Crystal structure of poly[[μ3-4,4'-(4,4'-bipyridine-2,6-diyl)dibenzoato]{μ2-4-[6-(4-carboxyphenyl)-4,4'-bipyridin-4'-ium-2-yl]benzoato}manganese(II)] hemi-hydrate].

The title compound, {[Mn(C24H14N2O4)(C24H16N2O4)]·0.5H2O} n , was obtained by the reaction of manganese nitrate with the ligand 4,4'-(4,4'-bi-pyridine-2,6-di-yl) di-benzoic acid under hydro-thermal conditions. The water O atom is located on a twofold rotation axis. The Mn(2+) ion is hepta-coordinated by six O atoms and one N atom from the ligands. In this structure, the ligands adopts two different forms, one completely deprotonated and one with a protonated N atom (pyridinium) and a carboxylic acid function. In the crystal, N-H⋯O and O-H⋯O hydrogen bonds consolidate the packing, forming a three-dimensional framework.

Related literature

For the preparation of the ligand 4,4′-(4,4′-bi­pyridine-2,6-di­yl) di­benzoic acid, see: Hou et al. (2010 ▶); Sharma et al. (2011 ▶); Song et al. (2012 ▶); Wei et al. (2013 ▶). For the structures and potential applications of metal-organic coordination polymers involving the 4,4′-(4,4′-bi­pyridine-2,6-di­yl) di­benzoic acid ligand, see: Eddaoudi et al. (2002 ▶); Hu et al. (2014 ▶); Iremonger et al. (2013 ▶).

Experimental

Crystal data

[Mn(C24H14N2O4)(C24H16N2O4)]·0.5H2O

M = 1709.42

Monoclinic,

a = 26.6396 (13) Å

b = 12.9853 (6) Å

c = 23.2326 (11) Å

β = 108.696 (1)°

V = 7612.6 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.42 mm−1

T = 173 K

0.21 × 0.17 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T min = 0.918, T max = 0.940

20674 measured reflections

7483 independent reflections

5375 reflections with I > 2σ(I)

R int = 0.044

Refinement

R[F 2 > 2σ(F 2)] = 0.061

wR(F 2) = 0.184

S = 1.08

7483 reflections

563 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.43 e Å−3

Δρmin = −0.73 e Å−3

Data collection: APEX2 (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; 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 ▶) and DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXTL and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S160053681402279X/bt6991sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681402279X/bt6991Isup2.hkl

Click here for additional data file.

x y z x y z x y z . DOI: 10.1107/S160053681402279X/bt6991fig1.tif

Extended asymmetric unit of the title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Lattice water mol­ecule has been omitted for clarity. Symmetry codes: i = −0.5 + x,0.5 − y,-0.5 + z; ii = −0.5 + x,0.5 + y,z; iii = x,-1 − y,0.5 + z.

Click here for additional data file.

. DOI: 10.1107/S160053681402279X/bt6991fig2.tif

View of the three-dimensional framework of the titled compound.

CCDC reference: 1029625

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Mn(C24H14N2O4)(C24H16N2O4)]·0.5H2O	F(000) = 3520
Mr = 1709.42	Dx = 1.491 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 7485 reflections
a = 26.6396 (13) Å	θ = 2.2–25.4°
b = 12.9853 (6) Å	µ = 0.42 mm−1
c = 23.2326 (11) Å	T = 173 K
β = 108.696 (1)°	Block, colourless
V = 7612.6 (6) Å3	0.21 × 0.17 × 0.15 mm
Z = 4

Bruker APEXII CCD diffractometer	7483 independent reflections
Radiation source: fine-focus sealed tube	5375 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
φ and ω scans	θmax = 26.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −32→30
Tmin = 0.918, Tmax = 0.940	k = −14→16
20674 measured reflections	l = −15→28

