A novel three-dimensional coordination polymer: poly[di-μ₃-acetato-di-μ₂-acetato-di-μ₃-hydr­oxido-octa-μ₃-triazolato-hepta­manganese(II)]

The title compound, [Mn₇(C₂H₂N₃)₈(C₂H₃O₂)₄(OH)₂]_n, is composed of centrosymmetric hepta­nuclear building units with the central Mn atom on an inversion center. In the building block, three Mn^II ions are held together by one μ₃-hydroxide group, two μ₂-triazolate (trz) ligands and two μ₂-acetate groups, forming an Mn₃ cluster. Two Mn₃ clusters are bridged by an Mn atom via two μ₂-trz ligands and two μ₂-O atoms from two acetate ions to construct a hepta­nuclear building block. The hepta­nuclear building units, lying parallel to each other along the b direction, form one-dimensional ladder-like chains and are further inter­linked, resulting in a three-dimensional framework through Mn—N_trz bonds.

S1. Comment

Synthesis of inorganic coordination polymeric complexes has developed rapidly in recent years owing to their fascinating variety of topologies as well as the potential applications in many fields such as catalysis, electrical conductivity, luminescene, magnetism and nonlinear optics (Cao et al., 2002; Janiak, 2003). Ligands used in construction polymers to bridge metals usually contain oxygen or nitrogen donors, in which multitopic carboxylate and pyridine ligands are most extensively exploited as linkers. However, more and more attention is being paid to ligands that could offer alternative tether lengths, different charge-balance requirements and orientations of donor groups, and 1,2,4-triazole is one such ligand (Ouellette et al., 2006). 1,2,4-Triazole and its derivatives are very interesting ligands that can bridge as well as chelate metals, with 1,2-bridging (Milios et al., 2006) or 1,2,4-bridging forms (Ouellette et al., 2006). It can also be used as a monodentate ligand (Li et al., 2007), and most complexes with this ligand exhibit antiferromagnetic coupling (Zhou et al., 2005; Ding et al., 2006).

On the other hand, Mn-based complexes have been widely reported over the past two decades, one of the most important reasons for this interest being their paramagnetic nature. Many exhibit large ground spin states (Jones et al., 2004), many of which are thought to be the origin of the magnetic bistability displayed by single-molecule magnets (Laye & McInnes, 2004).

With this in mind, we decided to introduce Mn^II into the triazole ligand, considering that such metal-organic frameworks would exhibit unusual magnetic exchanging behavior (Tangoulis et al., 1998). The title complex, (I), was obtained by solvothermal reaction of 1,2,4-triazole (Htrz) with Mn(CH₃COO)₂·4H₂O at 423 K or with Mn(CH₃COCHCOCH₃)₂ at 443 K.

Single crystal structure analysis reveals that complex (I) is composed of heptanuclear [Mn₇(trz)₈(CH₃COO)₄(OH)₂] building units, which are further interlinked through bonds formed by Mn and N atoms into a three-dimensional polymer. The heptanuclear Mn building unit, consisting of two [Mn_3.5(trz)₄(CH₃COO)₂(OH)] subunits with atom Mn4 lying on an inversion center, is centrosymmetric (Fig. 1).

In the asymmetric unit of (I), atoms Mn1, Mn2 and Mn3 are held together by three distinct bridging systems to form an Mn₃ cluster, viz. (i) two µ₂-bridging acetate ligands, with Mn—O distances of 2.121 (O4—Mn2), 2.175 (O2—Mn3), 2.158 (Mn3—O3) and 2.424 Å (O2—Mn1) [please check; atom labelling used in text and Fig. 1 seems to be different from that used in the CIF, and values of bond lengths and angles quoted in the text do not appear to match those provided in the CIF; s.u. values should also be given for all distances and angles where available], which are within the range 1.857–2.443 Å reported by Ouellette et al. (2006) for a similar compound; (ii) two 1,2-bridging trz ligands, with an Mn3—N5 distance of 2.198 Å, Mn1—N4 of 2.221 Å, Mn1—N1 of 2.250 Å and an Mn2—N2 distance of 2.231 Å, which are slightly longer than those reported by Milios et al. (2006); (iii) the O atom of the tridentate hydroxy group, lying out of the plane defined by the Mn₃ triangle by 0.6686 Å, with distances from each of the Mn atoms of 2.2241 (Mn1), 2.1009 (Mn2) and 2.2328 Å (please check values and provide s.u. values) (Mn3), and these are also longer than those in related compounds (Ouellette et al., 2006; Milios et al., 2006). Two Mn₃ clusters are bridged by the Mn4 atom via two µ₂-trz ligands and two µ₂-O atoms from two acetate ions to construct a heptanuclear building block, with an Mn4—O2 distance of 2.240 Å, Mn1—N7 of 2.219 Å and Mn4—N8 of 2.180 Å. To the best of our knowledge, this kind of heptanuclear building block is unprecedented.

