Poly[[diaqua-bis-(μ(3)-3,5-dicarb-oxy-benzo-ato-κ(3)O(1):O(3):O(5))bis-(μ(3)-5-carb-oxy-ben-zene-1,3-dicarboxyl-ato-κ(3)O(1):O(3):O(5))tetrakis(methylformamide-κO)tri-man-ganese(II)] dimethyl-formamide tetra-solvate].

In the title complex, {[Mn(3)(C(9)H(4)O(6))(2)(C(9)H(5)O(6))(2)(C(3)H(7)NO)(4)(H(2)O)(2)]·4C(3)H(7)NO}(n), one Mn(II) ion sits on an inversion center, and is six-coordinated by four O atoms from four anions (monoanionic and dianionic) derived from benzene-1,3,5-tricarboxylic acid and by two dimethyl-formamide (DMF) mol-ecules in a slightly distorted octa-hedral geometry. The other Mn(II) ion is six-coordinated by four O atoms from four monoanionic and dianionic ligands, one DMF mol-ecule and one water mol-ecule in a distorted octa-hedral geometry. The monoanionic and dianionic ligands bridge the Mn(II) ions, resulting in the formation of a layered structure parallel to (111) in which all of the carboxyl-ate groups of the anionic ligands coordinate the Mn(II) ions in a monodentate manner. Intra- and inter-molecular O-H⋯O hydrogen bonds are present in the structure.

Related literature

For background information on complexes based on aromatic polycarboxyl­ate ligands see: Hu et al. (2011 ▶); Prajapati et al. (2009 ▶).

Experimental

Crystal data

[Mn3(C9H4O6)2(C9H5O6)2(C3H7NO)4(H2O)2]·4C3H7NO

M = 1620.12

Triclinic,

a = 9.826 (2) Å

b = 13.290 (3) Å

c = 14.698 (3) Å

α = 73.22 (3)°

β = 83.32 (3)°

γ = 89.79 (3)°

V = 1824.2 (6) Å3

Z = 1

Mo Kα radiation

μ = 0.61 mm−1

T = 293 K

0.19 × 0.15 × 0.13 mm

Data collection

Rigaku Saturn CCD diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2004 ▶) T min = 0.894, T max = 0.925

18985 measured reflections

6589 independent reflections

5527 reflections with I > 2σ(I)

R int = 0.041

Refinement

R[F 2 > 2σ(F 2)] = 0.058

wR(F 2) = 0.116

S = 1.13

6589 reflections

478 parameters

H-atom parameters constrained

Δρmax = 0.33 e Å−3

Δρmin = −0.33 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2004 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812017734/pk2407sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812017734/pk2407Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Mn3(C9H4O6)2(C9H5O6)2(C3H7NO)4(H2O)2]·4C3H7NO	Z = 1
Mr = 1620.12	F(000) = 841
Triclinic, P1	Dx = 1.475 Mg m−3
a = 9.826 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.290 (3) Å	Cell parameters from 4578 reflections
c = 14.698 (3) Å	θ = 2.1–27.9°
α = 73.22 (3)°	µ = 0.61 mm−1
β = 83.32 (3)°	T = 293 K
γ = 89.79 (3)°	Prism, pale yellow
V = 1824.2 (6) Å3	0.19 × 0.15 × 0.13 mm

Rigaku Saturn CCD diffractometer	6589 independent reflections
Radiation source: fine-focus sealed tube	5527 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
Detector resolution: 28.6 pixels mm-1	θmax = 25.3°, θmin = 1.5°
ω scans	h = −11→11
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2004)	k = −15→15
Tmin = 0.894, Tmax = 0.925	l = −17→17
18985 measured reflections

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116	H-atom parameters constrained
S = 1.13	w = 1/[σ2(Fo2) + (0.0375P)2 + 1.4521P] where P = (Fo2 + 2Fc2)/3
6589 reflections	(Δ/σ)max = 0.001
478 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.33 e Å−3

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.

