Hydroxonium hydrate tris­(2,4,6-tri­amino-1,3,5-triazin-1-ium) bis­[bis­(pyri­dine-2,6-dicarboxyl­ato)manganate(II/III)] hydroxide pyridine-2,6-di­carboxylic acid solvate penta­hydrate

For charge balance in the title compound, (H₅O₂)(C₃H₇N₆)₃[Mn(C₇H₃NO₄)₂]₂(OH)·C₇H₅NO₄·5H₂O, it is assumed that the metal atom site is disordered Mn^II/Mn^III, probably due to partial air oxidation of the starting Mn^II species. The formula unit of the complex contains a hydroxonium hydrate cation, H₅O₂⁺, also known as the Zundel cation, with twofold symmetry. The O...O [2.445 (10) Å] and O...H distances [1.24 (2) Å] in the H₅O₂⁺ cation indicate a strong hydrogen bond. In addition, there is a hydroxide ion that is disordered with respect to a twofold rotation axis. One of the melaminium groups and the pyridine-2,6-dicarboxyl­ate (pydc) ligand also reside on crystallographic twofold axes. The coordination environment of the Mn ion is distorted octa­hedral. Three inter­molecular C=O...π inter­actions are observed, with distances of 3.536 (4), 3.262 (4) and 3.750 (4) Å between carboxyl­ate C=O groups and the centroids of the aromatic rings of pydc and melaminium. There are numerous O—H...O, O—H...N, N—H...O, N—H...N and C—H...O hydrogen bonds. Most of the components of the structure are organized into one plane.

S1. Comment

Melamine, used in the synthesis of plastics, has recently been implicated in the food industry as an impurity in powdered milk and pet food products and as a causative agent in the production of kidney stones in infants and in pets. With oxalic acid, one of the main constituents of kidney fluids, a proton-transfer salt of [melaminiumH₂][C₂O₂H]₂ is formed (Zhang et al., 2005). Melamine is also known to form melaminiumH₂²⁺ salts with trifluoroacetic acid (Perpétuo & Janczak, 2006) and other strong acids. With somewhat weaker acids, such as pyridine-2,6-dicarboxylic acid (pydcH₂) both the mono- and di-protonated species have been described (Sharif et al., 2006). It is pertinent to study these proton-transfer salts in combination with metal ions in order to model the biological species that may exist in kidney disease. The crystal structures of metal complexes involving Cd^II (Aghabozorg, Aghajani & Sharif, 2006), Zn^II (Aghajani et al., 2006), Bi^III (Sharif, Aghabozorg & Moghimi, 2007), Pb^II (Sharif et al., 2006), Co^II (Aghabozorg et al., 2008) and Ni^II (Sharif, Aghajani & Aghabozorg, 2007) are known. In the asymmetric unit of the title compound, (I), one-and-a-half molecules of melamine are each mono-protonated and crystallize with bis(pyridine-2,6-dicarboxylato)manganate(II/III), a neutral molecule of pydcH₂, one-half of a H₅O₂⁺ cation, one-half of a hydroxide anion and two-and-a-half molecules of water. Although it is beyond the scope of this report to compare all the metal complexes, it is significant that the synthesis of these complexes can be accomplished by a one-pot method, mixing acid, base and simple metal salt to form crystalline products. We were surprised to find that the product material in this case contains the Zundel cation, H₅O₂⁺, and that the Mn is apparently in a disordered mixed-valent (II/III) state. Both Mn^II and Mn^III complexes of salts of the bis complex, Mn(pydc)₂, have been described previously, for example, with Mn^II (MacDonald et al., 2004; Aghabozorg, Ghasemikhah et al., 2006) and with Mn^III (Limburg et al., 1997).

Compound (I) is depicted in Fig. 1. Mn is hexacoordinated by two N atoms (N1 and N2) and four O atoms (O1, O3, O5 and O7) from carboxylate groups of two (pydc)^2- groups in a distorted octahedral arrangement. The dihedral angle between these two coordinated pydc groups is 88.63 (5)°, which shows that the ligands are almost perpendicular to each other. For charge balance, it was assumed that the metal atom site is disordered Mn^II/Mn^III, probably due to partial air oxidation of Mn^II. However, this assumption has not been confirmed by any non-crystallographic methods. No difference map peaks satisfied the alternative models, i.e. that the melaminiumH⁺ was melaminiumH₂²⁺ or that one of the coordinated carboxylate groups or water molecules was protonated.

The Mn—N and Mn—O distances (Table 1) are longer than those seen in related Mn^III complexes, which average 2.020 (8) and 2.01 (13) Å, respectively (Limburg et al., 1997; Huang et al., 2004). However, they are also shorter than the average of 34 observations [Cambridge Structural Database (CSD), Version?; Allen, 2002) for Mn^II in pydc coordination compounds, namely 2.22 (6) and 2.30 (7) Å for Mn—N and Mn—O, respectively (CSD refcodes BIPJER, EJAMEH, IHELAI, LOYYON, LOYYUT, MABNIN, MABNOT, NEQPEF, QARZEP, SAQQUX, XEGDIW, XENJEG, MIGZEI and XIMHAD).

The formula unit of the complex contains one hydroxonium hydrate H₅O₂⁺ cation that resides on a twofold rotation axis. One of the melaminiumH⁺ groups and the pydcH₂ also reside on crystallographic twofold axes. In addition, there is an OH^- (O15—H15) ion that is disordered with respect to a twofold rotation axis.

There are three notable C═O···π intermolecular interactions between C═ O groups and the centroids of the aromatic rings of pyridine-2,6-dicarboxylate and melaminiumH⁺ (Table 3). As shown in Fig. 2, the packing of the structure can be described by layers that contain almost all the consituent species. The main parts that are not in these layers are the perpendicular pydc^2- ligands. By reference to Fig. 1, the hydrogen bonding that leads to these layers can be envisioned. A notable grouping of two melaminiumH⁺ cations, water and pydcH₂ yields seven strong hydrogen bonds.

In pet food contamination studies involving dogs and cats (Filigenzi et al., 2008), melamine and its metabolites are present in kidney tissue. In consideration of the number of intermolecular interactions present in this and similar structures and the rich carboxylic acid environment in the kidneys, the pathology of melamine is not at all surprising.

Related literature

For related literature, see: Aghabozorg et al. (2008); Aghabozorg, Aghajani & Sharif (2006); Aghabozorg, Ghasemikhah, Soleimannejad, Ghadermazi & Attar Gharamaleki (2006); Aghajani et al. (2006); Allen (2002); Filigenzi et al. (2008); Huang et al. (2004); Limburg et al. (1997); MacDonald et al. (2004); Perpétuo & Janczak (2006); Sharif et al. (2006); Sharif, Aghabozorg & Moghimi (2007); Sharif, Aghajani & Aghabozorg (2007); Zhang et al. (2005).

S2. Experimental

The reaction between pyridine-2,6-dicarboxylic acid (pydcH₂) (100 mg, 1 mmol) in water (10 ml), 2,4,6-triamino-1,3,5-triazine (melamine) (110 mg, 1 mmol) in water (10 ml) and Mn(CH₃COO)₂ (72 mg, 0.5 mmol) in water (5 ml) at a 2:2:1 molar ratio gave pale-yellow needles after slow evaporation of the solvent at room temperature.

S3. Refinement

The C-bound and N-bound H atoms were positioned geometrically with C—H = 0.95 and N—H = 0.88 Å, and allowed to ride on their parent atoms with U_iso(H) = 1.2 U_eq(C). H atoms bonded to O were located in a difference Fourier map and allowed to refine with distance restraints of O—H = 0.84 (1) Å and H···H (in water) = 1.30 (2) Å, except for atom H12E, part of the H₅O₂⁺ cation, which resides on a twofold axis and was not restrained. This atom was freely refined but displays a large isotropic displacement parameter of 0.11 that causes an Alert A in checkCIF. We suggest that it is slightly disordered with respect to its position on the twofold axis. The H atom bonded to O15, part of the OH^- ion that is disordered with respect to the twofold axis, was located in a difference map and refined with a distance restraint of 0.86 (1) Å and U_iso = 1.2U_eq(O15).

Computing details

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. A view of the various constituents of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry codes: (i) -x, y, 3/2 - z, (ii) -x, y, 1/2 - z.]
	Fig. 2. A packing diagram for (I), viewed perpendicular to the [101] direction, showing the presence of perpendicular layers in the structure.

Hydroxonium hydrate tris(2,4,6-triamino-1,3,5-triazin-1-ium) bis[bis(pyridine-2,6-dicarboxylato)manganate(II/III)] hydroxide pyridine-2,6-dicarboxylic acid solvate pentahydrate

Crystal data

(H5O2)(C3H7N6)3[Mn(C7H3NO4)2]2(OH)·C7H5NO4·5H2O	F(000) = 3012
Mr = 1462.98	Dx = 1.669 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6275 reflections
a = 27.1406 (16) Å	θ = 2.8–31.8°
b = 23.1672 (13) Å	µ = 0.55 mm^−1
c = 9.7838 (6) Å	T = 90 K
β = 108.819 (3)°	Needle, pale yellow
V = 5822.9 (6) Å^3	0.55 × 0.18 × 0.08 mm
Z = 4

Data collection

Bruker SMART APEXII diffractometer	6671 independent reflections
Radiation source: fine-focus sealed tube	6153 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
Detector resolution: 8.3 pixels mm^-1	θmax = 27.5°, θmin = 2.7°
ω scans	h = −35→35
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −30→30
Tmin = 0.754, Tmax = 0.958	l = −12→12
32194 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)] = 0.078	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.189	H atoms treated by a mixture of independent and constrained refinement
S = 1.33	w = 1/[σ^2(Fo^2) + 92.6062P] where P = (Fo^2 + 2Fc^2)/3
6671 reflections	(Δ/σ)max < 0.001
484 parameters	Δρmax = 0.56 e Å^−3
11 restraints	Δρmin = −0.57 e Å^−3

Special details

Experimental. The IR spectrum of (I) contains at least 25 peaks in the region between 1610 and 1710 cm^-1 where water and hydroxonium hydrate stretching frequencies are found.

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	−0.15668 (3)	0.63547 (3)	0.56112 (8)	0.01248 (17)
O1	−0.09524 (16)	0.62982 (16)	0.4534 (5)	0.0293 (9)
O2	−0.0379 (2)	0.56998 (18)	0.4078 (7)	0.0513 (16)
O3	−0.21016 (13)	0.58718 (14)	0.6487 (4)	0.0163 (7)
O4	−0.24064 (14)	0.49904 (15)	0.6749 (4)	0.0204 (7)
O5	−0.21304 (13)	0.66806 (14)	0.3553 (4)	0.0172 (7)
O6	−0.25181 (14)	0.74622 (16)	0.2345 (4)	0.0199 (7)
O7	−0.10369 (13)	0.66055 (14)	0.7802 (4)	0.0175 (7)
O8	−0.07583 (13)	0.73355 (15)	0.9377 (4)	0.0172 (7)
N1	−0.14288 (16)	0.54536 (18)	0.5358 (4)	0.0160 (8)
N2	−0.16389 (15)	0.72795 (16)	0.5854 (4)	0.0117 (7)
C1	−0.0769 (3)	0.5800 (2)	0.4426 (8)	0.0329 (14)
C2	−0.1054 (2)	0.5293 (2)	0.4832 (7)	0.0255 (12)
C3	−0.0939 (2)	0.4721 (2)	0.4712 (8)	0.0332 (15)
H3	−0.0676	0.4611	0.4316	0.040*
C4	−0.1219 (2)	0.4307 (2)	0.5188 (7)	0.0265 (12)
H4	−0.1146	0.3909	0.5131	0.032*
C5	−0.1606 (2)	0.4480 (2)	0.5747 (6)	0.0199 (10)
H5	−0.1800	0.4204	0.6080	0.024*
C6	−0.17009 (18)	0.5065 (2)	0.5806 (5)	0.0160 (9)
C7	−0.21091 (18)	0.5325 (2)	0.6397 (5)	0.0133 (9)
C8	−0.22193 (18)	0.7215 (2)	0.3438 (5)	0.0154 (9)
C9	−0.19396 (17)	0.7587 (2)	0.4735 (5)	0.0138 (9)
C10	−0.19749 (18)	0.8186 (2)	0.4801 (6)	0.0180 (10)
H10	−0.2188	0.8400	0.4000	0.022*
C11	−0.16876 (19)	0.8461 (2)	0.6076 (6)	0.0180 (10)
H11	−0.1705	0.8869	0.6157	0.022*
C12	−0.13763 (18)	0.8138 (2)	0.7227 (5)	0.0158 (9)
H12	−0.1179	0.8320	0.8103	0.019*
C13	−0.13602 (18)	0.7541 (2)	0.7066 (5)	0.0137 (9)
C14	−0.10260 (17)	0.7129 (2)	0.8186 (5)	0.0128 (9)
N3	0.18329 (15)	0.80126 (16)	0.4822 (4)	0.0138 (8)
H3A	0.2005	0.7822	0.5609	0.019 (15)*
N4	0.16034 (16)	0.88993 (17)	0.3619 (4)	0.0150 (8)
N5	0.12517 (15)	0.80009 (17)	0.2460 (4)	0.0143 (8)
N6	0.21724 (16)	0.88635 (17)	0.5951 (4)	0.0163 (8)
H6A	0.2199	0.9242	0.5968	0.020*
H6B	0.2347	0.8660	0.6712	0.020*
N7	0.10282 (16)	0.88688 (18)	0.1318 (5)	0.0185 (9)
H7A	0.1046	0.9248	0.1289	0.022*
H7B	0.0828	0.8678	0.0566	0.022*
N8	0.15134 (16)	0.71480 (17)	0.3693 (5)	0.0168 (8)
H8A	0.1319	0.6952	0.2942	0.020*
H8B	0.1698	0.6965	0.4480	0.020*
C15	0.18722 (18)	0.86026 (19)	0.4790 (5)	0.0140 (9)
C16	0.13022 (18)	0.8586 (2)	0.2495 (5)	0.0146 (9)
C17	0.15280 (18)	0.7721 (2)	0.3639 (5)	0.0142 (9)
N9	0.02796 (15)	0.83044 (17)	−0.1269 (4)	0.0146 (8)
N10	0.0000	0.7433 (2)	−0.2500	0.0144 (11)
H10A	0.0000	0.7056	−0.2500	0.006 (17)*
N11	0.0000	0.9146 (2)	−0.2500	0.0177 (12)
H11B	0.0182	0.9341	−0.1699	0.021*
N12	0.05381 (17)	0.74296 (18)	−0.0139 (5)	0.0203 (9)
H12A	0.0724	0.7610	0.0651	0.024*
H12B	0.0530	0.7050	−0.0164	0.024*
C18	0.0000	0.8573 (3)	−0.2500	0.0143 (12)
C19	0.02721 (17)	0.7729 (2)	−0.1287 (5)	0.0144 (9)
O9	0.06440 (16)	0.98913 (16)	−0.0198 (4)	0.0287 (9)
O10	0.09882 (14)	1.07099 (15)	0.0856 (4)	0.0187 (7)
H10B	0.120 (3)	1.052 (4)	0.152 (8)	0.10 (4)*
N13	0.0000	1.0481 (2)	−0.2500	0.0164 (11)
C20	0.0000	1.1684 (3)	−0.2500	0.0155 (13)
H20	0.0000	1.2094	−0.2500	0.019*
C21	0.03155 (18)	1.1384 (2)	−0.1322 (5)	0.0163 (9)
H21	0.0533	1.1582	−0.0496	0.020*
C22	0.03059 (18)	1.0779 (2)	−0.1378 (5)	0.0151 (9)
C23	0.06589 (19)	1.0411 (2)	−0.0183 (5)	0.0159 (9)
O11	0.0000	0.5142 (2)	−0.2500	0.0339 (15)
H11C	0.016 (4)	0.493 (4)	−0.290 (11)	0.08 (3)*
O12	−0.0175 (2)	0.6622 (2)	0.1181 (5)	0.0454 (13)
H12C	−0.034 (3)	0.682 (3)	0.047 (5)	0.06 (3)*
H12D	0.001 (3)	0.640 (3)	0.086 (7)	0.05 (2)*
H12E	0.0000	0.669 (7)	0.2500	0.11 (6)*
O13	0.17175 (14)	1.00644 (15)	0.2652 (4)	0.0191 (7)
H13A	0.163 (3)	0.9738 (15)	0.289 (9)	0.07 (3)*
H13B	0.196 (2)	0.998 (3)	0.232 (9)	0.06 (3)*
O14	0.21524 (15)	0.65307 (16)	0.6113 (4)	0.0211 (8)
H14A	0.228 (2)	0.6783 (16)	0.674 (4)	0.015 (14)*
H14B	0.209 (3)	0.6261 (17)	0.661 (5)	0.04 (2)*
O15	−0.0058 (3)	0.6310 (3)	−0.1978 (8)	0.0212 (15)	0.50
H15	−0.007 (7)	0.600 (4)	−0.245 (16)	0.025*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0140 (3)	0.0095 (3)	0.0134 (3)	−0.0001 (3)	0.0036 (3)	−0.0017 (3)
O1	0.038 (2)	0.0125 (17)	0.051 (3)	−0.0052 (16)	0.033 (2)	−0.0097 (17)
O2	0.059 (3)	0.016 (2)	0.111 (5)	−0.006 (2)	0.072 (3)	−0.008 (2)
O3	0.0173 (16)	0.0133 (16)	0.0195 (17)	0.0013 (13)	0.0076 (14)	0.0001 (13)
O4	0.0221 (18)	0.0152 (17)	0.030 (2)	−0.0036 (14)	0.0161 (16)	−0.0014 (15)
O5	0.0216 (17)	0.0129 (16)	0.0145 (16)	−0.0030 (13)	0.0021 (14)	0.0014 (13)
O6	0.0191 (17)	0.0203 (18)	0.0141 (17)	−0.0011 (14)	−0.0032 (14)	0.0020 (14)
O7	0.0192 (17)	0.0116 (16)	0.0185 (17)	−0.0001 (13)	0.0018 (14)	0.0004 (13)
O8	0.0162 (16)	0.0211 (18)	0.0108 (16)	0.0005 (13)	−0.0006 (13)	−0.0036 (13)
N1	0.0171 (19)	0.0150 (19)	0.018 (2)	−0.0012 (15)	0.0080 (16)	−0.0027 (16)
N2	0.0122 (18)	0.0131 (18)	0.0096 (18)	−0.0008 (14)	0.0033 (14)	−0.0005 (14)
C1	0.042 (3)	0.017 (3)	0.056 (4)	−0.006 (2)	0.039 (3)	−0.007 (3)
C2	0.029 (3)	0.017 (2)	0.040 (3)	−0.006 (2)	0.025 (3)	−0.008 (2)
C3	0.040 (3)	0.017 (3)	0.060 (4)	−0.005 (2)	0.040 (3)	−0.013 (3)
C4	0.031 (3)	0.014 (2)	0.042 (3)	−0.003 (2)	0.022 (3)	−0.008 (2)
C5	0.022 (2)	0.017 (2)	0.025 (3)	−0.0063 (19)	0.014 (2)	−0.007 (2)
C6	0.014 (2)	0.017 (2)	0.017 (2)	−0.0042 (17)	0.0040 (18)	−0.0064 (18)
C7	0.015 (2)	0.014 (2)	0.009 (2)	−0.0003 (17)	0.0021 (17)	−0.0026 (17)
C8	0.015 (2)	0.016 (2)	0.014 (2)	−0.0023 (17)	0.0031 (18)	0.0018 (18)
C9	0.011 (2)	0.013 (2)	0.016 (2)	−0.0014 (17)	0.0030 (17)	0.0020 (17)
C10	0.014 (2)	0.016 (2)	0.022 (2)	0.0014 (18)	0.0017 (19)	0.0026 (19)
C11	0.016 (2)	0.011 (2)	0.024 (3)	0.0003 (17)	0.0035 (19)	−0.0004 (19)
C12	0.016 (2)	0.014 (2)	0.016 (2)	−0.0028 (17)	0.0043 (18)	−0.0069 (18)
C13	0.013 (2)	0.016 (2)	0.013 (2)	−0.0021 (17)	0.0056 (17)	−0.0030 (17)
C14	0.013 (2)	0.016 (2)	0.010 (2)	−0.0002 (17)	0.0049 (17)	−0.0010 (17)
N3	0.0175 (19)	0.0089 (18)	0.0133 (19)	0.0022 (15)	0.0029 (15)	0.0049 (15)
N4	0.0174 (19)	0.0114 (18)	0.017 (2)	−0.0003 (15)	0.0064 (16)	0.0006 (15)
N5	0.0175 (19)	0.0103 (18)	0.0151 (19)	0.0014 (15)	0.0055 (16)	0.0031 (15)
N6	0.020 (2)	0.0101 (18)	0.018 (2)	0.0016 (15)	0.0061 (17)	0.0018 (15)
N7	0.020 (2)	0.0137 (19)	0.018 (2)	−0.0009 (16)	0.0010 (17)	0.0012 (16)
N8	0.019 (2)	0.0119 (19)	0.017 (2)	0.0006 (15)	0.0026 (16)	0.0057 (16)
C15	0.015 (2)	0.009 (2)	0.022 (2)	0.0018 (17)	0.0113 (18)	0.0015 (18)
C16	0.013 (2)	0.015 (2)	0.017 (2)	0.0017 (17)	0.0070 (18)	0.0020 (18)
C17	0.013 (2)	0.014 (2)	0.017 (2)	0.0005 (17)	0.0073 (18)	0.0012 (17)
N9	0.0141 (18)	0.0117 (18)	0.016 (2)	−0.0009 (15)	0.0026 (16)	0.0001 (15)
N10	0.017 (3)	0.009 (2)	0.018 (3)	0.000	0.005 (2)	0.000
N11	0.022 (3)	0.010 (3)	0.018 (3)	0.000	0.003 (2)	0.000
N12	0.021 (2)	0.0113 (19)	0.027 (2)	0.0009 (16)	0.0064 (18)	0.0003 (17)
C18	0.014 (3)	0.012 (3)	0.018 (3)	0.000	0.007 (3)	0.000
C19	0.012 (2)	0.013 (2)	0.019 (2)	0.0004 (17)	0.0069 (18)	0.0005 (18)
O9	0.037 (2)	0.0122 (18)	0.023 (2)	−0.0008 (16)	−0.0083 (17)	0.0022 (15)
O10	0.0179 (17)	0.0144 (17)	0.0185 (18)	−0.0011 (13)	−0.0014 (14)	−0.0023 (14)
N13	0.021 (3)	0.010 (3)	0.021 (3)	0.000	0.010 (2)	0.000
C20	0.017 (3)	0.011 (3)	0.019 (3)	0.000	0.006 (3)	0.000
C21	0.014 (2)	0.014 (2)	0.021 (2)	−0.0025 (17)	0.0053 (19)	−0.0018 (19)
C22	0.014 (2)	0.011 (2)	0.020 (2)	0.0009 (17)	0.0052 (19)	0.0019 (18)
C23	0.019 (2)	0.014 (2)	0.013 (2)	−0.0015 (18)	0.0021 (18)	−0.0020 (17)
O11	0.054 (4)	0.013 (3)	0.051 (4)	0.000	0.040 (4)	0.000
O12	0.062 (3)	0.039 (3)	0.041 (3)	0.034 (2)	0.025 (3)	0.022 (2)
O13	0.0161 (17)	0.0174 (18)	0.0232 (19)	0.0013 (14)	0.0054 (15)	0.0052 (14)
O14	0.0277 (19)	0.0204 (18)	0.0118 (17)	−0.0043 (15)	0.0018 (15)	0.0009 (14)
O15	0.019 (3)	0.011 (3)	0.032 (4)	0.004 (3)	0.007 (3)	0.004 (3)

Geometric parameters (Å, º)

Mn1—N1	2.149 (4)	N5—C16	1.362 (6)
Mn1—N2	2.172 (4)	N6—C15	1.313 (6)
Mn1—O3	2.213 (3)	N6—H6A	0.8800
Mn1—O5	2.231 (3)	N6—H6B	0.8800
Mn1—O7	2.238 (4)	N7—C16	1.325 (6)
Mn1—O1	2.245 (4)	N7—H7A	0.8800
O1—C1	1.276 (7)	N7—H7B	0.8800
O2—C1	1.235 (7)	N8—C17	1.330 (6)
O3—C7	1.269 (6)	N8—H8A	0.8800
O4—C7	1.245 (6)	N8—H8B	0.8800
O5—C8	1.259 (6)	N9—C19	1.334 (6)
O6—C8	1.253 (6)	N9—C18	1.350 (5)
O7—C14	1.266 (6)	N10—C19	1.364 (5)
O8—C14	1.253 (6)	N10—C19^i	1.364 (5)
N1—C6	1.325 (6)	N10—H10A	0.8722
N1—C2	1.332 (6)	N11—C18	1.329 (8)
N2—C13	1.329 (6)	N11—H11B	0.9000
N2—C9	1.341 (6)	N12—C19	1.319 (6)
C1—C2	1.527 (7)	N12—H12A	0.8800
C2—C3	1.377 (7)	N12—H12B	0.8800
C3—C4	1.393 (8)	C18—N9^i	1.350 (5)
C3—H3	0.9500	O9—C23	1.204 (6)
C4—C5	1.391 (7)	O10—C23	1.314 (6)
C4—H4	0.9500	O10—H10B	0.841 (10)
C5—C6	1.384 (7)	N13—C22	1.335 (6)
C5—H5	0.9500	N13—C22^i	1.335 (6)
C6—C7	1.529 (6)	C20—C21^i	1.382 (6)
C8—C9	1.519 (7)	C20—C21	1.382 (6)
C9—C10	1.393 (7)	C20—H20	0.9500
C10—C11	1.394 (7)	C21—C22	1.403 (6)
C10—H10	0.9500	C21—H21	0.9500
C11—C12	1.389 (7)	C22—C23	1.513 (6)
C11—H11	0.9500	O11—H11C	0.83 (9)
C12—C13	1.395 (6)	O12—H12C	0.837 (10)
C12—H12	0.9500	O12—H12D	0.836 (10)
C13—C14	1.514 (6)	O12—H12E	1.23 (2)
N3—C17	1.365 (6)	O13—H13A	0.841 (10)
N3—C15	1.372 (6)	O13—H13B	0.841 (10)
N3—H3A	0.8800	O14—H14A	0.839 (10)
N4—C15	1.333 (6)	O14—H14B	0.838 (10)
N4—C16	1.351 (6)	O15—H15	0.861 (10)
N5—C17	1.325 (6)
N1—Mn1—N2	174.99 (15)	N2—C13—C14	113.2 (4)
N1—Mn1—O3	73.38 (14)	C12—C13—C14	125.3 (4)
N2—Mn1—O3	111.27 (13)	O8—C14—O7	126.4 (4)
N1—Mn1—O5	108.61 (14)	O8—C14—C13	117.6 (4)
N2—Mn1—O5	72.85 (13)	O7—C14—C13	116.0 (4)
O3—Mn1—O5	100.14 (13)	C17—N3—C15	120.2 (4)
N1—Mn1—O7	106.28 (14)	C17—N3—H3A	119.9
N2—Mn1—O7	72.05 (13)	C15—N3—H3A	119.9
O3—Mn1—O7	93.41 (13)	C15—N4—C16	116.2 (4)
O5—Mn1—O7	144.88 (12)	C17—N5—C16	116.2 (4)
N1—Mn1—O1	72.91 (14)	C15—N6—H6A	120.0
N2—Mn1—O1	102.46 (14)	C15—N6—H6B	120.0
O3—Mn1—O1	146.27 (13)	H6A—N6—H6B	120.0
O5—Mn1—O1	89.60 (15)	C16—N7—H7A	120.0
O7—Mn1—O1	96.86 (15)	C16—N7—H7B	120.0
C1—O1—Mn1	117.4 (3)	H7A—N7—H7B	120.0
C7—O3—Mn1	118.4 (3)	C17—N8—H8A	120.0
C8—O5—Mn1	118.0 (3)	C17—N8—H8B	120.0
C14—O7—Mn1	118.6 (3)	H8A—N8—H8B	120.0
C6—N1—C2	121.0 (4)	N6—C15—N4	121.4 (4)
C6—N1—Mn1	119.0 (3)	N6—C15—N3	118.0 (4)
C2—N1—Mn1	119.9 (3)	N4—C15—N3	120.6 (4)
C13—N2—C9	120.5 (4)	N7—C16—N4	117.7 (4)
C13—N2—Mn1	120.1 (3)	N7—C16—N5	116.5 (4)
C9—N2—Mn1	119.2 (3)	N4—C16—N5	125.8 (4)
O2—C1—O1	125.8 (5)	N5—C17—N8	120.5 (4)
O2—C1—C2	118.7 (5)	N5—C17—N3	120.9 (4)
O1—C1—C2	115.4 (5)	N8—C17—N3	118.6 (4)
N1—C2—C3	121.6 (5)	C19—N9—C18	116.5 (4)
N1—C2—C1	113.7 (5)	C19—N10—C19^i	119.6 (6)
C3—C2—C1	124.7 (5)	C19—N10—H10A	120.2
C2—C3—C4	118.0 (5)	C19^i—N10—H10A	120.2
C2—C3—H3	121.0	C18—N11—H11B	120.0
C4—C3—H3	121.0	C19—N12—H12A	120.0
C5—C4—C3	119.8 (5)	C19—N12—H12B	120.0
C5—C4—H4	120.1	H12A—N12—H12B	120.0
C3—C4—H4	120.1	N11—C18—N9^i	117.4 (3)
C6—C5—C4	118.2 (5)	N11—C18—N9	117.4 (3)
C6—C5—H5	120.9	N9^i—C18—N9	125.2 (6)
C4—C5—H5	120.9	N12—C19—N9	120.8 (4)
N1—C6—C5	121.3 (4)	N12—C19—N10	118.1 (4)
N1—C6—C7	114.0 (4)	N9—C19—N10	121.1 (4)
C5—C6—C7	124.7 (4)	C23—O10—H10B	116 (8)
O4—C7—O3	126.9 (4)	C22—N13—C22^i	117.7 (6)
O4—C7—C6	118.2 (4)	C21^i—C20—C21	119.5 (6)
O3—C7—C6	115.0 (4)	C21^i—C20—H20	120.2
O6—C8—O5	125.3 (5)	C21—C20—H20	120.2
O6—C8—C9	117.7 (4)	C20—C21—C22	118.1 (5)
O5—C8—C9	117.0 (4)	C20—C21—H21	120.9
N2—C9—C10	121.6 (4)	C22—C21—H21	120.9
N2—C9—C8	112.9 (4)	N13—C22—C21	123.3 (5)
C10—C9—C8	125.5 (4)	N13—C22—C23	114.5 (4)
C9—C10—C11	118.0 (5)	C21—C22—C23	122.2 (4)
C9—C10—H10	121.0	O9—C23—O10	123.2 (5)
C11—C10—H10	121.0	O9—C23—C22	122.9 (4)
C12—C11—C10	119.8 (4)	O10—C23—C22	113.8 (4)
C12—C11—H11	120.1	H12C—O12—H12D	104 (3)
C10—C11—H11	120.1	H12C—O12—H12E	136 (9)
C11—C12—C13	118.5 (4)	H12D—O12—H12E	114 (6)
C11—C12—H12	120.8	H13A—O13—H13B	101 (2)
C13—C12—H12	120.8	H14A—O14—H14B	102 (2)
N2—C13—C12	121.5 (4)
N1—Mn1—O1—C1	−7.6 (5)	Mn1—O3—C7—O4	−175.2 (4)
N2—Mn1—O1—C1	170.4 (5)	Mn1—O3—C7—C6	5.5 (5)
O3—Mn1—O1—C1	−9.4 (6)	N1—C6—C7—O4	175.1 (4)
O5—Mn1—O1—C1	−117.3 (5)	C5—C6—C7—O4	−5.9 (7)
O7—Mn1—O1—C1	97.3 (5)	N1—C6—C7—O3	−5.5 (6)
N1—Mn1—O3—C7	−3.2 (3)	C5—C6—C7—O3	173.5 (5)
N2—Mn1—O3—C7	178.8 (3)	Mn1—O5—C8—O6	178.8 (4)
O5—Mn1—O3—C7	103.4 (3)	Mn1—O5—C8—C9	−1.2 (5)
O7—Mn1—O3—C7	−109.1 (3)	C13—N2—C9—C10	−0.5 (7)
O1—Mn1—O3—C7	−1.4 (5)	Mn1—N2—C9—C10	−176.0 (4)
N1—Mn1—O5—C8	−172.8 (3)	C13—N2—C9—C8	178.9 (4)
N2—Mn1—O5—C8	2.2 (3)	Mn1—N2—C9—C8	3.4 (5)
O3—Mn1—O5—C8	111.5 (3)	O6—C8—C9—N2	178.7 (4)
O7—Mn1—O5—C8	0.4 (5)	O5—C8—C9—N2	−1.4 (6)
O1—Mn1—O5—C8	−101.0 (4)	O6—C8—C9—C10	−2.0 (7)
N1—Mn1—O7—C14	176.6 (3)	O5—C8—C9—C10	178.0 (5)
N2—Mn1—O7—C14	1.5 (3)	N2—C9—C10—C11	−0.2 (7)
O3—Mn1—O7—C14	−109.7 (3)	C8—C9—C10—C11	−179.5 (4)
O5—Mn1—O7—C14	3.3 (5)	C9—C10—C11—C12	0.4 (7)
O1—Mn1—O7—C14	102.5 (3)	C10—C11—C12—C13	0.1 (7)
N2—Mn1—N1—C6	158.3 (16)	C9—N2—C13—C12	1.0 (7)
O3—Mn1—N1—C6	−0.2 (4)	Mn1—N2—C13—C12	176.5 (3)
O5—Mn1—N1—C6	−95.6 (4)	C9—N2—C13—C14	−177.4 (4)
O7—Mn1—N1—C6	88.5 (4)	Mn1—N2—C13—C14	−1.9 (5)
O1—Mn1—N1—C6	−179.2 (4)	C11—C12—C13—N2	−0.8 (7)
N2—Mn1—N1—C2	−18 (2)	C11—C12—C13—C14	177.4 (4)
O3—Mn1—N1—C2	−176.5 (5)	Mn1—O7—C14—O8	178.8 (4)
O5—Mn1—N1—C2	88.1 (4)	Mn1—O7—C14—C13	−3.0 (5)
O7—Mn1—N1—C2	−87.8 (4)	N2—C13—C14—O8	−178.5 (4)
O1—Mn1—N1—C2	4.5 (4)	C12—C13—C14—O8	3.2 (7)
N1—Mn1—N2—C13	−70.9 (19)	N2—C13—C14—O7	3.2 (6)
O3—Mn1—N2—C13	87.0 (3)	C12—C13—C14—O7	−175.1 (4)
O5—Mn1—N2—C13	−178.5 (4)	C16—N4—C15—N6	−179.2 (4)
O7—Mn1—N2—C13	0.4 (3)	C16—N4—C15—N3	−0.6 (6)
O1—Mn1—N2—C13	−92.9 (4)	C17—N3—C15—N6	−179.6 (4)
N1—Mn1—N2—C9	104.6 (18)	C17—N3—C15—N4	1.7 (7)
O3—Mn1—N2—C9	−97.5 (3)	C15—N4—C16—N7	179.7 (4)
O5—Mn1—N2—C9	−3.0 (3)	C15—N4—C16—N5	0.0 (7)
O7—Mn1—N2—C9	175.9 (4)	C17—N5—C16—N7	179.8 (4)
O1—Mn1—N2—C9	82.6 (4)	C17—N5—C16—N4	−0.5 (7)
Mn1—O1—C1—O2	−168.0 (6)	C16—N5—C17—N8	−178.4 (4)
Mn1—O1—C1—C2	9.3 (8)	C16—N5—C17—N3	1.6 (6)
C6—N1—C2—C3	0.9 (9)	C15—N3—C17—N5	−2.3 (7)
Mn1—N1—C2—C3	177.1 (5)	C15—N3—C17—N8	177.7 (4)
C6—N1—C2—C1	−177.7 (5)	C19—N9—C18—N11	179.6 (3)
Mn1—N1—C2—C1	−1.5 (7)	C19—N9—C18—N9^i	−0.4 (3)
O2—C1—C2—N1	172.1 (6)	C18—N9—C19—N12	179.3 (4)
O1—C1—C2—N1	−5.3 (9)	C18—N9—C19—N10	0.9 (6)
O2—C1—C2—C3	−6.4 (11)	C19^i—N10—C19—N12	−178.9 (5)
O1—C1—C2—C3	176.1 (7)	C19^i—N10—C19—N9	−0.5 (3)
N1—C2—C3—C4	−1.3 (10)	C21^i—C20—C21—C22	0.6 (3)
C1—C2—C3—C4	177.2 (6)	C22^i—N13—C22—C21	0.7 (3)
C2—C3—C4—C5	0.8 (10)	C22^i—N13—C22—C23	−177.2 (5)
C3—C4—C5—C6	0.2 (9)	C20—C21—C22—N13	−1.4 (7)
C2—N1—C6—C5	0.1 (8)	C20—C21—C22—C23	176.4 (4)
Mn1—N1—C6—C5	−176.1 (4)	N13—C22—C23—O9	−4.3 (7)
C2—N1—C6—C7	179.2 (5)	C21—C22—C23—O9	177.7 (5)
Mn1—N1—C6—C7	2.9 (5)	N13—C22—C23—O10	174.6 (4)
C4—C5—C6—N1	−0.7 (8)	C21—C22—C23—O10	−3.4 (7)
C4—C5—C6—C7	−179.6 (5)

Symmetry code: (i) −x, y, −z−1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N7—H7A···O9	0.88	2.12	2.811 (5)	135
N7—H7B···N9	0.88	2.11	2.988 (6)	172
N8—H8B···O14	0.88	1.95	2.830 (6)	174
N10—H10A···O15	0.87	1.82	2.665 (9)	161
N11—H11B···O9	0.90	2.04	2.925 (5)	167
N12—H12A···N5	0.88	2.09	2.964 (6)	172
O10—H10B···O13	0.84 (8)	1.82 (8)	2.645 (5)	167 (11)
O13—H13A···N4	0.83 (6)	2.08 (2)	2.910 (5)	167 (7)
O15—H15···O11	0.86 (1)	1.98 (8)	2.767 (9)	151 (15)
N3—H3A···O6^ii	0.88	1.89	2.757 (5)	168
N6—H6A···O4^iii	0.88	2.05	2.856 (5)	152
N6—H6B···O5^ii	0.88	2.06	2.924 (5)	168
N10—H10A···O15^i	0.87	1.82	2.665 (9)	161
N12—H12B···O1^iv	0.88	2.07	2.838 (6)	146
O11—H11C···O2^v	0.83 (9)	2.07 (9)	2.875 (6)	165 (10)
O12—H12C···O8^vi	0.83 (6)	1.75 (7)	2.560 (6)	162 (7)
O12—H12D···O2^iv	0.85 (5)	1.91 (7)	2.671 (6)	151 (7)
O12—H12E···O12^iv	1.24 (2)	1.24 (2)	2.445 (10)	163 (15)
O13—H13B···O4^vii	0.84 (5)	1.99 (6)	2.794 (5)	163 (7)
O14—H14A···O6^ii	0.84 (4)	1.87 (2)	2.646 (5)	153 (5)
O14—H14B···O3^viii	0.84 (5)	2.06 (3)	2.841 (5)	154 (5)
C12—H12···O10^ix	0.95	2.45	3.236 (6)	140

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