Di-[mu]-acetato-bis­[bis(4-amino­benzoato)(2,2'-bipyridyl)­manganese(II)]

In the title compound, [Mn₂(C₇H₆NO₂)₂(C₂H₃O₂)₂(C₁₀H₈N₂)₂], the two Mn^II atoms are each coordinated by one 2,2'-bi­pyridyl mol­ecule, one 4-amino­benzoate ion and two acetate ions. The two Mn atoms exhibit different coordination environments: one is coordinated by two N and four O atoms, while the other is coordinated by two N and three O atoms. The two Mn atoms are bridged by two acetate ions in a syn-anti mode, with an Mn...Mn distance of 4.081 (1) Å.

S1. Comment

As a bifunctional organic ligand, 4-aminobenzoic acid (4-abzH) has been extensively reported in coordination chemistry because of the richness of its coordination modes.

(i) 4-abzH can act as a carboxylic acid synthon and also as a good monodentate ligand through the amine group (Fur et al., 1996; Chen et al., 2002).

(ii) Deprotonated 4-aminobenzoic acid can act as a monodentate ligand through a carboxylate O atom (Sundberg et al., 1998; Chandrasekhar et al., 1988; Amiraslanov et al., 1979), and as a chelating and/or bridging ligand through its amine and/or carboxylate groups (Zheng et al., 2001; Rzaezynska et al., 1994; Hauptmann et al., 2000).

(iii) 4-abzH may be protonated to form organic cation templating agents (Wang et al., 2002).

Although some complexes containing mixed 4-aminobenzoate and other nitrogen-donor ligands have been synthesized and characterized, complexes containing mixed 4-aminobenzoate and 2,2'-bipyridine (2,2'-bipy) ligands have rarely been reported. To the best of our knowledge, there are only three reports of structures with 4-aminobenzoate/2,2'-bipyridine ligands, viz. [Cu(2,2'-bipy)(4-abz)₂]·0.5H₂O (Naldini et al., 1984), [Cu(2,2'-bipy)(4-abzH)(4-abz)]₂(NO₃)₂·1.5H₂O and {[Cu(2,2'-bipy)(4,4'-bipy)_0.5(4-abz)](ClO₄)·0.5H₂O}_n (Hu et al., 2003). We report here the synthesis and characterization of the title complex, (I), in which the amine group of the 4-aminobenzoate moiety is uncoordinated.

Compound (I) consists of dimeric unit, [Mn₂(MeCOO)₂(2,2'-bipy)₂(4-abz)₂] (Fig. 1). The coordination geometry around atom Mn1 is distorted octahedral, the six coordination sites being occupied by two N atoms from a 2,2'-bipy molecule and four O atoms from a 4-aminobenzoate and two acetate ligands. The Mn—N distances are 2.242 (3) and 2.296 (3) Å, and the Mn—O distances range from 2.087 (3) Å to 2.454 (3) Å (Table 1). In the Mn1 coordination environment, the 4-aminobenzoate molecule exhibits a bidentate chelating coordination mode, while in the Mn2 coordination environment, the 4-aminobenzoate molecule exhibits a monodentate coordination mode, the Mn2···O8 distance being 2.655 (3) Å. Atom Mn2 is coordinated by two N atoms from a 2,2'-bipy ligand and three O atoms from a 4-aminobenzoate and two acetate ions, forming a highly distorted square pyramid. The apical position of the pyramid is occupied by atom O2, with an Mn—O distance of 2.146 (2) Å, while the equatorial plane is defined by atoms N5, N6, O4 and O7, with Mn—N distances of 2.253 (3) and 2.298 (3) Å, and Mn—O distances of 2.069 (2)–2.155 (2) Å.

Atoms N3 and N4 of the 4-aminobenzoate ligands are uncoordinated but link the molecules via hydrogen bonds (Table 2). A C—H···π interaction is also present (Table 2; Cg is the centroid of the C23–C28 ring of the 4-aminobenzoate ligand). Thus, the binuclear complexes are bound together through N—H···O hydrogen bonds and C—H···π interactions into a three-dimensional network (Fig. 2). There are no π–π stacking interactions.

In (I), atoms Mn1 and Mn2 are bridged by the two acetate groups in a syn–anti fashion, and the Mn—O_syn bond distances are longer than the Mn—O_anti distances (Table 3). This configuration is in contrast to the reverse relationship observed in another two syn–anti diacetate-bridged complexes, [Mn₂(µ-MeCOO)₂(tpa)₂](TCNQ)₂·2CH₃CN, (II) [tpa is tris(2-pyridylmethyl)amine and TCNQ is tetracyanoquinodimethane; Oshio et al., 1993], and [Mn₂(µ-MeCOO)₂(bpia)₂](ClO₄)₂, (III) [bpia is bis(picolyl)(N-methylimidazol-2-yl)amine; Triller et al., 2002]. This difference may be attributed to the different coordination geometry around the Mn atoms and the influence of the coexisting ligands. The Mn1···Mn2 distance of 4.081 (1) Å in (I) is comparable to those in (II) and (III), but is considerably shorter than those in the other syn–anti dicarboxylate-bridged complexes [Mn₂(µ-EtCOO)₂(2,2'-bipy)₄](ClO₄)₂, (IV) [4.653 (3) Å; Zhang et al., 2001], and [Mn₂(µ-PhCOO)₂(2,2'-bipy)₄](ClO₄)₂, (V) [4.509 (1) Å; Albela et al., 1998]. The longer Mn···Mn distances in (IV) and (V) may be attributed to the fact that the Mn—O—C angles of the EtCOO and PhCOO bridges are larger than those of the MeCOO bridge.