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.184	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0915P)2 + 12.2614P] where P = (Fo2 + 2Fc2)/3
7483 reflections	(Δ/σ)max = 0.005
563 parameters	Δρmax = 0.43 e Å−3
2 restraints	Δρmin = −0.73 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	0.15804 (14)	−0.1097 (3)	0.08907 (18)	0.0344 (8)
C2	0.18395 (13)	−0.1986 (3)	0.06874 (16)	0.0293 (7)
C3	0.23710 (14)	−0.2152 (3)	0.09876 (16)	0.0326 (8)
H3	0.2562	−0.1694	0.1300	0.039*
C4	0.26243 (14)	−0.2981 (3)	0.08354 (16)	0.0318 (8)
H4	0.2991	−0.3081	0.1042	0.038*
C5	0.23562 (13)	−0.3677 (3)	0.03863 (15)	0.0266 (7)
C6	0.18188 (14)	−0.3499 (3)	0.00811 (17)	0.0338 (8)
H6	0.1627	−0.3962	−0.0228	0.041*
C7	0.15633 (13)	−0.2654 (3)	0.02249 (17)	0.0340 (8)
H7	0.1200	−0.2531	0.0008	0.041*
C8	0.26298 (13)	−0.4577 (2)	0.02238 (15)	0.0269 (7)
C9	0.31506 (13)	−0.4836 (3)	0.05586 (15)	0.0287 (7)
H9	0.3344	−0.4435	0.0900	0.034*
C10	0.33808 (12)	−0.5687 (3)	0.03856 (15)	0.0269 (7)
C11	0.30880 (12)	−0.6252 (3)	−0.01208 (15)	0.0272 (7)
H11	0.3238	−0.6835	−0.0251	0.033*
C12	0.25691 (12)	−0.5943 (2)	−0.04327 (15)	0.0258 (7)
C13	0.22326 (12)	−0.6493 (3)	−0.09783 (15)	0.0263 (7)
C14	0.23137 (13)	−0.7519 (3)	−0.10911 (16)	0.0312 (8)
H14	0.2599	−0.7886	−0.0815	0.037*
C15	0.19837 (13)	−0.8015 (3)	−0.16011 (15)	0.0299 (8)
H15	0.2048	−0.8714	−0.1676	0.036*
C16	0.15599 (12)	−0.7494 (3)	−0.20014 (15)	0.0272 (7)
C17	0.14738 (13)	−0.6464 (3)	−0.18881 (15)	0.0289 (8)
H17	0.1182	−0.6102	−0.2157	0.035*
C18	0.18100 (13)	−0.5974 (3)	−0.13884 (16)	0.0305 (8)
H18	0.1753	−0.5268	−0.1321	0.037*
C19	0.11957 (13)	−0.8022 (3)	−0.25523 (16)	0.0313 (8)
C20	0.39234 (13)	−0.6008 (3)	0.07505 (15)	0.0274 (7)
C21	0.43358 (14)	−0.5290 (3)	0.09350 (18)	0.0362 (9)
H21	0.4277	−0.4592	0.0809	0.043*
C22	0.48295 (14)	−0.5609 (3)	0.13019 (18)	0.0392 (9)
H22	0.5113	−0.5130	0.1425	0.047*
C23	0.45268 (14)	−0.7284 (3)	0.13116 (16)	0.0345 (8)
H23	0.4598	−0.7974	0.1450	0.041*
C24	0.40293 (13)	−0.7023 (3)	0.09369 (15)	0.0296 (8)
H24	0.3761	−0.7532	0.0807	0.036*
C25	0.60244 (15)	0.3586 (3)	0.60941 (17)	0.0338 (8)
C26	0.57244 (14)	0.2860 (3)	0.56016 (16)	0.0317 (8)
C27	0.59484 (14)	0.1928 (3)	0.55209 (16)	0.0318 (8)
H27	0.6298	0.1761	0.5769	0.038*
C28	0.56647 (13)	0.1237 (3)	0.50800 (16)	0.0301 (8)
H28	0.5823	0.0604	0.5027	0.036*
C29	0.51525 (13)	0.1466 (3)	0.47165 (15)	0.0265 (7)
C30	0.49341 (14)	0.2411 (3)	0.47997 (16)	0.0319 (8)
H30	0.4584	0.2580	0.4553	0.038*
C31	0.52148 (14)	0.3096 (3)	0.52296 (16)	0.0322 (8)
H31	0.5060	0.3738	0.5274	0.039*
C32	0.48572 (13)	0.0733 (3)	0.42392 (15)	0.0269 (7)
C33	0.43125 (13)	0.0773 (3)	0.39712 (15)	0.0285 (7)
H33	0.4112	0.1278	0.4096	0.034*
C34	0.40595 (13)	0.0070 (3)	0.35177 (15)	0.0268 (7)
C35	0.43732 (13)	−0.0673 (3)	0.33699 (15)	0.0280 (7)
H35	0.4216	−0.1176	0.3069	0.034*
C36	0.49143 (13)	−0.0679 (3)	0.36618 (15)	0.0274 (7)
C37	0.52608 (13)	−0.1435 (3)	0.34994 (15)	0.0292 (8)
C38	0.57489 (14)	−0.1129 (3)	0.34588 (17)	0.0399 (9)
H38	0.5876	−0.0453	0.3578	0.048*
C39	0.60491 (14)	−0.1801 (4)	0.32468 (17)	0.0444 (10)
H39	0.6380	−0.1580	0.3216	0.053*
C40	0.58758 (16)	−0.2789 (3)	0.30785 (16)	0.0427 (10)
C41	0.54046 (17)	−0.3112 (3)	0.31473 (17)	0.0414 (10)
H41	0.5291	−0.3803	0.3052	0.050*
C42	0.50987 (15)	−0.2447 (3)	0.33512 (16)	0.0361 (8)
H42	0.4773	−0.2679	0.3392	0.043*
C43	0.6166 (2)	−0.3465 (5)	0.27726 (19)	0.0629 (15)
C44	0.34825 (13)	0.0117 (3)	0.32027 (15)	0.0273 (7)
C45	0.31961 (13)	−0.0753 (3)	0.29198 (16)	0.0316 (8)
H45	0.3368	−0.1400	0.2943	0.038*
C46	0.26630 (13)	−0.0657 (3)	0.26079 (17)	0.0323 (8)
H46	0.2475	−0.1252	0.2418	0.039*
C47	0.26692 (14)	0.1056 (3)	0.28296 (17)	0.0349 (8)
H47	0.2486	0.1691	0.2799	0.042*
C48	0.32012 (13)	0.1033 (3)	0.31498 (16)	0.0314 (8)
H48	0.3377	0.1643	0.3335	0.038*
N1	0.23494 (10)	−0.5126 (2)	−0.02606 (12)	0.0272 (6)
N2	0.49093 (11)	−0.6582 (3)	0.14826 (14)	0.0360 (7)
H2A	0.5220 (11)	−0.683 (4)	0.1709 (19)	0.072 (15)*
N3	0.51581 (11)	0.0015 (2)	0.40859 (13)	0.0284 (6)
N4	0.23962 (11)	0.0226 (2)	0.25578 (13)	0.0309 (7)
O1W	0.0000	−0.6159 (6)	−0.2500	0.152 (3)
H1W	0.0212	−0.6573	−0.2578	0.228*
O1	0.10826 (10)	−0.0956 (2)	0.05641 (13)	0.0434 (7)
H1A	0.093 (2)	−0.042 (3)	0.067 (3)	0.10 (2)*
O2	0.18203 (10)	−0.0563 (2)	0.13208 (12)	0.0422 (7)
O3	0.07424 (10)	−0.7629 (2)	−0.27753 (14)	0.0529 (8)
O4	0.13619 (11)	−0.8777 (2)	−0.27658 (12)	0.0443 (7)
O5	0.58121 (10)	0.44425 (19)	0.61444 (13)	0.0424 (7)
O6	0.64591 (12)	0.3330 (2)	0.64400 (13)	0.0508 (8)
O7	0.5949 (2)	−0.4275 (3)	0.2519 (2)	0.1033 (16)
O8	0.65938 (15)	−0.3180 (4)	0.27336 (17)	0.1032 (17)
Mn1	0.15272 (2)	0.03181 (4)	0.20581 (2)	0.03203 (18)

