Diaqua[N,N′-bis(5-methoxysalicylidene)ethylenediaminato-κ⁴O,N,N′,O′]manganese(III) perchlorate, aqua[N,N′-bis(3,5-dichlorosalicylidene)ethylenediaminato-κ⁴O,N,N′,O′](methanol-κO)manganese(III) perchlorate and bis­[μ-N,N′-bis(3-methoxy­salicyl­idene)ethyl­enediaminato-κ⁵O,N,N′,O′:O]bis[(methanol-κO)manganese(III)] diperchlorate

The title compounds, a hydrogen-bonded linear chain, [Mn(C₁₈H₁₈N₂O₄)(H₂O)₂]ClO₄, (I), a hydrogen-bonded pseudo-dimer, [Mn(C₁₆H₁₀Cl₄N₂O₂)(CH₄O)(H₂O)]ClO₄, (II), and a dimer, [Mn₂(C₁₈H₁₈N₂O₄)₂(CH₄O)₂](ClO₄)₂, (III), respectively, have been structurally characterized. The three complexes are completely different in their structural features, despite identical counter-anions and only slight modification of the substituents in the ligands. Complex (I) affords an elongated octa­hedral coordination environment, with axial Mn—O(water) distances of 2.259 (3) and 2.313 (3) Å, which forms hydrogen-bonded linear chains along the crystallographic c axis. Hydrogen-bonded pseudo-dimeric compound (II) also affords an elongated octa­hedral coordination environment, with axial Mn—O(CH₃OH) = 2.222 (3) Å and Mn—O(water) = 2.266 (3) Å. Dimeric complex (III) is centrosymmetric and consists of distorted octa­hedral Mn atoms, with axial Mn—O(CH₃OH) = 2.242 (2) Å and Mn—O(phenolate) = 2.348 (1) Å, connected via bridging O atoms from one of the ligands. The magnetic properties of the three complexes are described.

S1. Comment

Recently, photomagnetic functional complexes have been studied widely (Sato, 2003; Sato et al., 2003). One of the hypotheses for the discovery of such materials is to examine complexes which exhibit ready structural changes and valence or spin transitions. For example, a certain Fe^II complex exhibits spin-crossover due to Jahn–Teller distortion (Marchivie et al., 2003; Kambara, 1979). Schiff base Mn^III complexes have attracted considerable attention due to their catalysis and magnetism. Chiral catalysts are often employed for Kochi–Jacobsen–Katsuki enantioselective epoxidation (Korendovych & Rybak-Akimova, 2004; Martinez et al., 2002; Reger & Janda, 2000; Khavrutskii et al., 2003a,b Which one?). Various photocatalytic reactions, including photocleavage of DNA (Sakamoto et al., 1998), photophysical properties (Cozzi et al., 2003) and photosystem II models (Ashmawy et al., 1985; Aurangzeb et al., 1994; Bermejo et al., 1996), have been studied for many years. On the other hand, numerous dimeric high-spin Schiff base Mn^III complexes exhibit ferromagnetism (Miyasaka et al., 2002). These building blocks have potential in the design of new single-molecule magnets (Choi et al., 2004), hydrogen-bonded assemblies (Wernsdorfer et al., 2002) or multi-nuclear clusters (Mukhopadhyay et al., 2004). However, axially compressed complexes undergoing the Jahn–Teller effect are rare for analogous Mn^III complexes (Shongwe et al., 2001). The ⁵D ground state may split into ⁵T_{2 g} and ⁵E_g terms, and Jahn–Teller distortion removes the orbital degeneracy of the ⁵E_g ground state to give the orbital singlet lowest in energy, either ⁵A_{1 g} or ⁵B_{1 g} (Kennedy & Murray, 1985). The spin degeneracy of the ⁵A_{1 g} or ⁵B_{1 g} states is further removed by spin-orbit coupling, which gives rise to zero-field splitting, D. Axial elongation results in the ⁵B_{1 g} level lying lowest with negative D, while axial compression leads to ⁵A_{1 g} with positive D. Here, we present three new Schiff base Mn^III complexes, the title compounds, (I)–(III). Despite only slight modification of the substituents and identical counteranions, they are different in their dimeric features involving the axial coordination bonds. The three complexes are a hydrogen-bonded chain of pseudo-dimers, (I), a pseudo-dimer, (II), and a dimer, (III).

In complex (I) (Fig. 1), the central Mn^III ion adopts an elongated octahedral coordination geometry, with the displacement of the Mn1 ion from the O1/N1/N2/O2 least-squares plane being 0.012 (2) Å. Both axial sites are occupied by water ligands with a T value of 0.842, where T = R_S/R_L denotes the ratio of equatorial and axial mean bond lengths undergoing the Jahn–Teller effect (Hathaway & Billing, 1970). The ethylenediamine moiety adopts a λ conformation, with an N1—C8A—C16A—N2 torsion angle of 48.3 (10)° [or N1—C8B—C16B—N2 = 46.0 (12)°]. The angle between the least-squares planes of the aromatic rings of the ligands is 4.43 (13) °, which indicates near planarity of the overall molecular structure.

In the crystal of (I), adjacent molecules are linked by hydrogen bonds [O5···O3ⁱ = 2.929 (3) Å, O5···O1ⁱ = 2.928 (3) Å, O5···O4ⁱ = 2.984 (3) Å, and O5···O2ⁱ = 2.949 (3) Å; symmetry code: (i) 1 − x, 1 − y, 1 − z] to form hydrogen-bonded pseudo-dimers, with additional face-to-face π–π stacking interactions between the phenyl groups (C5···C9 = 3.54 Å and C4···C10 = 3.56 Å). Furthermore, intermolecular hydrogen bonds [O6···O8 = 3.029 (6) Å and O6···O8ⁱⁱ = 2.839 (6) Å; symmetry code: (ii) 1 − x, 1 − y, 2 − z] between these pseudo-dimers and perchlorate counter-ions result in hydrogen-bonded linear chains along the crystallographic c axis. Finally, there is an additional edge-to-face interaction to the phenyl group of a molecule adjacent to the linear chain (symmetry code: 1 − x, y − 1/2, 3/2 − z), with C4···C10 = 3.30 Å.

In pseudo-dimeric complex, (II) (Fig. 2), the central Mn^III ion also adopts an elongated octahedral coordination geometry, in which the displacement of the Mn1 ion from the O1/N1/N2/O2 least-squares plane is 0.029 (2) Å. The two axial ligands are water and methanol, and the mean T value is 0.866. The ethylenediamine moiety again adopts a λ conformation, with an N1—C8—C16—N2 torsion angle of 44.4 (4)°. Although the angle between the least-squares planes of the aromatic rings on both sides of the ligand is 3.00 (18)°, the overall molecular shape is a stepped conformation.

In the crystal of (II), adjacent molecules form centrosymmetric hydrogen-bonded pseudo-dimers [O4···O1ⁱⁱⁱ = 2.845 (3) Å, O4···O2ⁱⁱⁱ = 2.970 (4) Å, O4···Cl2ⁱⁱⁱ = 3.270 (1) Å and O4···Cl3ⁱⁱⁱ = 3.246 (3) Å; symmetry code: (iii) 1 − x, 1 − y, −z], with the shortest π–π stacking interaction between the phenyl groups, C4···C13 = 3.42 Å. Moreover, hydrogen bonds [O3···O7 = 2.834 (6) Å] are formed between the axial methanol and the perchlorate ion.

As observed for (I) and (II), the Mn^III ion of the dimeric complex, (III) (Fig. 3), shows an elongated octahedral coordination geometry, which comprises the tetradentate Schiff base ligand. A methanol ligand occupies the outer axial site, while the phenolate O atom of the adjacent monomer occupies the inner axial site. The geometric parameters of the bridging moiety are O1—Mn1^iv = 2.348 (1) Å, O1—Mn1—O1^iv = 80.26 (5)°, Mn1—O1—Mn1^iv = 99.74 (5)° and Mn1···Mn1^iv = 3.275 (1) Å [symmetry code: (iv) 1 − x, 1 − y, 1 − z]. The displacement of the Mn1 ion from the O1/N1/N2/O2 least-squares plane is 0.055 (1) Å. The T values are 0.865 and 0.826 (average 0.846) for the methanol and phenolate O atoms, respectively. It should be noted that the in-plane coordination bond distance [Mn1—O1 = 1.921 (1) Å] is considerably longer than usual, because the phenolate atom O1 also takes part in bridging, forming the dimers. The ethylenediamine moiety adopts a λ conformation, with an N1—C8—C16—N2 torsion angle of 44.9 (2)°. The angle between the least-squares planes of the aromatic rings of the ligands is 18.70 (7)°, which results from an overall stepped conformation.

In the crystal of (III), the perchlorate anions and dimers are packed alternately, with the shortest π–π stacking distance being between atom C1 and atom C14 in the adjacent phenyl group (symmetry code: 1 − x, 1 − y, 1 − z), of about 3.33 Å. An intramolecular hydrogen bond [O5···O8 = 2.767 (3) Å] is formed between the axial methanol and the perchlorate ion.

The three complexes are quite different in their structural features. It is likely that substitution of the aromatic ring at the 5-position by methoxy in (I) and Cl in (II) prevents the formation of dimers, as seen for (III), and instead hydrogen-bonded pseudo-dimeric systems are formed. Indeed, both the steric and electronic features of Schiff base ligands, namely the electron-donating methoxy group and the electron-withdrawing Cl group, considerably influence the Jahn–Teller distortion of the axial Mn—O bonds. It is expected that electron-donating substituent groups result in a large Jahn–Teller elongation and ferromagnetism, due to the orthogonal e_g and dπ orbitals of the Mn^III ion.

