The cocrystal {4,4′-dimeth­oxy-2,2′-[pro­pane-1,2-diylbis(nitrilo­methyl­idyne)]diphenolato}methanol(pyridine)manganese(III) hexa­fluorido­phosphate–{4,4′-dimeth­oxy-2,2′-[ethane-1,2-diyl­bis(nitrilo­methyl­idyne)]diphenolato}methanol(pyridine)manganese(III) hexa­fluorido­phosphate (1/1)

The title cocrystal, [Mn(C₁₉H₂₀N₂O₂)(C₅H₅N)(CH₃OH)]PF₆·[Mn(C₁₈H₁₈N₂O₂)(C₅H₅N)(CH₃OH)]PF₆, is a 1:1 co-crystal of two Mn^III complexes with Schiff base ligands. In each structure, the Mn^III centre is in a six-coordinate distorted octa­hedral N₃O₃ environment, with the N₂O₂ donor atoms of the tetra­dentate Schiff base ligand as the equatorial plane and the pyridine and methanol mol­ecules in the two axial positions. The difference in the two components of the co-crystal, which are disordered over the same site, is the addition of a methyl group to one of the two methyl­ene C atoms linking the imine N atoms of the Schiff base ligand in one component. In the crystal structure, inter­molecular O—H...O hydrogen bonds and weak inter­molecular C—H...O inter­actions link the mol­ecules into a network. A weak C—H...N intra­molecular inter­action is also observed in the structure of [Mn(C₁₉H₂₀N₂O₂)(C₅H₅N)(CH₃OH)]PF₆.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.003 Å
• Disorder in main residue
• R factor = 0.049
• wR factor = 0.138
• Data-to-parameter ratio = 21.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.25
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.45 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       4.00 Ratio
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         P1
PLAT301_ALERT_3_C Main Residue  Disorder .........................       1.00 Perc.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          1

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C49 H56 F12 Mn2 N6 O10 P2
            Atom count from _chemical_formula_moiety:

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

Transition metal compounds containing Schiff base ligands have been of interest for many years (Kani et al., 2000; Habibi et al., 2007; Paschke et al., 2002), since they play an important role in the development of coordination chemistry, particularly in relation to catalysis and enzymatic reactions, as well as molecular magnetism (Cozzi et al., 2004; Darensbourg et al., 2006; Dimauro & Kozlowski, 2002). A considerable number of complexes with multidentate Schiff bases containing O,N donor atoms have been studied (Clarke et al., 1998; Marchetti et al., 1999). In this paper, we report the crystal structure of two co-crystallized Mn^III-Schiff base complexes.

The asymmetric unit of the cocrystal (Fig. 1) consists of a mixture of 0.5[Mn(C₁₉H₂₀N₂O₂)(C₅H₅N)(CH₃OH)], 0.5[Mn(C₁₈H₁₈N₂O₂)(C₅H₅N)(CH₃OH)] and PF₆. The difference between the two components of the co-crystal concerned the substituents on the C21 atom; in one case two H atoms were attached whereas in the other component one H atom is replaced by the methyl group (C22). The environment around Mn^III shows a distorted octahedral geometry with the N₂O₂ of tetradentate Schiff base ligand as the basal plane. The two phenolic O atoms and two imine N atoms are in cis positions. The pyridine and methanol molecules are in the two axial positions. The Mn1—O1 and Mn1—O2 distances of 1.8909 (13) Å and 1.8655 (14) Å, and Mn—N1 and Mn1—N2 distances of 1.9764 (17) Å and 1.9887 (16) Å, respectively lie in the same range as observed for closely related Mn^III complexes of Schiff base ligands (Mitra et al., 2006; Naskar et al., 2004). However there are elongations of the axial bonds Mn1—O5 = 2.2986 (16) Å and Mn1—N3 = 2.3532 (18) Å. The dihedral angle between the two benzene rings of the Schiff base ligand is 18.83 (9)°. One methoxy group is coplanar with the attached benzene ring while another one is slightly twisted out of the ring plane as indicated by the torsion angles C23—O3—C4—C5 = 0.6 (3)° and C24—O4—C11—C10 = -16.7 (4)°. Other bond lengths and angles in the ligands are in normal ranges (Allen et al., 1987).

