catena-Poly[[[triaqua-[3-(4-carb-oxy-phen-oxy)phthalato-κO(2)]manganese(II)]-μ-4,4'-bipyridine-κ(2)N:N'] 4,4'-bipyridine monosolvate dihydrate].

In the title compound, {[Mn(C(15)H(8)O(7))(C(10)H(8)N(2))(H(2)O)(3)]·C(10)H(8)N(2)·2H(2)O}(n), the bridging mode of the coordinating 4,4'-bipyridine ligands leads to the formation of polymeric zigzag chains parallel to [0-11]. The chains are separated by 4,4'-bipyridine and water solvent mol-ecules. Within a chain, the Mn(II) atom is six-coordinated by two N atoms of the bridging 4,4'-bipyridine ligands, three water O atoms and one carboxyl-ate O atom of a single deprotonated 3-(4-carb-oxy-phen-oxy)phthalic acid ligand. Both coordinating and solvent 4,4'-bipyridine mol-ecules are situated on centres of inversion. An intricate network of O-H⋯O and O-H⋯N hydrogen bonds involving the carb-oxy group, the coordinating water mol-ecules and the two types of solvent mol-ecules leads to the formation of a three-dimensional network.

Related literature

For applications of metal-organic coordination polymers, see: Leininger et al. (2000 ▶). For a related structure, see: Wang et al. (2009 ▶). For synthetic details, see: Cai (2011 ▶); Wang et al. (2010 ▶).

Experimental

Crystal data

[Mn(C15H8O7)(C10H8N2)(H2O)3]·C10H8N2·2H2O

M = 757.60

Triclinic,

a = 10.765 (1) Å

b = 11.883 (2) Å

c = 14.574 (1) Å

α = 110.275 (3)°

β = 95.028 (1)°

γ = 94.970 (1)°

V = 1728.4 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.45 mm−1

T = 293 K

0.18 × 0.14 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.923, T max = 0.956

9338 measured reflections

6673 independent reflections

5695 reflections with I > 2σ(I)

R int = 0.016

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.095

S = 1.07

6673 reflections

469 parameters

18 restraints

H-atom parameters constrained

Δρmax = 0.25 e Å−3

Δρmin = −0.28 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813000585/wm2704sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813000585/wm2704Isup2.hkl

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

[Mn(C15H8O7)(C10H8N2)(H2O)3]·C10H8N2·2H2O	Z = 2
Mr = 757.60	F(000) = 786
Triclinic, P1	Dx = 1.456 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 10.765 (1) Å	Cell parameters from 4836 reflections
b = 11.883 (2) Å	θ = 2.8–27.3°
c = 14.574 (1) Å	µ = 0.45 mm−1
α = 110.275 (3)°	T = 293 K
β = 95.028 (1)°	Block, pale yellow
γ = 94.970 (1)°	0.18 × 0.14 × 0.10 mm
V = 1728.4 (4) Å3

Bruker APEXII CCD area-detector diffractometer	6673 independent reflections
Radiation source: fine-focus sealed tube	5695 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
φ and ω scans	θmax = 26.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −13→13
Tmin = 0.923, Tmax = 0.956	k = −14→11
9338 measured reflections	l = −17→17