	U11	U22	U33	U12	U13	U23
C1	0.0324 (19)	0.0280 (19)	0.044 (2)	0.0034 (15)	0.0143 (17)	0.0026 (17)
C2	0.0343 (18)	0.0250 (17)	0.0314 (18)	0.0023 (14)	0.0145 (16)	0.0003 (15)
C3	0.0362 (19)	0.0307 (19)	0.0272 (18)	0.0016 (15)	0.0049 (15)	−0.0042 (15)
C4	0.0271 (17)	0.0338 (19)	0.0310 (18)	0.0062 (15)	0.0046 (15)	−0.0047 (16)
C5	0.0242 (16)	0.0286 (18)	0.0247 (17)	0.0034 (13)	0.0046 (14)	−0.0010 (14)
C6	0.0294 (18)	0.0320 (19)	0.035 (2)	0.0013 (15)	0.0030 (16)	−0.0069 (16)
C7	0.0240 (17)	0.036 (2)	0.040 (2)	0.0056 (15)	0.0083 (15)	0.0005 (17)
C8	0.0255 (17)	0.0280 (18)	0.0248 (17)	−0.0011 (14)	0.0046 (14)	−0.0027 (14)
C9	0.0264 (17)	0.0289 (18)	0.0259 (17)	0.0013 (14)	0.0013 (14)	−0.0040 (15)
C10	0.0214 (16)	0.0293 (17)	0.0274 (18)	0.0009 (13)	0.0041 (14)	−0.0010 (15)
C11	0.0213 (16)	0.0293 (18)	0.0292 (18)	0.0049 (13)	0.0057 (14)	−0.0039 (15)
C12	0.0226 (16)	0.0270 (17)	0.0258 (17)	0.0006 (13)	0.0050 (14)	−0.0030 (14)
C13	0.0202 (15)	0.0289 (18)	0.0263 (17)	−0.0009 (13)	0.0024 (13)	−0.0047 (14)
C14	0.0241 (17)	0.0330 (19)	0.0313 (19)	0.0062 (14)	0.0014 (15)	−0.0030 (16)
C15	0.0292 (18)	0.0270 (18)	0.0306 (18)	−0.0001 (14)	0.0058 (15)	−0.0072 (15)
C16	0.0236 (16)	0.0309 (18)	0.0243 (17)	−0.0031 (14)	0.0038 (14)	−0.0030 (14)
C17	0.0237 (16)	0.0302 (18)	0.0276 (18)	0.0015 (14)	0.0010 (14)	−0.0007 (15)
C18	0.0259 (17)	0.0283 (18)	0.0320 (19)	0.0012 (14)	0.0018 (15)	−0.0041 (15)
C19	0.0289 (18)	0.0287 (19)	0.0330 (19)	−0.0078 (15)	0.0050 (15)	−0.0027 (16)
C20	0.0227 (16)	0.0336 (19)	0.0225 (16)	0.0035 (14)	0.0026 (13)	−0.0056 (14)
C21	0.0274 (18)	0.0311 (19)	0.044 (2)	0.0019 (15)	0.0023 (16)	−0.0023 (17)
C22	0.0261 (18)	0.043 (2)	0.042 (2)	−0.0049 (16)	0.0024 (17)	−0.0054 (18)
C23	0.0318 (19)	0.037 (2)	0.0338 (19)	0.0085 (16)	0.0086 (16)	0.0018 (16)
C24	0.0244 (17)	0.0329 (19)	0.0284 (18)	0.0016 (14)	0.0040 (14)	−0.0038 (15)
C25	0.044 (2)	0.029 (2)	0.0313 (19)	−0.0137 (16)	0.0172 (18)	−0.0035 (16)
C26	0.041 (2)	0.0253 (18)	0.0304 (19)	−0.0086 (15)	0.0140 (16)	−0.0005 (15)
C27	0.0335 (19)	0.0294 (19)	0.0308 (19)	−0.0025 (15)	0.0079 (15)	0.0021 (15)
C28	0.0326 (18)	0.0244 (17)	0.0318 (19)	0.0007 (14)	0.0080 (15)	0.0012 (15)
C29	0.0273 (17)	0.0256 (17)	0.0264 (17)	−0.0030 (13)	0.0084 (14)	−0.0016 (14)
C30	0.0272 (17)	0.0319 (19)	0.036 (2)	0.0003 (15)	0.0100 (15)	−0.0010 (16)