S2. Experimental

An ethanol solution (8 ml) of 2,2'-bipyridine (1.2 mmol) and 4-aminobenzoic acid (1.6 mmol) was added slowly to an aqueous solution (10 ml) of Mn(CH₃CO₂)₂·4H₂O (1 mmol) with continuous stirring. After half an hour, the reaction mixture was allowed to stand at room temperature undisturbed for two weeks, resulting in yellow crystals (yield 61%). Analysis calculated for C₃₈H₃₄Mn₂N₆O₈: C 56.17, H 4.22, N 10.34%; found: C 56.01, H4.31, N 10.37%. IR (KBr, cm⁻¹): 3421 (s), 3325 (s), 3221 (s), 1639 (s), 1574 (s), 1443 (s), 1383 (s), 1306 (m), 1173 (m), 1016 (m), 854 (m), 791 (s), 773 (s), 627 (m).

S3. Refinement

All H atoms were positioned geometrically and treated as riding, with N—H distance of 0.86 Å and C—H distances of 0.93–0.96 Å, and with U_iso(H) values of 1.2U_eq(parent atom) or 1.5U_eq(C_methyl). The maximum residual density is located 1.76 Å from atom H1A, and the minimum density is 0.72 Å from atom Mn1.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SAINT (Siemens, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1994); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The molecular structure of (I), showing atomic displacement ellipsoids at the 30% probability level.
	Fig. 2. The crystal structure of (I). Broken lines indicate hydrogen bonds.

Di-µ-acetato-bis[bis(4-aminobenzoato)(2,2'-bipyridyl)manganese(II)]

Crystal data

[Mn2(C7H6NO2)2(C2H3O2)2(C10H8N2)2]	Dx = 1.513 Mg m^−3
Mr = 812.59	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pca21	Cell parameters from 7843 reflections
a = 20.8346 (7) Å	θ = 3.0–27.5°
b = 8.0289 (3) Å	µ = 0.77 mm^−1
c = 21.3189 (8) Å	T = 293 K
V = 3566.2 (2) Å^3	Prism, yellow
Z = 4	0.44 × 0.40 × 0.16 mm
F(000) = 1672

Data collection

Siemens SMART CCD diffractometer	7506 independent reflections
Radiation source: fine-focus sealed tube	7084 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
ω scans	θmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −26→26
Tmin = 0.759, Tmax = 0.884	k = −10→10
26202 measured reflections	l = −22→27

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.040	H-atom parameters constrained
wR(F^2) = 0.101	w = 1/[σ^2(Fo^2) + (0.0547P)^2 + 1.202P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
7506 reflections	Δρmax = 0.97 e Å^−3
487 parameters	Δρmin = −0.26 e Å^−3
1 restraint	Absolute structure: Flack (1983), 3306 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.446 (15)

