Diaqua-bis-(pyridine-2-carboxyl-ato-κN,O)manganese(II) dimethyl-formamide hemisolvate.

There are two crystallographically independent complex mol-ecules with very similar geometries in the unit cell of the title compound, [Mn(C(6)H(4)NO(2))(2)(H(2)O)(2)]·0.5C(3)H(7)NO. The central ion is situated in a distorted octa-hedral environment of two N- and four O-donor atoms from two pyridine-2-carboxyl-ate ligands and two cis-disposed water mol-ecules. The carboxyl-ate ligands are coordinated in a chelate fashion with the formation of two five-membered rings. In the crystal, the complex mol-ecules are connected by O-H⋯O hydrogen bonds between the coordinated water mol-ecules and the uncoordinated carboxyl-ate O atoms, thus forming hydrogen-bonded walls disposed perpendicularly to the bc plane.

Related literature

For the use of hydroxamate and carboxyl­ate ligands in the synthesis of polynuclear compounds, see: Sliva et al. (1997 ▶); Fritsky et al. (1998 ▶); Mokhir et al. (2002 ▶); Sachse et al. (2008 ▶). For hydrolytic destruction of hydroxamate ligands upon complex formation, see: Dobosz et al. (1999 ▶); Świątek-Kozłowska et al. (2000 ▶). For the synthesis of pyridine-2-hydroxamic acid, see: Hynes (1970 ▶). For related structures, see: Krämer & Fritsky (2000 ▶); Fritsky et al. (2001 ▶); Kovbasyuk et al. (2004 ▶); Wörl et al. (2005a ▶,b ▶); Moroz et al. (2010 ▶).

Experimental

Crystal data

[Mn(C6H4NO2)2(H2O)2]·0.5C3H7NO

M = 371.73

Triclinic,

a = 8.6860 (17) Å

b = 13.532 (3) Å

c = 14.871 (3) Å

α = 73.18 (3)°

β = 73.53 (3)°

γ = 72.37 (3)°

V = 1557.4 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.89 mm−1

T = 120 K

0.21 × 0.15 × 0.06 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997 ▶) T min = 0.834, T max = 0.932

13428 measured reflections

7243 independent reflections

5370 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.056

wR(F 2) = 0.157

S = 1.04

7243 reflections

426 parameters

H-atom parameters constrained

Δρmax = 1.73 e Å−3

Δρmin = −0.87 e Å−3

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811042218/zl2414sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811042218/zl2414Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Mn(C6H4NO2)2(H2O)2]·0.5C3H7NO	Z = 4
Mr = 371.73	F(000) = 764
Triclinic, P1	Dx = 1.585 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.6860 (17) Å	Cell parameters from 4574 reflections
b = 13.532 (3) Å	θ = 3.0–27.5°
c = 14.871 (3) Å	µ = 0.89 mm−1
α = 73.18 (3)°	T = 120 K
β = 73.53 (3)°	Block, pale yellow
γ = 72.37 (3)°	0.21 × 0.15 × 0.06 mm
V = 1557.4 (7) Å3

Nonius KappaCCD diffractometer	7243 independent reflections
Radiation source: fine-focus sealed tube	5370 reflections with I > 2σ(I)
horizontally mounted graphite crystal	Rint = 0.029
Detector resolution: 9 pixels mm-1	θmax = 28.8°, θmin = 2.9°
φ scans and ω scans with κ offset	h = −11→11
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	k = −17→18
Tmin = 0.834, Tmax = 0.932	l = −19→19
13428 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.157	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.1017P)2] where P = (Fo2 + 2Fc2)/3
7243 reflections	(Δ/σ)max < 0.001
426 parameters	Δρmax = 1.73 e Å−3
0 restraints	Δρmin = −0.87 e Å−3