C31	0.0366 (19)	0.0257 (18)	0.037 (2)	−0.0009 (15)	0.0154 (17)	−0.0017 (15)
C32	0.0280 (17)	0.0246 (17)	0.0288 (18)	−0.0025 (14)	0.0099 (14)	0.0005 (14)
C33	0.0271 (17)	0.0282 (18)	0.0306 (18)	0.0019 (14)	0.0098 (15)	−0.0024 (15)
C34	0.0239 (16)	0.0298 (18)	0.0280 (17)	−0.0002 (14)	0.0101 (14)	0.0007 (14)
C35	0.0271 (17)	0.0312 (18)	0.0257 (17)	0.0008 (14)	0.0084 (14)	−0.0048 (15)
C36	0.0276 (17)	0.0306 (18)	0.0264 (17)	−0.0001 (14)	0.0120 (14)	0.0000 (15)
C37	0.0241 (17)	0.037 (2)	0.0244 (17)	0.0042 (14)	0.0054 (14)	−0.0029 (15)
C38	0.0272 (19)	0.050 (2)	0.040 (2)	0.0027 (16)	0.0085 (17)	−0.0037 (19)
C39	0.0243 (18)	0.074 (3)	0.035 (2)	0.0143 (19)	0.0096 (16)	−0.002 (2)
C40	0.045 (2)	0.056 (3)	0.0226 (18)	0.032 (2)	0.0046 (17)	0.0037 (18)
C41	0.059 (3)	0.033 (2)	0.031 (2)	0.0160 (18)	0.0136 (19)	0.0010 (17)
C42	0.040 (2)	0.039 (2)	0.0318 (19)	0.0010 (16)	0.0154 (17)	−0.0003 (17)
C43	0.066 (3)	0.089 (4)	0.032 (2)	0.051 (3)	0.012 (2)	0.008 (2)
C44	0.0265 (17)	0.0320 (18)	0.0245 (17)	0.0004 (14)	0.0098 (14)	−0.0038 (15)
C45	0.0247 (17)	0.0300 (18)	0.039 (2)	0.0043 (14)	0.0080 (15)	−0.0021 (16)
C46	0.0284 (18)	0.0307 (19)	0.036 (2)	−0.0004 (15)	0.0079 (16)	−0.0075 (16)
C47	0.0307 (19)	0.0295 (19)	0.043 (2)	0.0057 (15)	0.0104 (17)	−0.0052 (17)
C48	0.0238 (17)	0.0345 (19)	0.036 (2)	−0.0018 (14)	0.0095 (15)	−0.0071 (16)
N1	0.0235 (14)	0.0294 (15)	0.0254 (15)	0.0022 (12)	0.0031 (12)	−0.0025 (12)
N2	0.0221 (15)	0.048 (2)	0.0312 (16)	0.0080 (14)	−0.0010 (13)	0.0013 (15)
N3	0.0259 (14)	0.0283 (15)	0.0315 (15)	0.0000 (12)	0.0098 (13)	−0.0038 (13)
N4	0.0234 (14)	0.0346 (17)	0.0318 (16)	0.0040 (12)	0.0047 (12)	−0.0031 (13)
O1W	0.149 (7)	0.129 (6)	0.172 (8)	0.000	0.042 (6)	0.000
O1	0.0311 (14)	0.0365 (15)	0.0582 (18)	0.0046 (12)	0.0081 (13)	−0.0120 (14)
O2	0.0382 (15)	0.0433 (15)	0.0389 (15)	0.0106 (12)	0.0038 (12)	−0.0126 (13)
O3	0.0278 (14)	0.0532 (18)	0.0603 (19)	−0.0012 (12)	−0.0104 (13)	−0.0183 (15)
O4	0.0503 (16)	0.0330 (14)	0.0421 (16)	−0.0022 (12)	0.0041 (13)	−0.0109 (13)
O5	0.0425 (15)	0.0308 (14)	0.0606 (19)	−0.0135 (12)	0.0258 (14)	−0.0171 (13)
O6	0.0585 (19)	0.0368 (15)	0.0405 (16)	−0.0039 (14)	−0.0073 (14)	−0.0072 (13)
O7	0.166 (5)	0.054 (2)	0.130 (4)	0.035 (3)	0.103 (4)	0.001 (3)
O8	0.051 (2)	0.186 (5)	0.067 (2)	0.044 (3)	0.0108 (19)	−0.044 (3)
Mn1	0.0287 (3)	0.0319 (3)	0.0309 (3)	0.0070 (2)	0.0030 (2)	0.0009 (2)