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.095	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0504P)2 + 0.3087P] where P = (Fo2 + 2Fc2)/3
6673 reflections	(Δ/σ)max = 0.001
469 parameters	Δρmax = 0.25 e Å−3
18 restraints	Δρmin = −0.28 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
C1	0.22064 (17)	0.38214 (17)	0.09394 (13)	0.0351 (4)
C2	0.21923 (16)	0.32151 (16)	0.16976 (12)	0.0306 (4)
C3	0.30439 (18)	0.23977 (18)	0.16908 (14)	0.0405 (4)
H3	0.3594	0.2230	0.1217	0.049*
C4	0.3092 (2)	0.1829 (2)	0.23714 (17)	0.0497 (5)
H4	0.3654	0.1271	0.2347	0.060*
C5	0.2290 (2)	0.2101 (2)	0.30932 (16)	0.0460 (5)
H5	0.2319	0.1736	0.3564	0.055*
C6	0.14559 (16)	0.29131 (17)	0.31048 (13)	0.0331 (4)
C7	0.13674 (15)	0.34762 (15)	0.24158 (12)	0.0279 (3)
C8	0.04632 (16)	0.44143 (16)	0.25351 (12)	0.0297 (4)
C9	−0.03649 (17)	0.26350 (17)	0.38774 (12)	0.0326 (4)
C10	−0.10301 (19)	0.31301 (19)	0.46616 (14)	0.0436 (5)
H10	−0.0692	0.3839	0.5175	0.052*
C11	−0.2197 (2)	0.25630 (19)	0.46742 (15)	0.0452 (5)
H11	−0.2649	0.2898	0.5198	0.054*
C12	−0.27071 (17)	0.14997 (17)	0.39170 (14)	0.0362 (4)
C13	−0.19944 (18)	0.09888 (18)	0.31669 (14)	0.0389 (4)
H13	−0.2310	0.0255	0.2673	0.047*
C14	−0.08209 (18)	0.15488 (18)	0.31369 (13)	0.0390 (4)
H14	−0.0352	0.1200	0.2629	0.047*
C15	−0.40006 (18)	0.09199 (19)	0.38805 (16)	0.0414 (5)
C16	−0.27139 (18)	0.5215 (2)	0.39115 (14)	0.0424 (5)
H16	−0.1840	0.5327	0.4007	0.051*
C17	−0.33425 (18)	0.5189 (2)	0.46953 (13)	0.0411 (5)
H17	−0.2889	0.5278	0.5294	0.049*
C18	−0.46457 (16)	0.50325 (16)	0.45902 (12)	0.0308 (4)
C19	−0.52447 (18)	0.4919 (2)	0.36711 (14)	0.0437 (5)
H19	−0.6118	0.4822	0.3558	0.052*
C20	−0.45483 (18)	0.4948 (2)	0.29281 (14)	0.0418 (5)
H20	−0.4977	0.4866	0.2322	0.050*
C21	−0.33741 (19)	0.22192 (17)	0.15354 (14)	0.0397 (4)
H21	−0.2945	0.2486	0.2170	0.048*
C22	−0.40125 (18)	0.10654 (17)	0.11631 (14)	0.0377 (4)
H22	−0.4018	0.0585	0.1549	0.045*
C23	−0.46453 (16)	0.06216 (15)	0.02145 (13)	0.0301 (4)
C24	−0.4605 (2)	0.14042 (18)	−0.03056 (14)	0.0427 (5)
H24	−0.5011	0.1153	−0.0947	0.051*
C25	−0.3962 (2)	0.25575 (18)	0.01303 (14)	0.0433 (5)
