Synthesis, crystal structure and magnetic properties of a one-dimensional Mn²⁺ com­plex constructed from (+)-di­benzoyl­tartaric acid and 2,2′-bi­pyridine

The self-assembly reaction of (+)-di­benzoyl­tartaric acid (D-H₂DBTA) with 2,2′-bi­pyridine (bpy) and Mn(CH₃CO₂)₂·4H₂O yielded a new coordination polymer, namely, catena-poly[[[di­aqua­(2,2′-bi­pyridine-κ²N,N′)manganese(II)]-μ-2,3-bis­(benzo­yloxy)butane­dioato-κ²O²:O³] dihydrate], {[Mn(C₁₈H₁₂O₈)(C₁₀H₈N₂)(H₂O)₂]·2H₂O}_n or {[Mn(DBTA)(bpy)(H₂O)₂]·2H₂O}_n, (I). Complex (I) has been characterized by elemental analysis, IR spectroscopy, thermo­gravimetric analysis (TGA) and single-crystal and powder X-ray diffraction. It crystallizes in the ortho­rhom­bic space group P2₁2₁2₁. In the com­plex, the Mn²⁺ cation displays a distorted octa­hedral {MnO₄N₂} geometry, formed from two carboxyl­ate O atoms of two DBTA²⁻ ligands, two cis-oriented N atoms from one chelating 2,2′-bi­pyridine ligand and two trans-oriented O atoms from coordinated water mol­ecules. The polymer displays a 1D chain with an Mn...Mn distance of 9.428 (1) Å. Due to the presence of flexible polycarboxyl­ate and rigid bipyridyl ligands in the mol­ecular structure, a high thermal stability of the com­plex is attained. The magnetic properties of (I) were analyzed based on the mononuclear Mn²⁺ model due to the long intra­molecular Mn...Mn distance. The zero field splitting (ZFS) contribution in the high-spin Mn²⁺ cation is almost negligible and there are weak anti­ferromagnetic couplings between 1D chains [zJ′ = −0.062 (5) cm⁻¹], corresponding to an inter­molecular Mn...Mn distance of 7.860 (2) Å.

Computing details

Data collection: HKL-2000 (Zbyszek & Wladek, 1997); cell refinement: XDS CORRECT (Kabsch, 2010); data reduction: XDS INTEGRATE (Kabsch, 2010); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b).

catena-Poly[[[diaqua(2,2'-bipyridine-κ²N,N')manganese(II)]-µ-2,3-bis(benzoyloxy)butanedioato-κ²O²:O³] dihydrate]

Crystal data

[Mn(C18H12O8)(C10H8N2)(H2O)2]·2H2O	Dx = 1.441 Mg m^−3
Mr = 639.46	Synchrotron radiation, λ = 0.750 Å
Orthorhombic, P212121	Cell parameters from 49038 reflections
a = 7.8600 (16) Å	θ = 1.5–31.0°
b = 16.2330 (9) Å	µ = 0.59 mm^−1
c = 23.103 (2) Å	T = 100 K
V = 2947.7 (7) Å^3	Block, yellow
Z = 4	0.30 × 0.20 × 0.20 mm
F(000) = 1324

Data collection

Mardtb with mar165 CCD diffractometer	7919 independent reflections
Radiation source: BSRF, beamline 3W1A	7592 reflections with I > 2σ(I)
Detector resolution: 0.079 pixels mm^-1	Rint = 0.043
phi scan	θmax = 30.9°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	h = −10→10
Tmin = 0.709, Tmax = 0.746	k = −22→22
55869 measured reflections	l = −31→31

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.042	w = 1/[σ^2(Fo^2) + (0.050P)^2 + 2.5P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.111	(Δ/σ)max = 0.001
S = 1.04	Δρmax = 0.86 e Å^−3
7919 reflections	Δρmin = −0.81 e Å^−3
396 parameters	Absolute structure: Flack x determined using 3225 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: 0.005 (3)
Primary atom site location: dual

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.

Refinement. Multi-scan program SADABS was used for absorption correction (Sheldrick, 2008). The structures were solved by the direct method and refined by the full-matrix least squares method on F² using the SHELXS2018 (Sheldrick, 2015). All the non-H atoms were refined anisotropically.