In the asymmetric unit of complex (I), four Mn^II ions have two different coordination modes. Mn1, Mn3 and Mn4 are six-coordinated in a slightly distorted octahedron with coordination angles in the ranges 82.0–98.5° or 166.4–180°. Atom Mn2 possesses a twisted trigonal-bipyramidal geometry, with the equatorial atoms O4, N6 and N2 and axial atoms N12 and O1. The O4—Mn2—N12, N12—Mn2—N2 and N6—Mn2—N2 angles are 83.9, 86.8 and 87.9°, respectively.

The heptanuclear units are aligned along the b direction parallel to each other in a shoulder-to-shoulder fashion, and both sides of the two adjacent units are connected by two trz ligands, resulting in the formation of one-dimension ladder-like chains along the b axis (Fig. 2). Each chain is further interlinked with four other chains by coordination of the remaining N atoms of the trz ligands to the Mn^II ions in neighboring chains. This leads to the construction of a three-dimensional framework (Fig. 3).

Related literature

For related literature, see: Cao, Sun, Liang, Hong, Tatsumi & Shi (2002); Ding et al. (2006); Janiak (2003); Jones et al. (2004); Laye & McInnes (2004); Li et al. (2007); Ouellette et al. (2006); Zhou et al. (2005).

S2. Experimental

The synthesis of complex (I) was achieved by two processes. In the first method, a solution of Htrz (60.1 mg, 0.87 mmol), Mn(CH₃COO)₂·4H₂O (245.3 mg, 1 mmol), triethylamine (0.1 ml), CH₃CN (8 ml), EtOH (8 ml) and water (1 ml) was stirred briefly before being moved into a 25 ml autoclave and heated at 423 K for 4 d, followed by slow cooling to room temperature. The product was washed with EtOH and water, and colorless block crystals suitable for X-ray diffraction were collected and dried in air (80 mg, 66% in yield). In the second method, a solution of Htrz (70.1 mg, 1.01 mmol), Mn(CH₃COCHCOCH₃)₂ (253 mg, 1 mmol), NaOH (40 mg, 1 mmol), CH₃CN (3 ml), EtOH (9 ml) and water (3 ml) was stirred briefly before being moved into a 25 ml autoclave and heated at 443 K for 3 d, followed by slow cooling to room temperature. The product was washed with EtOH and water, and colorless block crystals suitable for X-ray diffraction were collected and dried in air (65 mg, 43% in yield).

S3. Refinement

The H atom of the hydroxy group were located in an electron density map and were refined with distance restraints [O—H = 0.84 (6) Å]. The other H atoms were refined as riding on their parent C atoms [U_iso(H) = 1.2U_eq(C)].

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART or SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures

	Fig. 1. A view of the Mn^II coordination environment in the polymeric structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and all H atoms have been omitted for clarity. [Symmetry codes: (i) x - 1/2, -y + 3/2, z - 1/2; (ii) -x + 1, -y + 2, -z; (iii) -x + 1/2, y + 1/2, -z + 1/2; (iv) x, y + 1, z; (v) -x, -y + 2, -z; (vi) x, y - 1, z; (vii) -x + 1/2, y - 1/2, -z + 1/2; (viii) x + 1/2, -y + 3/2, z + 1/2.]
	Fig. 2. The ladder-like one-dimensional chain of (I) along the b axis.
	Fig. 3. The three-dimensional packing of (I).

poly[di-µ₃-acetato-di-µ₂-acetato-di-µ₃-hydroxy-octa-µ₃– triazolato-heptamanganese(II)]