H25	−0.3966	0.3069	−0.0229	0.052*
C26	−0.1322 (3)	−0.1451 (2)	0.10978 (18)	0.0611 (6)
H26	−0.2113	−0.1668	0.1239	0.073*
C27	−0.1236 (2)	−0.0724 (2)	0.05370 (17)	0.0540 (5)
H27	−0.1954	−0.0462	0.0316	0.065*
C28	−0.0072 (2)	−0.03880 (19)	0.03055 (15)	0.0456 (5)
C29	0.0937 (3)	−0.0820 (3)	0.0666 (2)	0.0759 (8)
H29	0.1740	−0.0628	0.0531	0.091*
C30	0.0760 (3)	−0.1537 (3)	0.1224 (2)	0.0828 (9)
H30	0.1459	−0.1811	0.1459	0.099*
C31	0.2674 (2)	0.1347 (2)	0.54507 (17)	0.0488 (5)
H31	0.3170	0.2031	0.5897	0.059*
C32	0.1434 (2)	0.1140 (2)	0.55870 (16)	0.0476 (5)
H32	0.1111	0.1678	0.6114	0.057*
C33	0.06698 (17)	0.01304 (17)	0.49382 (13)	0.0346 (4)
C34	0.1222 (2)	−0.0622 (2)	0.41663 (16)	0.0470 (5)
H34	0.0751	−0.1310	0.3704	0.056*
C35	0.2468 (2)	−0.0349 (2)	0.40867 (17)	0.0503 (5)
H35	0.2820	−0.0869	0.3567	0.060*
N1	−0.33367 (14)	0.29750 (13)	0.10383 (11)	0.0338 (3)
N2	−0.32931 (14)	0.50875 (13)	0.30290 (10)	0.0322 (3)
N3	−0.0353 (3)	−0.18546 (18)	0.14443 (15)	0.0660 (6)
N4	0.31901 (15)	0.06186 (16)	0.47140 (13)	0.0441 (4)
O1	0.31950 (14)	0.38603 (18)	0.05648 (12)	0.0632 (5)
O2	0.12403 (13)	0.42516 (15)	0.07502 (11)	0.0503 (4)
O3	0.09298 (13)	0.54964 (12)	0.29372 (11)	0.0482 (4)
O4	−0.06826 (11)	0.40345 (11)	0.22663 (9)	0.0348 (3)
O5	0.07611 (12)	0.33003 (12)	0.39048 (9)	0.0390 (3)
O6	−0.45077 (14)	0.00500 (14)	0.31796 (12)	0.0570 (4)
O7	−0.45369 (14)	0.14505 (15)	0.46598 (12)	0.0591 (4)
H7A	−0.5359	0.1073	0.4620	0.089*
O8	−0.09546 (13)	0.65753 (11)	0.24523 (10)	0.0428 (3)
H8B	−0.0773	0.6960	0.2039	0.064*
H8A	−0.0193	0.6391	0.2712	0.064*
O9	−0.13290 (12)	0.43834 (12)	0.03593 (9)	0.0394 (3)
H9A	−0.0496	0.4192	0.0454	0.059*
H9B	−0.1268	0.4886	0.0025	0.059*
O10	−0.34951 (13)	0.57337 (13)	0.10870 (10)	0.0467 (4)
H10A	−0.3992	0.6371	0.1457	0.070*
H10B	−0.3349	0.5845	0.0581	0.070*
O11	0.47994 (18)	0.25126 (16)	0.77447 (14)	0.0716 (5)
H11B	0.5591	0.2710	0.7688	0.107*
H11A	0.4599	0.1757	0.7487	0.107*
O12	0.7365 (2)	0.32408 (19)	0.78175 (19)	0.0974 (7)
H12A	0.7474	0.3571	0.7392	0.146*
H12B	0.7518	0.3767	0.8394	0.146*
Mn1	−0.21832 (2)	0.48542 (2)	0.172224 (18)	0.02771 (9)