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

	x	y	z	Uiso*/Ueq
C1	0.6801 (4)	0.35400 (18)	0.88298 (12)	0.0199 (5)
C2	0.8440 (4)	0.36044 (17)	0.91469 (11)	0.0180 (5)
C3	0.9946 (4)	0.3849 (2)	0.88758 (13)	0.0257 (6)
H3	0.9926	0.4020	0.8482	0.031*
C4	1.1483 (4)	0.3845 (2)	0.91804 (14)	0.0296 (7)
H4	1.2505	0.4010	0.8994	0.036*
C5	1.1510 (4)	0.3598 (2)	0.97540 (14)	0.0267 (6)
H5	1.2558	0.3591	0.9959	0.032*
C6	1.0018 (4)	0.33601 (18)	1.00333 (13)	0.0220 (6)
H6	1.0046	0.3197	1.0428	0.026*
C7	0.8486 (4)	0.33633 (18)	0.97308 (12)	0.0190 (5)
H7	0.7467	0.3202	0.9920	0.023*
C8	0.5874 (4)	0.30870 (15)	0.75124 (11)	0.0169 (5)
C9	0.5440 (4)	0.37940 (14)	0.79317 (10)	0.0158 (4)
H9A	0.4401	0.3645	0.8159	0.019*
C10	0.5106 (4)	0.45915 (15)	0.75943 (11)	0.0162 (5)
H10	0.4196	0.4491	0.7300	0.019*
C11	0.4551 (5)	0.53015 (16)	0.79991 (11)	0.0216 (5)
C12	0.6547 (3)	0.53885 (16)	0.68964 (11)	0.0138 (4)
C13	0.9751 (4)	0.5401 (2)	0.69427 (14)	0.0277 (6)
H13	0.9733	0.4975	0.7225	0.033*
C14	0.8232 (3)	0.56918 (16)	0.67063 (11)	0.0144 (4)
C15	1.1287 (4)	0.5736 (3)	0.67637 (18)	0.0386 (9)
H15	1.2320	0.5545	0.6930	0.046*
C16	1.1331 (4)	0.6350 (2)	0.63436 (16)	0.0317 (7)
H16	1.2388	0.6579	0.6226	0.038*
C17	0.9835 (4)	0.6625 (2)	0.60976 (15)	0.0303 (7)
H17	0.9863	0.7033	0.5803	0.036*
C18	0.8279 (4)	0.63035 (19)	0.62826 (13)	0.0229 (6)
H18	0.7248	0.6502	0.6119	0.027*
C19	0.4632 (5)	0.38398 (18)	0.59209 (13)	0.0306 (7)
H19	0.4640	0.3998	0.6317	0.037*
C20	0.4639 (8)	0.4451 (2)	0.55046 (16)	0.0472 (11)
H20	0.4628	0.5017	0.5612	0.057*
C21	0.4663 (9)	0.4220 (2)	0.49276 (17)	0.0615 (16)
H21	0.4713	0.4625	0.4632	0.074*
C22	0.4611 (8)	0.3389 (3)	0.47868 (15)	0.0495 (11)
H22	0.4587	0.3220	0.4393	0.059*
C23	0.4596 (5)	0.28034 (19)	0.52309 (12)	0.0268 (6)
C24	0.4591 (5)	0.18962 (19)	0.51186 (12)	0.0260 (6)
C25	0.4709 (7)	0.1573 (2)	0.45609 (14)	0.0437 (10)
H25	0.4792	0.1927	0.4235	0.052*
C26	0.4703 (7)	0.0716 (3)	0.44913 (16)	0.0495 (11)
H26	0.4785	0.0480	0.4116	0.059*
C27	0.4576 (7)	0.0221 (2)	0.49719 (16)	0.0459 (10)
H27	0.4570	−0.0362	0.4935	0.055*
C28	0.4458 (7)	0.0589 (2)	0.55099 (14)	0.0412 (9)
H28	0.4357	0.0245	0.5841	0.049*