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

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
Mn1	0.41145 (6)	0.09669 (4)	0.28566 (3)	0.01596 (13)
O1	0.4153 (3)	−0.16990 (17)	0.51623 (15)	0.0198 (5)
O2	0.4925 (3)	−0.03998 (17)	0.39416 (15)	0.0197 (5)
O3	0.8614 (3)	0.13230 (19)	0.08858 (18)	0.0284 (5)
O4	0.6391 (3)	0.14520 (17)	0.21013 (15)	0.0202 (5)
O1W	0.2631 (3)	0.22912 (17)	0.20112 (15)	0.0234 (5)
H1W1	0.2914	0.2536	0.1417	0.035*
H1W2	0.1736	0.2753	0.2312	0.035*
O2W	0.3491 (3)	0.19490 (18)	0.38793 (16)	0.0225 (5)
H2W1	0.2781	0.2528	0.3900	0.034*
H2W2	0.4144	0.1814	0.4245	0.034*
N1	0.1996 (3)	0.0162 (2)	0.34259 (17)	0.0178 (5)
N2	0.5325 (3)	0.0018 (2)	0.16917 (18)	0.0182 (5)
C1	0.2246 (4)	−0.0686 (2)	0.4167 (2)	0.0168 (6)
C2	0.1082 (4)	−0.1278 (3)	0.4631 (2)	0.0230 (7)
H2	0.1292	−0.1872	0.5147	0.028*
C3	−0.0404 (4)	−0.0984 (3)	0.4327 (2)	0.0258 (7)
H3	−0.1225	−0.1376	0.4636	0.031*
C4	−0.0671 (4)	−0.0119 (3)	0.3574 (2)	0.0238 (7)
H4	−0.1675	0.0094	0.3356	0.029*
C5	0.0555 (4)	0.0434 (3)	0.3142 (2)	0.0217 (7)
H5	0.0370	0.1030	0.2623	0.026*
C6	0.3907 (4)	−0.0943 (2)	0.4446 (2)	0.0180 (6)
C7	0.6736 (4)	0.0260 (2)	0.1121 (2)	0.0181 (6)
C8	0.7645 (4)	−0.0236 (3)	0.0377 (2)	0.0221 (7)
H8	0.8622	−0.0039	−0.0021	0.027*
C9	0.7103 (4)	−0.1031 (3)	0.0222 (2)	0.0231 (7)
H9	0.7702	−0.1383	−0.0286	0.028*
C10	0.5679 (4)	−0.1299 (3)	0.0819 (2)	0.0245 (7)
H10	0.5294	−0.1847	0.0736	0.029*
C11	0.4819 (4)	−0.0751 (2)	0.1546 (2)	0.0211 (6)
H11	0.3836	−0.0931	0.1953	0.025*
C12	0.7307 (4)	0.1088 (2)	0.1381 (2)	0.0183 (6)
Mn2	0.79814 (5)	0.40535 (4)	0.21576 (3)	0.01583 (13)
O5	1.0811 (3)	0.35722 (19)	0.42074 (17)	0.0279 (5)
O6	0.9995 (3)	0.35619 (17)	0.29141 (15)	0.0196 (5)
O7	0.7687 (3)	0.66837 (17)	−0.01771 (15)	0.0196 (5)
O8	0.8505 (3)	0.54221 (17)	0.10592 (15)	0.0188 (4)
O3W	0.6997 (3)	0.27064 (17)	0.30053 (15)	0.0234 (5)
H3W1	0.6725	0.2504	0.3606	0.035*
H3W2	0.6863	0.2297	0.2718	0.035*
O4W	0.9233 (3)	0.30931 (18)	0.11082 (16)	0.0226 (5)
H4W1	0.9111	0.2518	0.1054	0.034*
H4W2	1.0101	0.3263	0.0727	0.034*
N3	0.7155 (3)	0.4956 (2)	0.33415 (18)	0.0174 (5)
N4	0.5622 (3)	0.4837 (2)	0.16008 (17)	0.0177 (5)
C13	0.5772 (4)	0.5718 (2)	0.3498 (2)	0.0208 (6)
H13	0.5033	0.5917	0.3077	0.025*
C14	0.5367 (4)	0.6234 (3)	0.4250 (2)	0.0225 (7)
H14	0.4383	0.6781	0.4332	0.027*
C15	0.6425 (4)	0.5936 (3)	0.4874 (2)	0.0236 (7)
H15	0.6168	0.6264	0.5401	0.028*
C16	0.7875 (4)	0.5145 (3)	0.4719 (2)	0.0216 (6)
H16	0.8622	0.4921	0.5138	0.026*
C17	0.8198 (4)	0.4693 (2)	0.3938 (2)	0.0181 (6)
C18	0.9806 (4)	0.3871 (2)	0.3680 (2)	0.0197 (6)
C19	0.5778 (4)	0.5680 (2)	0.0848 (2)	0.0165 (6)
C20	0.4495 (4)	0.6252 (2)	0.0383 (2)	0.0204 (6)
H20	0.4640	0.6836	−0.0146	0.024*
C21	0.2996 (4)	0.5961 (3)	0.0700 (2)	0.0238 (7)
H21	0.2100	0.6341	0.0392	0.029*
C22	0.2830 (4)	0.5102 (3)	0.1475 (2)	0.0236 (7)
H22	0.1815	0.4889	0.1709	0.028*
C23	0.4172 (4)	0.4558 (3)	0.1901 (2)	0.0213 (6)
H23	0.4058	0.3966	0.2425	0.026*
C24	0.7461 (4)	0.5947 (2)	0.0553 (2)	0.0175 (6)
O9	0.2692 (4)	0.7270 (3)	0.2913 (3)	0.0718 (12)
N5	0.0270 (4)	0.7605 (3)	0.2458 (2)	0.0367 (8)
C25	0.1253 (6)	0.7140 (4)	0.3062 (4)	0.0586 (14)
H25	0.0863	0.6681	0.3644	0.070*
C26	0.0813 (5)	0.8336 (4)	0.1558 (3)	0.0434 (10)
H26A	0.0243	0.9070	0.1607	0.065*
H26B	0.0550	0.8178	0.1024	0.065*
H26C	0.2010	0.8249	0.1442	0.065*
C27	−0.1407 (6)	0.7521 (5)	0.2627 (4)	0.078 (2)
H27A	−0.1711	0.7089	0.3274	0.117*
H27B	−0.1499	0.7184	0.2150	0.117*
H27C	−0.2152	0.8233	0.2574	0.117*