The structural differences reflect the overall magnetic properties for compounds (I)–(III). The variable-temperature magnetic susceptibility was measured in the range 2–300 K, and the plot of effective magnetic moment versus T is given in Fig. 4. On lowering the temperature to about 50 K, the magnetic moment was kept almost constant for (I)–(III). It then gradually increased to more than 6 BM at 8 K and then decreased for (I), while (II) and (III) showed a decrease at about 20 K and reached less than 2 BM at 2 K. By analogy with related complexes (Saha et al., 2004), the overall magnetic interaction of (I) is ferromagnetic, obeying χ = [Ng²β²/k(T-α)][A/B], where A = 30 + 14exp(−8 J/kT) + 5exp(−14 J/kT) + exp(−18 J/kT), B = 9 + 7exp(−8 J/kT) + 5exp(−14 J/kT) + 3exp(−18 K/kT) + exp(−10 J/kT), with the best-fit parameters of J,K = 1.25 K, g = 1.99, and α = −0.2 K. Suitable geometry of one-dimensional hydrogen-bonded chains of (I) results in a positive J value, which indicates ferromagnetic interaction. On the other hand, compounds (II) and (III) show antiferromagnetic interaction, indicating typical Curie–Weiss behaviour. The Weiss constants for (II) and (III) are −9.04 K and −0.37 K, respectively. We attempted to analyse the data for (III) to obtain J. However, in contrast with many dimers, it is difficult to fit, because there is no inflection point in the plot of u_eff versus T. Also, the treatment of the molecular field approximation is unclear. The diffuse reflectance spectra at 294 K support the ⁵B_{1 g} ground state of the Mn^III ion (S = 2) for (I)–(III).

In addition, we irradiated the crystals with UV and visible light at 8 K, which resulted in a reversible change of the IR band intensity around 3100 cm⁻¹ (O—H band) for the axial ligands for (I)–(III). In contrast with the analogous Cu^II complex (Akitsu & Einaga, 2004), photo-irradiation did not affect the axial Jahn–Teller distortion for the three rigid Mn^III complexes, (I)–(III).

S2. Experimental

For (I), treatment of equimolar quantities of 5-methoxysalicylaldehyde (0.30 g, 2.00 mmol), ethylenediamine (0.30 g, 0.50 mmol) and manganese(III) acetate dihydrate (0.27 g, 1.00 mmol) in methanol (50 ml) at 323 K for 2 h gave a brown solution. After adding sodium perchlorate hydrate (0.70 g, 5.00 mmol) and stirring for 323 K for 1 h, the resulting solution was filtered and allowed to stand for two weeks at 298 K. Brown crystals of (I) suitable for X-ray crystallography were obtained from the filtrate. Analysis, found: C 41.50, H 4.29, N 5.17%; calculated for C₁₈H₂₂ClMnN₂O₁₀: C 41.84, H 4.29, N 5.42%; IR (KBr): 1627 cm⁻¹ (C═N band); m.p. 604 K (decomposition); UV–vis (diffuse reflectance): 13300, 16700 and 18300 cm⁻¹; magnetic moment 4.77 BM at 294 K. For (II), the same preparation procedure was employed as given for (I), using 3,5-dichlorosalicylaldehyde (0.38 g, 2.00 mmol) instead of 5-methoxysalicylaldehyde. Analysis, found: C 33.60, H 2.60, N 4.55%.; calculated for C₃₄H₃₆CuN₂O₄: C 68.04, H 6.05, N 4.67%; IR (KBr): 1636 cm⁻¹ (C═N); m.p. 542 K (decomposition); UV–vis (diffuse reflectance): 13200 and 16700 cm⁻¹; magnetic moment 4.54 BM at 294 K. For (III), the same preparation procedure was employed as given for (I), with 3-methoxysalicylaldehyde (0.30 g, 2.00 mmol) instead of 5-methoxysalicylaldehyde. Analysis found: C 44.50, H 4.29, N 5.17%; calculated for C₁₉H₂₂ClMnN₂O₉: C 44.50, H 4.32, N 5.46%; IR (KBr): 1621 cm⁻¹ (C═N); m.p. 560 K (decomposition); UV–vis (diffuse reflectance): 18300 cm⁻¹; magnetic moment 4.48 BM at 294 K.

S3. Refinement

For (I), all H atoms were located in a difference Fourier map and refined using a riding model, with O—H = 0.96 Å and U_iso(H) = 1.2U_eq(O), and C—H = 0.93–0.97 Å and U_iso(H) = 1.2U_eq(C). There is positional disorder of atoms C8 and C16 over two equally occupied sites. It was assumed that the ethylenediamine moiety has two possible conformations, namely N1—C8A(H8A1/H8A2)—C16A(H16A/H16B)—N2 and N1—C8B(H8B1/H8B2)—C16B(H16C/H16D)—N2. For (II), H atoms were placed in geometrically calculated positions and refined using a riding model, with O—H = 0.84 Å and U_iso(H) = 1.2U_eq(O), and C—H = 0.93–0.97 Å and U_iso(H) = 1.2U_eq(C). Atoms H17A–C and H17D–F, bound to the methyl group C17, were modelled as idealized disordered groups with equal occupancy factors. For (III), H atoms were located in a difference Fourier map and refined using a riding model, with C—H = 0.93–0.97 Å and U_iso(H) = 1.2U_eq(C), except for atom H5, which was fixed in its difference map position. Atoms H19A–C and H19D–F, bound to methyl group C19, were modelled as idealized disordered groups with equal occupancy factors.

Computing details

For all compounds, data collection: WinAFC Diffractometer Control Software (Rigaku, 1999); cell refinement: WinAFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1989); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN.

Figures

	Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. Thin lines indicate possible hydrogen bonds.
	Fig. 2. The molecular structure of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. Thin lines indicate possible hydrogen bonds.
	Fig. 3. The molecular structure of (III), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. Thin lines indicate possible hydrogen bonds.
	Fig. 4. Plot of the effective magnetic moment versus T for (I)–(III), measured under 5000 G.

(I) Diaqua[N,N'-bis(5-methoxysalicylidene)ethylenediaminato- κ⁴O,N,N',O']manganese(III) perchlorate

Crystal data

[Mn(C18H18N2O4)(H2O)2]ClO4	F(000) = 2128
Mr = 516.77	Dx = 1.611 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 25 reflections
a = 22.751 (9) Å	θ = 10.2–14.0°
b = 14.016 (6) Å	µ = 0.80 mm^−1
c = 13.36 (1) Å	T = 297 K
V = 4260 (4) Å^3	Plate, brown
Z = 8	0.46 × 0.46 × 0.10 mm

Data collection

Rigaku AFC-7R diffractometer	3324 reflections with I > 2σ(I)
Radiation source: Rigaku rotating anode generator	Rint = 0.000
Graphite monochromator	θmax = 27.5°
ω/2θ scans	h = 0→29
Absorption correction: ψ scan (North et al., 1968)	k = −7→18
Tmin = 0.698, Tmax = 0.923	l = −17→7
4892 measured reflections	3 standard reflections every 150 reflections
4892 independent reflections	intensity decay: 0.3%