Mn1	0.45461 (6)	0.20347 (2)	0.64733 (2)	0.01842 (11)
N1	0.4616 (4)	0.30312 (15)	0.57917 (10)	0.0224 (5)
N2	0.4479 (5)	0.14086 (16)	0.55878 (11)	0.0291 (6)
O1	0.3069 (3)	0.52435 (13)	0.82011 (10)	0.0296 (5)
O2	0.5641 (4)	0.58649 (13)	0.80903 (10)	0.0304 (5)
O3	0.6675 (2)	0.47900 (11)	0.73030 (8)	0.0144 (3)
O4	0.5203 (3)	0.56348 (14)	0.67142 (10)	0.0239 (4)
O5	0.6829 (3)	0.39501 (12)	0.83244 (8)	0.0203 (4)
O6	0.5571 (3)	0.3158 (2)	0.90007 (11)	0.0436 (8)
O7	0.7286 (3)	0.27436 (14)	0.75475 (10)	0.0266 (5)
O8	0.4698 (3)	0.29230 (12)	0.71571 (8)	0.0219 (4)
O9	0.7362 (3)	0.18918 (14)	0.65257 (11)	0.0267 (5)
H9B	0.753 (6)	0.213 (3)	0.685 (2)	0.036 (11)*
H9C	0.745 (7)	0.140 (3)	0.659 (2)	0.048 (14)*
O10	0.1762 (4)	0.2176 (2)	0.65488 (13)	0.0516 (8)
H10A	0.1328	0.2534	0.6773	0.062*
H10B	0.2085	0.2356	0.6221	0.062*
O12	0.0623 (5)	0.0663 (2)	0.65920 (15)	0.0547 (8)
H12A	0.0948	0.1136	0.6479	0.066*
H12B	0.1536	0.0498	0.6752	0.066*
O11	0.0711 (5)	0.3090 (5)	0.7435 (3)	0.160 (4)
H11A	−0.0096	0.2870	0.7624	0.193*
H11B	0.0696	0.3603	0.7357	0.193*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0233 (13)	0.0209 (12)	0.0155 (12)	0.0047 (11)	0.0055 (10)	0.0054 (10)
C2	0.0225 (13)	0.0162 (11)	0.0152 (11)	0.0021 (10)	0.0052 (10)	0.0005 (9)
C3	0.0287 (16)	0.0317 (15)	0.0168 (11)	−0.0061 (12)	0.0066 (10)	−0.0017 (11)
C4	0.0256 (15)	0.0365 (17)	0.0268 (15)	−0.0089 (13)	0.0070 (12)	−0.0050 (13)
C5	0.0237 (14)	0.0275 (15)	0.0290 (15)	0.0018 (12)	−0.0027 (12)	−0.0044 (12)
C6	0.0270 (14)	0.0194 (12)	0.0196 (12)	0.0053 (10)	0.0003 (10)	0.0006 (10)
C7	0.0222 (13)	0.0182 (12)	0.0167 (12)	0.0039 (10)	0.0051 (10)	0.0039 (9)
C8	0.0263 (13)	0.0096 (11)	0.0147 (10)	−0.0004 (9)	−0.0005 (9)	0.0025 (8)
C9	0.0264 (12)	0.0099 (9)	0.0110 (9)	−0.0024 (10)	0.0011 (10)	0.0010 (8)
C10	0.0228 (12)	0.0108 (10)	0.0149 (11)	−0.0005 (9)	0.0073 (9)	0.0015 (8)
C11	0.0393 (15)	0.0113 (10)	0.0143 (11)	0.0020 (12)	0.0109 (12)	0.0026 (8)
C12	0.0147 (11)	0.0130 (11)	0.0136 (10)	0.0002 (9)	0.0002 (9)	0.0030 (8)
C13	0.0142 (12)	0.0394 (17)	0.0294 (14)	0.0042 (12)	−0.0011 (11)	0.0104 (12)
C14	0.0115 (10)	0.0176 (11)	0.0140 (10)	−0.0003 (9)	−0.0002 (9)	0.0010 (9)
