Tetra-aqua-bis[μ-N-(5-nitro-2-oxido-benzyl-idene)glycylglycinato]manganese(II)dinickel(II) tetra-hydrate.

The two unique Ni(II) atoms of the title complex, [MnNi(2)(C(11)H(8)N(3)O(6))(2)(H(2)O)(4)]·4H(2)O, have a slightly distorted square-planar coordination environment with a tetra-dentate N-(5-nitro-2-oxidobenzyl-idene)glycylglycinate Schiff base trianion. The Ni(II) atoms are coordinated by one phenolate O atom, one imine N atom, one amido N atom and one carboxyl-ate O atom. The Mn(II )atom is connected via the carboxyl-ate groups, forming a hetero-trinuclear Ni(II)-Mn(II)-Ni(II) system. The Mn(II) atom is six-coordinated in an octa-hedral geometry by four O atoms from two carboxyl-ate groups and four water mol-ecules. The Ni(II)-Mn(II)-Ni(II) hetero-trinuclear mol-ecules are stacked in the crystal and cross-linked through O-H⋯O hydrogen bonds.

Related literature

Transition metal complexes of n class="Chemical">salicylaldehyde-peptides and salicylaldehyde-amino acid Schiff bases are non-enzymatic models for pyridoxal-amino acid systems, which are of considerable importance as key inter­mediates in many metabolic reactions of amino acids catalysed by enzymes, see: Bkouche-Waksman et al. (1988 ▶); Wetmore et al. (2001 ▶); Zabinski & Toney (2001 ▶). For the preparation, structural characterization, appropriate spectroscopy and magnetic studies of Schiff-base complexes derived from salicylaldehyde and amino acids, see: Ganguly et al. (2008 ▶) and references cited therein. For Schiff bases derived from simple peptides, see: Zou et al. (2003 ▶).

Experimental

Crystal data

[MnNi2(C11H8N3O6)2(H2O)4]·4H2O

M = 872.90

Monoclinic,

a = 7.250 (1) Å

b = 11.581 (2) Å

c = 38.058 (6) Å

β = 90.29 (1)°

V = 3195.4 (9) Å3

Z = 4

Mo Kα radiation

μ = 1.65 mm−1

T = 293 K

0.25 × 0.20 × 0.15 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker 2003 ▶) T min = 0.68, T max = 0.78

15513 measured reflections

5600 independent reflections

2635 reflections with I > 2σ(I)

R int = 0.111

Refinement

R[F 2 > 2σ(F 2)] = 0.065

wR(F 2) = 0.161

S = 0.93

5600 reflections

460 parameters

387 restraints

H-atom parameters constrained

Δρmax = 0.59 e Å−3

Δρmin = −0.54 e Å−3

Data collection: SMART (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: DIAMOND (Brandenburg, 2000 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810011293/jh2139sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810011293/jh2139Isup2.hkl

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

[MnNi2(C11H8N3O6)2(H2O)4]·4H2O	F(000) = 1788
Mr = 872.90	Dx = 1.814 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2635 reflections
a = 7.250 (1) Å	θ = 1.8–25°
b = 11.581 (2) Å	µ = 1.65 mm−1
c = 38.058 (6) Å	T = 293 K
β = 90.29 (1)°	Block, orange
V = 3195.4 (9) Å3	0.25 × 0.20 × 0.15 mm
Z = 4

Bruker SMART CCD diffractometer	5600 independent reflections
Radiation source: fine-focus sealed tube	2635 reflections with I > 2σ(I)
graphite	Rint = 0.111
2θ/ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker 2003)	h = −8→8
Tmin = 0.68, Tmax = 0.78	k = −13→13
15513 measured reflections	l = −36→45

