A cyanide-bridged Fe^III–Mn^II heterobimetallic one-dimensional coordination polymer: synthesis, crystal structure, experimental and theoretical magnetism investigation

A new cyanide-bridged Fe^III–Mn^II heterobimetallic coordination polymer (CP), namely catena-poly[[[N,N′-(1,2-phenyl­ene)bis­(pyridine-2-carboxamidato)-κ⁴N,N′,N′′,N′′′]iron(III)]-μ-cyanido-κ²C:N-[bis­(4,4′-bi­pyridine-κN)bis­(methanol-κO)manganese(II)]-μ-cyanido-κ²N:C], {[FeMn(C₁₈H₁₂N₄O₂)(CN)₂(C₁₀H₈N₂)₂(CH₃OH)₂]ClO₄}_n, (1), was prepared by the self-assembly of the trans-di­cyanidoiron(III)-containing building block [Fe(bpb)(CN)₂]⁻ [bpb²⁻ = N,N′-(1,2-phenyl­ene)bis­(pyridine-2-carboxamidate)], [Mn(ClO₄)₂]·6H₂O and 4,4′-bi­pyridine, and was structurally characterized by elemental analysis, IR spectroscopy, single-crystal X-ray crystallography and powder X-ray diffraction (PXRD). Single-crystal X-ray diffraction analysis shows that CP 1 possesses a cationic linear chain structure consisting of alternating cyanide-bridged Fe–Mn units, with free perchlorate as the charge-balancing anion, which can be further extended into a two-dimensional supra­molecular sheet structure via inter-chain π–π inter­actions between the 4,4′-bi­pyridine ligands. Within the chain, each Mn^II ion is six-coordinated by an N₆ unit and is involved in a slightly distorted octa­hedral coordination geometry. Investigation of the magnetic properties of 1 reveals an anti­ferromagnetic coupling between the cyanide-bridged Fe^III and Mn^II ions. A best fit of the magnetic susceptibility based on the one-dimensional alternating chain model leads to the magnetic coupling constants J₁ = −1.35 and J₂ = −1.05 cm⁻¹, and the anti­ferromagnetic coupling was further confirmed by spin Hamiltonian-based density functional theoretical (DFT) calculations.

Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015b).

catena-Poly[[[N,N'-(1,2-phenylene)bis(pyridine-2-carboxamidato)-κ⁴N,N',N'',N''']iron(III)]-µ-cyanido-κ²C:N-[bis(4,4'-bipyridine-κN)bis(methanol-κO)manganese(II)]-µ-cyanido-κ²N:C]

Crystal data

[FeMn(C18H12N4O2)(CN)2(C10H8N2)2(CH4O)2]ClO4	Z = 2
Mr = 955.05	F(000) = 980
Triclinic, P1	Dx = 1.524 Mg m^−3
a = 10.404 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.969 (4) Å	Cell parameters from 1980 reflections
c = 16.226 (4) Å	θ = 2.7–25.0°
α = 113.317 (4)°	µ = 0.78 mm^−1
β = 104.231 (4)°	T = 293 K
γ = 90.973 (4)°	Block, dark-brown
V = 2081.8 (9) Å^3	0.29 × 0.23 × 0.19 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	Rint = 0.030
Radiation source: fine-focus sealed tube	θmax = 25.1°, θmin = 2.1°
φ and ω scans	h = −12→9
10291 measured reflections	k = −12→16
7320 independent reflections	l = −18→19
4047 reflections with I > 2σ(I)

Refinement

Refinement on F^2	2 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.059	H-atom parameters constrained
wR(F^2) = 0.177	w = 1/[σ^2(Fo^2) + (0.0922P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.98	(Δ/σ)max = 0.019
7320 reflections	Δρmax = 0.74 e Å^−3
570 parameters	Δρmin = −0.74 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.

