Synthesis, characterization and structural analysis of com­plexes from 2,2′:6′,2′′-terpyridine derivatives with transition metals

The synthesis and structural characterization of three families of coordination com­plexes synthesized from 4′-phenyl-2,2′:6′,2′′-terpyridine (8, Ph-TPY), 4′-(4-chloro­phen­yl)-2,2′:6′,2′′-terpyridine (9, ClPh-TPY) and 4′-(4-meth­oxy­phen­yl)-2,2′:6′,2′′-terpyridine (10, MeOPh-TPY) ligands with the divalent metals Co²⁺, Fe²⁺, Mn²⁺ and Ni²⁺ are reported. The com­pounds were synthesized from a 1:2 mixture of the metal and ligand, resulting in a series of com­plexes with the general formula [M(R-TPY)₂](ClO₄)₂ (where M = Co²⁺, Fe²⁺, Mn²⁺ and Ni²⁺, and R-TPY = Ph-TPY, ClPh-TPY and MeOPh-TPY). The general formula and structural and supra­molecular features were determinated by single-crystal X-ray diffraction for bis­(4′-phenyl-2,2′:6′,2′′-terpyridine)­nickel(II) bis­(per­chlo­rate), [Ni(C₂₁H₁₅N₃)₂](ClO₄)₂ or [Ni(Ph-TPY)₂](ClO₄)₂, bis­[4′-(4-meth­oxy­phen­yl)-2,2′:6′,2′′-terpyridine]­manganese(II) bis­(per­chlo­rate), [Mn(C₂₂H₁₇N₃O)₂](ClO₄)₂ or [Mn(MeOPh-TPY)₂](ClO₄)₂, and bis­(4′-phenyl-2,2′:6′,2′′-ter­py­ridine)­manganese(II) bis­(per­chlo­rate), [Mn(C₂₁H₁₅N₃)₂](ClO₄)₂ or [Mn(Ph-TPY)₂](ClO₄)₂. In all three cases, the com­plexes present distorted octa­hedral coordination polyhedra and the crystal packing is determined mainly by weak C—H⋯π inter­actions. All the com­pounds (except for the Ni derivatives, for which FT–IR, UV–Vis and thermal analysis are reported) were fully characterized by spectroscopic (FT–IR, UV–Vis and NMR spectroscopy) and thermal (TGA–DSC, thermogravimetric analysis–differential scanning calorimetry) methods.

Computing details

Bis[4'-(4-methoxyphenyl)-2,2':6',2''-terpyridine]manganese(II) bis(perchlorate) (MnMeOTPY)

Crystal data

[Mn(C22H17N3O)2](ClO4)2	Z = 2
Mr = 932.61	F(000) = 958
Triclinic, P1	Dx = 1.505 Mg m^−3
a = 8.93282 (10) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.32698 (13) Å	Cell parameters from 44860 reflections
c = 18.86081 (19) Å	θ = 2.6–34.1°
α = 89.8757 (8)°	µ = 0.52 mm^−1
β = 85.6122 (8)°	T = 100 K
γ = 83.5667 (9)°	Block, light yellow
V = 2057.68 (4) Å^3	0.15 × 0.10 × 0.08 mm

Data collection

Rigaku XtaLAB Synergy Dualflex diffractometer with a HyPix detector	10630 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Mo) X-ray Source	9347 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.029
Detector resolution: 10.0000 pixels mm^-1	θmax = 28.7°, θmin = 2.5°
ω scans	h = −12→12
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2022)	k = −16→16
Tmin = 0.662, Tmax = 1.000	l = −25→25
57826 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.031	H-atom parameters constrained
wR(F^2) = 0.083	w = 1/[σ^2(Fo^2) + (0.0393P)^2 + 0.9933P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
10630 reflections	Δρmax = 0.49 e Å^−3
570 parameters	Δρmin = −0.42 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 crystals suitable for X-ray analysis were obtained by slow evaporation from acetonitrile using diethyl ether as antisolvent. Diffraction data for all the compounds were collected at room temperature on a Rigaku Synergy S diffractometer using photonjet microfocus source Mo Kα (λ = 0.71073 Å) radiation. The unit-cell parameters were determined using all reflections with CrysAlis PRO software (Agilent, 2014). Data integration and scaling were performed using CrysAlis PRO software (Agilent, 2014). The structures were solved and refined with SHELXT (Sheldrick, 2015a) and SHELXL (Sheldrick, 2015b) software, respectively, including in OLEX2 (Dolomanov et al., 2009). In all cases, non-H atoms were clearly resolved and full-matrix least-squares refinement with anisotropic displacement parameters was performed. In addition, the H atoms were stereochemically positioned and refined using the riding model (Sheldrick, 2008). The Mn compound [which one?] was refined using the SQUEEZE routine (Spek, 2015) in PLATON (Spek, 2020) to decrease the contribution of the disordered solvent (water molecule) to calculate the structure factors and improve the refinement values. Displacement ellipsoid plots for all structures were prepared with DIAMOND (Brandenburg et al., 2006). MERCURY were used for the preparation of artwork (Macrae et al., 2020). The CIF file of the complexes was deposited in the Cambridge Structural Data Base under the codes CCDC 2331329-2331331.

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

	x	y	z	Uiso*/Ueq
Mn1	0.84071 (2)	0.20014 (2)	0.74163 (2)	0.01322 (5)
Cl2	0.27866 (3)	0.73931 (2)	0.86546 (2)	0.01663 (7)
Cl1	0.44773 (4)	0.27267 (3)	0.51211 (2)	0.01862 (7)
O2	1.04363 (12)	0.38092 (8)	0.19702 (5)	0.0220 (2)
O1	0.61146 (13)	−0.26205 (9)	1.20844 (5)	0.0259 (2)
O8	0.13467 (11)	0.80637 (8)	0.87487 (5)	0.0219 (2)
O7	0.32762 (13)	0.73117 (9)	0.79090 (5)	0.0267 (2)
O9	0.26411 (13)	0.63223 (8)	0.89400 (6)	0.0276 (2)
O10	0.38971 (12)	0.78935 (9)	0.90230 (6)	0.0276 (2)
N4	0.71778 (12)	0.36568 (9)	0.72566 (6)	0.0156 (2)
N5	0.90456 (12)	0.25287 (8)	0.63304 (5)	0.0136 (2)
N1	0.94458 (12)	0.27627 (9)	0.83268 (6)	0.0147 (2)
N2	0.78219 (12)	0.11127 (8)	0.83983 (5)	0.01317 (19)
N6	1.01949 (12)	0.06923 (9)	0.69056 (6)	0.0147 (2)
O5	0.38629 (13)	0.17013 (9)	0.52369 (7)	0.0359 (3)
N3	0.68141 (12)	0.07699 (9)	0.71536 (5)	0.0147 (2)
O3	0.50570 (17)	0.27764 (11)	0.43929 (6)	0.0432 (3)
O6	0.33038 (15)	0.36195 (10)	0.52570 (7)	0.0391 (3)
O4	0.56453 (17)	0.27922 (11)	0.55862 (8)	0.0502 (4)
C11	0.64293 (14)	0.00707 (10)	0.76733 (6)	0.0135 (2)
C10	0.69668 (13)	0.02828 (10)	0.83820 (6)	0.0128 (2)
C6	0.83885 (13)	0.13535 (10)	0.90126 (6)	0.0131 (2)
C5	0.92485 (14)	0.23205 (10)	0.89801 (6)	0.0134 (2)
C7	0.81556 (14)	0.07495 (10)	0.96256 (6)	0.0138 (2)
H7	0.860232	0.092242	1.004630	0.017*
C27	0.83919 (14)	0.34763 (10)	0.60817 (6)	0.0133 (2)
C19	0.64295 (15)	−0.19800 (11)	1.15164 (7)	0.0171 (2)
C37	0.99495 (14)	0.33887 (10)	0.41620 (6)	0.0153 (2)
C12	0.56352 (14)	−0.08050 (10)	0.75412 (7)	0.0161 (2)
H12	0.535070	−0.127319	0.791654	0.019*
C4	0.97795 (15)	0.27649 (10)	0.95764 (7)	0.0168 (2)
H4	0.962878	0.244320	1.003077	0.020*
C16	0.69693 (14)	−0.07642 (10)	1.02729 (6)	0.0130 (2)
C9	0.66467 (14)	−0.03336 (10)	0.89824 (6)	0.0135 (2)
H9	0.601377	−0.090036	0.895816	0.016*
C26	0.72713 (14)	0.40883 (10)	0.65978 (6)	0.0138 (2)
C18	0.72148 (14)	−0.10719 (10)	1.15389 (6)	0.0157 (2)
H18	0.757195	−0.085778	1.197323	0.019*
C8	0.72601 (13)	−0.01167 (10)	0.96239 (6)	0.0126 (2)
C29	0.96743 (14)	0.31363 (10)	0.49237 (6)	0.0146 (2)
C17	0.74767 (14)	−0.04769 (10)	1.09233 (6)	0.0152 (2)
H17	0.801575	0.014272	1.094492	0.018*
C31	1.00055 (14)	0.18737 (10)	0.58924 (6)	0.0138 (2)
C13	0.52625 (15)	−0.09870 (11)	0.68529 (7)	0.0181 (2)
H13	0.473910	−0.159061	0.674975	0.022*
C25	0.63432 (15)	0.50116 (10)	0.64175 (7)	0.0174 (2)
H25	0.641606	0.529612	0.594921	0.021*