C15	0.0135 (13)	0.056 (2)	0.046 (2)	0.0007 (15)	−0.0036 (13)	0.0099 (18)
C16	0.0164 (13)	0.0425 (19)	0.0363 (17)	−0.0112 (13)	0.0061 (12)	−0.0027 (14)
C17	0.0266 (16)	0.0321 (16)	0.0324 (15)	−0.0117 (13)	0.0044 (12)	0.0105 (13)
C18	0.0151 (12)	0.0267 (14)	0.0268 (13)	−0.0052 (11)	−0.0029 (10)	0.0111 (11)
C19	0.052 (2)	0.0179 (13)	0.0218 (13)	0.0026 (15)	0.0022 (14)	0.0033 (10)
C20	0.092 (3)	0.0205 (15)	0.0290 (16)	0.009 (2)	0.005 (2)	0.0068 (12)
C21	0.129 (5)	0.0297 (18)	0.0260 (17)	0.019 (3)	0.007 (2)	0.0145 (14)
C22	0.094 (4)	0.0364 (19)	0.0175 (14)	0.015 (2)	0.003 (2)	0.0066 (13)
C23	0.0392 (16)	0.0258 (14)	0.0156 (11)	0.0000 (14)	0.0010 (12)	0.0021 (10)
C24	0.0351 (15)	0.0275 (14)	0.0153 (11)	−0.0071 (13)	0.0012 (11)	−0.0018 (10)
C25	0.076 (3)	0.0380 (19)	0.0175 (14)	−0.011 (2)	0.0054 (17)	−0.0052 (12)
C26	0.085 (3)	0.041 (2)	0.0221 (15)	−0.018 (2)	0.0085 (19)	−0.0146 (14)
C27	0.081 (3)	0.0274 (16)	0.0297 (16)	−0.015 (2)	0.005 (2)	−0.0129 (13)
C28	0.080 (3)	0.0208 (14)	0.0229 (14)	−0.0156 (19)	0.0043 (18)	−0.0048 (11)
Mn1	0.0315 (2)	0.01179 (17)	0.01201 (16)	−0.00413 (17)	0.00102 (16)	−0.00020 (13)
N1	0.0342 (13)	0.0179 (10)	0.0152 (10)	−0.0013 (12)	−0.0005 (10)	0.0009 (8)
N2	0.0524 (17)	0.0192 (11)	0.0157 (10)	−0.0101 (13)	0.0016 (12)	−0.0017 (9)
O1	0.0446 (14)	0.0152 (9)	0.0291 (11)	0.0043 (9)	0.0200 (10)	0.0030 (8)
O2	0.0522 (15)	0.0138 (9)	0.0253 (10)	−0.0060 (10)	0.0150 (11)	−0.0048 (8)
O3	0.0172 (8)	0.0130 (8)	0.0130 (8)	0.0010 (7)	0.0028 (7)	0.0032 (6)
O4	0.0112 (9)	0.0277 (10)	0.0328 (11)	−0.0001 (8)	0.0004 (8)	0.0145 (9)
O5	0.0341 (11)	0.0153 (9)	0.0116 (8)	−0.0088 (8)	−0.0019 (8)	0.0020 (7)
O6	0.0190 (10)	0.076 (2)	0.0360 (13)	−0.0046 (12)	−0.0007 (10)	0.0379 (13)
O7	0.0282 (11)	0.0224 (10)	0.0292 (11)	0.0062 (9)	−0.0068 (9)	−0.0064 (8)
O8	0.0301 (10)	0.0162 (8)	0.0194 (8)	0.0033 (9)	−0.0075 (8)	−0.0052 (7)
O9	0.0363 (12)	0.0170 (10)	0.0269 (11)	0.0013 (9)	0.0089 (10)	−0.0008 (9)
O10	0.0310 (13)	0.088 (3)	0.0363 (14)	−0.0164 (15)	−0.0018 (11)	0.0070 (16)
O12	0.0506 (18)	0.0461 (17)	0.067 (2)	0.0069 (15)	−0.0061 (17)	0.0064 (15)
O11	0.029 (2)	0.238 (9)	0.215 (7)	−0.011 (3)	0.016 (3)	−0.136 (7)