Crystal data

[Mn7(C2H2N3)8(C2H3O2)4(OH)2]	Z = 2
Mr = 1199.30	F(000) = 1194
Monoclinic, P21/n	Dx = 1.832 Mg m^−3
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 14.677 (2) Å	θ = 1.6–25.0°
b = 9.2626 (15) Å	µ = 2.05 mm^−1
c = 16.990 (3) Å	T = 298 K
β = 109.717 (2)°	Block, colorless
V = 2174.3 (6) Å^3	0.22 × 0.20 × 0.17 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3788 independent reflections
Radiation source: fine-focus sealed tube	2800 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.061
phi and ω scans	θmax = 25.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −17→13
Tmin = 0.662, Tmax = 0.723	k = −11→11
10662 measured reflections	l = −18→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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0507P)^2 + 1.8699P] where P = (Fo^2 + 2Fc^2)/3
3788 reflections	(Δ/σ)max = 0.001
298 parameters	Δρmax = 1.12 e Å^−3
2 restraints	Δρmin = −0.44 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	0.75874 (4)	0.58288 (7)	0.05458 (4)	0.02058 (18)
Mn2	1.01098 (5)	0.58805 (7)	0.19767 (4)	0.02079 (18)
Mn3	0.5000	0.5000	0.0000	0.0217 (2)
Mn4	0.88824 (5)	0.25403 (6)	0.13261 (4)	0.02212 (18)
N1	0.8443 (3)	0.7891 (4)	0.0833 (2)	0.0272 (8)
N2	0.9352 (3)	0.7896 (4)	0.1424 (2)	0.0263 (8)
N3	0.8961 (3)	1.0172 (4)	0.1041 (2)	0.0317 (9)
N4	0.6778 (3)	0.6400 (4)	0.1398 (2)	0.0324 (9)
N5	0.5842 (3)	0.6016 (4)	0.1177 (2)	0.0305 (9)
N6	0.6240 (3)	0.7009 (4)	0.2427 (2)	0.0346 (9)
N7	0.6471 (3)	0.6946 (4)	−0.0583 (2)	0.0273 (8)
N8	0.5525 (3)	0.6570 (4)	−0.0762 (2)	0.0292 (9)
N9	0.5613 (3)	0.7933 (4)	−0.1807 (2)	0.0313 (9)
N10	0.8408 (3)	0.4749 (4)	−0.0165 (2)	0.0256 (8)
N11	0.8865 (3)	0.3456 (4)	0.0123 (2)	0.0272 (8)
N12	0.9242 (3)	0.4126 (4)	−0.0989 (2)	0.0257 (8)
O1	0.8749 (2)	0.4857 (3)	0.16275 (17)	0.0216 (6)
O2	0.6402 (2)	0.3942 (3)	0.01183 (19)	0.0291 (7)
O3	0.7334 (2)	0.2210 (4)	0.0860 (2)	0.0438 (9)
O4	1.1104 (3)	0.4285 (4)	0.2638 (2)	0.0429 (9)
O5	1.0453 (2)	0.2377 (3)	0.1882 (2)	0.0376 (8)
C1	0.9622 (3)	0.9269 (5)	0.1526 (3)	0.0305 (10)
H1	1.0214	0.9572	0.1898	0.037*
C2	0.8256 (4)	0.9262 (5)	0.0631 (3)	0.0362 (11)
H2	0.7680	0.9569	0.0234	0.043*
C3	0.5556 (3)	0.6412 (5)	0.1802 (3)	0.0326 (11)
H3	0.4927	0.6279	0.1801	0.039*
C4	0.6986 (4)	0.6970 (6)	0.2144 (3)	0.0454 (14)
H4	0.7599	0.7317	0.2449	0.054*
C5	0.5050 (4)	0.7173 (5)	−0.1486 (3)	0.0354 (11)
H5	0.4386	0.7079	−0.1749	0.042*
C6	0.6483 (3)	0.7756 (5)	−0.1216 (3)	0.0311 (11)
H6	0.7046	0.8170	−0.1251	0.037*
C7	0.9344 (3)	0.3150 (5)	−0.0378 (3)	0.0306 (10)
H7	0.9725	0.2328	−0.0318	0.037*
C8	0.8650 (3)	0.5084 (5)	−0.0813 (3)	0.0262 (10)
H8	0.8431	0.5915	−0.1127	0.031*
C9	0.6590 (3)	0.2616 (4)	0.0307 (3)	0.0252 (9)
C10	0.5874 (4)	0.1493 (6)	−0.0158 (4)	0.0509 (15)
H10A	0.6024	0.1186	−0.0640	0.061*
H10B	0.5233	0.1894	−0.0333	0.061*
H10C	0.5906	0.0680	0.0201	0.061*
C11	1.1119 (3)	0.2985 (5)	0.2448 (3)	0.0293 (10)
C12	1.1990 (5)	0.2119 (7)	0.2903 (4)	0.0657 (18)
H12A	1.1994	0.1248	0.2598	0.079*
H12B	1.1978	0.1881	0.3449	0.079*
H12C	1.2562	0.2670	0.2956	0.079*
H15	0.852 (5)	0.482 (8)	0.202 (3)	0.098*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0180 (3)	0.0224 (3)	0.0190 (3)	0.0014 (3)	0.0033 (3)	−0.0005 (3)
Mn2	0.0201 (3)	0.0208 (3)	0.0186 (3)	0.0007 (3)	0.0027 (3)	−0.0017 (3)
Mn3	0.0190 (5)	0.0260 (5)	0.0166 (4)	−0.0020 (4)	0.0015 (4)	0.0000 (4)
Mn4	0.0252 (4)	0.0183 (3)	0.0199 (3)	0.0004 (3)	0.0038 (3)	0.0030 (3)
N1	0.022 (2)	0.0206 (19)	0.0319 (19)	0.0015 (15)	−0.0005 (16)	0.0008 (16)
N2	0.024 (2)	0.0213 (19)	0.0273 (19)	0.0018 (15)	0.0001 (16)	−0.0024 (16)
N3	0.032 (2)	0.0176 (19)	0.037 (2)	0.0012 (17)	0.0004 (18)	0.0003 (17)
N4	0.022 (2)	0.047 (2)	0.0282 (19)	−0.0059 (18)	0.0085 (17)	−0.0126 (18)
N5	0.023 (2)	0.043 (2)	0.0233 (18)	−0.0021 (18)	0.0049 (16)	−0.0082 (17)
N6	0.031 (2)	0.045 (2)	0.0252 (19)	−0.0030 (19)	0.0069 (18)	−0.0105 (18)
N7	0.024 (2)	0.031 (2)	0.0216 (18)	−0.0012 (16)	0.0008 (15)	0.0073 (16)
N8	0.021 (2)	0.036 (2)	0.0246 (18)	0.0021 (17)	0.0002 (16)	0.0104 (17)
N9	0.034 (2)	0.034 (2)	0.0212 (18)	−0.0029 (18)	0.0031 (17)	0.0083 (17)
N10	0.028 (2)	0.0251 (19)	0.0207 (17)	0.0017 (16)	0.0045 (16)	0.0019 (15)
N11	0.036 (2)	0.0241 (19)	0.0228 (18)	0.0048 (17)	0.0118 (17)	0.0036 (16)
N12	0.028 (2)	0.0256 (19)	0.0245 (18)	0.0013 (16)	0.0098 (16)	−0.0005 (16)
O1	0.0207 (15)	0.0223 (15)	0.0200 (14)	0.0008 (12)	0.0044 (12)	0.0025 (12)
O2	0.0233 (17)	0.0239 (16)	0.0361 (17)	0.0035 (13)	0.0046 (14)	0.0021 (13)
O3	0.0241 (19)	0.041 (2)	0.054 (2)	−0.0011 (15)	−0.0035 (17)	0.0138 (17)
O4	0.043 (2)	0.0336 (19)	0.0390 (18)	0.0103 (16)	−0.0036 (16)	0.0024 (16)
O5	0.0299 (19)	0.0368 (19)	0.0424 (19)	−0.0003 (15)	0.0074 (16)	0.0012 (16)
C1	0.024 (2)	0.025 (2)	0.036 (2)	−0.0014 (19)	0.001 (2)	−0.003 (2)
C2	0.030 (3)	0.025 (2)	0.040 (3)	0.001 (2)	−0.006 (2)	−0.001 (2)
C3	0.024 (3)	0.045 (3)	0.026 (2)	−0.005 (2)	0.005 (2)	−0.006 (2)
C4	0.025 (3)	0.072 (4)	0.036 (3)	−0.012 (3)	0.007 (2)	−0.027 (3)
C5	0.027 (3)	0.044 (3)	0.028 (2)	−0.004 (2)	−0.001 (2)	0.009 (2)
C6	0.022 (2)	0.038 (3)	0.028 (2)	−0.005 (2)	0.002 (2)	0.003 (2)
C7	0.036 (3)	0.028 (2)	0.028 (2)	0.007 (2)	0.011 (2)	0.003 (2)
C8	0.028 (2)	0.024 (2)	0.027 (2)	0.0039 (19)	0.010 (2)	0.0048 (19)
C9	0.020 (2)	0.022 (2)	0.035 (2)	0.0007 (18)	0.010 (2)	−0.0019 (19)
C10	0.038 (3)	0.030 (3)	0.069 (4)	−0.005 (2)	−0.004 (3)	−0.004 (3)
C11	0.025 (2)	0.034 (3)	0.029 (2)	−0.001 (2)	0.009 (2)	0.001 (2)
C12	0.053 (4)	0.048 (3)	0.072 (4)	0.018 (3)	−0.010 (3)	0.001 (3)

