Manganese(II) com­plexes derived from acyclic ligands having flexible alcohol arms: structural chracterization and SOD and catalase mimetic studies

In this work, a series of seven Mn^II com­plexes of noncyclic flexible ligands derived from 2,6-di­formyl­pyridine and ethano­lamine or alkyl-substituted ethano­lamines were prepared and characterized, six structurally by single-crystal X-ray diffraction studies. The com­plexes are di­chlorido­{2,2′-[(pyridine-2,6-di­yl)bis­(nitrilo­methanylyl­idene)]di­ethanol}manganese(II), [MnCl₂(C₁₁H₁₅N₃O₂)] or [MnCl₂(L1)], (2), bis­{μ-2,2′-[(pyridine-2,6-di­yl)bis­(nitrilo­methanylyl­idene)]di­ethanol}bis­[di­thio­cyanato­manganese(II)], [Mn₂(NCS)₄(C₁₁H₁₅N₃O₂)₂] or [Mn₂(NCS)₄(L1)₂], (3), chlorido­{1,1′-[(pyridine-2,6-di­yl)bis­(nitrilo­methanylyl­idene)]bis­(propan-2-ol)}manganese(II) chloride monohydrate, [MnCl(C₁₃H₁₉N₃O₂)(H₂O)]Cl·H₂O or [MnCl(L2)(H₂O)]Cl·H₂O, (4), {1,1′-[(pyridine-2,6-di­yl)bis­(nitrilo­methanylyl­idene)]bis­(propan-2-ol)}di­thio­cyanato­manganese(II), [Mn(NCS)₂(C₁₃H₁₉N₃O₂)] or [Mn(NCS)₂(L2)], (5), aqua­dichlorido­{2,2′-dimethyl-2,2′-[(pyridine-2,6-di­yl)bis­(nitrilo­methanylyl­idene)]bis­(propan-1-ol)}manganese(II) 0.3-hydrate, [MnCl₂(C₁₅H₂₃N₃O₂)(H₂O)]·0.3H₂O or [MnCl₂(L3)(H₂O)]·0.3H₂O, (6), (di­methyl­formamide){2,2′-dimethyl-2,2′-[(pyridine-2,6-di­yl)bis­(nitrilo­methan­yl­yl­idene)]bis­(propan-1-ol)}di­thio­cyanato­manganese(II), [Mn(NCS)₂(C₁₅H₂₃N₃O₂)(C₃H₇NO)] or [Mn(NCS)₂(L3)(DMF)], (7), and (di­methyl­form­amide){2,2′-[(pyridine-2,6-di­yl)bis­(nitrilo­methanylyl­idene)]bis­(butan-1-ol)}di­thio­cyan­ato­manganese(II) di­methyl­formamide monosolvate, [Mn(NCS)₂(C₁₅H₂₃N₃O₂)(C₃H₇NO)]·C₃H₇NO or [Mn(NCS)₂(L4)(DMF)]·DMF, (8). The crystal structure of ligand L1 is also reported, but that of (5) is not. All four ligands (L1–L4) have five potential donor atoms in an N₃O₂ donor set, i.e. three N (pyridine/di­imine donors) and two alcohol O atoms, to coordinate the Mn^II centre. The N₃O₂ donor set coordinates to the metal centre in a penta­gonal planar arrangement; seven-coordinated Mn^II com­plexes were obtained via coordination of two auxiliary ligands (anions or water mol­ecules) at the axial positions. However, in some cases, the alcohol O-atom donors remain uncoordinated, resulting in five- or six-coordinated Mn^II com­plexes. The structurally characterized com­plexes were tested for their catalytic scavenging of superoxide and peroxide. The results indicated that the com­plexes with coordinated exogenous water or chloride ligands showed higher SOD activity than those with exogenous thio­cyanate ligands.

Computing details

For all structures, data collection: APEX2 (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

2,2'-[(Pyridine-2,6-diyl)bis(nitrilomethanylylidene)]diethanol}manganese(II) (1)

Crystal data

C11H15N3O2	F(000) = 472
Mr = 221.26	Dx = 1.330 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.874 (3) Å	Cell parameters from 1048 reflections
b = 4.5259 (12) Å	θ = 2.5–24.5°
c = 24.792 (7) Å	µ = 0.09 mm^−1
β = 94.393 (5)°	T = 150 K
V = 1104.7 (5) Å^3	Plate, colourless
Z = 4	0.50 × 0.28 × 0.04 mm

Data collection

Bruker APEXII CCD diffractometer	1442 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.066
Absorption correction: multi-scan (SADABS; Bruker, 2009)	θmax = 26.4°, θmin = 1.7°
Tmin = 0.582, Tmax = 0.745	h = −12→12
9082 measured reflections	k = −5→5
2256 independent reflections	l = −30→31

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.052	H-atom parameters constrained
wR(F^2) = 0.148	w = 1/[σ^2(Fo^2) + (0.0728P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
2256 reflections	Δρmax = 0.31 e Å^−3
147 parameters	Δρmin = −0.28 e Å^−3

Special details

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

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

	x	y	z	Uiso*/Ueq
O1	1.15414 (18)	0.4340 (4)	0.21965 (7)	0.0315 (5)
H1	1.1382	0.4014	0.2519	0.047*
C1	1.1400 (2)	0.7430 (6)	0.20850 (10)	0.0278 (6)
H1A	1.2297	0.8270	0.2016	0.033*
H1B	1.1072	0.8448	0.2404	0.033*
C2	1.0414 (2)	0.7953 (6)	0.15995 (10)	0.0275 (6)
H2A	1.0473	1.0040	0.1484	0.033*
H2B	1.0663	0.6687	0.1297	0.033*
N1	0.90154 (19)	0.7288 (5)	0.17243 (8)	0.0248 (5)
C3	0.8359 (2)	0.5444 (5)	0.14214 (9)	0.0237 (6)
H3	0.8800	0.4565	0.1134	0.028*
C4	0.6943 (2)	0.4601 (5)	0.14938 (9)	0.0216 (5)
C5	0.6222 (2)	0.5775 (5)	0.19028 (9)	0.0236 (6)
H5	0.6641	0.7139	0.2155	0.028*
C6	0.4889 (2)	0.4932 (5)	0.19383 (9)	0.0244 (6)
H6	0.4376	0.5720	0.2214	0.029*
C7	0.4309 (2)	0.2933 (5)	0.15693 (9)	0.0238 (6)
H7	0.3390	0.2339	0.1585	0.029*
C8	0.5096 (2)	0.1797 (5)	0.11728 (9)	0.0217 (5)
N2	0.63962 (19)	0.2601 (4)	0.11339 (8)	0.0232 (5)
C9	0.4539 (2)	−0.0404 (5)	0.07759 (9)	0.0231 (6)
H9	0.5107	−0.1197	0.0519	0.028*
N3	0.3321 (2)	−0.1247 (5)	0.07725 (8)	0.0265 (5)
C10	0.2823 (3)	−0.3428 (5)	0.03700 (10)	0.0271 (6)
H10A	0.2550	−0.5248	0.0555	0.033*
H10B	0.3559	−0.3947	0.0137	0.033*
C11	0.1622 (3)	−0.2217 (6)	0.00246 (10)	0.0297 (6)
H11A	0.1200	−0.3840	−0.0197	0.036*
H11B	0.0938	−0.1482	0.0264	0.036*
O2	0.1971 (2)	0.0110 (4)	−0.03238 (7)	0.0335 (5)
H2	0.2433	−0.0570	−0.0566	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0355 (11)	0.0285 (10)	0.0311 (10)	0.0053 (8)	0.0071 (9)	0.0060 (8)
C1	0.0232 (13)	0.0264 (14)	0.0335 (14)	−0.0001 (11)	0.0006 (11)	0.0014 (11)
C2	0.0242 (13)	0.0310 (15)	0.0275 (13)	−0.0027 (11)	0.0037 (11)	0.0024 (11)
N1	0.0215 (11)	0.0284 (12)	0.0242 (11)	−0.0014 (9)	0.0003 (9)	0.0027 (9)
C3	0.0229 (13)	0.0280 (14)	0.0202 (12)	0.0014 (11)	0.0014 (10)	0.0004 (11)
C4	0.0208 (13)	0.0246 (13)	0.0188 (12)	0.0016 (10)	−0.0032 (10)	0.0027 (10)
C5	0.0228 (14)	0.0258 (14)	0.0218 (12)	0.0012 (11)	−0.0013 (10)	0.0014 (10)
C6	0.0262 (14)	0.0267 (13)	0.0204 (12)	0.0020 (11)	0.0027 (10)	0.0006 (11)
C7	0.0202 (13)	0.0282 (14)	0.0228 (12)	−0.0002 (10)	0.0012 (10)	0.0051 (11)
C8	0.0241 (13)	0.0212 (12)	0.0191 (12)	0.0001 (10)	−0.0019 (10)	0.0053 (10)
N2	0.0233 (11)	0.0250 (11)	0.0212 (10)	0.0001 (9)	0.0003 (8)	0.0011 (9)
C9	0.0256 (14)	0.0238 (14)	0.0196 (12)	0.0034 (11)	−0.0004 (10)	0.0012 (10)
N3	0.0260 (12)	0.0268 (12)	0.0259 (11)	−0.0009 (9)	−0.0043 (9)	−0.0005 (9)
C10	0.0281 (14)	0.0231 (14)	0.0296 (14)	−0.0020 (11)	−0.0013 (11)	−0.0019 (11)
C11	0.0276 (14)	0.0364 (16)	0.0246 (13)	−0.0027 (12)	−0.0013 (11)	−0.0015 (12)
O2	0.0429 (12)	0.0324 (11)	0.0260 (10)	0.0053 (9)	0.0070 (8)	−0.0003 (8)

Geometric parameters (Å, º)

O1—C1	1.430 (3)	C6—H6	0.9500
O1—H1	0.8400	C7—C8	1.397 (3)
C1—C2	1.508 (3)	C7—H7	0.9500
C1—H1A	0.9900	C8—N2	1.345 (3)
C1—H1B	0.9900	C8—C9	1.476 (3)
C2—N1	1.470 (3)	C9—N3	1.261 (3)
C2—H2A	0.9900	C9—H9	0.9500
C2—H2B	0.9900	N3—C10	1.462 (3)
N1—C3	1.267 (3)	C10—C11	1.512 (3)
C3—C4	1.473 (3)	C10—H10A	0.9900
C3—H3	0.9500	C10—H10B	0.9900
C4—N2	1.354 (3)	C11—O2	1.421 (3)
C4—C5	1.389 (3)	C11—H11A	0.9900
C5—C6	1.379 (3)	C11—H11B	0.9900
C5—H5	0.9500	O2—H2	0.8400
C6—C7	1.379 (3)
C1—O1—H1	109.5	C7—C6—H6	120.4
O1—C1—C2	110.8 (2)	C6—C7—C8	118.9 (2)
O1—C1—H1A	109.5	C6—C7—H7	120.5
C2—C1—H1A	109.5	C8—C7—H7	120.5
O1—C1—H1B	109.5	N2—C8—C7	122.4 (2)
C2—C1—H1B	109.5	N2—C8—C9	116.3 (2)
H1A—C1—H1B	108.1	C7—C8—C9	121.3 (2)
N1—C2—C1	111.1 (2)	C8—N2—C4	117.9 (2)
N1—C2—H2A	109.4	N3—C9—C8	121.0 (2)
C1—C2—H2A	109.4	N3—C9—H9	119.5
N1—C2—H2B	109.4	C8—C9—H9	119.5
C1—C2—H2B	109.4	C9—N3—C10	118.7 (2)
H2A—C2—H2B	108.0	N3—C10—C11	110.5 (2)
C3—N1—C2	117.2 (2)	N3—C10—H10A	109.6
N1—C3—C4	123.1 (2)	C11—C10—H10A	109.6
N1—C3—H3	118.5	N3—C10—H10B	109.6
C4—C3—H3	118.5	C11—C10—H10B	109.6
N2—C4—C5	122.4 (2)	H10A—C10—H10B	108.1
N2—C4—C3	115.3 (2)	O2—C11—C10	113.4 (2)
C5—C4—C3	122.3 (2)	O2—C11—H11A	108.9
C6—C5—C4	119.1 (2)	C10—C11—H11A	108.9
C6—C5—H5	120.5	O2—C11—H11B	108.9
C4—C5—H5	120.5	C10—C11—H11B	108.9
C5—C6—C7	119.3 (2)	H11A—C11—H11B	107.7
C5—C6—H6	120.4	C11—O2—H2	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1^i	0.84	2.10	2.924 (3)	168
O2—H2···N2^ii	0.84	2.10	2.939 (3)	175
C5—H5···O1^iii	0.95	2.52	3.422 (3)	158

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

Dichlorido{2,2'-[(pyridine-2,6-diyl)bis(nitrilomethanylylidene)]diethanol}manganese(II) (2)

Crystal data

[MnCl2(C11H15N3O2)]	Z = 8
Mr = 347.10	F(000) = 1416
Triclinic, P1	Dx = 1.595 Mg m^−3
a = 12.9256 (18) Å	Mo Kα radiation, λ = 0.71073 Å
b = 14.278 (2) Å	Cell parameters from 7111 reflections
c = 17.022 (2) Å	θ = 2.5–29.9°
α = 75.820 (2)°	µ = 1.28 mm^−1
β = 78.056 (2)°	T = 150 K
γ = 73.644 (2)°	Block, yellow
V = 2890.2 (7) Å^3	0.44 × 0.39 × 0.16 mm

Data collection

Bruker APEXII CCD diffractometer	9542 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.025
Absorption correction: multi-scan (SADABS; Bruker, 2009)	θmax = 27.0°, θmin = 1.3°
Tmin = 0.622, Tmax = 0.746	h = −16→16
27027 measured reflections	k = −18→18
12569 independent reflections	l = −21→21

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.042	H-atom parameters constrained
wR(F^2) = 0.121	w = 1/[σ^2(Fo^2) + (0.061P)^2 + 1.0911P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
12569 reflections	Δρmax = 1.15 e Å^−3
685 parameters	Δρmin = −0.80 e Å^−3