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)] = 0.056	Hydrogen site location: mixed
wR(F^2) = 0.174	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.1051P)^2 + 1.1428P] where P = (Fo^2 + 2Fc^2)/3
3324 reflections	(Δ/σ)max = 0.001
311 parameters	Δρmax = 0.96 e Å^−3
1 restraint	Δρmin = −0.39 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Mn1	0.47722 (2)	0.56188 (3)	0.66443 (4)	0.04181 (18)
O1	0.44546 (9)	0.44564 (15)	0.62138 (19)	0.0482 (5)
O2	0.55420 (9)	0.52355 (16)	0.63654 (19)	0.0499 (5)
O3	0.42953 (10)	0.27573 (15)	0.55799 (19)	0.0507 (5)
O4	0.64807 (10)	0.43386 (16)	0.5844 (2)	0.0537 (6)
O5	0.46361 (10)	0.62901 (16)	0.51244 (16)	0.0464 (5)
H5A	0.5007	0.6336	0.4784	0.070*
H5B	0.4372	0.5903	0.4739	0.070*
O6	0.48747 (18)	0.4948 (3)	0.8217 (2)	0.0879 (11)
H6A	0.4720	0.5377	0.8711	0.132*
H6B	0.5283	0.4833	0.8350	0.132*
N1	0.39890 (14)	0.61118 (19)	0.7031 (2)	0.0556 (7)
N2	0.50266 (14)	0.6890 (2)	0.7112 (2)	0.0566 (7)
C1	0.34305 (14)	0.4696 (3)	0.6610 (3)	0.0498 (7)
C2	0.28576 (16)	0.4295 (3)	0.6580 (3)	0.0623 (10)
H2	0.2539	0.4650	0.6807	0.075*
C3	0.27681 (17)	0.3400 (3)	0.6226 (3)	0.0661 (10)
H3	0.2390	0.3148	0.6214	0.079*
C4	0.32373 (16)	0.2854 (3)	0.5878 (3)	0.0580 (9)
H4	0.3171	0.2241	0.5638	0.070*
C5	0.37984 (13)	0.3218 (2)	0.5887 (2)	0.0434 (7)
C6	0.39050 (13)	0.4152 (2)	0.6240 (2)	0.0421 (7)
C7	0.35010 (17)	0.5652 (3)	0.6966 (3)	0.0573 (9)
H7	0.3163	0.5970	0.7169	0.069*
C8A	0.3956 (5)	0.7166 (5)	0.7182 (10)	0.061 (3)	0.50
H8A1	0.3625	0.7339	0.7603	0.073*	0.50
H8A2	0.3925	0.7501	0.6548	0.073*	0.50
C8B	0.4067 (6)	0.7048 (6)	0.7568 (10)	0.075 (4)	0.50
H8B1	0.4130	0.6924	0.8275	0.091*	0.50
H8B2	0.3709	0.7419	0.7503	0.091*	0.50
C9	0.60684 (16)	0.6684 (2)	0.6754 (2)	0.0463 (7)
C10	0.66191 (17)	0.7149 (3)	0.6779 (3)	0.0539 (9)
H10	0.6640	0.7786	0.6972	0.065*
C11	0.71160 (18)	0.6676 (3)	0.6526 (3)	0.0602 (9)
H11	0.7477	0.6986	0.6559	0.072*
C12	0.70908 (15)	0.5724 (3)	0.6215 (3)	0.0526 (8)
H12	0.7435	0.5406	0.6044	0.063*
C13	0.65611 (13)	0.5253 (2)	0.6161 (2)	0.0446 (7)
C14	0.60343 (14)	0.5723 (2)	0.6438 (2)	0.0429 (7)
C15	0.55579 (17)	0.7212 (2)	0.7069 (3)	0.0539 (8)
H15	0.5616	0.7843	0.7258	0.065*
C16A	0.4539 (3)	0.7378 (5)	0.7697 (6)	0.0475 (16)	0.50
H16A	0.4606	0.8061	0.7717	0.057*	0.50
H16B	0.4531	0.7141	0.8379	0.057*	0.50
C16B	0.4581 (4)	0.7629 (6)	0.7167 (8)	0.067 (2)	0.50
H16C	0.4495	0.7898	0.6514	0.080*	0.50
H16D	0.4692	0.8135	0.7624	0.080*	0.50
C17	0.4245 (2)	0.1767 (2)	0.5324 (3)	0.0617 (9)
H17A	0.4134	0.1409	0.5907	0.093*
H17B	0.4616	0.1538	0.5080	0.093*
H17C	0.3951	0.1690	0.4815	0.093*
C18	0.70024 (16)	0.3802 (3)	0.5601 (4)	0.0691 (11)
H18A	0.7214	0.4121	0.5077	0.104*
H18B	0.6893	0.3174	0.5382	0.104*
H18C	0.7248	0.3753	0.6184	0.104*
Cl1	0.62535 (4)	0.43152 (7)	0.98279 (9)	0.0634 (3)
O7	0.6351 (3)	0.4513 (4)	0.8850 (5)	0.175 (3)
O8	0.56508 (16)	0.4420 (3)	0.9973 (4)	0.1180 (15)
O9	0.64602 (19)	0.3415 (3)	1.0081 (4)	0.1219 (16)
O10	0.6543 (3)	0.5000 (4)	1.0367 (7)	0.206 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0414 (3)	0.0333 (3)	0.0507 (3)	0.00330 (18)	−0.00026 (19)	−0.00596 (19)
O1	0.0376 (11)	0.0361 (11)	0.0709 (15)	−0.0011 (9)	0.0068 (10)	−0.0036 (10)
O2	0.0368 (11)	0.0381 (11)	0.0750 (15)	0.0014 (9)	−0.0062 (10)	−0.0137 (10)
O3	0.0499 (12)	0.0346 (11)	0.0675 (14)	−0.0036 (9)	−0.0043 (11)	−0.0037 (10)
O4	0.0385 (11)	0.0406 (12)	0.0820 (17)	0.0011 (9)	−0.0039 (11)	−0.0091 (11)
O5	0.0446 (12)	0.0430 (12)	0.0518 (12)	−0.0036 (9)	−0.0011 (9)	−0.0059 (9)
O6	0.116 (3)	0.089 (2)	0.0592 (18)	0.033 (2)	−0.0061 (16)	0.0072 (15)
N1	0.0575 (18)	0.0400 (15)	0.0692 (18)	0.0105 (13)	0.0185 (15)	0.0011 (13)
N2	0.0577 (17)	0.0425 (15)	0.0696 (19)	0.0093 (14)	−0.0129 (15)	−0.0202 (13)
C1	0.0420 (16)	0.0559 (19)	0.0514 (18)	0.0040 (15)	0.0018 (14)	0.0082 (15)
C2	0.0362 (16)	0.086 (3)	0.064 (2)	0.0068 (17)	0.0020 (15)	0.012 (2)
C3	0.0449 (19)	0.081 (3)	0.072 (2)	−0.0141 (19)	−0.0097 (17)	0.012 (2)
C4	0.0512 (19)	0.064 (2)	0.059 (2)	−0.0181 (17)	−0.0099 (16)	0.0054 (17)
C5	0.0438 (16)	0.0455 (17)	0.0408 (15)	−0.0037 (13)	−0.0058 (12)	0.0077 (13)
C6	0.0392 (15)	0.0432 (16)	0.0439 (15)	−0.0009 (13)	−0.0022 (12)	0.0074 (12)
C7	0.0485 (19)	0.057 (2)	0.067 (2)	0.0134 (16)	0.0095 (16)	0.0070 (17)
C8A	0.053 (5)	0.033 (5)	0.097 (9)	0.012 (4)	0.010 (5)	0.005 (4)
C8B	0.087 (10)	0.030 (4)	0.109 (11)	0.019 (5)	0.039 (8)	0.005 (5)
C9	0.0583 (19)	0.0411 (16)	0.0395 (16)	−0.0095 (14)	−0.0101 (13)	−0.0027 (12)
C10	0.068 (2)	0.0448 (17)	0.0492 (18)	−0.0150 (16)	−0.0089 (15)	−0.0025 (14)
C11	0.061 (2)	0.057 (2)	0.062 (2)	−0.0253 (18)	−0.0092 (17)	0.0041 (17)
C12	0.0431 (17)	0.055 (2)	0.0600 (19)	−0.0087 (15)	−0.0046 (14)	0.0060 (15)
C13	0.0411 (16)	0.0411 (16)	0.0515 (17)	−0.0029 (13)	−0.0043 (13)	0.0038 (13)
C14	0.0452 (16)	0.0373 (15)	0.0463 (16)	−0.0039 (12)	−0.0107 (13)	0.0003 (12)
C15	0.069 (2)	0.0386 (16)	0.0544 (19)	0.0001 (15)	−0.0183 (17)	−0.0127 (14)
C16A	0.056 (4)	0.032 (3)	0.055 (4)	0.010 (3)	0.000 (4)	−0.014 (3)
C16B	0.087 (6)	0.046 (5)	0.067 (6)	0.017 (4)	−0.004 (5)	−0.008 (4)
C17	0.077 (2)	0.0347 (17)	0.073 (2)	−0.0053 (17)	−0.0101 (19)	−0.0050 (16)
C18	0.051 (2)	0.048 (2)	0.108 (3)	0.0124 (16)	−0.005 (2)	−0.007 (2)
Cl1	0.0501 (5)	0.0553 (5)	0.0848 (7)	0.0129 (4)	0.0008 (4)	0.0054 (5)
O7	0.204 (6)	0.184 (6)	0.137 (4)	0.082 (5)	0.083 (4)	0.071 (4)
O8	0.057 (2)	0.136 (4)	0.161 (4)	0.029 (2)	0.006 (2)	0.010 (3)
O9	0.098 (3)	0.069 (2)	0.199 (5)	0.033 (2)	0.017 (3)	0.045 (3)
O10	0.170 (5)	0.097 (3)	0.351 (10)	0.039 (3)	−0.163 (6)	−0.058 (5)

Geometric parameters (Å, º)

