(6-Oxido-2-oxo-1,2-dihydro­pyrimidine-5-carboxyl­ato-κ²O⁵,O⁶)bis­[2-(2-pyrid­yl)-1H-benz­imidazole-κ²N²,N³]manganese(II) monohydrate

In the title compound, [Mn(C₅H₂N₂O₄)(C₁₂H₉N₃)₂]·H₂O, the Mn^II centre is surrounded by three bidentate chelating ligands, namely, one 6-oxido-2-oxo-1,2-dihydro­pyrimidine-5-carboxyl­ate (or uracil-5-carboxyl­ate, Huca²⁻) ligand [Mn—O = 2.136 (2) and 2.156 (3) Å] and two 2-(2-pyrid­yl)-1H-benzimidazole (Hpybim) ligands [Mn—N = 2.213 (3)–2.331 (3) Å], and it displays a severely distorted octa­hedral geometry, with cis angles ranging from 73.05 (10) to 105.77 (10)°. Inter­molecular N—H...O hydrogen bonds both between the Hpybim and the Huca²⁻ ligands and between the Huca²⁻ ligands link the mol­ecules into infinite chains. The lattice water mol­ecule acts as a hydrogen-bond donor to form double O...H—O—H...O hydrogen bonds with the Huca²⁻ O atoms, crosslinking the chains to afford an infinite two-dimensional sheet; a third hydrogen bond (N—H...O) formed by the water mol­ecule as a hydrogen-bond acceptor and a Hpybim N atom further links these sheets to yield a three-dimensional supra­molecular framework. Possible partial π–π stacking inter­actions involving the Hpybim rings are also observed in the crystal structure.

S1. Comment

Manganese-containing small molecular species have been found to play an important role at the active sites of several redox-based enzymes (Weighardt, 1989). The peripheral ligation around the Mn centre(s) in these enzymes is believed to include both the carboxyl and/or phenol hydroxy groups and the imidazole ring from various amino acid residues, affording a predominant N/O coordination sphere (Pecoraro & Butler, 1986). Simple carboxylate, phenoxide and imidazole-containing molecules are often used in place of the peptide side chains in preparing molecule [molecular?] models of the active sites of these enzymes. Uracil-5-carboxylic acid (H₃uca) (systematic name: 2,4-dihydroxypyrimidine-5-carboxylic acid), which possesses a biologically important pyrimidine heterocycle bearing both one carboxyl group and two hydroxy groups, could [may?] display diverse coordination modes to metal ions only or simultaneously through the carboxyl oxygen atoms, and the hydroxy oxygen atoms as well as the pyrimidine nitrogen atoms. As part of our study on manganese biochemistry, we have investigated manganese complexation by uracil-5-carboxylic acid, during which some α,α'-diimine molecules strongly favouring bidentate chelation coordination, such as 2,2'-bipyridine and 2-(2-pyridyl)benzimidazole, are introduced to prevent formation of uracil-5-carboxylic acid bridging manganese polymeric complexes, and thus small molecular manganese compounds are expected. In the present work, reaction of disodium uracil-5-carboxylic acid with manganese acetate in the presence of 2-(2-pyridyl)benzimidazole affords pale yellow crystals of the title compound, (I), which represents a rare example of mononuclear six-coordinate transition metal complexes with mixed ligands including uracil-5-carboxylic acid, though several eight-coordinate lanthanide complexes with a similar mixed-ligand system have been reported recently (Xiong et al., 2008; Sun & Jin, 2004; Xing et al., 2008; Liu et al., 2009).

Compound (I) consists of one neutral [Mn(Huca)(Hpybim)₂] monomer [Hpybim is 2-(2-pyridyl)benzimidazole] and one solvate water molecule, all in general positions in the asymmetric unit. The Mn^II atom is surrounded by three bidentate chelating ligands, coordinated via four N atoms (N3, N4, N6 and N7) from a pair of neutral Hpybim ligands, and via two O atoms (O1 and O3) from one dianionic Huca^2- ligand, as shown in Fig. 1. The complex displays a severely distorted octahedral geometry around the Mn centre (Table 1), in which three N atoms (N4, N6 and N7) of the Hpybim ligands and one hydroxyl O atom (O3) of the Huca^2- ligand define a best octahedral equatorial plane [the mean out-of-plane deviation is 0.027 (5) Å, and the maximum out-of-plane deviation of 0.030 (7) Å is for atom N7], with the Mn atom displaced from the plane by 0.053 (5) Å. The pyridyl N atom (N3) of the Hpybim ligand and one carboxylate O atom (O1) of the Huca^2- ligand complete the distorted octahedron through coordination in the axial positions, with an O1—Mn1—N3 angle of 160.52 (9)°.