In the crystal packing (Fig. 2), the methanol molecule is involved in an intermolecular O—H···O hydrogen bond and weak C–H···O intermolecular interactions linking the molecules into a network (Table 1, Fig. 2). Morover in the structure of [Mn(C₁₉H₂₀N₂O₂)(C₅H₅N)(CH₃OH)] ion, a weak C–H···N interaction between the pyridine and the C22 methyl group was also present [C22—H22C···N3].

Related literature

For values of bond lengths and angles, see Allen et al. (1987). For related structures, see, for example: Mitra et al. (2006); Naskar et al. (2004). For details of Schiff base complexes and their applications, see, for example: Clarke et al. (1998); Cozzi et al. (2004); Darensbourg et al. (2006); Dimauro & Kozlowski (2002); Habibi et al. (2007); Marchetti et al. (1999); Kani et al. (2000); Paschke et al. (2002).

S2. Experimental

To a stirred solution of Mn(CH₃COO)₂·2H₂O (0.0662 g, 0.5 mmol) in methanol (25 ml) was added an equimolar quantity of (2-hydroxy 5-methoxy benzaldehyde and 1,2 diamino propane (0.171 g, 0.5 mmol). The pink solution turned dark brown immediately upon formation of the Mn^II complexes. To this solution was added 4 mmol of pyridine, and air was bubbled through the reaction mixture for about 3 h. 0.5 mmol of NH₄PF₆ was then added to the resulting dark brown solution and stirred for 5 minutes. A dark brown microcrystalline solid was formed by slow evaporation of methanol at room temperature. Brown single crystals of the Mn^III complexes suitable for x-ray structure determination were obtained after recrystallization by slow evaporation from methanol/propanol (2:1 v/v) solution at room temperature after several days.

S3. Refinement

The H atom attached to the O atom of the methanol ligand was located in a difference map and isotropically refined. The remaining H atoms were positioned geometrically and allowed to ride on their parent atoms, with the C—H distances in the range 0.93–0.98 Å. The U_iso values were constrained to be 1.5U_eq of the carrier atom for methyl H atoms and 1.2U_eq for the remaining H atoms. A rotating group model was used for the methyl groups.

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL (Sheldrick, 1998); molecular graphics: SHELXTL (Sheldrick, 1998); software used to prepare material for publication: SHELXTL (Sheldrick, 1998) and PLATON (Spek, 2003).

Figures

	Fig. 1. The molecular structure of the title cocrystal, showing 50% probability displacement ellipsoids and the atomic numbering. Bonds to the C22 methyl group of the second component of the co-crystal are drawn as open lines. All other bonds are shown as filled lines.
	Fig. 2. The crystal packing of the title compound, viewed approximately along the b axis. C—H···O and O—H···O interactions were drawn as dashed lines.

{4,4'-dimethoxy-2,2'-[propane-1,2- diylbis(nitrilomethylidyne)]diphenolato}methanol(pyridine)manganese(III) hexafluorophosphate–{4,4'-dimethoxy-2,2'-[ethane-1,2- diylbis(nitrilomethylidyne)]diphenolato}methanol(pyridine)manganese(III) hexafluorophosphate (1/1)

Crystal data

[Mn(C19H20N2O2)(C5H5N)(CH4O)]PF6·[Mn(C18H18N2O2)(C5H5N)(CH4O)]PF6	F(000) = 2640
Mr = 1288.82	Dx = 1.563 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 7977 reflections
a = 23.4332 (6) Å	θ = 1.7–30.0°
b = 16.3878 (4) Å	µ = 0.62 mm^−1
c = 14.2963 (4) Å	T = 100 K
β = 93.988 (1)°	Block, brown
V = 5476.8 (2) Å^3	0.57 × 0.26 × 0.23 mm
Z = 4

Data collection

Bruker SMART APEX2 CCD area-detector diffractometer	7977 independent reflections
Radiation source: fine-focus sealed tube	6665 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
Detector resolution: 8.33 pixels mm^-1	θmax = 30.0°, θmin = 1.7°
ω scans	h = −32→32
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −23→23
Tmin = 0.716, Tmax = 0.871	l = −19→20
43484 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.138	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0685P)^2 + 11.1129P] where P = (Fo^2 + 2Fc^2)/3
7977 reflections	(Δ/σ)max = 0.001
379 parameters	Δρmax = 1.40 e Å^−3
0 restraints	Δρmin = −0.62 e Å^−3