	U11	U22	U33	U12	U13	U23
C1	0.0356 (10)	0.0460 (11)	0.0300 (9)	0.0099 (8)	0.0119 (7)	0.0183 (8)
C2	0.0266 (8)	0.0398 (10)	0.0286 (8)	0.0061 (7)	0.0056 (7)	0.0151 (7)
C3	0.0353 (10)	0.0514 (12)	0.0410 (10)	0.0162 (9)	0.0126 (8)	0.0198 (9)
C4	0.0471 (12)	0.0560 (13)	0.0590 (13)	0.0237 (10)	0.0119 (10)	0.0313 (11)
C5	0.0468 (12)	0.0570 (13)	0.0485 (11)	0.0110 (10)	0.0060 (9)	0.0354 (10)
C6	0.0276 (9)	0.0441 (10)	0.0303 (9)	−0.0006 (8)	0.0040 (7)	0.0178 (8)
C7	0.0232 (8)	0.0353 (9)	0.0258 (8)	0.0018 (7)	0.0028 (6)	0.0120 (7)
C8	0.0317 (9)	0.0367 (10)	0.0230 (8)	0.0058 (7)	0.0089 (7)	0.0121 (7)
C9	0.0309 (9)	0.0435 (10)	0.0289 (8)	0.0010 (8)	0.0043 (7)	0.0204 (8)
C10	0.0453 (11)	0.0454 (11)	0.0346 (10)	−0.0045 (9)	0.0110 (8)	0.0082 (8)
C11	0.0442 (11)	0.0477 (12)	0.0438 (11)	0.0029 (9)	0.0202 (9)	0.0137 (9)
C12	0.0340 (10)	0.0403 (10)	0.0401 (10)	0.0038 (8)	0.0058 (8)	0.0215 (8)
C13	0.0383 (10)	0.0393 (10)	0.0352 (10)	−0.0006 (8)	0.0011 (8)	0.0107 (8)
C14	0.0383 (10)	0.0473 (11)	0.0308 (9)	0.0042 (9)	0.0095 (8)	0.0124 (8)
C15	0.0349 (10)	0.0448 (11)	0.0529 (12)	0.0052 (9)	0.0066 (9)	0.0277 (10)
C16	0.0278 (9)	0.0636 (13)	0.0347 (10)	−0.0014 (9)	0.0081 (8)	0.0170 (9)
C17	0.0303 (10)	0.0649 (13)	0.0255 (9)	−0.0017 (9)	0.0054 (7)	0.0141 (9)
C18	0.0299 (9)	0.0355 (9)	0.0267 (8)	0.0017 (7)	0.0084 (7)	0.0103 (7)
C19	0.0274 (10)	0.0747 (15)	0.0362 (10)	0.0059 (9)	0.0084 (8)	0.0278 (10)
C20	0.0344 (10)	0.0663 (13)	0.0301 (9)	0.0061 (9)	0.0074 (8)	0.0232 (9)
C21	0.0447 (11)	0.0381 (10)	0.0356 (10)	−0.0010 (8)	−0.0047 (8)	0.0160 (8)
C22	0.0436 (11)	0.0337 (10)	0.0388 (10)	0.0023 (8)	−0.0007 (8)	0.0186 (8)
C23	0.0245 (8)	0.0324 (9)	0.0349 (9)	0.0049 (7)	0.0071 (7)	0.0129 (7)
C24	0.0513 (12)	0.0432 (11)	0.0331 (10)	−0.0078 (9)	−0.0046 (8)	0.0185 (8)
C25	0.0511 (12)	0.0425 (11)	0.0395 (10)	−0.0071 (9)	−0.0020 (9)	0.0234 (9)
C26	0.0784 (18)	0.0490 (13)	0.0538 (14)	−0.0004 (12)	0.0223 (13)	0.0144 (11)