Mn1—O2	1.870 (2)	C7—H7	0.9300
Mn1—O1	1.873 (2)	C8A—C16A	1.523 (8)
Mn1—N2	1.975 (3)	C8A—H8A1	0.9700
Mn1—N1	1.980 (3)	C8A—H8A2	0.9700
Mn1—O5	2.259 (3)	C8B—C16B	1.521 (9)
Mn1—O6	2.313 (3)	C8B—H8B1	0.9700
O1—C6	1.322 (4)	C8B—H8B2	0.9700
O2—C14	1.316 (4)	C9—C14	1.413 (4)
O3—C5	1.365 (4)	C9—C10	1.413 (5)
O3—C17	1.434 (4)	C9—C15	1.440 (5)
O4—C13	1.362 (4)	C10—C11	1.353 (6)
O4—C18	1.442 (4)	C10—H10	0.9300
O5—H5A	0.9600	C11—C12	1.399 (5)
O5—H5B	0.9600	C11—H11	0.9300
O6—H6A	0.9600	C12—C13	1.376 (4)
O6—H6B	0.9600	C12—H12	0.9300
N1—C7	1.287 (5)	C13—C14	1.417 (5)
N1—C8A	1.494 (8)	C15—H15	0.9300
N1—C8B	1.506 (8)	C16A—H16A	0.9700
N2—C15	1.292 (5)	C16A—H16B	0.9700
N2—C16B	1.452 (7)	C16B—H16C	0.9700
N2—C16A	1.520 (6)	C16B—H16D	0.9700
C1—C6	1.411 (5)	C17—H17A	0.9600
C1—C2	1.420 (5)	C17—H17B	0.9600
C1—C7	1.431 (6)	C17—H17C	0.9600
C2—C3	1.356 (6)	C18—H18A	0.9600
C2—H2	0.9300	C18—H18B	0.9600
C3—C4	1.393 (6)	C18—H18C	0.9600
C3—H3	0.9300	Cl1—O7	1.354 (6)
C4—C5	1.375 (4)	Cl1—O10	1.370 (5)
C4—H4	0.9300	Cl1—O9	1.388 (3)
C5—C6	1.412 (5)	Cl1—O8	1.393 (4)
O2—Mn1—O1	92.88 (10)	C16A—C8A—H8A2	111.4
O2—Mn1—N2	92.73 (11)	H8A1—C8A—H8A2	109.2
O1—Mn1—N2	174.36 (11)	N1—C8B—C16B	112.9 (8)
O2—Mn1—N1	174.58 (12)	N1—C8B—H8B1	109.0
O1—Mn1—N1	92.10 (11)	C16B—C8B—H8B1	109.0
N2—Mn1—N1	82.32 (13)	N1—C8B—H8B2	109.0
O2—Mn1—O5	93.95 (10)	C16B—C8B—H8B2	109.0
O1—Mn1—O5	91.92 (10)	H8B1—C8B—H8B2	107.8
N2—Mn1—O5	87.08 (12)	C14—C9—C10	119.7 (3)
N1—Mn1—O5	88.04 (11)	C14—C9—C15	122.2 (3)
O2—Mn1—O6	88.27 (13)	C10—C9—C15	118.1 (3)
O1—Mn1—O6	87.95 (13)	C11—C10—C9	120.5 (3)
N2—Mn1—O6	92.83 (14)	C11—C10—H10	119.7
N1—Mn1—O6	89.75 (14)	C9—C10—H10	119.7
O5—Mn1—O6	177.78 (11)	C10—C11—C12	120.5 (3)
C6—O1—Mn1	129.6 (2)	C10—C11—H11	119.8
C14—O2—Mn1	129.3 (2)	C12—C11—H11	119.8
C5—O3—C17	117.6 (3)	C13—C12—C11	120.6 (4)
C13—O4—C18	116.7 (3)	C13—C12—H12	119.7
Mn1—O5—H5A	109.5	C11—C12—H12	119.7
Mn1—O5—H5B	109.5	O4—C13—C12	125.8 (3)
H5A—O5—H5B	109.5	O4—C13—C14	113.9 (3)
Mn1—O6—H6A	109.5	C12—C13—C14	120.2 (3)
Mn1—O6—H6B	109.5	O2—C14—C9	124.3 (3)
H6A—O6—H6B	109.5	O2—C14—C13	117.3 (3)
C7—N1—C8A	117.5 (5)	C9—C14—C13	118.4 (3)
C7—N1—C8B	124.8 (6)	N2—C15—C9	126.0 (3)
C7—N1—Mn1	125.7 (2)	N2—C15—H15	117.0
C8A—N1—Mn1	115.2 (5)	C9—C15—H15	117.0
C8B—N1—Mn1	108.8 (5)	N2—C16A—C8A	108.4 (7)
C15—N2—C16B	114.0 (5)	N2—C16A—H16A	110.0
C15—N2—C16A	123.3 (4)	C8A—C16A—H16A	110.0
C15—N2—Mn1	125.1 (2)	N2—C16A—H16B	110.0
C16B—N2—Mn1	117.1 (4)	C8A—C16A—H16B	110.0
C16A—N2—Mn1	110.8 (4)	H16A—C16A—H16B	108.4
C6—C1—C2	118.6 (3)	N2—C16B—C8B	99.9 (8)
C6—C1—C7	122.5 (3)	N2—C16B—H16C	111.8
C2—C1—C7	118.9 (3)	C8B—C16B—H16C	111.8
C3—C2—C1	120.9 (4)	N2—C16B—H16D	111.8
C3—C2—H2	119.5	C8B—C16B—H16D	111.8
C1—C2—H2	119.5	H16C—C16B—H16D	109.5
C2—C3—C4	120.6 (4)	O3—C17—H17A	109.5
C2—C3—H3	119.7	O3—C17—H17B	109.5
C4—C3—H3	119.7	H17A—C17—H17B	109.5
C5—C4—C3	120.3 (4)	O3—C17—H17C	109.5
C5—C4—H4	119.9	H17A—C17—H17C	109.5
C3—C4—H4	119.9	H17B—C17—H17C	109.5
O3—C5—C4	126.2 (3)	O4—C18—H18A	109.5
O3—C5—C6	113.4 (3)	O4—C18—H18B	109.5
C4—C5—C6	120.5 (3)	H18A—C18—H18B	109.5
O1—C6—C1	123.9 (3)	O4—C18—H18C	109.5
O1—C6—C5	117.0 (3)	H18A—C18—H18C	109.5
C1—C6—C5	119.1 (3)	H18B—C18—H18C	109.5
N1—C7—C1	126.0 (3)	O7—Cl1—O10	106.6 (5)
N1—C7—H7	117.0	O7—Cl1—O9	111.5 (3)
C1—C7—H7	117.0	O10—Cl1—O9	110.2 (3)
N1—C8A—C16A	102.1 (6)	O7—Cl1—O8	105.9 (4)
N1—C8A—H8A1	111.4	O10—Cl1—O8	109.0 (4)
C16A—C8A—H8A1	111.4	O9—Cl1—O8	113.3 (3)
N1—C8A—H8A2	111.4
O2—Mn1—O1—C6	175.4 (3)	O3—C5—C6—O1	0.9 (4)
N1—Mn1—O1—C6	−2.4 (3)	C4—C5—C6—O1	−179.1 (3)
O5—Mn1—O1—C6	−90.5 (3)	O3—C5—C6—C1	−178.0 (3)
O6—Mn1—O1—C6	87.3 (3)	C4—C5—C6—C1	1.9 (4)
O1—Mn1—O2—C14	176.4 (3)	C8A—N1—C7—C1	165.4 (7)
N2—Mn1—O2—C14	−3.0 (3)	C8B—N1—C7—C1	−169.0 (7)
O5—Mn1—O2—C14	84.2 (3)	Mn1—N1—C7—C1	0.5 (6)
O6—Mn1—O2—C14	−95.8 (3)	C6—C1—C7—N1	−2.8 (6)
O1—Mn1—N1—C7	1.7 (3)	C2—C1—C7—N1	−179.6 (4)
N2—Mn1—N1—C7	−179.2 (4)	C7—N1—C8A—C16A	154.4 (6)
O5—Mn1—N1—C7	93.5 (3)	C8B—N1—C8A—C16A	39.5 (17)
O6—Mn1—N1—C7	−86.3 (3)	Mn1—N1—C8A—C16A	−39.1 (10)
O1—Mn1—N1—C8A	−163.6 (6)	C7—N1—C8B—C16B	−154.9 (7)
N2—Mn1—N1—C8A	15.6 (6)	C8A—N1—C8B—C16B	−76 (2)
O5—Mn1—N1—C8A	−71.7 (6)	Mn1—N1—C8B—C16B	34.2 (11)
O6—Mn1—N1—C8A	108.5 (6)	C14—C9—C10—C11	−1.6 (5)
O1—Mn1—N1—C8B	172.5 (6)	C15—C9—C10—C11	177.6 (3)
N2—Mn1—N1—C8B	−8.3 (6)	C9—C10—C11—C12	1.3 (5)
O5—Mn1—N1—C8B	−95.6 (6)	C10—C11—C12—C13	0.1 (6)
O6—Mn1—N1—C8B	84.6 (6)	C18—O4—C13—C12	3.9 (5)
O2—Mn1—N2—C15	5.8 (3)	C18—O4—C13—C14	−176.8 (3)
N1—Mn1—N2—C15	−176.4 (3)	C11—C12—C13—O4	178.1 (3)
O5—Mn1—N2—C15	−88.0 (3)	C11—C12—C13—C14	−1.2 (5)
O6—Mn1—N2—C15	94.2 (3)	Mn1—O2—C14—C9	−0.4 (5)
O2—Mn1—N2—C16B	162.4 (5)	Mn1—O2—C14—C13	−179.2 (2)
N1—Mn1—N2—C16B	−19.8 (5)	C10—C9—C14—O2	−178.3 (3)
O5—Mn1—N2—C16B	68.6 (5)	C15—C9—C14—O2	2.5 (5)
O6—Mn1—N2—C16B	−109.2 (5)	C10—C9—C14—C13	0.5 (4)
O2—Mn1—N2—C16A	−164.3 (4)	C15—C9—C14—C13	−178.7 (3)
N1—Mn1—N2—C16A	13.5 (4)	O4—C13—C14—O2	0.4 (4)
O5—Mn1—N2—C16A	101.9 (4)	C12—C13—C14—O2	179.8 (3)
O6—Mn1—N2—C16A	−75.9 (4)	O4—C13—C14—C9	−178.4 (3)
C6—C1—C2—C3	1.5 (5)	C12—C13—C14—C9	0.9 (5)
C7—C1—C2—C3	178.4 (4)	C16B—N2—C15—C9	−162.8 (5)
C1—C2—C3—C4	−0.3 (6)	C16A—N2—C15—C9	163.3 (5)
C2—C3—C4—C5	−0.2 (6)	Mn1—N2—C15—C9	−5.6 (5)
C17—O3—C5—C4	−7.4 (5)	C14—C9—C15—N2	0.8 (5)
C17—O3—C5—C6	172.5 (3)	C10—C9—C15—N2	−178.4 (3)
C3—C4—C5—O3	179.2 (3)	C15—N2—C16A—C8A	150.3 (6)
C3—C4—C5—C6	−0.7 (5)	C16B—N2—C16A—C8A	68.9 (11)
Mn1—O1—C6—C1	1.0 (5)	Mn1—N2—C16A—C8A	−39.4 (8)
Mn1—O1—C6—C5	−177.9 (2)	N1—C8A—C16A—N2	48.3 (10)
C2—C1—C6—O1	178.9 (3)	C15—N2—C16B—C8B	−161.1 (7)
C7—C1—C6—O1	2.1 (5)	C16A—N2—C16B—C8B	−45.9 (9)
C2—C1—C6—C5	−2.3 (5)	Mn1—N2—C16B—C8B	39.7 (9)
C7—C1—C6—C5	−179.0 (3)	N1—C8B—C16B—N2	−46.0 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O3^i	0.96	2.09	2.929 (3)	145
O5—H5A···O1^i	0.96	2.12	2.928 (3)	140
O5—H5B···O4^i	0.96	2.12	2.984 (3)	150
O5—H5B···O2^i	0.96	2.18	2.949 (3)	136
O6—H6A···O8^ii	0.96	1.97	2.839 (6)	150
O6—H6B···O8	0.96	2.40	3.029 (6)	123

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

(II) aqua[N,N'-bis(3,5-dichlorosalicylidene)ethylendiaminato- κ⁴O,N,N',O'](methanol-κO)manganese(III) perchlorate

Crystal data

[Mn(C16H10Cl4N2O2)(CH4O)(H2O)]ClO4	F(000) = 1224
Mr = 608.51	Dx = 1.786 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 8.072 (5) Å	θ = 10.0–14.4°
b = 21.27 (1) Å	µ = 1.22 mm^−1
c = 13.712 (7) Å	T = 297 K
β = 106.01 (6)°	Prism, brown
V = 2263 (2) Å^3	0.60 × 0.30 × 0.30 mm
Z = 4

Data collection

Rigaku AFC-7R diffractometer	4367 reflections with I > 2σ(I)
Radiation source: Rigaku rotating anode generator	Rint = 0.072
Graphite monochromator	θmax = 27.5°
ω/2θ scans	h = −10→10
Absorption correction: ψ scan (North et al., 1968)	k = 0→27
Tmin = 0.651, Tmax = 0.693	l = 0→17
5879 measured reflections	3 standard reflections every 150 reflections
5194 independent reflections	intensity decay: 0.2%