Geometric parameters (Å, º)

C1—O6	1.214 (4)	C18—H18	0.9500
C1—O5	1.344 (3)	C19—N1	1.346 (4)
C1—C2	1.486 (4)	C19—C20	1.382 (4)
C2—C3	1.397 (4)	C19—H19	0.9500
C2—C7	1.405 (4)	C20—C21	1.385 (5)
C3—C4	1.398 (5)	C20—H20	0.9500
C3—H3	0.9500	C21—C22	1.388 (6)
C4—C5	1.384 (5)	C21—H21	0.9500
C4—H4	0.9500	C22—C23	1.399 (4)
C5—C6	1.393 (4)	C22—H22	0.9500
C5—H5	0.9500	C23—N1	1.347 (3)
C6—C7	1.392 (4)	C23—C24	1.495 (4)
C6—H6	0.9500	C24—N2	1.345 (4)
C7—H7	0.9500	C24—C25	1.394 (4)
C8—O7	1.244 (4)	C25—C26	1.400 (6)
C8—O8	1.265 (3)	C25—H25	0.9500
C8—C9	1.540 (3)	C26—C27	1.375 (6)
C9—O5	1.443 (3)	C26—H26	0.9500
C9—C10	1.534 (3)	C27—C28	1.382 (4)
C9—H9A	1.0000	C27—H27	0.9500
C10—O3	1.441 (3)	C28—N2	1.343 (4)
C10—C11	1.547 (3)	C28—H28	0.9500
C10—H10	1.0000	Mn1—O8	2.1423 (19)
C11—O1	1.258 (4)	Mn1—O2^i	2.155 (2)
C11—O2	1.271 (4)	Mn1—O10	2.207 (3)
C12—O4	1.205 (3)	Mn1—O9	2.229 (3)
C12—O3	1.355 (3)	Mn1—N1	2.258 (2)
C12—C14	1.480 (3)	Mn1—N2	2.285 (2)
C13—C15	1.388 (5)	Mn1—H10B	2.0858
C13—C14	1.395 (4)	O2—Mn1^ii	2.155 (2)
C13—H13	0.9500	O9—H9B	0.85 (5)
C14—C18	1.395 (4)	O9—H9C	0.82 (5)
C15—C16	1.391 (6)	O10—H10A	0.8504
C15—H15	0.9500	O10—H10B	0.8498
C16—C17	1.380 (5)	O12—H12A	0.8507
C16—H16	0.9500	O12—H12B	0.8501
C17—C18	1.397 (4)	O11—H11A	0.8497
C17—H17	0.9500	O11—H11B	0.8508
O6—C1—O5	123.3 (3)	C21—C20—H20	120.8
O6—C1—C2	124.5 (3)	C20—C21—C22	119.3 (3)
O5—C1—C2	112.3 (2)	C20—C21—H21	120.4
C3—C2—C7	119.2 (3)	C22—C21—H21	120.4
C3—C2—C1	122.3 (2)	C21—C22—C23	119.3 (3)
C7—C2—C1	118.4 (3)	C21—C22—H22	120.4
C2—C3—C4	120.3 (3)	C23—C22—H22	120.4
C2—C3—H3	119.8	N1—C23—C22	121.2 (3)
C4—C3—H3	119.8	N1—C23—C24	115.9 (2)
C5—C4—C3	119.8 (3)	C22—C23—C24	122.8 (3)
C5—C4—H4	120.1	N2—C24—C25	121.9 (3)
C3—C4—H4	120.1	N2—C24—C23	116.1 (2)
C4—C5—C6	120.7 (3)	C25—C24—C23	122.1 (3)
C4—C5—H5	119.7	C24—C25—C26	118.7 (3)
C6—C5—H5	119.7	C24—C25—H25	120.7
C7—C6—C5	119.6 (3)	C26—C25—H25	120.7
C7—C6—H6	120.2	C27—C26—C25	119.3 (3)
C5—C6—H6	120.2	C27—C26—H26	120.4
C6—C7—C2	120.3 (3)	C25—C26—H26	120.4
C6—C7—H7	119.8	C26—C27—C28	118.6 (3)
C2—C7—H7	119.8	C26—C27—H27	120.7
O7—C8—O8	126.9 (3)	C28—C27—H27	120.7
O7—C8—C9	119.4 (2)	N2—C28—C27	123.2 (3)
O8—C8—C9	113.8 (2)	N2—C28—H28	118.4
O5—C9—C10	107.5 (2)	C27—C28—H28	118.4
O5—C9—C8	111.0 (2)	O8—Mn1—O2^i	104.59 (8)
C10—C9—C8	110.32 (19)	O8—Mn1—O10	85.83 (11)
O5—C9—H9A	109.3	O2^i—Mn1—O10	89.23 (12)
C10—C9—H9A	109.3	O8—Mn1—O9	88.54 (9)
C8—C9—H9A	109.3	O2^i—Mn1—O9	87.18 (10)
O3—C10—C9	106.2 (2)	O10—Mn1—O9	172.35 (10)
O3—C10—C11	110.9 (2)	O8—Mn1—N1	91.76 (8)
C9—C10—C11	111.7 (2)	O2^i—Mn1—N1	163.56 (9)
O3—C10—H10	109.3	O10—Mn1—N1	90.29 (12)
C9—C10—H10	109.3	O9—Mn1—N1	95.07 (10)
C11—C10—H10	109.3	O8—Mn1—N2	163.93 (9)
O1—C11—O2	128.1 (3)	O2^i—Mn1—N2	91.45 (9)
O1—C11—C10	115.4 (3)	O10—Mn1—N2	95.39 (13)
O2—C11—C10	116.5 (3)	O9—Mn1—N2	91.45 (11)
O4—C12—O3	123.1 (2)	N1—Mn1—N2	72.23 (9)
O4—C12—C14	124.8 (2)	O8—Mn1—H10B	95.1
O3—C12—C14	112.2 (2)	O2^i—Mn1—H10B	106.7
C15—C13—C14	119.7 (3)	O10—Mn1—H10B	22.6
C15—C13—H13	120.2	O9—Mn1—H10B	164.2
C14—C13—H13	120.2	N1—Mn1—H10B	69.5
C18—C14—C13	119.6 (3)	N2—Mn1—H10B	80.8
C18—C14—C12	117.9 (2)	C19—N1—C23	118.7 (2)
C13—C14—C12	122.5 (2)	C19—N1—Mn1	122.96 (19)
C13—C15—C16	120.7 (3)	C23—N1—Mn1	118.28 (19)
C13—C15—H15	119.7	C28—N2—C24	118.4 (3)
C16—C15—H15	119.7	C28—N2—Mn1	124.1 (2)
C17—C16—C15	119.9 (3)	C24—N2—Mn1	117.28 (19)
C17—C16—H16	120.1	C11—O2—Mn1^ii	131.7 (2)
C15—C16—H16	120.1	C12—O3—C10	114.8 (2)
C16—C17—C18	119.9 (3)	C1—O5—C9	116.5 (2)
C16—C17—H17	120.0	C8—O8—Mn1	131.38 (19)
C18—C17—H17	120.0	Mn1—O9—H9B	99 (3)
C14—C18—C17	120.2 (3)	Mn1—O9—H9C	101 (4)
C14—C18—H18	119.9	H9B—O9—H9C	105 (5)
C17—C18—H18	119.9	Mn1—O10—H10A	121.1
N1—C19—C20	123.1 (3)	Mn1—O10—H10B	70.7
N1—C19—H19	118.4	H10A—O10—H10B	115.2
C20—C19—H19	118.4	H12A—O12—H12B	99.5
C19—C20—C21	118.3 (3)	H11A—O11—H11B	120.7
C19—C20—H20	120.8
O6—C1—C2—C3	162.1 (3)	C19—C20—C21—C22	2.5 (10)
O5—C1—C2—C3	−17.4 (4)	C20—C21—C22—C23	−2.2 (10)
O6—C1—C2—C7	−14.1 (5)	C21—C22—C23—N1	0.6 (8)
O5—C1—C2—C7	166.4 (2)	C21—C22—C23—C24	−178.3 (5)