	U11	U22	U33	U12	U13	U23
Mn1	0.0194 (2)	0.0161 (2)	0.0105 (2)	−0.00402 (18)	−0.00322 (17)	−0.00040 (17)
O1	0.0257 (11)	0.0179 (11)	0.0129 (10)	−0.0041 (9)	−0.0060 (9)	0.0016 (8)
O2	0.0207 (11)	0.0202 (11)	0.0167 (11)	−0.0061 (9)	−0.0060 (9)	0.0013 (9)
O3	0.0245 (12)	0.0319 (13)	0.0314 (13)	−0.0125 (10)	0.0067 (10)	−0.0172 (11)
O4	0.0245 (11)	0.0213 (11)	0.0153 (11)	−0.0066 (9)	−0.0014 (9)	−0.0066 (9)
O1W	0.0281 (12)	0.0219 (12)	0.0109 (10)	0.0021 (9)	−0.0033 (9)	0.0008 (8)
O2W	0.0215 (11)	0.0256 (12)	0.0211 (12)	0.0012 (9)	−0.0077 (9)	−0.0103 (9)
N1	0.0212 (13)	0.0184 (13)	0.0119 (12)	−0.0023 (10)	−0.0043 (10)	−0.0022 (10)
N2	0.0191 (13)	0.0192 (13)	0.0156 (13)	−0.0035 (10)	−0.0044 (10)	−0.0036 (10)
C1	0.0202 (14)	0.0184 (15)	0.0112 (14)	−0.0042 (12)	−0.0015 (11)	−0.0046 (11)
C2	0.0285 (17)	0.0224 (16)	0.0152 (15)	−0.0073 (13)	−0.0027 (13)	−0.0002 (12)
C3	0.0254 (17)	0.0305 (19)	0.0225 (17)	−0.0121 (14)	−0.0017 (13)	−0.0051 (14)
C4	0.0230 (16)	0.0295 (18)	0.0189 (16)	−0.0066 (14)	−0.0048 (13)	−0.0051 (13)
C5	0.0255 (16)	0.0253 (17)	0.0121 (14)	−0.0066 (13)	−0.0046 (12)	0.0000 (12)
C6	0.0258 (16)	0.0178 (15)	0.0101 (14)	−0.0030 (12)	−0.0037 (12)	−0.0050 (11)
C7	0.0213 (15)	0.0174 (15)	0.0158 (15)	−0.0034 (12)	−0.0053 (12)	−0.0040 (11)
C8	0.0216 (15)	0.0250 (17)	0.0182 (16)	−0.0008 (13)	−0.0041 (12)	−0.0079 (13)
C9	0.0249 (16)	0.0215 (16)	0.0240 (17)	−0.0004 (13)	−0.0065 (13)	−0.0108 (13)
C10	0.0295 (17)	0.0219 (17)	0.0262 (18)	−0.0063 (13)	−0.0094 (14)	−0.0083 (13)
C11	0.0220 (15)	0.0194 (15)	0.0222 (16)	−0.0060 (12)	−0.0047 (12)	−0.0039 (12)
C12	0.0204 (15)	0.0164 (15)	0.0174 (15)	−0.0031 (12)	−0.0034 (12)	−0.0048 (12)
Mn2	0.0197 (2)	0.0157 (2)	0.0107 (2)	−0.00441 (18)	−0.00352 (17)	−0.00042 (17)
O5	0.0278 (12)	0.0315 (13)	0.0285 (13)	0.0045 (10)	−0.0161 (10)	−0.0150 (11)