Special details

Experimental. The low-temparture data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Mn1	0.086000 (11)	0.179324 (17)	0.64225 (2)	0.01968 (9)
P1	0.22652 (3)	0.50955 (5)	0.58969 (6)	0.04204 (17)
F1	0.23555 (11)	0.46971 (17)	0.69076 (15)	0.0831 (7)
F2	0.28040 (8)	0.46209 (14)	0.55735 (16)	0.0696 (6)
F3	0.17260 (8)	0.55855 (15)	0.62030 (19)	0.0787 (7)
F4	0.21769 (8)	0.54870 (12)	0.48656 (14)	0.0568 (5)
F5	0.26607 (8)	0.58567 (14)	0.62166 (17)	0.0716 (6)
F6	0.18576 (9)	0.43551 (12)	0.55787 (15)	0.0648 (5)
O1	0.01672 (6)	0.23882 (8)	0.63767 (10)	0.0216 (3)
O2	0.04976 (6)	0.08047 (8)	0.61213 (11)	0.0225 (3)
O3	−0.01802 (6)	0.57202 (8)	0.61205 (11)	0.0262 (3)
O4	0.12736 (7)	−0.23205 (9)	0.55721 (13)	0.0325 (4)
O5	0.07737 (6)	0.15465 (9)	0.79891 (11)	0.0243 (3)
N1	0.13089 (7)	0.27512 (10)	0.68817 (14)	0.0257 (4)
N2	0.16274 (7)	0.12696 (10)	0.64994 (13)	0.0240 (3)
N3	0.10136 (7)	0.21039 (11)	0.48527 (13)	0.0258 (3)
C1	0.01127 (8)	0.32005 (11)	0.63213 (13)	0.0193 (3)
C2	−0.04206 (8)	0.35280 (12)	0.60048 (13)	0.0205 (3)
H2A	−0.0723	0.3178	0.5833	0.025*
C3	−0.05027 (8)	0.43644 (12)	0.59452 (14)	0.0218 (4)
H3A	−0.0859	0.4569	0.5735	0.026*
C4	−0.00546 (9)	0.49047 (11)	0.61986 (13)	0.0214 (4)
C5	0.04696 (8)	0.45992 (11)	0.65106 (13)	0.0206 (3)
H5A	0.0768	0.4955	0.6683	0.025*
C6	0.05608 (8)	0.37491 (11)	0.65722 (13)	0.0200 (3)
C7	0.11259 (8)	0.34918 (12)	0.69061 (15)	0.0237 (4)
H7A	0.1377	0.3888	0.7157	0.028*
C8	0.17357 (8)	0.05123 (12)	0.63493 (15)	0.0243 (4)
H8A	0.2117	0.0352	0.6386	0.029*
C9	0.13105 (8)	−0.01061 (11)	0.61284 (14)	0.0214 (4)
C10	0.15082 (8)	−0.09082 (12)	0.59678 (15)	0.0241 (4)
H10A	0.1899	−0.1016	0.6008	0.029*
C11	0.11268 (9)	−0.15269 (12)	0.57541 (15)	0.0241 (4)
C12	0.05378 (9)	−0.13682 (12)	0.57161 (15)	0.0243 (4)
H12A	0.0279	−0.1791	0.5589	0.029*
C13	0.03392 (8)	−0.05904 (12)	0.58664 (14)	0.0226 (4)
H13A	−0.0053	−0.0497	0.5845	0.027*
C14	0.07180 (8)	0.00630 (11)	0.60511 (14)	0.0205 (3)
C15	0.10906 (9)	0.14901 (14)	0.42499 (17)	0.0297 (4)
H15A	0.1081	0.0957	0.4472	0.036*
C16	0.11828 (13)	0.16116 (16)	0.33226 (19)	0.0413 (6)
H16A	0.1224	0.1169	0.2925	0.050*