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	0.441724 (18)	0.37865 (5)	0.07105 (2)	0.02938 (10)
Mn2	0.300631 (18)	0.11253 (5)	0.15812 (2)	0.02957 (10)
N1	0.50561 (11)	0.4663 (3)	0.15237 (14)	0.0332 (5)
N2	0.53860 (12)	0.4458 (3)	0.03283 (13)	0.0348 (5)
N3	0.17865 (14)	0.5497 (4)	−0.21161 (15)	0.0479 (7)
H3A	0.1608	0.6454	−0.2165	0.057*
H3B	0.1651	0.4652	−0.2325	0.057*
N4	0.57318 (14)	0.0422 (4)	0.44227 (15)	0.0474 (7)
H4A	0.5838	0.1339	0.4603	0.057*
H4B	0.5945	−0.0474	0.4498	0.057*
N5	0.20844 (12)	0.0075 (3)	0.19664 (13)	0.0331 (5)
N6	0.23470 (11)	0.0440 (3)	0.07567 (13)	0.0339 (5)
O1	0.36361 (12)	0.4306 (4)	0.12909 (15)	0.0641 (8)
O2	0.26433 (10)	0.3608 (3)	0.14697 (14)	0.0491 (6)
O3	0.47251 (10)	0.1318 (3)	0.08998 (13)	0.0435 (6)
O4	0.37405 (10)	0.0337 (3)	0.09992 (13)	0.0474 (6)
O5	0.39973 (11)	0.5880 (3)	−0.00207 (13)	0.0464 (6)
O6	0.39416 (10)	0.3173 (3)	−0.01756 (12)	0.0425 (5)
O7	0.34967 (10)	0.1759 (3)	0.24387 (11)	0.0425 (5)
O8	0.35159 (12)	−0.0980 (3)	0.24023 (14)	0.0519 (6)
C1	0.28627 (19)	0.6418 (4)	0.1201 (2)	0.0570 (11)
H1A	0.3233	0.7071	0.1096	0.085*
H1B	0.2664	0.6869	0.1570	0.085*
H1C	0.2563	0.6444	0.0859	0.085*
C2	0.30614 (13)	0.4660 (4)	0.13237 (16)	0.0325 (6)
C3	0.46103 (19)	−0.1535 (4)	0.1141 (2)	0.0584 (11)
H3C	0.5071	−0.1485	0.1138	0.088*
H3D	0.4467	−0.2294	0.0822	0.088*
H3E	0.4465	−0.1913	0.1543	0.088*
C4	0.43427 (14)	0.0164 (4)	0.10126 (16)	0.0322 (6)
C5	0.37720 (13)	0.4654 (4)	−0.03159 (15)	0.0337 (6)
C6	0.32768 (13)	0.4897 (3)	−0.08101 (14)	0.0290 (6)
C7	0.30458 (14)	0.3556 (4)	−0.11594 (16)	0.0355 (7)
H7A	0.3220	0.2502	−0.1097	0.043*
C8	0.25663 (16)	0.3767 (4)	−0.15939 (16)	0.0388 (7)
H8A	0.2422	0.2851	−0.1821	0.047*
C9	0.22902 (14)	0.5320 (4)	−0.17022 (15)	0.0352 (6)
C10	0.25242 (17)	0.6657 (4)	−0.13549 (17)	0.0440 (8)
H10A	0.2351	0.7711	−0.1419	0.053*
C11	0.30038 (15)	0.6453 (4)	−0.09208 (19)	0.0420 (8)
H11A	0.3149	0.7371	−0.0696	0.050*
C12	0.48738 (16)	0.4642 (4)	0.21246 (17)	0.0417 (7)
H12A	0.4457	0.4308	0.2219	0.050*
C13	0.52729 (18)	0.5089 (5)	0.26095 (19)	0.0512 (9)
H13A	0.5130	0.5055	0.3023	0.061*
C14	0.5893 (2)	0.5594 (6)	0.2469 (2)	0.0622 (11)
H14A	0.6172	0.5919	0.2786	0.075*
C15	0.60875 (17)	0.5608 (5)	0.1857 (2)	0.0498 (8)
H15A	0.6502	0.5941	0.1754	0.060*
C16	0.56636 (14)	0.5121 (4)	0.13905 (16)	0.0327 (7)
C17	0.58388 (12)	0.5050 (3)	0.07151 (18)	0.0304 (6)
C18	0.64387 (14)	0.5527 (4)	0.04914 (18)	0.0438 (8)
H18A	0.6743	0.5977	0.0762	0.053*
C19	0.65761 (16)	0.5321 (5)	−0.01388 (19)	0.0501 (9)
H19A	0.6976	0.5622	−0.0295	0.060*
C20	0.61187 (17)	0.4671 (5)	−0.05312 (18)	0.0474 (8)
H20A	0.6204	0.4502	−0.0955	0.057*
C21	0.55273 (15)	0.4276 (4)	−0.02783 (17)	0.0424 (7)
H21A	0.5212	0.3862	−0.0544	0.051*