O6	0.0217 (11)	0.0216 (11)	0.0150 (11)	−0.0018 (9)	−0.0039 (8)	−0.0071 (9)
O7	0.0253 (11)	0.0184 (11)	0.0127 (10)	−0.0069 (9)	−0.0027 (8)	0.0004 (8)
O8	0.0203 (11)	0.0195 (11)	0.0144 (11)	−0.0071 (9)	−0.0041 (8)	0.0024 (8)
O3W	0.0395 (13)	0.0236 (12)	0.0099 (10)	−0.0171 (10)	−0.0037 (9)	0.0005 (8)
O4W	0.0243 (12)	0.0240 (12)	0.0209 (12)	−0.0108 (9)	0.0016 (9)	−0.0080 (9)
N3	0.0197 (12)	0.0154 (12)	0.0166 (13)	−0.0046 (10)	−0.0045 (10)	−0.0019 (10)
N4	0.0228 (13)	0.0174 (13)	0.0122 (12)	−0.0050 (10)	−0.0047 (10)	−0.0012 (10)
C13	0.0219 (15)	0.0202 (16)	0.0201 (16)	−0.0037 (12)	−0.0069 (12)	−0.0033 (12)
C14	0.0218 (16)	0.0173 (15)	0.0261 (17)	−0.0018 (12)	−0.0030 (13)	−0.0066 (13)
C15	0.0261 (16)	0.0248 (17)	0.0208 (16)	−0.0088 (13)	0.0009 (13)	−0.0093 (13)
C16	0.0231 (16)	0.0234 (16)	0.0204 (16)	−0.0052 (13)	−0.0057 (13)	−0.0073 (13)
C17	0.0203 (15)	0.0190 (15)	0.0144 (14)	−0.0051 (12)	−0.0041 (12)	−0.0022 (12)
C18	0.0218 (15)	0.0161 (15)	0.0215 (16)	−0.0051 (12)	−0.0044 (12)	−0.0044 (12)
C19	0.0249 (15)	0.0152 (14)	0.0076 (13)	−0.0036 (12)	−0.0034 (11)	−0.0012 (11)
C20	0.0276 (16)	0.0183 (15)	0.0151 (15)	−0.0049 (13)	−0.0066 (12)	−0.0021 (12)
C21	0.0219 (16)	0.0253 (17)	0.0252 (17)	−0.0011 (13)	−0.0096 (13)	−0.0074 (13)
C22	0.0200 (15)	0.0295 (18)	0.0225 (17)	−0.0088 (13)	−0.0014 (13)	−0.0079 (14)
C23	0.0242 (16)	0.0212 (16)	0.0176 (15)	−0.0053 (13)	−0.0043 (12)	−0.0031 (12)
C24	0.0237 (15)	0.0167 (15)	0.0110 (14)	−0.0041 (12)	−0.0019 (11)	−0.0039 (11)
O9	0.048 (2)	0.081 (3)	0.097 (3)	0.0190 (18)	−0.046 (2)	−0.042 (2)
N5	0.0288 (16)	0.046 (2)	0.0344 (18)	−0.0097 (14)	−0.0108 (14)	−0.0021 (15)
C25	0.050 (3)	0.063 (3)	0.056 (3)	0.018 (2)	−0.027 (2)	−0.021 (3)
C26	0.036 (2)	0.048 (3)	0.043 (2)	−0.0126 (19)	−0.0038 (18)	−0.006 (2)
C27	0.046 (3)	0.075 (4)	0.098 (5)	−0.037 (3)	−0.027 (3)	0.041 (3)