Refinement. Single crystal of 1 with suitable dimensions for X-ray diffraction analyses was mounted on a glass rod, and the crystal data were collected on a Bruker APEX2 CCD diffractometer with a Mo Kα sealed tube (λ = 0.71073 Å ) at 293 K, using the ω scan mode. The structures were solved using the direct method and expanded using Fourier difference techniques with the SHELXTL-2018 program package (Sheldrick, 2015). The non-hydrogen atoms were refined anisotropically with anisotropic displacement coefficients.

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

	x	y	z	Uiso*/Ueq
Fe1	0.50753 (6)	0.28795 (6)	0.25225 (5)	0.0403 (2)
Mn1	0.00801 (7)	0.26107 (6)	0.25935 (5)	0.0420 (2)
Cl1	0.3802 (2)	0.89834 (17)	0.29993 (16)	0.0885 (6)
O1	0.6767 (5)	0.5512 (4)	0.4782 (3)	0.1092 (19)
O2	0.3711 (5)	0.2781 (4)	−0.0049 (3)	0.0841 (14)
O3	0.0209 (5)	0.4300 (3)	0.3324 (4)	0.0976 (17)
H3A	0.046896	0.463845	0.304678	0.117*
O4	−0.0118 (3)	0.0879 (3)	0.1839 (2)	0.0517 (9)
H4A	−0.029357	0.056797	0.213959	0.062*
O5	0.3063 (8)	0.8183 (6)	0.2954 (7)	0.198 (4)
O6	0.421 (2)	0.8681 (10)	0.2258 (9)	0.412 (12)
O7	0.3212 (6)	0.9881 (5)	0.3115 (6)	0.178 (3)
O8	0.4944 (8)	0.9207 (8)	0.3594 (11)	0.308 (8)
N1	0.5679 (4)	0.4313 (3)	0.3268 (3)	0.0511 (11)
N2	0.4738 (4)	0.3318 (3)	0.1542 (3)	0.0478 (11)
N3	0.4384 (4)	0.1467 (3)	0.1458 (3)	0.0419 (10)
N4	0.5553 (4)	0.2793 (4)	0.3760 (3)	0.0490 (11)
N5	0.2172 (4)	0.2825 (4)	0.2673 (3)	0.0528 (12)
N6	−0.0399 (4)	0.2751 (3)	0.1160 (3)	0.0527 (12)
N7	−0.0684 (7)	0.4556 (4)	−0.2385 (4)	0.0804 (16)
N8	0.0505 (4)	0.2345 (3)	0.3938 (3)	0.0509 (11)
N9	0.1013 (5)	0.0347 (4)	0.7390 (3)	0.0629 (13)
N10	−0.2049 (4)	0.2444 (4)	0.2446 (3)	0.0575 (12)
C1	0.5665 (5)	0.4935 (5)	0.2788 (5)	0.0611 (16)
C2	0.6119 (7)	0.6016 (5)	0.3154 (6)	0.085 (2)
H2	0.647107	0.638945	0.379540	0.102*
C3	0.6049 (9)	0.6524 (6)	0.2577 (8)	0.106 (3)
H3	0.635393	0.723780	0.282417	0.127*
C4	0.5527 (9)	0.5973 (7)	0.1631 (8)	0.104 (3)
H4	0.547011	0.632720	0.124689	0.125*
C5	0.5084 (7)	0.4912 (6)	0.1231 (5)	0.0787 (19)
H5	0.475056	0.455312	0.058662	0.094*
C6	0.5144 (5)	0.4388 (4)	0.1808 (4)	0.0560 (15)