C27	0.0596 (14)	0.0508 (13)	0.0529 (13)	0.0089 (11)	0.0139 (11)	0.0181 (10)
C28	0.0546 (13)	0.0408 (11)	0.0398 (10)	0.0057 (9)	0.0086 (9)	0.0119 (9)
C29	0.0595 (16)	0.091 (2)	0.100 (2)	0.0088 (15)	0.0103 (15)	0.0625 (18)
C30	0.080 (2)	0.091 (2)	0.099 (2)	0.0118 (17)	0.0021 (17)	0.0623 (19)
C31	0.0391 (11)	0.0498 (12)	0.0545 (13)	−0.0025 (9)	0.0011 (9)	0.0180 (10)
C32	0.0404 (11)	0.0472 (12)	0.0470 (11)	0.0034 (9)	0.0087 (9)	0.0062 (9)
C33	0.0323 (10)	0.0382 (10)	0.0359 (9)	0.0061 (8)	0.0036 (7)	0.0162 (8)
C34	0.0413 (11)	0.0472 (12)	0.0455 (11)	0.0034 (9)	0.0085 (9)	0.0075 (9)
C35	0.0452 (12)	0.0560 (13)	0.0531 (12)	0.0142 (10)	0.0201 (10)	0.0184 (11)
N1	0.0328 (8)	0.0338 (8)	0.0363 (8)	0.0010 (6)	0.0055 (6)	0.0150 (7)
N2	0.0312 (8)	0.0373 (8)	0.0299 (7)	0.0030 (6)	0.0108 (6)	0.0131 (6)
N3	0.0975 (18)	0.0476 (11)	0.0549 (12)	0.0008 (11)	0.0103 (12)	0.0225 (10)
N4	0.0341 (9)	0.0530 (10)	0.0556 (10)	0.0065 (8)	0.0080 (8)	0.0315 (9)
O1	0.0452 (9)	0.1113 (14)	0.0665 (10)	0.0290 (9)	0.0302 (8)	0.0637 (10)
O2	0.0394 (8)	0.0806 (11)	0.0559 (9)	0.0230 (7)	0.0185 (7)	0.0490 (8)
O3	0.0433 (8)	0.0358 (8)	0.0540 (9)	0.0023 (6)	0.0000 (7)	0.0039 (6)
O4	0.0253 (6)	0.0415 (7)	0.0448 (7)	0.0058 (5)	0.0076 (5)	0.0232 (6)
O5	0.0361 (7)	0.0532 (8)	0.0275 (6)	−0.0054 (6)	0.0077 (5)	0.0159 (6)
O6	0.0451 (9)	0.0530 (9)	0.0670 (10)	−0.0094 (7)	0.0011 (8)	0.0191 (8)
O7	0.0371 (8)	0.0688 (10)	0.0696 (10)	−0.0007 (7)	0.0192 (7)	0.0212 (8)
O8	0.0461 (8)	0.0319 (6)	0.0512 (7)	0.0025 (5)	0.0080 (6)	0.0159 (5)
O9	0.0374 (7)	0.0511 (8)	0.0389 (6)	0.0107 (6)	0.0165 (5)	0.0238 (5)
O10	0.0509 (9)	0.0626 (9)	0.0447 (8)	0.0262 (7)	0.0211 (6)	0.0336 (7)
O11	0.0669 (11)	0.0617 (11)	0.0820 (12)	0.0184 (9)	0.0249 (10)	0.0142 (9)
O12	0.0856 (15)	0.0685 (13)	0.1202 (18)	−0.0170 (11)	0.0203 (13)	0.0158 (12)
Mn1	0.02765 (15)	0.03050 (15)	0.02832 (15)	0.00391 (10)	0.00967 (10)	0.01315 (11)