The high spin d⁵ Mn²⁺ ion favours the formation of the octahedral d²sp³ hybrid orbitals, with the cis-angles equal to 90°. The rigid chelating Hpybim ligand usually gives a narrow bite of less than 75° at a central Mn atom. The strong distortion deviating from an ideal Mn octahedron in (I), with the cis-angles ranging from 73.05 (10) to 105.77 (10)°, is obviously due to the double chelation of the two Hpybim ligands. The average Mn—N distance [2.28 (5) Å], as well as the N—Mn—N chelate angles [74.34 (11) and 73.05 (10)°] are comparable with those observed in the reported pybim-containing monomeric Mn^II complex [Mn(ptl)₂(Hpybim)] [ptl is p-toluate; 2.2274 (19) Å, and 74.45 (5)°, respectively; Ma et al., 2007] and, as expected, the Mn—N(imidazole) distances in (I) are shorter than the Mn—N(pyridine) ones, since the benzene group in the ortho position enhances the electron density on the imidazole N atom. Two Hpybim ligands are each reasonably planar, with maximum out-of plane deviations of 0.107 (2) and 0.146 (3) Å for atoms H14A and H27A, respectively. A very small dihedral angle of 4.2 (1)° is observed between the N3-containing Hpybim ligand plane and the chelate plane N3/N4/Mn1. However, the other Hpybim ligand makes a larger dihedral angle [16.9 (1)°] with its chelate plane N6/N7/Mn1.

The Huca^2- dianion in (I) acts as a bidentate ligand to chelate to the Mn atom through one carboxylate O atom and one hydroxy O atom, with a second carboxylate O atom, and the carbonyl O atom in the 2-positon, as well as two pyrimidine N atoms uncoordinated. Difference map plots unequivocally located the lone ring H atom as being bonded to N1, between the two oxygens O3 and O4. The position of the protonated N atom differs from that found in [Mn(Huca)(H₂O)₂]_n (Chen et al., 2007), where the H is clearly established as being bonded to the other ring N atom. The Mn—O distances (Table 1) and the O3—Mn—O1 chelate angle of 84.07 (9)° are comparable to those observed in [Mn(H₂uca)₂] (Maistralis et al., 1991) and [Mn(Huca)(H₂O)₂]_n (Chen et al., 2007). The Huca^2- ligand is also reasonably planar, with a maximum out-of plane deviation of 0.101 (5) Å for atom O4. The ligand plane folds with the chelate plane O1/O3/Mn1, at an angle of 16.0 (1)°.

As shown in Fig. 2, with details in Table 2, extensive intermolecular hydrogen bonding produces a three-dimensional hydrogen-bonded framework. The uncoordinated imidazole N8—H8 of the Hpybim ligand donates the H atom to the carboxyl O1 atom of the molecule related by the inversion centre at (1/2, 1/2, 1/2) (see figure S1 in the Supplementary material). Similarly, the protonated N1—H1 moiety of the Huca^2- ligand donates the H1 atom to the uncoordinated carbonyl O4 atom of the molecule related by the inversion centre at (1/2, 1/2, 0) to yield a one-dimensional chain extending in the c direction (fig. S2 in the Supplementary material). The lattice water molecule (O5) connects to three [Mn(Huca)(Hpybim)₂] monomers (Table 2 and Fig. S3), to produce a three-dimensional hydrogen-bonded framework. There are, in addition, two types of partial π–π stacking interactions between inversion-related pybim ligands. The centroid-to-centroid separations are 3.705 (3) Å between the N3, C6–C10 rings at (x, y, z) and (-x, 1 - y, -z) and 3.797 (3) Å between the ring N6, C18–C22 at (x, y, z) and the ring C24–C29 at (1 - x, 1 - y, 1 - z).

Related literature

For related literature, see: Chen et al. (2007); Liu et al. (2009); Ma et al. (2007); Sun & Jin (2004); Weighardt (1989); Xing et al. (2008).

S2. Experimental

To a hot water–dimethylformamide (15 ml, ca 2/1) solution containing uracil-5-carboxylic acid (0.5 mmol), sodium hydroxide (1.0 mmol) and 2-(2-pyridyl)benzimidazole (1.0 mmol), solid manganese acetate tetrahydrate (0.5 mmol) was added in portions, with continuous stirring. The mixture was refluxed for 30 min and then filtered to remove the precipitate. The light yellow filtrate was allowed to stand undisturbed for 1 month or so at room temperature, during which time pale yellow crystals of (I) suitable for X-ray diffraction analysis were deposited in ca 30% yield. Analysis calculated for C₂₉H₂₂MnN₈O₅: C 56.41, H 3.59, N 18.15%; found C 56.50, H 3.51, N 18.24%. FT–IR (KBr, cm^–1): 3467 (vs, br.), 2022(w), 1622(vs), 1538(m), 1455(w), 1441(w), 1385(s), 1320(w), 1300(s), 1231(w), 1208(w), 1183(w), 1150(w),1050(w), 994(w), 976(w), 898(w), 849(w), 811(m), 751(s), 647(s), 582(w), 501(m), 431(w), 406(w).