C1—O2	1.216 (4)	C28—H28	0.9500
C1—O1	1.312 (4)	C29—C30	1.397 (5)
C1—C2	1.497 (5)	C29—C32	1.482 (5)
C2—C3	1.380 (5)	C30—C31	1.368 (5)
C2—C7	1.394 (5)	C30—H30	0.9500
C3—C4	1.376 (5)	C31—H31	0.9500
C3—H3	0.9500	C32—N3	1.349 (4)
C4—C5	1.392 (5)	C32—C33	1.384 (5)
C4—H4	0.9500	C33—C34	1.393 (5)
C5—C6	1.398 (5)	C33—H33	0.9500
C5—C8	1.489 (5)	C34—C35	1.390 (5)
C6—C7	1.387 (5)	C34—C44	1.477 (5)
C6—H6	0.9500	C35—C36	1.383 (5)
C7—H7	0.9500	C35—H35	0.9500
C8—N1	1.339 (4)	C36—N3	1.339 (4)
C8—C9	1.397 (5)	C36—C37	1.477 (5)
C9—C10	1.384 (5)	C37—C38	1.391 (5)
C9—H9	0.9500	C37—C42	1.392 (5)
C10—C11	1.394 (5)	C38—C39	1.376 (5)
C10—C20	1.482 (4)	C38—H38	0.9500
C11—C12	1.398 (4)	C39—C40	1.378 (6)
C11—H11	0.9500	C39—H39	0.9500
C12—N1	1.334 (4)	C40—C41	1.380 (6)
C12—C13	1.481 (4)	C40—C43	1.491 (6)
C13—C14	1.387 (5)	C41—C42	1.372 (5)
C13—C18	1.394 (5)	C41—H41	0.9500
C14—C15	1.387 (5)	C42—H42	0.9500
C14—H14	0.9500	C43—O8	1.230 (7)
C15—C16	1.387 (5)	C43—O7	1.253 (7)
C15—H15	0.9500	C44—C48	1.390 (5)
C16—C17	1.395 (5)	C44—C45	1.403 (5)
C16—C19	1.502 (5)	C45—C46	1.378 (5)
C17—C18	1.374 (5)	C45—H45	0.9500
C17—H17	0.9500	C46—N4	1.334 (4)
C18—H18	0.9500	C46—H46	0.9500
C19—O4	1.242 (4)	C47—N4	1.339 (4)
C19—O3	1.260 (4)	C47—C48	1.374 (5)
C20—C24	1.387 (5)	C47—H47	0.9500
C20—C21	1.400 (5)	C48—H48	0.9500
C21—C22	1.382 (5)	N2—H2A	0.885 (19)
C21—H21	0.9500	N4—Mn1	2.236 (3)
C22—N2	1.326 (5)	O1W—H1W	0.8398
C22—H22	0.9500	O1—H1A	0.88 (2)
C23—N2	1.330 (5)	O2—Mn1	2.390 (3)
C23—C24	1.375 (5)	O4—Mn1ii	2.117 (3)
C23—H23	0.9500	O5—Mn1i	2.375 (3)
C24—H24	0.9500	O6—Mn1i	2.238 (3)
C25—O6	1.225 (5)	O7—Mn1iii	2.202 (4)
C25—O5	1.270 (4)	O8—Mn1iii	2.474 (4)
C25—C26	1.499 (5)	Mn1—O4iv	2.117 (3)
C25—Mn1i	2.629 (4)	Mn1—O7v	2.202 (4)
C26—C31	1.390 (5)	Mn1—O6vi	2.238 (3)
C26—C27	1.389 (5)	Mn1—O5vi	2.375 (3)
C27—C28	1.388 (5)	Mn1—O8v	2.474 (4)
C27—H27	0.9500	Mn1—C25vi	2.629 (4)
C28—C29	1.387 (5)
O2—C1—O1	124.3 (3)	C26—C31—H31	119.8
O2—C1—C2	121.7 (3)	N3—C32—C33	122.2 (3)
O1—C1—C2	114.1 (3)	N3—C32—C29	115.1 (3)
C3—C2—C7	119.7 (3)	C33—C32—C29	122.7 (3)
C3—C2—C1	117.6 (3)	C32—C33—C34	119.9 (3)
C7—C2—C1	122.7 (3)	C32—C33—H33	120.0
C4—C3—C2	120.1 (3)	C34—C33—H33	120.0
C4—C3—H3	120.0	C35—C34—C33	117.3 (3)
C2—C3—H3	120.0	C35—C34—C44	121.3 (3)
C3—C4—C5	121.6 (3)	C33—C34—C44	121.5 (3)
C3—C4—H4	119.2	C36—C35—C34	119.8 (3)
C5—C4—H4	119.2	C36—C35—H35	120.1
C4—C5—C6	118.0 (3)	C34—C35—H35	120.1
C4—C5—C8	121.6 (3)	N3—C36—C35	122.7 (3)
C6—C5—C8	120.4 (3)	N3—C36—C37	116.1 (3)
C7—C6—C5	120.7 (3)	C35—C36—C37	121.1 (3)