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)] = 0.046	Hydrogen site location: mixed
wR(F^2) = 0.137	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0722P)^2 + 2.6279P] where P = (Fo^2 + 2Fc^2)/3
5194 reflections	(Δ/σ)max = 0.001
298 parameters	Δρmax = 1.24 e Å^−3
1 restraint	Δρmin = −0.99 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Mn1	0.68517 (5)	0.519425 (18)	0.17247 (3)	0.03100 (14)
Cl1	0.63138 (12)	0.85813 (3)	0.10842 (7)	0.0519 (2)
Cl2	0.21479 (9)	0.65680 (4)	0.03931 (7)	0.0445 (2)
Cl3	0.18402 (10)	0.38958 (4)	0.09674 (7)	0.0487 (2)
Cl4	0.57509 (14)	0.18117 (4)	0.17422 (7)	0.0552 (2)
O1	0.5340 (2)	0.58409 (9)	0.10597 (16)	0.0354 (4)
O2	0.5120 (3)	0.45682 (9)	0.15883 (16)	0.0369 (4)
O3	0.6572 (3)	0.54904 (11)	0.32249 (17)	0.0474 (5)
H3	0.7118	0.5809	0.3501	0.057*
O4	0.7327 (3)	0.48859 (10)	0.02433 (17)	0.0423 (5)
H4A	0.6708	0.4572	0.0014	0.051*
H4B	0.7079	0.5181	−0.0179	0.051*
N1	0.8870 (3)	0.57626 (11)	0.18980 (19)	0.0339 (5)
N2	0.8676 (3)	0.45896 (11)	0.24102 (19)	0.0366 (5)
C1	0.7274 (3)	0.67300 (12)	0.1419 (2)	0.0318 (5)
C2	0.5617 (3)	0.64553 (12)	0.1093 (2)	0.0299 (5)
C3	0.4216 (3)	0.68738 (13)	0.0773 (2)	0.0319 (5)
C4	0.4414 (4)	0.75180 (13)	0.0763 (2)	0.0359 (6)
H4	0.3459	0.7779	0.0549	0.043*
C5	0.6066 (4)	0.77698 (13)	0.1079 (2)	0.0368 (6)
C6	0.7478 (4)	0.73888 (13)	0.1398 (2)	0.0364 (6)
H6	0.8575	0.7564	0.1602	0.044*
C7	0.8817 (3)	0.63602 (13)	0.1767 (2)	0.0337 (6)
H7	0.9864	0.6572	0.1909	0.040*
C8	1.0535 (4)	0.54315 (15)	0.2209 (3)	0.0443 (7)
H8A	1.1437	0.5716	0.2569	0.053*
H8B	1.0838	0.5271	0.1619	0.053*
C9	0.6933 (4)	0.36482 (13)	0.2023 (2)	0.0358 (6)
C10	0.5327 (4)	0.39496 (12)	0.1655 (2)	0.0327 (5)
C11	0.3871 (4)	0.35535 (13)	0.1359 (2)	0.0352 (6)
C12	0.3983 (4)	0.29024 (14)	0.1384 (2)	0.0400 (6)
H12	0.2996	0.2656	0.1176	0.048*
C13	0.5588 (4)	0.26275 (13)	0.1724 (2)	0.0407 (7)
C14	0.7049 (4)	0.29855 (14)	0.2055 (2)	0.0412 (7)
H14	0.8116	0.2792	0.2300	0.049*
C15	0.8523 (4)	0.39903 (14)	0.2430 (2)	0.0382 (6)
H15	0.9509	0.3758	0.2728	0.046*
C16	1.0343 (4)	0.48957 (15)	0.2893 (3)	0.0451 (8)
H16A	1.1280	0.4598	0.2968	0.054*
H16B	1.0358	0.5053	0.3559	0.054*
C17	0.5917 (8)	0.5136 (2)	0.3903 (4)	0.0807 (15)
H17A	0.5951	0.5384	0.4493	0.121*	0.50
H17B	0.6605	0.4765	0.4101	0.121*	0.50
H17C	0.4748	0.5017	0.3577	0.121*	0.50
H17D	0.5584	0.4727	0.3621	0.121*	0.50
H17E	0.4931	0.5346	0.4013	0.121*	0.50
H17F	0.6788	0.5093	0.4537	0.121*	0.50
Cl5	1.01104 (12)	0.64470 (5)	0.47254 (7)	0.0608 (3)
O5	1.0463 (5)	0.68547 (16)	0.5564 (2)	0.0798 (10)
O6	0.9708 (10)	0.5828 (2)	0.5067 (5)	0.146 (2)
O7	0.8489 (8)	0.6578 (2)	0.4037 (4)	0.140 (2)
O8	1.1459 (9)	0.6347 (4)	0.4364 (6)	0.215 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0246 (2)	0.0249 (2)	0.0377 (2)	−0.00169 (14)	−0.00118 (16)	0.00047 (15)
Cl1	0.0618 (5)	0.0262 (3)	0.0628 (5)	−0.0026 (3)	0.0089 (4)	−0.0002 (3)
Cl2	0.0274 (3)	0.0405 (4)	0.0603 (5)	0.0006 (3)	0.0035 (3)	−0.0004 (3)
Cl3	0.0329 (4)	0.0449 (4)	0.0640 (5)	−0.0084 (3)	0.0063 (3)	−0.0026 (4)
Cl4	0.0789 (6)	0.0276 (4)	0.0571 (5)	−0.0038 (4)	0.0155 (4)	−0.0007 (3)
O1	0.0276 (9)	0.0269 (9)	0.0447 (11)	−0.0019 (7)	−0.0019 (8)	0.0006 (8)
O2	0.0314 (10)	0.0269 (9)	0.0468 (11)	−0.0041 (8)	0.0016 (8)	−0.0001 (8)
O3	0.0549 (14)	0.0405 (12)	0.0447 (12)	−0.0126 (10)	0.0099 (10)	−0.0077 (10)
O4	0.0427 (12)	0.0357 (11)	0.0421 (11)	−0.0042 (9)	0.0010 (9)	−0.0028 (9)
N1	0.0252 (10)	0.0315 (11)	0.0405 (12)	−0.0030 (9)	0.0015 (9)	−0.0020 (9)
N2	0.0292 (11)	0.0319 (11)	0.0416 (13)	−0.0004 (9)	−0.0019 (10)	0.0035 (10)
C1	0.0300 (13)	0.0280 (12)	0.0348 (13)	−0.0018 (10)	0.0045 (10)	−0.0009 (10)
C2	0.0309 (13)	0.0273 (12)	0.0298 (12)	−0.0003 (10)	0.0053 (10)	−0.0004 (10)
C3	0.0281 (12)	0.0319 (13)	0.0329 (13)	−0.0002 (10)	0.0038 (10)	0.0003 (10)
C4	0.0380 (14)	0.0315 (13)	0.0356 (14)	0.0060 (11)	0.0057 (11)	0.0018 (11)
C5	0.0458 (16)	0.0260 (12)	0.0385 (15)	−0.0025 (11)	0.0114 (12)	0.0002 (11)
C6	0.0353 (14)	0.0302 (13)	0.0405 (15)	−0.0054 (11)	0.0051 (11)	−0.0008 (11)
C7	0.0260 (12)	0.0311 (13)	0.0397 (14)	−0.0042 (10)	0.0021 (10)	−0.0004 (11)
C8	0.0252 (13)	0.0362 (15)	0.065 (2)	−0.0001 (11)	0.0023 (13)	0.0001 (14)
C9	0.0383 (15)	0.0297 (13)	0.0362 (14)	−0.0023 (11)	0.0049 (11)	0.0017 (11)
C10	0.0375 (14)	0.0280 (12)	0.0305 (13)	−0.0046 (11)	0.0059 (11)	−0.0010 (10)
C11	0.0355 (14)	0.0339 (14)	0.0342 (14)	−0.0068 (11)	0.0062 (11)	−0.0014 (11)
C12	0.0521 (17)	0.0323 (14)	0.0355 (14)	−0.0120 (13)	0.0117 (13)	−0.0037 (11)
C13	0.0600 (19)	0.0264 (13)	0.0353 (15)	−0.0034 (12)	0.0125 (13)	0.0001 (11)
C14	0.0477 (17)	0.0308 (14)	0.0412 (15)	0.0025 (12)	0.0059 (13)	0.0038 (12)
C15	0.0335 (14)	0.0316 (13)	0.0431 (15)	0.0039 (11)	−0.0001 (12)	0.0057 (11)
C16	0.0279 (14)	0.0358 (15)	0.0593 (19)	−0.0004 (11)	−0.0086 (13)	0.0029 (14)
C17	0.115 (4)	0.070 (3)	0.066 (3)	−0.031 (3)	0.040 (3)	−0.006 (2)
Cl5	0.0460 (5)	0.0799 (7)	0.0531 (5)	−0.0148 (4)	0.0081 (4)	−0.0233 (5)
O5	0.087 (2)	0.088 (2)	0.0622 (18)	−0.0322 (18)	0.0157 (16)	−0.0275 (17)
O6	0.214 (7)	0.078 (3)	0.148 (5)	−0.037 (4)	0.052 (5)	−0.016 (3)
O7	0.153 (4)	0.101 (3)	0.111 (3)	0.035 (3)	−0.055 (3)	−0.029 (3)
O8	0.143 (5)	0.339 (10)	0.205 (7)	−0.102 (6)	0.119 (5)	−0.159 (7)

Geometric parameters (Å, º)

Mn1—O1	1.897 (2)	C6—H6	0.93
Mn1—O2	1.902 (2)	C7—H7	0.93
Mn1—N2	1.985 (3)	C8—C16	1.511 (5)
Mn1—N1	1.990 (2)	C8—H8A	0.97
Mn1—O3	2.222 (3)	C8—H8B	0.97
Mn1—O4	2.266 (3)	C9—C10	1.409 (4)
Cl1—C5	1.737 (3)	C9—C14	1.412 (4)
Cl2—C3	1.732 (3)	C9—C15	1.447 (4)
Cl3—C11	1.738 (3)	C10—C11	1.412 (4)
Cl4—C13	1.740 (3)	C11—C12	1.388 (4)
O1—C2	1.324 (3)	C12—C13	1.380 (5)
O2—C10	1.326 (3)	C12—H12	0.93
O3—C17	1.409 (5)	C13—C14	1.371 (5)
O3—H3	0.84	C14—H14	0.93
O4—H4A	0.84	C15—H15	0.93
O4—H4B	0.84	C16—H16A	0.97
N1—C7	1.283 (4)	C16—H16B	0.97
N1—C8	1.473 (4)	C17—H17A	0.96
N2—C15	1.282 (4)	C17—H17B	0.96
N2—C16	1.477 (4)	C17—H17C	0.96
C1—C6	1.412 (4)	C17—H17D	0.96
C1—C2	1.414 (4)	C17—H17E	0.96
C1—C7	1.438 (4)	C17—H17F	0.96
C2—C3	1.411 (4)	Cl5—O8	1.332 (5)
C3—C4	1.380 (4)	Cl5—O5	1.406 (3)
C4—C5	1.391 (4)	Cl5—O7	1.414 (5)
C4—H4	0.93	Cl5—O6	1.463 (5)
C5—C6	1.368 (4)
O1—Mn1—O2	95.89 (10)	H8A—C8—H8B	108.5
O1—Mn1—N2	172.73 (10)	C10—C9—C14	120.8 (3)
O2—Mn1—N2	91.25 (11)	C10—C9—C15	122.7 (3)
O1—Mn1—N1	90.79 (10)	C14—C9—C15	116.5 (3)
O2—Mn1—N1	172.96 (9)	O2—C10—C9	124.2 (3)
N2—Mn1—N1	82.02 (11)	O2—C10—C11	119.5 (3)
O1—Mn1—O3	91.34 (10)	C9—C10—C11	116.2 (3)
O2—Mn1—O3	91.72 (10)	C12—C11—C10	123.0 (3)
N2—Mn1—O3	89.81 (11)	C12—C11—Cl3	118.4 (2)
N1—Mn1—O3	90.35 (11)	C10—C11—Cl3	118.6 (2)
O1—Mn1—O4	91.41 (10)	C13—C12—C11	118.7 (3)
O2—Mn1—O4	90.62 (10)	C13—C12—H12	120.7
N2—Mn1—O4	87.14 (11)	C11—C12—H12	120.7
N1—Mn1—O4	86.98 (10)	C14—C13—C12	121.2 (3)
O3—Mn1—O4	176.20 (9)	C14—C13—Cl4	119.6 (3)
C2—O1—Mn1	128.22 (17)	C12—C13—Cl4	119.2 (2)
C10—O2—Mn1	127.78 (19)	C13—C14—C9	120.0 (3)
C17—O3—Mn1	127.7 (2)	C13—C14—H14	120.0
C17—O3—H3	112.3	C9—C14—H14	120.0
Mn1—O3—H3	118.2	N2—C15—C9	124.9 (3)
Mn1—O4—H4A	109.5	N2—C15—H15	117.5
Mn1—O4—H4B	109.5	C9—C15—H15	117.5
H4A—O4—H4B	109.4	N2—C16—C8	106.9 (2)
C7—N1—C8	120.5 (2)	N2—C16—H16A	110.3
C7—N1—Mn1	126.2 (2)	C8—C16—H16A	110.3
C8—N1—Mn1	113.34 (19)	N2—C16—H16B	110.3
C15—N2—C16	120.7 (2)	C8—C16—H16B	110.3
C15—N2—Mn1	126.2 (2)	H16A—C16—H16B	108.6
C16—N2—Mn1	113.06 (19)	O3—C17—H17A	109.5
C6—C1—C2	120.6 (3)	O3—C17—H17B	109.5
C6—C1—C7	117.0 (2)	H17A—C17—H17B	109.5
C2—C1—C7	122.4 (2)	O3—C17—H17C	109.5
O1—C2—C3	119.9 (2)	H17A—C17—H17C	109.5
O1—C2—C1	123.7 (2)	H17B—C17—H17C	109.5
C3—C2—C1	116.4 (2)	O3—C17—H17D	109.5
C4—C3—C2	123.0 (3)	H17A—C17—H17D	141.1
C4—C3—Cl2	118.3 (2)	H17B—C17—H17D	56.3
C2—C3—Cl2	118.7 (2)	H17C—C17—H17D	56.3
C3—C4—C5	118.9 (3)	O3—C17—H17E	109.5
C3—C4—H4	120.6	H17A—C17—H17E	56.3
C5—C4—H4	120.6	H17B—C17—H17E	141.1
C6—C5—C4	120.9 (3)	H17C—C17—H17E	56.3
C6—C5—Cl1	120.2 (2)	H17D—C17—H17E	109.5
C4—C5—Cl1	118.9 (2)	O3—C17—H17F	109.5
C5—C6—C1	120.2 (3)	H17A—C17—H17F	56.3
C5—C6—H6	119.9	H17B—C17—H17F	56.3
C1—C6—H6	119.9	H17C—C17—H17F	141.1
N1—C7—C1	125.5 (2)	H17D—C17—H17F	109.5
N1—C7—H7	117.2	H17E—C17—H17F	109.5
C1—C7—H7	117.2	O8—Cl5—O5	113.7 (3)
N1—C8—C16	107.4 (3)	O8—Cl5—O7	119.0 (5)
N1—C8—H8A	110.2	O5—Cl5—O7	111.5 (3)
C16—C8—H8A	110.2	O8—Cl5—O6	104.6 (5)
N1—C8—H8B	110.2	O5—Cl5—O6	107.8 (3)
C16—C8—H8B	110.2	O7—Cl5—O6	98.3 (4)
O2—Mn1—O1—C2	162.0 (2)	Cl2—C3—C4—C5	179.2 (2)
N1—Mn1—O1—C2	−20.3 (2)	C3—C4—C5—C6	−0.2 (4)
O3—Mn1—O1—C2	70.1 (2)	C3—C4—C5—Cl1	−179.1 (2)
O4—Mn1—O1—C2	−107.3 (2)	C4—C5—C6—C1	−0.5 (5)
O1—Mn1—O2—C10	160.7 (2)	Cl1—C5—C6—C1	178.4 (2)
N2—Mn1—O2—C10	−18.0 (2)	C2—C1—C6—C5	1.2 (4)
O3—Mn1—O2—C10	−107.8 (2)	C7—C1—C6—C5	−179.8 (3)
O4—Mn1—O2—C10	69.2 (2)	C8—N1—C7—C1	176.9 (3)
O1—Mn1—O3—C17	118.9 (4)	Mn1—N1—C7—C1	−3.3 (4)
O2—Mn1—O3—C17	23.0 (4)	C6—C1—C7—N1	175.2 (3)
N2—Mn1—O3—C17	−68.3 (4)	C2—C1—C7—N1	−5.8 (5)
N1—Mn1—O3—C17	−150.3 (4)	C7—N1—C8—C16	145.5 (3)
O1—Mn1—N1—C7	13.0 (3)	Mn1—N1—C8—C16	−34.4 (3)
N2—Mn1—N1—C7	−168.1 (3)	Mn1—O2—C10—C9	12.0 (4)
O3—Mn1—N1—C7	−78.3 (3)	Mn1—O2—C10—C11	−169.0 (2)
O4—Mn1—N1—C7	104.4 (3)	C14—C9—C10—O2	−178.9 (3)
O1—Mn1—N1—C8	−167.2 (2)	C15—C9—C10—O2	4.1 (5)
N2—Mn1—N1—C8	11.7 (2)	C14—C9—C10—C11	2.0 (4)
O3—Mn1—N1—C8	101.5 (2)	C15—C9—C10—C11	−175.0 (3)
O4—Mn1—N1—C8	−75.8 (2)	O2—C10—C11—C12	178.4 (3)
O2—Mn1—N2—C15	14.8 (3)	C9—C10—C11—C12	−2.5 (4)
N1—Mn1—N2—C15	−163.1 (3)	O2—C10—C11—Cl3	−2.8 (4)
O3—Mn1—N2—C15	106.5 (3)	C9—C10—C11—Cl3	176.3 (2)
O4—Mn1—N2—C15	−75.7 (3)	C10—C11—C12—C13	0.7 (5)
O2—Mn1—N2—C16	−167.5 (2)	Cl3—C11—C12—C13	−178.1 (2)
N1—Mn1—N2—C16	14.6 (2)	C11—C12—C13—C14	1.5 (5)
O3—Mn1—N2—C16	−75.8 (2)	C11—C12—C13—Cl4	−179.1 (2)
O4—Mn1—N2—C16	102.0 (2)	C12—C13—C14—C9	−1.9 (5)
Mn1—O1—C2—C3	−163.5 (2)	Cl4—C13—C14—C9	178.7 (2)
Mn1—O1—C2—C1	17.9 (4)	C10—C9—C14—C13	0.0 (5)
C6—C1—C2—O1	177.6 (3)	C15—C9—C14—C13	177.3 (3)
C7—C1—C2—O1	−1.4 (4)	C16—N2—C15—C9	176.9 (3)
C6—C1—C2—C3	−1.1 (4)	Mn1—N2—C15—C9	−5.6 (5)
C7—C1—C2—C3	179.9 (3)	C10—C9—C15—N2	−7.1 (5)
O1—C2—C3—C4	−178.3 (3)	C14—C9—C15—N2	175.8 (3)
C1—C2—C3—C4	0.4 (4)	C15—N2—C16—C8	141.2 (3)
O1—C2—C3—Cl2	2.8 (4)	Mn1—N2—C16—C8	−36.6 (3)
C1—C2—C3—Cl2	−178.5 (2)	N1—C8—C16—N2	44.4 (4)
C2—C3—C4—C5	0.3 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O7	0.84	2.00	2.834 (6)	174
O3—H3···Cl5	0.84	2.87	3.645 (3)	154
O4—H4A···O1^i	0.84	2.08	2.845 (3)	151
O4—H4B···O2^i	0.84	2.30	2.970 (4)	137
O4—H4A···Cl2^i	0.84	2.71	3.270 (1)	126
O4—H4B···Cl3^i	0.84	2.51	3.246 (3)	147
C4—H4···O5^ii	0.93	2.55	3.398 (5)	153
C12—H12···O7^iii	0.93	2.57	3.408 (6)	151

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

(III) bis[µ-N,N'-bis(3-methoxysalicylidene)ethylenediaminato- κ⁵O,N,N',O':O]bis[(methanol-κO)manganese(III)] diperchlorate

Crystal data

[Mn2(C18H18N2O4)2(CH4O)2](ClO4)2	F(000) = 1056
Mr = 1025.55	Dx = 1.603 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 15.226 (6) Å	θ = 10.3–12.9°
b = 13.026 (4) Å	µ = 0.80 mm^−1
c = 10.865 (4) Å	T = 297 K
β = 99.58 (3)°	Prism, brown
V = 2124.9 (13) Å^3	0.72 × 0.56 × 0.31 mm
Z = 2

Data collection

Rigaku AFC-7R diffractometer	4252 reflections with I > 2σ(I)
Radiation source: Rigaku rotating anode generator	Rint = 0.000
Graphite monochromator	θmax = 27.5°
ω/2θ scans	h = −19→19
Absorption correction: ψ scan (North et al., 1968)	k = 0→16
Tmin = 0.589, Tmax = 0.780	l = 0→14
4865 measured reflections	3 standard reflections every 150 reflections
4865 independent reflections	intensity decay: 0.2%