Special details

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

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

	x	y	z	Uiso*/Ueq
O1	0.33586 (17)	0.36984 (15)	0.22500 (12)	0.0334 (5)
H16B	0.3753	0.3195	0.2071	0.050*
C1	0.3411 (3)	0.4584 (2)	0.16516 (19)	0.0442 (8)
H1A	0.3111	0.4575	0.1164	0.053*
H1B	0.4180	0.4626	0.1477	0.053*
C2	0.2775 (3)	0.5454 (2)	0.20085 (17)	0.0375 (7)
H2A	0.2900	0.6076	0.1635	0.045*
H2B	0.1987	0.5481	0.2092	0.045*
N1	0.3131 (2)	0.53528 (18)	0.27914 (14)	0.0293 (5)
C3	0.3143 (2)	0.6092 (2)	0.30687 (17)	0.0288 (6)
H3	0.3000	0.6747	0.2747	0.035*
C4	0.3387 (2)	0.5898 (2)	0.39118 (17)	0.0249 (6)
N2	0.35412 (18)	0.49407 (16)	0.42819 (13)	0.0232 (5)
C5	0.3405 (2)	0.6631 (2)	0.43115 (18)	0.0284 (6)
H5	0.3307	0.7307	0.4035	0.034*
C6	0.3568 (2)	0.6354 (2)	0.51232 (17)	0.0286 (6)
H6	0.3581	0.6841	0.5412	0.034*
C7	0.3713 (2)	0.5354 (2)	0.55156 (17)	0.0263 (6)
H7	0.3818	0.5148	0.6074	0.032*
C8	0.3697 (2)	0.4675 (2)	0.50658 (16)	0.0232 (5)
C9	0.3867 (2)	0.3587 (2)	0.53856 (16)	0.0273 (6)
H9	0.3968	0.3304	0.5939	0.033*
N3	0.38704 (19)	0.30523 (17)	0.48912 (14)	0.0279 (5)
C10	0.3992 (3)	0.1972 (2)	0.51267 (18)	0.0348 (7)
H10A	0.3268	0.1821	0.5312	0.042*
H10B	0.4430	0.1688	0.5581	0.042*
C11	0.4556 (3)	0.1536 (2)	0.43855 (19)	0.0362 (7)
H11A	0.5316	0.1608	0.4247	0.043*
H11B	0.4574	0.0818	0.4498	0.043*
O2	0.39789 (17)	0.20443 (15)	0.37330 (12)	0.0327 (5)
H17A	0.4130	0.1742	0.3343	0.049*
Mn1	0.35780 (3)	0.37682 (3)	0.35586 (2)	0.02384 (11)
Cl1	0.56211 (6)	0.36142 (5)	0.30374 (4)	0.02870 (15)
Cl2	0.16047 (6)	0.38011 (5)	0.39954 (4)	0.03180 (16)
Mn4	0.13537 (3)	−0.01433 (3)	0.27308 (2)	0.02326 (10)
Cl7	0.31154 (6)	−0.12302 (5)	0.25935 (4)	0.03206 (16)
Cl8	−0.00877 (6)	−0.06227 (5)	0.37002 (4)	0.03296 (17)
N6	0.6686 (2)	−0.01566 (18)	0.21991 (14)	0.0295 (5)
C21	0.6815 (3)	−0.0163 (2)	0.30330 (17)	0.0369 (7)
H21A	0.7389	−0.0751	0.3228	0.044*
H21B	0.6123	−0.0194	0.3408	0.044*
C22	0.7127 (3)	0.0774 (2)	0.30166 (18)	0.0366 (7)
H22A	0.7099	0.0856	0.3582	0.044*
H22B	0.7878	0.0749	0.2725	0.044*
O4	0.63855 (18)	0.15722 (15)	0.26098 (12)	0.0376 (5)
H15B	0.6243	0.2088	0.2806	0.056*
Mn2	0.61967 (3)	0.14017 (3)	0.13483 (2)	0.02403 (11)
Cl3	0.81489 (6)	0.15026 (5)	0.09076 (4)	0.03163 (16)
Cl4	0.42194 (6)	0.15481 (5)	0.19308 (4)	0.02990 (16)
O7	0.38576 (19)	−0.0243 (2)	0.38746 (15)	0.0572 (7)
H7A	0.3840	−0.0259	0.3388	0.086*
C34	0.2827 (3)	−0.0260 (3)	0.43660 (19)	0.0447 (8)
H34A	0.2923	−0.0433	0.4950	0.054*
H34B	0.2554	−0.0791	0.4255	0.054*
C35	0.1983 (3)	0.0711 (2)	0.42187 (18)	0.0355 (7)
H35A	0.1317	0.0671	0.4622	0.043*
H35B	0.2265	0.1253	0.4298	0.043*
N10	0.17114 (18)	0.09394 (17)	0.33889 (14)	0.0261 (5)
C36	0.1669 (2)	0.1815 (2)	0.29787 (18)	0.0301 (6)
H36	0.1836	0.2297	0.3199	0.036*
C37	0.1353 (2)	0.2076 (2)	0.21483 (18)	0.0290 (6)
N11	0.11664 (18)	0.13165 (17)	0.19179 (14)	0.0263 (5)
C38	0.1245 (2)	0.3016 (2)	0.1641 (2)	0.0406 (8)
H38	0.1374	0.3554	0.1812	0.049*
C39	0.0943 (2)	0.3143 (3)	0.0878 (2)	0.0470 (9)
H39	0.0861	0.3777	0.0521	0.056*
C40	0.0762 (2)	0.2361 (3)	0.0636 (2)	0.0417 (8)
H40	0.0555	0.2447	0.0114	0.050*
C41	0.0890 (2)	0.1436 (2)	0.11708 (17)	0.0307 (7)
C42	0.0813 (2)	0.0509 (2)	0.09768 (17)	0.0331 (7)
H42	0.0668	0.0503	0.0454	0.040*
N12	0.09446 (19)	−0.02831 (19)	0.15272 (14)	0.0299 (5)
C43	0.0912 (3)	−0.1229 (2)	0.1341 (2)	0.0396 (8)
H43A	0.1404	−0.1788	0.1660	0.048*
H43B	0.1178	−0.1226	0.0752	0.048*
C44	−0.0223 (3)	−0.1384 (2)	0.15463 (18)	0.0372 (7)
H44A	−0.0186	−0.2093	0.1572	0.045*
H44B	−0.0548	−0.1232	0.2094	0.045*
O8	−0.09057 (17)	−0.07803 (16)	0.09667 (12)	0.0360 (5)
H8	−0.1124	−0.0199	0.1059	0.054*
O5	0.62310 (17)	0.49154 (16)	0.12114 (12)	0.0358 (5)
H5A	0.6180	0.5017	0.1685	0.054*
C23	0.7216 (2)	0.5111 (2)	0.07370 (17)	0.0314 (6)
H23A	0.7346	0.5701	0.0872	0.038*
H23B	0.7141	0.5269	0.0149	0.038*
C24	0.8182 (2)	0.4239 (2)	0.08885 (16)	0.0286 (6)
H24A	0.8037	0.3635	0.0790	0.034*
H24B	0.8835	0.4376	0.0504	0.034*
N7	0.83849 (18)	0.40674 (16)	0.17351 (13)	0.0230 (5)
C25	0.8456 (2)	0.3206 (2)	0.21816 (16)	0.0251 (6)
H25	0.8352	0.2679	0.1981	0.030*
C26	0.8705 (2)	0.3040 (2)	0.30222 (16)	0.0230 (6)
N8	0.87832 (17)	0.38629 (16)	0.32233 (13)	0.0225 (5)
C27	0.8867 (2)	0.2127 (2)	0.35601 (17)	0.0270 (6)
H27	0.8807	0.1549	0.3409	0.032*
C28	0.9119 (2)	0.2081 (2)	0.43268 (17)	0.0292 (6)
H28	0.9244	0.1463	0.4704	0.035*
C29	0.9188 (2)	0.2928 (2)	0.45416 (17)	0.0294 (6)
H29	0.9350	0.2906	0.5066	0.035*
C30	0.9015 (2)	0.3818 (2)	0.39692 (16)	0.0241 (6)
C31	0.9029 (2)	0.4793 (2)	0.41173 (16)	0.0265 (6)
H31	0.9134	0.4856	0.4636	0.032*
N9	0.88974 (19)	0.55450 (17)	0.35312 (14)	0.0265 (5)
C32	0.8920 (2)	0.6513 (2)	0.36703 (18)	0.0313 (6)
H32A	0.8722	0.6523	0.4263	0.038*
H32B	0.8378	0.7048	0.3376	0.038*
C33	1.0043 (3)	0.6701 (2)	0.33704 (18)	0.0338 (7)
H33A	1.0296	0.6560	0.2811	0.041*
H33B	1.0003	0.7411	0.3340	0.041*
O6	1.08037 (17)	0.61004 (16)	0.38910 (13)	0.0367 (5)
H6A	1.0976	0.5513	0.3815	0.055*
Mn3	0.85670 (3)	0.52780 (3)	0.23450 (2)	0.02444 (11)
Cl5	0.67640 (6)	0.62923 (5)	0.24165 (4)	0.03376 (17)
Cl6	0.99157 (7)	0.58149 (6)	0.13063 (4)	0.03814 (18)
O3	0.57664 (17)	0.31789 (15)	0.10150 (13)	0.0357 (5)
H15A	0.5904	0.3480	0.1333	0.054*
C12	0.5965 (3)	0.3557 (2)	0.01528 (19)	0.0375 (7)
H12A	0.6758	0.3409	−0.0046	0.045*
H12B	0.5670	0.4288	0.0031	0.045*
C13	0.5413 (3)	0.3064 (2)	−0.02571 (19)	0.0358 (7)
H13A	0.4612	0.3275	−0.0108	0.043*
H13B	0.5598	0.3247	−0.0860	0.043*
N4	0.57970 (19)	0.19899 (16)	0.00216 (14)	0.0265 (5)
C14	0.5950 (2)	0.1398 (2)	−0.04572 (17)	0.0279 (6)
H14	0.5860	0.1634	−0.1017	0.033*
C15	0.6275 (2)	0.0323 (2)	−0.01063 (16)	0.0238 (6)
N5	0.64164 (17)	0.01196 (16)	0.06805 (13)	0.0232 (5)
C16	0.6377 (2)	−0.0419 (2)	−0.05331 (17)	0.0277 (6)
H16	0.6279	−0.0260	−0.1092	0.033*
C17	0.6628 (2)	−0.1400 (2)	−0.01180 (18)	0.0306 (6)
H17	0.6695	−0.1926	−0.0390	0.037*
C18	0.6780 (2)	−0.1611 (2)	0.06922 (18)	0.0306 (6)
H18	0.6956	−0.2280	0.0983	0.037*
C19	0.6671 (2)	−0.0824 (2)	0.10752 (17)	0.0261 (6)
C20	0.6828 (2)	−0.0941 (2)	0.19306 (17)	0.0306 (6)
H20	0.7029	−0.1582	0.2267	0.037*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0396 (12)	0.0338 (12)	0.0299 (11)	−0.0098 (9)	−0.0002 (9)	−0.0150 (9)
C1	0.053 (2)	0.047 (2)	0.0303 (17)	−0.0003 (16)	−0.0166 (15)	−0.0071 (15)
C2	0.054 (2)	0.0369 (17)	0.0241 (15)	−0.0115 (15)	−0.0134 (14)	−0.0031 (13)
N1	0.0365 (14)	0.0308 (13)	0.0210 (12)	−0.0102 (11)	−0.0046 (10)	−0.0036 (10)
C3	0.0373 (16)	0.0237 (14)	0.0246 (14)	−0.0077 (12)	−0.0058 (12)	−0.0019 (11)
C4	0.0249 (14)	0.0243 (14)	0.0265 (14)	−0.0056 (11)	−0.0053 (11)	−0.0063 (11)
N2	0.0217 (11)	0.0258 (12)	0.0224 (11)	−0.0052 (9)	−0.0020 (9)	−0.0069 (9)
C5	0.0296 (15)	0.0240 (14)	0.0322 (15)	−0.0055 (12)	−0.0043 (12)	−0.0079 (12)
C6	0.0254 (14)	0.0337 (16)	0.0306 (15)	−0.0073 (12)	−0.0013 (12)	−0.0160 (12)
C7	0.0189 (13)	0.0378 (16)	0.0236 (14)	−0.0055 (12)	−0.0028 (11)	−0.0105 (12)
C8	0.0192 (13)	0.0293 (14)	0.0213 (13)	−0.0053 (11)	−0.0018 (10)	−0.0069 (11)
C9	0.0246 (14)	0.0344 (16)	0.0200 (13)	−0.0083 (12)	−0.0016 (11)	−0.0001 (11)
N3	0.0297 (13)	0.0255 (12)	0.0245 (12)	−0.0061 (10)	0.0004 (10)	−0.0023 (10)
C10	0.0389 (17)	0.0305 (16)	0.0282 (15)	−0.0065 (13)	−0.0031 (13)	0.0034 (12)
C11	0.0365 (17)	0.0259 (15)	0.0450 (19)	−0.0048 (13)	−0.0064 (14)	−0.0080 (13)
O2	0.0371 (12)	0.0294 (11)	0.0323 (11)	−0.0077 (9)	−0.0015 (9)	−0.0108 (9)
Mn1	0.0284 (2)	0.0233 (2)	0.0209 (2)	−0.00833 (17)	−0.00133 (17)	−0.00606 (16)
Cl1	0.0301 (4)	0.0325 (4)	0.0264 (3)	−0.0115 (3)	−0.0006 (3)	−0.0097 (3)
Cl2	0.0273 (4)	0.0345 (4)	0.0366 (4)	−0.0101 (3)	−0.0008 (3)	−0.0127 (3)
Mn4	0.0279 (2)	0.0221 (2)	0.0191 (2)	−0.00485 (17)	−0.00624 (17)	−0.00198 (16)
Cl7	0.0350 (4)	0.0274 (4)	0.0287 (4)	0.0014 (3)	−0.0067 (3)	−0.0052 (3)
Cl8	0.0394 (4)	0.0338 (4)	0.0255 (3)	−0.0144 (3)	−0.0009 (3)	−0.0026 (3)
N6	0.0359 (14)	0.0313 (13)	0.0230 (12)	−0.0118 (11)	−0.0038 (10)	−0.0044 (10)
C21	0.051 (2)	0.0396 (18)	0.0206 (14)	−0.0142 (15)	−0.0084 (14)	−0.0005 (13)
C22	0.0386 (18)	0.0439 (19)	0.0272 (15)	−0.0026 (14)	−0.0102 (13)	−0.0112 (14)
O4	0.0474 (13)	0.0341 (12)	0.0345 (12)	−0.0016 (10)	−0.0126 (10)	−0.0166 (9)
Mn2	0.0273 (2)	0.0234 (2)	0.0210 (2)	−0.00505 (17)	−0.00187 (17)	−0.00622 (16)
Cl3	0.0282 (4)	0.0334 (4)	0.0341 (4)	−0.0089 (3)	−0.0034 (3)	−0.0076 (3)
Cl4	0.0282 (4)	0.0361 (4)	0.0284 (3)	−0.0103 (3)	0.0012 (3)	−0.0135 (3)
O7	0.0376 (14)	0.089 (2)	0.0490 (15)	0.0007 (13)	−0.0179 (12)	−0.0301 (14)
C34	0.057 (2)	0.052 (2)	0.0279 (16)	−0.0089 (17)	−0.0178 (16)	−0.0077 (15)
C35	0.0383 (17)	0.0470 (19)	0.0271 (15)	−0.0148 (15)	−0.0018 (13)	−0.0156 (14)
N10	0.0237 (12)	0.0292 (13)	0.0255 (12)	−0.0066 (10)	0.0002 (9)	−0.0086 (10)
C36	0.0235 (14)	0.0305 (16)	0.0373 (16)	−0.0088 (12)	0.0031 (12)	−0.0125 (13)
C37	0.0176 (13)	0.0240 (14)	0.0395 (16)	−0.0023 (11)	−0.0008 (12)	−0.0017 (12)
N11	0.0203 (11)	0.0282 (12)	0.0252 (12)	−0.0038 (9)	−0.0032 (9)	0.0019 (10)
C38	0.0214 (15)	0.0268 (16)	0.062 (2)	−0.0041 (12)	0.0015 (15)	0.0045 (15)
C39	0.0245 (16)	0.0394 (19)	0.056 (2)	−0.0023 (14)	−0.0031 (15)	0.0214 (16)
C40	0.0229 (15)	0.051 (2)	0.0347 (17)	−0.0014 (14)	−0.0058 (13)	0.0134 (15)
C41	0.0165 (13)	0.0429 (18)	0.0240 (14)	−0.0024 (12)	−0.0031 (11)	0.0038 (12)
C42	0.0241 (14)	0.053 (2)	0.0183 (14)	−0.0038 (13)	−0.0072 (11)	−0.0021 (13)
N12	0.0263 (12)	0.0389 (14)	0.0251 (12)	−0.0036 (10)	−0.0088 (10)	−0.0082 (11)
C43	0.0404 (18)	0.0423 (19)	0.0380 (18)	0.0043 (14)	−0.0166 (15)	−0.0192 (15)
C44	0.052 (2)	0.0332 (17)	0.0290 (16)	−0.0068 (15)	−0.0152 (14)	−0.0065 (13)
O8	0.0376 (12)	0.0396 (12)	0.0348 (12)	−0.0044 (10)	−0.0126 (10)	−0.0146 (10)
O5	0.0331 (12)	0.0452 (13)	0.0280 (11)	−0.0016 (10)	−0.0098 (9)	−0.0103 (9)
C23	0.0406 (17)	0.0308 (16)	0.0240 (14)	−0.0078 (13)	−0.0130 (13)	−0.0020 (12)
C24	0.0344 (16)	0.0315 (15)	0.0202 (13)	−0.0073 (12)	−0.0060 (12)	−0.0048 (11)
N7	0.0224 (11)	0.0245 (12)	0.0213 (11)	−0.0040 (9)	−0.0050 (9)	−0.0036 (9)
C25	0.0243 (14)	0.0272 (14)	0.0244 (14)	−0.0060 (11)	−0.0016 (11)	−0.0081 (11)
C26	0.0166 (12)	0.0248 (14)	0.0239 (13)	−0.0015 (10)	−0.0033 (10)	−0.0020 (11)
N8	0.0194 (11)	0.0253 (12)	0.0214 (11)	−0.0045 (9)	−0.0057 (9)	−0.0012 (9)
C27	0.0207 (13)	0.0241 (14)	0.0330 (15)	−0.0043 (11)	−0.0040 (11)	−0.0009 (12)
C28	0.0254 (14)	0.0262 (15)	0.0302 (15)	−0.0040 (12)	−0.0077 (12)	0.0055 (12)
C29	0.0203 (13)	0.0379 (17)	0.0255 (14)	−0.0054 (12)	−0.0084 (11)	0.0039 (12)
C30	0.0181 (13)	0.0308 (15)	0.0213 (13)	−0.0053 (11)	−0.0040 (10)	−0.0014 (11)
C31	0.0226 (14)	0.0359 (16)	0.0216 (13)	−0.0066 (12)	−0.0075 (11)	−0.0040 (12)
N9	0.0263 (12)	0.0283 (13)	0.0263 (12)	−0.0055 (10)	−0.0094 (10)	−0.0048 (10)
C32	0.0353 (16)	0.0280 (15)	0.0325 (16)	−0.0027 (12)	−0.0121 (13)	−0.0094 (12)
C33	0.0511 (19)	0.0286 (15)	0.0248 (15)	−0.0142 (14)	−0.0065 (13)	−0.0054 (12)
O6	0.0355 (12)	0.0388 (12)	0.0411 (12)	−0.0054 (10)	−0.0117 (10)	−0.0168 (10)
Mn3	0.0307 (2)	0.0219 (2)	0.0206 (2)	−0.00581 (17)	−0.00902 (17)	−0.00018 (16)
Cl5	0.0364 (4)	0.0307 (4)	0.0282 (4)	0.0013 (3)	−0.0080 (3)	−0.0030 (3)
Cl6	0.0492 (5)	0.0403 (4)	0.0268 (4)	−0.0215 (4)	−0.0023 (3)	−0.0006 (3)
O3	0.0421 (13)	0.0283 (11)	0.0369 (12)	−0.0083 (9)	−0.0007 (10)	−0.0116 (9)
C12	0.0446 (19)	0.0233 (15)	0.0401 (18)	−0.0035 (13)	−0.0119 (15)	0.0012 (13)
C13	0.0395 (18)	0.0243 (15)	0.0366 (17)	0.0005 (13)	−0.0114 (14)	0.0023 (12)
N4	0.0275 (12)	0.0225 (12)	0.0262 (12)	−0.0026 (10)	−0.0046 (10)	−0.0024 (10)
C14	0.0256 (14)	0.0331 (16)	0.0222 (14)	−0.0046 (12)	−0.0031 (11)	−0.0036 (12)
C15	0.0182 (13)	0.0292 (14)	0.0225 (13)	−0.0045 (11)	0.0006 (10)	−0.0067 (11)
N5	0.0189 (11)	0.0257 (12)	0.0239 (11)	−0.0040 (9)	−0.0005 (9)	−0.0072 (9)
C16	0.0212 (14)	0.0381 (16)	0.0250 (14)	−0.0072 (12)	0.0006 (11)	−0.0119 (12)
C17	0.0277 (15)	0.0325 (16)	0.0349 (16)	−0.0077 (12)	−0.0009 (12)	−0.0153 (13)
C18	0.0315 (16)	0.0225 (14)	0.0372 (16)	−0.0056 (12)	−0.0045 (13)	−0.0063 (12)
C19	0.0257 (14)	0.0240 (14)	0.0275 (14)	−0.0046 (11)	−0.0038 (11)	−0.0049 (11)
C20	0.0381 (17)	0.0242 (14)	0.0275 (15)	−0.0078 (12)	−0.0048 (13)	−0.0015 (12)

Geometric parameters (Å, º)

O1—C1	1.425 (4)	C37—N11	1.335 (4)
O1—Mn1	2.332 (2)	C37—C38	1.394 (4)
C1—C2	1.475 (4)	N11—C41	1.350 (4)
C2—N1	1.459 (3)	C38—C39	1.387 (5)
N1—C3	1.262 (4)	C39—C40	1.374 (5)
N1—Mn1	2.299 (2)	C40—C41	1.397 (4)
C3—C4	1.476 (4)	C41—C42	1.474 (4)
C4—N2	1.335 (3)	C42—N12	1.275 (4)
C4—C5	1.389 (4)	N12—C43	1.474 (4)
N2—C8	1.336 (3)	C43—C44	1.502 (5)
N2—Mn1	2.294 (2)	C44—O8	1.418 (3)
C5—C6	1.384 (4)	O5—C23	1.420 (4)
C6—C7	1.397 (4)	C23—C24	1.509 (4)
C7—C8	1.381 (4)	C24—N7	1.467 (3)
C8—C9	1.483 (4)	N7—C25	1.267 (3)
C9—N3	1.266 (4)	N7—Mn3	2.309 (2)
N3—C10	1.466 (4)	C25—C26	1.479 (4)
N3—Mn1	2.310 (2)	C26—N8	1.337 (3)
C10—C11	1.504 (4)	C26—C27	1.386 (4)
C11—O2	1.400 (4)	N8—C30	1.347 (3)
O2—Mn1	2.324 (2)	N8—Mn3	2.184 (2)
Mn1—Cl2	2.4951 (9)	C27—C28	1.391 (4)
Mn1—Cl1	2.5707 (9)	C28—C29	1.377 (4)
Mn4—N11	2.182 (2)	C29—C30	1.392 (4)
Mn4—N12	2.286 (2)	C30—C31	1.480 (4)
Mn4—N10	2.307 (2)	C31—N9	1.272 (3)
Mn4—Cl8	2.3570 (8)	N9—C32	1.468 (4)
Mn4—Cl7	2.3697 (8)	N9—Mn3	2.287 (2)
N6—C20	1.264 (4)	C32—C33	1.511 (4)
N6—C21	1.461 (3)	C33—O6	1.415 (4)
N6—Mn2	2.336 (2)	Mn3—Cl6	2.3592 (9)
C21—C22	1.496 (4)	Mn3—Cl5	2.3689 (9)
C22—O4	1.403 (4)	O3—C12	1.430 (4)
O4—Mn2	2.288 (2)	C12—C13	1.490 (4)
Mn2—N5	2.306 (2)	C13—N4	1.462 (3)
Mn2—N4	2.320 (2)	N4—C14	1.262 (4)
Mn2—O3	2.388 (2)	C14—C15	1.478 (4)
Mn2—Cl4	2.5122 (9)	C15—N5	1.339 (3)
Mn2—Cl3	2.5137 (9)	C15—C16	1.388 (4)
O7—C34	1.422 (4)	N5—C19	1.332 (3)
C34—C35	1.506 (5)	C16—C17	1.385 (4)
C35—N10	1.463 (4)	C17—C18	1.381 (4)
N10—C36	1.267 (4)	C18—C19	1.392 (4)
C36—C37	1.483 (4)	C19—C20	1.475 (4)
C1—O1—Mn1	114.60 (17)	N6—Mn2—Cl3	92.43 (6)
O1—C1—C2	109.1 (3)	O3—Mn2—Cl3	85.49 (6)
N1—C2—C1	107.9 (3)	Cl4—Mn2—Cl3	169.39 (3)
C3—N1—C2	122.7 (3)	O7—C34—C35	113.7 (3)
C3—N1—Mn1	120.30 (19)	N10—C35—C34	111.0 (2)
C2—N1—Mn1	116.85 (18)	C36—N10—C35	117.8 (2)
N1—C3—C4	117.4 (3)	C36—N10—Mn4	115.62 (19)
N2—C4—C5	122.0 (3)	C35—N10—Mn4	126.62 (18)
N2—C4—C3	113.5 (2)	N10—C36—C37	118.8 (3)
C5—C4—C3	124.4 (3)	N11—C37—C38	121.6 (3)
C4—N2—C8	119.4 (2)	N11—C37—C36	113.6 (2)
C4—N2—Mn1	119.75 (17)	C38—C37—C36	124.8 (3)
C8—N2—Mn1	120.80 (18)	C37—N11—C41	120.4 (2)
C6—C5—C4	118.4 (3)	C37—N11—Mn4	120.33 (19)
C5—C6—C7	119.7 (3)	C41—N11—Mn4	119.3 (2)
C8—C7—C6	117.9 (3)	C39—C38—C37	118.0 (3)
N2—C8—C7	122.6 (3)	C40—C39—C38	120.5 (3)
N2—C8—C9	113.0 (2)	C39—C40—C41	118.7 (3)
C7—C8—C9	124.4 (2)	N11—C41—C40	120.8 (3)
N3—C9—C8	117.3 (2)	N11—C41—C42	113.9 (2)
C9—N3—C10	123.4 (2)	C40—C41—C42	125.2 (3)
C9—N3—Mn1	120.55 (19)	N12—C42—C41	118.5 (3)
C10—N3—Mn1	115.97 (18)	C42—N12—C43	119.7 (3)
N3—C10—C11	107.4 (2)	C42—N12—Mn4	116.0 (2)
O2—C11—C10	108.2 (2)	C43—N12—Mn4	124.08 (19)
C11—O2—Mn1	113.98 (17)	N12—C43—C44	111.3 (3)
N2—Mn1—N1	68.69 (8)	O8—C44—C43	112.7 (3)
N2—Mn1—N3	68.38 (8)	O5—C23—C24	112.2 (2)
N1—Mn1—N3	136.86 (8)	N7—C24—C23	110.0 (2)
N2—Mn1—O2	138.51 (8)	C25—N7—C24	119.4 (2)
N1—Mn1—O2	152.70 (8)	C25—N7—Mn3	116.06 (18)
N3—Mn1—O2	70.42 (8)	C24—N7—Mn3	124.54 (17)
N2—Mn1—O1	138.76 (8)	N7—C25—C26	118.5 (2)
N1—Mn1—O1	70.12 (8)	N8—C26—C27	121.8 (3)
N3—Mn1—O1	152.84 (8)	N8—C26—C25	113.5 (2)
O2—Mn1—O1	82.60 (7)	C27—C26—C25	124.7 (3)
N2—Mn1—Cl2	94.27 (6)	C26—N8—C30	119.8 (2)
N1—Mn1—Cl2	90.26 (6)	C26—N8—Mn3	120.63 (17)
N3—Mn1—Cl2	88.86 (6)	C30—N8—Mn3	119.53 (18)
O2—Mn1—Cl2	89.64 (5)	C26—C27—C28	118.2 (3)
O1—Mn1—Cl2	87.85 (5)	C29—C28—C27	120.3 (3)
N2—Mn1—Cl1	90.84 (6)	C28—C29—C30	118.2 (3)
N1—Mn1—Cl1	91.70 (6)	N8—C30—C29	121.6 (3)
N3—Mn1—Cl1	92.92 (6)	N8—C30—C31	113.8 (2)
O2—Mn1—Cl1	86.45 (5)	C29—C30—C31	124.6 (2)
O1—Mn1—Cl1	88.38 (5)	N9—C31—C30	118.3 (2)
Cl2—Mn1—Cl1	174.89 (3)	C31—N9—C32	118.6 (2)
N11—Mn4—N12	72.19 (9)	C31—N9—Mn3	116.29 (19)
N11—Mn4—N10	71.64 (9)	C32—N9—Mn3	125.02 (17)
N12—Mn4—N10	143.76 (9)	N9—C32—C33	110.3 (2)
N11—Mn4—Cl8	122.74 (6)	O6—C33—C32	111.9 (2)
N12—Mn4—Cl8	102.65 (7)	N8—Mn3—N9	72.00 (8)
N10—Mn4—Cl8	98.54 (6)	N8—Mn3—N7	71.26 (8)
N11—Mn4—Cl7	115.85 (6)	N9—Mn3—N7	143.26 (8)
N12—Mn4—Cl7	94.90 (6)	N8—Mn3—Cl6	126.21 (6)
N10—Mn4—Cl7	98.70 (6)	N9—Mn3—Cl6	105.79 (6)
Cl8—Mn4—Cl7	121.41 (3)	N7—Mn3—Cl6	95.62 (6)
C20—N6—C21	123.2 (3)	N8—Mn3—Cl5	115.15 (6)
C20—N6—Mn2	120.1 (2)	N9—Mn3—Cl5	95.39 (6)
C21—N6—Mn2	116.75 (18)	N7—Mn3—Cl5	100.19 (6)
N6—C21—C22	107.6 (2)	Cl6—Mn3—Cl5	118.51 (3)
O4—C22—C21	107.7 (3)	C12—O3—Mn2	112.57 (16)
C22—O4—Mn2	114.54 (17)	O3—C12—C13	107.5 (2)
O4—Mn2—N5	137.43 (8)	N4—C13—C12	107.2 (2)
O4—Mn2—N4	154.35 (8)	C14—N4—C13	120.9 (2)
N5—Mn2—N4	68.23 (8)	C14—N4—Mn2	120.65 (19)
O4—Mn2—N6	69.37 (8)	C13—N4—Mn2	118.38 (18)
N5—Mn2—N6	68.10 (8)	N4—C14—C15	116.9 (2)
N4—Mn2—N6	136.25 (8)	N5—C15—C16	122.3 (3)
O4—Mn2—O3	85.53 (7)	N5—C15—C14	113.9 (2)
N5—Mn2—O3	136.95 (8)	C16—C15—C14	123.7 (3)
N4—Mn2—O3	68.85 (8)	C19—N5—C15	119.6 (2)
N6—Mn2—O3	154.90 (8)	C19—N5—Mn2	120.44 (18)
O4—Mn2—Cl4	85.22 (6)	C15—N5—Mn2	119.95 (18)
N5—Mn2—Cl4	97.38 (6)	C17—C16—C15	117.9 (3)
N4—Mn2—Cl4	91.98 (6)	C18—C17—C16	119.8 (3)
N6—Mn2—Cl4	91.06 (6)	C17—C18—C19	118.8 (3)
O3—Mn2—Cl4	87.10 (5)	N5—C19—C18	121.6 (3)
O4—Mn2—Cl3	86.64 (6)	N5—C19—C20	113.9 (2)
N5—Mn2—Cl3	93.22 (6)	C18—C19—C20	124.5 (3)
N4—Mn2—Cl3	92.42 (6)	N6—C20—C19	117.4 (3)
Mn1—O1—C1—C2	−43.7 (3)	C41—C42—N12—Mn4	−2.4 (3)
O1—C1—C2—N1	50.6 (4)	C42—N12—C43—C44	−90.7 (3)
C1—C2—N1—C3	147.7 (3)	Mn4—N12—C43—C44	94.3 (3)
C1—C2—N1—Mn1	−36.1 (3)	N12—C43—C44—O8	75.2 (3)
C2—N1—C3—C4	172.5 (3)	O5—C23—C24—N7	−65.5 (3)
Mn1—N1—C3—C4	−3.6 (4)	C23—C24—N7—C25	127.3 (3)
N1—C3—C4—N2	−1.5 (4)	C23—C24—N7—Mn3	−51.8 (3)
N1—C3—C4—C5	−178.4 (3)	C24—N7—C25—C26	177.6 (2)
C5—C4—N2—C8	1.3 (4)	Mn3—N7—C25—C26	−3.3 (3)
C3—C4—N2—C8	−175.6 (2)	N7—C25—C26—N8	2.6 (4)
C5—C4—N2—Mn1	−177.2 (2)	N7—C25—C26—C27	−176.2 (3)
C3—C4—N2—Mn1	5.9 (3)	C27—C26—N8—C30	−0.6 (4)
N2—C4—C5—C6	−1.2 (4)	C25—C26—N8—C30	−179.5 (2)
C3—C4—C5—C6	175.4 (3)	C27—C26—N8—Mn3	178.27 (19)
C4—C5—C6—C7	0.2 (4)	C25—C26—N8—Mn3	−0.6 (3)
C5—C6—C7—C8	0.6 (4)	N8—C26—C27—C28	−0.1 (4)
C4—N2—C8—C7	−0.4 (4)	C25—C26—C27—C28	178.6 (2)
Mn1—N2—C8—C7	178.08 (19)	C26—C27—C28—C29	0.9 (4)
C4—N2—C8—C9	−179.4 (2)	C27—C28—C29—C30	−0.9 (4)
Mn1—N2—C8—C9	−1.0 (3)	C26—N8—C30—C29	0.6 (4)
C6—C7—C8—N2	−0.6 (4)	Mn3—N8—C30—C29	−178.28 (19)
C6—C7—C8—C9	178.4 (2)	C26—N8—C30—C31	−177.5 (2)
N2—C8—C9—N3	1.6 (4)	Mn3—N8—C30—C31	3.6 (3)
C7—C8—C9—N3	−177.4 (3)	C28—C29—C30—N8	0.1 (4)
C8—C9—N3—C10	−177.9 (2)	C28—C29—C30—C31	178.1 (3)
C8—C9—N3—Mn1	−1.6 (3)	N8—C30—C31—N9	−4.4 (4)
C9—N3—C10—C11	−149.5 (3)	C29—C30—C31—N9	177.5 (3)
Mn1—N3—C10—C11	34.1 (3)	C30—C31—N9—C32	−179.5 (2)
N3—C10—C11—O2	−52.8 (3)	C30—C31—N9—Mn3	3.1 (3)
C10—C11—O2—Mn1	48.5 (3)	C31—N9—C32—C33	96.3 (3)
C20—N6—C21—C22	152.6 (3)	Mn3—N9—C32—C33	−86.5 (3)
Mn2—N6—C21—C22	−27.2 (3)	N9—C32—C33—O6	−72.8 (3)
N6—C21—C22—O4	50.1 (3)	Mn2—O3—C12—C13	50.9 (3)
C21—C22—O4—Mn2	−52.7 (3)	O3—C12—C13—N4	−53.6 (3)
O7—C34—C35—N10	65.5 (3)	C12—C13—N4—C14	−143.8 (3)
C34—C35—N10—C36	−133.9 (3)	C12—C13—N4—Mn2	33.4 (3)
C34—C35—N10—Mn4	45.8 (3)	C13—N4—C14—C15	−176.5 (2)
C35—N10—C36—C37	−177.7 (2)	Mn2—N4—C14—C15	6.4 (3)
Mn4—N10—C36—C37	2.6 (3)	N4—C14—C15—N5	−3.1 (4)
N10—C36—C37—N11	−1.4 (4)	N4—C14—C15—C16	174.0 (3)
N10—C36—C37—C38	178.2 (3)	C16—C15—N5—C19	0.4 (4)
C38—C37—N11—C41	1.6 (4)	C14—C15—N5—C19	177.5 (2)
C36—C37—N11—C41	−178.9 (2)	C16—C15—N5—Mn2	−178.78 (19)
C38—C37—N11—Mn4	179.7 (2)	C14—C15—N5—Mn2	−1.7 (3)
C36—C37—N11—Mn4	−0.7 (3)	N5—C15—C16—C17	0.4 (4)
N11—C37—C38—C39	−0.5 (4)	C14—C15—C16—C17	−176.4 (3)
C36—C37—C38—C39	180.0 (3)	C15—C16—C17—C18	−0.8 (4)
C37—C38—C39—C40	−0.2 (4)	C16—C17—C18—C19	0.3 (4)
C38—C39—C40—C41	−0.1 (5)	C15—N5—C19—C18	−0.9 (4)
C37—N11—C41—C40	−1.9 (4)	Mn2—N5—C19—C18	178.3 (2)
Mn4—N11—C41—C40	179.9 (2)	C15—N5—C19—C20	178.6 (2)
C37—N11—C41—C42	174.5 (2)	Mn2—N5—C19—C20	−2.2 (3)
Mn4—N11—C41—C42	−3.6 (3)	C17—C18—C19—N5	0.5 (4)
C39—C40—C41—N11	1.2 (4)	C17—C18—C19—C20	−178.9 (3)
C39—C40—C41—C42	−174.8 (3)	C21—N6—C20—C19	−180.0 (3)
N11—C41—C42—N12	3.9 (4)	Mn2—N6—C20—C19	−0.1 (4)
C40—C41—C42—N12	−179.8 (3)	N5—C19—C20—N6	1.5 (4)
C41—C42—N12—C43	−177.7 (3)	C18—C19—C20—N6	−179.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8···Cl3^i	0.84	2.32	3.127 (2)	162
O6—H6A···Cl2^ii	0.84	2.31	3.124 (2)	163
O1—H16B···Cl4	0.84	2.32	3.099 (2)	155
O2—H17A···Cl4	0.84	2.46	3.249 (2)	157
O4—H15B···Cl1	0.84	2.20	3.021 (2)	164
O7—H7A···Cl7	0.84	2.61	3.286 (3)	139
O5—H5A···Cl1	0.84	2.77	3.273 (2)	120
O5—H5A···Cl5	0.84	2.78	3.445 (2)	138
O3—H15A···O5	0.84	2.16	2.819 (3)	135
O3—H15A···Cl1	0.84	2.90	3.604 (2)	143

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

Bis{µ-2,2'-[(pyridine-2,6-diyl)bis(nitrilomethanylylidene)]diethanol}bis[dithiocyanatomanganese(II)] (3)

Crystal data

[Mn2(NCS)4(C11H15N3O2)2]	F(000) = 804
Mr = 784.72	Dx = 1.556 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.2639 (12) Å	Cell parameters from 2277 reflections
b = 24.655 (4) Å	θ = 2.3–23.1°
c = 9.4710 (16) Å	µ = 1.05 mm^−1
β = 98.994 (3)°	T = 150 K
V = 1675.3 (5) Å^3	Block, orange
Z = 2	0.36 × 0.27 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer	2591 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.056
Absorption correction: multi-scan (SADABS; Bruker, 2009)	θmax = 26.4°, θmin = 1.7°
Tmin = 0.623, Tmax = 0.745	h = −9→9
14661 measured reflections	k = −30→30
3422 independent reflections	l = −11→11

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.039	H-atom parameters constrained
wR(F^2) = 0.092	w = 1/[σ^2(Fo^2) + (0.0397P)^2 + 0.280P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
3422 reflections	Δρmax = 0.31 e Å^−3
208 parameters	Δρmin = −0.37 e Å^−3

Special details

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

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

	x	y	z	Uiso*/Ueq
Mn1	0.02633 (5)	0.37690 (2)	0.07088 (4)	0.02574 (13)
O1	0.0901 (3)	0.34168 (8)	0.3119 (2)	0.0370 (5)
H1	0.0016	0.3354	0.3569	0.055*
C1	0.2027 (4)	0.29371 (12)	0.3278 (3)	0.0369 (7)
H1A	0.1354	0.2629	0.2764	0.044*
H1B	0.2362	0.2840	0.4300	0.044*
C2	0.3747 (4)	0.30736 (12)	0.2644 (3)	0.0349 (7)
H2A	0.4523	0.3338	0.3260	0.042*
H2B	0.4497	0.2742	0.2570	0.042*
N1	0.3154 (3)	0.33052 (9)	0.1225 (2)	0.0278 (5)
C3	0.4139 (4)	0.32348 (11)	0.0254 (3)	0.0308 (6)
H3	0.5258	0.3030	0.0426	0.037*
C4	0.3498 (4)	0.34801 (11)	−0.1148 (3)	0.0286 (6)
C5	0.4483 (4)	0.34430 (11)	−0.2301 (3)	0.0354 (7)
H5	0.5620	0.3246	−0.2218	0.042*
C6	0.3768 (4)	0.36975 (12)	−0.3555 (3)	0.0397 (8)
H6	0.4425	0.3684	−0.4346	0.048*
C7	0.2093 (4)	0.39743 (12)	−0.3673 (3)	0.0379 (7)
H7	0.1579	0.4149	−0.4540	0.046*
C8	0.1180 (4)	0.39893 (11)	−0.2476 (3)	0.0311 (6)
N2	0.1881 (3)	0.37511 (8)	−0.1243 (2)	0.0266 (5)
C9	−0.0615 (4)	0.42629 (11)	−0.2477 (3)	0.0323 (6)
H9	−0.1260	0.4420	−0.3329	0.039*
N3	−0.1296 (3)	0.42855 (8)	−0.1310 (2)	0.0272 (5)
C10	−0.3057 (4)	0.45724 (11)	−0.1333 (3)	0.0323 (6)
H10A	−0.3876	0.4361	−0.0796	0.039*
H10B	−0.3692	0.4607	−0.2333	0.039*
C11	−0.2742 (4)	0.51322 (11)	−0.0676 (3)	0.0307 (6)
H13A	−0.3951	0.5284	−0.0505	0.037*
H13B	−0.1921	0.5102	0.0259	0.037*
O2	−0.1915 (3)	0.54924 (7)	−0.1577 (2)	0.0316 (4)
H2	−0.2793	0.5570	−0.2233	0.047*
N4	−0.2024 (3)	0.40905 (10)	0.1781 (3)	0.0374 (6)
C12	−0.2848 (4)	0.42616 (11)	0.2635 (3)	0.0301 (6)
S1	−0.40334 (10)	0.45031 (3)	0.38397 (8)	0.0360 (2)
N5	−0.1071 (3)	0.30084 (10)	0.0071 (3)	0.0350 (6)
C13	−0.1442 (3)	0.25552 (12)	0.0161 (3)	0.0277 (6)
S2	−0.20166 (11)	0.19153 (3)	0.02770 (9)	0.0385 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0261 (2)	0.0218 (2)	0.0314 (2)	0.00077 (17)	0.01104 (17)	−0.00003 (17)
O1	0.0409 (12)	0.0350 (11)	0.0381 (12)	0.0067 (9)	0.0157 (9)	0.0086 (9)
C1	0.0451 (18)	0.0306 (16)	0.0350 (17)	0.0005 (14)	0.0063 (14)	0.0076 (13)
C2	0.0343 (16)	0.0313 (16)	0.0378 (17)	0.0080 (13)	0.0015 (13)	0.0032 (13)
N1	0.0248 (12)	0.0226 (12)	0.0365 (13)	0.0002 (9)	0.0068 (10)	−0.0004 (10)
C3	0.0221 (14)	0.0258 (15)	0.0460 (18)	0.0007 (11)	0.0094 (13)	−0.0033 (13)
C4	0.0251 (14)	0.0236 (14)	0.0396 (16)	−0.0035 (11)	0.0130 (12)	−0.0070 (12)
C5	0.0361 (16)	0.0288 (16)	0.0458 (18)	−0.0061 (13)	0.0209 (14)	−0.0111 (14)
C6	0.0432 (18)	0.0410 (18)	0.0402 (18)	−0.0109 (15)	0.0231 (15)	−0.0133 (14)
C7	0.0493 (19)	0.0372 (17)	0.0290 (16)	−0.0106 (15)	0.0115 (14)	−0.0027 (13)
C8	0.0377 (16)	0.0253 (14)	0.0315 (16)	−0.0042 (12)	0.0096 (13)	−0.0047 (12)
N2	0.0307 (12)	0.0226 (12)	0.0287 (12)	−0.0023 (10)	0.0114 (10)	−0.0027 (10)
C9	0.0403 (17)	0.0279 (15)	0.0275 (15)	−0.0039 (13)	0.0012 (13)	0.0006 (12)
N3	0.0285 (12)	0.0186 (11)	0.0338 (13)	−0.0017 (9)	0.0032 (10)	−0.0022 (9)
C10	0.0278 (15)	0.0252 (15)	0.0428 (17)	−0.0022 (12)	0.0019 (13)	−0.0006 (12)
C11	0.0275 (15)	0.0293 (15)	0.0363 (16)	−0.0008 (12)	0.0087 (12)	−0.0006 (12)
O2	0.0356 (11)	0.0248 (10)	0.0348 (11)	−0.0012 (8)	0.0068 (9)	0.0016 (8)
N4	0.0358 (14)	0.0391 (15)	0.0405 (15)	0.0083 (12)	0.0163 (12)	0.0043 (12)
C12	0.0275 (15)	0.0280 (15)	0.0349 (16)	0.0022 (12)	0.0055 (13)	0.0049 (12)
S1	0.0377 (4)	0.0385 (4)	0.0338 (4)	0.0081 (3)	0.0118 (3)	−0.0001 (3)
N5	0.0308 (13)	0.0278 (14)	0.0483 (16)	−0.0025 (11)	0.0121 (11)	−0.0046 (11)
C13	0.0187 (14)	0.0354 (17)	0.0295 (15)	0.0030 (12)	0.0059 (11)	−0.0059 (12)
S2	0.0385 (4)	0.0284 (4)	0.0514 (5)	−0.0039 (3)	0.0155 (4)	0.0007 (3)

Geometric parameters (Å, º)

Mn1—N5	2.154 (2)	C5—C6	1.371 (4)
Mn1—N4	2.224 (2)	C6—C7	1.384 (4)
Mn1—O2^i	2.2633 (18)	C7—C8	1.402 (4)
Mn1—N2	2.341 (2)	C8—N2	1.335 (4)
Mn1—N1	2.374 (2)	C8—C9	1.468 (4)
Mn1—O1	2.4181 (19)	C9—N3	1.281 (3)
Mn1—N3	2.426 (2)	N3—C10	1.459 (3)
O1—C1	1.433 (3)	C10—C11	1.517 (4)
C1—C2	1.507 (4)	C11—O2	1.428 (3)
C2—N1	1.462 (3)	O2—Mn1^i	2.2633 (18)
N1—C3	1.262 (3)	N4—C12	1.158 (3)
C3—C4	1.468 (4)	C12—S1	1.645 (3)
C4—N2	1.342 (3)	N5—C13	1.156 (3)
C4—C5	1.399 (4)	C13—S2	1.640 (3)
N5—Mn1—N4	95.90 (9)	C2—N1—Mn1	120.10 (17)
N5—Mn1—O2^i	172.85 (8)	N1—C3—C4	117.9 (2)
N4—Mn1—O2^i	86.48 (8)	N2—C4—C5	122.0 (3)
N5—Mn1—N2	91.24 (8)	N2—C4—C3	114.6 (2)
N4—Mn1—N2	150.50 (9)	C5—C4—C3	123.4 (3)
O2^i—Mn1—N2	89.95 (7)	C6—C5—C4	118.4 (3)
N5—Mn1—N1	89.04 (8)	C5—C6—C7	120.3 (3)
N4—Mn1—N1	141.03 (9)	C6—C7—C8	118.0 (3)
O2^i—Mn1—N1	84.91 (7)	N2—C8—C7	122.1 (3)
N2—Mn1—N1	67.44 (8)	N2—C8—C9	114.9 (2)
N5—Mn1—O1	87.91 (8)	C7—C8—C9	123.0 (3)
N4—Mn1—O1	75.14 (8)	C8—N2—C4	119.2 (2)
O2^i—Mn1—O1	86.18 (7)	C8—N2—Mn1	120.80 (18)
N2—Mn1—O1	133.85 (7)	C4—N2—Mn1	119.92 (18)
N1—Mn1—O1	66.42 (7)	N3—C9—C8	118.8 (3)
N5—Mn1—N3	95.84 (8)	C9—N3—C10	117.7 (2)
N4—Mn1—N3	83.27 (8)	C9—N3—Mn1	117.50 (19)
O2^i—Mn1—N3	91.13 (7)	C10—N3—Mn1	124.51 (18)
N2—Mn1—N3	67.51 (8)	N3—C10—C11	111.1 (2)
N1—Mn1—N3	134.76 (8)	O2—C11—C10	111.8 (2)
O1—Mn1—N3	158.37 (7)	C11—O2—Mn1^i	122.13 (16)
C1—O1—Mn1	114.71 (16)	C12—N4—Mn1	162.4 (2)
O1—C1—C2	105.6 (2)	N4—C12—S1	179.5 (3)
N1—C2—C1	108.1 (2)	C13—N5—Mn1	157.1 (2)
C3—N1—C2	119.8 (2)	N5—C13—S2	178.7 (3)
C3—N1—Mn1	120.01 (19)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···S2^ii	0.84	2.45	3.270 (2)	167
O2—H2···S1^iii	0.84	2.56	3.359 (2)	159

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

Chlorido{1,1'-[(pyridine-2,6-diyl)bis(nitrilomethanylylidene)]bis(propan-2-ol)}manganese(II) chloride monohydrate (4)

Crystal data

[MnCl(C13H19N3O2)(H2O)]Cl·H2O	F(000) = 852
Mr = 411.18	Dx = 1.440 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.9211 (8) Å	Cell parameters from 5118 reflections
b = 12.0382 (9) Å	θ = 2.2–28.1°
c = 15.3331 (11) Å	µ = 1.00 mm^−1
β = 109.830 (1)°	T = 150 K
V = 1896.3 (2) Å^3	Lath, orange
Z = 4	0.30 × 0.22 × 0.13 mm

Data collection

Bruker APEXII CCD diffractometer	3639 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.028
Absorption correction: multi-scan (SADABS; Bruker, 2009)	θmax = 28.3°, θmin = 2.0°
Tmin = 0.509, Tmax = 0.746	h = −14→14
18855 measured reflections	k = −16→16
4723 independent reflections	l = −20→20

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.042	H-atom parameters constrained
wR(F^2) = 0.118	w = 1/[σ^2(Fo^2) + (0.0585P)^2 + 1.1194P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
4723 reflections	Δρmax = 0.79 e Å^−3
210 parameters	Δρmin = −0.50 e Å^−3

Special details

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

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

	x	y	z	Uiso*/Ueq
Mn1	0.19455 (3)	0.10537 (3)	0.74646 (2)	0.03400 (12)
O1	0.02020 (15)	0.21397 (14)	0.66318 (11)	0.0407 (4)
H1'	0.0345	0.2796	0.6506	0.061*
C1	−0.1773 (3)	0.2337 (3)	0.5294 (2)	0.0587 (8)
H1A	−0.2292	0.2440	0.5699	0.088*
H1B	−0.2303	0.1966	0.4721	0.088*
H1C	−0.1487	0.3062	0.5144	0.088*
C2	−0.0597 (2)	0.1630 (2)	0.57840 (17)	0.0459 (6)
H2	−0.0071	0.1534	0.5368	0.055*
C3	−0.0952 (2)	0.0493 (2)	0.60508 (19)	0.0473 (6)
H3A	−0.1537	0.0569	0.6419	0.057*
H3B	−0.1407	0.0054	0.5488	0.057*
N1	0.02525 (19)	−0.00581 (18)	0.65970 (14)	0.0394 (5)
C4	0.0397 (2)	−0.1104 (2)	0.66098 (18)	0.0420 (6)
H4	−0.0294	−0.1581	0.6271	0.050*
C5	0.1681 (2)	−0.1549 (2)	0.71712 (18)	0.0399 (5)
C6	0.2048 (3)	−0.2653 (2)	0.7180 (2)	0.0471 (6)
H6	0.1447	−0.3195	0.6833	0.057*
C7	0.3302 (3)	−0.2951 (2)	0.7702 (2)	0.0493 (7)
H7	0.3575	−0.3702	0.7710	0.059*
C8	0.4163 (3)	−0.2156 (2)	0.82142 (18)	0.0441 (6)
H8	0.5030	−0.2349	0.8578	0.053*
C9	0.3726 (2)	−0.10657 (19)	0.81817 (17)	0.0376 (5)
N2	0.25101 (19)	−0.07766 (16)	0.76652 (14)	0.0364 (4)
C10	0.4524 (2)	−0.0124 (2)	0.86830 (17)	0.0389 (5)
H10	0.5400	−0.0228	0.9076	0.047*
N3	0.39976 (19)	0.08298 (16)	0.85692 (14)	0.0375 (4)
C11	0.4655 (2)	0.1818 (2)	0.90468 (19)	0.0480 (6)
H11A	0.5593	0.1773	0.9130	0.058*
H11B	0.4571	0.1858	0.9669	0.058*
C12	0.4096 (3)	0.2830 (2)	0.8518 (2)	0.0563 (8)
H12	0.4428	0.2852	0.7985	0.068*
O2	0.27425 (16)	0.27268 (14)	0.81258 (12)	0.0472 (5)
H2'	0.2416	0.3282	0.7797	0.071*
C13	0.4529 (3)	0.3902 (2)	0.9037 (2)	0.0532 (7)
H13A	0.4153	0.4530	0.8626	0.080*
H13B	0.5480	0.3951	0.9249	0.080*
H13C	0.4234	0.3924	0.9573	0.080*
Cl1	0.29005 (6)	0.11186 (5)	0.61894 (4)	0.04378 (16)
Cl2	0.13489 (7)	0.45169 (5)	0.67050 (5)	0.04720 (17)
O3	0.10792 (18)	0.10270 (15)	0.85605 (13)	0.0477 (4)
H3C	0.1471	0.1189	0.9142	0.072*
H3D	0.0507	0.0518	0.8545	0.072*
O4	0.25378 (19)	0.14900 (19)	1.03228 (13)	0.0581 (5)
H4B	0.2301	0.1159	1.0745	0.087*
H4A	0.1933	0.1996	1.0172	0.087*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.02767 (18)	0.02776 (18)	0.0371 (2)	−0.00212 (13)	−0.00129 (14)	−0.00330 (14)
O1	0.0332 (8)	0.0391 (9)	0.0394 (9)	0.0004 (7)	−0.0012 (7)	−0.0006 (7)
C1	0.0362 (14)	0.082 (2)	0.0480 (15)	0.0099 (14)	0.0015 (12)	0.0016 (15)
C2	0.0296 (11)	0.0612 (17)	0.0365 (12)	0.0011 (11)	−0.0023 (10)	−0.0064 (12)
C3	0.0298 (12)	0.0554 (16)	0.0473 (14)	−0.0061 (11)	0.0007 (10)	−0.0125 (12)
N1	0.0302 (10)	0.0410 (11)	0.0422 (11)	−0.0085 (8)	0.0061 (8)	−0.0093 (9)
C4	0.0388 (13)	0.0396 (13)	0.0468 (14)	−0.0154 (10)	0.0134 (11)	−0.0128 (11)
C5	0.0460 (13)	0.0307 (11)	0.0455 (13)	−0.0102 (10)	0.0190 (11)	−0.0052 (10)
C6	0.0621 (17)	0.0289 (12)	0.0562 (15)	−0.0111 (11)	0.0275 (14)	−0.0058 (11)
C7	0.0712 (19)	0.0277 (12)	0.0594 (16)	0.0033 (12)	0.0358 (15)	0.0032 (11)
C8	0.0498 (14)	0.0355 (13)	0.0500 (14)	0.0059 (11)	0.0211 (12)	0.0081 (11)
C9	0.0398 (12)	0.0304 (11)	0.0427 (13)	0.0022 (9)	0.0140 (10)	0.0058 (9)
N2	0.0353 (10)	0.0287 (9)	0.0425 (11)	−0.0038 (8)	0.0098 (8)	−0.0010 (8)
C10	0.0304 (11)	0.0377 (12)	0.0429 (13)	0.0019 (9)	0.0051 (10)	0.0060 (10)
N3	0.0312 (10)	0.0315 (10)	0.0401 (10)	−0.0015 (8)	−0.0004 (8)	0.0012 (8)
C11	0.0380 (13)	0.0387 (13)	0.0491 (14)	−0.0048 (11)	−0.0092 (11)	−0.0029 (11)
C12	0.0342 (13)	0.0373 (14)	0.080 (2)	−0.0037 (11)	−0.0032 (13)	−0.0063 (13)
O2	0.0394 (9)	0.0306 (9)	0.0525 (11)	−0.0025 (7)	−0.0092 (8)	−0.0001 (7)
C13	0.0441 (15)	0.0351 (13)	0.0669 (18)	−0.0096 (11)	0.0011 (13)	−0.0074 (12)
Cl1	0.0351 (3)	0.0460 (3)	0.0470 (3)	−0.0066 (2)	0.0097 (3)	−0.0041 (3)
Cl2	0.0519 (4)	0.0320 (3)	0.0519 (4)	0.0073 (3)	0.0101 (3)	0.0017 (3)
O3	0.0398 (9)	0.0542 (11)	0.0422 (10)	−0.0120 (8)	0.0051 (8)	−0.0070 (8)
O4	0.0504 (11)	0.0705 (14)	0.0507 (11)	−0.0129 (10)	0.0134 (9)	−0.0104 (10)

Geometric parameters (Å, º)

Mn1—O3	2.1905 (19)	C5—N2	1.339 (3)
Mn1—N2	2.281 (2)	C5—C6	1.388 (4)
Mn1—O2	2.2897 (17)	C6—C7	1.378 (4)
Mn1—N1	2.3046 (19)	C7—C8	1.385 (4)
Mn1—O1	2.3056 (16)	C8—C9	1.391 (3)
Mn1—N3	2.3213 (19)	C9—N2	1.341 (3)
Mn1—Cl1	2.5101 (8)	C9—C10	1.477 (3)
O1—C2	1.435 (3)	C10—N3	1.269 (3)
C1—C2	1.511 (4)	N3—C11	1.453 (3)
C2—C3	1.516 (4)	C11—C12	1.476 (4)
C3—N1	1.458 (3)	C12—O2	1.400 (3)
N1—C4	1.268 (3)	C12—C13	1.506 (4)
C4—C5	1.475 (4)
O3—Mn1—N2	92.85 (7)	C4—N1—C3	123.0 (2)
O3—Mn1—O2	82.62 (7)	C4—N1—Mn1	119.77 (17)
N2—Mn1—O2	138.19 (7)	C3—N1—Mn1	117.27 (16)
O3—Mn1—N1	87.91 (7)	N1—C4—C5	117.3 (2)
N2—Mn1—N1	69.15 (7)	N2—C5—C6	121.4 (3)
O2—Mn1—N1	151.21 (7)	N2—C5—C4	113.9 (2)
O3—Mn1—O1	86.72 (7)	C6—C5—C4	124.7 (2)
N2—Mn1—O1	139.22 (7)	C7—C6—C5	118.8 (2)
O2—Mn1—O1	82.24 (6)	C6—C7—C8	119.9 (2)
N1—Mn1—O1	70.09 (7)	C7—C8—C9	118.2 (3)
O3—Mn1—N3	89.99 (7)	N2—C9—C8	121.7 (2)
N2—Mn1—N3	68.87 (7)	N2—C9—C10	113.5 (2)
O2—Mn1—N3	69.59 (6)	C8—C9—C10	124.8 (2)
N1—Mn1—N3	137.79 (7)	C5—N2—C9	119.9 (2)
O1—Mn1—N3	151.82 (7)	C5—N2—Mn1	119.63 (17)
O3—Mn1—Cl1	178.66 (5)	C9—N2—Mn1	119.91 (15)
N2—Mn1—Cl1	88.30 (6)	N3—C10—C9	117.6 (2)
O2—Mn1—Cl1	96.98 (5)	C10—N3—C11	123.2 (2)
N1—Mn1—Cl1	91.86 (6)	C10—N3—Mn1	119.05 (16)
O1—Mn1—Cl1	91.96 (5)	C11—N3—Mn1	117.54 (15)
N3—Mn1—Cl1	91.07 (6)	N3—C11—C12	110.94 (19)
C2—O1—Mn1	113.17 (14)	O2—C12—C11	110.0 (2)
O1—C2—C1	111.3 (2)	O2—C12—C13	113.5 (2)
O1—C2—C3	105.9 (2)	C11—C12—C13	114.8 (2)
C1—C2—C3	113.0 (2)	C12—O2—Mn1	117.12 (16)
N1—C3—C2	107.58 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4B···Cl2^i	0.87	2.23	3.084 (2)	169
O3—H3D···Cl2^ii	0.87	2.28	3.1257 (19)	165
O4—H4A···Cl1^i	0.87	2.75	3.139 (2)	108
C10—H10···O4^iii	0.95	2.61	3.465 (3)	150
O1—H1′···Cl2	0.84	2.32	3.1105 (19)	158
O2—H2′···Cl2	0.84	2.25	3.0752 (18)	169
O3—H3C···O4	0.87	1.83	2.689 (3)	171

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

aquadichlorido{2,2'-dimethyl-2,2'-[(pyridine-2,6-diyl)bis(nitrilomethanylylidene)]bis(propan-1-ol)}manganese(II) 0.3-hydrate (6)

Crystal data

[MnCl2(C15H23N3O2)(H2O)]·0.3H2O	F(000) = 888
Mr = 426.62	Dx = 1.450 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.4544 (6) Å	Cell parameters from 7733 reflections
b = 8.6208 (4) Å	θ = 2.5–28.9°
c = 16.9691 (7) Å	µ = 0.97 mm^−1
β = 112.426 (1)°	T = 150 K
V = 1954.58 (15) Å^3	Trigonal, yellow
Z = 4	0.31 × 0.25 × 0.24 mm

Data collection

Bruker APEXII CCD diffractometer	5164 independent reflections
Radiation source: fine-focus sealed tube	4487 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
ω rotation with narrow frames scans	θmax = 28.9°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −19→19
Tmin = 0.653, Tmax = 0.746	k = −11→11
20073 measured reflections	l = −23→23

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)] = 0.029	Hydrogen site location: mixed
wR(F^2) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0361P)^2 + 0.8413P] where P = (Fo^2 + 2Fc^2)/3
5164 reflections	(Δ/σ)max = 0.001
249 parameters	Δρmax = 0.49 e Å^−3
6 restraints	Δρmin = −0.45 e Å^−3

Special details

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

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Mn1	0.29062 (2)	0.64380 (2)	0.36981 (2)	0.01581 (6)
N1	0.36598 (9)	0.80218 (14)	0.29540 (8)	0.0169 (2)
N2	0.21753 (9)	0.59382 (14)	0.23256 (7)	0.0166 (2)
N3	0.16139 (9)	0.45566 (14)	0.34874 (8)	0.0179 (2)
Cl1	0.16715 (3)	0.85961 (4)	0.35996 (2)	0.02476 (9)
Cl2	0.38919 (3)	0.66426 (4)	0.52141 (2)	0.02183 (8)
O2	0.03633 (10)	0.62641 (15)	0.41362 (10)	0.0369 (3)
H2	0.0627 (19)	0.683 (3)	0.3894 (16)	0.055*
C2	0.44489 (11)	0.92131 (17)	0.33305 (9)	0.0205 (3)	0.75
C1	0.4059 (2)	1.0275 (3)	0.3876 (2)	0.0219 (5)	0.75
H1A	0.386627	0.962404	0.426928	0.026*	0.75
H1B	0.460607	1.097251	0.422565	0.026*	0.75
O1	0.32182 (13)	1.1191 (2)	0.33664 (11)	0.0327 (4)*	0.75
H1C	0.273 (2)	1.070 (4)	0.3403 (19)	0.049*	0.75
C2'	0.44489 (11)	0.92131 (17)	0.33305 (9)	0.0205 (3)	0.25
C1'	0.4037 (9)	1.0514 (11)	0.3676 (6)	0.026 (3)*	0.25
H1'A	0.362271	1.007065	0.397023	0.031*	0.25
H1'B	0.460160	1.107285	0.410864	0.031*	0.25
O1'	0.3451 (4)	1.1595 (5)	0.3063 (3)	0.0297 (10)*	0.25
H1'C	0.288416	1.116028	0.286890	0.045*	0.25
C3	0.47353 (17)	1.0119 (3)	0.26930 (12)	0.0464 (5)
H3A	0.525704	1.087393	0.299577	0.070*
H3B	0.498785	0.940443	0.237243	0.070*
H3C	0.414628	1.066575	0.229822	0.070*
C4	0.53581 (13)	0.8372 (2)	0.39624 (12)	0.0322 (4)
H4A	0.589972	0.911826	0.422708	0.048*
H4B	0.517687	0.788002	0.440419	0.048*
H4C	0.558179	0.757685	0.366167	0.048*
C5	0.32945 (11)	0.78059 (16)	0.21517 (9)	0.0183 (3)
H5	0.352821	0.840116	0.179394	0.022*
C6	0.25067 (10)	0.66285 (15)	0.17782 (9)	0.0168 (3)
C7	0.21356 (11)	0.62538 (17)	0.09154 (9)	0.0201 (3)
H7	0.238587	0.674746	0.053669	0.024*
C8	0.13893 (11)	0.51384 (17)	0.06242 (9)	0.0217 (3)
H8	0.111283	0.486932	0.003699	0.026*
C9	0.10488 (11)	0.44185 (17)	0.11924 (9)	0.0221 (3)
H9	0.054280	0.364583	0.100347	0.027*
C10	0.14649 (10)	0.48533 (16)	0.20466 (9)	0.0182 (3)
C11	0.11605 (11)	0.41648 (17)	0.27111 (9)	0.0209 (3)
H11	0.062901	0.343383	0.255835	0.025*
C12	0.13193 (11)	0.38812 (17)	0.41615 (9)	0.0204 (3)
C13	0.03987 (12)	0.2834 (2)	0.38356 (11)	0.0308 (4)
H13A	−0.016285	0.340163	0.341913	0.046*
H13B	0.022229	0.251232	0.431456	0.046*
H13C	0.054566	0.191439	0.356389	0.046*
C14	0.22302 (12)	0.3001 (2)	0.47681 (11)	0.0274 (3)
H14A	0.233413	0.206344	0.448537	0.041*
H14B	0.211681	0.270895	0.528227	0.041*
H14C	0.282388	0.366455	0.492572	0.041*
C15	0.11365 (12)	0.52586 (19)	0.46560 (10)	0.0269 (3)
H15A	0.095680	0.486025	0.512622	0.032*
H15B	0.176439	0.585943	0.491267	0.032*
O3	0.38394 (9)	0.43908 (14)	0.36572 (8)	0.0278 (2)
H3D	0.3611 (17)	0.353 (3)	0.3506 (15)	0.042*
H3E	0.4422 (18)	0.429 (3)	0.3975 (14)	0.042*
O4	0.1621 (3)	1.0443 (6)	0.2059 (3)	0.0395 (11)	0.3
H4D	0.110 (3)	1.078 (9)	0.171 (4)	0.059*	0.3
H4E	0.156 (5)	1.006 (9)	0.247 (3)	0.059*	0.3

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.01677 (11)	0.01679 (11)	0.01403 (11)	−0.00103 (8)	0.00606 (8)	−0.00120 (8)
N1	0.0174 (5)	0.0157 (5)	0.0194 (6)	−0.0015 (4)	0.0088 (5)	−0.0019 (4)
N2	0.0173 (5)	0.0167 (5)	0.0159 (5)	−0.0017 (4)	0.0065 (4)	−0.0015 (4)
N3	0.0172 (5)	0.0179 (6)	0.0195 (6)	−0.0002 (4)	0.0082 (5)	0.0015 (5)
Cl1	0.02438 (18)	0.02311 (18)	0.02712 (19)	0.00536 (13)	0.01020 (14)	−0.00029 (14)
Cl2	0.01981 (16)	0.02832 (18)	0.01591 (16)	0.00068 (13)	0.00520 (12)	−0.00165 (13)
O2	0.0330 (7)	0.0328 (7)	0.0543 (8)	0.0097 (5)	0.0272 (6)	0.0108 (6)
C2	0.0209 (7)	0.0211 (7)	0.0204 (7)	−0.0067 (6)	0.0089 (6)	−0.0048 (5)
C1	0.0250 (12)	0.0184 (11)	0.0219 (14)	−0.0041 (9)	0.0085 (11)	−0.0057 (11)
C2'	0.0209 (7)	0.0211 (7)	0.0204 (7)	−0.0067 (6)	0.0089 (6)	−0.0048 (5)
C3	0.0540 (12)	0.0554 (13)	0.0307 (9)	−0.0363 (10)	0.0170 (9)	−0.0038 (9)
C4	0.0232 (8)	0.0331 (9)	0.0344 (9)	−0.0019 (7)	0.0043 (7)	−0.0080 (7)
C5	0.0207 (7)	0.0173 (6)	0.0191 (7)	−0.0017 (5)	0.0099 (5)	−0.0009 (5)
C6	0.0184 (6)	0.0161 (6)	0.0161 (6)	0.0008 (5)	0.0068 (5)	0.0000 (5)
C7	0.0232 (7)	0.0203 (7)	0.0170 (7)	0.0020 (5)	0.0079 (5)	0.0004 (5)
C8	0.0256 (7)	0.0221 (7)	0.0149 (6)	0.0002 (6)	0.0050 (6)	−0.0033 (5)
C9	0.0220 (7)	0.0214 (7)	0.0206 (7)	−0.0035 (6)	0.0054 (6)	−0.0038 (6)
C10	0.0174 (6)	0.0177 (6)	0.0187 (7)	−0.0011 (5)	0.0059 (5)	−0.0006 (5)
C11	0.0198 (7)	0.0197 (7)	0.0231 (7)	−0.0051 (5)	0.0081 (6)	−0.0014 (6)
C12	0.0197 (7)	0.0211 (7)	0.0217 (7)	−0.0026 (5)	0.0095 (6)	0.0027 (6)
C13	0.0276 (8)	0.0338 (9)	0.0301 (9)	−0.0104 (7)	0.0101 (7)	0.0053 (7)
C14	0.0264 (8)	0.0261 (8)	0.0289 (8)	0.0004 (6)	0.0094 (6)	0.0086 (6)
C15	0.0300 (8)	0.0284 (8)	0.0280 (8)	0.0013 (6)	0.0176 (7)	0.0025 (6)
O3	0.0227 (6)	0.0272 (6)	0.0295 (6)	0.0065 (5)	0.0054 (5)	−0.0030 (5)
O4	0.028 (2)	0.048 (3)	0.031 (2)	−0.0131 (19)	−0.0024 (17)	0.020 (2)

Geometric parameters (Å, º)

Mn1—N2	2.2021 (11)	C2—C1	1.553 (3)
Mn1—O3	2.2384 (12)	C1—O1	1.431 (3)
Mn1—N1	2.3863 (12)	C2'—C1'	1.491 (10)
Mn1—N3	2.3954 (12)	C2'—C3	1.514 (2)
Mn1—Cl2	2.4254 (4)	C2'—C4	1.526 (2)
Mn1—Cl1	2.5391 (4)	C1'—O1'	1.413 (9)
N1—C5	1.2722 (18)	C5—C6	1.4758 (19)
N1—C2'	1.4859 (18)	C6—C7	1.3916 (19)
N1—C2	1.4859 (18)	C7—C8	1.388 (2)
N2—C10	1.3351 (18)	C8—C9	1.385 (2)
N2—C6	1.3363 (18)	C9—C10	1.392 (2)
N3—C11	1.2729 (19)	C10—C11	1.482 (2)
N3—C12	1.4835 (18)	C12—C13	1.527 (2)
O2—C15	1.424 (2)	C12—C14	1.528 (2)
C2—C3	1.514 (2)	C12—C15	1.534 (2)
C2—C4	1.526 (2)
N2—Mn1—O3	82.21 (4)	N1—C2—C1	105.69 (14)
N2—Mn1—N1	71.58 (4)	C3—C2—C1	112.46 (18)
O3—Mn1—N1	91.87 (4)	C4—C2—C1	105.80 (17)
N2—Mn1—N3	71.18 (4)	O1—C1—C2	112.5 (2)
O3—Mn1—N3	84.63 (5)	N1—C2'—C1'	109.4 (5)
N1—Mn1—N3	142.73 (4)	N1—C2'—C3	115.06 (13)
N2—Mn1—Cl2	170.67 (3)	C1'—C2'—C3	98.8 (4)
O3—Mn1—Cl2	88.46 (3)	N1—C2'—C4	106.72 (12)
N1—Mn1—Cl2	108.52 (3)	C1'—C2'—C4	116.6 (4)
N3—Mn1—Cl2	108.46 (3)	C3—C2'—C4	110.51 (15)
N2—Mn1—Cl1	91.84 (3)	O1'—C1'—C2'	115.1 (7)
O3—Mn1—Cl1	172.95 (4)	N1—C5—C6	119.83 (13)
N1—Mn1—Cl1	89.84 (3)	N2—C6—C7	122.10 (13)
N3—Mn1—Cl1	89.88 (3)	N2—C6—C5	115.49 (12)
Cl2—Mn1—Cl1	97.486 (14)	C7—C6—C5	122.42 (13)
C5—N1—C2'	119.89 (12)	C8—C7—C6	118.09 (13)
C5—N1—C2	119.89 (12)	C9—C8—C7	119.79 (13)
C5—N1—Mn1	113.31 (9)	C8—C9—C10	118.49 (13)
C2'—N1—Mn1	126.76 (9)	N2—C10—C9	121.75 (13)
C2—N1—Mn1	126.76 (9)	N2—C10—C11	114.98 (12)
C10—N2—C6	119.78 (12)	C9—C10—C11	123.28 (13)
C10—N2—Mn1	120.39 (9)	N3—C11—C10	119.74 (13)
C6—N2—Mn1	119.57 (9)	N3—C12—C13	114.82 (12)
C11—N3—C12	120.53 (12)	N3—C12—C14	106.70 (12)
C11—N3—Mn1	113.49 (9)	C13—C12—C14	110.98 (13)
C12—N3—Mn1	125.98 (9)	N3—C12—C15	106.14 (12)
N1—C2—C3	115.06 (13)	C13—C12—C15	110.35 (13)
N1—C2—C4	106.72 (12)	C14—C12—C15	107.46 (13)
C3—C2—C4	110.51 (15)	O2—C15—C12	113.00 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1^a—H1^Ba···Cl2^i	0.99	2.88	3.837 (3)	164
O1^a—H1^Ca···Cl1	0.85 (3)	2.47 (3)	3.291 (2)	162 (3)
O2—H2···Cl1	0.82 (3)	2.33 (3)	3.1241 (14)	164 (2)
C1′^b—H1^′Ab···Cl1	0.99	2.93	3.755 (12)	141
C1′^b—H1^′Bb···Cl2^i	0.99	2.83	3.771 (12)	158
O1′^b—H1^′Cb···O4	0.84	1.92	2.729 (6)	160
O3—H3D···O1^aii	0.82 (2)	2.08 (2)	2.885 (2)	168 (2)
O3—H3^D^···O1^′b^ii	0.82 (2)	1.80 (2)	2.590 (5)	161 (2)
O3—H3E···Cl2^iii	0.81 (2)	2.43 (2)	3.2286 (12)	166 (2)
O4—H4D···O2^iv	0.81 (2)	2.10 (3)	2.899 (4)	169 (8)
O4—H4E···Cl1	0.80 (2)	2.25 (2)	3.038 (4)	166 (7)

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

(Dimethylformamide){2,2'-dimethyl-2,2'-[(pyridine-2,6-diyl)bis(nitrilomethanylylidene)]bis(propan-1-ol)}dithiocyanatomanganese(II) (7)

Crystal data

[Mn(NCS)2(C15H23N3O2)]·C3H7NO	F(000) = 1092
Mr = 521.56	Dx = 1.383 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.5916 (4) Å	Cell parameters from 6505 reflections
b = 8.2974 (4) Å	θ = 2.4–26.3°
c = 35.1501 (18) Å	µ = 0.73 mm^−1
β = 91.731 (1)°	T = 150 K
V = 2504.6 (2) Å^3	Block, yellow
Z = 4	0.41 × 0.11 × 0.07 mm

Data collection

Bruker APEXII CCD diffractometer	4270 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.031
Absorption correction: multi-scan (SADABS; Bruker, 2009)	θmax = 26.4°, θmin = 1.2°
Tmin = 0.509, Tmax = 0.746	h = −10→10
21498 measured reflections	k = −10→10
5140 independent reflections	l = −43→43

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.030	H-atom parameters constrained
wR(F^2) = 0.088	w = 1/[σ^2(Fo^2) + (0.0462P)^2 + 0.6263P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max = 0.006
5140 reflections	Δρmax = 0.36 e Å^−3
295 parameters	Δρmin = −0.45 e Å^−3

Special details

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

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

	x	y	z	Uiso*/Ueq
Mn1	0.52970 (3)	0.19081 (3)	0.11620 (2)	0.01850 (9)
O1	0.31572 (17)	0.17639 (17)	0.15275 (4)	0.0323 (3)
H1	0.2958	0.2383	0.1709	0.048*
C1	0.2689 (2)	0.0151 (2)	0.16086 (5)	0.0267 (4)
H1A	0.1709	0.0159	0.1750	0.032*
H1B	0.3501	−0.0394	0.1768	0.032*
C2	0.2447 (2)	−0.0747 (2)	0.12298 (5)	0.0210 (4)
C3	0.1031 (2)	−0.0060 (2)	0.10099 (6)	0.0277 (4)
H3A	0.1213	0.1080	0.0953	0.041*
H3B	0.0106	−0.0163	0.1164	0.041*
H3C	0.0870	−0.0656	0.0771	0.041*
C4	0.2255 (2)	−0.2534 (2)	0.13122 (6)	0.0278 (4)
H4A	0.2013	−0.3109	0.1074	0.042*
H4B	0.1405	−0.2686	0.1488	0.042*
H4C	0.3224	−0.2958	0.1427	0.042*
N1	0.38329 (17)	−0.03787 (18)	0.10076 (4)	0.0194 (3)
C5	0.4263 (2)	−0.1262 (2)	0.07351 (5)	0.0202 (4)
H5	0.3732	−0.2235	0.0673	0.024*
C6	0.5622 (2)	−0.0722 (2)	0.05172 (5)	0.0193 (4)
C7	0.6162 (2)	−0.1522 (2)	0.01997 (5)	0.0226 (4)
H7	0.5698	−0.2501	0.0114	0.027*
C8	0.7403 (2)	−0.0844 (2)	0.00114 (5)	0.0248 (4)
H8	0.7804	−0.1364	−0.0206	0.030*
C9	0.8054 (2)	0.0592 (2)	0.01409 (5)	0.0235 (4)
H9	0.8882	0.1083	0.0010	0.028*
C10	0.7467 (2)	0.1300 (2)	0.04663 (5)	0.0201 (4)
N2	0.62709 (17)	0.06449 (18)	0.06469 (4)	0.0194 (3)
C11	0.8071 (2)	0.2809 (2)	0.06400 (5)	0.0209 (4)
H11	0.8896	0.3393	0.0530	0.025*
N3	0.74442 (17)	0.32922 (18)	0.09416 (4)	0.0198 (3)
C12	0.7961 (2)	0.4758 (2)	0.11478 (5)	0.0219 (4)
C13	0.9227 (2)	0.4229 (2)	0.14388 (6)	0.0271 (4)
H13A	0.8857	0.3297	0.1582	0.041*
H13B	0.9460	0.5118	0.1615	0.041*
H13C	1.0171	0.3934	0.1306	0.041*
C14	0.8520 (2)	0.6095 (2)	0.08892 (6)	0.0294 (4)
H14A	0.9520	0.5788	0.0784	0.044*
H14B	0.8648	0.7092	0.1036	0.044*
H14C	0.7752	0.6266	0.0681	0.044*
C15	0.6520 (2)	0.5365 (2)	0.13485 (6)	0.0251 (4)
H15A	0.6815	0.6243	0.1527	0.030*
H15B	0.5753	0.5795	0.1159	0.030*
O2	0.58495 (15)	0.40528 (15)	0.15524 (4)	0.0247 (3)
H2	0.5109	0.4338	0.1688	0.037*
N4	0.6653 (2)	0.0372 (2)	0.15643 (5)	0.0300 (4)
C16	0.7516 (2)	−0.0394 (2)	0.17439 (5)	0.0237 (4)
S1	0.87401 (6)	−0.14844 (7)	0.20021 (2)	0.03127 (13)
N5	0.3880 (2)	0.3497 (2)	0.07900 (5)	0.0296 (4)
C17	0.3128 (2)	0.4203 (2)	0.05670 (5)	0.0220 (4)
S2	0.20409 (7)	0.51625 (7)	0.02506 (2)	0.03647 (15)
O3	0.32769 (16)	0.43950 (17)	0.19804 (4)	0.0300 (3)
C18	0.2566 (2)	0.5365 (2)	0.21790 (5)	0.0255 (4)
H18	0.1477	0.5209	0.2201	0.031*
N6	0.32046 (19)	0.6601 (2)	0.23625 (4)	0.0258 (4)
C19	0.4865 (3)	0.6903 (3)	0.23594 (7)	0.0408 (6)
H19A	0.5392	0.5971	0.2250	0.061*
H19B	0.5261	0.7081	0.2620	0.061*
H19C	0.5065	0.7861	0.2205	0.061*
C20	0.2261 (3)	0.7694 (3)	0.25868 (6)	0.0339 (5)
H20C	0.1190	0.7289	0.2592	0.051*
H20B	0.2264	0.8769	0.2472	0.051*
H20A	0.2696	0.7754	0.2847	0.051*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.02080 (15)	0.01883 (15)	0.01586 (15)	−0.00245 (11)	0.00077 (10)	−0.00177 (11)
O1	0.0395 (8)	0.0288 (8)	0.0293 (8)	−0.0119 (6)	0.0144 (6)	−0.0127 (6)
C1	0.0292 (10)	0.0302 (11)	0.0210 (10)	−0.0097 (8)	0.0050 (8)	−0.0021 (8)
C2	0.0220 (9)	0.0211 (9)	0.0199 (9)	−0.0045 (7)	0.0022 (7)	−0.0012 (7)
C3	0.0233 (10)	0.0315 (11)	0.0282 (10)	−0.0011 (8)	0.0010 (8)	0.0011 (9)
C4	0.0282 (10)	0.0247 (10)	0.0308 (11)	−0.0056 (8)	0.0058 (8)	0.0025 (8)
N1	0.0211 (8)	0.0213 (8)	0.0156 (7)	−0.0017 (6)	−0.0006 (6)	0.0019 (6)
C5	0.0241 (9)	0.0178 (9)	0.0186 (9)	−0.0019 (7)	−0.0012 (7)	−0.0007 (7)
C6	0.0225 (9)	0.0175 (9)	0.0178 (9)	0.0022 (7)	−0.0017 (7)	0.0016 (7)
C7	0.0280 (10)	0.0198 (9)	0.0200 (9)	0.0025 (8)	−0.0016 (8)	−0.0031 (7)
C8	0.0291 (10)	0.0279 (10)	0.0176 (9)	0.0056 (8)	0.0033 (8)	−0.0038 (8)
C9	0.0235 (9)	0.0260 (10)	0.0210 (9)	0.0021 (8)	0.0028 (7)	0.0021 (8)
C10	0.0194 (9)	0.0230 (9)	0.0177 (9)	0.0023 (7)	−0.0003 (7)	0.0009 (7)
N2	0.0213 (8)	0.0197 (8)	0.0172 (7)	0.0005 (6)	−0.0003 (6)	−0.0004 (6)
C11	0.0201 (9)	0.0217 (9)	0.0209 (9)	−0.0015 (7)	0.0008 (7)	0.0031 (7)
N3	0.0208 (8)	0.0195 (8)	0.0190 (8)	−0.0015 (6)	−0.0024 (6)	0.0005 (6)
C12	0.0240 (9)	0.0198 (9)	0.0217 (9)	−0.0045 (7)	−0.0013 (7)	−0.0022 (7)
C13	0.0261 (10)	0.0286 (11)	0.0262 (10)	−0.0043 (8)	−0.0053 (8)	−0.0016 (8)
C14	0.0326 (11)	0.0259 (10)	0.0295 (11)	−0.0083 (9)	−0.0006 (9)	0.0013 (9)
C15	0.0280 (10)	0.0206 (10)	0.0267 (10)	−0.0038 (8)	0.0002 (8)	−0.0023 (8)
O2	0.0265 (7)	0.0249 (7)	0.0231 (7)	−0.0031 (6)	0.0055 (5)	−0.0039 (6)
N4	0.0344 (9)	0.0293 (9)	0.0260 (9)	−0.0037 (8)	−0.0050 (8)	0.0015 (7)
C16	0.0274 (10)	0.0237 (10)	0.0201 (9)	−0.0055 (8)	0.0035 (8)	−0.0043 (8)
S1	0.0298 (3)	0.0360 (3)	0.0277 (3)	0.0069 (2)	−0.0033 (2)	−0.0006 (2)
N5	0.0307 (9)	0.0286 (9)	0.0293 (9)	0.0013 (7)	−0.0043 (7)	−0.0006 (7)
C17	0.0258 (9)	0.0197 (9)	0.0204 (9)	−0.0025 (8)	0.0018 (8)	−0.0055 (8)
S2	0.0513 (3)	0.0315 (3)	0.0260 (3)	0.0125 (3)	−0.0100 (2)	−0.0012 (2)
O3	0.0369 (8)	0.0277 (7)	0.0257 (7)	−0.0014 (6)	0.0084 (6)	−0.0059 (6)
C18	0.0296 (10)	0.0290 (10)	0.0179 (9)	−0.0002 (8)	0.0017 (8)	0.0019 (8)
N6	0.0311 (9)	0.0265 (9)	0.0198 (8)	0.0020 (7)	0.0008 (7)	−0.0034 (7)
C19	0.0338 (12)	0.0406 (13)	0.0478 (14)	−0.0036 (10)	−0.0035 (10)	−0.0091 (11)
C20	0.0459 (13)	0.0332 (12)	0.0225 (10)	0.0090 (10)	0.0009 (9)	−0.0056 (9)

Geometric parameters (Å, º)

Mn1—N5	2.1987 (17)	C9—C10	1.394 (3)
Mn1—N4	2.2094 (17)	C10—N2	1.339 (2)
Mn1—N2	2.2734 (15)	C10—C11	1.481 (3)
Mn1—O1	2.2776 (14)	C11—N3	1.269 (2)
Mn1—O2	2.2883 (13)	N3—C12	1.477 (2)
Mn1—N3	2.3256 (15)	C12—C14	1.522 (3)
Mn1—N1	2.3315 (15)	C12—C15	1.528 (3)
O1—C1	1.429 (2)	C12—C13	1.534 (3)
C1—C2	1.534 (3)	C15—O2	1.434 (2)
C2—N1	1.476 (2)	N4—C16	1.151 (3)
C2—C4	1.521 (3)	C16—S1	1.640 (2)
C2—C3	1.531 (3)	N5—C17	1.159 (2)
N1—C5	1.270 (2)	C17—S2	1.637 (2)
C5—C6	1.485 (3)	O3—C18	1.239 (2)
C6—N2	1.338 (2)	C18—N6	1.322 (3)
C6—C7	1.390 (3)	N6—C19	1.449 (3)
C7—C8	1.390 (3)	N6—C20	1.463 (3)
C8—C9	1.387 (3)
N5—Mn1—N4	176.70 (7)	N2—C6—C7	122.17 (17)
N5—Mn1—N2	90.76 (6)	N2—C6—C5	113.95 (15)
N4—Mn1—N2	92.53 (6)	C7—C6—C5	123.85 (17)
N5—Mn1—O1	85.71 (6)	C8—C7—C6	117.95 (17)
N4—Mn1—O1	91.59 (6)	C9—C8—C7	119.89 (17)
N2—Mn1—O1	138.40 (5)	C8—C9—C10	118.62 (17)
N5—Mn1—O2	89.50 (6)	N2—C10—C9	121.32 (17)
N4—Mn1—O2	88.23 (6)	N2—C10—C11	114.35 (15)
N2—Mn1—O2	139.60 (5)	C9—C10—C11	124.33 (17)
O1—Mn1—O2	81.89 (5)	C6—N2—C10	120.01 (15)
N5—Mn1—N3	86.34 (6)	C6—N2—Mn1	120.18 (12)
N4—Mn1—N3	95.15 (6)	C10—N2—Mn1	119.78 (12)
N2—Mn1—N3	69.37 (5)	N3—C11—C10	117.34 (16)
O1—Mn1—N3	151.13 (5)	C11—N3—C12	122.76 (16)
O2—Mn1—N3	70.33 (5)	C11—N3—Mn1	118.92 (12)
N5—Mn1—N1	93.70 (6)	C12—N3—Mn1	118.22 (11)
N4—Mn1—N1	87.12 (6)	N3—C12—C14	113.76 (15)
N2—Mn1—N1	69.41 (5)	N3—C12—C15	105.21 (14)
O1—Mn1—N1	69.48 (5)	C14—C12—C15	108.05 (16)
O2—Mn1—N1	150.83 (5)	N3—C12—C13	106.75 (15)
N3—Mn1—N1	138.78 (5)	C14—C12—C13	112.13 (16)
C1—O1—Mn1	113.50 (11)	C15—C12—C13	110.74 (16)
O1—C1—C2	108.26 (15)	O2—C15—C12	108.88 (15)
N1—C2—C4	113.37 (15)	C15—O2—Mn1	111.71 (10)
N1—C2—C3	107.27 (15)	C16—N4—Mn1	171.26 (16)
C4—C2—C3	111.73 (16)	N4—C16—S1	179.69 (19)
N1—C2—C1	105.57 (14)	C17—N5—Mn1	172.85 (16)
C4—C2—C1	108.73 (16)	N5—C17—S2	178.69 (18)
C3—C2—C1	109.99 (16)	O3—C18—N6	125.08 (19)
C5—N1—C2	122.52 (15)	C18—N6—C19	121.65 (17)
C5—N1—Mn1	118.56 (12)	C18—N6—C20	121.00 (17)
C2—N1—Mn1	118.92 (11)	C19—N6—C20	117.32 (17)
N1—C5—C6	117.79 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3	0.84	1.94	2.7021 (19)	151
O2—H2···O3	0.84	1.91	2.7258 (19)	165

(Dimethylformamide){2,2'-[(pyridine-2,6-diyl)bis(nitrilomethanylylidene)]bis(butan-1-ol)}dithiocyanatomanganese(II) dimethylformamide monosolvate (8)

Crystal data

[Mn(NCS)2(C15H23N3O2)(C3H7NO)]·C3H7NO	F(000) = 1252
Mr = 594.65	Dx = 1.314 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.9551 (12) Å	Cell parameters from 6961 reflections
b = 11.0509 (9) Å	θ = 2.3–28.1°
c = 18.4767 (14) Å	µ = 0.62 mm^−1
β = 100.043 (1)°	T = 150 K
V = 3006.8 (4) Å^3	Block, yellow
Z = 4	0.39 × 0.21 × 0.07 mm

Data collection

Bruker APEXII CCD diffractometer	5593 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.035
Absorption correction: multi-scan (SADABS; Bruker, 2009)	θmax = 28.3°, θmin = 1.4°
Tmin = 0.509, Tmax = 0.746	h = −19→19
30036 measured reflections	k = −14→14
7485 independent reflections	l = −24→24

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.046	H-atom parameters constrained
wR(F^2) = 0.139	w = 1/[σ^2(Fo^2) + (0.068P)^2 + 1.9609P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
7485 reflections	Δρmax = 1.81 e Å^−3
342 parameters	Δρmin = −1.08 e Å^−3

Special details

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

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

	x	y	z	Uiso*/Ueq
Mn1	0.20138 (2)	0.25184 (3)	−0.06832 (2)	0.02130 (10)
N1	0.16906 (13)	0.46245 (17)	−0.08500 (10)	0.0244 (4)
O1	0.25478 (12)	0.60947 (17)	−0.17887 (10)	0.0383 (4)
H1	0.2930	0.6372	−0.2028	0.057*
C4	0.2015 (2)	0.5589 (3)	0.07419 (15)	0.0470 (7)
H4A	0.1708	0.6375	0.0679	0.070*
H4B	0.2332	0.5507	0.1250	0.070*
H4C	0.1565	0.4940	0.0631	0.070*
C3	0.26952 (19)	0.5503 (2)	0.02235 (14)	0.0372 (6)
H3A	0.2994	0.4701	0.0284	0.045*
H3B	0.3170	0.6126	0.0361	0.045*
C2	0.22702 (16)	0.5672 (2)	−0.05831 (13)	0.0295 (5)
H2	0.1886	0.6418	−0.0631	0.035*
C1	0.29860 (17)	0.5804 (2)	−0.10669 (14)	0.0341 (5)
H1A	0.3419	0.6452	−0.0873	0.041*
H1B	0.3329	0.5038	−0.1071	0.041*
C5	0.08901 (15)	0.4842 (2)	−0.11957 (12)	0.0270 (5)
H5	0.0677	0.5652	−0.1253	0.032*
C6	0.03001 (15)	0.3838 (2)	−0.15038 (12)	0.0253 (4)
C7	−0.05712 (15)	0.3997 (2)	−0.19124 (12)	0.0306 (5)
H7	−0.0823	0.4783	−0.2002	0.037*
C8	−0.10603 (16)	0.2976 (3)	−0.21841 (13)	0.0326 (5)
H8	−0.1651	0.3058	−0.2468	0.039*
C9	−0.06831 (15)	0.1844 (2)	−0.20393 (12)	0.0302 (5)
H9	−0.1009	0.1138	−0.2223	0.036*
C10	0.01810 (15)	0.1752 (2)	−0.16202 (11)	0.0249 (4)
N2	0.06568 (12)	0.27332 (17)	−0.13679 (10)	0.0236 (4)
C11	0.06492 (15)	0.0592 (2)	−0.14265 (12)	0.0262 (5)
H11	0.0360	−0.0149	−0.1589	0.031*
N3	0.14433 (12)	0.05883 (17)	−0.10398 (10)	0.0241 (4)
O2	0.26092 (13)	−0.01949 (16)	−0.19874 (10)	0.0377 (4)
H2A	0.2552	0.0560	−0.2027	0.057*
C12	0.19103 (16)	−0.0578 (2)	−0.09007 (13)	0.0275 (5)
H12	0.1511	−0.1240	−0.1143	0.033*
C14	0.21379 (19)	−0.0813 (2)	−0.00756 (13)	0.0363 (6)
H14A	0.2507	−0.1560	0.0010	0.044*
H14B	0.2511	−0.0135	0.0162	0.044*
C15	0.1308 (2)	−0.0949 (3)	0.02820 (15)	0.0476 (7)
H15A	0.0973	−0.0184	0.0245	0.071*
H15B	0.1497	−0.1163	0.0801	0.071*
H15C	0.0918	−0.1589	0.0032	0.071*
N4	0.33586 (14)	0.2355 (2)	−0.01229 (12)	0.0335 (5)
C16	0.40478 (17)	0.2160 (3)	0.02365 (14)	0.0374 (6)
S1	0.50189 (6)	0.18447 (15)	0.07443 (5)	0.0880 (4)
N5	0.13801 (15)	0.24749 (18)	0.02893 (11)	0.0317 (4)
C17	0.10478 (16)	0.24511 (19)	0.08145 (13)	0.0253 (4)
S2	0.05937 (4)	0.24206 (5)	0.15586 (3)	0.03147 (15)
O3	0.25406 (11)	0.23637 (14)	−0.17677 (9)	0.0275 (3)
C18	0.25787 (15)	0.3199 (2)	−0.22184 (12)	0.0266 (5)
H18	0.2295	0.3945	−0.2138	0.032*
N6	0.29812 (14)	0.31234 (18)	−0.27952 (10)	0.0292 (4)
C19	0.3387 (2)	0.2003 (3)	−0.29965 (16)	0.0447 (7)
H19A	0.3555	0.1496	−0.2559	0.067*
H19B	0.3930	0.2188	−0.3206	0.067*
H19C	0.2948	0.1569	−0.3361	0.067*
C20	0.2952 (2)	0.4133 (2)	−0.33105 (14)	0.0398 (6)
H20A	0.2655	0.4829	−0.3124	0.060*
H20B	0.2609	0.3893	−0.3790	0.060*
H20C	0.3572	0.4355	−0.3363	0.060*
O4	0.63068 (17)	0.3186 (2)	0.26804 (13)	0.0620 (6)
C21	0.5998 (2)	0.2167 (3)	0.27399 (16)	0.0427 (6)
H21	0.6157	0.1552	0.2426	0.051*
N7	0.54657 (15)	0.1865 (2)	0.32050 (13)	0.0435 (6)
C22	0.5197 (3)	0.2736 (4)	0.37067 (19)	0.0691 (11)
H22A	0.5496	0.3512	0.3651	0.104*
H22B	0.5375	0.2445	0.4212	0.104*
H22C	0.4537	0.2845	0.3598	0.104*
C23	0.5121 (2)	0.0639 (3)	0.3230 (2)	0.0677 (11)
H23A	0.5311	0.0157	0.2839	0.102*
H23B	0.4456	0.0658	0.3161	0.102*
H23C	0.5363	0.0276	0.3708	0.102*
C13	0.27799 (16)	−0.0517 (2)	−0.12330 (14)	0.0334 (5)
H13A	0.3198	0.0084	−0.0957	0.040*
H13B	0.3085	−0.1315	−0.1177	0.040*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.02034 (17)	0.02493 (18)	0.01884 (17)	0.00175 (12)	0.00397 (12)	0.00157 (12)
N1	0.0273 (9)	0.0245 (9)	0.0231 (9)	0.0021 (7)	0.0093 (7)	0.0018 (7)
O1	0.0417 (10)	0.0407 (10)	0.0345 (9)	−0.0054 (8)	0.0123 (8)	0.0079 (8)
C4	0.072 (2)	0.0350 (14)	0.0366 (15)	0.0022 (14)	0.0180 (14)	−0.0025 (12)
C3	0.0459 (15)	0.0328 (13)	0.0322 (13)	−0.0020 (11)	0.0045 (11)	−0.0041 (10)
C2	0.0319 (12)	0.0258 (11)	0.0318 (12)	−0.0011 (9)	0.0081 (10)	−0.0011 (9)
C1	0.0344 (13)	0.0307 (12)	0.0386 (13)	−0.0032 (10)	0.0101 (11)	0.0008 (10)
C5	0.0289 (11)	0.0268 (11)	0.0270 (11)	0.0058 (9)	0.0101 (9)	0.0054 (9)
C6	0.0247 (11)	0.0311 (11)	0.0217 (10)	0.0043 (9)	0.0090 (8)	0.0044 (9)
C7	0.0261 (11)	0.0405 (13)	0.0262 (11)	0.0075 (10)	0.0073 (9)	0.0085 (10)
C8	0.0224 (11)	0.0515 (15)	0.0239 (11)	0.0040 (10)	0.0039 (9)	0.0061 (11)
C9	0.0242 (11)	0.0446 (14)	0.0222 (11)	−0.0034 (10)	0.0052 (9)	0.0009 (10)
C10	0.0230 (10)	0.0345 (12)	0.0182 (10)	−0.0016 (9)	0.0066 (8)	0.0006 (9)
N2	0.0214 (9)	0.0297 (10)	0.0206 (9)	0.0013 (7)	0.0062 (7)	0.0025 (7)
C11	0.0272 (11)	0.0298 (11)	0.0223 (10)	−0.0035 (9)	0.0061 (8)	−0.0013 (9)
N3	0.0273 (9)	0.0237 (9)	0.0230 (9)	0.0010 (7)	0.0088 (7)	0.0002 (7)
O2	0.0498 (11)	0.0310 (9)	0.0371 (10)	−0.0017 (8)	0.0209 (8)	−0.0046 (8)
C12	0.0326 (12)	0.0222 (10)	0.0277 (11)	0.0014 (9)	0.0054 (9)	−0.0013 (9)
C14	0.0499 (16)	0.0298 (12)	0.0277 (12)	0.0034 (11)	0.0030 (11)	0.0029 (10)
C15	0.073 (2)	0.0405 (15)	0.0330 (14)	−0.0017 (14)	0.0199 (14)	0.0061 (12)
N4	0.0286 (10)	0.0443 (13)	0.0266 (10)	0.0076 (9)	0.0020 (8)	0.0006 (9)
C16	0.0281 (12)	0.0587 (17)	0.0264 (12)	−0.0027 (11)	0.0078 (10)	−0.0037 (11)
S1	0.0273 (4)	0.1893 (14)	0.0449 (5)	0.0081 (6)	−0.0010 (3)	0.0254 (7)
N5	0.0373 (11)	0.0349 (11)	0.0249 (10)	0.0020 (9)	0.0107 (8)	0.0021 (8)
C17	0.0282 (11)	0.0224 (10)	0.0258 (11)	0.0016 (9)	0.0062 (9)	0.0009 (8)
S2	0.0376 (3)	0.0335 (3)	0.0268 (3)	0.0037 (2)	0.0153 (2)	0.0024 (2)
O3	0.0304 (8)	0.0316 (9)	0.0221 (8)	0.0012 (7)	0.0091 (6)	0.0022 (6)
C18	0.0277 (11)	0.0306 (12)	0.0214 (10)	−0.0020 (9)	0.0042 (8)	−0.0011 (9)
N6	0.0346 (11)	0.0321 (11)	0.0223 (9)	−0.0048 (8)	0.0086 (8)	−0.0005 (8)
C19	0.0597 (18)	0.0419 (15)	0.0386 (15)	0.0049 (14)	0.0251 (13)	−0.0009 (12)
C20	0.0562 (17)	0.0382 (14)	0.0261 (12)	−0.0126 (12)	0.0106 (11)	0.0035 (10)
O4	0.0809 (17)	0.0579 (14)	0.0553 (13)	−0.0261 (12)	0.0347 (12)	−0.0048 (11)
C21	0.0427 (15)	0.0501 (16)	0.0393 (15)	−0.0052 (13)	0.0179 (12)	−0.0022 (13)
N7	0.0343 (12)	0.0550 (15)	0.0445 (13)	0.0017 (10)	0.0158 (10)	0.0105 (11)
C22	0.062 (2)	0.107 (3)	0.0438 (18)	0.013 (2)	0.0262 (17)	−0.0032 (19)
C23	0.0441 (18)	0.063 (2)	0.094 (3)	−0.0082 (16)	0.0070 (18)	0.033 (2)
C13	0.0333 (13)	0.0299 (12)	0.0384 (13)	0.0036 (10)	0.0099 (10)	−0.0023 (10)

Geometric parameters (Å, º)

Mn1—N4	2.103 (2)	C10—C11	1.475 (3)
Mn1—N5	2.173 (2)	C11—N3	1.275 (3)
Mn1—N2	2.2090 (19)	N3—C12	1.467 (3)
Mn1—O3	2.2839 (16)	O2—C13	1.418 (3)
Mn1—N3	2.3485 (19)	C12—C14	1.525 (3)
Mn1—N1	2.3861 (18)	C12—C13	1.533 (3)
N1—C5	1.278 (3)	C14—C15	1.511 (4)
N1—C2	1.478 (3)	N4—C16	1.145 (3)
O1—C1	1.417 (3)	C16—S1	1.624 (3)
C4—C3	1.517 (4)	N5—C17	1.165 (3)
C3—C2	1.526 (3)	C17—S2	1.637 (2)
C2—C1	1.516 (3)	O3—C18	1.251 (3)
C5—C6	1.469 (3)	C18—N6	1.315 (3)
C6—N2	1.339 (3)	N6—C19	1.455 (3)
C6—C7	1.398 (3)	N6—C20	1.463 (3)
C7—C8	1.389 (4)	O4—C21	1.230 (4)
C8—C9	1.380 (4)	C21—N7	1.312 (3)
C9—C10	1.390 (3)	N7—C22	1.441 (4)
C10—N2	1.335 (3)	N7—C23	1.453 (4)
N4—Mn1—N5	96.24 (8)	C8—C9—C10	118.9 (2)
N4—Mn1—N2	174.43 (8)	N2—C10—C9	121.5 (2)
N5—Mn1—N2	89.22 (7)	N2—C10—C11	114.81 (19)
N4—Mn1—O3	88.79 (7)	C9—C10—C11	123.7 (2)
N5—Mn1—O3	172.17 (7)	C10—N2—C6	120.3 (2)
N2—Mn1—O3	85.90 (6)	C10—N2—Mn1	119.55 (15)
N4—Mn1—N3	109.25 (8)	C6—N2—Mn1	120.11 (15)
N5—Mn1—N3	91.28 (7)	N3—C11—C10	119.7 (2)
N2—Mn1—N3	71.60 (7)	C11—N3—C12	117.99 (19)
O3—Mn1—N3	81.36 (6)	C11—N3—Mn1	114.32 (15)
N4—Mn1—N1	107.57 (8)	C12—N3—Mn1	127.61 (14)
N5—Mn1—N1	91.19 (7)	N3—C12—C14	109.96 (19)
N2—Mn1—N1	71.10 (7)	N3—C12—C13	107.59 (18)
O3—Mn1—N1	93.02 (6)	C14—C12—C13	110.5 (2)
N3—Mn1—N1	142.57 (7)	C15—C14—C12	113.4 (2)
C5—N1—C2	117.60 (19)	C16—N4—Mn1	171.3 (2)
C5—N1—Mn1	113.53 (15)	N4—C16—S1	178.5 (3)
C2—N1—Mn1	128.81 (14)	C17—N5—Mn1	179.4 (2)
C4—C3—C2	113.4 (2)	N5—C17—S2	179.3 (2)
N1—C2—C1	108.18 (19)	C18—O3—Mn1	126.26 (15)
N1—C2—C3	110.50 (19)	O3—C18—N6	125.0 (2)
C1—C2—C3	111.8 (2)	C18—N6—C19	122.1 (2)
O1—C1—C2	108.6 (2)	C18—N6—C20	120.9 (2)
N1—C5—C6	119.9 (2)	C19—N6—C20	116.7 (2)
N2—C6—C7	121.2 (2)	O4—C21—N7	124.8 (3)
N2—C6—C5	115.04 (19)	C21—N7—C22	121.4 (3)
C7—C6—C5	123.7 (2)	C21—N7—C23	121.1 (3)
C8—C7—C6	118.4 (2)	C22—N7—C23	117.5 (3)
C9—C8—C7	119.6 (2)	O2—C13—C12	112.6 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4^i	0.84	1.86	2.695 (3)	171
O2—H2A···O3	0.84	2.05	2.861 (2)	162

Symmetry code: (i) −x+1, −y+1, −z.