	x	y	z	Uiso*/Ueq
Mn1	1.0000	0.0000	1.0000	0.02695 (18)
Mn2	0.64081 (5)	0.63958 (4)	0.66415 (3)	0.02946 (15)
O1	1.0590 (2)	−0.06181 (19)	1.14191 (14)	0.0397 (6)
O2	0.8883 (3)	−0.04824 (19)	1.25050 (16)	0.0455 (7)
O3	1.3739 (2)	−0.35363 (17)	1.21994 (15)	0.0367 (6)
H3	1.4278	−0.3959	1.2067	0.044*
O4	1.3256 (2)	−0.48344 (17)	1.35625 (15)	0.0347 (6)
O5	0.8257 (2)	−0.31041 (18)	1.56693 (15)	0.0368 (6)
O6	0.9930 (2)	−0.42307 (18)	1.60883 (14)	0.0366 (6)
H6	0.9436	−0.4415	1.6601	0.044*
O7	0.9379 (2)	0.14743 (17)	1.02342 (16)	0.0399 (6)
O8	0.7940 (3)	0.11542 (18)	1.15860 (16)	0.0433 (6)
H8	0.8405	0.0635	1.1760	0.052*
O9	0.9107 (2)	0.49197 (19)	0.77771 (15)	0.0404 (6)
O10	0.7326 (2)	0.59048 (17)	0.79841 (14)	0.0352 (6)
O11	0.5417 (2)	0.55479 (17)	1.13690 (15)	0.0361 (6)
O12	0.5501 (2)	0.39777 (18)	1.24445 (15)	0.0371 (6)
O13	0.7895 (3)	−0.0676 (2)	1.03997 (18)	0.0452 (6)
O14	0.6417 (3)	0.8009 (2)	0.67832 (19)	0.0494 (7)
O15	0.7270 (3)	0.2236 (3)	0.4303 (3)	0.0780 (10)
O16	0.5669 (4)	0.7479 (2)	0.3566 (2)	0.0724 (10)
O17	0.5163 (3)	0.6835 (2)	0.54908 (16)	0.0487 (7)
H1W	0.4309	0.6935	0.5578	0.058*
H2W	0.5356	0.7017	0.4886	0.058*
N1	0.6125 (4)	−0.1482 (3)	0.9988 (3)	0.0671 (11)
N2	0.5441 (4)	0.9589 (3)	0.6541 (3)	0.0635 (11)
N3	0.9217 (3)	0.1958 (3)	0.3439 (3)	0.0556 (9)
N4	0.7209 (3)	0.6531 (3)	0.2913 (2)	0.0518 (9)
C1	0.9950 (3)	−0.0916 (2)	1.2233 (2)	0.0286 (7)
C2	1.3077 (3)	−0.3950 (2)	1.3036 (2)	0.0280 (7)
C3	0.9364 (3)	−0.3492 (2)	1.5497 (2)	0.0278 (7)
C4	1.0434 (3)	−0.1846 (2)	1.2955 (2)	0.0248 (7)
C5	1.1553 (3)	−0.2386 (2)	1.2693 (2)	0.0251 (7)
H5A	1.2024	−0.2142	1.2081	0.030*
C6	1.1979 (3)	−0.3284 (2)	1.3335 (2)	0.0249 (7)
C7	1.1277 (3)	−0.3631 (2)	1.4253 (2)	0.0267 (7)
H7A	1.1563	−0.4225	1.4692	0.032*
C8	1.0154 (3)	−0.3099 (2)	1.4523 (2)	0.0248 (7)
C9	0.9725 (3)	−0.2219 (2)	1.3868 (2)	0.0256 (7)
H9A	0.8956	−0.1874	1.4039	0.031*
C10	0.8490 (3)	0.1743 (2)	1.0777 (2)	0.0277 (7)
C11	0.8095 (3)	0.5173 (2)	0.8280 (2)	0.0294 (7)