C17	0.12144 (14)	0.24039 (17)	0.29851 (19)	0.0448 (6)
H17A	0.1274	0.2501	0.2358	0.054*
C18	0.11554 (13)	0.30451 (15)	0.36011 (18)	0.0403 (6)
H18A	0.1188	0.3583	0.3403	0.048*
C19	0.10472 (11)	0.28675 (14)	0.45162 (16)	0.0329 (5)
H19A	0.0995	0.3300	0.4923	0.039*
C20	0.18887 (10)	0.25330 (15)	0.7290 (2)	0.0430 (6)
H20A	0.1871	0.2342	0.7930	0.052*
H20B	0.2141	0.3003	0.7292	0.052*
C21	0.21073 (9)	0.18537 (13)	0.6669 (2)	0.0375 (6)
H21A	0.2419	0.1570	0.7028	0.045*
H21B	0.2231	0.2068	0.6092	0.045*	0.50
C22	0.2334 (2)	0.2189 (3)	0.5850 (4)	0.0370 (10)	0.50
H22A	0.2450	0.1754	0.5456	0.055*	0.50
H22B	0.2658	0.2525	0.6031	0.055*	0.50
H22C	0.2046	0.2512	0.5514	0.055*	0.50
C23	0.02777 (10)	0.62700 (12)	0.63792 (16)	0.0291 (4)
H23A	0.0143	0.6822	0.6315	0.044*
H23B	0.0584	0.6185	0.5978	0.044*
H23C	0.0413	0.6172	0.7018	0.044*
C24	0.18388 (13)	−0.24614 (17)	0.5361 (3)	0.0666 (11)
H24A	0.1873	−0.3007	0.5127	0.100*
H24B	0.2088	−0.2395	0.5918	0.100*
H24C	0.1943	−0.2079	0.4894	0.100*
C25	0.08497 (9)	0.07339 (13)	0.83507 (16)	0.0272 (4)
H25A	0.0795	0.0733	0.9010	0.041*
H25B	0.1229	0.0549	0.8252	0.041*
H25C	0.0576	0.0376	0.8032	0.041*
H1O5	0.0485 (13)	0.1735 (18)	0.820 (2)	0.036 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.01588 (14)	0.01570 (14)	0.02743 (16)	−0.00017 (9)	0.00126 (10)	−0.00030 (11)
P1	0.0271 (3)	0.0463 (4)	0.0540 (4)	−0.0051 (3)	0.0123 (3)	0.0030 (3)
F1	0.0822 (15)	0.115 (2)	0.0517 (12)	−0.0267 (15)	0.0045 (11)	0.0177 (13)
F2	0.0533 (11)	0.0738 (13)	0.0848 (15)	0.0268 (10)	0.0260 (10)	0.0223 (11)
F3	0.0429 (10)	0.0824 (15)	0.1151 (19)	−0.0016 (10)	0.0375 (11)	−0.0248 (14)
F4	0.0494 (10)	0.0566 (11)	0.0648 (12)	0.0035 (8)	0.0067 (8)	0.0195 (9)
F5	0.0468 (10)	0.0760 (14)	0.0926 (16)	−0.0250 (10)	0.0103 (10)	−0.0108 (12)
F6	0.0711 (13)	0.0595 (12)	0.0652 (12)	−0.0296 (10)	0.0135 (10)	−0.0030 (10)
O1	0.0177 (6)	0.0156 (6)	0.0316 (7)	0.0000 (5)	0.0021 (5)	0.0012 (5)
O2	0.0169 (6)	0.0165 (6)	0.0340 (8)	0.0001 (5)	0.0010 (5)	−0.0021 (5)
O3	0.0312 (7)	0.0160 (6)	0.0310 (8)	0.0016 (5)	0.0004 (6)	−0.0002 (6)
O4	0.0333 (8)	0.0180 (7)	0.0475 (10)	0.0032 (6)	0.0121 (7)	−0.0022 (6)
O5	0.0214 (6)	0.0211 (6)	0.0309 (8)	0.0022 (5)	0.0053 (5)	0.0007 (6)
N1	0.0184 (7)	0.0206 (8)	0.0374 (10)	0.0000 (6)	−0.0025 (6)	−0.0008 (7)
N2	0.0166 (7)	0.0208 (8)	0.0347 (9)	−0.0009 (6)	0.0019 (6)	0.0006 (7)
N3	0.0249 (8)	0.0247 (8)	0.0276 (9)	0.0025 (6)	0.0012 (6)	−0.0014 (7)
C1	0.0205 (8)	0.0176 (8)	0.0202 (8)	0.0004 (6)	0.0039 (6)	0.0004 (7)
C2	0.0201 (8)	0.0203 (8)	0.0213 (9)	−0.0004 (6)	0.0020 (6)	−0.0004 (7)
C3	0.0236 (8)	0.0200 (8)	0.0219 (9)	0.0032 (7)	0.0023 (7)	0.0009 (7)
C4	0.0298 (9)	0.0166 (8)	0.0182 (8)	0.0012 (7)	0.0049 (7)	0.0002 (7)
C5	0.0246 (8)	0.0179 (8)	0.0198 (8)	−0.0021 (7)	0.0045 (7)	−0.0011 (7)
C6	0.0216 (8)	0.0177 (8)	0.0209 (9)	0.0000 (6)	0.0028 (6)	0.0003 (7)
C7	0.0220 (8)	0.0194 (8)	0.0296 (10)	−0.0027 (7)	0.0012 (7)	−0.0020 (8)
C8	0.0182 (8)	0.0216 (9)	0.0335 (10)	0.0015 (7)	0.0040 (7)	0.0021 (8)
C9	0.0193 (8)	0.0189 (8)	0.0265 (9)	0.0012 (6)	0.0048 (7)	0.0013 (7)
C10	0.0227 (9)	0.0204 (9)	0.0298 (10)	0.0042 (7)	0.0065 (7)	0.0031 (8)
C11	0.0275 (9)	0.0178 (8)	0.0276 (10)	0.0030 (7)	0.0066 (7)	0.0027 (7)
C12	0.0262 (9)	0.0183 (8)	0.0286 (10)	−0.0013 (7)	0.0035 (7)	0.0015 (7)
C13	0.0213 (8)	0.0189 (8)	0.0276 (10)	−0.0003 (7)	0.0029 (7)	0.0000 (7)
C14	0.0211 (8)	0.0184 (8)	0.0223 (9)	0.0010 (6)	0.0034 (7)	0.0015 (7)
C15	0.0292 (10)	0.0261 (10)	0.0339 (11)	−0.0007 (8)	0.0034 (8)	−0.0040 (9)
C16	0.0591 (16)	0.0320 (12)	0.0333 (13)	0.0033 (11)	0.0065 (11)	−0.0090 (10)
C17	0.0682 (18)	0.0389 (13)	0.0279 (12)	0.0129 (13)	0.0071 (12)	−0.0003 (10)
C18	0.0598 (16)	0.0284 (11)	0.0328 (12)	0.0155 (11)	0.0038 (11)	0.0028 (10)
C19	0.0436 (12)	0.0265 (10)	0.0285 (11)	0.0109 (9)	0.0020 (9)	−0.0006 (9)
C20	0.0249 (10)	0.0292 (11)	0.0723 (19)	0.0044 (8)	−0.0146 (11)	−0.0136 (12)
C21	0.0186 (9)	0.0229 (10)	0.0709 (18)	−0.0023 (7)	0.0032 (10)	−0.0033 (11)
C22	0.027 (2)	0.030 (2)	0.054 (3)	−0.0042 (17)	0.0057 (19)	0.003 (2)
C23	0.0385 (11)	0.0178 (9)	0.0307 (11)	−0.0025 (8)	−0.0010 (8)	−0.0008 (8)
C24	0.0460 (16)	0.0268 (12)	0.132 (3)	0.0040 (11)	0.0426 (19)	−0.0128 (17)
C25	0.0290 (10)	0.0243 (9)	0.0287 (10)	0.0027 (8)	0.0049 (8)	0.0029 (8)

