)	0.0339 (11)	0.0291 (11)	0.0095 (9)	0.0041 (9)	0.0053 (9)
C18	0.0375 (11)	0.0313 (10)	0.0328 (11)	0.0113 (9)	0.0053 (9)	0.0103 (8)
C19	0.0546 (17)	0.0564 (17)	0.070 (2)	−0.0079 (13)	0.0071 (15)	−0.0127 (15)
C20	0.062 (2)	0.068 (3)	0.074 (3)	−0.022 (2)	0.011 (2)	−0.007 (2)
C20'	0.050 (8)	0.051 (8)	0.051 (9)	−0.002 (7)	0.003 (7)	−0.007 (7)
C20"	0.062 (2)	0.068 (3)	0.074 (3)	−0.022 (2)	0.011 (2)	−0.007 (2)

Geometric parameters (Å, º)

Mn1—O1	2.2076 (14)	C1—C7	1.509 (3)
Mn1—O1^i	2.2077 (14)	C2—C3	1.391 (3)
Mn1—N1^i	2.2579 (16)	C2—H2A	0.9300
Mn1—N1	2.2579 (16)	C3—C4	1.389 (3)
Mn1—N3	2.2753 (16)	C3—C8^iii	1.516 (3)
Mn1—N3^i	2.2754 (16)	C4—C5	1.388 (3)
Mn2—O2	2.1551 (13)	C4—H4A	0.9300
Mn2—O2^ii	2.1551 (13)	C5—C6	1.385 (3)
Mn2—N5^ii	2.2045 (16)	C5—C9^iv	1.513 (3)
Mn2—N5	2.2045 (16)	C6—H6A	0.9300
Mn2—O5^ii	2.2687 (16)	C7—H7A	0.9700
Mn2—O5	2.2687 (16)	C7—H7B	0.9700
S1—O4	1.4523 (15)	C8—C3^v	1.516 (3)
S1—O1	1.4756 (14)	C8—H8A	0.9700
S1—O2	1.4804 (14)	C8—H8B	0.9700
S1—O3	1.4818 (16)	C9—C5^iv	1.513 (3)
O5—C19	1.424 (3)	C9—H9A	0.9700
O5—H5A	0.8200	C9—H9B	0.9700
O6—C20	1.421 (7)	C10—C11	1.354 (3)
O6—H6B	0.8200	C10—H10A	0.9300
O6'—C20'	1.405 (9)	C11—H11A	0.9300
O6'—H6'	0.8200	C12—H12A	0.9300
O6"—C20"	1.402 (7)	C13—C14	1.351 (3)
O6"—H6"A	0.8200	C13—H13A	0.9300
N1—C12	1.316 (3)	C14—H14A	0.9300
N1—C11	1.372 (3)	C15—H15A	0.9300
N2—C12	1.351 (2)	C16—C17	1.351 (3)
N2—C10	1.372 (3)	C16—H16A	0.9300
N2—C7	1.464 (3)	C17—H17A	0.9300
N3—C15	1.311 (3)	C18—H18A	0.9300
N3—C14	1.376 (3)	C19—C20"	1.480 (5)
N4—C15	1.343 (3)	C19—C20	1.480 (5)
N4—C13	1.361 (3)	C19—C20'	1.48 (2)
N4—C8	1.459 (3)	C19—H19A	0.9700
N5—C18	1.321 (3)	C19—H19B	0.9700
N5—C17	1.369 (3)	C20—H20A	0.9700
N6—C18	1.338 (2)	C20—H20B	0.9700
N6—C16	1.373 (3)	C20'—H20C	0.9700
N6—C9	1.461 (2)	C20'—H20D	0.9700
C1—C2	1.392 (3)	C20"—H20E	0.9700
C1—C6	1.392 (3)	C20"—H20F	0.9700
O1—Mn1—O1^i	180.0	C4—C5—C9^iv	117.71 (17)
O1—Mn1—N1^i	87.90 (6)	C5—C6—C1	120.33 (17)
O1^i—Mn1—N1^i	92.10 (6)	C5—C6—H6A	119.8
O1—Mn1—N1	92.10 (6)	C1—C6—H6A	119.8
O1^i—Mn1—N1	87.90 (6)	N2—C7—C1	112.88 (16)
N1^i—Mn1—N1	180.0	N2—C7—H7A	109.0
O1—Mn1—N3	87.45 (6)	C1—C7—H7A	109.0
O1^i—Mn1—N3	92.55 (6)	N2—C7—H7B	109.0
N1^i—Mn1—N3	89.81 (6)	C1—C7—H7B	109.0
N1—Mn1—N3	90.19 (6)	H7A—C7—H7B	107.8
O1—Mn1—N3^i	92.55 (6)	N4—C8—C3^v	112.87 (17)
O1^i—Mn1—N3^i	87.45 (6)	N4—C8—H8A	109.0
N1^i—Mn1—N3^i	90.19 (6)	C3^v—C8—H8A	109.0
N1—Mn1—N3^i	89.81 (6)	N4—C8—H8B	109.0
N3—Mn1—N3^i	180.0	C3^v—C8—H8B	109.0
O2—Mn2—O2^ii	180.0	H8A—C8—H8B	107.8
O2—Mn2—N5^ii	90.08 (6)	N6—C9—C5^iv	113.21 (16)
O2^ii—Mn2—N5^ii	89.92 (6)	N6—C9—H9A	108.9
O2—Mn2—N5	89.92 (6)	C5^iv—C9—H9A	108.9
O2^ii—Mn2—N5	90.08 (6)	N6—C9—H9B	108.9
N5^ii—Mn2—N5	180.0	C5^iv—C9—H9B	108.9
O2—Mn2—O5^ii	90.61 (5)	H9A—C9—H9B	107.7
O2^ii—Mn2—O5^ii	89.39 (5)	C11—C10—N2	106.47 (18)
N5^ii—Mn2—O5^ii	88.43 (7)	C11—C10—H10A	126.8
N5—Mn2—O5^ii	91.57 (7)	N2—C10—H10A	126.8
O2—Mn2—O5	89.39 (5)	C10—C11—N1	109.63 (19)
O2^ii—Mn2—O5	90.61 (5)	C10—C11—H11A	125.2
N5^ii—Mn2—O5	91.57 (7)	N1—C11—H11A	125.2
N5—Mn2—O5	88.43 (7)	N1—C12—N2	111.43 (17)
O5^ii—Mn2—O5	180.0	N1—C12—H12A	124.3
O4—S1—O1	110.43 (9)	N2—C12—H12A	124.3
O4—S1—O2	110.33 (9)	C14—C13—N4	106.2 (2)
O1—S1—O2	108.17 (9)	C14—C13—H13A	126.9
O4—S1—O3	110.72 (10)	N4—C13—H13A	126.9
O1—S1—O3	108.70 (10)	C13—C14—N3	110.2 (2)
O2—S1—O3	108.43 (9)	C13—C14—H14A	124.9
S1—O1—Mn1	146.27 (10)	N3—C14—H14A	124.9
S1—O2—Mn2	135.37 (9)	N3—C15—N4	112.28 (19)
C19—O5—Mn2	123.12 (15)	N3—C15—H15A	123.9
C19—O5—H5A	109.5	N4—C15—H15A	123.9
Mn2—O5—H5A	105.1	C17—C16—N6	106.42 (18)
C20—O6—H6B	109.5	C17—C16—H16A	126.8
C20'—O6'—H6'	109.5	N6—C16—H16A	126.8
C20"—O6"—H6"A	109.5	C16—C17—N5	109.62 (19)
C12—N1—C11	105.78 (16)	C16—C17—H17A	125.2
C12—N1—Mn1	131.20 (13)	N5—C17—H17A	125.2
C11—N1—Mn1	123.01 (14)	N5—C18—N6	111.60 (19)
C12—N2—C10	106.68 (17)	N5—C18—H18A	124.2
C12—N2—C7	127.16 (17)	N6—C18—H18A	124.2
C10—N2—C7	126.09 (17)	O5—C19—C20"	115.1 (3)
C15—N3—C14	104.56 (18)	O5—C19—C20	115.1 (3)
C15—N3—Mn1	125.64 (14)	O5—C19—C20'	102.4 (8)
C14—N3—Mn1	129.39 (15)	O5—C19—H19A	108.5
C15—N4—C13	106.81 (18)	C20—C19—H19A	108.5
C15—N4—C8	125.7 (2)	O5—C19—H19B	108.5
C13—N4—C8	127.4 (2)	C20—C19—H19B	108.5
C18—N5—C17	105.53 (17)	H19A—C19—H19B	107.5
C18—N5—Mn2	126.19 (14)	O6—C20—C19	107.2 (6)
C17—N5—Mn2	128.10 (14)	O6—C20—H20A	110.3
C18—N6—C16	106.83 (17)	C19—C20—H20A	110.3
C18—N6—C9	126.53 (18)	O6—C20—H20B	110.3
C16—N6—C9	126.56 (17)	C19—C20—H20B	110.3
C2—C1—C6	119.60 (17)	H20A—C20—H20B	108.5
C2—C1—C7	119.96 (18)	O6'—C20'—C19	118.4 (16)
C6—C1—C7	120.44 (17)	O6'—C20'—H20C	107.7
C3—C2—C1	120.52 (18)	C19—C20'—H20C	107.7
C3—C2—H2A	119.7	O6'—C20'—H20D	107.7
C1—C2—H2A	119.7	C19—C20'—H20D	107.7
C4—C3—C2	119.01 (18)	H20C—C20'—H20D	107.1
C4—C3—C8^iii	118.93 (17)	O6"—C20"—C19	116.6 (5)
C2—C3—C8^iii	121.93 (18)	O6"—C20"—H20E	108.1
C5—C4—C3	121.05 (17)	C19—C20"—H20E	108.1
C5—C4—H4A	119.5	O6"—C20"—H20F	108.1
C3—C4—H4A	119.5	C19—C20"—H20F	108.1
C6—C5—C4	119.47 (17)	H20E—C20"—H20F	107.3
C6—C5—C9^iv	122.81 (17)
O4—S1—O1—Mn1	62.5 (2)	Mn1—N1—C11—C10	−179.97 (15)
O2—S1—O1—Mn1	−176.66 (15)	C11—N1—C12—N2	0.3 (2)
O3—S1—O1—Mn1	−59.1 (2)	Mn1—N1—C12—N2	179.67 (12)
O4—S1—O2—Mn2	−111.07 (13)	C10—N2—C12—N1	0.0 (2)
O1—S1—O2—Mn2	128.04 (12)	C7—N2—C12—N1	177.12 (17)
O3—S1—O2—Mn2	10.33 (16)	C15—N4—C13—C14	0.4 (3)
C6—C1—C2—C3	0.5 (3)	C8—N4—C13—C14	176.8 (2)
C7—C1—C2—C3	179.74 (19)	N4—C13—C14—N3	−0.7 (3)
C1—C2—C3—C4	−1.4 (3)	C15—N3—C14—C13	0.7 (3)
C1—C2—C3—C8^iii	−177.2 (2)	Mn1—N3—C14—C13	−172.10 (16)
C2—C3—C4—C5	0.9 (3)	C14—N3—C15—N4	−0.5 (2)
C8^iii—C3—C4—C5	176.9 (2)	Mn1—N3—C15—N4	172.70 (12)
C3—C4—C5—C6	0.4 (3)	C13—N4—C15—N3	0.1 (2)
C3—C4—C5—C9^iv	179.9 (2)	C8—N4—C15—N3	−176.46 (17)
C4—C5—C6—C1	−1.3 (3)	C18—N6—C16—C17	−0.5 (3)
C9^iv—C5—C6—C1	179.23 (19)	C9—N6—C16—C17	176.40 (19)
C2—C1—C6—C5	0.8 (3)	N6—C16—C17—N5	0.2 (3)
C7—C1—C6—C5	−178.41 (17)	C18—N5—C17—C16	0.1 (3)
C12—N2—C7—C1	117.3 (2)	Mn2—N5—C17—C16	−175.17 (16)
C10—N2—C7—C1	−66.2 (3)	C17—N5—C18—N6	−0.5 (3)
C2—C1—C7—N2	85.4 (2)	Mn2—N5—C18—N6	174.96 (14)
C6—C1—C7—N2	−95.4 (2)	C16—N6—C18—N5	0.6 (3)
C15—N4—C8—C3^v	96.8 (3)	C9—N6—C18—N5	−176.29 (18)
C13—N4—C8—C3^v	−79.0 (3)	Mn2—O5—C19—C20"	177.4 (3)
C18—N6—C9—C5^iv	−129.0 (2)	Mn2—O5—C19—C20	177.4 (3)
C16—N6—C9—C5^iv	54.7 (3)	Mn2—O5—C19—C20'	151.2 (8)
C12—N2—C10—C11	−0.4 (2)	O5—C19—C20—O6	70.5 (6)
C7—N2—C10—C11	−177.49 (18)	O5—C19—C20'—O6'	−58.6 (17)
N2—C10—C11—N1	0.6 (3)	O5—C19—C20"—O6"	49.5 (8)
C12—N1—C11—C10	−0.5 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O3^ii	0.82	1.83	2.606 (2)	159
O6—H6B···O3^ii	0.82	2.85	3.303 (13)	117

Symmetry code: (ii) −x, −y+2, −z+1.