S3. Refinement

The aromatic H atoms were placed in calculated positions, with C—H distances of 0.93 Å and N—H distances of 0.86 Å, and treated as riding atoms [U_iso(H) = 1.2U_eq(C or N)]. The locations of the water H atoms were not well defined in difference maps; the O—H distances were normalized at 0.85 Å then allowed for as riding atoms with U_iso(H) = 1.5U_eq(O)].

Computing details

Data collection: CrystalClear (Rigaku/MSC, 2004); cell refinement: CrystalClear (Rigaku/MSC, 2004); data reduction: CrystalClear (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXL97 (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. A view of the molecule of (I), showing the atom-labelling scheme and 20% probability displacement ellipsoids. H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A packing diagram for (I), showing part of the two-dimensional hydrogen-bonded network derived from the crosslinkage of the one-dimensional chains hydrogen-bonded via O5—H5A···O2 and O5—H5B···O4 hydrogen bonds. Atoms labelled with a plus sign (+) are at the symmetry position (x, -y + 3/2, z + 1/2).

(6-Oxido-2-oxo-1,2-dihydropyrimidine-5-carboxylato- κ²O⁵,O⁶)bis[2-(2-pyridyl)-1H-benzimidazole- κ²N²,N³)manganese(II) monohydrate

Crystal data

[Mn(C5H2N2O4)(C12H9N3)2]·H2O	F(000) = 1268
Mr = 617.49	Dx = 1.508 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P2ybc	Cell parameters from 6364 reflections
a = 10.915 (6) Å	θ = 2.5–27.5°
b = 15.42 (1) Å	µ = 0.54 mm^−1
c = 17.972 (12) Å	T = 293 K
β = 115.945 (2)°	Tiny block, yellow
V = 2720 (3) Å^3	0.20 × 0.12 × 0.05 mm
Z = 4

Data collection

Rigaku MERCURY CCD diffractometer	6139 independent reflections
Radiation source: fine-focus sealed tube	4436 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.049
ϕ and ω scans	θmax = 27.5°, θmin = 2.5°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −12→14
Tmin = 0.910, Tmax = 0.981	k = −19→17
20068 measured reflections	l = −23→22

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.182	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0851P)^2 + 0.6684P] where P = (Fo^2 + 2Fc^2)/3
6139 reflections	(Δ/σ)max < 0.001
388 parameters	Δρmax = 0.53 e Å^−3
0 restraints	Δρmin = −0.32 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	0.33627 (5)	0.52565 (3)	0.27082 (3)	0.04716 (18)
N1	0.5162 (3)	0.55119 (17)	0.10162 (15)	0.0487 (6)
H1	0.4629	0.5148	0.0658	0.058*
N2	0.6961 (3)	0.6526 (2)	0.13721 (19)	0.0650 (8)
N3	0.1345 (3)	0.47808 (18)	0.16395 (17)	0.0566 (7)
N4	0.2072 (3)	0.64258 (17)	0.22493 (16)	0.0530 (6)
N5	0.0023 (3)	0.7003 (2)	0.14407 (19)	0.0690 (8)
H5	−0.0801	0.7042	0.1062	0.083*
N6	0.4455 (3)	0.40145 (18)	0.34349 (16)	0.0530 (6)
N7	0.2682 (3)	0.50619 (18)	0.37145 (16)	0.0496 (6)
N8	0.3265 (3)	0.45442 (17)	0.49928 (16)	0.0528 (6)
H8A	0.3675	0.4240	0.5434	0.063*
O1	0.5187 (2)	0.60047 (16)	0.33798 (13)	0.0577 (6)
O2	0.6852 (3)	0.6947 (2)	0.35855 (17)	0.0879 (9)
O3	0.4162 (2)	0.51072 (16)	0.18224 (14)	0.0601 (6)
O4	0.5996 (3)	0.58793 (17)	0.01004 (14)	0.0655 (7)
O5	0.7647 (3)	0.7596 (2)	0.5107 (2)	0.1187 (14)
H5A	0.7576	0.7499	0.4622	0.178*
H5B	0.7082	0.7987	0.5091	0.178*
C1	0.5960 (3)	0.6188 (2)	0.23259 (18)	0.0485 (7)
C2	0.5059 (3)	0.5582 (2)	0.17522 (18)	0.0469 (7)
C3	0.6052 (3)	0.5978 (2)	0.08043 (19)	0.0516 (7)
C4	0.6866 (4)	0.6603 (2)	0.2088 (2)	0.0626 (9)
H4	0.7483	0.6980	0.2475	0.075*
C5	0.6010 (3)	0.6401 (2)	0.31423 (19)	0.0536 (8)
C6	0.1021 (4)	0.3968 (3)	0.1321 (3)	0.0719 (10)
H6	0.1668	0.3532	0.1547	0.086*
C7	−0.0219 (5)	0.3759 (3)	0.0682 (3)	0.0834 (12)
H7	−0.0396	0.3195	0.0479	0.100*
C8	−0.1199 (4)	0.4397 (3)	0.0345 (3)	0.0800 (12)
H8	−0.2051	0.4268	−0.0079	0.096*
C9	−0.0883 (4)	0.5237 (3)	0.0651 (2)	0.0661 (10)
H9	−0.1517	0.5681	0.0430	0.079*
C10	0.0384 (4)	0.5402 (2)	0.1289 (2)	0.0556 (8)
C11	0.0816 (4)	0.6276 (2)	0.16471 (19)	0.0542 (8)
C12	0.0788 (4)	0.7666 (2)	0.1954 (2)	0.0658 (9)
C13	0.0492 (5)	0.8534 (3)	0.2024 (3)	0.0876 (13)
H13	−0.0345	0.8778	0.1680	0.105*
C14	0.1513 (6)	0.9011 (3)	0.2633 (3)	0.0966 (15)
H14	0.1349	0.9589	0.2708	0.116*
C15	0.2785 (6)	0.8651 (3)	0.3141 (3)	0.0875 (13)
H15	0.3438	0.8998	0.3543	0.105*
C16	0.3100 (4)	0.7800 (2)	0.3066 (2)	0.0686 (10)
H16	0.3954	0.7571	0.3400	0.082*
C17	0.2075 (4)	0.7294 (2)	0.2461 (2)	0.0573 (8)
C18	0.5288 (4)	0.3489 (2)	0.3268 (2)	0.0640 (9)
H18	0.5328	0.3554	0.2764	0.077*
C19	0.6087 (4)	0.2858 (2)	0.3809 (3)	0.0693 (10)
H19	0.6637	0.2501	0.3667	0.083*
C20	0.6055 (4)	0.2763 (2)	0.4571 (3)	0.0679 (10)
H20	0.6590	0.2349	0.4950	0.082*
C21	0.5198 (3)	0.3309 (2)	0.4748 (2)	0.0564 (8)
H21	0.5155	0.3266	0.5252	0.068*
C22	0.4419 (3)	0.3911 (2)	0.41739 (19)	0.0487 (7)
C23	0.3470 (3)	0.4508 (2)	0.42997 (18)	0.0460 (7)
C24	0.2265 (3)	0.5168 (2)	0.4853 (2)	0.0512 (7)
C25	0.1657 (4)	0.5470 (2)	0.5346 (2)	0.0632 (9)
H25	0.1930	0.5270	0.5884	0.076*
C26	0.0633 (4)	0.6079 (3)	0.4997 (3)	0.0716 (11)
H26	0.0210	0.6298	0.5308	0.086*
C27	0.0221 (4)	0.6369 (2)	0.4188 (3)	0.0668 (10)
H27	−0.0492	0.6765	0.3968	0.080*
C28	0.0837 (3)	0.6089 (2)	0.3702 (2)	0.0613 (9)
H28	0.0564	0.6298	0.3167	0.074*
C29	0.1889 (3)	0.5479 (2)	0.4048 (2)	0.0505 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0514 (3)	0.0516 (3)	0.0393 (3)	0.0031 (2)	0.0206 (2)	0.00512 (19)
N1	0.0529 (15)	0.0514 (14)	0.0414 (13)	−0.0031 (12)	0.0202 (12)	−0.0006 (11)
N2	0.0694 (19)	0.070 (2)	0.0612 (17)	−0.0199 (16)	0.0342 (16)	−0.0124 (15)
N3	0.0664 (18)	0.0521 (16)	0.0501 (15)	0.0018 (14)	0.0244 (14)	0.0033 (12)
N4	0.0577 (16)	0.0482 (15)	0.0507 (15)	0.0024 (13)	0.0215 (13)	0.0053 (12)
N5	0.0681 (19)	0.0623 (19)	0.0617 (18)	0.0189 (16)	0.0147 (15)	0.0031 (15)
N6	0.0573 (16)	0.0520 (15)	0.0525 (15)	0.0020 (13)	0.0268 (13)	0.0004 (12)
N7	0.0505 (15)	0.0550 (15)	0.0447 (14)	0.0029 (12)	0.0221 (12)	0.0061 (12)
N8	0.0615 (17)	0.0535 (15)	0.0446 (14)	0.0016 (13)	0.0241 (13)	0.0033 (12)
O1	0.0618 (14)	0.0696 (15)	0.0399 (11)	0.0032 (12)	0.0204 (10)	−0.0005 (10)
O2	0.0781 (18)	0.116 (2)	0.0685 (17)	−0.0293 (18)	0.0307 (15)	−0.0404 (17)
O3	0.0700 (15)	0.0691 (15)	0.0525 (13)	−0.0168 (12)	0.0372 (13)	−0.0104 (11)
O4	0.0782 (17)	0.0738 (16)	0.0537 (13)	−0.0177 (13)	0.0374 (13)	−0.0062 (12)
O5	0.081 (2)	0.147 (3)	0.115 (3)	−0.006 (2)	0.0315 (19)	−0.080 (3)
C1	0.0465 (16)	0.0537 (18)	0.0437 (16)	0.0049 (14)	0.0182 (14)	0.0000 (13)
C2	0.0514 (17)	0.0476 (16)	0.0432 (15)	0.0038 (14)	0.0220 (14)	0.0023 (13)
C3	0.0577 (19)	0.0516 (18)	0.0479 (17)	0.0019 (15)	0.0253 (15)	0.0021 (14)
C4	0.059 (2)	0.069 (2)	0.061 (2)	−0.0117 (17)	0.0269 (18)	−0.0136 (18)
C5	0.0477 (17)	0.065 (2)	0.0437 (16)	0.0053 (16)	0.0164 (14)	−0.0046 (15)
C6	0.089 (3)	0.053 (2)	0.069 (2)	−0.001 (2)	0.029 (2)	0.0014 (18)
C7	0.094 (3)	0.061 (2)	0.080 (3)	−0.017 (2)	0.025 (3)	−0.012 (2)
C8	0.067 (2)	0.084 (3)	0.074 (3)	−0.009 (2)	0.017 (2)	−0.008 (2)
C9	0.060 (2)	0.071 (2)	0.063 (2)	0.0006 (18)	0.0232 (19)	−0.0010 (18)
C10	0.0565 (19)	0.058 (2)	0.0500 (18)	0.0011 (16)	0.0216 (16)	0.0021 (15)
C11	0.062 (2)	0.0535 (19)	0.0455 (16)	0.0090 (16)	0.0221 (16)	0.0038 (14)
C12	0.086 (3)	0.054 (2)	0.058 (2)	0.0078 (19)	0.032 (2)	0.0022 (17)
C13	0.120 (4)	0.063 (3)	0.083 (3)	0.029 (3)	0.047 (3)	0.007 (2)
C14	0.148 (5)	0.055 (2)	0.102 (4)	0.007 (3)	0.069 (4)	−0.007 (2)
C15	0.121 (4)	0.060 (2)	0.095 (3)	−0.021 (3)	0.059 (3)	−0.017 (2)
C16	0.085 (3)	0.056 (2)	0.070 (2)	−0.0124 (19)	0.039 (2)	−0.0054 (18)
C17	0.072 (2)	0.0508 (19)	0.0557 (19)	−0.0002 (17)	0.0338 (18)	0.0042 (15)
C18	0.069 (2)	0.065 (2)	0.069 (2)	0.0024 (19)	0.039 (2)	−0.0061 (18)
C19	0.063 (2)	0.057 (2)	0.092 (3)	0.0047 (18)	0.038 (2)	−0.006 (2)
C20	0.065 (2)	0.050 (2)	0.084 (3)	0.0055 (17)	0.027 (2)	0.0067 (19)
C21	0.0559 (19)	0.0540 (19)	0.0567 (18)	−0.0010 (16)	0.0224 (16)	0.0034 (15)
C22	0.0524 (17)	0.0481 (17)	0.0463 (16)	−0.0039 (14)	0.0222 (14)	−0.0020 (13)
C23	0.0467 (16)	0.0502 (17)	0.0419 (15)	−0.0045 (13)	0.0200 (13)	−0.0012 (13)
C24	0.0544 (18)	0.0512 (18)	0.0528 (18)	−0.0065 (15)	0.0279 (16)	−0.0038 (14)
C25	0.073 (2)	0.064 (2)	0.066 (2)	−0.0114 (18)	0.043 (2)	−0.0111 (17)
C26	0.077 (2)	0.068 (2)	0.088 (3)	−0.006 (2)	0.053 (2)	−0.017 (2)
C27	0.063 (2)	0.060 (2)	0.085 (3)	0.0041 (17)	0.039 (2)	−0.004 (2)
C28	0.060 (2)	0.061 (2)	0.064 (2)	0.0068 (17)	0.0279 (18)	0.0077 (17)
C29	0.0515 (18)	0.0511 (18)	0.0530 (18)	−0.0006 (14)	0.0268 (15)	0.0006 (14)

Geometric parameters (Å, º)

Mn1—O3	2.136 (2)	C7—C8	1.383 (6)
Mn1—O1	2.156 (3)	C7—H7	0.9300
Mn1—N4	2.213 (3)	C8—C9	1.390 (6)
Mn1—N7	2.256 (3)	C8—H8	0.9300
Mn1—N3	2.319 (3)	C9—C10	1.380 (5)
Mn1—N6	2.331 (3)	C9—H9	0.9300
N1—C2	1.380 (4)	C10—C11	1.480 (5)
N1—C3	1.389 (4)	C12—C13	1.395 (5)
N1—H1	0.8600	C12—C17	1.419 (5)
N2—C4	1.341 (5)	C13—C14	1.384 (7)
N2—C3	1.361 (4)	C13—H13	0.9300
N3—C10	1.354 (4)	C14—C15	1.400 (7)
N3—C6	1.358 (5)	C14—H14	0.9300
N4—C11	1.343 (4)	C15—C16	1.378 (6)
N4—C17	1.392 (4)	C15—H15	0.9300
N5—C11	1.365 (4)	C16—C17	1.407 (5)
N5—C12	1.385 (5)	C16—H16	0.9300
N5—H5	0.8600	C18—C19	1.384 (5)
N6—C18	1.346 (4)	C18—H18	0.9300
N6—C22	1.355 (4)	C19—C20	1.392 (5)
N7—C23	1.336 (4)	C19—H19	0.9300
N7—C29	1.405 (4)	C20—C21	1.395 (5)
N8—C23	1.360 (4)	C20—H20	0.9300
N8—C24	1.392 (4)	C21—C22	1.371 (4)
N8—H8A	0.8600	C21—H21	0.9300
O1—C5	1.303 (4)	C22—C23	1.475 (4)
O2—C5	1.244 (4)	C24—C25	1.399 (5)
O3—C2	1.272 (4)	C24—C29	1.404 (5)
O4—C3	1.249 (4)	C25—C26	1.383 (6)
O5—H5A	0.8537	C25—H25	0.9300
O5—H5B	0.8539	C26—C27	1.394 (6)
C1—C4	1.393 (5)	C26—H26	0.9300
C1—C2	1.419 (4)	C27—C28	1.385 (5)
C1—C5	1.481 (4)	C27—H27	0.9300
C4—H4	0.9300	C28—C29	1.403 (5)
C6—C7	1.377 (6)	C28—H28	0.9300
C6—H6	0.9300
O3—Mn1—O1	84.07 (9)	C10—C9—C8	119.1 (4)
O3—Mn1—N4	102.18 (11)	C10—C9—H9	120.5
O1—Mn1—N4	93.10 (10)	C8—C9—H9	120.5
O3—Mn1—N7	165.53 (11)	N3—C10—C9	123.1 (3)
O1—Mn1—N7	99.77 (10)	N3—C10—C11	114.0 (3)
N4—Mn1—N7	91.59 (10)	C9—C10—C11	122.8 (3)
O3—Mn1—N3	84.16 (11)	N4—C11—N5	112.4 (3)
O1—Mn1—N3	160.52 (9)	N4—C11—C10	121.7 (3)
N4—Mn1—N3	74.34 (11)	N5—C11—C10	125.9 (3)
N7—Mn1—N3	95.47 (11)	N5—C12—C13	132.2 (4)
O3—Mn1—N6	93.08 (10)	N5—C12—C17	105.6 (3)
O1—Mn1—N6	90.31 (10)	C13—C12—C17	122.2 (4)
N4—Mn1—N6	164.63 (9)	C14—C13—C12	116.3 (4)
N7—Mn1—N6	73.05 (10)	C14—C13—H13	121.8
N3—Mn1—N6	105.77 (10)	C12—C13—H13	121.8
C2—N1—C3	125.6 (3)	C13—C14—C15	122.1 (4)
C2—N1—H1	117.2	C13—C14—H14	119.0
C3—N1—H1	117.2	C15—C14—H14	119.0
C4—N2—C3	115.9 (3)	C16—C15—C14	122.2 (4)
C10—N3—C6	116.8 (3)	C16—C15—H15	118.9
C10—N3—Mn1	115.0 (2)	C14—C15—H15	118.9
C6—N3—Mn1	128.2 (3)	C15—C16—C17	117.1 (4)
C11—N4—C17	105.3 (3)	C15—C16—H16	121.5
C11—N4—Mn1	114.8 (2)	C17—C16—H16	121.5
C17—N4—Mn1	139.2 (2)	N4—C17—C16	130.6 (3)
C11—N5—C12	107.4 (3)	N4—C17—C12	109.3 (3)
C11—N5—H5	126.3	C16—C17—C12	120.1 (3)
C12—N5—H5	126.3	N6—C18—C19	123.1 (3)
C18—N6—C22	117.4 (3)	N6—C18—H18	118.5
C18—N6—Mn1	126.8 (2)	C19—C18—H18	118.5
C22—N6—Mn1	114.8 (2)	C18—C19—C20	119.1 (3)
C23—N7—C29	105.1 (2)	C18—C19—H19	120.4
C23—N7—Mn1	113.07 (19)	C20—C19—H19	120.4
C29—N7—Mn1	139.6 (2)	C19—C20—C21	117.9 (3)
C23—N8—C24	107.0 (3)	C19—C20—H20	121.0
C23—N8—H8A	126.5	C21—C20—H20	121.0
C24—N8—H8A	126.5	C22—C21—C20	119.6 (3)
C5—O1—Mn1	131.9 (2)	C22—C21—H21	120.2
C2—O3—Mn1	126.5 (2)	C20—C21—H21	120.2
H5A—O5—H5B	110.3	N6—C22—C21	122.9 (3)
C4—C1—C2	116.0 (3)	N6—C22—C23	113.6 (3)
C4—C1—C5	118.5 (3)	C21—C22—C23	123.5 (3)
C2—C1—C5	125.4 (3)	N7—C23—N8	112.8 (3)
O3—C2—N1	116.0 (3)	N7—C23—C22	122.1 (3)
O3—C2—C1	128.7 (3)	N8—C23—C22	125.0 (3)
N1—C2—C1	115.3 (3)	N8—C24—C25	131.8 (3)
O4—C3—N2	122.1 (3)	N8—C24—C29	106.0 (3)
O4—C3—N1	119.0 (3)	C25—C24—C29	122.2 (3)
N2—C3—N1	118.9 (3)	C26—C25—C24	116.9 (4)
N2—C4—C1	128.1 (3)	C26—C25—H25	121.6
N2—C4—H4	116.0	C24—C25—H25	121.6
C1—C4—H4	116.0	C25—C26—C27	121.3 (3)
O2—C5—O1	122.0 (3)	C25—C26—H26	119.4
O2—C5—C1	118.8 (3)	C27—C26—H26	119.4
O1—C5—C1	119.2 (3)	C28—C27—C26	122.2 (4)
N3—C6—C7	123.2 (4)	C28—C27—H27	118.9
N3—C6—H6	118.4	C26—C27—H27	118.9
C7—C6—H6	118.4	C27—C28—C29	117.3 (3)
C6—C7—C8	119.3 (4)	C27—C28—H28	121.3
C6—C7—H7	120.4	C29—C28—H28	121.3
C8—C7—H7	120.4	C28—C29—C24	120.0 (3)
C7—C8—C9	118.6 (4)	C28—C29—N7	130.9 (3)
C7—C8—H8	120.7	C24—C29—N7	109.0 (3)
C9—C8—H8	120.7
O3—Mn1—N3—C10	−106.6 (2)	C6—C7—C8—C9	1.6 (7)
O1—Mn1—N3—C10	−53.6 (4)	C7—C8—C9—C10	−1.1 (6)
N4—Mn1—N3—C10	−2.2 (2)	C6—N3—C10—C9	1.4 (5)
N7—Mn1—N3—C10	87.9 (2)	Mn1—N3—C10—C9	−179.3 (3)
N6—Mn1—N3—C10	161.8 (2)	C6—N3—C10—C11	−178.3 (3)
O3—Mn1—N3—C6	72.6 (3)	Mn1—N3—C10—C11	1.0 (4)
O1—Mn1—N3—C6	125.6 (3)	C8—C9—C10—N3	−0.5 (6)
N4—Mn1—N3—C6	177.0 (3)	C8—C9—C10—C11	179.2 (3)
N7—Mn1—N3—C6	−92.9 (3)	C17—N4—C11—N5	1.9 (4)
N6—Mn1—N3—C6	−19.0 (3)	Mn1—N4—C11—N5	174.3 (2)
O3—Mn1—N4—C11	83.4 (2)	C17—N4—C11—C10	−176.4 (3)
O1—Mn1—N4—C11	168.0 (2)	Mn1—N4—C11—C10	−3.9 (4)
N7—Mn1—N4—C11	−92.1 (2)	C12—N5—C11—N4	−1.8 (4)
N3—Mn1—N4—C11	3.1 (2)	C12—N5—C11—C10	176.4 (3)
N6—Mn1—N4—C11	−89.4 (4)	N3—C10—C11—N4	1.9 (5)
O3—Mn1—N4—C17	−107.8 (3)	C9—C10—C11—N4	−177.8 (3)
O1—Mn1—N4—C17	−23.2 (3)	N3—C10—C11—N5	−176.1 (3)
N7—Mn1—N4—C17	76.7 (3)	C9—C10—C11—N5	4.3 (6)
N3—Mn1—N4—C17	171.9 (3)	C11—N5—C12—C13	−179.1 (4)
N6—Mn1—N4—C17	79.4 (5)	C11—N5—C12—C17	0.9 (4)
O3—Mn1—N6—C18	1.6 (3)	N5—C12—C13—C14	178.3 (4)
O1—Mn1—N6—C18	−82.5 (3)	C17—C12—C13—C14	−1.7 (6)
N4—Mn1—N6—C18	174.6 (4)	C12—C13—C14—C15	1.3 (7)
N7—Mn1—N6—C18	177.4 (3)	C13—C14—C15—C16	0.1 (7)
N3—Mn1—N6—C18	86.4 (3)	C14—C15—C16—C17	−1.1 (6)
O3—Mn1—N6—C22	169.5 (2)	C11—N4—C17—C16	178.3 (3)
O1—Mn1—N6—C22	85.4 (2)	Mn1—N4—C17—C16	8.8 (6)
N4—Mn1—N6—C22	−17.5 (5)	C11—N4—C17—C12	−1.2 (4)
N7—Mn1—N6—C22	−14.7 (2)	Mn1—N4—C17—C12	−170.7 (3)
N3—Mn1—N6—C22	−105.7 (2)	C15—C16—C17—N4	−178.7 (4)
O3—Mn1—N7—C23	32.6 (5)	C15—C16—C17—C12	0.8 (5)
O1—Mn1—N7—C23	−71.8 (2)	N5—C12—C17—N4	0.2 (4)
N4—Mn1—N7—C23	−165.2 (2)	C13—C12—C17—N4	−179.8 (3)
N3—Mn1—N7—C23	120.4 (2)	N5—C12—C17—C16	−179.3 (3)
N6—Mn1—N7—C23	15.5 (2)	C13—C12—C17—C16	0.7 (6)
O3—Mn1—N7—C29	−167.7 (3)	C22—N6—C18—C19	0.4 (5)
O1—Mn1—N7—C29	88.0 (3)	Mn1—N6—C18—C19	168.0 (3)
N4—Mn1—N7—C29	−5.4 (3)	N6—C18—C19—C20	−1.1 (6)
N3—Mn1—N7—C29	−79.8 (3)	C18—C19—C20—C21	0.8 (6)
N6—Mn1—N7—C29	175.3 (3)	C19—C20—C21—C22	0.3 (5)
O3—Mn1—O1—C5	21.4 (3)	C18—N6—C22—C21	0.8 (5)
N4—Mn1—O1—C5	−80.5 (3)	Mn1—N6—C22—C21	−168.3 (2)
N7—Mn1—O1—C5	−172.6 (3)	C18—N6—C22—C23	−179.5 (3)
N3—Mn1—O1—C5	−31.6 (5)	Mn1—N6—C22—C23	11.4 (3)
N6—Mn1—O1—C5	114.5 (3)	C20—C21—C22—N6	−1.1 (5)
O1—Mn1—O3—C2	−19.6 (3)	C20—C21—C22—C23	179.2 (3)
N4—Mn1—O3—C2	72.3 (3)	C29—N7—C23—N8	−1.1 (4)
N7—Mn1—O3—C2	−125.9 (4)	Mn1—N7—C23—N8	165.5 (2)
N3—Mn1—O3—C2	144.8 (3)	C29—N7—C23—C22	177.2 (3)
N6—Mn1—O3—C2	−109.6 (3)	Mn1—N7—C23—C22	−16.3 (4)
Mn1—O3—C2—N1	−163.6 (2)	C24—N8—C23—N7	0.2 (4)
Mn1—O3—C2—C1	15.3 (5)	C24—N8—C23—C22	−178.1 (3)
C3—N1—C2—O3	178.9 (3)	N6—C22—C23—N7	3.1 (4)
C3—N1—C2—C1	−0.2 (4)	C21—C22—C23—N7	−177.1 (3)
C4—C1—C2—O3	178.4 (3)	N6—C22—C23—N8	−178.8 (3)
C5—C1—C2—O3	−1.2 (5)	C21—C22—C23—N8	0.9 (5)
C4—C1—C2—N1	−2.7 (4)	C23—N8—C24—C25	179.7 (3)
C5—C1—C2—N1	177.7 (3)	C23—N8—C24—C29	0.9 (3)
C4—N2—C3—O4	176.8 (3)	N8—C24—C25—C26	−177.1 (3)
C4—N2—C3—N1	−3.5 (5)	C29—C24—C25—C26	1.6 (5)
C2—N1—C3—O4	−176.8 (3)	C24—C25—C26—C27	0.6 (6)
C2—N1—C3—N2	3.5 (5)	C25—C26—C27—C28	−2.1 (6)
C3—N2—C4—C1	0.5 (6)	C26—C27—C28—C29	1.3 (6)
C2—C1—C4—N2	2.7 (6)	C27—C28—C29—C24	0.9 (5)
C5—C1—C4—N2	−177.6 (4)	C27—C28—C29—N7	178.6 (3)
Mn1—O1—C5—O2	164.8 (3)	N8—C24—C29—C28	176.6 (3)
Mn1—O1—C5—C1	−16.1 (5)	C25—C24—C29—C28	−2.4 (5)
C4—C1—C5—O2	0.5 (5)	N8—C24—C29—N7	−1.6 (4)
C2—C1—C5—O2	−179.9 (3)	C25—C24—C29—N7	179.4 (3)
C4—C1—C5—O1	−178.6 (3)	C23—N7—C29—C28	−176.3 (3)
C2—C1—C5—O1	1.0 (5)	Mn1—N7—C29—C28	23.0 (6)
C10—N3—C6—C7	−0.8 (6)	C23—N7—C29—C24	1.6 (4)
Mn1—N3—C6—C7	180.0 (3)	Mn1—N7—C29—C24	−159.1 (3)
N3—C6—C7—C8	−0.6 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4^i	0.86	2.00	2.830 (4)	160
N5—H5···O5^ii	0.86	1.89	2.722 (4)	162
N8—H8A···O1^iii	0.86	1.98	2.793 (4)	158
O5—H5A···O2	0.85	1.88	2.675 (4)	154
O5—H5B···O4^iv	0.85	2.12	2.959 (4)	169

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