C12	0.5792 (3)	0.4611 (2)	1.1633 (2)	0.0273 (7)
C13	0.7994 (3)	0.2843 (2)	1.0503 (2)	0.0255 (7)
C14	0.8347 (3)	0.3501 (2)	0.9576 (2)	0.0263 (7)
H14A	0.8927	0.3267	0.9139	0.032*
C15	0.7838 (3)	0.4499 (2)	0.9307 (2)	0.0261 (7)
C16	0.7011 (3)	0.4862 (2)	0.9972 (2)	0.0274 (7)
H16A	0.6671	0.5535	0.9789	0.033*
C17	0.6688 (3)	0.4234 (2)	1.0903 (2)	0.0241 (7)
C18	0.7168 (3)	0.3212 (2)	1.1157 (2)	0.0249 (7)
H18A	0.6930	0.2774	1.1774	0.030*
C19	0.7395 (4)	−0.1154 (3)	0.9906 (3)	0.0559 (11)
H19A	0.7990	−0.1296	0.9421	0.067*
C20	0.5644 (6)	−0.2077 (5)	0.9397 (5)	0.116 (2)
H20A	0.6388	−0.2159	0.8942	0.139*
H20B	0.4923	−0.1710	0.9064	0.139*
H20C	0.5303	−0.2757	0.9794	0.139*
C21	0.5122 (5)	−0.1282 (4)	1.0712 (4)	0.098 (2)
H21A	0.5550	−0.0888	1.1061	0.117*
H21B	0.4759	−0.1939	1.1144	0.117*
H21C	0.4392	−0.0888	1.0412	0.117*
C22	0.5480 (4)	0.8594 (3)	0.6588 (3)	0.0552 (11)
H22	0.4695	0.8301	0.6456	0.066*
C23	0.6581 (6)	1.0127 (4)	0.6741 (5)	0.114 (2)
H23A	0.7306	0.9646	0.6903	0.137*
H23B	0.6298	1.0402	0.7267	0.137*
H23C	0.6903	1.0695	0.6185	0.137*
C24	0.4228 (6)	1.0195 (5)	0.6292 (5)	0.127 (3)
H24A	0.3539	0.9750	0.6180	0.153*
H24B	0.4468	1.0768	0.5724	0.153*
H24C	0.3879	1.0467	0.6809	0.153*
C25	0.8121 (5)	0.2499 (4)	0.3601 (4)	0.0607 (12)
H25A	0.7995	0.3129	0.3142	0.073*
C26	1.0185 (5)	0.2309 (4)	0.2581 (3)	0.0760 (14)
H26A	0.9883	0.2951	0.2171	0.091*
H26B	1.0241	0.1780	0.2251	0.091*
H26C	1.1071	0.2427	0.2752	0.091*
C27	0.9503 (5)	0.0999 (4)	0.4130 (4)	0.0749 (14)
H27A	0.8797	0.0847	0.4664	0.090*
H27B	1.0372	0.1073	0.4346	0.090*
H27C	0.9533	0.0435	0.3842	0.090*
C28	0.6549 (5)	0.7381 (3)	0.2937 (3)	0.0561 (11)
H28	0.6772	0.7976	0.2421	0.067*
C29	0.8230 (5)	0.6526 (4)	0.2122 (4)	0.0839 (17)
H29A	0.8311	0.7212	0.1666	0.101*
H29B	0.7959	0.6020	0.1819	0.101*
H29C	0.9097	0.6342	0.2355	0.101*
C30	0.6934 (5)	0.5587 (4)	0.3695 (4)	0.0809 (16)
H30A	0.6237	0.5713	0.4161	0.097*
H30B	0.7757	0.5383	0.3986	0.097*
H30C	0.6625	0.5034	0.3461	0.097*