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.161	H-atom parameters constrained
S = 0.93	w = 1/[σ2(Fo2) + (0.0546P)2] where P = (Fo2 + 2Fc2)/3
5600 reflections	(Δ/σ)max < 0.001
460 parameters	Δρmax = 0.59 e Å−3
387 restraints	Δρmin = −0.54 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 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
Ni1	−0.13915 (11)	0.32785 (5)	0.362499 (18)	0.0266 (2)
Ni2	0.13623 (11)	−0.16406 (5)	0.138128 (18)	0.0263 (2)
Mn1	0.07802 (13)	0.22949 (7)	0.21569 (2)	0.0299 (2)
C1	−0.2519 (8)	0.2158 (5)	0.42448 (14)	0.0343 (6)
C2	−0.2786 (8)	0.1139 (5)	0.44456 (14)	0.0363 (7)
H2A	−0.2503	0.0425	0.4347	0.044*
C3	−0.3441 (8)	0.1186 (5)	0.47744 (15)	0.0376 (7)
H3A	−0.3623	0.0506	0.4900	0.045*
C4	−0.3853 (8)	0.2253 (5)	0.49316 (14)	0.0397 (6)
C5	−0.3575 (8)	0.3253 (5)	0.47496 (14)	0.0365 (7)
H5A	−0.3839	0.3956	0.4856	0.044*
C6	−0.2909 (8)	0.3237 (5)	0.44104 (14)	0.0348 (6)
C7	−0.2654 (8)	0.4335 (5)	0.42340 (14)	0.0345 (7)
H7A	−0.2963	0.5003	0.4356	0.041*
C8	−0.1714 (8)	0.5609 (4)	0.37804 (14)	0.0351 (7)
H8A	−0.0790	0.6008	0.3920	0.042*
H8B	−0.2845	0.6056	0.3786	0.042*
C9	−0.1063 (8)	0.5487 (4)	0.34098 (14)	0.0332 (7)
C10	−0.0249 (8)	0.4045 (4)	0.29709 (14)	0.0341 (7)
H10A	0.0979	0.4339	0.2925	0.041*
H10B	−0.1076	0.4318	0.2788	0.041*
C11	−0.0235 (8)	0.2740 (5)	0.29821 (14)	0.0363 (6)
C12	0.2613 (8)	−0.1431 (4)	0.06885 (14)	0.0341 (6)
C13	0.3061 (8)	−0.0732 (5)	0.03937 (14)	0.0353 (7)
H13B	0.2925	0.0065	0.0407	0.042*
C14	0.3657 (8)	−0.1209 (5)	0.00931 (15)	0.0368 (7)
H14B	0.3987	−0.0733	−0.0093	0.044*
C15	0.3803 (8)	−0.2388 (5)	0.00598 (14)	0.0378 (6)
C16	0.3400 (8)	−0.3108 (5)	0.03311 (14)	0.0355 (7)
H16B	0.3521	−0.3903	0.0304	0.043*
C17	0.2800 (8)	−0.2648 (5)	0.06529 (14)	0.0334 (6)
C18	0.2295 (8)	−0.3429 (4)	0.09273 (14)	0.0316 (7)
H18A	0.2388	−0.4216	0.0882	0.038*
C19	0.1324 (8)	−0.4005 (4)	0.14912 (13)	0.0322 (7)
H19A	0.2407	−0.4471	0.1540	0.039*
H19B	0.0356	−0.4507	0.1403	0.039*
C20	0.0680 (8)	−0.3401 (4)	0.18241 (14)	0.0313 (7)