C40	1.03554 (15)	0.36605 (10)	0.26877 (6)	0.0163 (2)
C32	1.05891 (14)	0.08155 (10)	0.62066 (6)	0.0141 (2)
C15	0.64223 (15)	0.05958 (11)	0.64927 (7)	0.0180 (2)
H15	0.667643	0.109285	0.612925	0.022*
C28	0.87030 (14)	0.38170 (10)	0.53876 (6)	0.0151 (2)
H28	0.825980	0.450420	0.523158	0.018*
C39	0.90529 (15)	0.41530 (11)	0.30658 (7)	0.0182 (2)
H39	0.830398	0.458098	0.282286	0.022*
C2	1.07214 (15)	0.41551 (11)	0.88302 (7)	0.0193 (3)
H2	1.122655	0.479037	0.876440	0.023*
C30	1.03336 (14)	0.21484 (10)	0.51903 (7)	0.0155 (2)
H30	1.100492	0.166791	0.488934	0.019*
C38	0.88507 (15)	0.40186 (11)	0.37951 (7)	0.0176 (2)
H38	0.796116	0.435527	0.404955	0.021*
C33	1.14230 (15)	−0.00195 (11)	0.58015 (7)	0.0183 (2)
H33	1.171358	0.009268	0.531410	0.022*
C21	0.61682 (16)	−0.16794 (11)	1.02645 (7)	0.0185 (2)
H21	0.580120	−0.189282	0.983226	0.022*
C42	1.12654 (15)	0.29330 (11)	0.37761 (7)	0.0175 (2)
H42	1.203204	0.252366	0.401874	0.021*
C24	0.53044 (16)	0.55112 (11)	0.69369 (7)	0.0204 (3)
H24	0.464647	0.613768	0.682531	0.024*
C20	0.59031 (17)	−0.22761 (11)	1.08730 (7)	0.0215 (3)
H20	0.535822	−0.289320	1.085407	0.026*
C41	1.14771 (15)	0.30650 (11)	0.30466 (7)	0.0178 (2)
H41	1.238156	0.275115	0.279320	0.021*
C34	1.18242 (15)	−0.10165 (11)	0.61178 (7)	0.0196 (3)
H34	1.238636	−0.159698	0.584944	0.023*
C1	1.01489 (15)	0.36672 (10)	0.82639 (7)	0.0175 (2)
H1	1.026035	0.399002	0.780781	0.021*
C14	0.56647 (15)	−0.02757 (12)	0.63175 (7)	0.0195 (3)
H14	0.542599	−0.038407	0.584233	0.023*
C36	1.05989 (15)	−0.02783 (11)	0.72056 (7)	0.0173 (2)
H36	1.032639	−0.036698	0.769740	0.021*
C22	0.61991 (16)	0.41617 (11)	0.77528 (7)	0.0203 (3)
H22	0.616045	0.387219	0.822024	0.024*
C23	0.52374 (16)	0.50879 (11)	0.76177 (8)	0.0223 (3)
H23	0.454971	0.542401	0.798274	0.027*
C35	1.13919 (15)	−0.11532 (11)	0.68323 (7)	0.0192 (3)
H35	1.163471	−0.183154	0.705976	0.023*
C3	1.05346 (15)	0.36884 (11)	0.94953 (7)	0.0190 (3)
H3	1.092140	0.399852	0.989435	0.023*
C44	0.66597 (17)	−0.23664 (13)	1.27535 (7)	0.0239 (3)
H44A	0.776624	−0.242867	1.270677	0.036*
H44B	0.632577	−0.287756	1.311509	0.036*
H44C	0.625952	−0.161930	1.289560	0.036*
C43	1.16290 (18)	0.31801 (13)	0.15575 (7)	0.0268 (3)
H43A	1.151537	0.331365	0.105101	0.040*
H43B	1.158859	0.240288	0.165714	0.040*
H43C	1.260281	0.339129	0.168069	0.040*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.01649 (10)	0.01185 (9)	0.01116 (9)	−0.00133 (7)	−0.00057 (7)	0.00234 (6)
Cl2	0.02027 (15)	0.01290 (13)	0.01747 (14)	−0.00286 (11)	−0.00480 (11)	0.00059 (10)
Cl1	0.01966 (15)	0.01990 (15)	0.01669 (14)	−0.00161 (11)	−0.00475 (11)	0.00003 (11)
O2	0.0324 (5)	0.0215 (5)	0.0112 (4)	0.0017 (4)	−0.0022 (4)	0.0034 (3)
O1	0.0392 (6)	0.0274 (5)	0.0136 (4)	−0.0154 (5)	−0.0022 (4)	0.0073 (4)
O8	0.0209 (5)	0.0186 (5)	0.0260 (5)	−0.0003 (4)	−0.0035 (4)	−0.0028 (4)
O7	0.0361 (6)	0.0235 (5)	0.0181 (5)	0.0055 (4)	−0.0003 (4)	0.0000 (4)
O9	0.0326 (6)	0.0167 (5)	0.0349 (6)	−0.0062 (4)	−0.0066 (5)	0.0092 (4)
O10	0.0264 (5)	0.0257 (5)	0.0331 (6)	−0.0076 (4)	−0.0118 (4)	−0.0033 (4)
N4	0.0178 (5)	0.0138 (5)	0.0150 (5)	−0.0007 (4)	−0.0001 (4)	0.0015 (4)
N5	0.0144 (5)	0.0129 (5)	0.0134 (5)	−0.0009 (4)	−0.0019 (4)	0.0014 (4)
N1	0.0165 (5)	0.0127 (5)	0.0151 (5)	−0.0018 (4)	−0.0016 (4)	0.0022 (4)
N2	0.0144 (5)	0.0126 (5)	0.0125 (5)	−0.0011 (4)	−0.0009 (4)	0.0006 (4)
N6	0.0153 (5)	0.0140 (5)	0.0150 (5)	−0.0012 (4)	−0.0029 (4)	0.0024 (4)
O5	0.0305 (6)	0.0240 (6)	0.0554 (8)	−0.0103 (5)	−0.0075 (5)	−0.0013 (5)
N3	0.0154 (5)	0.0159 (5)	0.0128 (5)	−0.0004 (4)	−0.0025 (4)	0.0024 (4)
O3	0.0614 (9)	0.0381 (7)	0.0224 (6)	0.0185 (6)	0.0113 (5)	0.0058 (5)
O6	0.0411 (7)	0.0273 (6)	0.0439 (7)	0.0083 (5)	0.0111 (5)	−0.0045 (5)
O4	0.0582 (9)	0.0434 (8)	0.0599 (9)	−0.0259 (7)	−0.0461 (7)	0.0206 (6)
C11	0.0131 (5)	0.0139 (5)	0.0129 (5)	0.0005 (4)	−0.0012 (4)	0.0003 (4)
C10	0.0129 (5)	0.0123 (5)	0.0127 (5)	0.0007 (4)	−0.0006 (4)	−0.0001 (4)
C6	0.0135 (5)	0.0118 (5)	0.0138 (5)	−0.0004 (4)	−0.0006 (4)	−0.0001 (4)
C5	0.0138 (5)	0.0117 (5)	0.0142 (5)	−0.0003 (4)	−0.0003 (4)	0.0015 (4)
C7	0.0159 (6)	0.0139 (5)	0.0120 (5)	−0.0018 (4)	−0.0018 (4)	0.0003 (4)
C27	0.0143 (5)	0.0123 (5)	0.0135 (5)	−0.0016 (4)	−0.0019 (4)	0.0007 (4)
C19	0.0209 (6)	0.0172 (6)	0.0127 (5)	−0.0023 (5)	0.0012 (5)	0.0035 (4)
C37	0.0170 (6)	0.0164 (6)	0.0127 (5)	−0.0027 (5)	−0.0011 (4)	0.0023 (4)
C12	0.0165 (6)	0.0161 (6)	0.0157 (6)	−0.0019 (5)	−0.0013 (4)	0.0002 (4)
C4	0.0197 (6)	0.0160 (6)	0.0153 (6)	−0.0035 (5)	−0.0026 (5)	0.0018 (4)
C16	0.0143 (5)	0.0120 (5)	0.0123 (5)	−0.0003 (4)	0.0003 (4)	0.0020 (4)
C9	0.0146 (5)	0.0119 (5)	0.0143 (5)	−0.0020 (4)	−0.0010 (4)	0.0004 (4)
C26	0.0156 (6)	0.0120 (5)	0.0139 (5)	−0.0020 (4)	−0.0011 (4)	0.0004 (4)
C18	0.0175 (6)	0.0170 (6)	0.0125 (5)	−0.0013 (5)	−0.0014 (4)	0.0008 (4)
C8	0.0131 (5)	0.0116 (5)	0.0125 (5)	0.0011 (4)	0.0008 (4)	0.0009 (4)
C29	0.0148 (5)	0.0169 (6)	0.0125 (5)	−0.0029 (4)	−0.0009 (4)	0.0025 (4)
C17	0.0173 (6)	0.0140 (6)	0.0146 (6)	−0.0018 (4)	−0.0019 (4)	0.0011 (4)
C31	0.0139 (5)	0.0136 (5)	0.0137 (5)	−0.0010 (4)	−0.0017 (4)	0.0010 (4)
C13	0.0179 (6)	0.0180 (6)	0.0187 (6)	−0.0026 (5)	−0.0033 (5)	−0.0023 (5)
C25	0.0204 (6)	0.0144 (6)	0.0168 (6)	0.0009 (5)	−0.0015 (5)	0.0022 (4)
C40	0.0228 (6)	0.0148 (6)	0.0120 (5)	−0.0048 (5)	−0.0019 (5)	0.0027 (4)
C32	0.0132 (5)	0.0138 (5)	0.0153 (5)	−0.0009 (4)	−0.0029 (4)	0.0017 (4)
C15	0.0192 (6)	0.0213 (6)	0.0137 (6)	−0.0016 (5)	−0.0030 (5)	0.0028 (5)
C28	0.0175 (6)	0.0137 (5)	0.0142 (5)	−0.0009 (4)	−0.0019 (4)	0.0030 (4)
C39	0.0206 (6)	0.0164 (6)	0.0175 (6)	0.0001 (5)	−0.0047 (5)	0.0053 (5)
C2	0.0214 (6)	0.0137 (6)	0.0238 (6)	−0.0046 (5)	−0.0042 (5)	0.0033 (5)
C30	0.0148 (6)	0.0170 (6)	0.0143 (6)	0.0003 (4)	−0.0009 (4)	0.0009 (4)
C38	0.0192 (6)	0.0165 (6)	0.0163 (6)	0.0004 (5)	−0.0008 (5)	0.0025 (5)
C33	0.0190 (6)	0.0179 (6)	0.0171 (6)	0.0008 (5)	−0.0013 (5)	0.0006 (5)
C21	0.0240 (6)	0.0193 (6)	0.0134 (6)	−0.0069 (5)	−0.0027 (5)	0.0010 (5)
C42	0.0160 (6)	0.0208 (6)	0.0157 (6)	−0.0005 (5)	−0.0025 (4)	0.0033 (5)
C24	0.0208 (6)	0.0161 (6)	0.0228 (6)	0.0033 (5)	0.0004 (5)	0.0015 (5)
C20	0.0293 (7)	0.0203 (6)	0.0172 (6)	−0.0126 (5)	−0.0020 (5)	0.0027 (5)
C41	0.0182 (6)	0.0211 (6)	0.0137 (6)	−0.0015 (5)	0.0001 (4)	0.0013 (5)
C34	0.0178 (6)	0.0155 (6)	0.0249 (7)	0.0017 (5)	−0.0032 (5)	−0.0013 (5)
C1	0.0204 (6)	0.0143 (6)	0.0181 (6)	−0.0030 (5)	−0.0015 (5)	0.0042 (5)
C14	0.0198 (6)	0.0248 (7)	0.0142 (6)	−0.0014 (5)	−0.0046 (5)	−0.0010 (5)
C36	0.0171 (6)	0.0168 (6)	0.0184 (6)	−0.0024 (5)	−0.0032 (5)	0.0049 (5)
C22	0.0246 (7)	0.0186 (6)	0.0161 (6)	0.0001 (5)	0.0042 (5)	0.0030 (5)
C23	0.0236 (7)	0.0183 (6)	0.0226 (7)	0.0033 (5)	0.0060 (5)	0.0001 (5)
C35	0.0170 (6)	0.0147 (6)	0.0264 (7)	−0.0011 (5)	−0.0055 (5)	0.0045 (5)
C3	0.0219 (6)	0.0169 (6)	0.0196 (6)	−0.0049 (5)	−0.0063 (5)	0.0002 (5)
C44	0.0294 (7)	0.0297 (7)	0.0127 (6)	−0.0048 (6)	−0.0005 (5)	0.0042 (5)
C43	0.0310 (8)	0.0343 (8)	0.0137 (6)	0.0001 (6)	0.0017 (5)	0.0008 (5)