	U11	U22	U33	U12	U13	U23
Mn1	0.0340 (4)	0.0230 (4)	0.0199 (3)	0.0078 (3)	0.0035 (3)	−0.0028 (3)
Mn2	0.0318 (3)	0.0259 (3)	0.0237 (3)	0.0107 (2)	0.0054 (2)	0.0004 (2)
O1	0.0471 (14)	0.0431 (14)	0.0181 (11)	0.0165 (12)	0.0016 (10)	0.0054 (10)
O2	0.0545 (16)	0.0367 (14)	0.0310 (13)	0.0262 (12)	0.0112 (12)	0.0059 (11)
O3	0.0433 (14)	0.0298 (13)	0.0285 (12)	0.0131 (11)	0.0158 (11)	−0.0034 (10)
O4	0.0436 (14)	0.0260 (12)	0.0286 (12)	0.0148 (11)	0.0033 (10)	−0.0020 (10)
O5	0.0352 (13)	0.0341 (13)	0.0299 (12)	0.0105 (11)	0.0121 (10)	0.0019 (10)
O6	0.0400 (14)	0.0389 (14)	0.0187 (11)	0.0138 (11)	0.0079 (10)	0.0062 (10)
O7	0.0531 (15)	0.0250 (13)	0.0356 (13)	0.0154 (11)	0.0092 (12)	−0.0051 (10)
O8	0.0528 (16)	0.0280 (13)	0.0353 (13)	0.0196 (12)	0.0081 (12)	0.0069 (11)
O9	0.0427 (14)	0.0458 (15)	0.0214 (11)	0.0187 (12)	0.0107 (10)	0.0024 (11)
O10	0.0445 (14)	0.0304 (13)	0.0230 (12)	0.0138 (11)	−0.0003 (10)	0.0028 (10)
O11	0.0420 (14)	0.0272 (13)	0.0334 (13)	0.0096 (11)	0.0120 (11)	−0.0061 (10)
O12	0.0383 (13)	0.0415 (14)	0.0226 (12)	0.0127 (11)	0.0104 (10)	−0.0009 (11)
O13	0.0425 (15)	0.0472 (16)	0.0432 (15)	−0.0054 (12)	0.0042 (12)	−0.0125 (13)
O14	0.0489 (16)	0.0382 (15)	0.0610 (17)	0.0145 (13)	−0.0058 (13)	−0.0146 (13)
O15	0.059 (2)	0.100 (3)	0.083 (2)	0.029 (2)	−0.0168 (19)	−0.037 (2)
O16	0.106 (3)	0.063 (2)	0.0425 (16)	0.0293 (19)	0.0030 (17)	−0.0113 (15)
O17	0.0462 (15)	0.0636 (18)	0.0297 (13)	0.0191 (13)	−0.0018 (11)	−0.0045 (12)
N1	0.048 (2)	0.051 (2)	0.091 (3)	−0.0097 (18)	−0.018 (2)	0.001 (2)
N2	0.063 (2)	0.0298 (18)	0.093 (3)	0.0087 (17)	0.012 (2)	−0.0193 (19)
N3	0.050 (2)	0.059 (2)	0.061 (2)	0.0103 (18)	−0.0139 (18)	−0.0199 (19)
N4	0.050 (2)	0.049 (2)	0.062 (2)	0.0134 (17)	−0.0142 (17)	−0.0202 (18)
C1	0.0355 (18)	0.0255 (17)	0.0224 (16)	0.0061 (14)	−0.0014 (14)	−0.0039 (14)
C2	0.0293 (17)	0.0297 (18)	0.0245 (16)	0.0071 (14)	0.0000 (14)	−0.0083 (14)
C3	0.0346 (18)	0.0228 (16)	0.0219 (16)	0.0029 (14)	0.0041 (14)	−0.0032 (13)