Geometric parameters (Å, º)

Mn1—O2	1.8655 (14)	C8—H8A	0.9300
Mn1—O1	1.8909 (13)	C9—C14	1.413 (3)
Mn1—N1	1.9764 (17)	C9—C10	1.418 (3)
Mn1—N2	1.9887 (16)	C10—C11	1.372 (3)
Mn1—O5	2.2986 (16)	C10—H10A	0.9300
Mn1—N3	2.3532 (18)	C11—C12	1.402 (3)
P1—F2	1.5792 (19)	C12—C13	1.379 (3)
P1—F3	1.584 (2)	C12—H12A	0.9300
P1—F1	1.586 (2)	C13—C14	1.404 (3)
P1—F6	1.5909 (19)	C13—H13A	0.9300
P1—F5	1.601 (2)	C15—C16	1.372 (4)
P1—F4	1.608 (2)	C15—H15A	0.9300
O1—C1	1.339 (2)	C16—C17	1.389 (4)
O2—C14	1.327 (2)	C16—H16A	0.9300
O3—C4	1.371 (2)	C17—C18	1.384 (4)
O3—C23	1.430 (3)	C17—H17A	0.9300
O4—C11	1.375 (2)	C18—C19	1.381 (3)
O4—C24	1.398 (3)	C18—H18A	0.9300
O5—C25	1.435 (2)	C19—H19A	0.9300
O5—H1O5	0.82 (3)	C20—C21	1.534 (4)
N1—C7	1.288 (3)	C20—H20A	0.9700
N1—C20	1.485 (3)	C20—H20B	0.9700
N2—C8	1.288 (3)	C21—C22	1.428 (6)
N2—C21	1.484 (3)	C21—H21A	0.9800
N3—C15	1.345 (3)	C21—H21B	0.9599
N3—C19	1.345 (3)	C22—H21B	0.4775
C1—C2	1.406 (3)	C22—H22A	0.9600
C1—C6	1.410 (3)	C22—H22B	0.9600
C2—C3	1.386 (3)	C22—H22C	0.9600
C2—H2A	0.9300	C23—H23A	0.9600
C3—C4	1.402 (3)	C23—H23B	0.9600
C3—H3A	0.9300	C23—H23C	0.9600
C4—C5	1.372 (3)	C24—H24A	0.9600
C5—C6	1.411 (3)	C24—H24B	0.9600
C5—H5A	0.9300	C24—H24C	0.9600
C6—C7	1.439 (3)	C25—H25A	0.9600
C7—H7A	0.9300	C25—H25B	0.9600
C8—C9	1.441 (3)	C25—H25C	0.9600
O2—Mn1—O1	93.66 (6)	C14—C9—C8	122.69 (17)
O2—Mn1—N1	171.76 (7)	C10—C9—C8	117.32 (17)
O1—Mn1—N1	92.16 (6)	C11—C10—C9	120.41 (18)
O2—Mn1—N2	91.92 (6)	C11—C10—H10A	119.8
O1—Mn1—N2	174.42 (6)	C9—C10—H10A	119.8
N1—Mn1—N2	82.30 (7)	C10—C11—O4	125.01 (18)
O2—Mn1—O5	90.15 (6)	C10—C11—C12	119.73 (18)
O1—Mn1—O5	89.48 (6)	O4—C11—C12	115.26 (18)
N1—Mn1—O5	84.08 (7)	C13—C12—C11	120.50 (18)
N2—Mn1—O5	90.61 (6)	C13—C12—H12A	119.7
O2—Mn1—N3	93.73 (6)	C11—C12—H12A	119.7
O1—Mn1—N3	92.48 (6)	C12—C13—C14	121.23 (18)
N1—Mn1—N3	91.83 (7)	C12—C13—H13A	119.4
N2—Mn1—N3	87.04 (7)	C14—C13—H13A	119.4
O5—Mn1—N3	175.53 (6)	O2—C14—C13	117.93 (16)
F2—P1—F3	178.74 (14)	O2—C14—C9	124.01 (17)
F2—P1—F1	90.30 (14)	C13—C14—C9	118.04 (17)
F3—P1—F1	90.88 (15)	N3—C15—C16	123.2 (2)
F2—P1—F6	90.97 (13)	N3—C15—H15A	118.4
F3—P1—F6	89.49 (12)	C16—C15—H15A	118.4
F1—P1—F6	89.19 (12)	C15—C16—C17	119.1 (2)
F2—P1—F5	90.50 (12)	C15—C16—H16A	120.4
F3—P1—F5	89.03 (12)	C17—C16—H16A	120.4
F1—P1—F5	91.31 (14)	C18—C17—C16	118.6 (2)
F6—P1—F5	178.45 (13)	C18—C17—H17A	120.7
F2—P1—F4	89.00 (11)	C16—C17—H17A	120.7
F3—P1—F4	89.82 (13)	C19—C18—C17	118.4 (2)
F1—P1—F4	179.15 (15)	C19—C18—H18A	120.8
F6—P1—F4	90.33 (11)	C17—C18—H18A	120.8
F5—P1—F4	89.19 (12)	N3—C19—C18	123.7 (2)
C1—O1—Mn1	126.35 (12)	N3—C19—H19A	118.2
C14—O2—Mn1	129.75 (12)	C18—C19—H19A	118.2
C4—O3—C23	116.11 (16)	N1—C20—C21	106.3 (2)
C11—O4—C24	116.77 (18)	N1—C20—H20A	110.5
C25—O5—Mn1	119.81 (12)	C21—C20—H20A	110.5
C25—O5—H1O5	108 (2)	N1—C20—H20B	110.5
Mn1—O5—H1O5	115 (2)	C21—C20—H20B	110.5
C7—N1—C20	120.88 (18)	H20A—C20—H20B	108.7
C7—N1—Mn1	125.93 (14)	C22—C21—N2	115.8 (3)
C20—N1—Mn1	113.00 (14)	C22—C21—C20	110.7 (3)
C8—N2—C21	119.55 (17)	N2—C21—C20	106.44 (18)
C8—N2—Mn1	126.47 (14)	C22—C21—H21A	107.7
C21—N2—Mn1	113.76 (13)	N2—C21—H21A	108.0
C15—N3—C19	116.9 (2)	C20—C21—H21A	107.9
C15—N3—Mn1	119.05 (15)	N2—C21—H21B	111.5
C19—N3—Mn1	123.99 (15)	C20—C21—H21B	111.4
O1—C1—C2	118.52 (17)	H21A—C21—H21B	111.3
O1—C1—C6	123.55 (17)	C21—C22—H22A	109.5
C2—C1—C6	117.92 (17)	C21—C22—H22B	109.5
C3—C2—C1	120.92 (18)	H22A—C22—H22B	109.5
C3—C2—H2A	119.5	C21—C22—H22C	109.5
C1—C2—H2A	119.5	H22A—C22—H22C	109.5
C2—C3—C4	120.70 (18)	H22B—C22—H22C	109.5
C2—C3—H3A	119.6	O3—C23—H23A	109.5
C4—C3—H3A	119.6	O3—C23—H23B	109.5
O3—C4—C5	124.35 (18)	H23A—C23—H23B	109.5
O3—C4—C3	116.23 (17)	O3—C23—H23C	109.5
C5—C4—C3	119.41 (17)	H23A—C23—H23C	109.5
C4—C5—C6	120.58 (18)	H23B—C23—H23C	109.5
C4—C5—H5A	119.7	O4—C24—H24A	109.5
C6—C5—H5A	119.7	O4—C24—H24B	109.5
C1—C6—C5	120.45 (17)	H24A—C24—H24B	109.5
C1—C6—C7	123.34 (17)	O4—C24—H24C	109.5
C5—C6—C7	116.21 (17)	H24A—C24—H24C	109.5
N1—C7—C6	124.55 (18)	H24B—C24—H24C	109.5
N1—C7—H7A	117.7	O5—C25—H25A	109.5
C6—C7—H7A	117.7	O5—C25—H25B	109.5
N2—C8—C9	124.98 (18)	H25A—C25—H25B	109.5
N2—C8—H8A	117.5	O5—C25—H25C	109.5
C9—C8—H8A	117.5	H25A—C25—H25C	109.5
C14—C9—C10	119.98 (18)	H25B—C25—H25C	109.5
O2—Mn1—O1—C1	−163.78 (16)	O1—C1—C6—C5	−178.93 (18)
N1—Mn1—O1—C1	22.05 (16)	C2—C1—C6—C5	0.4 (3)
O5—Mn1—O1—C1	106.10 (16)	O1—C1—C6—C7	0.6 (3)
N3—Mn1—O1—C1	−69.88 (16)	C2—C1—C6—C7	179.99 (19)
O1—Mn1—O2—C14	−177.40 (17)	C4—C5—C6—C1	−0.5 (3)
N2—Mn1—O2—C14	2.71 (18)	C4—C5—C6—C7	179.89 (18)