Geometric parameters (Å, º)

Mn1—N4	2.2375 (11)	C9—C8	1.4042 (17)
Mn1—N5	2.2002 (10)	C26—C25	1.3886 (17)
Mn1—N1	2.2666 (11)	C18—H18	0.9500
Mn1—N2	2.2081 (10)	C18—C17	1.3906 (17)
Mn1—N6	2.2970 (11)	C29—C28	1.3951 (17)
Mn1—N3	2.2738 (11)	C29—C30	1.4017 (17)
Cl2—O8	1.4480 (10)	C17—H17	0.9500
Cl2—O7	1.4406 (10)	C31—C32	1.4886 (17)
Cl2—O9	1.4401 (10)	C31—C30	1.3838 (17)
Cl2—O10	1.4462 (10)	C13—H13	0.9500
Cl1—O5	1.4432 (12)	C13—C14	1.3888 (19)
Cl1—O3	1.4338 (12)	C25—H25	0.9500
Cl1—O6	1.4413 (12)	C25—C24	1.3911 (18)
Cl1—O4	1.4226 (12)	C40—C39	1.3956 (19)
O2—C40	1.3626 (15)	C40—C41	1.3920 (18)
O2—C43	1.4259 (17)	C32—C33	1.3939 (18)
O1—C19	1.3602 (15)	C15—H15	0.9500
O1—C44	1.4344 (17)	C15—C14	1.3856 (19)
N4—C26	1.3509 (16)	C28—H28	0.9500
N4—C22	1.3353 (17)	C39—H39	0.9500
N5—C27	1.3461 (15)	C39—C38	1.3856 (18)
N5—C31	1.3450 (16)	C2—H2	0.9500
N1—C5	1.3535 (15)	C2—C1	1.3855 (19)
N1—C1	1.3403 (16)	C2—C3	1.3852 (18)
N2—C10	1.3453 (16)	C30—H30	0.9500
N2—C6	1.3459 (15)	C38—H38	0.9500
N6—C32	1.3509 (16)	C33—H33	0.9500
N6—C36	1.3467 (16)	C33—C34	1.3877 (18)
N3—C11	1.3537 (15)	C21—H21	0.9500
N3—C15	1.3443 (16)	C21—C20	1.3812 (18)
C11—C10	1.4878 (16)	C42—H42	0.9500
C11—C12	1.3894 (17)	C42—C41	1.3863 (17)
C10—C9	1.3916 (16)	C24—H24	0.9500
C6—C5	1.4873 (17)	C24—C23	1.3846 (19)
C6—C7	1.3887 (16)	C20—H20	0.9500
C5—C4	1.3902 (17)	C41—H41	0.9500
C7—H7	0.9500	C34—H34	0.9500
C7—C8	1.4042 (17)	C34—C35	1.3882 (19)
C27—C26	1.4845 (17)	C1—H1	0.9500
C27—C28	1.3912 (16)	C14—H14	0.9500
C19—C18	1.3883 (18)	C36—H36	0.9500
C19—C20	1.3982 (18)	C36—C35	1.3844 (19)
C37—C29	1.4773 (16)	C22—H22	0.9500
C37—C38	1.4057 (17)	C22—C23	1.3853 (19)
C37—C42	1.3964 (18)	C23—H23	0.9500
C12—H12	0.9500	C35—H35	0.9500
C12—C13	1.3895 (17)	C3—H3	0.9500
C4—H4	0.9500	C44—H44A	0.9800
C4—C3	1.3892 (18)	C44—H44B	0.9800
C16—C8	1.4820 (16)	C44—H44C	0.9800
C16—C17	1.3995 (17)	C43—H43A	0.9800
C16—C21	1.4028 (17)	C43—H43B	0.9800
C9—H9	0.9500	C43—H43C	0.9800
N4—Mn1—N1	86.42 (4)	C28—C29—C30	117.88 (11)
N4—Mn1—N6	143.89 (4)	C30—C29—C37	119.53 (11)
N4—Mn1—N3	106.58 (4)	C16—C17—H17	119.0
N5—Mn1—N4	72.05 (4)	C18—C17—C16	121.92 (12)
N5—Mn1—N1	117.76 (4)	C18—C17—H17	119.0
N5—Mn1—N2	167.42 (4)	N5—C31—C32	114.98 (10)
N5—Mn1—N6	72.00 (4)	N5—C31—C30	121.56 (11)
N5—Mn1—N3	98.94 (4)	C30—C31—C32	123.34 (11)
N1—Mn1—N6	107.36 (4)	C12—C13—H13	120.4
N1—Mn1—N3	143.30 (4)	C14—C13—C12	119.18 (12)
N2—Mn1—N4	118.25 (4)	C14—C13—H13	120.4
N2—Mn1—N1	71.82 (4)	C26—C25—H25	120.7
N2—Mn1—N6	97.84 (4)	C26—C25—C24	118.64 (12)
N2—Mn1—N3	71.82 (4)	C24—C25—H25	120.7
N3—Mn1—N6	82.42 (4)	O2—C40—C39	116.01 (11)
O7—Cl2—O8	109.56 (6)	O2—C40—C41	124.01 (12)
O7—Cl2—O10	108.81 (7)	C41—C40—C39	119.98 (12)
O9—Cl2—O8	109.74 (6)	N6—C32—C31	115.67 (11)
O9—Cl2—O7	109.98 (7)	N6—C32—C33	121.80 (11)
O9—Cl2—O10	109.41 (7)	C33—C32—C31	122.45 (11)
O10—Cl2—O8	109.33 (6)	N3—C15—H15	118.5
O3—Cl1—O5	108.85 (8)	N3—C15—C14	122.99 (12)
O3—Cl1—O6	108.44 (7)	C14—C15—H15	118.5
O6—Cl1—O5	109.88 (8)	C27—C28—C29	119.13 (11)
O4—Cl1—O5	108.68 (8)	C27—C28—H28	120.4
O4—Cl1—O3	110.75 (10)	C29—C28—H28	120.4
O4—Cl1—O6	110.22 (9)	C40—C39—H39	120.0
C40—O2—C43	117.30 (11)	C38—C39—C40	120.08 (12)
C19—O1—C44	118.33 (11)	C38—C39—H39	120.0
C26—N4—Mn1	117.98 (8)	C1—C2—H2	121.0
C22—N4—Mn1	122.76 (9)	C3—C2—H2	121.0
C22—N4—C26	118.57 (11)	C3—C2—C1	117.97 (12)
C27—N5—Mn1	120.08 (8)	C29—C30—H30	120.0
C31—N5—Mn1	120.43 (8)	C31—C30—C29	119.93 (11)
C31—N5—C27	119.31 (10)	C31—C30—H30	120.0
C5—N1—Mn1	117.79 (8)	C37—C38—H38	119.7
C1—N1—Mn1	123.69 (8)	C39—C38—C37	120.61 (12)
C1—N1—C5	118.35 (11)	C39—C38—H38	119.7
C10—N2—Mn1	120.46 (8)	C32—C33—H33	120.4
C10—N2—C6	119.11 (10)	C34—C33—C32	119.28 (12)
C6—N2—Mn1	120.32 (8)	C34—C33—H33	120.4
C32—N6—Mn1	116.15 (8)	C16—C21—H21	119.4
C36—N6—Mn1	123.91 (9)	C20—C21—C16	121.23 (12)
C36—N6—C32	118.19 (11)	C20—C21—H21	119.4
C11—N3—Mn1	117.30 (8)	C37—C42—H42	119.3
C15—N3—Mn1	123.53 (9)	C41—C42—C37	121.41 (12)
C15—N3—C11	118.41 (11)	C41—C42—H42	119.3
N3—C11—C10	115.35 (11)	C25—C24—H24	120.3
N3—C11—C12	121.82 (11)	C23—C24—C25	119.45 (12)
C12—C11—C10	122.80 (11)	C23—C24—H24	120.3
N2—C10—C11	114.65 (10)	C19—C20—H20	119.7
N2—C10—C9	121.95 (11)	C21—C20—C19	120.58 (12)
C9—C10—C11	123.38 (11)	C21—C20—H20	119.7
N2—C6—C5	114.61 (10)	C40—C41—H41	120.2
N2—C6—C7	121.95 (11)	C42—C41—C40	119.56 (12)
C7—C6—C5	123.43 (11)	C42—C41—H41	120.2
N1—C5—C6	115.12 (11)	C33—C34—H34	120.5
N1—C5—C4	121.87 (11)	C33—C34—C35	119.02 (12)
C4—C5—C6	122.99 (11)	C35—C34—H34	120.5
C6—C7—H7	120.0	N1—C1—C2	123.33 (12)
C6—C7—C8	120.03 (11)	N1—C1—H1	118.3
C8—C7—H7	120.0	C2—C1—H1	118.3
N5—C27—C26	114.31 (10)	C13—C14—H14	120.8
N5—C27—C28	122.14 (11)	C15—C14—C13	118.43 (12)
C28—C27—C26	123.49 (11)	C15—C14—H14	120.8
O1—C19—C18	124.66 (12)	N6—C36—H36	118.4
O1—C19—C20	116.13 (12)	N6—C36—C35	123.19 (12)
C18—C19—C20	119.20 (11)	C35—C36—H36	118.4
C38—C37—C29	121.13 (11)	N4—C22—H22	118.5
C42—C37—C29	120.39 (11)	N4—C22—C23	123.05 (12)
C42—C37—C38	118.29 (11)	C23—C22—H22	118.5
C11—C12—H12	120.4	C24—C23—C22	118.28 (12)
C11—C12—C13	119.14 (12)	C24—C23—H23	120.9
C13—C12—H12	120.4	C22—C23—H23	120.9
C5—C4—H4	120.6	C34—C35—H35	120.8
C3—C4—C5	118.74 (12)	C36—C35—C34	118.49 (12)
C3—C4—H4	120.6	C36—C35—H35	120.8
C17—C16—C8	120.96 (11)	C4—C3—H3	120.1
C17—C16—C21	117.28 (11)	C2—C3—C4	119.72 (12)
C21—C16—C8	121.75 (11)	C2—C3—H3	120.1
C10—C9—H9	120.0	O1—C44—H44A	109.5
C10—C9—C8	119.92 (11)	O1—C44—H44B	109.5
C8—C9—H9	120.0	O1—C44—H44C	109.5
N4—C26—C27	114.89 (11)	H44A—C44—H44B	109.5
N4—C26—C25	121.96 (11)	H44A—C44—H44C	109.5
C25—C26—C27	123.11 (11)	H44B—C44—H44C	109.5
C19—C18—H18	120.1	O2—C43—H43A	109.5
C19—C18—C17	119.77 (12)	O2—C43—H43B	109.5
C17—C18—H18	120.1	O2—C43—H43C	109.5
C7—C8—C16	121.30 (11)	H43A—C43—H43B	109.5
C9—C8—C7	116.97 (11)	H43A—C43—H43C	109.5
C9—C8—C16	121.73 (11)	H43B—C43—H43C	109.5
C28—C29—C37	122.47 (11)
Mn1—N4—C26—C27	−9.44 (14)	C27—N5—C31—C30	−0.27 (18)
Mn1—N4—C26—C25	168.29 (10)	C27—C26—C25—C24	178.49 (12)
Mn1—N4—C22—C23	−168.08 (11)	C19—C18—C17—C16	0.04 (19)
Mn1—N5—C27—C26	0.53 (14)	C37—C29—C28—C27	174.07 (11)
Mn1—N5—C27—C28	−176.72 (9)	C37—C29—C30—C31	−175.90 (11)
Mn1—N5—C31—C32	−1.14 (14)	C37—C42—C41—C40	−0.2 (2)
Mn1—N5—C31—C30	174.88 (9)	C12—C11—C10—N2	174.79 (11)
Mn1—N1—C5—C6	1.48 (14)	C12—C11—C10—C9	−3.98 (19)
Mn1—N1—C5—C4	−176.77 (9)	C12—C13—C14—C15	−0.2 (2)
Mn1—N1—C1—C2	177.01 (10)	C16—C21—C20—C19	0.0 (2)
Mn1—N2—C10—C11	−2.43 (14)	C26—N4—C22—C23	2.2 (2)
Mn1—N2—C10—C9	176.36 (9)	C26—C27—C28—C29	−174.25 (11)
Mn1—N2—C6—C5	6.85 (14)	C26—C25—C24—C23	0.9 (2)
Mn1—N2—C6—C7	−174.19 (9)	C18—C19—C20—C21	0.5 (2)
Mn1—N6—C32—C31	9.74 (14)	C8—C16—C17—C18	179.92 (11)
Mn1—N6—C32—C33	−167.10 (10)	C8—C16—C21—C20	−179.95 (12)
Mn1—N6—C36—C35	164.11 (10)	C29—C37—C38—C39	−173.07 (12)
Mn1—N3—C11—C10	6.67 (13)	C29—C37—C42—C41	173.18 (12)
Mn1—N3—C11—C12	−171.06 (9)	C17—C16—C8—C7	5.23 (18)
Mn1—N3—C15—C14	168.71 (10)	C17—C16—C8—C9	−174.26 (12)
O2—C40—C39—C38	178.05 (12)	C17—C16—C21—C20	−0.5 (2)
O2—C40—C41—C42	−177.99 (12)	C31—N5—C27—C26	175.70 (11)
O1—C19—C18—C17	179.83 (12)	C31—N5—C27—C28	−1.55 (18)
O1—C19—C20—C21	−179.83 (13)	C31—C32—C33—C34	−174.73 (12)
N4—C26—C25—C24	1.0 (2)	C25—C24—C23—C22	−1.2 (2)
N4—C22—C23—C24	−0.4 (2)	C40—C39—C38—C37	0.1 (2)
N5—C27—C26—N4	5.83 (16)	C32—N6—C36—C35	−0.20 (19)
N5—C27—C26—C25	−171.86 (12)	C32—C31—C30—C29	176.52 (12)
N5—C27—C28—C29	2.75 (19)	C32—C33—C34—C35	−0.4 (2)
N5—C31—C32—N6	−5.90 (16)	C15—N3—C11—C10	177.08 (11)
N5—C31—C32—C33	170.91 (12)	C15—N3—C11—C12	−0.65 (18)
N5—C31—C30—C29	0.84 (19)	C28—C27—C26—N4	−176.96 (12)
N1—C5—C4—C3	−0.08 (19)	C28—C27—C26—C25	5.3 (2)
N2—C10—C9—C8	−1.93 (18)	C28—C29—C30—C31	0.36 (19)
N2—C6—C5—N1	−5.27 (16)	C39—C40—C41—C42	2.3 (2)
N2—C6—C5—C4	172.95 (11)	C30—C29—C28—C27	−2.07 (18)
N2—C6—C7—C8	−2.40 (18)	C30—C31—C32—N6	178.16 (12)
N6—C32—C33—C34	1.90 (19)	C30—C31—C32—C33	−5.02 (19)
N6—C36—C35—C34	1.6 (2)	C38—C37—C29—C28	−27.63 (19)
N3—C11—C10—N2	−2.91 (16)	C38—C37—C29—C30	148.45 (13)
N3—C11—C10—C9	178.31 (11)	C38—C37—C42—C41	−1.9 (2)
N3—C11—C12—C13	1.86 (19)	C33—C34—C35—C36	−1.2 (2)
N3—C15—C14—C13	1.5 (2)	C21—C16—C8—C7	−175.33 (12)
C11—N3—C15—C14	−1.06 (19)	C21—C16—C8—C9	5.17 (18)
C11—C10—C9—C8	176.75 (11)	C21—C16—C17—C18	0.46 (19)
C11—C12—C13—C14	−1.37 (19)	C42—C37—C29—C28	157.44 (13)
C10—N2—C6—C5	−176.95 (10)	C42—C37—C29—C30	−26.48 (18)
C10—N2—C6—C7	2.01 (18)	C42—C37—C38—C39	2.0 (2)
C10—C11—C12—C13	−175.70 (11)	C20—C19—C18—C17	−0.5 (2)
C10—C9—C8—C7	1.49 (17)	C41—C40—C39—C38	−2.2 (2)
C10—C9—C8—C16	−178.99 (11)	C1—N1—C5—C6	176.91 (11)
C6—N2—C10—C11	−178.63 (10)	C1—N1—C5—C4	−1.34 (18)
C6—N2—C10—C9	0.16 (18)	C1—C2—C3—C4	−0.6 (2)
C6—C5—C4—C3	−178.19 (12)	C36—N6—C32—C31	175.27 (11)
C6—C7—C8—C16	−178.95 (11)	C36—N6—C32—C33	−1.57 (18)
C6—C7—C8—C9	0.58 (17)	C22—N4—C26—C27	179.77 (11)
C5—N1—C1—C2	1.87 (19)	C22—N4—C26—C25	−2.51 (19)
C5—C6—C7—C8	176.47 (11)	C3—C2—C1—N1	−0.9 (2)
C5—C4—C3—C2	1.0 (2)	C44—O1—C19—C18	−1.7 (2)
C7—C6—C5—N1	175.78 (11)	C44—O1—C19—C20	178.59 (13)
C7—C6—C5—C4	−5.99 (19)	C43—O2—C40—C39	−170.34 (12)
C27—N5—C31—C32	−176.28 (11)	C43—O2—C40—C41	9.96 (19)

Bis(4'-phenyl-2,2':6',2''-terpyridine)manganese(II) bis(perchlorate) (MnPhTPY)

Crystal data

[Mn(C21H15N3)2](ClO4)2	F(000) = 1788
Mr = 872.56	Dx = 1.567 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.51026 (18) Å	Cell parameters from 38088 reflections
b = 12.5149 (2) Å	θ = 2.6–34.1°
c = 31.2962 (6) Å	µ = 0.57 mm^−1
β = 96.8780 (18)°	T = 100 K
V = 3698.07 (12) Å^3	Block, yellow
Z = 4	0.30 × 0.11 × 0.03 mm

Data collection

Rigaku XtaLAB Synergy Dualflex diffractometer with a HyPix detector	9547 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Mo) X-ray Source	8250 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.032
Detector resolution: 10.0000 pixels mm^-1	θmax = 28.7°, θmin = 2.6°
ω scans	h = −13→14
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2022)	k = −19→19
	l = −48→45
63288 measured reflections