C21	0.0135 (8)	−0.1520 (4)	0.20698 (14)	0.0313 (7)
H21A	0.0953	−0.1595	0.2271	0.038*
H21B	−0.1113	−0.1692	0.2144	0.038*
C22	0.0243 (8)	−0.0315 (4)	0.19229 (14)	0.0326 (6)
N1	−0.4516 (7)	0.2300 (4)	0.52840 (12)	0.0482 (8)
N2	−0.2042 (7)	0.4442 (4)	0.39261 (11)	0.0345 (7)
N3	−0.0881 (6)	0.4422 (3)	0.33140 (11)	0.0326 (7)
N4	0.4505 (7)	−0.2882 (4)	−0.02607 (12)	0.0437 (8)
N5	0.1731 (6)	−0.3116 (3)	0.12300 (11)	0.0310 (7)
N6	0.0683 (6)	−0.2311 (3)	0.17905 (11)	0.0304 (7)
O1	−0.1939 (5)	0.2064 (3)	0.39269 (9)	0.0344 (7)
O2	−0.4768 (7)	0.1386 (4)	0.54427 (11)	0.0642 (12)
O3	−0.4846 (7)	0.3229 (4)	0.54206 (11)	0.0600 (11)
O4	−0.0787 (6)	0.6368 (3)	0.32280 (10)	0.0368 (10)
O5	0.0188 (6)	0.2181 (3)	0.27154 (10)	0.0417 (7)
O6	−0.0703 (5)	0.2253 (3)	0.32661 (9)	0.0366 (7)
O7	0.2050 (5)	−0.0921 (3)	0.09717 (9)	0.0348 (7)
O8	0.4990 (6)	−0.2206 (3)	−0.04983 (10)	0.0560 (11)
O9	0.4621 (6)	−0.3915 (3)	−0.02960 (11)	0.0560 (11)
O10	0.0257 (5)	−0.3997 (3)	0.20923 (9)	0.0341 (10)
O11	−0.0247 (5)	0.0516 (3)	0.21069 (9)	0.0353 (7)
O12	0.0853 (5)	−0.0228 (3)	0.16104 (9)	0.0316 (7)
O13	−0.1904 (5)	0.2964 (3)	0.20329 (11)	0.0541 (10)
H13A	−0.2458	0.3118	0.2223	0.081*
H13D	−0.2508	0.2456	0.1919	0.081*
O14	0.3433 (5)	0.1613 (3)	0.22748 (10)	0.0437 (9)
H14A	0.3580	0.1596	0.2496	0.066*
H14D	0.4251	0.2044	0.2184	0.066*
O15	0.1896 (6)	0.4015 (3)	0.21661 (10)	0.0427 (10)
H15B	0.3018	0.3994	0.2102	0.064*
H15C	0.1284	0.4438	0.2025	0.064*
O16	0.1345 (6)	0.2113 (3)	0.15781 (9)	0.0425 (10)
H16C	0.2093	0.1558	0.1547	0.064*
H16D	0.0341	0.1973	0.1470	0.064*
O17	0.5613 (6)	0.4713 (3)	0.21007 (11)	0.0573 (15)
H17B	0.5287	0.5210	0.1948	0.086*
H17C	0.5642	0.5026	0.2302	0.086*
O18	0.3366 (6)	0.3427 (4)	0.11301 (11)	0.0700 (17)
H18B	0.3322	0.3135	0.0925	0.105*
H18D	0.4479	0.3445	0.1201	0.105*
O19	0.6018 (6)	0.4872 (3)	0.13746 (11)	0.0641 (16)
H19C	0.6778	0.5328	0.1473	0.096*
H19E	0.5347	0.5248	0.1231	0.096*
O20	0.8821 (7)	0.3487 (4)	0.11641 (12)	0.0738 (17)
H20D	0.7738	0.3294	0.1225	0.089*
H20A	0.8938	0.3398	0.0944	0.111*