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)] = 0.035	Hydrogen site location: mixed
wR(F^2) = 0.101	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0569P)^2 + 0.9717P] where P = (Fo^2 + 2Fc^2)/3
4865 reflections	(Δ/σ)max = 0.001
291 parameters	Δρmax = 0.65 e Å^−3
0 restraints	Δρmin = −0.58 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Mn1	0.522542 (17)	0.614641 (19)	0.55873 (2)	0.02823 (9)
O1	0.43146 (8)	0.55761 (9)	0.43384 (11)	0.0307 (3)
O2	0.60197 (8)	0.64808 (10)	0.45183 (11)	0.0345 (3)
O3	0.06956 (10)	0.58154 (16)	0.44222 (16)	0.0596 (4)
O4	0.95299 (10)	0.77380 (16)	0.52765 (16)	0.0612 (5)
O5	0.46142 (11)	0.77152 (11)	0.53550 (17)	0.0545 (4)
H5	0.4076	0.7894	0.5438	0.065*
N1	0.44963 (10)	0.58114 (12)	0.68903 (13)	0.0315 (3)
N2	0.60945 (10)	0.65668 (12)	0.70712 (13)	0.0321 (3)
C1	0.30857 (12)	0.57650 (14)	0.54929 (17)	0.0332 (4)
C2	0.21636 (13)	0.58002 (16)	0.54605 (18)	0.0393 (4)
H2	0.1939	0.5837	0.6205	0.047*
C3	0.15805 (13)	0.57813 (16)	0.4340 (2)	0.0413 (4)
C4	0.19217 (13)	0.57331 (16)	0.32306 (19)	0.0405 (4)
H4	0.1535	0.5724	0.2471	0.049*
C5	0.28344 (12)	0.56976 (14)	0.32491 (17)	0.0352 (4)
H5A	0.3051	0.5671	0.2498	0.042*
C6	0.34330 (11)	0.57008 (12)	0.43647 (16)	0.0301 (3)
C7	0.36462 (12)	0.57159 (14)	0.67056 (17)	0.0345 (4)
H7	0.3371	0.5608	0.7398	0.041*
C8	0.50368 (13)	0.57091 (16)	0.81409 (16)	0.0385 (4)
H8A	0.5323	0.5042	0.8234	0.046*
H8B	0.4666	0.5784	0.8780	0.046*
C9	0.73346 (12)	0.69305 (13)	0.60029 (17)	0.0334 (4)
C10	0.82402 (13)	0.72350 (15)	0.62019 (19)	0.0395 (4)
H10	0.8546	0.7320	0.7011	0.047*
C11	0.86669 (13)	0.74052 (17)	0.5202 (2)	0.0436 (4)
C12	0.82055 (14)	0.72511 (18)	0.3996 (2)	0.0466 (5)
H12	0.8497	0.7358	0.3320	0.056*
C13	0.73308 (13)	0.69451 (16)	0.37838 (18)	0.0409 (4)
H13	0.7041	0.6847	0.2969	0.049*
C14	0.68671 (12)	0.67776 (13)	0.47837 (16)	0.0322 (3)
C15	0.69133 (12)	0.68172 (14)	0.70879 (16)	0.0348 (4)
H15	0.7262	0.6935	0.7863	0.042*
C16	0.57279 (13)	0.65548 (17)	0.82511 (17)	0.0398 (4)
H16A	0.5457	0.7212	0.8380	0.048*
H16B	0.6198	0.6424	0.8952	0.048*
C17	0.00726 (15)	0.5540 (2)	0.3358 (3)	0.0614 (6)
H17A	−0.0510	0.5490	0.3581	0.092*
H17B	0.0236	0.4890	0.3046	0.092*
H17C	0.0069	0.6055	0.2724	0.092*
C18	1.00918 (16)	0.7713 (2)	0.6445 (3)	0.0652 (7)
H18A	1.0145	0.7019	0.6746	0.098*
H18B	0.9843	0.8133	0.7027	0.098*
H18C	1.0670	0.7969	0.6360	0.098*
C19	0.5013 (2)	0.85512 (19)	0.4826 (3)	0.0687 (7)
H19A	0.4640	0.9146	0.4815	0.103*	0.50
H19B	0.5085	0.8382	0.3988	0.103*	0.50
H19C	0.5586	0.8692	0.5315	0.103*	0.50
H19D	0.5567	0.8334	0.4597	0.103*	0.50
H19E	0.5122	0.9098	0.5424	0.103*	0.50
H19F	0.4622	0.8789	0.4097	0.103*	0.50
Cl1	0.27822 (4)	0.95224 (5)	0.56401 (5)	0.05215 (15)
O6	0.2918 (2)	0.9810 (3)	0.4462 (2)	0.1214 (11)
O7	0.18749 (14)	0.9636 (2)	0.5787 (2)	0.0967 (8)
O8	0.2990 (2)	0.8455 (2)	0.5788 (4)	0.1327 (13)
O9	0.33274 (19)	1.0075 (3)	0.6563 (2)	0.1174 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.02978 (15)	0.02986 (15)	0.02698 (14)	−0.00265 (9)	0.01038 (10)	−0.00302 (9)
O1	0.0299 (6)	0.0341 (6)	0.0295 (6)	−0.0001 (5)	0.0093 (5)	−0.0031 (5)
O2	0.0342 (6)	0.0400 (7)	0.0312 (6)	−0.0047 (5)	0.0109 (5)	−0.0017 (5)
O3	0.0308 (7)	0.0914 (13)	0.0572 (10)	0.0038 (8)	0.0092 (7)	−0.0038 (9)
O4	0.0375 (8)	0.0884 (13)	0.0600 (10)	−0.0158 (8)	0.0153 (7)	0.0122 (9)
O5	0.0513 (9)	0.0331 (7)	0.0838 (12)	0.0065 (6)	0.0250 (8)	0.0067 (7)
N1	0.0354 (7)	0.0329 (7)	0.0277 (7)	−0.0022 (6)	0.0099 (6)	−0.0019 (6)
N2	0.0355 (7)	0.0345 (7)	0.0285 (7)	−0.0022 (6)	0.0116 (6)	−0.0053 (6)
C1	0.0329 (8)	0.0327 (8)	0.0359 (9)	−0.0004 (7)	0.0116 (7)	−0.0005 (7)
C2	0.0346 (9)	0.0446 (10)	0.0415 (10)	0.0009 (8)	0.0148 (8)	−0.0015 (8)
C3	0.0318 (9)	0.0433 (10)	0.0499 (11)	0.0034 (8)	0.0100 (8)	0.0019 (9)
C4	0.0371 (9)	0.0439 (10)	0.0391 (9)	0.0036 (8)	0.0022 (7)	0.0025 (8)
C5	0.0364 (9)	0.0361 (9)	0.0339 (9)	0.0024 (7)	0.0080 (7)	0.0025 (7)
C6	0.0314 (8)	0.0261 (7)	0.0342 (8)	0.0010 (6)	0.0097 (6)	0.0006 (6)
C7	0.0367 (9)	0.0371 (9)	0.0332 (8)	−0.0020 (7)	0.0159 (7)	−0.0020 (7)
C8	0.0409 (10)	0.0469 (10)	0.0289 (8)	−0.0029 (8)	0.0098 (7)	0.0023 (7)
C9	0.0340 (9)	0.0308 (8)	0.0378 (9)	−0.0019 (7)	0.0128 (7)	−0.0018 (7)
C10	0.0362 (9)	0.0420 (10)	0.0415 (10)	−0.0059 (8)	0.0099 (7)	−0.0001 (8)
C11	0.0341 (9)	0.0465 (11)	0.0529 (11)	−0.0048 (8)	0.0150 (8)	0.0041 (9)
C12	0.0426 (10)	0.0553 (12)	0.0465 (11)	−0.0047 (9)	0.0212 (9)	0.0070 (9)
C13	0.0398 (10)	0.0503 (11)	0.0348 (9)	−0.0043 (8)	0.0127 (7)	0.0012 (8)
C14	0.0351 (8)	0.0281 (8)	0.0357 (9)	−0.0009 (7)	0.0124 (7)	0.0002 (7)
C15	0.0368 (9)	0.0364 (9)	0.0319 (8)	−0.0039 (7)	0.0084 (7)	−0.0038 (7)
C16	0.0400 (9)	0.0533 (11)	0.0282 (8)	−0.0061 (9)	0.0119 (7)	−0.0070 (8)
C17	0.0375 (11)	0.0767 (17)	0.0674 (15)	−0.0034 (11)	0.0010 (10)	0.0023 (13)
C18	0.0415 (12)	0.0852 (19)	0.0672 (16)	−0.0173 (12)	0.0045 (11)	0.0088 (14)
C19	0.0873 (19)	0.0361 (11)	0.090 (2)	0.0029 (12)	0.0361 (16)	0.0104 (12)
Cl1	0.0518 (3)	0.0646 (3)	0.0410 (3)	0.0081 (2)	0.0106 (2)	−0.0028 (2)
O6	0.123 (2)	0.191 (3)	0.0552 (13)	0.022 (2)	0.0298 (14)	0.0378 (17)
O7	0.0596 (12)	0.130 (2)	0.1043 (17)	0.0112 (13)	0.0236 (12)	−0.0452 (15)
O8	0.125 (2)	0.0745 (17)	0.224 (4)	0.0305 (16)	0.101 (2)	0.025 (2)
O9	0.0959 (18)	0.164 (3)	0.0822 (16)	−0.0116 (19)	−0.0143 (14)	−0.0355 (18)

Geometric parameters (Å, º)