C7—C2—C3—C4	0.7 (5)	N1—C23—C24—N2	4.7 (5)
C1—C2—C3—C4	−175.4 (3)	C22—C23—C24—N2	−176.4 (4)
C2—C3—C4—C5	−0.1 (5)	N1—C23—C24—C25	−174.7 (4)
C3—C4—C5—C6	−0.5 (5)	C22—C23—C24—C25	4.2 (7)
C4—C5—C6—C7	0.6 (5)	N2—C24—C25—C26	0.3 (7)
C5—C6—C7—C2	0.0 (4)	C23—C24—C25—C26	179.7 (4)
C3—C2—C7—C6	−0.7 (4)	C24—C25—C26—C27	0.2 (8)
C1—C2—C7—C6	175.6 (3)	C25—C26—C27—C28	0.0 (9)
O7—C8—C9—O5	−0.3 (3)	C26—C27—C28—N2	−0.8 (9)
O8—C8—C9—O5	180.0 (2)	C20—C19—N1—C23	−0.3 (6)
O7—C8—C9—C10	118.8 (3)	C20—C19—N1—Mn1	−178.6 (4)
O8—C8—C9—C10	−60.9 (3)	C22—C23—N1—C19	0.7 (6)
O5—C9—C10—O3	58.5 (2)	C24—C23—N1—C19	179.6 (3)
C8—C9—C10—O3	−62.6 (3)	C22—C23—N1—Mn1	179.0 (4)
O5—C9—C10—C11	−62.5 (3)	C24—C23—N1—Mn1	−2.1 (4)
C8—C9—C10—C11	176.3 (2)	C27—C28—N2—C24	1.2 (8)
O3—C10—C11—O1	169.2 (2)	C27—C28—N2—Mn1	−173.8 (4)
C9—C10—C11—O1	−72.5 (3)	C25—C24—N2—C28	−0.9 (6)
O3—C10—C11—O2	−11.3 (3)	C23—C24—N2—C28	179.6 (4)
C9—C10—C11—O2	107.0 (3)	C25—C24—N2—Mn1	174.4 (3)
C15—C13—C14—C18	1.5 (5)	C23—C24—N2—Mn1	−5.1 (4)
C15—C13—C14—C12	−177.2 (3)	O1—C11—O2—Mn1^ii	−8.5 (5)
O4—C12—C14—C18	−0.5 (4)	C10—C11—O2—Mn1^ii	172.10 (18)
O3—C12—C14—C18	179.2 (2)	O4—C12—O3—C10	−12.8 (4)
O4—C12—C14—C13	178.2 (3)	C14—C12—O3—C10	167.4 (2)
O3—C12—C14—C13	−2.1 (4)	C9—C10—O3—C12	168.1 (2)
C14—C13—C15—C16	−1.2 (6)	C11—C10—O3—C12	−70.3 (3)
C13—C15—C16—C17	−0.5 (6)	O6—C1—O5—C9	−11.5 (4)
C15—C16—C17—C18	1.8 (6)	C2—C1—O5—C9	168.0 (2)
C13—C14—C18—C17	−0.2 (5)	C10—C9—O5—C1	147.8 (2)
C12—C14—C18—C17	178.5 (3)	C8—C9—O5—C1	−91.4 (3)
C16—C17—C18—C14	−1.4 (5)	O7—C8—O8—Mn1	−0.5 (4)
N1—C19—C20—C21	−1.3 (8)	C9—C8—O8—Mn1	179.16 (16)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O11—H11A···O7^iii	0.85	2.08	2.763 (5)	138
O12—H12B···O2^i	0.85	2.33	3.044 (5)	142
O12—H12A···O10	0.85	1.81	2.616 (5)	157
O10—H10A···O11	0.85	1.84	2.660 (7)	161
O9—H9C···O1^i	0.82 (5)	1.97 (5)	2.770 (3)	163 (5)
O9—H9B···O7	0.85 (5)	1.91 (5)	2.736 (3)	165 (5)
C19—H19···O8	0.95	2.61	3.221 (4)	122

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