O5—Mn1—O2—C14	−87.91 (17)	C20—N1—C7—C6	−176.6 (2)
N3—Mn1—O2—C14	89.87 (17)	Mn1—N1—C7—C6	−1.9 (3)
O2—Mn1—O5—C25	38.30 (14)	C1—C6—C7—N1	10.8 (3)
O1—Mn1—O5—C25	131.96 (14)	C5—C6—C7—N1	−169.7 (2)
N1—Mn1—O5—C25	−135.81 (14)	C21—N2—C8—C9	−176.6 (2)
N2—Mn1—O5—C25	−53.61 (14)	Mn1—N2—C8—C9	−2.4 (3)
O1—Mn1—N1—C7	−11.3 (2)	N2—C8—C9—C14	0.1 (3)
N2—Mn1—N1—C7	168.0 (2)	N2—C8—C9—C10	178.9 (2)
O5—Mn1—N1—C7	−100.59 (19)	C14—C9—C10—C11	−1.2 (3)
N3—Mn1—N1—C7	81.22 (19)	C8—C9—C10—C11	−179.99 (19)
O1—Mn1—N1—C20	163.71 (18)	C9—C10—C11—O4	178.9 (2)
N2—Mn1—N1—C20	−16.97 (18)	C9—C10—C11—C12	−1.5 (3)
O5—Mn1—N1—C20	74.46 (18)	C24—O4—C11—C10	−16.7 (4)
N3—Mn1—N1—C20	−103.73 (18)	C24—O4—C11—C12	163.7 (3)
O2—Mn1—N2—C8	1.1 (2)	C10—C11—C12—C13	1.8 (3)
N1—Mn1—N2—C8	175.2 (2)	O4—C11—C12—C13	−178.60 (19)
O5—Mn1—N2—C8	91.29 (19)	C11—C12—C13—C14	0.7 (3)
N3—Mn1—N2—C8	−92.52 (19)	Mn1—O2—C14—C13	176.23 (14)
O2—Mn1—N2—C21	175.65 (17)	Mn1—O2—C14—C9	−5.4 (3)
N1—Mn1—N2—C21	−10.24 (17)	C12—C13—C14—O2	175.21 (19)
O5—Mn1—N2—C21	−94.18 (17)	C12—C13—C14—C9	−3.3 (3)
N3—Mn1—N2—C21	82.00 (17)	C10—C9—C14—O2	−174.86 (19)
O2—Mn1—N3—C15	−30.74 (16)	C8—C9—C14—O2	3.9 (3)
O1—Mn1—N3—C15	−124.58 (16)	C10—C9—C14—C13	3.5 (3)
N1—Mn1—N3—C15	143.18 (16)	C8—C9—C14—C13	−177.73 (19)
N2—Mn1—N3—C15	60.99 (16)	C19—N3—C15—C16	−2.0 (3)
O2—Mn1—N3—C19	151.36 (18)	Mn1—N3—C15—C16	179.99 (19)
O1—Mn1—N3—C19	57.52 (18)	N3—C15—C16—C17	1.8 (4)
N1—Mn1—N3—C19	−34.72 (18)	C15—C16—C17—C18	0.4 (4)
N2—Mn1—N3—C19	−116.91 (18)	C16—C17—C18—C19	−2.3 (4)
Mn1—O1—C1—C2	160.46 (14)	C15—N3—C19—C18	−0.1 (4)
Mn1—O1—C1—C6	−20.2 (3)	Mn1—N3—C19—C18	177.9 (2)
O1—C1—C2—C3	179.18 (18)	C17—C18—C19—N3	2.2 (4)
C6—C1—C2—C3	−0.2 (3)	C7—N1—C20—C21	−145.7 (2)
C1—C2—C3—C4	0.1 (3)	Mn1—N1—C20—C21	39.0 (3)
C23—O3—C4—C5	0.6 (3)	C8—N2—C21—C22	84.9 (3)
C23—O3—C4—C3	−179.98 (17)	Mn1—N2—C21—C22	−90.0 (3)
C2—C3—C4—O3	−179.58 (17)	C8—N2—C21—C20	−151.6 (2)
C2—C3—C4—C5	−0.2 (3)	Mn1—N2—C21—C20	33.5 (3)
O3—C4—C5—C6	179.76 (18)	N1—C20—C21—C22	81.6 (3)
C3—C4—C5—C6	0.4 (3)	N1—C20—C21—N2	−45.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H1O5···O1^i	0.82 (3)	1.99 (3)	2.804 (2)	169 (3)
C17—H17A···O4^ii	0.93	2.57	3.465 (3)	161
C22—H22C···N3	0.96	2.62	3.318 (5)	130

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