C4	0.0301 (16)	0.0206 (16)	0.0205 (15)	0.0041 (13)	0.0000 (13)	−0.0020 (13)
C5	0.0311 (17)	0.0238 (16)	0.0178 (15)	0.0033 (13)	0.0024 (13)	−0.0042 (13)
C6	0.0261 (16)	0.0250 (16)	0.0213 (15)	0.0053 (13)	0.0038 (13)	−0.0059 (13)
C7	0.0312 (17)	0.0241 (16)	0.0206 (15)	0.0079 (14)	−0.0011 (13)	−0.0006 (13)
C8	0.0284 (16)	0.0267 (17)	0.0170 (15)	0.0047 (13)	0.0026 (13)	−0.0048 (13)
C9	0.0295 (17)	0.0245 (16)	0.0211 (15)	0.0082 (13)	0.0005 (13)	−0.0055 (13)
C10	0.0335 (18)	0.0233 (17)	0.0232 (16)	0.0077 (14)	−0.0033 (14)	−0.0021 (14)
C11	0.0358 (18)	0.0261 (17)	0.0216 (16)	0.0066 (15)	0.0011 (14)	−0.0013 (14)
C12	0.0258 (16)	0.0291 (18)	0.0240 (16)	0.0019 (14)	0.0036 (13)	−0.0058 (14)
C13	0.0294 (17)	0.0233 (16)	0.0221 (16)	0.0086 (13)	−0.0040 (13)	−0.0035 (13)
C14	0.0300 (17)	0.0287 (17)	0.0184 (15)	0.0101 (14)	0.0037 (13)	−0.0065 (13)
C15	0.0305 (17)	0.0259 (17)	0.0181 (15)	0.0093 (14)	−0.0003 (13)	−0.0012 (13)
C16	0.0304 (17)	0.0215 (16)	0.0258 (16)	0.0078 (13)	−0.0006 (14)	−0.0011 (13)
C17	0.0251 (16)	0.0260 (16)	0.0190 (15)	0.0056 (13)	0.0015 (13)	−0.0050 (13)
C18	0.0296 (16)	0.0229 (16)	0.0177 (15)	0.0032 (13)	0.0022 (13)	−0.0009 (13)
C19	0.053 (3)	0.045 (2)	0.062 (3)	0.003 (2)	−0.005 (2)	−0.005 (2)
C20	0.111 (5)	0.082 (4)	0.162 (6)	−0.023 (4)	−0.067 (5)	−0.027 (4)
C21	0.057 (3)	0.081 (4)	0.114 (5)	−0.011 (3)	0.006 (3)	0.030 (3)
C22	0.050 (2)	0.043 (2)	0.075 (3)	0.008 (2)	−0.003 (2)	−0.022 (2)
C23	0.108 (5)	0.063 (4)	0.181 (7)	−0.008 (3)	−0.005 (5)	−0.055 (4)
C24	0.102 (5)	0.064 (4)	0.218 (8)	0.044 (4)	−0.017 (5)	−0.045 (5)
C25	0.057 (3)	0.058 (3)	0.077 (3)	0.016 (2)	−0.036 (3)	−0.025 (3)
C26	0.059 (3)	0.086 (4)	0.082 (4)	−0.011 (3)	−0.011 (3)	−0.022 (3)
C27	0.076 (3)	0.065 (3)	0.086 (4)	0.027 (3)	−0.018 (3)	−0.021 (3)
C28	0.074 (3)	0.050 (3)	0.041 (2)	0.013 (2)	−0.006 (2)	−0.007 (2)
C29	0.051 (3)	0.100 (4)	0.116 (4)	0.006 (3)	0.008 (3)	−0.061 (4)
C30	0.092 (4)	0.048 (3)	0.104 (4)	0.023 (3)	−0.034 (3)	−0.014 (3)