C7—C6—H6	119.7	C38—C37—C42	118.4 (3)
C5—C6—H6	119.7	C38—C37—C36	120.1 (3)
C6—C7—C2	120.0 (3)	C42—C37—C36	121.4 (3)
C6—C7—H7	120.0	C39—C38—C37	120.4 (4)
C2—C7—H7	120.0	C39—C38—H38	119.8
N1—C8—C9	121.8 (3)	C37—C38—H38	119.8
N1—C8—C5	116.4 (3)	C38—C39—C40	120.7 (4)
C9—C8—C5	121.9 (3)	C38—C39—H39	119.6
C10—C9—C8	119.0 (3)	C40—C39—H39	119.6
C10—C9—H9	120.5	C39—C40—C41	119.0 (3)
C8—C9—H9	120.5	C39—C40—C43	120.4 (4)
C9—C10—C11	119.0 (3)	C41—C40—C43	120.4 (4)
C9—C10—C20	120.0 (3)	C42—C41—C40	120.8 (4)
C11—C10—C20	120.9 (3)	C42—C41—H41	119.6
C10—C11—C12	118.6 (3)	C40—C41—H41	119.6
C10—C11—H11	120.7	C41—C42—C37	120.6 (4)
C12—C11—H11	120.7	C41—C42—H42	119.7
N1—C12—C11	121.9 (3)	C37—C42—H42	119.7
N1—C12—C13	115.9 (3)	O8—C43—O7	121.0 (5)
C11—C12—C13	122.1 (3)	O8—C43—C40	119.5 (6)
C14—C13—C18	118.4 (3)	O7—C43—C40	119.2 (5)
C14—C13—C12	122.5 (3)	C48—C44—C45	116.8 (3)
C18—C13—C12	119.1 (3)	C48—C44—C34	121.7 (3)
C13—C14—C15	120.9 (3)	C45—C44—C34	121.5 (3)
C13—C14—H14	119.6	C46—C45—C44	119.2 (3)
C15—C14—H14	119.6	C46—C45—H45	120.4
C16—C15—C14	120.2 (3)	C44—C45—H45	120.4
C16—C15—H15	119.9	N4—C46—C45	123.7 (3)
C14—C15—H15	119.9	N4—C46—H46	118.2
C15—C16—C17	119.2 (3)	C45—C46—H46	118.2
C15—C16—C19	120.8 (3)	N4—C47—C48	123.2 (3)
C17—C16—C19	119.9 (3)	N4—C47—H47	118.4
C18—C17—C16	120.1 (3)	C48—C47—H47	118.4
C18—C17—H17	120.0	C47—C48—C44	120.0 (3)
C16—C17—H17	120.0	C47—C48—H48	120.0
C17—C18—C13	121.2 (3)	C44—C48—H48	120.0
C17—C18—H18	119.4	C12—N1—C8	119.7 (3)
C13—C18—H18	119.4	C22—N2—C23	121.9 (3)
O4—C19—O3	124.9 (3)	C22—N2—H2A	124 (3)
O4—C19—C16	119.1 (3)	C23—N2—H2A	114 (3)
O3—C19—C16	116.0 (3)	C36—N3—C32	118.0 (3)
C24—C20—C21	118.4 (3)	C46—N4—C47	117.2 (3)
C24—C20—C10	120.6 (3)	C46—N4—Mn1	121.7 (2)
C21—C20—C10	120.9 (3)	C47—N4—Mn1	121.2 (2)
C22—C21—C20	119.2 (3)	C1—O1—H1A	114 (4)
C22—C21—H21	120.4	C1—O2—Mn1	131.0 (2)
C20—C21—H21	120.4	C19—O4—Mn1ii	161.0 (3)
N2—C22—C21	120.4 (3)	C25—O5—Mn1i	86.8 (2)
N2—C22—H22	119.8	C25—O6—Mn1i	94.2 (2)
C21—C22—H22	119.8	C43—O7—Mn1iii	98.2 (4)
N2—C23—C24	120.7 (3)	C43—O8—Mn1iii	86.0 (3)
N2—C23—H23	119.6	O4iv—Mn1—O7v	84.95 (14)
C24—C23—H23	119.6	O4iv—Mn1—N4	95.40 (11)
C23—C24—C20	119.4 (3)	O7v—Mn1—N4	121.96 (17)
C23—C24—H24	120.3	O4iv—Mn1—O6vi	152.41 (11)
C20—C24—H24	120.3	O7v—Mn1—O6vi	101.41 (13)
O6—C25—O5	122.1 (3)	N4—Mn1—O6vi	103.44 (11)
O6—C25—C26	119.4 (3)	O4iv—Mn1—O5vi	98.02 (10)
O5—C25—C26	118.4 (3)	O7v—Mn1—O5vi	85.26 (16)
O6—C25—Mn1i	58.08 (19)	N4—Mn1—O5vi	150.64 (10)
O5—C25—Mn1i	64.38 (19)	O6vi—Mn1—O5vi	56.42 (9)