C1—O1	1.242 (2)	C23—C24	1.389 (3)
C1—O2	1.248 (2)	C23—C23ii	1.496 (3)
C1—C2	1.514 (2)	C24—C25	1.384 (3)
C2—C3	1.390 (3)	C24—H24	0.9300
C2—C7	1.402 (2)	C25—N1	1.335 (2)
C3—C4	1.380 (3)	C25—H25	0.9300
C3—H3	0.9300	C26—N3	1.317 (4)
C4—C5	1.388 (3)	C26—C27	1.382 (3)
C4—H4	0.9300	C26—H26	0.9300
C5—C6	1.371 (3)	C27—C28	1.387 (3)
C5—H5	0.9300	C27—H27	0.9300
C6—C7	1.388 (2)	C28—C29	1.379 (4)
C6—O5	1.404 (2)	C28—C28iii	1.495 (4)
C7—C8	1.518 (2)	C29—C30	1.380 (4)
C8—O3	1.250 (2)	C29—H29	0.9300
C8—O4	1.255 (2)	C30—N3	1.324 (4)
C9—O5	1.378 (2)	C30—H30	0.9300
C9—C14	1.380 (3)	C31—N4	1.325 (3)
C9—C10	1.384 (3)	C31—C32	1.381 (3)
C10—C11	1.378 (3)	C31—H31	0.9300
C10—H10	0.9300	C32—C33	1.384 (3)
C11—C12	1.387 (3)	C32—H32	0.9300
C11—H11	0.9300	C33—C34	1.389 (3)
C12—C13	1.386 (3)	C33—C33iv	1.488 (4)
C12—C15	1.487 (3)	C34—C35	1.377 (3)
C13—C14	1.387 (3)	C34—H34	0.9300
C13—H13	0.9300	C35—N4	1.324 (3)
C14—H14	0.9300	C35—H35	0.9300
C15—O6	1.218 (3)	N1—Mn1	2.2982 (15)
C15—O7	1.305 (3)	N2—Mn1	2.2852 (14)
C16—N2	1.332 (2)	O4—Mn1	2.1842 (12)
C16—C17	1.385 (3)	O7—H7A	0.9440
C16—H16	0.9300	O8—Mn1	2.2002 (13)
C17—C18	1.387 (3)	O8—H8B	0.8974
C17—H17	0.9300	O8—H8A	0.9473
C18—C19	1.391 (3)	O9—Mn1	2.1780 (12)
C18—C18i	1.493 (3)	O9—H9A	0.9544
C19—C20	1.378 (3)	O9—H9B	0.8941
C19—H19	0.9300	O10—Mn1	2.1543 (13)
C20—N2	1.336 (2)	O10—H10A	0.9941
C20—H20	0.9300	O10—H10B	0.8189
C21—N1	1.335 (2)	O11—H11B	0.8822
C21—C22	1.379 (3)	O11—H11A	0.8438
C21—H21	0.9300	O12—H12A	0.8519
C22—C23	1.386 (2)	O12—H12B	0.8467
C22—H22	0.9300
O1—C1—O2	125.40 (17)	C23—C24—H24	120.0
O1—C1—C2	116.66 (16)	N1—C25—C24	123.56 (17)
O2—C1—C2	117.94 (15)	N1—C25—H25	118.2
C3—C2—C7	119.39 (16)	C24—C25—H25	118.2
C3—C2—C1	118.72 (16)	N3—C26—C27	124.1 (2)
C7—C2—C1	121.88 (15)	N3—C26—H26	117.9
C4—C3—C2	121.53 (18)	C27—C26—H26	117.9
C4—C3—H3	119.2	C26—C27—C28	119.6 (2)
C2—C3—H3	119.2	C26—C27—H27	120.2
C3—C4—C5	119.19 (18)	C28—C27—H27	120.2
C3—C4—H4	120.4	C29—C28—C27	116.0 (2)
C5—C4—H4	120.4	C29—C28—C28iii	122.3 (3)
C6—C5—C4	119.33 (18)	C27—C28—C28iii	121.7 (3)
C6—C5—H5	120.3	C28—C29—C30	120.3 (3)
C4—C5—H5	120.3	C28—C29—H29	119.9
C5—C6—C7	122.68 (17)	C30—C29—H29	119.9
C5—C6—O5	119.04 (16)	N3—C30—C29	123.5 (3)
C7—C6—O5	117.88 (16)	N3—C30—H30	118.2
C6—C7—C2	117.85 (16)	C29—C30—H30	118.2
C6—C7—C8	118.13 (15)	N4—C31—C32	123.0 (2)
C2—C7—C8	123.80 (15)	N4—C31—H31	118.5
O3—C8—O4	126.15 (16)	C32—C31—H31	118.5
O3—C8—C7	116.44 (15)	C31—C32—C33	119.97 (19)
O4—C8—C7	117.32 (15)	C31—C32—H32	120.0
O5—C9—C14	123.86 (16)	C33—C32—H32	120.0
O5—C9—C10	115.14 (16)	C32—C33—C34	116.35 (18)
C14—C9—C10	121.01 (17)	C32—C33—C33iv	121.7 (2)
C11—C10—C9	119.41 (18)	C34—C33—C33iv	122.0 (2)
C11—C10—H10	120.3	C35—C34—C33	119.9 (2)
C9—C10—H10	120.3	C35—C34—H34	120.1