Mn1—O2W	2.154 (2)	O5—C18	1.237 (4)
Mn1—O2	2.156 (2)	O6—C18	1.276 (4)
Mn1—O1W	2.161 (2)	O7—C24	1.257 (4)
Mn1—O4	2.168 (2)	O8—C24	1.257 (4)
Mn1—N1	2.256 (3)	O3W—H3W1	0.8410
Mn1—N2	2.279 (3)	O3W—H3W2	0.8406
O1—C6	1.262 (4)	O4W—H4W1	0.8452
O2—C6	1.259 (4)	O4W—H4W2	0.8548
O3—C12	1.241 (4)	N3—C13	1.338 (4)
O4—C12	1.268 (4)	N3—C17	1.346 (4)
O1W—H1W1	0.8405	N4—C23	1.341 (4)
O1W—H1W2	0.9305	N4—C19	1.357 (4)
O2W—H2W1	0.8402	C13—C14	1.394 (4)
O2W—H2W2	0.8402	C13—H13	0.9500
N1—C5	1.346 (4)	C14—C15	1.382 (5)
N1—C1	1.353 (4)	C14—H14	0.9500
N2—C11	1.335 (4)	C15—C16	1.395 (4)
N2—C7	1.350 (4)	C15—H15	0.9500
C1—C2	1.384 (4)	C16—C17	1.388 (4)
C1—C6	1.525 (4)	C16—H16	0.9500
C2—C3	1.395 (5)	C17—C18	1.529 (4)
C2—H2	0.9500	C19—C20	1.387 (4)
C3—C4	1.380 (5)	C19—C24	1.525 (4)
C3—H3	0.9500	C20—C21	1.389 (5)
C4—C5	1.387 (5)	C20—H20	0.9500
C4—H4	0.9500	C21—C22	1.390 (5)
C5—H5	0.9500	C21—H21	0.9500
C7—C8	1.382 (4)	C22—C23	1.390 (4)
C7—C12	1.532 (4)	C22—H22	0.9500
C8—C9	1.395 (4)	C23—H23	0.9500
C8—H8	0.9500	O9—C25	1.263 (6)
C9—C10	1.383 (5)	N5—C25	1.309 (5)
C9—H9	0.9500	N5—C27	1.440 (5)
C10—C11	1.396 (4)	N5—C26	1.466 (5)
C10—H10	0.9500	C25—H25	0.9500
C11—H11	0.9500	C26—H26A	0.9800
Mn2—O8	2.155 (2)	C26—H26B	0.9800
Mn2—O3W	2.156 (2)	C26—H26C	0.9800
Mn2—O4W	2.159 (2)	C27—H27A	0.9800
Mn2—O6	2.179 (2)	C27—H27B	0.9800
Mn2—N3	2.259 (3)	C27—H27C	0.9800
Mn2—N4	2.269 (3)
O2W—Mn1—O2	89.21 (9)	O6—Mn2—N3	73.39 (9)
O2W—Mn1—O1W	86.34 (9)	O8—Mn2—N4	74.84 (9)
O2—Mn1—O1W	163.98 (9)	O3W—Mn2—N4	90.88 (9)
O2W—Mn1—O4	94.13 (9)	O4W—Mn2—N4	97.90 (9)
O2—Mn1—O4	102.52 (9)	O6—Mn2—N4	166.54 (9)
O1W—Mn1—O4	93.15 (9)	N3—Mn2—N4	93.21 (9)
O2W—Mn1—N1	99.52 (9)	C18—O6—Mn2	120.26 (19)
O2—Mn1—N1	75.12 (9)	C24—O8—Mn2	118.9 (2)
O1W—Mn1—N1	90.44 (9)	Mn2—O3W—H3W1	129.6
O4—Mn1—N1	166.09 (9)	Mn2—O3W—H3W2	118.4
O2W—Mn1—N2	167.35 (9)	H3W1—O3W—H3W2	112.0
O2—Mn1—N2	90.93 (9)	Mn2—O4W—H4W1	131.6
O1W—Mn1—N2	96.76 (9)	Mn2—O4W—H4W2	115.2
O4—Mn1—N2	73.50 (9)	H4W1—O4W—H4W2	112.5
N1—Mn1—N2	92.74 (9)	C13—N3—C17	117.8 (3)
C6—O2—Mn1	118.29 (19)	C13—N3—Mn2	127.1 (2)