Refinement

Refinement on F^2	3 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.031	H-atom parameters constrained
wR(F^2) = 0.084	w = 1/[σ^2(Fo^2) + (0.0383P)^2 + 2.5012P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.002
9547 reflections	Δρmax = 0.43 e Å^−3
560 parameters	Δρmin = −0.51 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 crystals suitable for X-ray analysis were obtained by slow evaporation from acetonitrile using diethyl ether as antisolvent. Diffraction data for all the compounds were collected at room temperature on a Rigaku Synergy S diffractometer using photonjet microfocus source Mo Kα (λ = 0.71073 Å) radiation. The unit-cell parameters were determined using all reflections with CrysAlis PRO software (Agilent, 2014). Data integration and scaling were performed using CrysAlis PRO software (Agilent, 2014). The structures were solved and refined with SHELXT (Sheldrick, 2015a) and SHELXL (Sheldrick, 2015b) software, respectively, including in OLEX2 (Dolomanov et al., 2009). In all cases, non-H atoms were clearly resolved and full-matrix least-squares refinement with anisotropic displacement parameters was performed. In addition, the H atoms were stereochemically positioned and refined using the riding model (Sheldrick, 2008). The Mn compound [which one?] was refined using the SQUEEZE routine (Spek, 2015) in PLATON (Spek, 2020) to decrease the contribution of the disordered solvent (water molecule) to calculate the structure factors and improve the refinement values. Displacement ellipsoid plots for all structures were prepared with DIAMOND (Brandenburg et al., 2006). MERCURY were used for the preparation of artwork (Macrae et al., 2020). The CIF file of the complexes was deposited in the Cambridge Structural Data Base under the codes CCDC 2331329-2331331.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Mn1	0.55217 (2)	0.66511 (2)	0.61483 (2)	0.01214 (6)
Cl2	0.03899 (4)	0.78696 (3)	0.51551 (2)	0.01592 (7)
Cl1	0.76703 (4)	0.90467 (3)	0.74675 (2)	0.02234 (8)
O8	0.03068 (13)	0.67290 (8)	0.50689 (4)	0.0236 (2)
O7	−0.02540 (12)	0.80943 (9)	0.55382 (3)	0.0241 (2)
O5	0.18577 (11)	0.81940 (9)	0.52167 (3)	0.0213 (2)
N5	0.60249 (12)	0.63127 (9)	0.68354 (3)	0.0132 (2)
O6	−0.03368 (13)	0.84378 (9)	0.47935 (4)	0.0276 (3)
N6	0.36831 (12)	0.72376 (9)	0.64782 (4)	0.0139 (2)
N2	0.48224 (12)	0.67389 (9)	0.54501 (4)	0.0123 (2)
N4	0.77714 (12)	0.60523 (9)	0.62545 (4)	0.0138 (2)
N1	0.43169 (12)	0.51278 (9)	0.59496 (4)	0.0141 (2)
N3	0.63622 (12)	0.81781 (9)	0.59029 (4)	0.0137 (2)
O1	0.65906 (16)	0.85930 (12)	0.71679 (4)	0.0420 (4)
C10	0.51562 (14)	0.75998 (10)	0.52251 (4)	0.0123 (2)
C11	0.60971 (14)	0.83862 (10)	0.54766 (4)	0.0129 (2)
C7	0.33460 (14)	0.60963 (11)	0.48354 (4)	0.0142 (2)
H7	0.273413	0.555629	0.470614	0.017*
C9	0.46060 (14)	0.77417 (11)	0.47975 (4)	0.0139 (2)
H9	0.487664	0.834390	0.464158	0.017*
C27	0.50548 (15)	0.65035 (11)	0.71035 (4)	0.0150 (3)
O3	0.7117 (8)	0.9230 (7)	0.78654 (16)	0.0558 (17)	0.63 (3)
C32	0.83040 (15)	0.58016 (10)	0.66632 (4)	0.0134 (2)
C37	0.69504 (15)	0.56670 (11)	0.81747 (4)	0.0140 (2)
C5	0.36273 (14)	0.50937 (10)	0.55456 (4)	0.0130 (2)
C39	0.85716 (15)	0.58695 (11)	0.88276 (4)	0.0165 (3)
H39	0.946484	0.609258	0.896764	0.020*
C29	0.66243 (15)	0.58427 (11)	0.77054 (4)	0.0144 (3)
C38	0.82713 (15)	0.59734 (11)	0.83840 (4)	0.0159 (3)
H38	0.896841	0.625481	0.822166	0.019*
C28	0.53130 (15)	0.62540 (12)	0.75376 (4)	0.0175 (3)
H28	0.459662	0.636353	0.772015	0.021*
C31	0.72924 (14)	0.59099 (10)	0.69895 (4)	0.0128 (2)
C22	0.25461 (15)	0.77547 (11)	0.62823 (4)	0.0160 (3)
H22	0.249169	0.788010	0.598135	0.019*
C30	0.76353 (15)	0.56662 (11)	0.74226 (4)	0.0149 (3)
H30	0.854065	0.538437	0.752509	0.018*
C16	0.29350 (15)	0.71704 (10)	0.41567 (4)	0.0141 (2)
C33	0.97100 (15)	0.55131 (11)	0.67687 (5)	0.0174 (3)
H33	1.006288	0.534072	0.705735	0.021*
C26	0.37499 (15)	0.70548 (11)	0.69054 (4)	0.0156 (3)
C1	0.40786 (15)	0.43499 (11)	0.62260 (4)	0.0170 (3)
H1	0.456432	0.437461	0.650936	0.020*
C15	0.71934 (15)	0.88546 (11)	0.61525 (4)	0.0170 (3)
H15	0.737822	0.870942	0.645190	0.020*
C23	0.14478 (15)	0.81139 (11)	0.64994 (5)	0.0177 (3)
H23	0.065895	0.847533	0.634981	0.021*
C40	0.75682 (16)	0.54398 (11)	0.90670 (4)	0.0170 (3)
H40	0.777778	0.535894	0.936980	0.020*
C6	0.39392 (14)	0.59966 (10)	0.52607 (4)	0.0127 (2)
C12	0.66710 (15)	0.92730 (11)	0.52940 (4)	0.0162 (3)
H12	0.647298	0.940444	0.499385	0.019*
C42	0.59376 (15)	0.52416 (11)	0.84167 (4)	0.0162 (3)
H42	0.503634	0.503029	0.827872	0.019*
C36	0.86477 (16)	0.60294 (11)	0.59492 (4)	0.0166 (3)
H36	0.828109	0.621775	0.566335	0.020*
C35	1.00601 (16)	0.57446 (11)	0.60306 (5)	0.0183 (3)
H35	1.064774	0.573173	0.580567	0.022*
C8	0.36532 (14)	0.69952 (11)	0.45980 (4)	0.0136 (2)
C14	0.77917 (16)	0.97545 (11)	0.59913 (5)	0.0186 (3)
H14	0.836793	1.022020	0.617733	0.022*
C24	0.15228 (16)	0.79362 (12)	0.69374 (5)	0.0213 (3)
H24	0.079328	0.818195	0.709534	0.026*
C34	1.05955 (16)	0.54793 (12)	0.64472 (5)	0.0193 (3)
H34	1.155959	0.527595	0.651278	0.023*
C17	0.15410 (16)	0.68177 (11)	0.40447 (4)	0.0167 (3)
H17	0.105846	0.645968	0.425177	0.020*
O2	0.8790 (7)	0.8296 (7)	0.7535 (3)	0.068 (2)	0.63 (3)
C18	0.08613 (16)	0.69891 (12)	0.36322 (5)	0.0185 (3)
H18	−0.007989	0.674014	0.355797	0.022*
C41	0.62557 (16)	0.51291 (12)	0.88606 (4)	0.0179 (3)
H41	0.556852	0.483697	0.902399	0.021*
C21	0.36073 (16)	0.77218 (12)	0.38509 (4)	0.0196 (3)
H21	0.454548	0.797856	0.392359	0.023*
C25	0.26879 (16)	0.73902 (13)	0.71425 (5)	0.0217 (3)
H25	0.275578	0.724815	0.744243	0.026*
C4	0.26772 (15)	0.42783 (11)	0.54152 (4)	0.0170 (3)
H4	0.219498	0.427119	0.513126	0.020*
C13	0.75362 (16)	0.99655 (11)	0.55536 (5)	0.0187 (3)
H13	0.794524	1.057186	0.543389	0.022*
C19	0.15471 (17)	0.75212 (13)	0.33278 (5)	0.0217 (3)
H19	0.108514	0.762657	0.304466	0.026*
C2	0.31509 (16)	0.35074 (11)	0.61163 (5)	0.0188 (3)
H2	0.300879	0.296708	0.632004	0.023*
O4	0.8043 (11)	1.0058 (4)	0.7301 (3)	0.0469 (14)	0.63 (3)
C20	0.29110 (18)	0.78976 (14)	0.34403 (5)	0.0248 (3)
H20	0.337486	0.827917	0.323519	0.030*
C3	0.24407 (16)	0.34735 (11)	0.57048 (5)	0.0188 (3)
H3	0.179972	0.290843	0.562074	0.023*
O3A	0.7150 (9)	0.9475 (18)	0.7823 (4)	0.071 (4)	0.37 (3)
O2A	0.8771 (11)	0.8339 (10)	0.7614 (4)	0.060 (3)	0.37 (3)
O4A	0.852 (2)	0.9827 (19)	0.7260 (5)	0.064 (4)	0.37 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.01269 (10)	0.01436 (10)	0.00917 (9)	−0.00060 (7)	0.00045 (7)	0.00137 (7)
Cl2	0.01597 (16)	0.01960 (16)	0.01186 (14)	0.00072 (11)	0.00028 (11)	0.00258 (11)
Cl1	0.02685 (19)	0.02322 (17)	0.01604 (16)	−0.00158 (14)	−0.00119 (13)	−0.00172 (13)
O8	0.0293 (6)	0.0202 (5)	0.0213 (5)	−0.0026 (4)	0.0025 (4)	0.0004 (4)
O7	0.0227 (6)	0.0319 (6)	0.0189 (5)	0.0048 (5)	0.0079 (4)	0.0014 (4)
O5	0.0160 (5)	0.0282 (6)	0.0198 (5)	−0.0017 (4)	0.0025 (4)	−0.0006 (4)
N5	0.0133 (5)	0.0149 (5)	0.0113 (5)	0.0008 (4)	0.0009 (4)	0.0003 (4)
O6	0.0316 (7)	0.0293 (6)	0.0191 (5)	−0.0003 (5)	−0.0084 (5)	0.0089 (4)
N6	0.0141 (6)	0.0151 (5)	0.0122 (5)	−0.0002 (4)	0.0005 (4)	0.0023 (4)
N2	0.0116 (5)	0.0133 (5)	0.0121 (5)	0.0004 (4)	0.0013 (4)	0.0000 (4)
N4	0.0151 (6)	0.0143 (5)	0.0123 (5)	−0.0001 (4)	0.0025 (4)	0.0001 (4)
N1	0.0145 (6)	0.0144 (5)	0.0134 (5)	0.0000 (4)	0.0013 (4)	0.0015 (4)
N3	0.0136 (5)	0.0148 (5)	0.0126 (5)	−0.0001 (4)	0.0011 (4)	0.0001 (4)
O1	0.0525 (9)	0.0480 (8)	0.0220 (6)	−0.0249 (7)	−0.0098 (6)	−0.0014 (5)
C10	0.0114 (6)	0.0126 (6)	0.0133 (6)	0.0013 (4)	0.0032 (5)	0.0004 (4)
C11	0.0112 (6)	0.0146 (6)	0.0129 (6)	0.0019 (5)	0.0012 (5)	−0.0002 (5)
C7	0.0141 (6)	0.0144 (6)	0.0135 (6)	0.0009 (5)	−0.0003 (5)	−0.0013 (5)
C9	0.0143 (6)	0.0147 (6)	0.0129 (6)	0.0010 (5)	0.0020 (5)	0.0017 (5)
C27	0.0136 (6)	0.0189 (6)	0.0124 (6)	0.0019 (5)	0.0012 (5)	0.0012 (5)
O3	0.074 (4)	0.079 (3)	0.0167 (19)	−0.008 (2)	0.0153 (17)	−0.009 (2)
C32	0.0156 (6)	0.0123 (6)	0.0126 (6)	0.0001 (5)	0.0022 (5)	0.0000 (5)
C37	0.0157 (6)	0.0150 (6)	0.0110 (6)	0.0026 (5)	0.0003 (5)	0.0006 (5)
C5	0.0130 (6)	0.0135 (6)	0.0127 (6)	0.0015 (5)	0.0020 (5)	−0.0003 (4)
C39	0.0155 (7)	0.0190 (6)	0.0144 (6)	0.0013 (5)	−0.0011 (5)	−0.0025 (5)
C29	0.0164 (7)	0.0157 (6)	0.0104 (6)	0.0000 (5)	−0.0009 (5)	0.0005 (5)
C38	0.0155 (7)	0.0188 (6)	0.0134 (6)	−0.0004 (5)	0.0021 (5)	−0.0002 (5)
C28	0.0166 (7)	0.0237 (7)	0.0126 (6)	0.0040 (5)	0.0037 (5)	0.0021 (5)
C31	0.0129 (6)	0.0128 (6)	0.0126 (6)	0.0003 (5)	0.0011 (5)	−0.0004 (4)
C22	0.0171 (7)	0.0157 (6)	0.0145 (6)	−0.0007 (5)	−0.0011 (5)	0.0031 (5)
C30	0.0141 (6)	0.0170 (6)	0.0132 (6)	0.0015 (5)	−0.0003 (5)	0.0008 (5)
C16	0.0169 (7)	0.0140 (6)	0.0113 (6)	0.0029 (5)	0.0010 (5)	−0.0010 (5)
C33	0.0161 (7)	0.0187 (6)	0.0173 (6)	0.0022 (5)	0.0014 (5)	0.0023 (5)
C26	0.0138 (6)	0.0187 (6)	0.0140 (6)	0.0024 (5)	0.0001 (5)	0.0026 (5)
C1	0.0186 (7)	0.0173 (6)	0.0147 (6)	−0.0003 (5)	0.0007 (5)	0.0029 (5)
C15	0.0158 (7)	0.0198 (7)	0.0150 (6)	−0.0005 (5)	0.0004 (5)	−0.0014 (5)
C23	0.0141 (7)	0.0176 (6)	0.0203 (7)	0.0012 (5)	−0.0022 (5)	0.0021 (5)
C40	0.0218 (7)	0.0186 (6)	0.0103 (6)	0.0031 (5)	0.0004 (5)	0.0000 (5)
C6	0.0123 (6)	0.0124 (6)	0.0136 (6)	0.0016 (5)	0.0024 (5)	0.0003 (4)
C12	0.0161 (7)	0.0172 (6)	0.0154 (6)	0.0000 (5)	0.0023 (5)	0.0024 (5)
C42	0.0146 (7)	0.0196 (6)	0.0141 (6)	0.0009 (5)	−0.0002 (5)	0.0012 (5)
C36	0.0203 (7)	0.0164 (6)	0.0138 (6)	−0.0006 (5)	0.0042 (5)	0.0005 (5)
C35	0.0194 (7)	0.0169 (6)	0.0200 (7)	0.0003 (5)	0.0084 (5)	0.0008 (5)
C8	0.0139 (6)	0.0155 (6)	0.0116 (6)	0.0031 (5)	0.0024 (5)	−0.0002 (5)
C14	0.0156 (7)	0.0185 (7)	0.0211 (7)	−0.0025 (5)	0.0002 (5)	−0.0031 (5)
C24	0.0167 (7)	0.0264 (7)	0.0210 (7)	0.0056 (6)	0.0032 (6)	−0.0001 (6)
C34	0.0144 (7)	0.0194 (7)	0.0246 (7)	0.0030 (5)	0.0046 (6)	0.0018 (5)
C17	0.0186 (7)	0.0155 (6)	0.0157 (6)	0.0003 (5)	0.0009 (5)	0.0018 (5)
O2	0.043 (3)	0.069 (4)	0.098 (4)	0.025 (3)	0.038 (3)	0.011 (3)
C18	0.0179 (7)	0.0194 (7)	0.0173 (6)	0.0014 (5)	−0.0015 (5)	−0.0014 (5)
C41	0.0188 (7)	0.0206 (7)	0.0146 (6)	0.0002 (5)	0.0037 (5)	0.0028 (5)
C21	0.0180 (7)	0.0266 (7)	0.0143 (6)	−0.0010 (6)	0.0025 (5)	0.0005 (5)
C25	0.0196 (7)	0.0321 (8)	0.0136 (6)	0.0071 (6)	0.0033 (5)	0.0029 (6)
C4	0.0180 (7)	0.0173 (6)	0.0151 (6)	−0.0017 (5)	0.0002 (5)	−0.0006 (5)
C13	0.0175 (7)	0.0158 (6)	0.0232 (7)	−0.0024 (5)	0.0035 (6)	0.0019 (5)
C19	0.0231 (8)	0.0296 (8)	0.0116 (6)	0.0027 (6)	−0.0011 (5)	0.0003 (5)
C2	0.0198 (7)	0.0168 (6)	0.0201 (7)	−0.0013 (5)	0.0040 (5)	0.0045 (5)
O4	0.053 (3)	0.0302 (18)	0.052 (2)	−0.0182 (17)	−0.014 (2)	0.0109 (14)
C20	0.0255 (8)	0.0369 (9)	0.0124 (6)	−0.0022 (6)	0.0043 (6)	0.0035 (6)
C3	0.0176 (7)	0.0160 (6)	0.0229 (7)	−0.0035 (5)	0.0027 (6)	0.0001 (5)
O3A	0.021 (3)	0.112 (8)	0.076 (7)	0.016 (3)	−0.005 (3)	−0.078 (6)
O2A	0.054 (6)	0.055 (5)	0.059 (4)	0.032 (4)	−0.041 (5)	−0.016 (3)
O4A	0.061 (7)	0.081 (8)	0.044 (4)	−0.047 (6)	−0.019 (4)	0.030 (5)