C7	0.4092 (6)	0.2616 (5)	0.0652 (4)	0.0576 (15)
C8	0.3891 (5)	0.1549 (4)	0.0641 (3)	0.0465 (13)
C9	0.3259 (5)	0.0680 (5)	−0.0176 (3)	0.0550 (15)
H9	0.292246	0.075503	−0.073075	0.066*
C10	0.3139 (5)	−0.0277 (5)	−0.0157 (4)	0.0627 (17)
H10	0.269536	−0.085970	−0.069449	0.075*
C11	0.3678 (5)	−0.0383 (4)	0.0666 (4)	0.0582 (15)
H11	0.364001	−0.103843	0.068815	0.070*
C12	0.4274 (5)	0.0511 (4)	0.1452 (4)	0.0502 (14)
H12	0.461830	0.044532	0.201065	0.060*
C13	0.6220 (6)	0.4635 (5)	0.4202 (4)	0.0673 (18)
C14	0.6112 (5)	0.3724 (5)	0.4470 (4)	0.0549 (15)
C15	0.6494 (6)	0.3852 (6)	0.5387 (4)	0.078 (2)
H15	0.687058	0.450553	0.586456	0.093*
C16	0.6312 (7)	0.3007 (7)	0.5582 (4)	0.081 (2)
H16	0.657851	0.307072	0.619360	0.097*
C17	0.5736 (6)	0.2071 (6)	0.4873 (4)	0.0701 (18)
H17	0.559861	0.148735	0.499583	0.084*
C18	0.5357 (5)	0.1988 (5)	0.3974 (4)	0.0583 (16)
H18	0.494752	0.134369	0.349592	0.070*
C19	0.3250 (5)	0.2893 (4)	0.2632 (3)	0.0417 (12)
C20	0.6871 (5)	0.2585 (4)	0.2452 (3)	0.0432 (12)
C21	0.0698 (7)	0.0270 (5)	0.1320 (4)	0.080 (2)
H21A	0.094282	0.060334	0.095480	0.120*
H21B	0.022054	−0.041513	0.091387	0.120*
H21C	0.149034	0.020551	0.173693	0.120*
C22	−0.0466 (15)	0.4915 (8)	0.3902 (8)	0.229 (7)
H22A	−0.133912	0.494058	0.354368	0.343*
H22B	0.001140	0.561182	0.423358	0.343*
H22C	−0.055147	0.463066	0.433872	0.343*
C23	0.0519 (7)	0.2609 (5)	0.0699 (4)	0.078 (2)
H23	0.126080	0.230385	0.088405	0.094*
C24	0.0448 (6)	0.2884 (5)	−0.0039 (4)	0.0719 (18)
H24	0.113423	0.276719	−0.032783	0.086*
C25	−0.0615 (6)	0.3325 (4)	−0.0346 (4)	0.0554 (15)
C26	−0.1605 (6)	0.3432 (6)	0.0097 (5)	0.090 (2)
H26	−0.237401	0.370707	−0.009228	0.108*
C27	−0.1451 (7)	0.3128 (6)	0.0829 (5)	0.081 (2)
H27	−0.214782	0.319801	0.110655	0.098*
C28	−0.0656 (6)	0.3729 (4)	−0.1065 (4)	0.0595 (15)
C29	0.0427 (8)	0.3703 (6)	−0.1435 (6)	0.106 (3)
H29	0.118342	0.341856	−0.123964	0.127*
C30	0.0362 (9)	0.4109 (6)	−0.2099 (6)	0.108 (3)
H30	0.107681	0.406835	−0.235523	0.130*
C31	−0.1671 (8)	0.4590 (5)	−0.2020 (4)	0.078 (2)
H31	−0.239578	0.491327	−0.219960	0.093*
C32	−0.1709 (6)	0.4181 (5)	−0.1389 (4)	0.0722 (18)
H32	−0.246461	0.420865	−0.117417	0.087*