C10—C11—C12	120.90 (18)	C33—C34—H34	120.1
C10—C11—H11	119.6	N4—C35—C34	123.2 (2)
C12—C11—H11	119.6	N4—C35—H35	118.4
C13—C12—C11	118.54 (17)	C34—C35—H35	118.4
C13—C12—C15	119.71 (18)	C25—N1—C21	116.29 (16)
C11—C12—C15	121.73 (18)	C25—N1—Mn1	123.23 (12)
C12—C13—C14	121.42 (18)	C21—N1—Mn1	120.44 (12)
C12—C13—H13	119.3	C16—N2—C20	116.29 (15)
C14—C13—H13	119.3	C16—N2—Mn1	120.71 (12)
C9—C14—C13	118.57 (17)	C20—N2—Mn1	122.44 (12)
C9—C14—H14	120.7	C26—N3—C30	116.5 (2)
C13—C14—H14	120.7	C35—N4—C31	117.55 (18)
O6—C15—O7	123.89 (19)	C8—O4—Mn1	130.26 (11)
O6—C15—C12	122.74 (19)	C9—O5—C6	119.08 (14)
O7—C15—C12	113.36 (18)	C15—O7—H7A	112.0
N2—C16—C17	123.57 (17)	Mn1—O8—H8B	113.1
N2—C16—H16	118.2	Mn1—O8—H8A	107.1
C17—C16—H16	118.2	H8B—O8—H8A	108.2
C16—C17—C18	120.29 (17)	Mn1—O9—H9A	111.3
C16—C17—H17	119.9	Mn1—O9—H9B	121.5
C18—C17—H17	119.9	H9A—O9—H9B	104.8
C17—C18—C19	115.83 (16)	Mn1—O10—H10A	126.1
C17—C18—C18i	121.8 (2)	Mn1—O10—H10B	118.1
C19—C18—C18i	122.4 (2)	H10A—O10—H10B	108.6
C20—C19—C18	120.22 (17)	H11B—O11—H11A	110.6
C20—C19—H19	119.9	H12A—O12—H12B	110.1
C18—C19—H19	119.9	O10—Mn1—O9	87.89 (5)
N2—C20—C19	123.78 (17)	O10—Mn1—O4	172.92 (5)
N2—C20—H20	118.1	O9—Mn1—O4	86.24 (5)
C19—C20—H20	118.1	O10—Mn1—O8	90.91 (6)
N1—C21—C22	123.81 (17)	O9—Mn1—O8	94.57 (5)
N1—C21—H21	118.1	O4—Mn1—O8	85.61 (5)
C22—C21—H21	118.1	O10—Mn1—N2	91.23 (5)
C21—C22—C23	120.05 (17)	O9—Mn1—N2	171.20 (5)
C21—C22—H22	120.0	O4—Mn1—N2	95.17 (5)
C23—C22—H22	120.0	O8—Mn1—N2	94.20 (5)
C22—C23—C24	116.28 (16)	O10—Mn1—N1	94.61 (6)
C22—C23—C23ii	121.71 (19)	O9—Mn1—N1	86.12 (5)
C24—C23—C23ii	122.0 (2)	O4—Mn1—N1	88.96 (5)
C25—C24—C23	119.98 (17)	O8—Mn1—N1	174.46 (5)
C25—C24—H24	120.0	N2—Mn1—N1	85.22 (5)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···N4v	0.94	1.64	2.577 (2)	170
O8—H8B···N3vi	0.90	1.94	2.814 (2)	166
O8—H8A···O3	0.95	1.76	2.662 (2)	158
O9—H9A···O2	0.95	1.87	2.8035 (19)	165
O9—H9B···O2vii	0.89	1.77	2.6595 (18)	174
O10—H10A···O11viii	0.99	1.78	2.771 (2)	173
O10—H10B···O1vii	0.82	1.84	2.6545 (19)	174
O11—H11B···O12	0.88	1.93	2.803 (3)	170
O11—H11A···O6iv	0.84	2.02	2.847 (2)	168
O12—H12A···O3ix	0.85	2.14	2.802 (3)	134
O12—H12B···O2ix	0.85	2.45	3.139 (3)	139

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7A⋯N4i	0.94	1.64	2.577 (2)	170
O8—H8B⋯N3ii	0.90	1.94	2.814 (2)	166
O8—H8A⋯O3	0.95	1.76	2.662 (2)	158
O9—H9A⋯O2	0.95	1.87	2.8035 (19)	165
O9—H9B⋯O2iii	0.89	1.77	2.6595 (18)	174
O10—H10A⋯O11iv	0.99	1.78	2.771 (2)	173
O10—H10B⋯O1iii	0.82	1.84	2.6545 (19)	174
O11—H11B⋯O12	0.88	1.93	2.803 (3)	170
O11—H11A⋯O6v	0.84	2.02	2.847 (2)	168
O12—H12A⋯O3vi	0.85	2.14	2.802 (3)	134
O12—H12B⋯O2vi	0.85	2.45	3.139 (3)	139

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .