A three-dimensional framework in 2,2′-biimidazolium bis­(2,2′-biimidazole-κ²N,N′)bis­(biphenyl-2,4′-di­carboxyl­ato-κO)manganese(II) hexa­hydrate

In the title salt, (C₆H₈N₄)[Mn(C₁₄H₈O₄)₂(C₆H₆N₄)₂]·6H₂O, the Mn^II atom lies on an inversion centre and is coordinated by four N atoms from two 2,2′-biimidazole (biim) ligands and two O atoms from two biphenyl-2,4′-dicarboxyl­ate (bpdc) anions to give a slightly distorted octa­hedral coordination, while the cation lies about another inversion centre. Adjacent [Mn(bpdc)₂(biim)₂]²⁻ anions are linked via two pairs of N—H...O hydrogen bonds, leading to an infinite chain along the [100] direction. The protonated [H₂biim]²⁺ moiety acts as a charge-compensating cation and space-filling structural subunit. It bridges two [Mn(bpdc)₂(biim)₂]²⁻ anions through two pairs of N—H...O hydrogen bonds, constructing two R₂²(9) rings, leading to a zigzag chain in the [2] direction, which gives rise to a ruffled set of [H₂biim]²⁺[Mn(bpdc)₂(biim)₂]²⁻ moieties in the [01] plane. The water mol­ecules give rise to a chain structure in which O—H...O hydrogen bonds generate a chain of alternating four- and six-membered water–oxygen R₄²(8) and R₆⁶(12) rings, each lying about independent inversion centres giving rise to a chain along the [100] direction. Within the water chain, the (H₂O)₆ water rings are hydrogen bonded to two O atoms from two [Mn(bpdc)₂(biim)₂]²⁻ anions, giving rise to a three-dimensional framework.

S1. Comment

The design and synthesis of coordination polymers is an attractive area of research owing to the fascinating structures and potential applications in the catalysis and gas storage fields (Desiraju, 1995; Yaghi et al., 1998; Belof et al., 2007). In the case of coordination complexes, the resulting structures will be affected by factors such as metal-to-ligand ratios, metal coordination modes, the type and flexibility of organic ligand and guest molecules. [With respect to]In these factors, not only can the organic components be introduced as ligands, bonded directly to a secondary metal site, but they can also serve as a charge-compensating ion or space-filling structural subunits. During the past decade, many coordination polymers have been successfully synthesized and reported, in which polycarboxylic acids combining with N-ligands have been used to assemble coordination polymers because of their multiple coordination sites and versatile coordination modes (Wang et al., 2004, 2010; Duan et al., 2007; Liu et al., 2008; Ghosh et al., 2009; Duan et al., 2010). Coordination polymers associated with the biphenyl-2,4'-dicarboxylic acid (Liu et al., 2010) and the 2,2'-biimidazole ligand have not often been reported (Larsson & Öhrström, 2003; Ye et al.., 2004; Fang et al., 2009). We report here on the structure of the title compound, C₆H₈N₄²⁺.[Mn(C₁₄H₈O₄)₂(C₆H₆N₄)₂]^2-.6H₂O, (I), [H₂biim]²⁺.[Mn(bpdc)₂(biim)₂]^2-.6H₂O [[H₂biim]²⁺ is 2,2'-biimidazolium and H₂bpdc is biphenyl-2,4'-dicarboxylic acid].

As shown in Fig. 1, the structural unit consists of a [Mn(bpdc)₂(biim)₂]^2- anion with the Mn atom chosen to lie on the inversion centre at (0.5,0.5,0.5) and one doubly protonated H₂biim²⁺ cation lying about an inversion centre at (-0.5,1,1); the asymmetric unit also has three water molecules. In the [Mn(bpdc)₂(biim)₂]^2- anion, the Mn²⁺ ion is coordinated by four N atoms from two biim ligands and two O atoms from two bpdc anions in a slightly distorted octahedral configuration. The unique Mn—O distance is 2.2880 (14) Å, while Mn—N lengths are 2.1965 (17) and 2.2338 (18) Å. The (bpdc)^2- moiety is monodentate with a dihedral angle of 31.99 (10)° between its two phenyl rings.

In the [Mn(bpdc)₂(biim)₂]^2- anion, the four NH donors form N—H···O hydrogen bonds with the carboxyl-group O atoms of adjacent anions, giving rise to a chain along the [100] direction as shown in Fig. 2 with geometric details in Table 1. The doubly protonated H₂biim²⁺ cation lying about an inversion centre (at -0.5,1,1) forms four N—H···O hydrogen bonds with two non-coordinative carboxyl groups in two [Mn(bpdc)₂(biim)₂]^2- anions through two pairs of N—H···O (N5—H5A···O4 and N6—H6A···O3^iv) hydrogen bonds (Table 1), forming two R₂²(9) rings (Bernstein et al., 1995). Alternate [Mn(bpdc)₂(biim)₂]^2- anion and H₂biim²⁺ cations give rise to a one-dimensional zigzag chain along the [211] direction (Fig. 3). The combination of this chain with that of the [Mn(bpdc)₂(biim)₂]^2- anions gives rise to a ruffled layer in the [011] plane.

The three water molecules give rise to a water chain as shown in Fig. 4 which extends in the a direction (geometric details in Table 1). The chain is composed of six-membered and four-membered water oxygen rings lying about inversion centres at (0,0,1/2)and (1/2,0,1/2), etc., with graph-set notations R₆⁶(12) and R₄²(8) for the six- and four-membered rings, respectively. The four oxygen atoms of the R₄²(8) ring are exactly coplanar because of the inversion symmetry while the six oxygen atoms within the hexamer are almost coplanar with a mean deviation 0.1383 (2) Å and construct an essentially equilateral hexagon. The O5 water molecules in each water chain are hydrogen bonded to O2 atoms from [Mn(bpdc)₂(biim)₂]^2- anions so that the two-dimensional zigzag layers are arranged into a three-dimensional framework.

Related literature

For related literature, see: Belof et al. (2007); Bernstein et al. (1995); Desiraju (1995); Duan et al. (2007, 2010); Fang et al. (2009); Ghosh et al. (2009); Larsson & Öhrström (2003); Liu et al. (2010); Wang et al. (2004, 2010); Yaghi et al. (1998); Ye et al. (2004).

S2. Experimental

A mixture of MnSO_4.H₂O (0.5 mmol, 0.085 g), bpdc (0.5 mmol, 0.17 g), biim (0.2 mmol, 0.04 g) and H₂O (15 ml) was placed in a Parr Teflon-lined stainless steel vessel (23 ml), which was sealed and heated at 403 K for 5 d. After the mixture slowly cooled to room temperature, colourless block crystals of (I) were obtained.

S3. Refinement

Water and nitrogen-bound H atoms were located in difference Fourier maps and refined with restraints [O—H = 0.85 (3) Å, H···H =1.34 (3) Å and N—H = 0.89 (3) Å] and with U_iso(H) = 1.2U_eq(N) or 1.5U_eq(O). The remaining H atoms were positioned geometrically and allowed for using a riding model, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C) for aromatic H atoms.

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Dashed lines indicate hydrogen bonds [Symmetry codes: (a) -x + 1, -y + 1, -z + 1; (b) -x - 1, -y + 2, -z + 2.]
	Fig. 2. View of the [Mn(bpdc)2(biim)2]^2- chain in the [100] direction [Symmetry codes: (a) -x + 1, -y + 1, -z + 1; (d) x + 1, y, z; (e) -x, -y + 1, -z + 1.]
	Fig. 3. View of the chain along the [211] direction [Symmetry codes: (a) -x + 1, -y + 1, -z + 1; (b) -x - 1, -y + 2, -z + 2; (c) x + 2, y - 1, z - 1.]
	Fig. 4. View of the water chain along the [100] direction [Symmetry codes: (*) -x + 1, -y, -z + 1; (#) -x, -y, -z + 1; ($) x - 1, y, z.]

2,2'-biimidazolium bis(2,2'-biimidazole-κ²N,N')bis(biphenyl- 2,4'-dicarboxylato-κO)manganese(II) hexahydrate

Crystal data

(C6H8N4)[Mn(C14H8O4)2(C6H6N4)2]·6H2O	Z = 1
Mr = 1047.90	F(000) = 545
Triclinic, P1	Dx = 1.458 Mg m^−3
Hall symbol: -p 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.278 (1) Å	Cell parameters from 3188 reflections
b = 11.977 (2) Å	θ = 2.9–26.8°
c = 14.268 (1) Å	µ = 0.36 mm^−1
α = 81.310 (2)°	T = 296 K
β = 76.269 (1)°	Block, colorless
γ = 85.793 (1)°	0.30 × 0.20 × 0.20 mm
V = 1193.4 (3) Å^3

Data collection

Bruker SMART APEX CCD area-detector diffractometer	4629 independent reflections
Radiation source: fine-focus sealed tube	3821 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
0.3° wide ω exposures scans	θmax = 26.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −8→8
Tmin = 0.900, Tmax = 0.932	k = −12→14
8661 measured reflections	l = −17→17

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0565P)^2 + 0.1622P] where P = (Fo^2 + 2Fc^2)/3
4629 reflections	(Δ/σ)max = 0.007
361 parameters	Δρmax = 0.39 e Å^−3
13 restraints	Δρmin = −0.30 e Å^−3

Special details

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

Refinement. 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 > 2sigma(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	0.5000	0.5000	0.5000	0.03364 (16)
C1	0.4427 (3)	0.29449 (18)	0.75308 (14)	0.0292 (5)
C2	0.5717 (3)	0.20347 (19)	0.74058 (16)	0.0352 (5)
H2	0.5682	0.1575	0.6941	0.042*
C3	0.7053 (3)	0.1801 (2)	0.79630 (17)	0.0406 (6)
H3	0.7928	0.1201	0.7859	0.049*
C4	0.7084 (3)	0.2456 (2)	0.86688 (17)	0.0425 (6)
H4	0.7981	0.2304	0.9044	0.051*
C5	0.5772 (3)	0.3344 (2)	0.88177 (17)	0.0397 (6)
H5	0.5784	0.3774	0.9308	0.048*
C6	0.4431 (3)	0.36170 (18)	0.82558 (15)	0.0308 (5)
C7	0.3037 (3)	0.45626 (19)	0.84833 (14)	0.0316 (5)
C8	0.1115 (3)	0.44612 (19)	0.85409 (15)	0.0336 (5)
H8	0.0694	0.3792	0.8424	0.040*
C9	−0.0172 (3)	0.5340 (2)	0.87693 (15)	0.0364 (5)
H9	−0.1441	0.5267	0.8782	0.044*
C10	0.0410 (3)	0.6330 (2)	0.89794 (15)	0.0367 (5)
C11	0.2315 (3)	0.6426 (2)	0.89566 (17)	0.0423 (6)
H11	0.2718	0.7077	0.9116	0.051*
C12	0.3607 (3)	0.5561 (2)	0.86996 (17)	0.0413 (6)
H12	0.4880	0.5645	0.8670	0.050*
C13	0.3122 (3)	0.31918 (19)	0.68379 (15)	0.0310 (5)
C14	−0.0952 (4)	0.7290 (2)	0.92210 (17)	0.0438 (6)
C15	0.1806 (3)	0.52812 (18)	0.40259 (14)	0.0286 (5)
C16	0.1258 (3)	0.3878 (2)	0.33330 (16)	0.0389 (5)
H16	0.0711	0.3421	0.3010	0.047*
C17	0.2846 (3)	0.3637 (2)	0.36640 (16)	0.0387 (5)
H17	0.3594	0.2976	0.3603	0.046*
C18	0.1729 (3)	0.63278 (18)	0.44231 (14)	0.0295 (5)
C19	0.1060 (3)	0.8022 (2)	0.48165 (17)	0.0411 (6)
H19	0.0496	0.8737	0.4881	0.049*
C20	0.2565 (3)	0.7564 (2)	0.51653 (17)	0.0398 (6)
H20	0.3211	0.7921	0.5518	0.048*
N1	0.3193 (2)	0.45164 (15)	0.41056 (13)	0.0330 (4)
N2	0.0607 (3)	0.49215 (17)	0.35628 (13)	0.0345 (4)
H2A	−0.047 (3)	0.525 (2)	0.3532 (17)	0.041*
N3	0.2994 (2)	0.64961 (15)	0.49209 (13)	0.0331 (4)
N4	0.0535 (3)	0.72228 (16)	0.43500 (13)	0.0343 (4)
H4A	−0.041 (3)	0.730 (2)	0.4037 (16)	0.041*
O1	0.3027 (2)	0.41793 (13)	0.63916 (10)	0.0361 (4)
O2	0.2191 (3)	0.23966 (14)	0.67405 (13)	0.0503 (5)
O3	−0.2451 (3)	0.73693 (19)	0.89000 (15)	0.0751 (7)
O4	−0.0595 (3)	0.79671 (16)	0.97303 (16)	0.0659 (6)
O5	0.2590 (3)	0.02831 (18)	0.61516 (15)	0.0621 (5)
H5WA	0.158 (4)	−0.005 (3)	0.645 (2)	0.093*
H5WB	0.254 (5)	0.089 (2)	0.637 (2)	0.093*
O6	0.3681 (3)	0.0717 (2)	0.40715 (17)	0.0725 (6)
H6WA	0.470 (4)	0.042 (3)	0.391 (3)	0.109*
H6WB	0.326 (5)	0.064 (3)	0.4655 (18)	0.109*
O7	−0.0874 (4)	−0.0748 (2)	0.69952 (18)	0.0794 (7)
H7WA	−0.095 (6)	−0.125 (3)	0.743 (3)	0.119*
H7WB	−0.176 (5)	−0.075 (4)	0.671 (3)	0.119*
N5	−0.2979 (3)	0.95417 (19)	1.05509 (16)	0.0478 (5)
H5A	−0.225 (4)	0.902 (2)	1.0233 (19)	0.057*
N6	−0.5122 (3)	1.08372 (18)	1.09946 (14)	0.0474 (5)
H6A	−0.601 (3)	1.137 (2)	1.100 (2)	0.057*
C21	−0.4536 (3)	1.0093 (2)	1.03718 (16)	0.0394 (5)
C22	−0.2575 (4)	0.9935 (2)	1.1320 (2)	0.0580 (7)
H22	−0.1564	0.9695	1.1604	0.070*
C23	−0.3897 (4)	1.0733 (2)	1.15938 (19)	0.0563 (7)
H23	−0.3967	1.1145	1.2105	0.068*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0289 (3)	0.0328 (3)	0.0428 (3)	0.0028 (2)	−0.0173 (2)	−0.0040 (2)
C1	0.0252 (11)	0.0287 (12)	0.0324 (11)	−0.0018 (9)	−0.0067 (8)	0.0000 (9)
C2	0.0354 (12)	0.0331 (13)	0.0368 (12)	0.0026 (10)	−0.0083 (10)	−0.0057 (9)
C3	0.0313 (12)	0.0372 (14)	0.0500 (14)	0.0088 (10)	−0.0099 (10)	0.0004 (11)
C4	0.0348 (13)	0.0472 (15)	0.0492 (14)	0.0020 (11)	−0.0211 (11)	−0.0017 (11)
C5	0.0397 (13)	0.0425 (14)	0.0415 (13)	−0.0006 (11)	−0.0176 (10)	−0.0076 (10)
C6	0.0275 (11)	0.0300 (12)	0.0346 (11)	−0.0001 (9)	−0.0077 (9)	−0.0026 (9)
C7	0.0327 (12)	0.0330 (12)	0.0305 (11)	0.0023 (10)	−0.0094 (9)	−0.0071 (9)
C8	0.0357 (12)	0.0340 (13)	0.0325 (11)	0.0002 (10)	−0.0084 (9)	−0.0082 (9)
C9	0.0312 (12)	0.0462 (15)	0.0323 (11)	0.0027 (11)	−0.0076 (9)	−0.0085 (10)
C10	0.0414 (13)	0.0386 (14)	0.0282 (11)	0.0085 (11)	−0.0059 (9)	−0.0072 (9)
C11	0.0468 (14)	0.0346 (14)	0.0475 (14)	−0.0002 (11)	−0.0112 (11)	−0.0129 (11)
C12	0.0352 (13)	0.0433 (15)	0.0485 (14)	0.0002 (11)	−0.0114 (11)	−0.0137 (11)
C13	0.0269 (11)	0.0357 (13)	0.0308 (11)	0.0061 (9)	−0.0077 (9)	−0.0078 (9)
C14	0.0471 (15)	0.0435 (15)	0.0376 (13)	0.0089 (12)	−0.0045 (11)	−0.0093 (11)
C15	0.0261 (11)	0.0320 (12)	0.0274 (10)	0.0003 (9)	−0.0080 (8)	−0.0005 (9)
C16	0.0461 (14)	0.0365 (14)	0.0390 (12)	−0.0026 (11)	−0.0159 (10)	−0.0104 (10)
C17	0.0458 (14)	0.0322 (13)	0.0399 (12)	0.0052 (11)	−0.0134 (10)	−0.0082 (10)
C18	0.0258 (11)	0.0311 (12)	0.0303 (10)	0.0002 (9)	−0.0065 (8)	−0.0010 (9)
C19	0.0444 (14)	0.0289 (13)	0.0531 (14)	0.0071 (11)	−0.0159 (11)	−0.0119 (11)
C20	0.0403 (13)	0.0355 (14)	0.0482 (13)	0.0005 (11)	−0.0162 (11)	−0.0118 (11)
N1	0.0312 (10)	0.0320 (10)	0.0378 (10)	0.0038 (8)	−0.0127 (8)	−0.0058 (8)
N2	0.0305 (10)	0.0386 (11)	0.0373 (10)	0.0018 (9)	−0.0138 (8)	−0.0061 (8)
N3	0.0309 (10)	0.0317 (11)	0.0384 (10)	0.0003 (8)	−0.0114 (8)	−0.0057 (8)
N4	0.0311 (10)	0.0338 (11)	0.0404 (10)	0.0069 (8)	−0.0144 (8)	−0.0071 (8)
O1	0.0331 (8)	0.0357 (9)	0.0383 (8)	0.0045 (7)	−0.0108 (7)	0.0003 (7)
O2	0.0554 (11)	0.0363 (10)	0.0725 (12)	0.0003 (8)	−0.0392 (9)	−0.0108 (8)
O3	0.0744 (14)	0.0890 (17)	0.0790 (14)	0.0460 (12)	−0.0431 (12)	−0.0484 (12)
O4	0.0537 (12)	0.0519 (12)	0.0996 (16)	0.0137 (10)	−0.0199 (11)	−0.0376 (12)
O5	0.0658 (13)	0.0545 (13)	0.0696 (14)	0.0069 (11)	−0.0170 (11)	−0.0224 (11)
O6	0.0737 (16)	0.0703 (16)	0.0713 (14)	0.0191 (12)	−0.0182 (12)	−0.0106 (12)
O7	0.0814 (17)	0.0829 (18)	0.0743 (16)	−0.0044 (14)	−0.0163 (13)	−0.0135 (12)
N5	0.0463 (13)	0.0429 (13)	0.0512 (13)	0.0096 (10)	−0.0083 (10)	−0.0070 (10)
N6	0.0610 (15)	0.0371 (13)	0.0402 (11)	0.0090 (10)	−0.0056 (10)	−0.0074 (10)
C21	0.0440 (14)	0.0328 (13)	0.0357 (12)	0.0041 (11)	−0.0018 (10)	−0.0019 (10)
C22	0.0630 (19)	0.0538 (18)	0.0602 (17)	−0.0018 (15)	−0.0241 (14)	−0.0015 (14)
C23	0.078 (2)	0.0498 (18)	0.0430 (14)	−0.0079 (16)	−0.0156 (14)	−0.0083 (12)

Geometric parameters (Å, º)

Mn1—N1^i	2.1966 (17)	C15—N1	1.326 (3)
Mn1—N1	2.1966 (17)	C15—N2	1.341 (3)
Mn1—N3	2.2334 (18)	C15—C18	1.444 (3)
Mn1—N3^i	2.2334 (18)	C16—C17	1.346 (3)
Mn1—O1	2.2879 (15)	C16—N2	1.363 (3)
Mn1—O1^i	2.2879 (15)	C16—H16	0.9300
C1—C2	1.390 (3)	C17—N1	1.373 (3)
C1—C6	1.404 (3)	C17—H17	0.9300
C1—C13	1.511 (3)	C18—N3	1.332 (3)
C2—C3	1.384 (3)	C18—N4	1.337 (3)
C2—H2	0.9300	C19—C20	1.355 (3)
C3—C4	1.372 (3)	C19—N4	1.368 (3)
C3—H3	0.9300	C19—H19	0.9300
C4—C5	1.383 (3)	C20—N3	1.371 (3)
C4—H4	0.9300	C20—H20	0.9300
C5—C6	1.395 (3)	N2—H2A	0.862 (19)
C5—H5	0.9300	N4—H4A	0.901 (19)
C6—C7	1.484 (3)	O5—H5WA	0.85 (2)
C7—C12	1.393 (3)	O5—H5WB	0.83 (2)
C7—C8	1.395 (3)	O6—H6WA	0.79 (2)
C8—C9	1.381 (3)	O6—H6WB	0.81 (2)
C8—H8	0.9300	O7—H7WA	0.79 (2)
C9—C10	1.384 (3)	O7—H7WB	0.84 (2)
C9—H9	0.9300	N5—C21	1.327 (3)
C10—C11	1.392 (3)	N5—C22	1.357 (3)
C10—C14	1.489 (3)	N5—H5A	0.89 (2)
C11—C12	1.379 (3)	N6—C21	1.330 (3)
C11—H11	0.9300	N6—C23	1.362 (3)
C12—H12	0.9300	N6—H6A	0.87 (2)
C13—O2	1.251 (3)	C21—C21^ii	1.437 (5)
C13—O1	1.261 (3)	C22—C23	1.338 (4)
C14—O4	1.246 (3)	C22—H22	0.9300
C14—O3	1.272 (3)	C23—H23	0.9300
N1^i—Mn1—N1	180.000 (1)	O1—C13—C1	118.71 (19)
N1^i—Mn1—N3	102.44 (6)	O4—C14—O3	123.1 (2)
N1—Mn1—N3	77.56 (6)	O4—C14—C10	119.3 (2)
N1^i—Mn1—N3^i	77.56 (6)	O3—C14—C10	117.6 (2)
N1—Mn1—N3^i	102.44 (6)	N1—C15—N2	110.84 (19)
N3—Mn1—N3^i	180.0	N1—C15—C18	120.31 (18)
N1^i—Mn1—O1	88.98 (6)	N2—C15—C18	128.84 (19)
N1—Mn1—O1	91.02 (6)	C17—C16—N2	106.68 (19)
N3—Mn1—O1	90.76 (6)	C17—C16—H16	126.7
N3^i—Mn1—O1	89.24 (6)	N2—C16—H16	126.7
N1^i—Mn1—O1^i	91.02 (6)	C16—C17—N1	109.5 (2)
N1—Mn1—O1^i	88.98 (6)	C16—C17—H17	125.2
N3—Mn1—O1^i	89.24 (6)	N1—C17—H17	125.2
N3^i—Mn1—O1^i	90.76 (6)	N3—C18—N4	111.61 (19)
O1—Mn1—O1^i	180.0	N3—C18—C15	119.72 (19)
C2—C1—C6	119.65 (18)	N4—C18—C15	128.65 (18)
C2—C1—C13	117.41 (18)	C20—C19—N4	106.3 (2)
C6—C1—C13	122.89 (19)	C20—C19—H19	126.9
C3—C2—C1	121.0 (2)	N4—C19—H19	126.9
C3—C2—H2	119.5	C19—C20—N3	110.0 (2)
C1—C2—H2	119.5	C19—C20—H20	125.0
C4—C3—C2	119.9 (2)	N3—C20—H20	125.0
C4—C3—H3	120.0	C15—N1—C17	105.58 (17)
C2—C3—H3	120.0	C15—N1—Mn1	111.58 (14)
C3—C4—C5	119.5 (2)	C17—N1—Mn1	142.39 (15)
C3—C4—H4	120.3	C15—N2—C16	107.38 (18)
C5—C4—H4	120.3	C15—N2—H2A	123.4 (16)
C4—C5—C6	122.1 (2)	C16—N2—H2A	128.2 (16)
C4—C5—H5	119.0	C18—N3—C20	104.95 (18)
C6—C5—H5	119.0	C18—N3—Mn1	110.58 (14)
C5—C6—C1	117.8 (2)	C20—N3—Mn1	144.43 (15)
C5—C6—C7	118.59 (19)	C18—N4—C19	107.17 (18)
C1—C6—C7	123.54 (18)	C18—N4—H4A	126.6 (15)
C12—C7—C8	118.0 (2)	C19—N4—H4A	126.2 (15)
C12—C7—C6	120.44 (19)	C13—O1—Mn1	128.94 (14)
C8—C7—C6	121.51 (19)	H5WA—O5—H5WB	107 (3)
C9—C8—C7	120.9 (2)	H6WA—O6—H6WB	113 (3)
C9—C8—H8	119.5	H7WA—O7—H7WB	111 (3)
C7—C8—H8	119.5	C21—N5—C22	107.7 (2)
C8—C9—C10	120.6 (2)	C21—N5—H5A	129.3 (18)
C8—C9—H9	119.7	C22—N5—H5A	122.9 (18)
C10—C9—H9	119.7	C21—N6—C23	107.0 (2)
C9—C10—C11	119.0 (2)	C21—N6—H6A	129.5 (19)
C9—C10—C14	121.4 (2)	C23—N6—H6A	123.0 (19)
C11—C10—C14	119.6 (2)	N5—C21—N6	109.6 (2)
C12—C11—C10	120.3 (2)	N5—C21—C21^ii	125.3 (3)
C12—C11—H11	119.8	N6—C21—C21^ii	125.1 (3)
C10—C11—H11	119.8	C23—C22—N5	107.5 (3)
C11—C12—C7	121.1 (2)	C23—C22—H22	126.2
C11—C12—H12	119.4	N5—C22—H22	126.2
C7—C12—H12	119.4	C22—C23—N6	108.2 (2)
O2—C13—O1	123.64 (19)	C22—C23—H23	125.9
O2—C13—C1	117.65 (19)	N6—C23—H23	125.9

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1^iii	0.86 (2)	1.92 (2)	2.771 (2)	172 (2)
N4—H4A···O2^iii	0.90 (2)	1.88 (2)	2.772 (2)	172 (2)
O5—H5WA···O7	0.85 (2)	1.96 (2)	2.810 (3)	173 (4)
O5—H5WB···O2	0.83 (2)	1.94 (2)	2.760 (3)	171 (4)
O6—H6WA···O5^iv	0.79 (2)	2.08 (3)	2.851 (3)	165 (4)
O6—H6WB···O5	0.81 (2)	2.06 (2)	2.861 (3)	171 (4)
O7—H7WB···O6^v	0.84 (2)	1.98 (2)	2.818 (3)	175 (4)
N5—H5A···O4	0.89 (2)	1.79 (2)	2.676 (3)	172 (3)
N6—H6A···O3^ii	0.87 (2)	1.82 (2)	2.678 (3)	169 (3)

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