C12—O4—Mn1	121.08 (19)	C17—N3—Mn2	115.1 (2)
Mn1—O1W—H1W1	125.2	C23—N4—C19	118.4 (3)
Mn1—O1W—H1W2	120.2	C23—N4—Mn2	128.8 (2)
H1W1—O1W—H1W2	112.7	C19—N4—Mn2	112.9 (2)
Mn1—O2W—H2W1	128.7	N3—C13—C14	123.0 (3)
Mn1—O2W—H2W2	117.1	N3—C13—H13	118.5
H2W1—O2W—H2W2	113.0	C14—C13—H13	118.5
C5—N1—C1	118.2 (3)	C15—C14—C13	118.7 (3)
C5—N1—Mn1	128.6 (2)	C15—C14—H14	120.6
C1—N1—Mn1	113.12 (19)	C13—C14—H14	120.6
C11—N2—C7	118.5 (3)	C14—C15—C16	119.0 (3)
C11—N2—Mn1	127.2 (2)	C14—C15—H15	120.5
C7—N2—Mn1	114.2 (2)	C16—C15—H15	120.5
N1—C1—C2	122.3 (3)	C17—C16—C15	118.4 (3)
N1—C1—C6	115.1 (3)	C17—C16—H16	120.8
C2—C1—C6	122.6 (3)	C15—C16—H16	120.8
C1—C2—C3	118.7 (3)	N3—C17—C16	123.1 (3)
C1—C2—H2	120.6	N3—C17—C18	115.2 (3)
C3—C2—H2	120.6	C16—C17—C18	121.7 (3)
C4—C3—C2	119.3 (3)	O5—C18—O6	125.6 (3)
C4—C3—H3	120.3	O5—C18—C17	118.8 (3)
C2—C3—H3	120.3	O6—C18—C17	115.6 (3)
C3—C4—C5	118.7 (3)	N4—C19—C20	122.1 (3)
C3—C4—H4	120.7	N4—C19—C24	115.1 (3)
C5—C4—H4	120.7	C20—C19—C24	122.7 (3)
N1—C5—C4	122.7 (3)	C19—C20—C21	119.2 (3)
N1—C5—H5	118.6	C19—C20—H20	120.4
C4—C5—H5	118.6	C21—C20—H20	120.4
O2—C6—O1	125.3 (3)	C20—C21—C22	118.8 (3)
O2—C6—C1	117.9 (3)	C20—C21—H21	120.6
O1—C6—C1	116.8 (3)	C22—C21—H21	120.6
N2—C7—C8	122.5 (3)	C21—C22—C23	118.9 (3)
N2—C7—C12	115.5 (3)	C21—C22—H22	120.5
C8—C7—C12	122.0 (3)	C23—C22—H22	120.5
C7—C8—C9	118.8 (3)	N4—C23—C22	122.6 (3)
C7—C8—H8	120.6	N4—C23—H23	118.7
C9—C8—H8	120.6	C22—C23—H23	118.7
C10—C9—C8	118.9 (3)	O7—C24—O8	125.3 (3)
C10—C9—H9	120.6	O7—C24—C19	117.0 (3)
C8—C9—H9	120.6	O8—C24—C19	117.7 (3)
C9—C10—C11	118.8 (3)	C25—N5—C27	125.1 (4)
C9—C10—H10	120.6	C25—N5—C26	119.9 (4)
C11—C10—H10	120.6	C27—N5—C26	114.8 (3)
N2—C11—C10	122.5 (3)	O9—C25—N5	123.6 (5)
N2—C11—H11	118.8	O9—C25—H25	118.2
C10—C11—H11	118.8	N5—C25—H25	118.2
O3—C12—O4	126.6 (3)	N5—C26—H26A	109.5
O3—C12—C7	117.8 (3)	N5—C26—H26B	109.5
O4—C12—C7	115.6 (3)	H26A—C26—H26B	109.5
O8—Mn2—O3W	163.73 (8)	N5—C26—H26C	109.5
O8—Mn2—O4W	88.27 (9)	H26A—C26—H26C	109.5
O3W—Mn2—O4W	86.00 (9)	H26B—C26—H26C	109.5
O8—Mn2—O6	103.96 (9)	N5—C27—H27A	109.5