Mn1—O2	1.862 (1)	C8—H8A	0.9700
Mn1—O1	1.921 (1)	C8—H8B	0.9700
Mn1—N2	1.985 (2)	C9—C14	1.410 (3)
Mn1—N1	1.987 (2)	C9—C10	1.416 (3)
Mn1—O5	2.242 (2)	C9—C15	1.440 (2)
Mn1—O1^i	2.348 (1)	C10—C11	1.373 (3)
Mn1—Mn1^i	3.275 (1)	C10—H10	0.9300
O1—C6	1.357 (2)	C11—C12	1.394 (3)
O1—Mn1^i	2.348 (1)	C12—C13	1.372 (3)
O2—C14	1.332 (2)	C12—H12	0.9300
O3—C3	1.366 (2)	C13—C14	1.408 (2)
O3—C17	1.414 (3)	C13—H13	0.9300
O4—C11	1.373 (2)	C15—H15	0.9300
O4—C18	1.409 (3)	C16—H16A	0.9700
O5—C19	1.415 (3)	C16—H16B	0.9700
O5—H5	0.8717	C17—H17A	0.9600
N1—C7	1.282 (2)	C17—H17B	0.9600
N1—C8	1.473 (2)	C17—H17C	0.9600
N2—C15	1.286 (2)	C18—H18A	0.9600
N2—C16	1.481 (2)	C18—H18B	0.9600
C1—C2	1.399 (2)	C18—H18C	0.9600
C1—C6	1.416 (2)	C19—H19A	0.9600
C1—C7	1.447 (3)	C19—H19B	0.9600
C2—C3	1.383 (3)	C19—H19C	0.9600
C2—H2	0.9300	C19—H19D	0.9600
C3—C4	1.391 (3)	C19—H19E	0.9600
C4—C5	1.387 (3)	C19—H19F	0.9600
C4—H4	0.9300	Cl1—O6	1.382 (2)
C5—C6	1.390 (3)	Cl1—O9	1.392 (3)
C5—H5A	0.9300	Cl1—O7	1.425 (2)
C7—H7	0.9300	Cl1—O8	1.429 (3)
C8—C16	1.514 (3)
O2—Mn1—O1	96.74 (6)	C10—C9—C15	117.30 (17)
O2—Mn1—N2	91.59 (6)	C11—C10—C9	120.07 (19)
O1—Mn1—N2	170.31 (6)	C11—C10—H10	120.0
O2—Mn1—N1	173.31 (6)	C9—C10—H10	120.0
O1—Mn1—N1	89.72 (6)	O4—C11—C10	125.3 (2)
N2—Mn1—N1	81.83 (7)	O4—C11—C12	115.37 (18)
O2—Mn1—O5	90.98 (6)	C10—C11—C12	119.29 (18)
O1—Mn1—O5	92.04 (6)	C13—C12—C11	121.54 (18)
N2—Mn1—O5	92.76 (7)	C13—C12—H12	119.2
N1—Mn1—O5	90.55 (6)	C11—C12—H12	119.2
O2—Mn1—O1^i	91.38 (5)	C12—C13—C14	120.83 (18)
O1—Mn1—O1^i	80.26 (5)	C12—C13—H13	119.6
N2—Mn1—O1^i	94.65 (6)	C14—C13—H13	119.6
N1—Mn1—O1^i	87.96 (5)	O2—C14—C13	118.05 (16)
O5—Mn1—O1^i	172.17 (5)	O2—C14—C9	124.33 (15)
O2—Mn1—Mn1^i	94.94 (4)	C13—C14—C9	117.62 (17)
O1—Mn1—Mn1^i	44.95 (4)	N2—C15—C9	125.25 (17)
N2—Mn1—Mn1^i	129.51 (5)	N2—C15—H15	117.4
N1—Mn1—Mn1^i	88.38 (5)	C9—C15—H15	117.4
O5—Mn1—Mn1^i	136.97 (5)	N2—C16—C8	107.23 (15)
O1^i—Mn1—Mn1^i	35.31 (3)	N2—C16—H16A	110.3
C6—O1—Mn1	122.62 (11)	C8—C16—H16A	110.3
C6—O1—Mn1^i	113.83 (10)	N2—C16—H16B	110.3
Mn1—O1—Mn1^i	99.74 (5)	C8—C16—H16B	110.3
C14—O2—Mn1	129.73 (11)	H16A—C16—H16B	108.5
C3—O3—C17	118.22 (19)	O3—C17—H17A	109.5
C11—O4—C18	118.52 (17)	O3—C17—H17B	109.5
C19—O5—Mn1	123.29 (15)	H17A—C17—H17B	109.5
C19—O5—H5	108.1	O3—C17—H17C	109.5
Mn1—O5—H5	127.7	H17A—C17—H17C	109.5
C7—N1—C8	122.01 (15)	H17B—C17—H17C	109.5
C7—N1—Mn1	125.36 (13)	O4—C18—H18A	109.5
C8—N1—Mn1	112.61 (11)	O4—C18—H18B	109.5
C15—N2—C16	119.65 (15)	H18A—C18—H18B	109.5
C15—N2—Mn1	126.52 (12)	O4—C18—H18C	109.5
C16—N2—Mn1	113.82 (12)	H18A—C18—H18C	109.5
C2—C1—C6	119.86 (17)	H18B—C18—H18C	109.5
C2—C1—C7	117.49 (16)	O5—C19—H19A	109.5
C6—C1—C7	122.47 (16)	O5—C19—H19B	109.5
C3—C2—C1	121.07 (17)	H19A—C19—H19B	109.5
C3—C2—H2	119.5	O5—C19—H19C	109.5
C1—C2—H2	119.5	H19A—C19—H19C	109.5
O3—C3—C2	115.94 (18)	H19B—C19—H19C	109.5
O3—C3—C4	124.97 (19)	O5—C19—H19D	109.5
C2—C3—C4	119.10 (18)	H19A—C19—H19D	141.1
C5—C4—C3	120.44 (18)	H19B—C19—H19D	56.3
C5—C4—H4	119.8	H19C—C19—H19D	56.3
C3—C4—H4	119.8	O5—C19—H19E	109.5
C4—C5—C6	121.49 (17)	H19A—C19—H19E	56.3
C4—C5—H5A	119.3	H19B—C19—H19E	141.1
C6—C5—H5A	119.3	H19C—C19—H19E	56.3
O1—C6—C5	119.24 (15)	H19D—C19—H19E	109.5
O1—C6—C1	122.58 (16)	O5—C19—H19F	109.5
C5—C6—C1	118.03 (16)	H19A—C19—H19F	56.3
N1—C7—C1	124.42 (16)	H19B—C19—H19F	56.3
N1—C7—H7	117.8	H19C—C19—H19F	141.1
C1—C7—H7	117.8	H19D—C19—H19F	109.5
N1—C8—C16	106.34 (15)	H19E—C19—H19F	109.5
N1—C8—H8A	110.5	O6—Cl1—O9	111.4 (2)
C16—C8—H8A	110.5	O6—Cl1—O7	111.88 (18)
N1—C8—H8B	110.5	O9—Cl1—O7	109.80 (16)
C16—C8—H8B	110.5	O6—Cl1—O8	107.7 (2)
H8A—C8—H8B	108.7	O9—Cl1—O8	109.1 (2)
C14—C9—C10	120.63 (16)	O7—Cl1—O8	106.79 (17)
C14—C9—C15	122.05 (16)
O2—Mn1—O1—C6	−143.12 (12)	C1—C2—C3—C4	−0.4 (3)
N1—Mn1—O1—C6	38.65 (13)	O3—C3—C4—C5	−179.8 (2)
O5—Mn1—O1—C6	−51.90 (13)	C2—C3—C4—C5	0.4 (3)
O1^i—Mn1—O1—C6	126.63 (14)	C3—C4—C5—C6	0.5 (3)
Mn1^i—Mn1—O1—C6	126.63 (14)	Mn1—O1—C6—C5	151.41 (13)
O2—Mn1—O1—Mn1^i	90.25 (6)	Mn1^i—O1—C6—C5	−88.44 (16)
N1—Mn1—O1—Mn1^i	−87.98 (6)	Mn1—O1—C6—C1	−33.0 (2)
O5—Mn1—O1—Mn1^i	−178.53 (5)	Mn1^i—O1—C6—C1	87.12 (17)
O1^i—Mn1—O1—Mn1^i	0.0	C4—C5—C6—O1	174.36 (17)
O1—Mn1—O2—C14	−169.01 (15)	C4—C5—C6—C1	−1.4 (3)
N2—Mn1—O2—C14	6.03 (16)	C2—C1—C6—O1	−174.22 (17)
O5—Mn1—O2—C14	98.82 (16)	C7—C1—C6—O1	0.8 (3)
O1^i—Mn1—O2—C14	−88.65 (15)	C2—C1—C6—C5	1.4 (3)
Mn1^i—Mn1—O2—C14	−123.85 (15)	C7—C1—C6—C5	176.44 (17)
O2—Mn1—O5—C19	−14.2 (2)	C8—N1—C7—C1	−177.25 (17)
O1—Mn1—O5—C19	−111.0 (2)	Mn1—N1—C7—C1	4.7 (3)
N2—Mn1—O5—C19	77.4 (2)	C2—C1—C7—N1	−170.69 (18)
N1—Mn1—O5—C19	159.3 (2)	C6—C1—C7—N1	14.2 (3)
Mn1^i—Mn1—O5—C19	−112.5 (2)	C7—N1—C8—C16	−137.90 (18)
O1—Mn1—N1—C7	−25.45 (16)	Mn1—N1—C8—C16	40.40 (18)
N2—Mn1—N1—C7	159.30 (16)	C14—C9—C10—C11	1.3 (3)
O5—Mn1—N1—C7	66.59 (16)	C15—C9—C10—C11	−176.80 (19)
O1^i—Mn1—N1—C7	−105.71 (16)	C18—O4—C11—C10	13.6 (4)
Mn1^i—Mn1—N1—C7	−70.39 (15)	C18—O4—C11—C12	−167.4 (2)
O1—Mn1—N1—C8	156.32 (13)	C9—C10—C11—O4	177.5 (2)
N2—Mn1—N1—C8	−18.93 (13)	C9—C10—C11—C12	−1.5 (3)
O5—Mn1—N1—C8	−111.63 (13)	O4—C11—C12—C13	−178.3 (2)
O1^i—Mn1—N1—C8	76.06 (12)	C10—C11—C12—C13	0.8 (3)
Mn1^i—Mn1—N1—C8	111.39 (12)	C11—C12—C13—C14	0.1 (3)
O2—Mn1—N2—C15	−7.91 (17)	Mn1—O2—C14—C13	177.49 (13)
N1—Mn1—N2—C15	170.87 (17)	Mn1—O2—C14—C9	−2.1 (3)
O5—Mn1—N2—C15	−98.97 (17)	C12—C13—C14—O2	−179.96 (19)
O1^i—Mn1—N2—C15	83.60 (16)	C12—C13—C14—C9	−0.3 (3)
Mn1^i—Mn1—N2—C15	89.82 (17)	C10—C9—C14—O2	179.21 (17)
O2—Mn1—N2—C16	173.41 (13)	C15—C9—C14—O2	−2.7 (3)
N1—Mn1—N2—C16	−7.81 (13)	C10—C9—C14—C13	−0.4 (3)
O5—Mn1—N2—C16	82.36 (14)	C15—C9—C14—C13	177.65 (17)
O1^i—Mn1—N2—C16	−95.07 (13)	C16—N2—C15—C9	−175.34 (18)
Mn1^i—Mn1—N2—C16	−88.86 (13)	Mn1—N2—C15—C9	6.1 (3)
C6—C1—C2—C3	−0.5 (3)	C14—C9—C15—N2	0.4 (3)
C7—C1—C2—C3	−175.80 (19)	C10—C9—C15—N2	178.56 (18)
C17—O3—C3—C2	−164.3 (2)	C15—N2—C16—C8	−147.28 (18)
C17—O3—C3—C4	15.9 (3)	Mn1—N2—C16—C8	31.50 (19)
C1—C2—C3—O3	179.76 (19)	N1—C8—C16—N2	−44.9 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O8	0.87	1.90	2.767 (3)	171