C33	−0.0420 (7)	0.2399 (6)	0.4383 (5)	0.082 (2)
H33	−0.118880	0.268252	0.421039	0.099*
C34	−0.0317 (7)	0.2063 (6)	0.5083 (5)	0.081 (2)
H34	−0.099666	0.213759	0.537519	0.098*
C35	0.0775 (5)	0.1622 (4)	0.5351 (4)	0.0483 (13)
C36	0.1746 (6)	0.1572 (5)	0.4897 (4)	0.0745 (19)
H36	0.251955	0.128290	0.504934	0.089*
C37	0.1569 (6)	0.1950 (6)	0.4219 (4)	0.076 (2)
H37	0.225532	0.192320	0.393873	0.091*
C38	0.0883 (5)	0.1206 (4)	0.6066 (4)	0.0486 (13)
C39	−0.0114 (7)	0.1241 (6)	0.6498 (5)	0.088 (2)
H39	−0.086371	0.156040	0.635736	0.106*
C40	−0.0014 (8)	0.0813 (6)	0.7127 (5)	0.090 (2)
H40	−0.071633	0.084942	0.739421	0.108*
C41	0.1957 (7)	0.0324 (6)	0.6993 (5)	0.091 (2)
H41	0.269299	−0.000065	0.715027	0.109*
C42	0.1952 (6)	0.0744 (6)	0.6354 (5)	0.084 (2)
H42	0.268371	0.071417	0.611535	0.101*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.0287 (4)	0.0472 (5)	0.0393 (4)	0.0018 (3)	0.0146 (3)	0.0091 (3)
Mn1	0.0301 (4)	0.0491 (5)	0.0483 (5)	0.0045 (3)	0.0163 (3)	0.0185 (4)
Cl1	0.0860 (14)	0.0820 (14)	0.1063 (16)	0.0097 (11)	0.0227 (11)	0.0501 (12)
O1	0.137 (5)	0.068 (3)	0.073 (3)	−0.030 (3)	0.031 (3)	−0.020 (3)
O2	0.099 (3)	0.102 (4)	0.058 (3)	0.001 (3)	0.012 (2)	0.045 (3)
O3	0.124 (4)	0.054 (3)	0.133 (4)	0.011 (3)	0.094 (4)	0.023 (3)
O4	0.056 (2)	0.052 (2)	0.057 (2)	0.0144 (18)	0.0272 (18)	0.0251 (19)
O5	0.167 (7)	0.122 (5)	0.341 (11)	−0.006 (5)	0.080 (7)	0.129 (7)
O6	0.90 (4)	0.294 (15)	0.246 (12)	0.31 (2)	0.325 (19)	0.212 (12)
O7	0.114 (5)	0.092 (5)	0.337 (11)	0.044 (4)	0.089 (6)	0.080 (6)
O8	0.085 (6)	0.209 (10)	0.488 (19)	0.001 (6)	−0.023 (9)	0.061 (11)
N1	0.039 (2)	0.047 (3)	0.061 (3)	0.002 (2)	0.023 (2)	0.011 (2)
N2	0.038 (2)	0.050 (3)	0.059 (3)	0.008 (2)	0.022 (2)	0.021 (2)
N3	0.035 (2)	0.052 (3)	0.034 (2)	0.004 (2)	0.0122 (18)	0.011 (2)
N4	0.035 (2)	0.061 (3)	0.039 (2)	0.003 (2)	0.0136 (19)	0.007 (2)
N5	0.034 (2)	0.076 (3)	0.048 (3)	0.008 (2)	0.019 (2)	0.021 (2)
N6	0.048 (3)	0.052 (3)	0.064 (3)	0.016 (2)	0.014 (2)	0.031 (2)
N7	0.103 (5)	0.058 (4)	0.077 (4)	0.007 (3)	0.019 (4)	0.029 (3)
N8	0.047 (3)	0.061 (3)	0.050 (3)	0.008 (2)	0.020 (2)	0.025 (2)
N9	0.058 (3)	0.070 (3)	0.072 (3)	0.007 (3)	0.017 (3)	0.041 (3)
N10	0.045 (3)	0.068 (3)	0.060 (3)	0.005 (2)	0.024 (2)	0.022 (2)
C1	0.047 (3)	0.051 (4)	0.086 (5)	0.010 (3)	0.036 (3)	0.019 (3)
C2	0.072 (5)	0.054 (4)	0.112 (6)	−0.001 (3)	0.031 (4)	0.013 (4)
C3	0.106 (7)	0.059 (5)	0.160 (9)	−0.003 (5)	0.057 (6)	0.040 (6)
C4	0.104 (6)	0.083 (6)	0.163 (9)	0.019 (5)	0.055 (6)	0.077 (6)
C5	0.077 (5)	0.073 (5)	0.100 (5)	0.009 (4)	0.034 (4)	0.046 (4)
C6	0.047 (3)	0.054 (4)	0.077 (4)	0.011 (3)	0.030 (3)	0.028 (3)
C7	0.057 (4)	0.069 (4)	0.052 (4)	0.010 (3)	0.022 (3)	0.026 (3)
C8	0.035 (3)	0.061 (4)	0.036 (3)	0.002 (2)	0.013 (2)	0.010 (3)
C9	0.055 (3)	0.068 (4)	0.035 (3)	0.004 (3)	0.010 (2)	0.015 (3)
C10	0.051 (3)	0.064 (4)	0.045 (3)	0.000 (3)	0.011 (3)	−0.005 (3)
C11	0.062 (4)	0.048 (3)	0.049 (3)	−0.002 (3)	0.017 (3)	0.004 (3)
C12	0.054 (3)	0.054 (4)	0.045 (3)	0.005 (3)	0.019 (3)	0.019 (3)
C13	0.056 (4)	0.064 (4)	0.057 (4)	−0.007 (3)	0.023 (3)	−0.003 (3)
C14	0.037 (3)	0.072 (4)	0.041 (3)	0.006 (3)	0.014 (2)	0.006 (3)
C15	0.055 (4)	0.102 (6)	0.043 (4)	0.010 (4)	0.008 (3)	0.000 (4)
C16	0.076 (5)	0.114 (6)	0.037 (4)	0.011 (4)	0.011 (3)	0.019 (4)
C17	0.065 (4)	0.104 (5)	0.055 (4)	0.017 (4)	0.019 (3)	0.044 (4)
C18	0.059 (4)	0.069 (4)	0.038 (3)	−0.008 (3)	0.008 (3)	0.018 (3)
C19	0.037 (3)	0.051 (3)	0.035 (3)	0.005 (2)	0.015 (2)	0.013 (2)
C20	0.037 (3)	0.045 (3)	0.043 (3)	0.000 (2)	0.016 (2)	0.010 (2)
C21	0.109 (6)	0.068 (4)	0.073 (4)	0.032 (4)	0.049 (4)	0.025 (4)
C22	0.37 (2)	0.104 (9)	0.219 (13)	−0.005 (11)	0.182 (14)	0.015 (8)
C23	0.073 (4)	0.111 (6)	0.055 (4)	0.046 (4)	0.023 (3)	0.036 (4)
C24	0.068 (4)	0.102 (5)	0.056 (4)	0.037 (4)	0.023 (3)	0.039 (4)
C25	0.060 (4)	0.046 (3)	0.058 (4)	0.001 (3)	0.007 (3)	0.024 (3)
C26	0.059 (4)	0.128 (7)	0.134 (6)	0.033 (4)	0.032 (4)	0.102 (6)
C27	0.065 (4)	0.105 (6)	0.110 (6)	0.021 (4)	0.038 (4)	0.073 (5)
C28	0.069 (4)	0.042 (3)	0.059 (4)	0.003 (3)	0.006 (3)	0.020 (3)
C29	0.103 (6)	0.116 (7)	0.162 (8)	0.047 (5)	0.070 (6)	0.101 (6)
C30	0.122 (7)	0.108 (7)	0.146 (8)	0.035 (6)	0.075 (6)	0.082 (6)
C31	0.083 (5)	0.084 (5)	0.059 (4)	0.006 (4)	−0.002 (4)	0.036 (4)
C32	0.071 (4)	0.086 (5)	0.063 (4)	0.008 (4)	0.008 (3)	0.041 (4)
C33	0.076 (4)	0.129 (6)	0.088 (5)	0.060 (4)	0.049 (4)	0.074 (5)
C34	0.075 (5)	0.121 (6)	0.098 (5)	0.051 (4)	0.057 (4)	0.075 (5)
C35	0.051 (3)	0.047 (3)	0.049 (3)	0.001 (3)	0.015 (3)	0.021 (3)
C36	0.051 (4)	0.124 (6)	0.072 (4)	0.024 (4)	0.021 (3)	0.061 (4)
C37	0.044 (3)	0.138 (6)	0.069 (4)	0.015 (4)	0.025 (3)	0.061 (4)
C38	0.053 (3)	0.044 (3)	0.048 (3)	−0.001 (3)	0.016 (3)	0.017 (3)
C39	0.078 (5)	0.138 (7)	0.100 (5)	0.054 (5)	0.049 (4)	0.086 (5)
C40	0.101 (6)	0.121 (6)	0.096 (5)	0.042 (5)	0.054 (5)	0.077 (5)
C41	0.063 (4)	0.137 (7)	0.119 (6)	0.026 (4)	0.029 (4)	0.098 (6)
C42	0.052 (4)	0.124 (6)	0.121 (6)	0.029 (4)	0.037 (4)	0.087 (5)

Geometric parameters (Å, º)

Fe1—N1	1.879 (4)	C10—C11	1.383 (8)
Fe1—N2	1.880 (4)	C10—H10	0.9300
Fe1—C20	1.941 (5)	C11—C12	1.377 (7)
Fe1—C19	1.951 (5)	C11—H11	0.9300
Fe1—N4	1.999 (4)	C12—H12	0.9300
Fe1—N3	2.009 (4)	C13—C14	1.509 (9)
Mn1—N5	2.157 (4)	C14—C15	1.379 (8)
Mn1—O3	2.165 (4)	C15—C16	1.358 (9)
Mn1—N10	2.167 (5)	C15—H15	0.9300
Mn1—O4	2.215 (3)	C16—C17	1.355 (9)
Mn1—N8	2.295 (4)	C16—H16	0.9300
Mn1—N6	2.343 (5)	C17—C18	1.370 (7)
Cl1—O8	1.275 (9)	C17—H17	0.9300
Cl1—O6	1.290 (10)	C18—H18	0.9300
Cl1—O5	1.314 (6)	C21—H21A	0.9600
Cl1—O7	1.371 (6)	C21—H21B	0.9600
O1—C13	1.229 (6)	C21—H21C	0.9600
O2—C7	1.222 (6)	C22—H22A	0.9600
O3—C22	1.348 (10)	C22—H22B	0.9600
O3—H3A	0.8507	C22—H22C	0.9600
O4—C21	1.401 (6)	C23—C24	1.382 (8)
O4—H4A	0.8183	C23—H23	0.9300
N1—C13	1.360 (7)	C24—C25	1.358 (8)
N1—C1	1.376 (7)	C24—H24	0.9300
N2—C7	1.370 (7)	C25—C26	1.372 (8)
N2—C6	1.407 (7)	C25—C28	1.476 (8)
N3—C12	1.335 (6)	C26—C27	1.387 (8)
N3—C8	1.350 (6)	C26—H26	0.9300
N4—C18	1.328 (7)	C27—H27	0.9300
N4—C14	1.348 (6)	C28—C32	1.370 (8)
N5—C19	1.143 (6)	C28—C29	1.396 (9)
N6—C27	1.311 (7)	C29—C30	1.391 (10)
N6—C23	1.324 (7)	C29—H29	0.9300
N7—C31	1.299 (8)	C30—H30	0.9300
N7—C30	1.339 (9)	C31—C32	1.364 (8)
N8—C37	1.306 (7)	C31—H31	0.9300
N8—C33	1.324 (7)	C32—H32	0.9300
N9—C41	1.294 (7)	C33—C34	1.372 (8)
N9—C40	1.330 (8)	C33—H33	0.9300
N10—C20^i	1.145 (6)	C34—C35	1.361 (8)
C1—C2	1.408 (8)	C34—H34	0.9300
C1—C6	1.417 (8)	C35—C36	1.376 (7)
C2—C3	1.373 (10)	C35—C38	1.472 (7)
C2—H2	0.9300	C36—C37	1.375 (8)
C3—C4	1.372 (11)	C36—H36	0.9300
C3—H3	0.9300	C37—H37	0.9300
C4—C5	1.378 (10)	C38—C42	1.371 (8)
C4—H4	0.9300	C38—C39	1.380 (7)
C5—C6	1.390 (8)	C39—C40	1.356 (8)
C5—H5	0.9300	C39—H39	0.9300
C7—C8	1.494 (8)	C40—H40	0.9300
C8—C9	1.390 (7)	C41—C42	1.377 (8)
C9—C10	1.353 (8)	C41—H41	0.9300
C9—H9	0.9300	C42—H42	0.9300
N1—Fe1—N2	83.4 (2)	C10—C11—H11	121.1
N1—Fe1—C20	91.54 (19)	N3—C12—C11	123.7 (5)
N2—Fe1—C20	94.05 (19)	N3—C12—H12	118.2
N1—Fe1—C19	97.66 (19)	C11—C12—H12	118.2
N2—Fe1—C19	95.39 (18)	O1—C13—N1	128.4 (7)
C20—Fe1—C19	167.5 (2)	O1—C13—C14	121.5 (6)
N1—Fe1—N4	82.5 (2)	N1—C13—C14	110.1 (5)
N2—Fe1—N4	165.85 (19)	N4—C14—C15	122.4 (6)
C20—Fe1—N4	87.52 (18)	N4—C14—C13	115.5 (5)
C19—Fe1—N4	85.34 (18)	C15—C14—C13	122.0 (6)
N1—Fe1—N3	165.2 (2)	C16—C15—C14	118.8 (6)
N2—Fe1—N3	81.87 (18)	C16—C15—H15	120.6
C20—Fe1—N3	88.14 (18)	C14—C15—H15	120.6
C19—Fe1—N3	85.09 (17)	C17—C16—C15	119.2 (6)
N4—Fe1—N3	112.26 (18)	C17—C16—H16	120.4
N5—Mn1—O3	87.99 (17)	C15—C16—H16	120.4
N5—Mn1—N10	176.10 (17)	C16—C17—C18	119.8 (6)
O3—Mn1—N10	90.67 (18)	C16—C17—H17	120.1
N5—Mn1—O4	93.73 (15)	C18—C17—H17	120.1
O3—Mn1—O4	178.26 (15)	N4—C18—C17	122.4 (5)
N10—Mn1—O4	87.59 (15)	N4—C18—H18	118.8
N5—Mn1—N8	93.20 (15)	C17—C18—H18	118.8
O3—Mn1—N8	93.61 (18)	N5—C19—Fe1	175.2 (5)
N10—Mn1—N8	90.54 (16)	N10^ii—C20—Fe1	177.1 (5)
O4—Mn1—N8	86.55 (14)	O4—C21—H21A	109.5
N5—Mn1—N6	87.80 (16)	O4—C21—H21B	109.5
O3—Mn1—N6	90.46 (18)	H21A—C21—H21B	109.5
N10—Mn1—N6	88.55 (16)	O4—C21—H21C	109.5
O4—Mn1—N6	89.36 (14)	H21A—C21—H21C	109.5
N8—Mn1—N6	175.84 (15)	H21B—C21—H21C	109.5
O8—Cl1—O6	97.7 (10)	O3—C22—H22A	109.5
O8—Cl1—O5	113.5 (7)	O3—C22—H22B	109.5
O6—Cl1—O5	108.2 (9)	H22A—C22—H22B	109.5
O8—Cl1—O7	109.8 (6)	O3—C22—H22C	109.5
O6—Cl1—O7	109.9 (6)	H22A—C22—H22C	109.5
O5—Cl1—O7	116.2 (5)	H22B—C22—H22C	109.5
C22—O3—Mn1	132.4 (6)	N6—C23—C24	124.2 (6)
C22—O3—H3A	108.6	N6—C23—H23	117.9
Mn1—O3—H3A	113.7	C24—C23—H23	117.9
C21—O4—Mn1	128.7 (3)	C25—C24—C23	120.6 (6)
C21—O4—H4A	105.8	C25—C24—H24	119.7
Mn1—O4—H4A	113.0	C23—C24—H24	119.7
C13—N1—C1	125.0 (5)	C24—C25—C26	115.8 (6)