O3W—Mn2—O6	91.74 (9)	N5—C27—H27B	109.5
O4W—Mn2—O6	95.46 (9)	H27A—C27—H27B	109.5
O8—Mn2—N3	92.93 (9)	N5—C27—H27C	109.5
O3W—Mn2—N3	95.66 (9)	H27A—C27—H27C	109.5
O4W—Mn2—N3	168.75 (9)	H27B—C27—H27C	109.5
O2W—Mn1—O2—C6	93.4 (2)	O3W—Mn2—O6—C18	−88.6 (2)
O1W—Mn1—O2—C6	19.6 (4)	O4W—Mn2—O6—C18	−174.8 (2)
O4—Mn1—O2—C6	−172.5 (2)	N3—Mn2—O6—C18	6.7 (2)
N1—Mn1—O2—C6	−6.7 (2)	N4—Mn2—O6—C18	12.5 (5)
N2—Mn1—O2—C6	−99.2 (2)	O3W—Mn2—O8—C24	21.9 (4)
O2W—Mn1—O4—C12	−179.7 (2)	O4W—Mn2—O8—C24	91.2 (2)
O2—Mn1—O4—C12	90.2 (2)	O6—Mn2—O8—C24	−173.6 (2)
O1W—Mn1—O4—C12	−93.1 (2)	N3—Mn2—O8—C24	−100.0 (2)
N1—Mn1—O4—C12	11.6 (5)	N4—Mn2—O8—C24	−7.4 (2)
N2—Mn1—O4—C12	3.0 (2)	O8—Mn2—N3—C13	70.6 (3)
O2W—Mn1—N1—C5	95.5 (3)	O3W—Mn2—N3—C13	−95.6 (3)
O2—Mn1—N1—C5	−177.9 (3)	O4W—Mn2—N3—C13	166.4 (4)
O1W—Mn1—N1—C5	9.2 (3)	O6—Mn2—N3—C13	174.3 (3)
O4—Mn1—N1—C5	−95.9 (4)	N4—Mn2—N3—C13	−4.4 (3)
N2—Mn1—N1—C5	−87.6 (3)	O8—Mn2—N3—C17	−108.6 (2)
O2W—Mn1—N1—C1	−82.5 (2)	O3W—Mn2—N3—C17	85.2 (2)
O2—Mn1—N1—C1	4.08 (19)	O4W—Mn2—N3—C17	−12.8 (6)
O1W—Mn1—N1—C1	−168.9 (2)	O6—Mn2—N3—C17	−4.9 (2)
O4—Mn1—N1—C1	86.1 (4)	N4—Mn2—N3—C17	176.4 (2)
N2—Mn1—N1—C1	94.3 (2)	O8—Mn2—N4—C23	−177.4 (3)
O2W—Mn1—N2—C11	162.7 (4)	O3W—Mn2—N4—C23	10.5 (3)
O2—Mn1—N2—C11	72.1 (3)	O4W—Mn2—N4—C23	96.6 (3)
O1W—Mn1—N2—C11	−93.8 (3)	O6—Mn2—N4—C23	−90.7 (5)
O4—Mn1—N2—C11	174.9 (3)	N3—Mn2—N4—C23	−85.2 (3)
N1—Mn1—N2—C11	−3.0 (3)	O8—Mn2—N4—C19	4.44 (19)
O2W—Mn1—N2—C7	−15.0 (5)	O3W—Mn2—N4—C19	−167.7 (2)
O2—Mn1—N2—C7	−105.6 (2)	O4W—Mn2—N4—C19	−81.6 (2)
O1W—Mn1—N2—C7	88.5 (2)	O6—Mn2—N4—C19	91.1 (4)
O4—Mn1—N2—C7	−2.8 (2)	N3—Mn2—N4—C19	96.6 (2)
N1—Mn1—N2—C7	179.3 (2)	C17—N3—C13—C14	−0.7 (5)
C5—N1—C1—C2	0.5 (4)	Mn2—N3—C13—C14	−179.9 (2)
Mn1—N1—C1—C2	178.7 (2)	N3—C13—C14—C15	−1.1 (5)
C5—N1—C1—C6	−180.0 (3)	C13—C14—C15—C16	1.3 (5)
Mn1—N1—C1—C6	−1.7 (3)	C14—C15—C16—C17	0.3 (5)
N1—C1—C2—C3	−0.5 (5)	C13—N3—C17—C16	2.4 (5)
C6—C1—C2—C3	−180.0 (3)	Mn2—N3—C17—C16	−178.3 (2)
C1—C2—C3—C4	0.2 (5)	C13—N3—C17—C18	−176.1 (3)
C2—C3—C4—C5	0.0 (5)	Mn2—N3—C17—C18	3.1 (3)
C1—N1—C5—C4	−0.2 (5)	C15—C16—C17—N3	−2.2 (5)