C22	0.37103 (13)	0.0364 (4)	0.26274 (16)	0.0351 (6)
C23	0.42170 (14)	0.0371 (4)	0.31252 (15)	0.0330 (6)
C24	0.43810 (14)	0.1818 (4)	0.34470 (16)	0.0368 (7)
H24A	0.4157	0.2796	0.3366	0.044*
C25	0.48702 (15)	0.1827 (4)	0.38843 (15)	0.0396 (7)
H25A	0.4967	0.2808	0.4096	0.048*
C26	0.52225 (14)	0.0388 (4)	0.40140 (15)	0.0349 (6)
C27	0.50637 (15)	−0.1062 (4)	0.36861 (17)	0.0396 (7)
H27A	0.5297	−0.2032	0.3757	0.048*
C28	0.45646 (16)	−0.1073 (4)	0.32580 (17)	0.0377 (7)
H28A	0.4459	−0.2061	0.3055	0.045*
C29	0.19764 (15)	−0.0110 (4)	0.25801 (17)	0.0427 (8)
H29A	0.2312	0.0099	0.2856	0.051*
C30	0.13974 (18)	−0.0592 (5)	0.28246 (19)	0.0504 (9)
H30A	0.1343	−0.0693	0.3256	0.060*
C31	0.09020 (16)	−0.0920 (5)	0.2424 (2)	0.0505 (8)
H31A	0.0502	−0.1230	0.2580	0.061*
C32	0.10006 (15)	−0.0786 (4)	0.17816 (17)	0.0414 (7)
H32A	0.0672	−0.1034	0.1501	0.050*
C33	0.16010 (12)	−0.0271 (3)	0.15636 (18)	0.0313 (6)
C34	0.17493 (14)	−0.0076 (3)	0.08928 (16)	0.0327 (7)
C35	0.13030 (16)	−0.0389 (5)	0.04195 (18)	0.0441 (8)
H35A	0.0890	−0.0737	0.0520	0.053*
C36	0.14785 (18)	−0.0178 (5)	−0.01975 (19)	0.0512 (9)
H36A	0.1188	−0.0393	−0.0519	0.061*
C37	0.20893 (19)	0.0354 (5)	−0.03303 (18)	0.0492 (8)
H37A	0.2218	0.0507	−0.0744	0.059*
C38	0.25104 (17)	0.0661 (4)	0.01542 (18)	0.0441 (7)
H38A	0.2922	0.1035	0.0060	0.053*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.02035 (18)	0.0344 (2)	0.0334 (2)	−0.00014 (14)	−0.00134 (17)	0.00223 (19)
Mn2	0.02219 (19)	0.0337 (2)	0.0328 (2)	−0.00080 (15)	−0.00199 (17)	0.00045 (19)
N1	0.0270 (11)	0.0361 (11)	0.0365 (15)	0.0002 (9)	0.0000 (11)	−0.0031 (11)
N2	0.0271 (12)	0.0420 (13)	0.0351 (16)	−0.0030 (10)	0.0015 (10)	0.0006 (11)
N3	0.0457 (16)	0.0572 (16)	0.0408 (18)	0.0069 (14)	−0.0155 (14)	−0.0023 (14)
N4	0.0420 (15)	0.0550 (16)	0.0451 (19)	−0.0020 (13)	−0.0156 (14)	0.0024 (14)
N5	0.0272 (12)	0.0415 (12)	0.0306 (14)	−0.0045 (10)	−0.0013 (10)	0.0017 (10)
N6	0.0265 (11)	0.0434 (12)	0.0318 (14)	−0.0005 (9)	−0.0021 (11)	−0.0009 (11)
O1	0.0316 (12)	0.0405 (11)	0.0552 (18)	0.0258 (13)	0.0090 (11)	0.0185 (16)
O2	0.0328 (11)	0.0384 (11)	0.076 (2)	−0.0032 (8)	−0.0144 (11)	0.0152 (11)
O3	0.0300 (10)	0.0361 (11)	0.0646 (18)	−0.0015 (8)	−0.0086 (10)	0.0054 (10)
O4	0.0258 (10)	0.0709 (16)	0.0455 (15)	0.0049 (10)	0.0028 (10)	−0.0050 (12)
O5	0.0412 (12)	0.0493 (12)	0.0486 (15)	−0.0031 (10)	−0.0134 (11)	−0.0051 (11)
O6	0.0374 (11)	0.0445 (11)	0.0457 (14)	0.0054 (9)	−0.0104 (10)	0.0037 (10)
O7	0.0415 (12)	0.0510 (12)	0.0351 (12)	0.0069 (10)	−0.0111 (10)	0.0010 (10)
O8	0.0432 (13)	0.0574 (14)	0.0550 (17)	−0.0075 (10)	−0.0126 (12)	−0.0104 (12)
C1	0.056 (2)	0.0335 (16)	0.082 (3)	0.0041 (15)	−0.004 (2)	0.0041 (17)
C2	0.0299 (14)	0.0380 (14)	0.0296 (16)	0.0061 (11)	−0.0015 (11)	−0.0014 (12)
C3	0.051 (2)	0.0346 (16)	0.089 (3)	0.0033 (15)	−0.013 (2)	0.0058 (18)
C4	0.0275 (13)	0.0348 (14)	0.0342 (17)	0.0006 (11)	−0.0024 (12)	−0.0052 (12)
C5	0.0249 (13)	0.0449 (15)	0.0313 (16)	−0.0013 (12)	0.0002 (12)	0.0018 (13)
C6	0.0241 (13)	0.0371 (13)	0.0259 (16)	−0.0007 (10)	0.0015 (11)	0.0030 (11)
C7	0.0329 (15)	0.0372 (14)	0.0364 (18)	0.0042 (11)	0.0007 (12)	0.0005 (12)
C8	0.0380 (16)	0.0415 (15)	0.0370 (17)	0.0005 (12)	−0.0045 (13)	−0.0096 (12)
C9	0.0284 (13)	0.0521 (17)	0.0252 (16)	0.0012 (12)	0.0015 (11)	0.0043 (13)
C10	0.0469 (18)	0.0332 (14)	0.052 (2)	0.0032 (13)	−0.0109 (15)	0.0084 (14)
C11	0.0425 (17)	0.0325 (13)	0.051 (2)	−0.0038 (12)	−0.0137 (14)	−0.0005 (14)
C12	0.0389 (17)	0.0495 (17)	0.0369 (18)	0.0010 (14)	0.0053 (14)	−0.0012 (14)
C13	0.061 (2)	0.059 (2)	0.034 (2)	−0.0002 (17)	0.0008 (17)	−0.0101 (16)
C14	0.056 (2)	0.084 (3)	0.047 (2)	−0.019 (2)	−0.0123 (19)	−0.013 (2)
C15	0.0365 (17)	0.065 (2)	0.048 (2)	−0.0128 (16)	−0.0056 (15)	−0.0096 (18)
C16	0.0285 (13)	0.0331 (13)	0.0363 (19)	−0.0013 (11)	−0.0012 (12)	−0.0021 (11)
C17	0.0234 (11)	0.0298 (11)	0.0381 (17)	−0.0010 (9)	0.0000 (13)	−0.0001 (12)
C18	0.0258 (14)	0.0532 (19)	0.052 (2)	−0.0096 (13)	0.0032 (13)	−0.0014 (15)
C19	0.0340 (17)	0.064 (2)	0.052 (2)	−0.0066 (15)	0.0154 (15)	0.0006 (17)
C20	0.0425 (18)	0.063 (2)	0.036 (2)	0.0023 (16)	0.0098 (14)	0.0068 (16)
C21	0.0333 (16)	0.0560 (18)	0.0377 (19)	−0.0021 (13)	−0.0001 (13)	0.0001 (15)
C22	0.0230 (13)	0.0501 (16)	0.0321 (17)	0.0001 (12)	0.0027 (12)	0.0010 (13)
C23	0.0270 (14)	0.0395 (14)	0.0325 (17)	0.0013 (11)	−0.0012 (12)	0.0038 (12)
C24	0.0386 (16)	0.0372 (15)	0.0347 (17)	0.0045 (12)	−0.0044 (12)	0.0001 (13)
C25	0.0429 (17)	0.0386 (15)	0.0375 (18)	−0.0012 (13)	−0.0086 (13)	−0.0042 (13)
C26	0.0311 (14)	0.0465 (16)	0.0270 (16)	−0.0028 (12)	0.0016 (12)	0.0054 (12)
C27	0.0339 (15)	0.0385 (15)	0.0466 (19)	0.0033 (12)	−0.0046 (14)	0.0077 (13)
C28	0.0373 (15)	0.0342 (15)	0.0418 (19)	−0.0018 (11)	−0.0025 (14)	−0.0006 (12)
C29	0.0387 (17)	0.0563 (19)	0.0332 (18)	−0.0081 (14)	−0.0032 (13)	0.0034 (14)
C30	0.047 (2)	0.067 (2)	0.037 (2)	−0.0045 (17)	0.0097 (15)	0.0060 (17)
C31	0.0304 (16)	0.063 (2)	0.058 (2)	−0.0088 (14)	0.0102 (16)	0.0027 (18)
C32	0.0282 (14)	0.0486 (16)	0.047 (2)	−0.0038 (12)	−0.0010 (13)	0.0000 (14)
C33	0.0246 (12)	0.0303 (12)	0.0391 (17)	−0.0011 (10)	−0.0030 (13)	−0.0011 (13)
C34	0.0264 (13)	0.0318 (13)	0.0398 (19)	0.0012 (10)	−0.0030 (12)	0.0004 (11)
C35	0.0310 (16)	0.056 (2)	0.045 (2)	−0.0071 (14)	−0.0071 (14)	0.0033 (15)
C36	0.053 (2)	0.064 (2)	0.037 (2)	−0.0072 (17)	−0.0170 (16)	−0.0034 (16)
C37	0.059 (2)	0.060 (2)	0.0292 (19)	−0.0049 (17)	−0.0030 (16)	0.0002 (15)
C38	0.0367 (16)	0.0560 (18)	0.0397 (19)	−0.0014 (14)	0.0034 (14)	−0.0002 (15)

Geometric parameters (Å, º)

Mn1—O1	2.087 (3)	C9—C10	1.392 (5)
Mn1—O3	2.122 (2)	C10—C11	1.372 (5)
Mn1—O6	2.189 (2)	C10—H10A	0.9300
Mn1—N2	2.242 (3)	C11—H11A	0.9300
Mn1—N1	2.296 (3)	C12—C13	1.375 (5)
Mn1—O5	2.454 (3)	C12—H12A	0.9300
Mn2—O4	2.069 (2)	C13—C14	1.387 (6)
Mn2—O2	2.146 (2)	C13—H13A	0.9300
Mn2—O7	2.155 (2)	C14—C15	1.365 (6)
Mn2—N5	2.253 (3)	C14—H14A	0.9300
Mn2—N6	2.298 (3)	C15—C16	1.386 (5)
N1—C12	1.336 (4)	C15—H15A	0.9300
N1—C16	1.348 (4)	C16—C17	1.486 (5)
N2—C17	1.340 (4)	C17—C18	1.391 (4)
N2—C21	1.334 (4)	C18—C19	1.384 (5)
N3—C9	1.379 (4)	C18—H18A	0.9300
N3—O8^i	3.074 (4)	C19—C20	1.371 (5)
N3—H3A	0.8600	C19—H19A	0.9300
N3—H3B	0.8600	C20—C21	1.382 (5)
N4—C26	1.373 (4)	C20—H20A	0.9300
N4—O6^ii	3.087 (4)	C21—H21A	0.9300
N4—H4A	0.8600	C22—C23	1.497 (4)
N4—H4B	0.8600	C23—C24	1.391 (4)
N5—C29	1.336 (5)	C23—C28	1.396 (4)
N5—C33	1.352 (4)	C24—C25	1.381 (4)
N6—C38	1.341 (4)	C24—H24A	0.9300
N6—C34	1.344 (4)	C25—C26	1.397 (4)
O1—C2	1.232 (4)	C25—H25A	0.9300
O2—C2	1.252 (4)	C26—C27	1.397 (5)
O3—C4	1.245 (4)	C27—C28	1.384 (5)
O4—C4	1.263 (4)	C27—H27A	0.9300
O5—C5	1.259 (4)	C28—H28A	0.9300
O6—C5	1.276 (4)	C29—C30	1.370 (5)
O7—C22	1.271 (4)	C29—H29A	0.9300
O8—C22	1.248 (4)	C30—C31	1.365 (6)
C1—C2	1.494 (4)	C30—H30A	0.9300
C1—H1A	0.9600	C31—C32	1.389 (5)
C1—H1B	0.9600	C31—H31A	0.9300
C1—H1C	0.9600	C32—C33	1.397 (4)
C3—C4	1.498 (4)	C32—H32A	0.9300
C3—H3C	0.9600	C33—C34	1.471 (5)
C3—H3D	0.9600	C34—C35	1.395 (5)
C3—H3E	0.9600	C35—C36	1.376 (5)
C5—C6	1.487 (4)	C35—H35A	0.9300
C6—C7	1.395 (4)	C36—C37	1.372 (5)
C6—C11	1.393 (4)	C36—H36A	0.9300
C7—C8	1.373 (5)	C37—C38	1.378 (5)
C7—H7A	0.9300	C37—H37A	0.9300
C8—C9	1.393 (4)	C38—H38A	0.9300
C8—H8A	0.9300
O1—Mn1—O3	108.04 (11)	C11—C10—C9	121.5 (3)
O1—Mn1—O6	101.75 (11)	C11—C10—H10A	119.3
O3—Mn1—O6	95.20 (9)	C9—C10—H10A	119.3
O1—Mn1—N2	150.39 (12)	C10—C11—C6	121.2 (3)
O3—Mn1—N2	91.24 (9)	C10—C11—H11A	119.4
O6—Mn1—N2	98.51 (9)	C6—C11—H11A	119.4
O1—Mn1—N1	86.74 (11)	N1—C12—C13	123.1 (3)
O3—Mn1—N1	88.14 (9)	N1—C12—H12A	118.5
O6—Mn1—N1	169.36 (9)	C13—C12—H12A	118.5
N2—Mn1—N1	71.27 (10)	C12—C13—C14	118.5 (4)
O1—Mn1—O5	87.80 (10)	C12—C13—H13A	120.8
O3—Mn1—O5	150.28 (9)	C14—C13—H13A	120.8
O6—Mn1—O5	56.26 (8)	C15—C14—C13	119.1 (4)
N2—Mn1—O5	85.72 (9)	C15—C14—H14A	120.5
N1—Mn1—O5	118.45 (8)	C13—C14—H14A	120.5
O4—Mn2—O2	118.58 (11)	C14—C15—C16	119.6 (3)
O4—Mn2—O7	103.32 (9)	C14—C15—H15A	120.2
O2—Mn2—O7	92.39 (9)	C16—C15—H15A	120.2
O4—Mn2—N5	137.28 (10)	N1—C16—C15	121.6 (3)
O2—Mn2—N5	95.02 (9)	N1—C16—C17	115.1 (3)
O7—Mn2—N5	100.56 (10)	C15—C16—C17	123.3 (3)
O4—Mn2—N6	84.84 (9)	N2—C17—C18	121.3 (3)
O2—Mn2—N6	85.81 (9)	N2—C17—C16	115.9 (2)
O7—Mn2—N6	171.44 (9)	C18—C17—C16	122.8 (3)
N5—Mn2—N6	71.31 (10)	C19—C18—C17	119.1 (3)
C12—N1—C16	118.2 (3)	C19—C18—H18A	120.5
C12—N1—Mn1	123.7 (2)	C17—C18—H18A	120.5
C16—N1—Mn1	117.9 (2)	C18—C19—C20	119.6 (3)
C17—N2—C21	118.7 (3)	C18—C19—H19A	120.2
C17—N2—Mn1	119.7 (2)	C20—C19—H19A	120.2
C21—N2—Mn1	121.6 (2)	C21—C20—C19	118.0 (4)
C9—N3—O8^i	117.7 (2)	C21—C20—H20A	121.0
C9—N3—H3A	120.0	C19—C20—H20A	121.0
C9—N3—H3B	120.0	N2—C21—C20	123.3 (3)
O8^i—N3—H3B	119.1	N2—C21—H21A	118.3
H3A—N3—H3B	120.0	C20—C21—H21A	118.3
C26—N4—O6^ii	109.1 (2)	O8—C22—O7	121.8 (3)
C26—N4—H4A	120.0	O8—C22—C23	120.3 (3)
O6^ii—N4—H4A	128.3	O7—C22—C23	117.9 (3)
C26—N4—H4B	120.0	C24—C23—C28	117.8 (3)
H4A—N4—H4B	120.0	C24—C23—C22	121.7 (3)
C29—N5—C33	118.3 (3)	C28—C23—C22	120.4 (3)
C29—N5—Mn2	122.8 (2)	C25—C24—C23	121.2 (3)
C33—N5—Mn2	118.7 (2)	C25—C24—H24A	119.4
C38—N6—C34	118.9 (3)	C23—C24—H24A	119.4
C38—N6—Mn2	123.3 (2)	C24—C25—C26	121.1 (3)
C34—N6—Mn2	117.6 (2)	C24—C25—H25A	119.4
C2—O1—Mn1	146.9 (3)	C26—C25—H25A	119.4
C2—O2—Mn2	114.13 (19)	N4—C26—C25	121.0 (3)
C4—O3—Mn1	122.56 (19)	N4—C26—C27	121.1 (3)
C4—O4—Mn2	139.0 (2)	C25—C26—C27	117.8 (3)
C5—O5—Mn1	85.12 (19)	C28—C27—C26	120.9 (3)
C5—O6—Mn1	96.77 (19)	C28—C27—H27A	119.6
C22—O7—Mn2	103.1 (2)	C26—C27—H27A	119.6
C2—C1—H1A	109.5	C27—C28—C23	121.2 (3)
C2—C1—H1B	109.5	C27—C28—H28A	119.4
H1A—C1—H1B	109.5	C23—C28—H28A	119.4
C2—C1—H1C	109.5	N5—C29—C30	123.5 (3)
H1A—C1—H1C	109.5	N5—C29—H29A	118.2
H1B—C1—H1C	109.5	C30—C29—H29A	118.2
O1—C2—O2	122.3 (3)	C29—C30—C31	118.8 (4)
O1—C2—C1	118.5 (3)	C29—C30—H30A	120.6
O2—C2—C1	119.2 (3)	C31—C30—H30A	120.6
C4—C3—H3C	109.5	C32—C31—C30	119.3 (3)
C4—C3—H3D	109.5	C32—C31—H31A	120.3
H3C—C3—H3D	109.5	C30—C31—H31A	120.3
C4—C3—H3E	109.5	C31—C32—C33	118.9 (3)
H3C—C3—H3E	109.5	C31—C32—H32A	120.5
H3D—C3—H3E	109.5	C33—C32—H32A	120.5
O3—C4—O4	123.3 (3)	N5—C33—C32	121.1 (3)
O3—C4—C3	118.3 (3)	N5—C33—C34	116.0 (2)
O4—C4—C3	118.3 (3)	C32—C33—C34	122.9 (3)
O5—C5—O6	120.5 (3)	N6—C34—C35	121.1 (3)
O5—C5—C6	120.7 (3)	N6—C34—C33	115.9 (3)
O6—C5—C6	118.7 (3)	C35—C34—C33	123.0 (3)
C7—C6—C11	117.5 (3)	C36—C35—C34	119.5 (3)
C7—C6—C5	121.1 (3)	C36—C35—H35A	120.2
C11—C6—C5	121.4 (3)	C34—C35—H35A	120.2
C8—C7—C6	121.1 (3)	C37—C36—C35	118.8 (3)
C8—C7—H7A	119.5	C37—C36—H36A	120.6
C6—C7—H7A	119.5	C35—C36—H36A	120.6
C7—C8—C9	121.5 (3)	C36—C37—C38	119.5 (4)
C7—C8—H8A	119.2	C36—C37—H37A	120.3
C9—C8—H8A	119.2	C38—C37—H37A	120.3
N3—C9—C10	121.8 (3)	N6—C38—C37	122.2 (3)
N3—C9—C8	120.9 (3)	N6—C38—H38A	118.9
C10—C9—C8	117.2 (3)	C37—C38—H38A	118.9
O1—Mn1—N1—C12	24.5 (2)	C5—C6—C7—C8	176.8 (3)
O3—Mn1—N1—C12	−83.7 (2)	C6—C7—C8—C9	−0.2 (5)
O6—Mn1—N1—C12	167.7 (4)	O8^i—N3—C9—C10	20.4 (4)
N2—Mn1—N1—C12	−175.7 (2)	O8^i—N3—C9—C8	−162.7 (2)
O5—Mn1—N1—C12	110.2 (2)	C7—C8—C9—N3	−176.6 (3)
O1—Mn1—N1—C16	−160.1 (2)	C7—C8—C9—C10	0.5 (5)
O3—Mn1—N1—C16	91.7 (2)	N3—C9—C10—C11	176.6 (3)
O6—Mn1—N1—C16	−16.9 (6)	C8—C9—C10—C11	−0.4 (5)
N2—Mn1—N1—C16	−0.3 (2)	C9—C10—C11—C6	0.0 (6)
O5—Mn1—N1—C16	−74.4 (2)	C7—C6—C11—C10	0.3 (5)
O1—Mn1—N2—C17	42.3 (3)	C5—C6—C11—C10	−176.7 (3)
O3—Mn1—N2—C17	−89.4 (2)	C16—N1—C12—C13	1.1 (5)
O6—Mn1—N2—C17	175.2 (2)	Mn1—N1—C12—C13	176.5 (3)
N1—Mn1—N2—C17	−1.8 (2)	N1—C12—C13—C14	0.3 (6)
O5—Mn1—N2—C17	120.2 (2)	C12—C13—C14—C15	−0.9 (6)
O1—Mn1—N2—C21	−138.0 (3)	C13—C14—C15—C16	0.1 (6)
O3—Mn1—N2—C21	90.3 (3)	C12—N1—C16—C15	−1.9 (4)
O6—Mn1—N2—C21	−5.2 (3)	Mn1—N1—C16—C15	−177.6 (3)
N1—Mn1—N2—C21	177.9 (3)	C12—N1—C16—C17	177.7 (3)
O5—Mn1—N2—C21	−60.1 (3)	Mn1—N1—C16—C17	2.0 (3)
O4—Mn2—N5—C29	119.4 (3)	C14—C15—C16—N1	1.4 (6)
O2—Mn2—N5—C29	−97.2 (3)	C14—C15—C16—C17	−178.2 (3)
O7—Mn2—N5—C29	−3.8 (3)	C21—N2—C17—C18	2.3 (4)
N6—Mn2—N5—C29	178.9 (3)	Mn1—N2—C17—C18	−178.1 (2)
O4—Mn2—N5—C33	−65.6 (3)	C21—N2—C17—C16	−176.3 (3)
O2—Mn2—N5—C33	77.9 (2)	Mn1—N2—C17—C16	3.4 (3)
O7—Mn2—N5—C33	171.2 (2)	N1—C16—C17—N2	−3.5 (4)
N6—Mn2—N5—C33	−5.99 (19)	C15—C16—C17—N2	176.1 (3)
O4—Mn2—N6—C38	−36.1 (2)	N1—C16—C17—C18	178.0 (3)
O2—Mn2—N6—C38	83.1 (2)	C15—C16—C17—C18	−2.4 (5)
N5—Mn2—N6—C38	179.9 (3)	N2—C17—C18—C19	−2.5 (5)
O4—Mn2—N6—C34	149.6 (2)	C16—C17—C18—C19	175.9 (3)
O2—Mn2—N6—C34	−91.2 (2)	C17—C18—C19—C20	0.7 (5)
N5—Mn2—N6—C34	5.6 (2)	C18—C19—C20—C21	1.3 (5)
O3—Mn1—O1—C2	−117.3 (5)	C17—N2—C21—C20	−0.2 (5)
O6—Mn1—O1—C2	−17.8 (5)	Mn1—N2—C21—C20	−179.8 (3)
N2—Mn1—O1—C2	114.4 (5)	C19—C20—C21—N2	−1.7 (5)
N1—Mn1—O1—C2	155.7 (5)	Mn2—O7—C22—O8	−14.1 (4)
O5—Mn1—O1—C2	37.0 (5)	Mn2—O7—C22—C23	164.8 (2)
O4—Mn2—O2—C2	−35.5 (3)	O8—C22—C23—C24	−170.9 (3)
O7—Mn2—O2—C2	71.1 (3)	O7—C22—C23—C24	10.2 (4)
N5—Mn2—O2—C2	171.9 (3)	O8—C22—C23—C28	12.4 (5)
N6—Mn2—O2—C2	−117.3 (3)	O7—C22—C23—C28	−166.5 (3)
O1—Mn1—O3—C4	38.0 (3)	C28—C23—C24—C25	−0.1 (5)
O6—Mn1—O3—C4	−66.2 (3)	C22—C23—C24—C25	−176.9 (3)
N2—Mn1—O3—C4	−164.8 (3)	C23—C24—C25—C26	0.7 (5)
N1—Mn1—O3—C4	124.0 (3)	O6^ii—N4—C26—C25	163.3 (2)
O5—Mn1—O3—C4	−81.3 (3)	O6^ii—N4—C26—C27	−20.6 (4)
O2—Mn2—O4—C4	99.4 (4)	C24—C25—C26—N4	176.3 (3)
O7—Mn2—O4—C4	−0.9 (4)	C24—C25—C26—C27	0.0 (5)
N5—Mn2—O4—C4	−123.1 (3)	N4—C26—C27—C28	−177.6 (3)
N6—Mn2—O4—C4	−178.2 (4)	C25—C26—C27—C28	−1.4 (5)
O1—Mn1—O5—C5	−99.2 (2)	C26—C27—C28—C23	2.0 (5)
O3—Mn1—O5—C5	24.7 (3)	C24—C23—C28—C27	−1.2 (5)
O6—Mn1—O5—C5	6.53 (17)	C22—C23—C28—C27	175.6 (3)
N2—Mn1—O5—C5	109.7 (2)	C33—N5—C29—C30	−1.7 (5)
N1—Mn1—O5—C5	175.74 (18)	Mn2—N5—C29—C30	173.4 (3)
O1—Mn1—O6—C5	72.8 (2)	N5—C29—C30—C31	0.7 (6)
O3—Mn1—O6—C5	−177.52 (18)	C29—C30—C31—C32	1.1 (6)
N2—Mn1—O6—C5	−85.47 (18)	C30—C31—C32—C33	−1.8 (5)
N1—Mn1—O6—C5	−69.5 (5)	C29—N5—C33—C32	0.9 (4)
O5—Mn1—O6—C5	−6.47 (17)	Mn2—N5—C33—C32	−174.4 (2)
O4—Mn2—O7—C22	−65.6 (2)	C29—N5—C33—C34	−178.9 (3)
O2—Mn2—O7—C22	174.23 (19)	Mn2—N5—C33—C34	5.8 (3)
N5—Mn2—O7—C22	78.67 (19)	C31—C32—C33—N5	0.8 (5)
Mn1—O1—C2—O2	103.5 (5)	C31—C32—C33—C34	−179.4 (3)
Mn1—O1—C2—C1	−78.2 (6)	C38—N6—C34—C35	0.3 (4)
Mn2—O2—C2—O1	−4.7 (5)	Mn2—N6—C34—C35	174.9 (2)
Mn2—O2—C2—C1	177.0 (3)	C38—N6—C34—C33	−179.2 (3)
Mn1—O3—C4—O4	3.0 (5)	Mn2—N6—C34—C33	−4.7 (3)
Mn1—O3—C4—C3	−180.0 (3)	N5—C33—C34—N6	−0.6 (4)
Mn2—O4—C4—O3	−84.4 (5)	C32—C33—C34—N6	179.5 (3)
Mn2—O4—C4—C3	98.6 (4)	N5—C33—C34—C35	179.8 (3)
Mn1—O5—C5—O6	−10.9 (3)	C32—C33—C34—C35	0.0 (5)
Mn1—O5—C5—C6	165.7 (3)	N6—C34—C35—C36	0.5 (5)
Mn1—O6—C5—O5	12.2 (3)	C33—C34—C35—C36	−180.0 (3)
Mn1—O6—C5—C6	−164.4 (2)	C34—C35—C36—C37	−0.7 (6)
O5—C5—C6—C7	177.0 (3)	C35—C36—C37—C38	0.1 (6)
O6—C5—C6—C7	−6.3 (4)	C34—N6—C38—C37	−0.9 (5)
O5—C5—C6—C11	−6.1 (5)	Mn2—N6—C38—C37	−175.2 (3)
O6—C5—C6—C11	170.5 (3)	C36—C37—C38—N6	0.7 (6)
C11—C6—C7—C8	−0.2 (5)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O8^i	0.86	2.27	3.074 (4)	155
N4—H4B···O6^ii	0.86	2.29	3.087 (4)	155
C36—H36A···Cg^iii	0.93	2.79	3.655	156

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