Geometric parameters (Å, º)

Mn1—N5	2.1876 (11)	C38—H38	0.9500
Mn1—N2	2.2091 (11)	C28—H28	0.9500
Mn1—N3	2.2423 (12)	C31—C30	1.3894 (18)
Mn1—N4	2.2537 (12)	C22—C23	1.387 (2)
Mn1—N6	2.2571 (12)	C22—H22	0.9500
Mn1—N1	2.2723 (12)	C30—H30	0.9500
Cl2—O7	1.4378 (11)	C16—C21	1.396 (2)
Cl2—O6	1.4412 (11)	C16—C17	1.401 (2)
Cl2—O5	1.4443 (11)	C16—C8	1.4819 (18)
Cl2—O8	1.4530 (11)	C33—C34	1.388 (2)
Cl1—O3A	1.381 (8)	C33—H33	0.9500
Cl1—O2A	1.406 (8)	C26—C25	1.388 (2)
Cl1—O2	1.417 (6)	C1—C2	1.391 (2)
Cl1—O1	1.4231 (13)	C1—H1	0.9500
Cl1—O3	1.427 (5)	C15—C14	1.384 (2)
Cl1—O4	1.429 (6)	C15—H15	0.9500
Cl1—O4A	1.466 (9)	C23—C24	1.382 (2)
N5—C27	1.3408 (18)	C23—H23	0.9500
N5—C31	1.3418 (17)	C40—C41	1.391 (2)
N6—C22	1.3437 (18)	C40—H40	0.9500
N6—C26	1.3504 (17)	C12—C13	1.389 (2)
N2—C6	1.3419 (17)	C12—H12	0.9500
N2—C10	1.3459 (17)	C42—C41	1.3929 (19)
N4—C36	1.3415 (18)	C42—H42	0.9500
N4—C32	1.3547 (17)	C36—C35	1.384 (2)
N1—C1	1.3397 (18)	C36—H36	0.9500
N1—C5	1.3532 (17)	C35—C34	1.382 (2)
N3—C15	1.3431 (18)	C35—H35	0.9500
N3—C11	1.3530 (17)	C14—C13	1.388 (2)
C10—C9	1.3885 (18)	C14—H14	0.9500
C10—C11	1.4901 (18)	C24—C25	1.391 (2)
C11—C12	1.3896 (19)	C24—H24	0.9500
C7—C6	1.3877 (18)	C34—H34	0.9500
C7—C8	1.3982 (19)	C17—C18	1.3896 (19)
C7—H7	0.9500	C17—H17	0.9500
C9—C8	1.3958 (19)	C18—C19	1.387 (2)
C9—H9	0.9500	C18—H18	0.9500
C27—C28	1.3870 (18)	C41—H41	0.9500
C27—C26	1.4887 (19)	C21—C20	1.391 (2)
C32—C33	1.3862 (19)	C21—H21	0.9500
C32—C31	1.4909 (18)	C25—H25	0.9500
C37—C38	1.3991 (19)	C4—C3	1.391 (2)
C37—C42	1.400 (2)	C4—H4	0.9500
C37—C29	1.4807 (18)	C13—H13	0.9500
C5—C4	1.3914 (19)	C19—C20	1.385 (2)
C5—C6	1.4911 (18)	C19—H19	0.9500
C39—C38	1.3895 (19)	C2—C3	1.381 (2)
C39—C40	1.390 (2)	C2—H2	0.9500
C39—H39	0.9500	C20—H20	0.9500
C29—C28	1.3925 (19)	C3—H3	0.9500
C29—C30	1.4003 (19)
N5—Mn1—N2	170.51 (4)	C30—C31—C32	123.57 (12)
N5—Mn1—N3	117.17 (4)	N6—C22—C23	122.99 (13)
N2—Mn1—N3	72.32 (4)	N6—C22—H22	118.5
N5—Mn1—N4	72.45 (4)	C23—C22—H22	118.5
N2—Mn1—N4	109.30 (4)	C31—C30—C29	118.90 (12)
N3—Mn1—N4	87.87 (4)	C31—C30—H30	120.5
N5—Mn1—N6	72.76 (4)	C29—C30—H30	120.5
N2—Mn1—N6	106.16 (4)	C21—C16—C17	118.78 (13)
N3—Mn1—N6	101.95 (4)	C21—C16—C8	120.96 (13)
N4—Mn1—N6	144.53 (4)	C17—C16—C8	120.21 (12)
N5—Mn1—N1	98.65 (4)	C32—C33—C34	119.13 (13)
N2—Mn1—N1	71.87 (4)	C32—C33—H33	120.4
N3—Mn1—N1	144.10 (4)	C34—C33—H33	120.4
N4—Mn1—N1	101.55 (4)	N6—C26—C25	121.81 (13)
N6—Mn1—N1	90.29 (4)	N6—C26—C27	115.39 (12)
O7—Cl2—O6	110.25 (7)	C25—C26—C27	122.77 (12)
O7—Cl2—O5	109.58 (7)	N1—C1—C2	122.87 (13)
O6—Cl2—O5	109.33 (7)	N1—C1—H1	118.6
O7—Cl2—O8	109.14 (7)	C2—C1—H1	118.6
O6—Cl2—O8	109.18 (7)	N3—C15—C14	122.69 (13)
O5—Cl2—O8	109.34 (7)	N3—C15—H15	118.7
O3A—Cl1—O2A	107.8 (7)	C14—C15—H15	118.7
O3A—Cl1—O1	112.7 (5)	C24—C23—C22	118.76 (13)
O2A—Cl1—O1	114.5 (5)	C24—C23—H23	120.6
O2—Cl1—O1	107.6 (4)	C22—C23—H23	120.6
O2—Cl1—O3	109.0 (4)	C39—C40—C41	119.58 (13)
O1—Cl1—O3	109.1 (3)	C39—C40—H40	120.2
O2—Cl1—O4	115.2 (5)	C41—C40—H40	120.2
O1—Cl1—O4	107.7 (3)	N2—C6—C7	121.51 (12)
O3—Cl1—O4	108.0 (4)	N2—C6—C5	114.79 (11)
O3A—Cl1—O4A	111.6 (8)	C7—C6—C5	123.68 (12)
O2A—Cl1—O4A	97.9 (10)	C13—C12—C11	119.48 (13)
O1—Cl1—O4A	111.4 (5)	C13—C12—H12	120.3
C27—N5—C31	119.85 (11)	C11—C12—H12	120.3
C27—N5—Mn1	119.65 (9)	C41—C42—C37	119.78 (13)
C31—N5—Mn1	120.50 (9)	C41—C42—H42	120.1
C22—N6—C26	118.25 (12)	C37—C42—H42	120.1
C22—N6—Mn1	124.96 (9)	N4—C36—C35	123.12 (13)
C26—N6—Mn1	116.79 (9)	N4—C36—H36	118.4
C6—N2—C10	119.83 (11)	C35—C36—H36	118.4
C6—N2—Mn1	120.06 (9)	C34—C35—C36	118.40 (13)
C10—N2—Mn1	119.70 (9)	C34—C35—H35	120.8
C36—N4—C32	118.27 (12)	C36—C35—H35	120.8
C36—N4—Mn1	124.18 (9)	C9—C8—C7	117.82 (12)
C32—N4—Mn1	117.22 (9)	C9—C8—C16	121.33 (12)
C1—N1—C5	118.68 (12)	C7—C8—C16	120.79 (12)
C1—N1—Mn1	123.48 (9)	C15—C14—C13	118.92 (13)
C5—N1—Mn1	117.01 (9)	C15—C14—H14	120.5
C15—N3—C11	118.64 (12)	C13—C14—H14	120.5
C15—N3—Mn1	123.18 (9)	C23—C24—C25	118.70 (14)
C11—N3—Mn1	118.02 (9)	C23—C24—H24	120.7
N2—C10—C9	121.43 (12)	C25—C24—H24	120.7
N2—C10—C11	114.62 (11)	C35—C34—C33	119.31 (14)
C9—C10—C11	123.91 (12)	C35—C34—H34	120.3
N3—C11—C12	121.56 (12)	C33—C34—H34	120.3
N3—C11—C10	115.03 (11)	C18—C17—C16	120.31 (13)
C12—C11—C10	123.42 (12)	C18—C17—H17	119.8
C6—C7—C8	119.68 (12)	C16—C17—H17	119.8
C6—C7—H7	120.2	C19—C18—C17	120.49 (14)
C8—C7—H7	120.2	C19—C18—H18	119.8
C10—C9—C8	119.67 (12)	C17—C18—H18	119.8
C10—C9—H9	120.2	C40—C41—C42	120.72 (13)
C8—C9—H9	120.2	C40—C41—H41	119.6
N5—C27—C28	121.24 (13)	C42—C41—H41	119.6
N5—C27—C26	115.07 (12)	C20—C21—C16	120.36 (14)
C28—C27—C26	123.59 (13)	C20—C21—H21	119.8
N4—C32—C33	121.75 (12)	C16—C21—H21	119.8
N4—C32—C31	115.25 (12)	C26—C25—C24	119.49 (13)
C33—C32—C31	122.93 (12)	C26—C25—H25	120.3
C38—C37—C42	119.23 (12)	C24—C25—H25	120.3
C38—C37—C29	119.57 (12)	C3—C4—C5	119.33 (13)
C42—C37—C29	121.15 (12)	C3—C4—H4	120.3
N1—C5—C4	121.48 (12)	C5—C4—H4	120.3
N1—C5—C6	115.21 (12)	C14—C13—C12	118.70 (13)
C4—C5—C6	123.30 (12)	C14—C13—H13	120.6
C38—C39—C40	120.17 (13)	C12—C13—H13	120.6
C38—C39—H39	119.9	C20—C19—C18	119.45 (13)
C40—C39—H39	119.9	C20—C19—H19	120.3
C28—C29—C30	118.14 (12)	C18—C19—H19	120.3
C28—C29—C37	120.05 (12)	C3—C2—C1	118.56 (13)
C30—C29—C37	121.70 (12)	C3—C2—H2	120.7
C39—C38—C37	120.52 (13)	C1—C2—H2	120.7
C39—C38—H38	119.7	C19—C20—C21	120.58 (14)
C37—C38—H38	119.7	C19—C20—H20	119.7
C27—C28—C29	119.88 (13)	C21—C20—H20	119.7
C27—C28—H28	120.1	C2—C3—C4	119.08 (13)
C29—C28—H28	120.1	C2—C3—H3	120.5
N5—C31—C30	121.94 (12)	C4—C3—H3	120.5
N5—C31—C32	114.42 (11)
C6—N2—C10—C9	−0.04 (19)	C28—C27—C26—N6	179.68 (13)
Mn1—N2—C10—C9	−172.69 (10)	N5—C27—C26—C25	−174.73 (14)
C6—N2—C10—C11	177.57 (12)	C28—C27—C26—C25	1.5 (2)
Mn1—N2—C10—C11	4.92 (15)	C5—N1—C1—C2	−0.1 (2)
C15—N3—C11—C12	0.5 (2)	Mn1—N1—C1—C2	169.18 (11)
Mn1—N3—C11—C12	−175.00 (10)	C11—N3—C15—C14	−0.1 (2)
C15—N3—C11—C10	−179.51 (12)	Mn1—N3—C15—C14	175.09 (11)
Mn1—N3—C11—C10	5.02 (15)	N6—C22—C23—C24	0.2 (2)
N2—C10—C11—N3	−6.41 (17)	C38—C39—C40—C41	−0.9 (2)
C9—C10—C11—N3	171.12 (12)	C10—N2—C6—C7	−0.4 (2)
N2—C10—C11—C12	173.61 (13)	Mn1—N2—C6—C7	172.17 (10)
C9—C10—C11—C12	−8.9 (2)	C10—N2—C6—C5	−178.75 (11)
N2—C10—C9—C8	1.9 (2)	Mn1—N2—C6—C5	−6.13 (15)
C11—C10—C9—C8	−175.48 (12)	C8—C7—C6—N2	−0.9 (2)
C31—N5—C27—C28	−2.5 (2)	C8—C7—C6—C5	177.22 (12)
Mn1—N5—C27—C28	177.06 (11)	N1—C5—C6—N2	−2.35 (17)
C31—N5—C27—C26	173.85 (12)	C4—C5—C6—N2	176.36 (13)
Mn1—N5—C27—C26	−6.57 (16)	N1—C5—C6—C7	179.39 (12)
C36—N4—C32—C33	−0.84 (19)	C4—C5—C6—C7	−1.9 (2)
Mn1—N4—C32—C33	−174.46 (10)	N3—C11—C12—C13	−0.1 (2)
C36—N4—C32—C31	176.34 (12)	C10—C11—C12—C13	179.88 (13)
Mn1—N4—C32—C31	2.72 (15)	C38—C37—C42—C41	0.0 (2)
C1—N1—C5—C4	0.5 (2)	C29—C37—C42—C41	−177.20 (13)
Mn1—N1—C5—C4	−169.42 (10)	C32—N4—C36—C35	1.1 (2)
C1—N1—C5—C6	179.25 (12)	Mn1—N4—C36—C35	174.29 (10)
Mn1—N1—C5—C6	9.31 (15)	N4—C36—C35—C34	−0.5 (2)
C38—C37—C29—C28	−136.00 (14)	C10—C9—C8—C7	−3.2 (2)
C42—C37—C29—C28	41.19 (19)	C10—C9—C8—C16	173.95 (12)
C38—C37—C29—C30	40.11 (19)	C6—C7—C8—C9	2.7 (2)
C42—C37—C29—C30	−142.71 (14)	C6—C7—C8—C16	−174.43 (12)
C40—C39—C38—C37	1.2 (2)	C21—C16—C8—C9	32.5 (2)
C42—C37—C38—C39	−0.8 (2)	C17—C16—C8—C9	−145.05 (14)
C29—C37—C38—C39	176.49 (13)	C21—C16—C8—C7	−150.48 (14)
N5—C27—C28—C29	3.0 (2)	C17—C16—C8—C7	31.98 (19)
C26—C27—C28—C29	−173.07 (13)	N3—C15—C14—C13	−0.6 (2)
C30—C29—C28—C27	−1.8 (2)	C22—C23—C24—C25	−0.9 (2)
C37—C29—C28—C27	174.48 (13)	C36—C35—C34—C33	−0.4 (2)
C27—N5—C31—C30	0.9 (2)	C32—C33—C34—C35	0.7 (2)
Mn1—N5—C31—C30	−178.69 (10)	C21—C16—C17—C18	1.9 (2)
C27—N5—C31—C32	−176.25 (12)	C8—C16—C17—C18	179.45 (13)
Mn1—N5—C31—C32	4.17 (15)	C16—C17—C18—C19	−0.7 (2)
N4—C32—C31—N5	−4.42 (17)	C39—C40—C41—C42	0.1 (2)
C33—C32—C31—N5	172.73 (13)	C37—C42—C41—C40	0.3 (2)
N4—C32—C31—C30	178.50 (12)	C17—C16—C21—C20	−1.2 (2)
C33—C32—C31—C30	−4.4 (2)	C8—C16—C21—C20	−178.81 (14)
C26—N6—C22—C23	0.5 (2)	N6—C26—C25—C24	−0.4 (2)
Mn1—N6—C22—C23	−179.10 (10)	C27—C26—C25—C24	177.60 (14)
N5—C31—C30—C29	0.3 (2)	C23—C24—C25—C26	1.0 (2)
C32—C31—C30—C29	177.14 (12)	N1—C5—C4—C3	−0.7 (2)
C28—C29—C30—C31	0.2 (2)	C6—C5—C4—C3	−179.30 (13)
C37—C29—C30—C31	−175.98 (12)	C15—C14—C13—C12	0.9 (2)
N4—C32—C33—C34	−0.1 (2)	C11—C12—C13—C14	−0.6 (2)
C31—C32—C33—C34	−177.02 (13)	C17—C18—C19—C20	−1.1 (2)
C22—N6—C26—C25	−0.3 (2)	N1—C1—C2—C3	−0.2 (2)
Mn1—N6—C26—C25	179.27 (12)	C18—C19—C20—C21	1.7 (2)
C22—N6—C26—C27	−178.49 (12)	C16—C21—C20—C19	−0.5 (2)
Mn1—N6—C26—C27	1.11 (16)	C1—C2—C3—C4	0.1 (2)
N5—C27—C26—N6	3.41 (18)	C5—C4—C3—C2	0.4 (2)

Bis(4'-phenyl-2,2':6',2''-terpyridine)nickel(II) bis(perchlorate) (NiPhTPY)

Crystal data

[Ni(C21H15N3)2](ClO4)2	F(000) = 1800
Mr = 876.33	Dx = 1.581 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.3581 (2) Å	Cell parameters from 24227 reflections
b = 12.6255 (3) Å	θ = 2.5–33.3°
c = 31.4046 (8) Å	µ = 0.74 mm^−1
β = 97.038 (2)°	T = 100 K
V = 3682.52 (15) Å^3	Block, light orange
Z = 4	0.10 × 0.08 × 0.06 mm

Data collection

Rigaku XtaLAB Synergy Dualflex diffractometer with a HyPix detector	9514 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Mo) X-ray Source	7295 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.053
Detector resolution: 10.0000 pixels mm^-1	θmax = 28.7°, θmin = 2.5°
ω scans	h = −12→12
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2022)	k = −16→17
Tmin = 0.815, Tmax = 1.000	l = −41→42
52589 measured reflections

Refinement

Refinement on F^2	435 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.037	H-atom parameters constrained
wR(F^2) = 0.094	w = 1/[σ^2(Fo^2) + (0.0352P)^2 + 3.3821P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
9514 reflections	Δρmax = 0.64 e Å^−3
560 parameters	Δρmin = −0.54 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 crystals suitable for X-ray analysis were obtained by slow evaporation from acetonitrile using diethyl ether as antisolvent. Diffraction data for all the compounds were collected at room temperature on a Rigaku Synergy S diffractometer using photonjet microfocus source Mo Kα (λ = 0.71073 Å) radiation. The unit-cell parameters were determined using all reflections with CrysAlis PRO software (Agilent, 2014). Data integration and scaling were performed using CrysAlis PRO software (Agilent, 2014). The structures were solved and refined with SHELXT (Sheldrick, 2015a) and SHELXL (Sheldrick, 2015b) software, respectively, including in OLEX2 (Dolomanov et al., 2009). In all cases, non-H atoms were clearly resolved and full-matrix least-squares refinement with anisotropic displacement parameters was performed. In addition, the H atoms were stereochemically positioned and refined using the riding model (Sheldrick, 2008). The Mn compound [which one?] was refined using the SQUEEZE routine (Spek, 2015) in PLATON (Spek, 2020) to decrease the contribution of the disordered solvent (water molecule) to calculate the structure factors and improve the refinement values. Displacement ellipsoid plots for all structures were prepared with DIAMOND (Brandenburg et al., 2006). MERCURY were used for the preparation of artwork (Macrae et al., 2020). The CIF file of the complexes was deposited in the Cambridge Structural Data Base under the codes CCDC 2331329-2331331.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ni1	0.45313 (2)	0.67165 (2)	0.38521 (2)	0.01333 (7)
Cl2	0.97887 (5)	0.78974 (4)	0.49141 (2)	0.02213 (11)
Cl1	0.21363 (5)	0.92269 (4)	0.24853 (2)	0.02422 (11)
O8	0.97982 (18)	0.67651 (12)	0.50010 (5)	0.0281 (3)
N2	0.51734 (16)	0.68107 (12)	0.44827 (5)	0.0141 (3)
N5	0.39922 (17)	0.65160 (12)	0.32226 (5)	0.0149 (3)
N3	0.36801 (16)	0.81949 (12)	0.40160 (5)	0.0150 (3)
N4	0.63665 (17)	0.73271 (12)	0.35939 (5)	0.0153 (3)
O7	1.03924 (17)	0.80845 (13)	0.45232 (5)	0.0300 (4)
O5	0.83213 (17)	0.82817 (13)	0.48676 (5)	0.0305 (4)
N1	0.56197 (16)	0.52504 (12)	0.39778 (5)	0.0150 (3)
N6	0.24101 (17)	0.61193 (12)	0.38221 (5)	0.0148 (3)
O6	1.0601 (2)	0.84318 (14)	0.52657 (6)	0.0431 (5)
O1	0.3281 (2)	0.86989 (15)	0.27412 (6)	0.0432 (5)
C11	0.39025 (19)	0.84361 (14)	0.44381 (6)	0.0150 (4)
C10	0.48180 (19)	0.76651 (14)	0.47042 (6)	0.0139 (4)
C6	0.60250 (19)	0.60519 (14)	0.46752 (6)	0.0144 (4)
C9	0.5328 (2)	0.77833 (14)	0.51354 (6)	0.0158 (4)
H9	0.505366	0.838169	0.528984	0.019*
C31	0.27142 (19)	0.60874 (14)	0.30761 (6)	0.0151 (4)
C7	0.6573 (2)	0.61277 (14)	0.51031 (6)	0.0160 (4)
H7	0.716632	0.557990	0.523523	0.019*
C32	0.1769 (2)	0.59386 (14)	0.34180 (6)	0.0150 (4)
C33	0.0324 (2)	0.56748 (15)	0.33329 (7)	0.0182 (4)
H33	−0.010507	0.555517	0.304683	0.022*
C22	0.7524 (2)	0.78050 (14)	0.38051 (7)	0.0168 (4)
H22	0.758400	0.787381	0.410801	0.020*
C15	0.2843 (2)	0.88344 (15)	0.37516 (7)	0.0182 (4)
H15	0.268385	0.866400	0.345495	0.022*
C26	0.6302 (2)	0.72212 (15)	0.31626 (6)	0.0175 (4)
C4	0.7234 (2)	0.43312 (15)	0.45043 (7)	0.0189 (4)
H4	0.771109	0.428984	0.478880	0.023*
C28	0.4712 (2)	0.64245 (16)	0.25252 (6)	0.0187 (4)
H28	0.543636	0.651977	0.234154	0.022*
C27	0.4976 (2)	0.67007 (15)	0.29544 (6)	0.0167 (4)
C12	0.3292 (2)	0.93257 (15)	0.46021 (7)	0.0179 (4)
H12	0.346711	0.948280	0.489981	0.022*
C1	0.5830 (2)	0.44934 (15)	0.36943 (7)	0.0185 (4)
H1	0.533945	0.454587	0.341178	0.022*
C5	0.63146 (19)	0.51687 (14)	0.43826 (6)	0.0156 (4)
C37	0.3043 (2)	0.57916 (14)	0.18980 (6)	0.0163 (4)
C16	0.6910 (2)	0.71515 (14)	0.57908 (6)	0.0157 (4)
C35	0.0159 (2)	0.57788 (15)	0.40844 (7)	0.0196 (4)
H35	−0.037684	0.572543	0.432174	0.024*
C8	0.6249 (2)	0.70170 (14)	0.53421 (6)	0.0156 (4)
C29	0.3376 (2)	0.60056 (15)	0.23647 (6)	0.0173 (4)
C36	0.1606 (2)	0.60499 (15)	0.41440 (6)	0.0172 (4)
H36	0.204585	0.619275	0.442713	0.021*
C30	0.2357 (2)	0.58350 (15)	0.26470 (6)	0.0173 (4)
H30	0.143624	0.555153	0.254680	0.021*
C34	−0.0484 (2)	0.55889 (15)	0.36731 (7)	0.0207 (4)
H34	−0.147292	0.540038	0.362293	0.025*
C23	0.8639 (2)	0.82028 (15)	0.35977 (7)	0.0188 (4)
H23	0.944400	0.853616	0.375677	0.023*
C41	0.1443 (2)	0.59859 (15)	0.12386 (6)	0.0184 (4)
H41	0.055045	0.621815	0.109131	0.022*
C38	0.4062 (2)	0.53171 (15)	0.16699 (7)	0.0184 (4)
H38	0.495769	0.508838	0.181598	0.022*
C17	0.8301 (2)	0.67636 (15)	0.59224 (6)	0.0179 (4)
H17	0.881722	0.641089	0.572203	0.021*
C39	0.3764 (2)	0.51794 (15)	0.12283 (7)	0.0192 (4)
H39	0.445643	0.485270	0.107395	0.023*
C40	0.2459 (2)	0.55169 (15)	0.10117 (7)	0.0194 (4)
H40	0.226335	0.542719	0.070986	0.023*
C13	0.2422 (2)	0.99840 (15)	0.43267 (7)	0.0212 (4)
H13	0.198772	1.059359	0.443304	0.025*
C42	0.1725 (2)	0.61162 (15)	0.16785 (7)	0.0185 (4)
H42	0.101948	0.642816	0.183223	0.022*
C14	0.2201 (2)	0.97352 (15)	0.38943 (7)	0.0203 (4)
H14	0.161769	1.017505	0.369838	0.024*
C18	0.8925 (2)	0.68926 (15)	0.63440 (7)	0.0207 (4)
H18	0.986327	0.662215	0.643073	0.025*
C25	0.7372 (2)	0.76024 (17)	0.29377 (7)	0.0219 (4)
H25	0.729760	0.752056	0.263507	0.026*
C2	0.6733 (2)	0.36346 (16)	0.37950 (7)	0.0217 (4)
H2	0.685611	0.311102	0.358536	0.026*
C21	0.6194 (2)	0.76877 (16)	0.60888 (7)	0.0202 (4)
H21	0.526164	0.796943	0.600356	0.024*
C24	0.8561 (2)	0.81078 (16)	0.31587 (7)	0.0217 (4)
H24	0.930358	0.838190	0.300956	0.026*
C19	0.8188 (2)	0.74132 (16)	0.66385 (7)	0.0227 (4)
H19	0.861245	0.749420	0.692732	0.027*
C20	0.6825 (2)	0.78154 (17)	0.65077 (7)	0.0247 (4)
H20	0.631991	0.818131	0.670745	0.030*
C3	0.7451 (2)	0.35530 (15)	0.42056 (7)	0.0216 (4)
H3	0.808152	0.297560	0.428217	0.026*
O3	0.2592 (13)	0.9531 (12)	0.2092 (3)	0.060 (3)	0.54 (2)
O4	0.1845 (15)	1.0198 (6)	0.2704 (2)	0.061 (2)	0.54 (2)
O2	0.0905 (8)	0.8607 (9)	0.2423 (3)	0.087 (3)	0.54 (2)
O3A	0.2646 (12)	0.9837 (15)	0.2166 (5)	0.062 (4)	0.46 (2)
O4A	0.1294 (12)	0.9826 (13)	0.2744 (2)	0.053 (3)	0.46 (2)
O2A	0.1196 (17)	0.8454 (6)	0.2258 (6)	0.085 (5)	0.46 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.01241 (11)	0.01601 (12)	0.01128 (12)	−0.00111 (9)	0.00028 (9)	−0.00063 (9)
Cl2	0.0235 (2)	0.0274 (2)	0.0151 (2)	−0.00382 (18)	0.00064 (19)	−0.00390 (18)
Cl1	0.0238 (2)	0.0324 (3)	0.0158 (2)	0.00260 (19)	−0.00016 (19)	0.0049 (2)
O8	0.0349 (9)	0.0294 (8)	0.0202 (8)	−0.0002 (7)	0.0036 (7)	−0.0005 (6)
N2	0.0116 (7)	0.0155 (7)	0.0149 (8)	−0.0020 (6)	0.0009 (6)	−0.0005 (6)
N5	0.0146 (7)	0.0167 (7)	0.0132 (8)	−0.0023 (6)	0.0006 (6)	0.0001 (6)
N3	0.0131 (7)	0.0170 (7)	0.0147 (8)	−0.0021 (6)	0.0003 (6)	0.0011 (6)
N4	0.0140 (7)	0.0178 (7)	0.0137 (8)	−0.0005 (6)	−0.0002 (6)	−0.0006 (6)
O7	0.0284 (8)	0.0374 (9)	0.0254 (9)	−0.0042 (7)	0.0081 (7)	0.0011 (7)
O5	0.0242 (8)	0.0382 (9)	0.0303 (9)	0.0025 (7)	0.0078 (7)	−0.0003 (7)
N1	0.0131 (7)	0.0169 (7)	0.0149 (8)	−0.0022 (6)	0.0013 (6)	−0.0014 (6)
N6	0.0151 (7)	0.0163 (7)	0.0127 (8)	−0.0003 (6)	0.0008 (6)	0.0001 (6)
O6	0.0548 (12)	0.0402 (10)	0.0284 (10)	−0.0048 (8)	−0.0185 (9)	−0.0116 (8)
O1	0.0499 (11)	0.0502 (11)	0.0260 (10)	0.0235 (9)	−0.0090 (8)	0.0041 (8)
C11	0.0128 (8)	0.0157 (8)	0.0163 (10)	−0.0030 (6)	0.0011 (7)	0.0013 (7)
C10	0.0113 (8)	0.0160 (8)	0.0144 (9)	−0.0016 (6)	0.0022 (7)	0.0007 (7)
C6	0.0141 (8)	0.0145 (8)	0.0146 (9)	−0.0007 (6)	0.0023 (7)	0.0012 (7)
C9	0.0172 (9)	0.0152 (8)	0.0152 (10)	−0.0008 (7)	0.0029 (7)	−0.0007 (7)
C31	0.0136 (8)	0.0169 (9)	0.0143 (10)	−0.0013 (7)	0.0005 (7)	0.0004 (7)
C7	0.0147 (8)	0.0161 (9)	0.0166 (10)	−0.0004 (7)	−0.0002 (7)	0.0025 (7)
C32	0.0147 (8)	0.0143 (8)	0.0159 (10)	−0.0011 (6)	0.0011 (7)	−0.0003 (7)
C33	0.0159 (9)	0.0197 (9)	0.0188 (10)	−0.0015 (7)	0.0004 (8)	−0.0039 (7)
C22	0.0163 (9)	0.0180 (9)	0.0156 (10)	0.0001 (7)	−0.0004 (7)	−0.0017 (7)
C15	0.0165 (9)	0.0212 (9)	0.0159 (10)	−0.0017 (7)	−0.0017 (7)	0.0033 (7)
C26	0.0161 (9)	0.0216 (9)	0.0148 (10)	−0.0039 (7)	0.0012 (7)	−0.0017 (7)
C4	0.0176 (9)	0.0197 (9)	0.0192 (10)	0.0001 (7)	0.0015 (8)	0.0023 (7)
C28	0.0168 (9)	0.0253 (10)	0.0143 (10)	−0.0026 (7)	0.0037 (8)	0.0006 (7)
C27	0.0147 (8)	0.0191 (9)	0.0162 (10)	−0.0027 (7)	0.0015 (7)	0.0009 (7)
C12	0.0181 (9)	0.0187 (9)	0.0168 (10)	−0.0014 (7)	0.0016 (8)	−0.0015 (7)
C1	0.0164 (9)	0.0208 (9)	0.0184 (10)	−0.0019 (7)	0.0020 (8)	−0.0037 (8)
C5	0.0139 (8)	0.0164 (8)	0.0168 (10)	−0.0024 (7)	0.0031 (7)	−0.0002 (7)
C37	0.0186 (9)	0.0169 (8)	0.0128 (9)	−0.0038 (7)	−0.0006 (7)	−0.0002 (7)
C16	0.0186 (9)	0.0151 (8)	0.0129 (9)	−0.0030 (7)	0.0005 (7)	0.0027 (7)
C35	0.0188 (9)	0.0204 (9)	0.0210 (11)	−0.0020 (7)	0.0083 (8)	−0.0023 (8)
C8	0.0148 (8)	0.0175 (9)	0.0147 (10)	−0.0030 (7)	0.0018 (7)	0.0010 (7)
C29	0.0180 (9)	0.0191 (9)	0.0142 (10)	−0.0009 (7)	−0.0001 (7)	−0.0005 (7)
C36	0.0190 (9)	0.0172 (9)	0.0155 (10)	−0.0002 (7)	0.0019 (7)	−0.0006 (7)
C30	0.0149 (9)	0.0196 (9)	0.0166 (10)	−0.0024 (7)	−0.0010 (7)	−0.0005 (7)
C34	0.0150 (9)	0.0210 (9)	0.0265 (11)	−0.0038 (7)	0.0044 (8)	−0.0046 (8)
C23	0.0136 (9)	0.0192 (9)	0.0229 (11)	−0.0021 (7)	−0.0005 (8)	−0.0013 (8)
C41	0.0174 (9)	0.0199 (9)	0.0168 (10)	−0.0010 (7)	−0.0024 (8)	0.0024 (7)
C38	0.0167 (9)	0.0199 (9)	0.0177 (10)	−0.0012 (7)	−0.0016 (8)	−0.0001 (7)
C17	0.0195 (9)	0.0184 (9)	0.0160 (10)	−0.0001 (7)	0.0027 (8)	−0.0004 (7)
C39	0.0201 (9)	0.0204 (9)	0.0171 (10)	−0.0003 (7)	0.0017 (8)	−0.0016 (7)
C40	0.0230 (10)	0.0205 (9)	0.0141 (10)	−0.0030 (7)	−0.0006 (8)	0.0010 (7)
C13	0.0184 (9)	0.0171 (9)	0.0283 (12)	0.0018 (7)	0.0033 (8)	0.0004 (8)
C42	0.0174 (9)	0.0195 (9)	0.0189 (10)	−0.0006 (7)	0.0033 (8)	−0.0009 (7)
C14	0.0173 (9)	0.0195 (9)	0.0233 (11)	0.0012 (7)	−0.0006 (8)	0.0058 (8)
C18	0.0202 (9)	0.0223 (10)	0.0184 (10)	−0.0002 (7)	−0.0020 (8)	0.0014 (8)
C25	0.0185 (9)	0.0324 (11)	0.0154 (10)	−0.0045 (8)	0.0039 (8)	−0.0011 (8)
C2	0.0210 (10)	0.0193 (9)	0.0250 (11)	−0.0001 (7)	0.0042 (8)	−0.0060 (8)
C21	0.0201 (10)	0.0240 (10)	0.0165 (10)	0.0006 (8)	0.0024 (8)	0.0022 (8)
C24	0.0169 (9)	0.0259 (10)	0.0230 (11)	−0.0052 (8)	0.0057 (8)	−0.0001 (8)
C19	0.0273 (11)	0.0276 (10)	0.0125 (10)	−0.0028 (8)	−0.0012 (8)	0.0019 (8)
C20	0.0273 (11)	0.0318 (11)	0.0158 (10)	0.0019 (9)	0.0063 (9)	−0.0012 (8)
C3	0.0200 (10)	0.0170 (9)	0.0278 (12)	0.0024 (7)	0.0037 (8)	−0.0016 (8)
O3	0.057 (5)	0.106 (8)	0.022 (3)	0.038 (4)	0.017 (2)	0.031 (3)
O4	0.077 (5)	0.050 (3)	0.060 (3)	0.026 (3)	0.029 (3)	−0.004 (2)
O2	0.053 (3)	0.144 (7)	0.067 (5)	−0.057 (4)	0.019 (4)	−0.004 (4)
O3A	0.018 (3)	0.095 (8)	0.075 (8)	0.002 (4)	0.016 (4)	0.060 (6)
O4A	0.040 (4)	0.091 (7)	0.030 (3)	0.034 (4)	0.011 (3)	0.003 (3)
O2A	0.107 (8)	0.049 (4)	0.081 (8)	−0.029 (4)	−0.069 (6)	0.012 (4)

Geometric parameters (Å, º)

Ni1—N2	2.0014 (16)	C4—C3	1.390 (3)
Ni1—N5	1.9956 (16)	C28—H28	0.9500
Ni1—N3	2.1174 (16)	C28—C27	1.385 (3)
Ni1—N4	2.1313 (16)	C28—C29	1.394 (3)
Ni1—N1	2.1263 (16)	C12—H12	0.9500
Ni1—N6	2.1148 (16)	C12—C13	1.389 (3)
Cl2—O8	1.4552 (16)	C1—H1	0.9500
Cl2—O7	1.4325 (17)	C1—C2	1.387 (3)
Cl2—O5	1.4468 (16)	C37—C29	1.485 (3)
Cl2—O6	1.4306 (17)	C37—C38	1.396 (3)
Cl1—O1	1.4239 (17)	C37—C42	1.398 (3)
Cl1—O3	1.407 (8)	C16—C8	1.478 (3)
Cl1—O4	1.447 (5)	C16—C17	1.404 (3)
Cl1—O2	1.387 (8)	C16—C21	1.392 (3)
Cl1—O3A	1.394 (9)	C35—H35	0.9500
Cl1—O4A	1.417 (6)	C35—C36	1.388 (3)
Cl1—O2A	1.443 (7)	C35—C34	1.377 (3)
N2—C10	1.347 (2)	C29—C30	1.396 (3)
N2—C6	1.342 (2)	C36—H36	0.9500
N5—C31	1.342 (2)	C30—H30	0.9500
N5—C27	1.342 (2)	C34—H34	0.9500
N3—C11	1.351 (2)	C23—H23	0.9500
N3—C15	1.340 (2)	C23—C24	1.377 (3)
N4—C22	1.342 (2)	C41—H41	0.9500
N4—C26	1.355 (3)	C41—C40	1.389 (3)
N1—C1	1.337 (2)	C41—C42	1.384 (3)
N1—C5	1.359 (3)	C38—H38	0.9500
N6—C32	1.355 (2)	C38—C39	1.391 (3)
N6—C36	1.335 (2)	C17—H17	0.9500
C11—C10	1.485 (3)	C17—C18	1.390 (3)
C11—C12	1.388 (3)	C39—H39	0.9500
C10—C9	1.387 (3)	C39—C40	1.390 (3)
C6—C7	1.382 (3)	C40—H40	0.9500
C6—C5	1.491 (3)	C13—H13	0.9500
C9—H9	0.9500	C13—C14	1.385 (3)
C9—C8	1.401 (3)	C42—H42	0.9500
C31—C32	1.485 (3)	C14—H14	0.9500
C31—C30	1.385 (3)	C18—H18	0.9500
C7—H7	0.9500	C18—C19	1.385 (3)
C7—C8	1.404 (3)	C25—H25	0.9500
C32—C33	1.387 (3)	C25—C24	1.392 (3)
C33—H33	0.9500	C2—H2	0.9500
C33—C34	1.386 (3)	C2—C3	1.383 (3)
C22—H22	0.9500	C21—H21	0.9500
C22—C23	1.389 (3)	C21—C20	1.384 (3)
C15—H15	0.9500	C24—H24	0.9500
C15—C14	1.386 (3)	C19—H19	0.9500
C26—C27	1.484 (3)	C19—C20	1.388 (3)
C26—C25	1.381 (3)	C20—H20	0.9500
C4—H4	0.9500	C3—H3	0.9500
C4—C5	1.387 (3)
N2—Ni1—N3	77.49 (6)	C29—C28—H28	120.2
N2—Ni1—N4	101.35 (6)	N5—C27—C26	113.66 (17)
N2—Ni1—N1	77.82 (6)	N5—C27—C28	120.86 (17)
N2—Ni1—N6	103.39 (6)	C28—C27—C26	125.48 (17)
N5—Ni1—N2	175.27 (6)	C11—C12—H12	120.3
N5—Ni1—N3	107.20 (6)	C11—C12—C13	119.32 (19)
N5—Ni1—N4	77.68 (6)	C13—C12—H12	120.3
N5—Ni1—N1	97.51 (6)	N1—C1—H1	118.6
N5—Ni1—N6	77.80 (6)	N1—C1—C2	122.82 (19)
N3—Ni1—N4	96.80 (6)	C2—C1—H1	118.6
N3—Ni1—N1	155.25 (6)	N1—C5—C6	114.67 (16)
N1—Ni1—N4	89.75 (6)	N1—C5—C4	121.68 (18)
N6—Ni1—N3	86.91 (6)	C4—C5—C6	123.63 (18)
N6—Ni1—N4	155.20 (6)	C38—C37—C29	120.70 (17)
N6—Ni1—N1	97.09 (6)	C38—C37—C42	119.30 (18)
O7—Cl2—O8	109.18 (10)	C42—C37—C29	119.91 (17)
O7—Cl2—O5	109.10 (10)	C17—C16—C8	120.36 (17)
O5—Cl2—O8	109.41 (10)	C21—C16—C8	121.14 (17)
O6—Cl2—O8	109.16 (10)	C21—C16—C17	118.48 (18)
O6—Cl2—O7	110.83 (11)	C36—C35—H35	120.8
O6—Cl2—O5	109.14 (11)	C34—C35—H35	120.8
O1—Cl1—O4	107.5 (4)	C34—C35—C36	118.44 (19)
O1—Cl1—O2A	109.5 (4)	C9—C8—C7	117.73 (18)
O3—Cl1—O1	109.5 (5)	C9—C8—C16	121.64 (17)
O3—Cl1—O4	106.3 (6)	C7—C8—C16	120.59 (17)
O2—Cl1—O1	111.7 (4)	C28—C29—C37	119.75 (17)
O2—Cl1—O3	111.5 (6)	C28—C29—C30	118.76 (18)
O2—Cl1—O4	110.1 (5)	C30—C29—C37	121.44 (17)
O3A—Cl1—O1	111.4 (5)	N6—C36—C35	123.06 (19)
O3A—Cl1—O4A	112.3 (7)	N6—C36—H36	118.5
O3A—Cl1—O2A	105.0 (7)	C35—C36—H36	118.5
O4A—Cl1—O1	111.1 (3)	C31—C30—C29	118.68 (17)
O4A—Cl1—O2A	107.2 (6)	C31—C30—H30	120.7
C10—N2—Ni1	119.70 (13)	C29—C30—H30	120.7
C6—N2—Ni1	119.55 (12)	C33—C34—H34	120.2
C6—N2—C10	120.63 (16)	C35—C34—C33	119.51 (18)
C31—N5—Ni1	119.83 (13)	C35—C34—H34	120.2
C31—N5—C27	120.40 (17)	C22—C23—H23	120.4
C27—N5—Ni1	119.35 (13)	C24—C23—C22	119.15 (18)
C11—N3—Ni1	114.82 (12)	C24—C23—H23	120.4
C15—N3—Ni1	126.11 (13)	C40—C41—H41	119.9
C15—N3—C11	118.69 (16)	C42—C41—H41	119.9
C22—N4—Ni1	127.86 (13)	C42—C41—C40	120.24 (18)
C22—N4—C26	118.20 (16)	C37—C38—H38	120.0
C26—N4—Ni1	113.93 (12)	C39—C38—C37	119.92 (18)
C1—N1—Ni1	127.21 (14)	C39—C38—H38	120.0
C1—N1—C5	118.43 (16)	C16—C17—H17	119.8
C5—N1—Ni1	113.78 (12)	C18—C17—C16	120.40 (19)
C32—N6—Ni1	114.04 (12)	C18—C17—H17	119.8
C36—N6—Ni1	127.06 (13)	C38—C39—H39	119.8
C36—N6—C32	118.18 (16)	C40—C39—C38	120.42 (18)
N3—C11—C10	114.42 (16)	C40—C39—H39	119.8
N3—C11—C12	121.72 (17)	C41—C40—C39	119.69 (19)
C12—C11—C10	123.85 (18)	C41—C40—H40	120.2
N2—C10—C11	113.33 (16)	C39—C40—H40	120.2
N2—C10—C9	120.86 (17)	C12—C13—H13	120.6
C9—C10—C11	125.77 (16)	C14—C13—C12	118.75 (18)
N2—C6—C7	121.19 (17)	C14—C13—H13	120.6
N2—C6—C5	113.53 (16)	C37—C42—H42	119.8
C7—C6—C5	125.28 (17)	C41—C42—C37	120.41 (18)
C10—C9—H9	120.1	C41—C42—H42	119.8
C10—C9—C8	119.76 (17)	C15—C14—H14	120.5
C8—C9—H9	120.1	C13—C14—C15	118.98 (18)
N5—C31—C32	112.85 (16)	C13—C14—H14	120.5
N5—C31—C30	121.69 (17)	C17—C18—H18	119.8
C30—C31—C32	125.46 (17)	C19—C18—C17	120.38 (19)
C6—C7—H7	120.1	C19—C18—H18	119.8
C6—C7—C8	119.77 (17)	C26—C25—H25	120.3
C8—C7—H7	120.1	C26—C25—C24	119.34 (19)
N6—C32—C31	114.91 (16)	C24—C25—H25	120.3
N6—C32—C33	122.05 (18)	C1—C2—H2	120.5
C33—C32—C31	123.00 (18)	C3—C2—C1	118.93 (19)
C32—C33—H33	120.6	C3—C2—H2	120.5
C34—C33—C32	118.75 (19)	C16—C21—H21	119.6
C34—C33—H33	120.6	C20—C21—C16	120.78 (19)
N4—C22—H22	118.7	C20—C21—H21	119.6
N4—C22—C23	122.51 (19)	C23—C24—C25	118.72 (18)
C23—C22—H22	118.7	C23—C24—H24	120.6
N3—C15—H15	118.7	C25—C24—H24	120.6
N3—C15—C14	122.54 (19)	C18—C19—H19	120.3
C14—C15—H15	118.7	C18—C19—C20	119.4 (2)
N4—C26—C27	114.62 (16)	C20—C19—H19	120.3
N4—C26—C25	122.07 (18)	C21—C20—C19	120.5 (2)
C25—C26—C27	123.28 (18)	C21—C20—H20	119.7
C5—C4—H4	120.3	C19—C20—H20	119.7
C5—C4—C3	119.32 (19)	C4—C3—H3	120.6
C3—C4—H4	120.3	C2—C3—C4	118.81 (18)
C27—C28—H28	120.2	C2—C3—H3	120.6
C27—C28—C29	119.52 (18)
Ni1—N2—C10—C11	2.4 (2)	C22—N4—C26—C25	−1.0 (3)
Ni1—N2—C10—C9	−175.73 (13)	C22—C23—C24—C25	−0.8 (3)
Ni1—N2—C6—C7	175.37 (13)	C15—N3—C11—C10	178.71 (16)
Ni1—N2—C6—C5	−3.7 (2)	C15—N3—C11—C12	−0.2 (3)
Ni1—N5—C31—C32	7.4 (2)	C26—N4—C22—C23	0.9 (3)
Ni1—N5—C31—C30	−173.34 (14)	C26—C25—C24—C23	0.6 (3)
Ni1—N5—C27—C26	−10.1 (2)	C28—C29—C30—C31	−0.1 (3)
Ni1—N5—C27—C28	170.51 (14)	C27—N5—C31—C32	179.84 (16)
Ni1—N3—C11—C10	5.28 (19)	C27—N5—C31—C30	−0.9 (3)
Ni1—N3—C11—C12	−173.62 (14)	C27—C26—C25—C24	178.11 (19)
Ni1—N3—C15—C14	172.82 (14)	C27—C28—C29—C37	174.92 (17)
Ni1—N4—C22—C23	−177.83 (14)	C27—C28—C29—C30	−2.6 (3)
Ni1—N4—C26—C27	−0.2 (2)	C12—C11—C10—N2	173.82 (17)
Ni1—N4—C26—C25	177.81 (16)	C12—C11—C10—C9	−8.1 (3)
Ni1—N1—C1—C2	170.22 (14)	C12—C13—C14—C15	0.5 (3)
Ni1—N1—C5—C6	7.63 (19)	C1—N1—C5—C6	179.54 (16)
Ni1—N1—C5—C4	−171.35 (14)	C1—N1—C5—C4	0.6 (3)
Ni1—N6—C32—C31	5.90 (19)	C1—C2—C3—C4	0.5 (3)
Ni1—N6—C32—C33	−171.75 (14)	C5—N1—C1—C2	−0.5 (3)
Ni1—N6—C36—C35	171.14 (14)	C5—C6—C7—C8	178.28 (17)
N2—C10—C9—C8	1.3 (3)	C5—C4—C3—C2	−0.4 (3)
N2—C6—C7—C8	−0.6 (3)	C37—C29—C30—C31	−177.60 (17)
N2—C6—C5—N1	−3.0 (2)	C37—C38—C39—C40	0.4 (3)
N2—C6—C5—C4	175.97 (17)	C16—C17—C18—C19	−0.5 (3)
N5—C31—C32—N6	−8.5 (2)	C16—C21—C20—C19	0.2 (3)
N5—C31—C32—C33	169.08 (17)	C8—C16—C17—C18	179.80 (17)
N5—C31—C30—C29	1.9 (3)	C8—C16—C21—C20	−179.63 (18)
N3—C11—C10—N2	−5.1 (2)	C29—C28—C27—N5	3.7 (3)
N3—C11—C10—C9	172.98 (17)	C29—C28—C27—C26	−175.53 (18)
N3—C11—C12—C13	0.4 (3)	C29—C37—C38—C39	−176.21 (17)
N3—C15—C14—C13	−0.4 (3)	C29—C37—C42—C41	175.59 (17)
N4—C22—C23—C24	0.1 (3)	C36—N6—C32—C31	176.85 (16)
N4—C26—C27—N5	6.3 (2)	C36—N6—C32—C33	−0.8 (3)
N4—C26—C27—C28	−174.36 (18)	C36—C35—C34—C33	−0.1 (3)
N4—C26—C25—C24	0.3 (3)	C30—C31—C32—N6	172.21 (18)
N1—C1—C2—C3	0.0 (3)	C30—C31—C32—C33	−10.2 (3)
N6—C32—C33—C34	−0.3 (3)	C34—C35—C36—N6	−1.1 (3)
C11—N3—C15—C14	0.2 (3)	C38—C37—C29—C28	43.2 (3)
C11—C10—C9—C8	−176.58 (17)	C38—C37—C29—C30	−139.3 (2)
C11—C12—C13—C14	−0.5 (3)	C38—C37—C42—C41	−1.1 (3)
C10—N2—C6—C7	−0.7 (3)	C38—C39—C40—C41	−0.6 (3)
C10—N2—C6—C5	−179.68 (15)	C17—C16—C8—C9	−145.75 (19)
C10—C11—C12—C13	−178.43 (17)	C17—C16—C8—C7	31.7 (3)
C10—C9—C8—C7	−2.5 (3)	C17—C16—C21—C20	−1.4 (3)
C10—C9—C8—C16	175.05 (17)	C17—C18—C19—C20	−0.7 (3)
C6—N2—C10—C11	178.45 (16)	C40—C41—C42—C37	0.9 (3)
C6—N2—C10—C9	0.3 (3)	C42—C37—C29—C28	−133.4 (2)
C6—C7—C8—C9	2.2 (3)	C42—C37—C29—C30	44.0 (3)
C6—C7—C8—C16	−175.42 (17)	C42—C37—C38—C39	0.5 (3)
C31—N5—C27—C26	177.36 (16)	C42—C41—C40—C39	−0.1 (3)
C31—N5—C27—C28	−2.0 (3)	C18—C19—C20—C21	0.8 (3)
C31—C32—C33—C34	−177.79 (17)	C25—C26—C27—N5	−171.62 (19)
C7—C6—C5—N1	178.03 (17)	C25—C26—C27—C28	7.7 (3)
C7—C6—C5—C4	−3.0 (3)	C21—C16—C8—C9	32.4 (3)
C32—N6—C36—C35	1.5 (3)	C21—C16—C8—C7	−150.07 (19)
C32—C31—C30—C29	−178.91 (18)	C21—C16—C17—C18	1.6 (3)
C32—C33—C34—C35	0.8 (3)	C3—C4—C5—N1	−0.1 (3)
C22—N4—C26—C27	−179.02 (16)	C3—C4—C5—C6	−179.01 (18)