Mn1—O1i	2.156 (2)	C3—C8	1.496 (4)
Mn1—O1	2.156 (2)	C4—C5	1.388 (4)
Mn1—O7i	2.159 (2)	C4—C9	1.390 (4)
Mn1—O7	2.159 (2)	C5—C6	1.388 (4)
Mn1—O13i	2.204 (3)	C5—H5A	0.9300
Mn1—O13	2.204 (3)	C6—C7	1.392 (4)
Mn2—O12ii	2.146 (2)	C7—C8	1.389 (4)
Mn2—O17	2.146 (3)	C7—H7A	0.9300
Mn2—O5iii	2.154 (2)	C8—C9	1.383 (4)
Mn2—O10	2.191 (2)	C9—H9A	0.9300
Mn2—O4i	2.199 (2)	C10—C13	1.496 (4)
Mn2—O14	2.213 (3)	C11—C15	1.509 (4)
O1—C1	1.239 (3)	C12—C17	1.504 (4)
O2—C1	1.274 (4)	C13—C18	1.383 (4)
O3—C2	1.290 (4)	C13—C14	1.394 (4)
O3—H3	0.8200	C14—C15	1.380 (4)
O4—C2	1.231 (4)	C14—H14A	0.9300
O4—Mn2i	2.199 (2)	C15—C16	1.390 (4)
O5—C3	1.233 (4)	C16—C17	1.382 (4)
O5—Mn2iv	2.154 (2)	C16—H16A	0.9300
O6—C3	1.283 (4)	C17—C18	1.396 (4)
O6—H6	0.8200	C18—H18A	0.9300
O7—C10	1.236 (4)	C19—H19A	0.9300
O8—C10	1.278 (4)	C20—H20A	0.9600
O8—H8	0.8200	C20—H20B	0.9600
O9—C11	1.273 (4)	C20—H20C	0.9600
O10—C11	1.238 (4)	C21—H21A	0.9600
O11—C12	1.261 (4)	C21—H21B	0.9600
O12—C12	1.247 (4)	C21—H21C	0.9600
O12—Mn2ii	2.146 (2)	C22—H22	0.9300
O13—C19	1.234 (5)	C23—H23A	0.9600
O14—C22	1.210 (4)	C23—H23B	0.9600
O15—C25	1.215 (5)	C23—H23C	0.9600
O16—C28	1.226 (5)	C24—H24A	0.9600
O17—H1W	0.8500	C24—H24B	0.9600
O17—H2W	0.8500	C24—H24C	0.9600
N1—C19	1.304 (5)	C25—H25A	0.9300
N1—C21	1.446 (6)	C26—H26A	0.9600
N1—C20	1.448 (6)	C26—H26B	0.9600
N2—C22	1.304 (5)	C26—H26C	0.9600
N2—C23	1.434 (6)	C27—H27A	0.9600
N2—C24	1.459 (6)	C27—H27B	0.9600
N3—C25	1.330 (5)	C27—H27C	0.9600
N3—C27	1.432 (5)	C28—H28	0.9300
N3—C26	1.448 (5)	C29—H29A	0.9600
N4—C28	1.308 (5)	C29—H29B	0.9600
N4—C30	1.438 (5)	C29—H29C	0.9600
N4—C29	1.446 (5)	C30—H30A	0.9600
C1—C4	1.496 (4)	C30—H30B	0.9600
C2—C6	1.500 (4)	C30—H30C	0.9600
O1i—Mn1—O1	180.00 (5)	O8—C10—C13	115.1 (3)
O1i—Mn1—O7i	93.27 (9)	O10—C11—O9	125.0 (3)
O1—Mn1—O7i	86.73 (9)	O10—C11—C15	119.5 (3)
O1i—Mn1—O7	86.73 (9)	O9—C11—C15	115.5 (3)
O1—Mn1—O7	93.27 (9)	O12—C12—O11	125.8 (3)
O7i—Mn1—O7	180.00 (11)	O12—C12—C17	117.5 (3)
O1i—Mn1—O13i	94.50 (10)	O11—C12—C17	116.7 (3)
O1—Mn1—O13i	85.50 (10)	C18—C13—C14	119.3 (3)
O7i—Mn1—O13i	92.31 (10)	C18—C13—C10	120.6 (3)
O7—Mn1—O13i	87.69 (10)	C14—C13—C10	120.1 (3)
O1i—Mn1—O13	85.50 (10)	C15—C14—C13	120.2 (3)
O1—Mn1—O13	94.50 (10)	C15—C14—H14A	119.9
O7i—Mn1—O13	87.69 (10)	C13—C14—H14A	119.9
O7—Mn1—O13	92.31 (10)	C14—C15—C16	119.8 (3)
O13i—Mn1—O13	180.0	C14—C15—C11	120.4 (3)
O12ii—Mn2—O17	85.30 (9)	C16—C15—C11	119.7 (3)
O12ii—Mn2—O5iii	175.24 (9)	C17—C16—C15	120.8 (3)
O17—Mn2—O5iii	91.68 (9)	C17—C16—H16A	119.6
O12ii—Mn2—O10	84.37 (9)	C15—C16—H16A	119.6
O17—Mn2—O10	169.63 (9)	C16—C17—C18	118.8 (3)
O5iii—Mn2—O10	98.57 (9)	C16—C17—C12	121.6 (3)
O12ii—Mn2—O4i	97.58 (9)	C18—C17—C12	119.6 (3)