C13—N1—Fe1	119.2 (4)	C24—C25—C28	121.9 (6)
C1—N1—Fe1	115.3 (4)	C26—C25—C28	122.2 (6)
C7—N2—C6	125.0 (5)	C25—C26—C27	119.6 (6)
C7—N2—Fe1	119.8 (4)	C25—C26—H26	120.2
C6—N2—Fe1	115.2 (4)	C27—C26—H26	120.2
C12—N3—C8	117.5 (4)	N6—C27—C26	125.0 (6)
C12—N3—Fe1	130.5 (3)	N6—C27—H27	117.5
C8—N3—Fe1	111.8 (3)	C26—C27—H27	117.5
C18—N4—C14	117.4 (5)	C32—C28—C29	115.6 (6)
C18—N4—Fe1	130.1 (4)	C32—C28—C25	123.5 (6)
C14—N4—Fe1	112.5 (4)	C29—C28—C25	120.8 (6)
C19—N5—Mn1	174.0 (4)	C30—C29—C28	119.2 (7)
C27—N6—C23	114.6 (5)	C30—C29—H29	120.4
C27—N6—Mn1	124.5 (4)	C28—C29—H29	120.4
C23—N6—Mn1	120.0 (4)	N7—C30—C29	123.0 (7)
C31—N7—C30	116.9 (6)	N7—C30—H30	118.5
C37—N8—C33	115.1 (5)	C29—C30—H30	118.5
C37—N8—Mn1	122.2 (4)	N7—C31—C32	124.0 (7)
C33—N8—Mn1	121.6 (4)	N7—C31—H31	118.0
C41—N9—C40	114.4 (5)	C32—C31—H31	118.0
C20^i—N10—Mn1	165.3 (5)	C31—C32—C28	121.3 (7)
N1—C1—C2	127.9 (6)	C31—C32—H32	119.4
N1—C1—C6	114.0 (5)	C28—C32—H32	119.4
C2—C1—C6	118.2 (6)	N8—C33—C34	124.3 (6)
C3—C2—C1	120.8 (7)	N8—C33—H33	117.9
C3—C2—H2	119.6	C34—C33—H33	117.9
C1—C2—H2	119.6	C35—C34—C33	120.3 (5)
C4—C3—C2	119.5 (7)	C35—C34—H34	119.8
C4—C3—H3	120.2	C33—C34—H34	119.8
C2—C3—H3	120.2	C34—C35—C36	115.7 (5)
C3—C4—C5	122.3 (8)	C34—C35—C38	121.6 (5)
C3—C4—H4	118.8	C36—C35—C38	122.7 (5)
C5—C4—H4	118.8	C37—C36—C35	119.9 (6)
C4—C5—C6	118.7 (7)	C37—C36—H36	120.1
C4—C5—H5	120.6	C35—C36—H36	120.1
C6—C5—H5	120.6	N8—C37—C36	124.7 (5)
C5—C6—N2	127.6 (6)	N8—C37—H37	117.7
C5—C6—C1	120.4 (6)	C36—C37—H37	117.6
N2—C6—C1	111.9 (5)	C42—C38—C39	114.0 (5)
O2—C7—N2	128.4 (6)	C42—C38—C35	124.0 (5)
O2—C7—C8	122.4 (5)	C39—C38—C35	122.0 (5)
N2—C7—C8	109.2 (5)	C40—C39—C38	120.7 (6)
N3—C8—C9	121.8 (5)	C40—C39—H39	119.6
N3—C8—C7	116.6 (4)	C38—C39—H39	119.6
C9—C8—C7	121.6 (5)	N9—C40—C39	124.9 (6)
C10—C9—C8	119.4 (5)	N9—C40—H40	117.5
C10—C9—H9	120.3	C39—C40—H40	117.5
C8—C9—H9	120.3	N9—C41—C42	124.9 (6)
C9—C10—C11	119.8 (5)	N9—C41—H41	117.6
C9—C10—H10	120.1	C42—C41—H41	117.6
C11—C10—H10	120.1	C38—C42—C41	120.9 (6)
C12—C11—C10	117.8 (6)	C38—C42—H42	119.5
C12—C11—H11	121.1	C41—C42—H42	119.5

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