Geometric parameters (Å, º)

Mn1—N10	2.211 (4)	N6—Mn4^vii	2.240 (4)
Mn1—N4	2.224 (4)	N7—C6	1.317 (5)
Mn1—O1	2.232 (3)	N7—N8	1.363 (5)
Mn1—N1	2.247 (4)	N8—C5	1.316 (6)
Mn1—N7	2.305 (3)	N9—C5	1.335 (6)
Mn1—O2	2.399 (3)	N9—C6	1.342 (6)
Mn2—O1	2.107 (3)	N9—Mn2^viii	2.234 (3)
Mn2—O4	2.114 (3)	N10—C8	1.303 (5)
Mn2—N12^i	2.191 (3)	N10—N11	1.379 (5)
Mn2—N2	2.213 (3)	N11—C7	1.305 (5)
Mn2—N9^ii	2.234 (3)	N12—C8	1.345 (5)
Mn3—N5	2.178 (4)	N12—C7	1.345 (5)
Mn3—N5^iii	2.178 (4)	N12—Mn2^i	2.191 (3)
Mn3—O2^iii	2.226 (3)	O1—H15	0.84 (6)
Mn3—O2	2.226 (3)	O2—C9	1.276 (5)
Mn3—N8^iii	2.248 (3)	O3—C9	1.234 (5)
Mn3—N8	2.248 (3)	O4—C11	1.250 (5)
Mn4—O3	2.162 (3)	O5—C11	1.250 (6)
Mn4—O5	2.181 (3)	C1—H1	0.9300
Mn4—N11	2.206 (3)	C2—H2	0.9300
Mn4—O1	2.230 (3)	C3—H3	0.9300
Mn4—N6^iv	2.240 (4)	C4—H4	0.9300
Mn4—N3^v	2.258 (4)	C5—H5	0.9300
N1—C2	1.320 (6)	C6—H6	0.9300
N1—N2	1.374 (5)	C7—H7	0.9300
N2—C1	1.325 (5)	C8—H8	0.9300
N3—C1	1.334 (6)	C9—C10	1.500 (6)
N3—C2	1.335 (6)	C10—H10A	0.9600
N3—Mn4^vi	2.258 (4)	C10—H10B	0.9600
N4—C4	1.310 (6)	C10—H10C	0.9600
N4—N5	1.344 (5)	C11—C12	1.486 (7)
N5—C3	1.320 (5)	C12—H12A	0.9600
N6—C3	1.313 (6)	C12—H12B	0.9600
N6—C4	1.337 (6)	C12—H12C	0.9600
N10—Mn1—N4	166.36 (14)	C6—N7—N8	104.9 (3)
N10—Mn1—O1	82.04 (12)	C6—N7—Mn1	137.2 (3)
N4—Mn1—O1	89.26 (13)	N8—N7—Mn1	117.1 (2)
N10—Mn1—N1	97.77 (13)	C5—N8—N7	106.1 (3)
N4—Mn1—N1	92.21 (14)	C5—N8—Mn3	129.5 (3)
O1—Mn1—N1	87.04 (12)	N7—N8—Mn3	123.9 (3)
N10—Mn1—N7	96.56 (13)	C5—N9—C6	101.1 (3)
N4—Mn1—N7	92.81 (14)	C5—N9—Mn2^viii	125.5 (3)
O1—Mn1—N7	175.83 (12)	C6—N9—Mn2^viii	133.4 (3)
N1—Mn1—N7	89.27 (13)	C8—N10—N11	105.5 (3)
N10—Mn1—O2	88.77 (12)	C8—N10—Mn1	135.0 (3)
N4—Mn1—O2	83.00 (12)	N11—N10—Mn1	119.3 (2)
O1—Mn1—O2	103.30 (10)	C7—N11—N10	105.2 (3)
N1—Mn1—O2	168.49 (12)	C7—N11—Mn4	132.9 (3)
N7—Mn1—O2	80.55 (12)	N10—N11—Mn4	121.0 (2)
O1—Mn2—O4	104.72 (13)	C8—N12—C7	100.6 (4)
O1—Mn2—N12^i	113.49 (12)	C8—N12—Mn2^i	130.7 (3)
O4—Mn2—N12^i	90.30 (14)	C7—N12—Mn2^i	128.7 (3)
O1—Mn2—N2	88.12 (12)	Mn2—O1—Mn4	110.43 (12)
O4—Mn2—N2	166.63 (14)	Mn2—O1—Mn1	116.03 (12)
N12^i—Mn2—N2	87.90 (13)	Mn4—O1—Mn1	107.50 (12)
O1—Mn2—N9^ii	117.89 (13)	Mn2—O1—H15	113 (5)
O4—Mn2—N9^ii	84.18 (14)	Mn4—O1—H15	104 (5)
N12^i—Mn2—N9^ii	128.03 (14)	Mn1—O1—H15	106 (5)
N2—Mn2—N9^ii	86.51 (13)	C9—O2—Mn3	124.1 (3)
N5—Mn3—N5^iii	180.0	C9—O2—Mn1	123.5 (3)
N5—Mn3—O2^iii	96.53 (13)	Mn3—O2—Mn1	105.11 (11)
N5^iii—Mn3—O2^iii	83.47 (13)	C9—O3—Mn4	141.9 (3)
N5—Mn3—O2	83.47 (13)	C11—O4—Mn2	127.3 (3)
N5^iii—Mn3—O2	96.53 (13)	C11—O5—Mn4	137.7 (3)
O2^iii—Mn3—O2	180.0	N2—C1—N3	113.5 (4)
N5—Mn3—N8^iii	87.11 (14)	N2—C1—H1	123.2
N5^iii—Mn3—N8^iii	92.89 (14)	N3—C1—H1	123.2
O2^iii—Mn3—N8^iii	81.43 (12)	N1—C2—N3	114.5 (4)
O2—Mn3—N8^iii	98.57 (12)	N1—C2—H2	122.7
N5—Mn3—N8	92.89 (14)	N3—C2—H2	122.7
N5^iii—Mn3—N8	87.11 (14)	N6—C3—N5	113.8 (4)
O2^iii—Mn3—N8	98.57 (12)	N6—C3—H3	123.1
O2—Mn3—N8	81.43 (12)	N5—C3—H3	123.1
N8^iii—Mn3—N8	180.0	N4—C4—N6	114.0 (4)
O3—Mn4—O5	167.34 (13)	N4—C4—H4	123.0
O3—Mn4—N11	91.90 (14)	N6—C4—H4	123.0
O5—Mn4—N11	96.21 (13)	N8—C5—N9	113.7 (4)
O3—Mn4—O1	93.28 (12)	N8—C5—H5	123.2
O5—Mn4—O1	97.41 (11)	N9—C5—H5	123.2
N11—Mn4—O1	82.43 (11)	N7—C6—N9	114.2 (4)
O3—Mn4—N6^iv	84.55 (14)	N7—C6—H6	122.9
O5—Mn4—N6^iv	89.18 (13)	N9—C6—H6	122.9
N11—Mn4—N6^iv	168.93 (14)	N11—C7—N12	114.4 (4)
O1—Mn4—N6^iv	87.30 (13)	N11—C7—H7	122.8
O3—Mn4—N3^v	84.71 (14)	N12—C7—H7	122.8
O5—Mn4—N3^v	84.41 (13)	N10—C8—N12	114.3 (4)
N11—Mn4—N3^v	99.23 (13)	N10—C8—H8	122.8
O1—Mn4—N3^v	177.41 (12)	N12—C8—H8	122.8
N6^iv—Mn4—N3^v	90.89 (14)	O3—C9—O2	123.0 (4)
C2—N1—N2	104.6 (3)	O3—C9—C10	118.2 (4)
C2—N1—Mn1	135.2 (3)	O2—C9—C10	118.8 (4)
N2—N1—Mn1	119.7 (2)	C9—C10—H10A	109.5
C1—N2—N1	105.8 (3)	C9—C10—H10B	109.5
C1—N2—Mn2	132.0 (3)	H10A—C10—H10B	109.5
N1—N2—Mn2	122.2 (2)	C9—C10—H10C	109.5
C1—N3—C2	101.5 (4)	H10A—C10—H10C	109.5
C1—N3—Mn4^vi	123.8 (3)	H10B—C10—H10C	109.5
C2—N3—Mn4^vi	129.7 (3)	O4—C11—O5	123.7 (4)
C4—N4—N5	105.1 (4)	O4—C11—C12	118.2 (5)
C4—N4—Mn1	136.4 (3)	O5—C11—C12	118.0 (4)
N5—N4—Mn1	118.4 (3)	C11—C12—H12A	109.5
C3—N5—N4	106.0 (3)	C11—C12—H12B	109.5
C3—N5—Mn3	128.5 (3)	H12A—C12—H12B	109.5
N4—N5—Mn3	125.5 (3)	C11—C12—H12C	109.5
C3—N6—C4	101.2 (4)	H12A—C12—H12C	109.5
C3—N6—Mn4^vii	125.0 (3)	H12B—C12—H12C	109.5
C4—N6—Mn4^vii	133.1 (3)
N10—Mn1—N1—C2	115.5 (4)	N12^i—Mn2—O1—Mn1	−61.26 (17)
N4—Mn1—N1—C2	−73.8 (5)	N2—Mn2—O1—Mn1	25.63 (15)
O1—Mn1—N1—C2	−162.9 (4)	N9^ii—Mn2—O1—Mn1	110.68 (16)
N7—Mn1—N1—C2	19.0 (5)	O3—Mn4—O1—Mn2	−172.02 (14)
O2—Mn1—N1—C2	−8.7 (9)	O5—Mn4—O1—Mn2	14.78 (14)
N10—Mn1—N1—N2	−73.8 (3)	N11—Mn4—O1—Mn2	−80.54 (14)
N4—Mn1—N1—N2	96.9 (3)	N6^iv—Mn4—O1—Mn2	103.59 (15)
O1—Mn1—N1—N2	7.7 (3)	O3—Mn4—O1—Mn1	−44.55 (14)
N7—Mn1—N1—N2	−170.3 (3)	O5—Mn4—O1—Mn1	142.25 (12)
O2—Mn1—N1—N2	162.0 (5)	N11—Mn4—O1—Mn1	46.93 (14)
C2—N1—N2—C1	0.4 (4)	N6^iv—Mn4—O1—Mn1	−128.93 (14)
Mn1—N1—N2—C1	−172.8 (3)	N10—Mn1—O1—Mn2	75.58 (15)
C2—N1—N2—Mn2	−177.2 (3)	N4—Mn1—O1—Mn2	−114.96 (15)
Mn1—N1—N2—Mn2	9.6 (4)	N1—Mn1—O1—Mn2	−22.70 (15)
O1—Mn2—N2—C1	161.1 (4)	O2—Mn1—O1—Mn2	162.41 (13)
O4—Mn2—N2—C1	−2.8 (8)	N10—Mn1—O1—Mn4	−48.57 (13)
N12^i—Mn2—N2—C1	−85.3 (4)	N4—Mn1—O1—Mn4	120.90 (14)
N9^ii—Mn2—N2—C1	43.1 (4)	N1—Mn1—O1—Mn4	−146.85 (14)
O1—Mn2—N2—N1	−21.9 (3)	O2—Mn1—O1—Mn4	38.27 (13)
O4—Mn2—N2—N1	174.1 (5)	N5—Mn3—O2—C9	107.1 (3)
N12^i—Mn2—N2—N1	91.7 (3)	N5^iii—Mn3—O2—C9	−72.9 (3)
N9^ii—Mn2—N2—N1	−140.0 (3)	N8^iii—Mn3—O2—C9	21.0 (3)
N10—Mn1—N4—C4	95.1 (8)	N8—Mn3—O2—C9	−159.0 (3)
O1—Mn1—N4—C4	44.9 (5)	N5—Mn3—O2—Mn1	−43.82 (13)
N1—Mn1—N4—C4	−42.1 (5)	N5^iii—Mn3—O2—Mn1	136.18 (13)
N7—Mn1—N4—C4	−131.5 (5)	N8^iii—Mn3—O2—Mn1	−129.89 (13)
O2—Mn1—N4—C4	148.4 (5)	N8—Mn3—O2—Mn1	50.11 (13)
N10—Mn1—N4—N5	−78.9 (7)	N10—Mn1—O2—C9	61.5 (3)
O1—Mn1—N4—N5	−129.1 (3)	N4—Mn1—O2—C9	−107.6 (3)
N1—Mn1—N4—N5	143.9 (3)	O1—Mn1—O2—C9	−20.0 (3)
N7—Mn1—N4—N5	54.5 (3)	N1—Mn1—O2—C9	−173.5 (6)
O2—Mn1—N4—N5	−25.6 (3)	N7—Mn1—O2—C9	158.4 (3)
C4—N4—N5—C3	1.1 (5)	N10—Mn1—O2—Mn3	−147.35 (14)
Mn1—N4—N5—C3	176.8 (3)	N4—Mn1—O2—Mn3	43.55 (14)
C4—N4—N5—Mn3	179.7 (4)	O1—Mn1—O2—Mn3	131.13 (12)
Mn1—N4—N5—Mn3	−4.6 (5)	N1—Mn1—O2—Mn3	−22.4 (7)
O2^iii—Mn3—N5—C3	32.4 (4)	N7—Mn1—O2—Mn3	−50.49 (13)
O2—Mn3—N5—C3	−147.6 (4)	O5—Mn4—O3—C9	−150.1 (5)
N8^iii—Mn3—N5—C3	−48.6 (4)	N11—Mn4—O3—C9	−20.2 (5)
N8—Mn3—N5—C3	131.4 (4)	O1—Mn4—O3—C9	62.3 (5)
O2^iii—Mn3—N5—N4	−145.9 (4)	N6^iv—Mn4—O3—C9	149.2 (5)
O2—Mn3—N5—N4	34.1 (4)	N3^v—Mn4—O3—C9	−119.3 (5)
N8^iii—Mn3—N5—N4	133.1 (4)	O1—Mn2—O4—C11	43.0 (4)
N8—Mn3—N5—N4	−46.9 (4)	N12^i—Mn2—O4—C11	−71.4 (4)
N10—Mn1—N7—C6	−50.2 (5)	N2—Mn2—O4—C11	−153.5 (5)
N4—Mn1—N7—C6	139.7 (5)	N9^ii—Mn2—O4—C11	160.4 (4)
N1—Mn1—N7—C6	47.5 (5)	O3—Mn4—O5—C11	−121.2 (6)
O2—Mn1—N7—C6	−137.8 (5)	N11—Mn4—O5—C11	109.3 (4)
N10—Mn1—N7—N8	117.8 (3)	O1—Mn4—O5—C11	26.2 (5)
N4—Mn1—N7—N8	−52.3 (3)	N6^iv—Mn4—O5—C11	−61.0 (5)
N1—Mn1—N7—N8	−144.4 (3)	N3^v—Mn4—O5—C11	−152.0 (5)
O2—Mn1—N7—N8	30.2 (3)	N1—N2—C1—N3	−0.4 (5)
C6—N7—N8—C5	0.4 (5)	Mn2—N2—C1—N3	176.9 (3)
Mn1—N7—N8—C5	−171.2 (3)	C2—N3—C1—N2	0.2 (5)
C6—N7—N8—Mn3	173.7 (3)	Mn4^vi—N3—C1—N2	157.4 (3)
Mn1—N7—N8—Mn3	2.1 (4)	N2—N1—C2—N3	−0.4 (5)
N5—Mn3—N8—C5	−141.1 (4)	Mn1—N1—C2—N3	171.3 (3)
N5^iii—Mn3—N8—C5	38.9 (4)	C1—N3—C2—N1	0.1 (6)
O2^iii—Mn3—N8—C5	−44.1 (4)	Mn4^vi—N3—C2—N1	−155.1 (3)
O2—Mn3—N8—C5	135.9 (4)	C4—N6—C3—N5	0.4 (6)
N5—Mn3—N8—N7	47.2 (3)	Mn4^vii—N6—C3—N5	−170.8 (3)
N5^iii—Mn3—N8—N7	−132.8 (3)	N4—N5—C3—N6	−1.0 (6)
O2^iii—Mn3—N8—N7	144.2 (3)	Mn3—N5—C3—N6	−179.5 (3)
O2—Mn3—N8—N7	−35.8 (3)	N5—N4—C4—N6	−1.0 (6)
N4—Mn1—N10—C8	168.7 (5)	Mn1—N4—C4—N6	−175.5 (4)
O1—Mn1—N10—C8	−140.5 (4)	C3—N6—C4—N4	0.4 (6)
N1—Mn1—N10—C8	−54.6 (4)	Mn4^vii—N6—C4—N4	170.6 (3)
N7—Mn1—N10—C8	35.6 (4)	N7—N8—C5—N9	−0.1 (6)
O2—Mn1—N10—C8	115.9 (4)	Mn3—N8—C5—N9	−172.9 (3)
N4—Mn1—N10—N11	−17.2 (7)	C6—N9—C5—N8	−0.3 (5)
O1—Mn1—N10—N11	33.7 (3)	Mn2^viii—N9—C5—N8	179.7 (3)
N1—Mn1—N10—N11	119.5 (3)	N8—N7—C6—N9	−0.6 (5)
N7—Mn1—N10—N11	−150.3 (3)	Mn1—N7—C6—N9	168.3 (3)
O2—Mn1—N10—N11	−70.0 (3)	C5—N9—C6—N7	0.6 (5)
C8—N10—N11—C7	0.6 (4)	Mn2^viii—N9—C6—N7	−179.4 (3)
Mn1—N10—N11—C7	−175.1 (3)	N10—N11—C7—N12	−0.7 (5)
C8—N10—N11—Mn4	170.9 (3)	Mn4—N11—C7—N12	−169.3 (3)
Mn1—N10—N11—Mn4	−4.8 (4)	C8—N12—C7—N11	0.4 (5)
O3—Mn4—N11—C7	−126.9 (4)	Mn2^i—N12—C7—N11	179.8 (3)
O5—Mn4—N11—C7	43.4 (4)	N11—N10—C8—N12	−0.4 (5)
O1—Mn4—N11—C7	140.0 (4)	Mn1—N10—C8—N12	174.3 (3)
N6^iv—Mn4—N11—C7	162.1 (7)	C7—N12—C8—N10	0.1 (5)
N3^v—Mn4—N11—C7	−42.0 (4)	Mn2^i—N12—C8—N10	−179.3 (3)
O3—Mn4—N11—N10	65.9 (3)	Mn4—O3—C9—O2	−45.7 (7)
O5—Mn4—N11—N10	−123.8 (3)	Mn4—O3—C9—C10	134.6 (5)
O1—Mn4—N11—N10	−27.1 (3)	Mn3—O2—C9—O3	−130.5 (4)
N6^iv—Mn4—N11—N10	−5.1 (9)	Mn1—O2—C9—O3	15.2 (6)
N3^v—Mn4—N11—N10	150.9 (3)	Mn3—O2—C9—C10	49.2 (5)
O4—Mn2—O1—Mn4	−35.54 (15)	Mn1—O2—C9—C10	−165.1 (3)
N12^i—Mn2—O1—Mn4	61.35 (16)	Mn2—O4—C11—O5	−10.2 (7)
N2—Mn2—O1—Mn4	148.24 (14)	Mn2—O4—C11—C12	167.9 (4)
N9^ii—Mn2—O1—Mn4	−126.71 (14)	Mn4—O5—C11—O4	−32.0 (7)
O4—Mn2—O1—Mn1	−158.16 (14)	Mn4—O5—C11—C12	149.8 (4)

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