C26—C25—Mn1i	172.5 (2)	O4iv—Mn1—O2	79.75 (11)
C31—C26—C27	119.0 (3)	O7v—Mn1—O2	154.57 (16)
C31—C26—C25	120.8 (3)	N4—Mn1—O2	79.91 (10)
C27—C26—C25	120.2 (3)	O6vi—Mn1—O2	83.88 (11)
C28—C27—C26	120.4 (3)	O5vi—Mn1—O2	76.98 (9)
C28—C27—H27	119.8	O4iv—Mn1—O8v	126.86 (15)
C26—C27—H27	119.8	O7v—Mn1—O8v	54.68 (16)
C29—C28—C27	120.5 (3)	N4—Mn1—O8v	82.01 (11)
C29—C28—H28	119.8	O6vi—Mn1—O8v	76.30 (14)
C27—C28—H28	119.8	O5vi—Mn1—O8v	109.74 (11)
C28—C29—C30	118.4 (3)	O2—Mn1—O8v	149.17 (13)
C28—C29—C32	120.0 (3)	O4iv—Mn1—C25vi	126.56 (11)
C30—C29—C32	121.5 (3)	O7v—Mn1—C25vi	92.25 (15)
C31—C30—C29	121.2 (3)	N4—Mn1—C25vi	129.14 (12)
C31—C30—H30	119.4	O6vi—Mn1—C25vi	27.68 (11)
C29—C30—H30	119.4	O5vi—Mn1—C25vi	28.84 (10)
C30—C31—C26	120.5 (3)	O2—Mn1—C25vi	80.96 (10)
C30—C31—H31	119.8	O8v—Mn1—C25vi	91.53 (13)
O2—C1—C2—C3	−3.1 (5)	C34—C35—C36—N3	−0.5 (5)
O1—C1—C2—C3	176.7 (3)	C34—C35—C36—C37	−177.7 (3)
O2—C1—C2—C7	175.2 (3)	N3—C36—C37—C38	−38.7 (5)
O1—C1—C2—C7	−5.1 (5)	C35—C36—C37—C38	138.7 (4)
C7—C2—C3—C4	−0.8 (5)	N3—C36—C37—C42	144.9 (3)
C1—C2—C3—C4	177.5 (3)	C35—C36—C37—C42	−37.7 (5)
C2—C3—C4—C5	−0.8 (5)	C42—C37—C38—C39	3.3 (5)
C3—C4—C5—C6	1.3 (5)	C36—C37—C38—C39	−173.2 (3)
C3—C4—C5—C8	−179.7 (3)	C37—C38—C39—C40	−0.8 (6)
C4—C5—C6—C7	−0.1 (5)	C38—C39—C40—C41	−2.5 (6)
C8—C5—C6—C7	−179.1 (3)	C38—C39—C40—C43	171.8 (4)
C5—C6—C7—C2	−1.5 (6)	C39—C40—C41—C42	3.2 (6)
C3—C2—C7—C6	2.0 (5)	C43—C40—C41—C42	−171.0 (3)
C1—C2—C7—C6	−176.2 (3)	C40—C41—C42—C37	−0.7 (6)
C4—C5—C8—N1	−172.5 (3)	C38—C37—C42—C41	−2.6 (5)
C6—C5—C8—N1	6.5 (5)	C36—C37—C42—C41	173.9 (3)
C4—C5—C8—C9	7.5 (5)	C39—C40—C43—O8	8.3 (6)
C6—C5—C8—C9	−173.5 (3)	C41—C40—C43—O8	−177.6 (4)
N1—C8—C9—C10	−0.3 (5)	C39—C40—C43—O7	−166.1 (4)
C5—C8—C9—C10	179.6 (3)	C41—C40—C43—O7	8.0 (6)
C8—C9—C10—C11	0.6 (5)	C35—C34—C44—C48	−153.3 (3)
C8—C9—C10—C20	−177.0 (3)	C33—C34—C44—C48	26.3 (5)
C9—C10—C11—C12	−0.6 (5)	C35—C34—C44—C45	23.9 (5)
C20—C10—C11—C12	177.1 (3)	C33—C34—C44—C45	−156.5 (3)
C10—C11—C12—N1	0.2 (5)	C48—C44—C45—C46	0.4 (5)
C10—C11—C12—C13	179.4 (3)	C34—C44—C45—C46	−177.0 (3)
N1—C12—C13—C14	−156.4 (3)	C44—C45—C46—N4	−0.2 (6)
C11—C12—C13—C14	24.4 (5)	N4—C47—C48—C44	0.1 (6)
N1—C12—C13—C18	22.0 (5)	C45—C44—C48—C47	−0.3 (5)
C11—C12—C13—C18	−157.2 (3)	C34—C44—C48—C47	177.0 (3)
C18—C13—C14—C15	0.3 (5)	C11—C12—N1—C8	0.1 (5)
C12—C13—C14—C15	178.7 (3)	C13—C12—N1—C8	−179.1 (3)
C13—C14—C15—C16	−1.2 (5)	C9—C8—N1—C12	−0.1 (5)
C14—C15—C16—C17	0.7 (5)	C5—C8—N1—C12	−180.0 (3)
C14—C15—C16—C19	−179.4 (3)	C21—C22—N2—C23	1.3 (6)
C15—C16—C17—C18	0.7 (5)	C24—C23—N2—C22	0.0 (6)
C19—C16—C17—C18	−179.2 (3)	C35—C36—N3—C32	1.4 (5)
C16—C17—C18—C13	−1.6 (5)	C37—C36—N3—C32	178.7 (3)
C14—C13—C18—C17	1.1 (5)	C33—C32—N3—C36	−0.4 (5)
C12—C13—C18—C17	−177.3 (3)	C29—C32—N3—C36	179.3 (3)
C15—C16—C19—O4	−24.3 (5)	C45—C46—N4—C47	0.0 (5)
C17—C16—C19—O4	155.6 (3)	C45—C46—N4—Mn1	−178.9 (3)
C15—C16—C19—O3	158.1 (3)	C48—C47—N4—C46	0.1 (6)
C17—C16—C19—O3	−22.0 (5)	C48—C47—N4—Mn1	178.9 (3)
C9—C10—C20—C24	129.8 (4)	O1—C1—O2—Mn1	33.0 (6)
C11—C10—C20—C24	−47.8 (5)	C2—C1—O2—Mn1	−147.3 (3)
C9—C10—C20—C21	−47.7 (5)	O3—C19—O4—Mn1ii	−88.5 (9)
C11—C10—C20—C21	134.7 (4)	C16—C19—O4—Mn1ii	94.1 (8)
C24—C20—C21—C22	−1.0 (5)	O6—C25—O5—Mn1i	−6.6 (4)
C10—C20—C21—C22	176.6 (3)	C26—C25—O5—Mn1i	172.2 (3)
C20—C21—C22—N2	−0.8 (6)	O5—C25—O6—Mn1i	7.0 (4)
N2—C23—C24—C20	−1.8 (5)	C26—C25—O6—Mn1i	−171.7 (3)
C21—C20—C24—C23	2.3 (5)	O8—C43—O7—Mn1iii	−3.5 (6)
C10—C20—C24—C23	−175.3 (3)	C40—C43—O7—Mn1iii	170.8 (3)
O6—C25—C26—C31	175.4 (3)	O7—C43—O8—Mn1iii	3.1 (5)
O5—C25—C26—C31	−3.4 (5)	C40—C43—O8—Mn1iii	−171.2 (3)
O6—C25—C26—C27	−3.0 (5)	C46—N4—Mn1—O4iv	29.1 (3)
O5—C25—C26—C27	178.3 (3)	C47—N4—Mn1—O4iv	−149.7 (3)
C31—C26—C27—C28	−0.7 (5)	C46—N4—Mn1—O7v	116.5 (3)
C25—C26—C27—C28	177.7 (3)	C47—N4—Mn1—O7v	−62.3 (3)
C26—C27—C28—C29	−0.4 (5)	C46—N4—Mn1—O6vi	−130.6 (3)
C27—C28—C29—C30	0.9 (5)	C47—N4—Mn1—O6vi	50.6 (3)
C27—C28—C29—C32	178.8 (3)	C46—N4—Mn1—O5vi	−87.9 (3)
C28—C29—C30—C31	−0.2 (5)	C47—N4—Mn1—O5vi	93.3 (3)
C32—C29—C30—C31	−178.1 (3)	C46—N4—Mn1—O2	−49.5 (3)
C29—C30—C31—C26	−0.9 (5)	C47—N4—Mn1—O2	131.7 (3)
C27—C26—C31—C30	1.4 (5)	C46—N4—Mn1—O8v	155.6 (3)
C25—C26—C31—C30	−177.0 (3)	C47—N4—Mn1—O8v	−23.2 (3)
C28—C29—C32—N3	−16.8 (5)	C46—N4—Mn1—C25vi	−119.0 (3)
C30—C29—C32—N3	161.0 (3)	C47—N4—Mn1—C25vi	62.3 (3)
C28—C29—C32—C33	162.8 (3)	C1—O2—Mn1—O4iv	61.8 (3)
C30—C29—C32—C33	−19.3 (5)	C1—O2—Mn1—O7v	7.9 (5)
N3—C32—C33—C34	−1.4 (5)	C1—O2—Mn1—N4	159.3 (3)
C29—C32—C33—C34	178.9 (3)	C1—O2—Mn1—O6vi	−95.9 (3)
C32—C33—C34—C35	2.2 (5)	C1—O2—Mn1—O5vi	−39.0 (3)
C32—C33—C34—C44	−177.3 (3)	C1—O2—Mn1—O8v	−145.8 (3)
C33—C34—C35—C36	−1.3 (5)	C1—O2—Mn1—C25vi	−68.1 (3)
C44—C34—C35—C36	178.2 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3vii	0.89 (2)	1.67 (2)	2.548 (4)	169 (5)
O1—H1A···O5vi	0.88 (2)	1.77 (3)	2.612 (4)	159 (6)
O1W—H1W···O3	0.84	2.12	2.963 (6)	180

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N2H2AO3i	0.89(2)	1.67(2)	2.548(4)	169(5)
O1H1AO5ii	0.88(2)	1.77(3)	2.612(4)	159(6)
O1WH1WO3	0.84	2.12	2.963(6)	180

Symmetry codes: (i) ; (ii) .