O17—Mn2—O4i	91.90 (10)	C13—C18—C17	121.0 (3)
O5iii—Mn2—O4i	86.18 (9)	C13—C18—H18A	119.5
O10—Mn2—O4i	90.35 (9)	C17—C18—H18A	119.5
O12ii—Mn2—O14	90.70 (10)	O13—C19—N1	127.2 (4)
O17—Mn2—O14	91.98 (10)	O13—C19—H19A	116.4
O5iii—Mn2—O14	85.72 (10)	N1—C19—H19A	116.4
O10—Mn2—O14	87.24 (10)	N1—C20—H20A	109.5
O4i—Mn2—O14	171.11 (9)	N1—C20—H20B	109.5
C1—O1—Mn1	134.2 (2)	H20A—C20—H20B	109.5
C2—O3—H3	109.5	N1—C20—H20C	109.5
C2—O4—Mn2i	135.3 (2)	H20A—C20—H20C	109.5
C3—O5—Mn2iv	136.4 (2)	H20B—C20—H20C	109.5
C3—O6—H6	109.5	N1—C21—H21A	109.5
C10—O7—Mn1	135.3 (2)	N1—C21—H21B	109.5
C10—O8—H8	109.5	H21A—C21—H21B	109.5
C11—O10—Mn2	130.3 (2)	N1—C21—H21C	109.5
C12—O12—Mn2ii	131.1 (2)	H21A—C21—H21C	109.5
C19—O13—Mn1	120.7 (3)	H21B—C21—H21C	109.5
C22—O14—Mn2	122.6 (3)	O14—C22—N2	127.6 (4)
Mn2—O17—H1W	122.8	O14—C22—H22	116.2
Mn2—O17—H2W	132.6	N2—C22—H22	116.2
H1W—O17—H2W	104.2	N2—C23—H23A	109.5
C19—N1—C21	120.3 (4)	N2—C23—H23B	109.5
C19—N1—C20	123.2 (5)	H23A—C23—H23B	109.5
C21—N1—C20	116.5 (4)	N2—C23—H23C	109.5
C22—N2—C23	121.5 (4)	H23A—C23—H23C	109.5
C22—N2—C24	121.2 (4)	H23B—C23—H23C	109.5
C23—N2—C24	117.3 (4)	N2—C24—H24A	109.5
C25—N3—C27	120.5 (4)	N2—C24—H24B	109.5
C25—N3—C26	122.5 (4)	H24A—C24—H24B	109.5
C27—N3—C26	116.9 (4)	N2—C24—H24C	109.5
C28—N4—C30	119.5 (4)	H24A—C24—H24C	109.5
C28—N4—C29	121.3 (4)	H24B—C24—H24C	109.5
C30—N4—C29	119.2 (4)	O15—C25—N3	125.2 (5)
O1—C1—O2	124.2 (3)	O15—C25—H25A	117.4
O1—C1—C4	119.2 (3)	N3—C25—H25A	117.4
O2—C1—C4	116.6 (3)	N3—C26—H26A	109.5
O4—C2—O3	125.1 (3)	N3—C26—H26B	109.5
O4—C2—C6	120.1 (3)	H26A—C26—H26B	109.5
O3—C2—C6	114.8 (3)	N3—C26—H26C	109.5
O5—C3—O6	125.7 (3)	H26A—C26—H26C	109.5
O5—C3—C8	119.5 (3)	H26B—C26—H26C	109.5
O6—C3—C8	114.8 (3)	N3—C27—H27A	109.5
C5—C4—C9	119.4 (3)	N3—C27—H27B	109.5
C5—C4—C1	119.6 (3)	H27A—C27—H27B	109.5
C9—C4—C1	120.8 (3)	N3—C27—H27C	109.5
C4—C5—C6	120.8 (3)	H27A—C27—H27C	109.5
C4—C5—H5A	119.6	H27B—C27—H27C	109.5
C6—C5—H5A	119.6	O16—C28—N4	127.1 (4)
C5—C6—C7	119.0 (3)	O16—C28—H28	116.5
C5—C6—C2	121.8 (3)	N4—C28—H28	116.5
C7—C6—C2	118.9 (3)	N4—C29—H29A	109.5
C8—C7—C6	120.7 (3)	N4—C29—H29B	109.5
C8—C7—H7A	119.6	H29A—C29—H29B	109.5
C6—C7—H7A	119.6	N4—C29—H29C	109.5
C9—C8—C7	119.5 (3)	H29A—C29—H29C	109.5
C9—C8—C3	119.5 (3)	H29B—C29—H29C	109.5
C7—C8—C3	120.9 (3)	N4—C30—H30A	109.5
C8—C9—C4	120.6 (3)	N4—C30—H30B	109.5
C8—C9—H9A	119.7	H30A—C30—H30B	109.5
C4—C9—H9A	119.7	N4—C30—H30C	109.5
O7—C10—O8	125.4 (3)	H30A—C30—H30C	109.5
O7—C10—C13	119.5 (3)	H30B—C30—H30C	109.5
O1i—Mn1—O1—C1	−5 (100)	O6—C3—C8—C9	−172.0 (3)
O7i—Mn1—O1—C1	−109.8 (3)	O5—C3—C8—C7	−169.0 (3)
O7—Mn1—O1—C1	70.2 (3)	O6—C3—C8—C7	10.8 (5)
O13i—Mn1—O1—C1	157.6 (3)	C7—C8—C9—C4	−2.0 (5)
O13—Mn1—O1—C1	−22.4 (3)	C3—C8—C9—C4	−179.3 (3)
O1i—Mn1—O7—C10	116.8 (3)	C5—C4—C9—C8	2.2 (5)
O1—Mn1—O7—C10	−63.2 (3)	C1—C4—C9—C8	178.0 (3)
O7i—Mn1—O7—C10	49 (100)	Mn1—O7—C10—O8	24.4 (5)
O13i—Mn1—O7—C10	−148.6 (3)	Mn1—O7—C10—C13	−156.3 (2)
O13—Mn1—O7—C10	31.4 (3)	Mn2—O10—C11—O9	42.7 (5)
O12ii—Mn2—O10—C11	117.4 (3)	Mn2—O10—C11—C15	−136.3 (3)
O17—Mn2—O10—C11	122.5 (5)	Mn2ii—O12—C12—O11	45.8 (5)
O5iii—Mn2—O10—C11	−66.3 (3)	Mn2ii—O12—C12—C17	−135.1 (2)
O4i—Mn2—O10—C11	19.9 (3)	O7—C10—C13—C18	−169.7 (3)
O14—Mn2—O10—C11	−151.6 (3)	O8—C10—C13—C18	9.7 (5)
O1i—Mn1—O13—C19	47.3 (3)	O7—C10—C13—C14	11.2 (5)
O1—Mn1—O13—C19	−132.7 (3)	O8—C10—C13—C14	−169.4 (3)
O7i—Mn1—O13—C19	−46.2 (3)	C18—C13—C14—C15	−2.2 (5)
O7—Mn1—O13—C19	133.8 (3)	C10—C13—C14—C15	176.9 (3)
O13i—Mn1—O13—C19	76 (100)	C13—C14—C15—C16	2.3 (5)
O12ii—Mn2—O14—C22	−55.8 (3)	C13—C14—C15—C11	−173.6 (3)
O17—Mn2—O14—C22	29.6 (3)	O10—C11—C15—C14	158.2 (3)
O5iii—Mn2—O14—C22	121.1 (3)	O9—C11—C15—C14	−20.9 (5)
O10—Mn2—O14—C22	−140.1 (3)	O10—C11—C15—C16	−17.7 (5)
O4i—Mn2—O14—C22	145.4 (5)	O9—C11—C15—C16	163.2 (3)
Mn1—O1—C1—O2	−37.4 (5)	C14—C15—C16—C17	−0.1 (5)
Mn1—O1—C1—C4	142.3 (3)	C11—C15—C16—C17	175.8 (3)
Mn2i—O4—C2—O3	−42.0 (5)	C15—C16—C17—C18	−2.2 (5)
Mn2i—O4—C2—C6	135.3 (3)	C15—C16—C17—C12	−179.9 (3)
Mn2iv—O5—C3—O6	−25.9 (6)	O12—C12—C17—C16	176.9 (3)
Mn2iv—O5—C3—C8	154.0 (2)	O11—C12—C17—C16	−3.9 (5)
O1—C1—C4—C5	−2.6 (5)	O12—C12—C17—C18	−0.8 (5)
O2—C1—C4—C5	177.0 (3)	O11—C12—C17—C18	178.4 (3)
O1—C1—C4—C9	−178.4 (3)	C14—C13—C18—C17	−0.2 (5)
O2—C1—C4—C9	1.2 (5)	C10—C13—C18—C17	−179.3 (3)
C9—C4—C5—C6	−0.7 (5)	C16—C17—C18—C13	2.3 (5)
C1—C4—C5—C6	−176.6 (3)	C12—C17—C18—C13	−179.9 (3)
C4—C5—C6—C7	−0.9 (5)	Mn1—O13—C19—N1	−171.1 (3)
C4—C5—C6—C2	172.7 (3)	C21—N1—C19—O13	0.9 (7)
O4—C2—C6—C5	−166.6 (3)	C20—N1—C19—O13	−177.4 (5)
O3—C2—C6—C5	11.0 (5)	Mn2—O14—C22—N2	−171.6 (3)
O4—C2—C6—C7	7.1 (5)	C23—N2—C22—O14	−0.8 (8)
O3—C2—C6—C7	−175.4 (3)	C24—N2—C22—O14	179.8 (5)
C5—C6—C7—C8	1.1 (5)	C27—N3—C25—O15	−2.2 (7)
C2—C6—C7—C8	−172.8 (3)	C26—N3—C25—O15	179.2 (4)
C6—C7—C8—C9	0.4 (5)	C30—N4—C28—O16	−1.1 (7)
C6—C7—C8—C3	177.6 (3)	C29—N4—C28—O16	−179.9 (4)
O5—C3—C8—C9	8.2 (5)

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8···O2	0.82	1.67	2.448 (3)	157
O17—H2W···O16	0.85	1.85	2.694 (4)	176
O6—H6···O9iv	0.82	1.69	2.452 (3)	153
O3—H3···O11v	0.82	1.69	2.463 (3)	157
O17—H1W···O15vi	0.85	1.92	2.713 (4)	155

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O8—H8⋯O2	0.82	1.67	2.448 (3)	157
O17—H2W⋯O16	0.85	1.85	2.694 (4)	176
O6—H6⋯O9i	0.82	1.69	2.452 (3)	153
O3—H3⋯O11ii	0.82	1.69	2.463 (3)	157
O17—H1W⋯O15iii	0.85	1.92	2.713 (4)	155

Symmetry codes: (i) ; (ii) ; (iii) .