Mn1—N1—C5—C4	−178.2 (2)	C15—C16—C17—C18	176.2 (3)
C3—C4—C5—N1	0.0 (5)	Mn2—O6—C18—O5	173.7 (3)
Mn1—O2—C6—O1	−173.0 (2)	Mn2—O6—C18—C17	−7.3 (3)
Mn1—O2—C6—C1	8.0 (3)	N3—C17—C18—O5	−178.5 (3)
N1—C1—C6—O2	−4.0 (4)	C16—C17—C18—O5	3.0 (5)
C2—C1—C6—O2	175.5 (3)	N3—C17—C18—O6	2.4 (4)
N1—C1—C6—O1	176.9 (2)	C16—C17—C18—O6	−176.1 (3)
C2—C1—C6—O1	−3.5 (4)	C23—N4—C19—C20	−0.3 (4)
C11—N2—C7—C8	1.9 (4)	Mn2—N4—C19—C20	178.1 (2)
Mn1—N2—C7—C8	179.8 (2)	C23—N4—C19—C24	179.9 (2)
C11—N2—C7—C12	−175.4 (3)	Mn2—N4—C19—C24	−1.8 (3)
Mn1—N2—C7—C12	2.4 (3)	N4—C19—C20—C21	0.5 (4)
N2—C7—C8—C9	−1.3 (5)	C24—C19—C20—C21	−179.7 (3)
C12—C7—C8—C9	175.9 (3)	C19—C20—C21—C22	0.0 (5)
C7—C8—C9—C10	−0.3 (5)	C20—C21—C22—C23	−0.5 (5)
C8—C9—C10—C11	1.1 (5)	C19—N4—C23—C22	−0.3 (4)
C7—N2—C11—C10	−1.0 (5)	Mn2—N4—C23—C22	−178.4 (2)
Mn1—N2—C11—C10	−178.6 (2)	C21—C22—C23—N4	0.7 (5)
C9—C10—C11—N2	−0.5 (5)	Mn2—O8—C24—O7	−171.5 (2)
Mn1—O4—C12—O3	178.6 (3)	Mn2—O8—C24—C19	9.0 (3)
Mn1—O4—C12—C7	−2.7 (3)	N4—C19—C24—O7	175.9 (3)
N2—C7—C12—O3	178.8 (3)	C20—C19—C24—O7	−3.9 (4)
C8—C7—C12—O3	1.5 (4)	N4—C19—C24—O8	−4.5 (4)
N2—C7—C12—O4	0.0 (4)	C20—C19—C24—O8	175.6 (3)
C8—C7—C12—O4	−177.4 (3)	C27—N5—C25—O9	−176.4 (5)
O8—Mn2—O6—C18	95.6 (2)	C26—N5—C25—O9	−1.2 (7)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O7i	0.84	1.97	2.729 (3)	150.
O1W—H1W2···O6ii	0.93	1.76	2.685 (3)	177.
O2W—H2W1···O5ii	0.84	1.90	2.713 (3)	164.
O2W—H2W2···O1iii	0.84	1.87	2.700 (3)	168.
O3W—H3W1···O1iii	0.84	1.92	2.723 (3)	160.
O3W—H3W2···O4	0.84	1.85	2.688 (3)	175.
O4W—H4W1···O3	0.85	1.89	2.734 (3)	174.
O4W—H4W2···O7iv	0.85	1.88	2.704 (3)	162.
C13—H13···O9	0.95	2.31	3.031 (5)	133.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W1⋯O7i	0.84	1.97	2.729 (3)	150
O1W—H1W2⋯O6ii	0.93	1.76	2.685 (3)	177
O2W—H2W1⋯O5ii	0.84	1.90	2.713 (3)	164
O2W—H2W2⋯O1iii	0.84	1.87	2.700 (3)	168
O3W—H3W1⋯O1iii	0.84	1.92	2.723 (3)	160
O3W—H3W2⋯O4	0.84	1.85	2.688 (3)	175
O4W—H4W1⋯O3	0.85	1.89	2.734 (3)	174
O4W—H4W2⋯O7iv	0.85	1.88	2.704 (3)	162

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .