[2-(2-Pyrid­yl)-1H-benzimidazole-[kappa]²N²,N³]bis­(p-toluato-[kappa]²O,O')­manganese(II)

In the title compound, [Mn(C₈H₇O₂)₂(C₁₂H₉N₃)], the manganese(II) centre is surrounded by three bidentate chelating ligands, namely, one 2-(2-pyrid­yl)benzimidazole ligand [Mn-N = 2.1954 (13) and 2.2595 (14) Å] and two p-toluate ligands [Mn-O = 2.1559 (13)-2.2748 (14) Å]. It displays a severely distorted octa­hedral geometry, with cis angles ranging from 58.87 (4) to 106.49 (5)°. Inter­molecular C-H...O hydrogen bonds between the p-toluate ligands link the mol­ecules into infinite chains, and every two neighbouring chains are further coupled by N-H...O and C-H...O hydrogen bonds between the 2-(2-pyrid­yl)benzimidazole and p-toluate ligands, leading to an infinite ribbon-like double-chain packing mode. The complete solid-state structure can be described as a three-dimensional supra­molecular framework, stabilized by these inter­molecular hydrogen-bonding inter­actions and possible C-H...[pi] inter­actions, as well as stacking inter­actions involving the 2-(2-pyrid­yl)benzimidazole ligands.

S1. Comment

Low molecular weight manganese carboxylate species play an important role at the active sites of various redox-based enzymes (Weighardt, 1989). Mn superoxide dismutase, Mn peroxidase and Mn dioxygenase are each believed to contain a mononuclear Mn site, which participates in the redox changes of biological systems (Law et al., 1999). X-ray crystallography reveals that the peripheral ligation around the Mn centre in these enzymes includes both the carboxylate groups of various binding modes and the imidazole rings from various amino acid residues (Pecoraro & Butler, 1986), and it suggests that changes in the carboxylate binding mode may be important to the action of these enzymes (Rardin et al., 1991). Carboxylic acid- and imidazole-containing molecule are often employed to prepare simple models for the active sites of these enzymes. Understanding the structural effects of imidazole ligation to the Mn centre and the different carboxylate binding modes in these models will undoubtedly be helpful in gaining insight into the structural aspects that may influence the mechanism of action of the enzyme active sites. As far as we are aware, for the great majority of six-coordinate Mn complexes with carboxylate ligation, the number of carboxylate ligands acting as a chelating ligand usually remains low so as to avoid (or reduce) the strain from small-angle chelation (the chelation angle is usually less than 60°), and thus far reports of mononuclear complexes with more than two carboxylate ligands chelating an octahedral Mn centre have been rare (Jha & Mishra, 1986; Chai et al., 2004; Moubaraki et al., 2003). In the present paper, we report the structure of the title compound, (I). Compound (I) is a rare example of a mononuclear manganese complex with three chelating ligands, including a pair of chelating carboxylate ligands and a third chelating imidazole-containing ligand, simultaneously in the coordination environment. A mononuclear seven-coordinate Mn^II complex with a similar chelating ligand situation has recently been reported (Viossat et al., 2003).

Compound (I) consists of neutral [Mn(ptl)2(pybim)] monomers [ptl is p-toluate and pybim is 2-(2-pyridyl)benzimidazole] lying in a crystallographic general position. The Mn^II atom is coordinated to one bidentate chelating pybim ligand via atoms N1 and N2, and a pair of anionic bidentate chelating ptl ligands via atoms O1, O2, O3 and O4, as shown in Fig. 1. The complex displays a highly distorted octahedral geometry around the Mn centre (Table 1), in which three O atoms (O1, O2 and O3) of the tpl ligands and one pyridyl N atom (N2) of the pybim ligand define the equatorial plane, with atom Mn1 displaced from the least-squares O1–O3/N2 plane by 0.163 (2) Å. Imidazole atom N1 of the pybim ligand and atom O4 of the tpl ligand complete the distorted octahedron through coordination in the axial positions, with an N1—Mn1—O4 angle of 155.83 (5)°.

The Mn—N distances and N—Mn—N pybim chelate angle (Table 1) are comparable to those observed in the only reported pybim-containing Mn^II complex [Mn₃(AcO)₆(pybim)₂] [2.197 (2) and 2.394 (2) Å, and 72.72 (6)°, respectively; Tangoulis et al., 1996], and the Mn–N(imidazole) distance in both compounds, perceptibly shorter than the Mn—N(pyridine) distance, indicates that the imidazole N of the pybim ligand is a stronger donor, since the phenyl group in ortho position enhances the electron density on this N atom. The Mn—O distances and O—Mn—O carboxylate chelate angles are as expected for Mn^II complexes with a similar coordination environment (Chai et al., 2004; Moubaraki et al., 2003; Viossat et al., 2003; Baumeister & Hartung 1997; Jha & Mishra, 1986).

The two chelate ring planes formed by the ptl ligands, O1/C7/O2/Mn1 and O3/C15/O4/Mn1, with a maximum out-of-plane deviation of 0.027 (1) Å for atom C7, are each almost coplanar with the respective attaching methylphenyl plane [C1–C6/C8 and C9–C14/C16, respectively], as indicated by the small dihedral angles of 7.9 (6) and 3.4 (1)°, respectively, observed between them. The pybim ligand and the pybim chelate ring (N1/C23/C24/N2/Mn1) are each reasonably planar, with a maximum out-of-plane deviation of 0.096 (6) Å for atom H28A and a very small dihedral angle of 3.3 (1)° observed between them, suggesting that the pybim plane can be extended to involve atom Mn1. The three Mn1-containing mean planes, denoting P1 (C1–C8/O1/O2/Mn1), P2 (C9–C16/O3/O4/Mn1) and P3 (C17–C28/N1–N3/Mn1), with maximum out-of-plane deviations of 0.137 (6) Å for atom O1, 0.062 (1) Å for atom C10 and 0.085 (9) Å for atom Mn1, respectively, make dihedral angles (P1/P2, P3/P1 and P3/P2) of 87.2 (2), 83.8 (6) and 71.0 (4)°, respectively, showing a profile of the approximate perpendicularity to each other (Fig. 2).

The high-spin d⁵ Mn²⁺ ion usually favors the formation of the octahedral d²sp³ hybrid orbital, with cis angles regular and close to 90°. The chelating carboxylate group usually gives a narrow bite of less than 60° at the central Mn atom, thus resulting in the distortion of the coordination environment, and the higher the number of chelating carboxylate groups, the more distorted the central metal coordination sphere and the more unstable the complex in keeping an octahedral coordination. Thus far, mononuclear Mn complexes with more than two chelating carboxylates have therefore rarely been encountered. The strong distortion deviating from an ideal Mn octahedron in (I), with the cis angles subtended at the Mn atom ranging from 58.87 (4) to 106.49 (5)°, is obviously due to the triple narrow bite of the three chelating ligands. The title compound provides a rare example of six-coordinate Mn compounds with an added N,N'-chelating ligand besides two chelating carboxylate ligations, though several similar complexes are found to have two added monodentate ligands in a more regular octahedral Mn coordination (Jha & Mishra, 1986; Chai et al., 2004; Moubaraki et al., 2003). Two seven-coordinate complexes with a dinuclear or mononuclear Mn centre have also been previously reported to possess a similar chelating ligand set, in which the central Mn coordination environments are approximately described as distorted capped octahedra (Viossat et al., 2003; Baumeister & Hartung, 1997).

As listed in Table 2, one normal intermolecular N—H···O hydrogen bond and five nonclassic intermolecular C—H···O hydrogen bonds are observed in the crystal structure. Four phenyl C atoms (C5, C6, C10 and C11) in one molecule donate their H atoms to the carboxyl O atoms (O1, O3, O2 and O4, respectively) of two symmetry-related molecules to generate infinite one-dimensional chains with the pybim ligands located at the same side of the chain (Fig. 3). Two molecules of neighbouring chains are further coupled via the N3—H3B···O2ⁱ [symmetry code: (i) –x, –y + 1, –z + 1] hydrogen bond and a fifth weak C25—H25A···O2ⁱ hydrogen bond to generate a centrosymmetric dimer (Fig. 4), thus resulting in the formation of an infinite hydrogen-bonded ribbon-shaped double-chain network (Fig. 5). All the pybim ligands are located within the region of hydrogen-bonded ribbon network, in which a normal and a weaker π-π stacking interactions (3.4 Å; Bondi, 1964) between inversion-related pybim ligands are observed (Fig. 6), with perpendicular pybim plane separations of 3.498 (4) and 3.669 (7) Å, respectively.

Three C—H···π interactions, with H···Cg distances of less than 3 Å (Cg is the centroid of the π ring) and γ less than 30° (γ is the angle formed by the H···Cg vector and the normal to the π-ring plane) (Spek, 2003) are also observed within the structure of (I) (Table 2). These C—H···π interactions link the monomer to adjacent symmetry-related monomers (Fig. 7), and complete an overall three-dimensional supramolecular network (Fig. 8). These intermolecular interactions together with numerous other van der Waals contacts ensure the solid-state crystalline cohesion of the title compound.

Related literature

For related literature, see: Baumeister & Hartung (1997); Bondi (1964); Chai et al. (2004); Jha & Mishra (1986); Law et al. (1999); Moubaraki et al. (2003); Pecoraro & Butler (1986); Rardin et al. (1991); Spek (2003); Tangoulis et al. (1996); Viossat et al. (2003); Weighardt (1989).

S2. Experimental

2-(2-Pyridyl)benzimidazole (1 mmol) dissolved in ethanol (15 ml) was dropwise added to an ethanol–DMF solution (30 ml, ca 1:1 v/v) containing manganese p-toluate tetrahydrate (1 mmol), with continuous stirring. The mixture was refluxed for 1 h and then filtered. The yellow filtrate was allowed to stand undisturbed for several weeks at room temperature, during which time yellow crystals of (I) suitable for X-ray diffraction analysis were deposited. Analysis calculated for C₂₈H₂₃MnN₃O₄: C 64.62, H 4.45, N 8.07%; found C 64.47, H 4.55, N 8.11%. FT–IR (KBr, cm^-1): 3066 (m), 2922(w), 1618 (s), 1587 (s), 1520 (vs), 1412 (vs), 1311 (m), 1299 (m), 1194 (m), 1058 (w), 980 (m), 863 (s), 787 (m), 774 (s), 746 (s), 622 (s), 544 (w), 486 (w).

S3. Refinement

H atoms on both phenyl/pyridyl rings and methyl groups were placed in calculated positions, with C—H distances of 0.93 and 0.96 Å, respectively, and were included in the final cycles of refinement as riding, with U_iso(H) = 1.2U_eq(C) and 1.5U_eq(C), respectively. The H atom on the imidazole N atom was located from difference maps and refined isotropically.

Computing details

Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear (Rigaku, 2000); data reduction: CrystalClear (Rigaku, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 1997) and PLATON (Spek, 2003).

Figures

Figure 1 A view of the molecule of (I), showing the atomic labelling scheme and 30% probability displacement ellipsoids. H atoms are shown as small spheres of arbitrary radii. Figure 2 A view of (I), showing the coplanarity of the central metal with each of the ligands and the approximately perpendicular interpenetration of the mean planes. Figure 3 The packing of (I), showing part of the one-dimensional hydrogen-bonded network. Atoms labelled with a dollar sign ($) or a hash (#) are at the symmetry positions (–1 + x, y, z) and (1 + x, y, z), respectively. H atoms not involved in the hydrogen bonding have been omitted. Figure 4 A view of the centrosymmetric dimer produced by N–H···O and C–H···O hydrogen bonds. The atom labelled with an ampersand (&) is at the symmetry position (–x, –y + 1, –z + 1). Figure 5 A packing diagram for (I), showing part of the one-dimensional hydrogen-bonded ribbon-shaped double-chain network. The signs (#, $ or &) denote symmetry codes identical to those in Figs. 3 and 4. H atoms not involved in the hydrogen bonding have been omitted. Figure 6 A view of the partial π–π stacking interactions between the pyridine rings of pybim ligands in (I). Figure 7 A partial packing diagram of (I), showing the three symmetry-independent C–H···π interactions. The π-ring centroids (Cg1, Cg2 and Cg3) labelled with a percent sign (%), an asterisk (*) or a plus sign (+) are at the symmetry positions (1 + x, 1/2 – y, 1/2 + z), (1 – x, -1/2 + y, 1/2 – z) and (–x, -1/2 + y, 1/2 – z), respectively. Cg1 and Cg3 denote the centroids of C1–C6 rings and Cg2 denotes the centroid of the C9–C14 ring. H atoms not involved in C–H···π interactions have been omitted. Figure 8 A partial packing diagram of (I), showing the formation of the three-dimensional supramolecular framework. Hydrogen-bonding and C–H···π interactions are depicted as dashed lines. H atoms not involved in the intermolecular interactions have been omitted for clarity.

[2-(2-Pyridyl)benzimidazole-κ²N²,N³]bis(p-toluato- κ²O,O')manganese(II)

Crystal data

[Mn(C8H7O2)2(C12H9N3)]	F(000) = 1076
Mr = 520.43	Dx = 1.415 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5667 reflections
a = 7.582 (2) Å	θ = 2.2–27.5°
b = 17.482 (5) Å	µ = 0.58 mm^−1
c = 18.731 (5) Å	T = 295 K
β = 100.368 (4)°	Prism, yellow
V = 2442.3 (11) Å^3	0.46 × 0.42 × 0.20 mm
Z = 4

Data collection

Rigaku Mercury CCD Diffractometer	5561 independent reflections
Radiation source: fine-focus sealed tube	4584 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
phi and ω scans	θmax = 27.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.760, Tmax = 0.890	k = −22→22
18797 measured reflections	l = −24→20

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.105	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.064P)^2 + 0.2429P] where P = (Fo^2 + 2Fc^2)/3
5561 reflections	(Δ/σ)max = 0.001
331 parameters	Δρmax = 0.22 e Å^−3
0 restraints	Δρmin = −0.30 e Å^−3

Special details

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
Mn1	0.30440 (3)	0.391974 (13)	0.631563 (13)	0.03934 (10)
O1	0.23328 (16)	0.26835 (7)	0.62196 (7)	0.0531 (3)
O2	0.01969 (15)	0.35321 (6)	0.62093 (6)	0.0421 (3)
O3	0.58797 (16)	0.38591 (6)	0.67383 (6)	0.0441 (3)
O4	0.40767 (16)	0.38786 (7)	0.75329 (7)	0.0512 (3)
N1	0.29988 (17)	0.42932 (7)	0.51934 (7)	0.0396 (3)
N2	0.23004 (18)	0.51722 (8)	0.62917 (7)	0.0420 (3)
N3	0.22728 (19)	0.51832 (8)	0.43451 (7)	0.0443 (3)
H3B	0.185 (3)	0.5603 (12)	0.4115 (11)	0.067 (6)*
C1	−0.0622 (2)	0.22119 (8)	0.62098 (7)	0.0371 (3)
C2	−0.0055 (2)	0.14537 (9)	0.62936 (8)	0.0414 (4)
H2A	0.1159	0.1337	0.6353	0.050*
C3	−0.1308 (3)	0.08734 (9)	0.62883 (9)	0.0477 (4)
H3A	−0.0920	0.0369	0.6346	0.057*
C4	−0.3120 (3)	0.10306 (9)	0.61988 (9)	0.0473 (4)
C5	−0.3676 (2)	0.17867 (10)	0.61226 (10)	0.0509 (4)
H5A	−0.4891	0.1903	0.6065	0.061*
C6	−0.2434 (2)	0.23713 (10)	0.61314 (9)	0.0463 (4)
H6A	−0.2824	0.2876	0.6084	0.056*
C7	0.0710 (2)	0.28391 (9)	0.62111 (8)	0.0377 (3)
C8	−0.4480 (3)	0.03972 (12)	0.61898 (12)	0.0699 (6)
H8A	−0.5378	0.0553	0.6461	0.105*
H8B	−0.3890	−0.0055	0.6405	0.105*
H8C	−0.5034	0.0290	0.5698	0.105*
C9	0.7228 (2)	0.37799 (8)	0.79847 (8)	0.0369 (3)
C10	0.8933 (2)	0.37288 (9)	0.78208 (9)	0.0428 (4)
H10A	0.9077	0.3704	0.7339	0.051*
C11	1.0432 (2)	0.37141 (10)	0.83699 (9)	0.0459 (4)
H11A	1.1569	0.3680	0.8251	0.055*
C12	1.0254 (2)	0.37493 (9)	0.90913 (9)	0.0445 (4)
C13	0.8537 (2)	0.37857 (10)	0.92542 (9)	0.0469 (4)
H13A	0.8394	0.3805	0.9737	0.056*
C14	0.7036 (2)	0.37933 (9)	0.87083 (8)	0.0421 (4)
H14A	0.5897	0.3807	0.8827	0.050*
C15	0.5632 (2)	0.38360 (8)	0.73887 (8)	0.0383 (3)
C16	1.1882 (3)	0.37569 (13)	0.96872 (11)	0.0668 (6)
H16A	1.2947	0.3742	0.9477	0.100*
H16B	1.1855	0.3319	0.9994	0.100*
H16C	1.1881	0.4215	0.9970	0.100*
C17	0.3176 (2)	0.39839 (9)	0.45318 (9)	0.0417 (4)
C18	0.3685 (3)	0.32505 (11)	0.43601 (10)	0.0553 (4)
H18A	0.3996	0.2880	0.4717	0.066*
C19	0.3709 (3)	0.30942 (13)	0.36400 (11)	0.0643 (5)
H19A	0.4036	0.2609	0.3508	0.077*
C20	0.3250 (3)	0.36530 (13)	0.31047 (11)	0.0634 (5)
H20A	0.3283	0.3528	0.2625	0.076*
C21	0.2752 (3)	0.43798 (12)	0.32643 (9)	0.0568 (5)
H21A	0.2452	0.4749	0.2905	0.068*
C22	0.2719 (2)	0.45368 (10)	0.39896 (9)	0.0438 (4)
C23	0.24584 (19)	0.50072 (9)	0.50566 (8)	0.0378 (3)
C24	0.2108 (2)	0.55194 (9)	0.56406 (8)	0.0387 (3)
C25	0.1633 (3)	0.62781 (10)	0.55485 (10)	0.0520 (4)
H25A	0.1503	0.6505	0.5093	0.062*
C26	0.1351 (3)	0.66971 (10)	0.61452 (11)	0.0582 (5)
H26A	0.1023	0.7210	0.6094	0.070*
C27	0.1556 (3)	0.63541 (11)	0.68080 (11)	0.0563 (5)
H27A	0.1387	0.6627	0.7216	0.068*
C28	0.2021 (3)	0.55922 (10)	0.68577 (9)	0.0526 (4)
H28A	0.2149	0.5357	0.7309	0.063*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.03876 (16)	0.04196 (15)	0.03671 (15)	0.00085 (10)	0.00515 (10)	0.00634 (9)
O1	0.0395 (7)	0.0473 (6)	0.0740 (8)	0.0020 (5)	0.0142 (6)	0.0015 (6)
O2	0.0426 (6)	0.0389 (6)	0.0464 (6)	0.0013 (5)	0.0122 (5)	0.0041 (5)
O3	0.0409 (6)	0.0564 (7)	0.0347 (6)	0.0028 (5)	0.0061 (5)	0.0019 (5)
O4	0.0364 (7)	0.0741 (8)	0.0436 (7)	0.0055 (5)	0.0088 (5)	0.0031 (6)
N1	0.0375 (7)	0.0444 (7)	0.0371 (6)	0.0001 (6)	0.0066 (5)	0.0055 (6)
N2	0.0418 (7)	0.0444 (7)	0.0390 (7)	0.0000 (6)	0.0050 (5)	0.0041 (6)
N3	0.0484 (8)	0.0439 (7)	0.0382 (7)	−0.0069 (6)	0.0008 (6)	0.0084 (6)
C1	0.0417 (8)	0.0385 (7)	0.0314 (7)	−0.0005 (6)	0.0074 (6)	−0.0003 (6)
C2	0.0417 (9)	0.0433 (8)	0.0388 (8)	0.0048 (7)	0.0059 (7)	0.0024 (7)
C3	0.0603 (11)	0.0374 (8)	0.0444 (9)	0.0031 (8)	0.0068 (8)	0.0048 (7)
C4	0.0523 (10)	0.0458 (9)	0.0418 (9)	−0.0088 (7)	0.0033 (7)	0.0036 (7)
C5	0.0403 (9)	0.0503 (9)	0.0615 (11)	−0.0018 (8)	0.0080 (8)	0.0039 (8)
C6	0.0433 (9)	0.0408 (8)	0.0558 (10)	0.0038 (7)	0.0115 (7)	0.0030 (7)
C7	0.0396 (8)	0.0436 (8)	0.0306 (7)	0.0016 (6)	0.0080 (6)	0.0017 (6)
C8	0.0665 (13)	0.0597 (12)	0.0783 (14)	−0.0189 (10)	−0.0005 (11)	0.0112 (10)
C9	0.0397 (8)	0.0368 (7)	0.0344 (7)	0.0032 (6)	0.0071 (6)	0.0002 (6)
C10	0.0421 (9)	0.0534 (9)	0.0341 (8)	0.0008 (7)	0.0101 (7)	0.0003 (7)
C11	0.0373 (9)	0.0566 (9)	0.0445 (9)	0.0000 (7)	0.0097 (7)	0.0042 (7)
C12	0.0446 (9)	0.0454 (8)	0.0419 (9)	−0.0028 (7)	0.0034 (7)	0.0043 (7)
C13	0.0513 (10)	0.0560 (9)	0.0343 (8)	0.0074 (8)	0.0098 (7)	0.0012 (7)
C14	0.0405 (9)	0.0496 (9)	0.0380 (8)	0.0084 (7)	0.0123 (7)	0.0025 (7)
C15	0.0401 (9)	0.0361 (7)	0.0389 (8)	0.0022 (6)	0.0080 (6)	0.0009 (6)
C16	0.0513 (12)	0.0947 (15)	0.0497 (11)	−0.0034 (10)	−0.0035 (9)	0.0086 (10)
C17	0.0338 (8)	0.0510 (9)	0.0401 (8)	−0.0042 (7)	0.0063 (6)	0.0035 (7)
C18	0.0569 (11)	0.0571 (10)	0.0521 (10)	0.0090 (9)	0.0107 (8)	0.0013 (8)
C19	0.0636 (13)	0.0698 (12)	0.0609 (12)	0.0066 (10)	0.0151 (10)	−0.0124 (10)
C20	0.0633 (13)	0.0851 (14)	0.0442 (10)	−0.0108 (11)	0.0159 (9)	−0.0101 (10)
C21	0.0630 (12)	0.0672 (12)	0.0398 (9)	−0.0139 (9)	0.0082 (8)	0.0043 (8)
C22	0.0394 (9)	0.0519 (9)	0.0396 (8)	−0.0108 (7)	0.0055 (6)	0.0030 (7)
C23	0.0320 (8)	0.0426 (8)	0.0374 (7)	−0.0071 (6)	0.0024 (6)	0.0070 (6)
C24	0.0307 (7)	0.0412 (8)	0.0429 (8)	−0.0059 (6)	0.0027 (6)	0.0029 (6)
C25	0.0543 (11)	0.0455 (9)	0.0539 (10)	−0.0015 (8)	0.0036 (8)	0.0110 (8)
C26	0.0606 (12)	0.0426 (9)	0.0707 (12)	0.0024 (8)	0.0096 (9)	−0.0027 (9)
C27	0.0576 (12)	0.0534 (10)	0.0583 (11)	0.0011 (9)	0.0118 (9)	−0.0095 (9)
C28	0.0597 (11)	0.0544 (10)	0.0440 (9)	0.0029 (8)	0.0102 (8)	−0.0007 (8)

Geometric parameters (Å, º)

Mn1—O3	2.1559 (13)	C9—C10	1.384 (2)
Mn1—N1	2.1954 (13)	C9—C14	1.389 (2)
Mn1—O1	2.2268 (13)	C9—C15	1.495 (2)
Mn1—O2	2.2370 (13)	C10—C11	1.389 (2)
Mn1—N2	2.2595 (14)	C10—H10A	0.9300
Mn1—O4	2.2748 (14)	C11—C12	1.383 (2)
Mn1—C15	2.5478 (17)	C11—H11A	0.9300
Mn1—C7	2.5720 (16)	C12—C13	1.391 (3)
O1—C7	1.2576 (19)	C12—C16	1.508 (2)
O2—C7	1.2722 (18)	C13—C14	1.386 (2)
O3—C15	1.2663 (19)	C13—H13A	0.9300
O4—C15	1.258 (2)	C14—H14A	0.9300
N1—C23	1.324 (2)	C16—H16A	0.9600
N1—C17	1.381 (2)	C16—H16B	0.9600
N2—C28	1.337 (2)	C16—H16C	0.9600
N2—C24	1.347 (2)	C17—C18	1.393 (2)
N3—C23	1.3501 (19)	C17—C22	1.400 (2)
N3—C22	1.384 (2)	C18—C19	1.379 (3)
N3—H3B	0.88 (2)	C18—H18A	0.9300
C1—C6	1.383 (2)	C19—C20	1.398 (3)
C1—C2	1.394 (2)	C19—H19A	0.9300
C1—C7	1.490 (2)	C20—C21	1.374 (3)
C2—C3	1.389 (2)	C20—H20A	0.9300
C2—H2A	0.9300	C21—C22	1.391 (2)
C3—C4	1.381 (3)	C21—H21A	0.9300
C3—H3A	0.9300	C23—C24	1.474 (2)
C4—C5	1.387 (2)	C24—C25	1.377 (2)
C4—C8	1.511 (2)	C25—C26	1.385 (3)
C5—C6	1.388 (2)	C25—H25A	0.9300
C5—H5A	0.9300	C26—C27	1.362 (3)
C6—H6A	0.9300	C26—H26A	0.9300
C8—H8A	0.9600	C27—C28	1.377 (3)
C8—H8B	0.9600	C27—H27A	0.9300
C8—H8C	0.9600	C28—H28A	0.9300
O3—Mn1—N1	102.06 (5)	C12—C11—C10	120.78 (16)
O3—Mn1—O1	101.12 (4)	C12—C11—H11A	119.6
N1—Mn1—O1	104.44 (5)	C10—C11—H11A	119.6
O3—Mn1—O2	154.21 (4)	C11—C12—C13	118.44 (16)
N1—Mn1—O2	98.99 (4)	C11—C12—C16	120.82 (17)
O1—Mn1—O2	58.87 (4)	C13—C12—C16	120.74 (16)
O3—Mn1—N2	106.49 (5)	C14—C13—C12	121.00 (15)
N1—Mn1—N2	74.45 (5)	C14—C13—H13A	119.5
O1—Mn1—N2	152.00 (5)	C12—C13—H13A	119.5
O2—Mn1—N2	93.35 (5)	C13—C14—C9	120.21 (15)
O3—Mn1—O4	59.32 (4)	C13—C14—H14A	119.9
N1—Mn1—O4	155.83 (5)	C9—C14—H14A	119.9
O1—Mn1—O4	94.87 (5)	O4—C15—O3	120.79 (15)
O2—Mn1—O4	103.43 (4)	O4—C15—C9	120.51 (15)
N2—Mn1—O4	95.17 (5)	O3—C15—C9	118.68 (14)
C23—N1—C17	105.79 (13)	C12—C16—H16A	109.5
C23—N1—Mn1	114.62 (10)	C12—C16—H16B	109.5
C17—N1—Mn1	139.09 (11)	H16A—C16—H16B	109.5
C28—N2—C24	117.63 (14)	C12—C16—H16C	109.5
C28—N2—Mn1	126.21 (11)	H16A—C16—H16C	109.5
C24—N2—Mn1	116.15 (10)	H16B—C16—H16C	109.5
C23—N3—C22	107.32 (14)	N1—C17—C18	130.04 (15)
C23—N3—H3B	129.5 (13)	N1—C17—C22	109.23 (14)
C22—N3—H3B	122.9 (13)	C18—C17—C22	120.72 (16)
C6—C1—C2	118.94 (15)	C19—C18—C17	117.45 (18)
C6—C1—C7	120.77 (14)	C19—C18—H18A	121.3
C2—C1—C7	120.28 (14)	C17—C18—H18A	121.3
C3—C2—C1	119.81 (16)	C18—C19—C20	121.16 (19)
C3—C2—H2A	120.1	C18—C19—H19A	119.4
C1—C2—H2A	120.1	C20—C19—H19A	119.4
C4—C3—C2	121.32 (15)	C21—C20—C19	122.19 (18)
C4—C3—H3A	119.3	C21—C20—H20A	118.9
C2—C3—H3A	119.3	C19—C20—H20A	118.9
C3—C4—C5	118.66 (15)	C20—C21—C22	116.69 (17)
C3—C4—C8	121.14 (16)	C20—C21—H21A	121.7
C5—C4—C8	120.19 (18)	C22—C21—H21A	121.7
C4—C5—C6	120.48 (17)	N3—C22—C21	132.84 (16)
C4—C5—H5A	119.8	N3—C22—C17	105.36 (14)
C6—C5—H5A	119.8	C21—C22—C17	121.79 (17)
C1—C6—C5	120.78 (15)	N1—C23—N3	112.30 (14)
C1—C6—H6A	119.6	N1—C23—C24	121.30 (13)
C5—C6—H6A	119.6	N3—C23—C24	126.39 (14)
O1—C7—O2	120.26 (14)	N2—C24—C25	122.06 (15)
O1—C7—C1	120.15 (14)	N2—C24—C23	113.19 (13)
O2—C7—C1	119.59 (14)	C25—C24—C23	124.75 (15)
C4—C8—H8A	109.5	C24—C25—C26	118.91 (17)
C4—C8—H8B	109.5	C24—C25—H25A	120.5
H8A—C8—H8B	109.5	C26—C25—H25A	120.5
C4—C8—H8C	109.5	C27—C26—C25	119.59 (17)
H8A—C8—H8C	109.5	C27—C26—H26A	120.2
H8B—C8—H8C	109.5	C25—C26—H26A	120.2
C10—C9—C14	118.92 (15)	C26—C27—C28	118.25 (17)
C10—C9—C15	120.11 (14)	C26—C27—H27A	120.9
C14—C9—C15	120.96 (15)	C28—C27—H27A	120.9
C9—C10—C11	120.62 (15)	N2—C28—C27	123.56 (17)
C9—C10—H10A	119.7	N2—C28—H28A	118.2
C11—C10—H10A	119.7	C27—C28—H28A	118.2
O3—Mn1—O1—C7	159.95 (9)	N1—Mn1—C7—O2	−82.31 (9)
N1—Mn1—O1—C7	−94.36 (9)	O1—Mn1—C7—O2	−175.73 (14)
O2—Mn1—O1—C7	−2.46 (8)	N2—Mn1—C7—O2	−1.52 (10)
N2—Mn1—O1—C7	−10.39 (16)	O4—Mn1—C7—O2	100.88 (8)
O4—Mn1—O1—C7	100.29 (9)	C15—Mn1—C7—O2	126.55 (8)
C15—Mn1—O1—C7	129.83 (9)	C14—C9—C10—C11	−1.9 (2)
O3—Mn1—O2—C7	−40.52 (14)	C15—C9—C10—C11	176.84 (14)
N1—Mn1—O2—C7	103.94 (9)	C9—C10—C11—C12	0.1 (3)
O1—Mn1—O2—C7	2.44 (8)	C10—C11—C12—C13	1.1 (2)
N2—Mn1—O2—C7	178.72 (9)	C10—C11—C12—C16	−178.18 (17)
O4—Mn1—O2—C7	−85.15 (9)	C11—C12—C13—C14	−0.5 (3)
C15—Mn1—O2—C7	−71.07 (10)	C16—C12—C13—C14	178.79 (17)
N1—Mn1—O3—C15	164.61 (9)	C12—C13—C14—C9	−1.3 (3)
O1—Mn1—O3—C15	−87.81 (9)	C10—C9—C14—C13	2.5 (2)
O2—Mn1—O3—C15	−51.34 (14)	C15—C9—C14—C13	−176.23 (14)
N2—Mn1—O3—C15	87.47 (9)	Mn1—O4—C15—O3	2.18 (14)
O4—Mn1—O3—C15	1.27 (8)	Mn1—O4—C15—C9	−179.61 (12)
C7—Mn1—O3—C15	−75.49 (10)	Mn1—O3—C15—O4	−2.30 (15)
O3—Mn1—O4—C15	−1.28 (8)	Mn1—O3—C15—C9	179.46 (12)
N1—Mn1—O4—C15	−44.50 (16)	C10—C9—C15—O4	179.63 (14)
O1—Mn1—O4—C15	98.77 (9)	C14—C9—C15—O4	−1.7 (2)
O2—Mn1—O4—C15	157.90 (8)	C10—C9—C15—O3	−2.1 (2)
N2—Mn1—O4—C15	−107.40 (9)	C14—C9—C15—O3	176.58 (14)
C7—Mn1—O4—C15	127.94 (9)	O3—Mn1—C15—O4	177.78 (14)
O3—Mn1—N1—C23	−108.61 (11)	N1—Mn1—C15—O4	157.83 (9)
O1—Mn1—N1—C23	146.39 (10)	O1—Mn1—C15—O4	−84.76 (9)
O2—Mn1—N1—C23	86.37 (11)	O2—Mn1—C15—O4	−28.66 (11)
N2—Mn1—N1—C23	−4.62 (10)	N2—Mn1—C15—O4	77.28 (9)
O4—Mn1—N1—C23	−71.58 (16)	C7—Mn1—C15—O4	−60.06 (10)
C15—Mn1—N1—C23	−98.63 (11)	N1—Mn1—C15—O3	−19.95 (11)
C7—Mn1—N1—C23	116.13 (11)	O1—Mn1—C15—O3	97.46 (9)
O3—Mn1—N1—C17	81.06 (16)	O2—Mn1—C15—O3	153.56 (8)
O1—Mn1—N1—C17	−23.93 (17)	N2—Mn1—C15—O3	−100.50 (9)
O2—Mn1—N1—C17	−83.95 (16)	O4—Mn1—C15—O3	−177.78 (14)
N2—Mn1—N1—C17	−174.94 (17)	C7—Mn1—C15—O3	122.16 (9)
O4—Mn1—N1—C17	118.10 (17)	C23—N1—C17—C18	−179.15 (18)
C15—Mn1—N1—C17	91.04 (17)	Mn1—N1—C17—C18	−8.3 (3)
C7—Mn1—N1—C17	−54.19 (17)	C23—N1—C17—C22	−0.16 (17)
O3—Mn1—N2—C28	−79.41 (15)	Mn1—N1—C17—C22	170.70 (12)
N1—Mn1—N2—C28	−177.68 (15)	N1—C17—C18—C19	178.60 (17)
O1—Mn1—N2—C28	90.70 (17)	C22—C17—C18—C19	−0.3 (3)
O2—Mn1—N2—C28	83.91 (15)	C17—C18—C19—C20	0.4 (3)
O4—Mn1—N2—C28	−19.91 (15)	C18—C19—C20—C21	−0.2 (3)
C15—Mn1—N2—C28	−48.80 (15)	C19—C20—C21—C22	−0.2 (3)
C7—Mn1—N2—C28	84.67 (15)	C23—N3—C22—C21	179.02 (18)
O3—Mn1—N2—C24	101.25 (11)	O2^i—N3—C22—C21	26.5 (3)
N1—Mn1—N2—C24	2.98 (10)	C23—N3—C22—C17	−0.28 (17)
O1—Mn1—N2—C24	−88.64 (15)	O2^i—N3—C22—C17	−152.80 (11)
O2—Mn1—N2—C24	−95.43 (11)	C20—C21—C22—N3	−178.95 (18)
O4—Mn1—N2—C24	160.75 (11)	C20—C21—C22—C17	0.3 (3)
C15—Mn1—N2—C24	131.86 (11)	N1—C17—C22—N3	0.27 (18)
C7—Mn1—N2—C24	−94.67 (11)	C18—C17—C22—N3	179.37 (15)
C6—C1—C2—C3	0.8 (2)	N1—C17—C22—C21	−179.13 (15)
C7—C1—C2—C3	−179.70 (13)	C18—C17—C22—C21	0.0 (3)
C1—C2—C3—C4	0.2 (2)	C17—N1—C23—N3	−0.02 (17)
C2—C3—C4—C5	−0.8 (3)	Mn1—N1—C23—N3	−173.45 (10)
C2—C3—C4—C8	179.72 (16)	C17—N1—C23—C24	179.48 (13)
C3—C4—C5—C6	0.4 (3)	Mn1—N1—C23—C24	6.05 (17)
C8—C4—C5—C6	179.91 (17)	C22—N3—C23—N1	0.19 (18)
C2—C1—C6—C5	−1.2 (2)	O2^i—N3—C23—N1	156.59 (10)
C7—C1—C6—C5	179.32 (15)	C22—N3—C23—C24	−179.28 (14)
C4—C5—C6—C1	0.5 (3)	O2^i—N3—C23—C24	−22.87 (19)
Mn1—O1—C7—O2	4.30 (14)	C28—N2—C24—C25	−0.3 (2)
Mn1—O1—C7—C1	−175.14 (12)	Mn1—N2—C24—C25	179.06 (13)
Mn1—O2—C7—O1	−4.28 (14)	C28—N2—C24—C23	179.58 (14)
Mn1—O2—C7—C1	175.16 (12)	Mn1—N2—C24—C23	−1.02 (16)
C6—C1—C7—O1	−173.84 (14)	N1—C23—C24—N2	−3.4 (2)
C2—C1—C7—O1	6.6 (2)	N3—C23—C24—N2	176.04 (14)
C6—C1—C7—O2	6.7 (2)	N1—C23—C24—C25	176.53 (15)
C2—C1—C7—O2	−172.79 (13)	N3—C23—C24—C25	−4.0 (2)
O3—Mn1—C7—O1	−25.36 (11)	N2—C24—C25—C26	0.3 (3)
N1—Mn1—C7—O1	93.42 (10)	C23—C24—C25—C26	−179.66 (16)
O2—Mn1—C7—O1	175.73 (14)	C24—C25—C26—C27	0.3 (3)
N2—Mn1—C7—O1	174.21 (9)	C25—C26—C27—C28	−0.8 (3)
O4—Mn1—C7—O1	−83.39 (9)	C24—N2—C28—C27	−0.1 (3)
C15—Mn1—C7—O1	−57.72 (10)	Mn1—N2—C28—C27	−179.48 (14)
O3—Mn1—C7—O2	158.91 (8)	C26—C27—C28—N2	0.7 (3)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···O2^i	0.88 (2)	2.18 (2)	2.9882 (19)	153.3 (18)
C5—H5A···O1^ii	0.93	2.57	3.442 (2)	157
C6—H6A···O3^ii	0.93	2.42	3.196 (2)	141
C10—H10A···O2^iii	0.93	2.44	3.345 (2)	166
C11—H11A···O4^iii	0.93	2.54	3.426 (2)	158
C25—H25A···O2^i	0.93	2.55	3.351 (2)	145
C13—H13A···Cg1^iv	0.93	2.90	3.794 (1)	163
C26—H26A···Cg2^v	0.93	2.79	3.654 (3)	155
C27—H27A···Cg3^vi	0.93	2.91	3.712 (1)	145

Symmetry codes: (i) −x, −y+1, −z+1; (ii) x−1, y, z; (iii) x+1, y, z; (iv) x+1, −y−1/2, z−1/2; (v) −x+1, y−1/2, −z+1/2; (vi) −x, y−1/2, −z+1/2.