	U11	U22	U33	U12	U13	U23
Ni1	0.0393 (5)	0.0211 (3)	0.0196 (4)	0.0026 (4)	0.0049 (3)	0.0005 (3)
Ni2	0.0400 (5)	0.0171 (3)	0.0220 (4)	0.0029 (4)	0.0017 (3)	0.0001 (3)
Mn1	0.0426 (6)	0.0215 (4)	0.0256 (5)	0.0016 (4)	0.0047 (4)	0.0000 (4)
C1	0.0433 (13)	0.0324 (10)	0.0274 (10)	−0.0038 (12)	0.0070 (11)	0.0030 (9)
C2	0.0443 (15)	0.0348 (11)	0.0298 (12)	−0.0036 (14)	0.0056 (13)	0.0047 (11)
C3	0.0459 (16)	0.0371 (11)	0.0298 (12)	−0.0078 (14)	0.0054 (13)	0.0061 (11)
C4	0.0496 (13)	0.0406 (11)	0.0290 (10)	−0.0097 (12)	0.0070 (11)	0.0015 (9)
C5	0.0453 (15)	0.0364 (12)	0.0280 (11)	−0.0070 (14)	0.0056 (13)	−0.0010 (10)
C6	0.0435 (13)	0.0340 (10)	0.0270 (10)	−0.0038 (12)	0.0064 (11)	−0.0004 (9)
C7	0.0456 (15)	0.0318 (11)	0.0262 (11)	0.0000 (14)	0.0100 (13)	−0.0031 (10)
C8	0.0508 (15)	0.0250 (11)	0.0295 (11)	0.0019 (14)	0.0100 (13)	−0.0024 (10)
C9	0.0478 (15)	0.0230 (10)	0.0289 (12)	−0.0008 (13)	0.0093 (13)	0.0001 (9)
C10	0.0487 (15)	0.0253 (10)	0.0283 (12)	−0.0046 (14)	0.0134 (13)	−0.0020 (10)
C11	0.0538 (13)	0.0254 (10)	0.0299 (9)	−0.0030 (12)	0.0157 (11)	−0.0046 (10)
C12	0.0466 (13)	0.0292 (10)	0.0265 (10)	−0.0019 (12)	0.0043 (11)	0.0014 (9)
C13	0.0474 (15)	0.0316 (12)	0.0270 (12)	−0.0032 (14)	0.0034 (13)	0.0023 (10)
C14	0.0479 (16)	0.0354 (11)	0.0272 (12)	−0.0055 (14)	0.0026 (13)	0.0010 (11)
C15	0.0496 (13)	0.0355 (10)	0.0284 (10)	−0.0063 (12)	0.0025 (11)	−0.0018 (9)
C16	0.0456 (15)	0.0319 (12)	0.0289 (11)	−0.0040 (14)	0.0031 (12)	−0.0031 (10)
C17	0.0440 (13)	0.0289 (10)	0.0273 (10)	−0.0019 (12)	0.0025 (11)	−0.0010 (9)
C18	0.0443 (15)	0.0235 (12)	0.0270 (11)	−0.0010 (14)	0.0024 (12)	−0.0038 (10)
C19	0.0475 (15)	0.0201 (11)	0.0289 (11)	0.0005 (14)	0.0033 (13)	−0.0006 (10)
C20	0.0469 (15)	0.0200 (10)	0.0271 (11)	0.0006 (13)	0.0028 (13)	0.0004 (10)
C21	0.0449 (15)	0.0207 (10)	0.0284 (12)	−0.0008 (13)	0.0071 (13)	−0.0008 (10)
C22	0.0470 (13)	0.0206 (9)	0.0302 (11)	−0.0008 (12)	0.0068 (11)	−0.0020 (9)
N1	0.0628 (17)	0.0497 (13)	0.0323 (13)	−0.0140 (15)	0.0127 (14)	0.0000 (11)
N2	0.0492 (16)	0.0281 (10)	0.0263 (11)	0.0012 (13)	0.0098 (12)	−0.0012 (9)
N3	0.0476 (15)	0.0235 (9)	0.0269 (11)	−0.0038 (13)	0.0113 (13)	−0.0022 (9)
N4	0.0584 (17)	0.0394 (12)	0.0333 (13)	−0.0085 (15)	0.0088 (14)	−0.0036 (11)
N5	0.0449 (15)	0.0201 (10)	0.0279 (10)	−0.0002 (13)	0.0050 (12)	−0.0022 (9)
N6	0.0456 (15)	0.0191 (9)	0.0267 (11)	−0.0012 (13)	0.0060 (12)	0.0002 (9)
O1	0.0462 (18)	0.0298 (12)	0.0272 (11)	−0.0009 (15)	0.0069 (13)	0.0017 (10)
O2	0.096 (3)	0.0608 (15)	0.0361 (19)	−0.018 (2)	0.025 (2)	0.0044 (16)
O3	0.080 (3)	0.0618 (15)	0.038 (2)	−0.005 (2)	0.027 (2)	−0.0038 (16)
O4	0.052 (2)	0.0251 (14)	0.0339 (18)	−0.0018 (18)	0.0044 (18)	0.0058 (14)
O5	0.0627 (16)	0.0301 (13)	0.0324 (10)	−0.0030 (15)	0.0174 (11)	−0.0070 (10)
O6	0.0546 (18)	0.0226 (11)	0.0327 (11)	−0.0025 (15)	0.0165 (14)	−0.0039 (10)
O7	0.0515 (18)	0.0264 (12)	0.0267 (11)	−0.0008 (15)	0.0055 (13)	0.0021 (10)
O8	0.082 (3)	0.0493 (17)	0.0368 (17)	−0.012 (2)	0.0166 (19)	−0.0006 (16)
O9	0.083 (3)	0.0416 (14)	0.043 (2)	−0.008 (2)	0.016 (2)	−0.0106 (15)
O10	0.048 (2)	0.0242 (16)	0.0300 (16)	0.0045 (18)	0.0046 (17)	0.0047 (13)
O11	0.0509 (15)	0.0233 (9)	0.0319 (14)	−0.0016 (11)	0.0061 (13)	−0.0050 (10)
O12	0.0471 (18)	0.0172 (11)	0.0305 (12)	−0.0018 (14)	0.0082 (13)	−0.0013 (10)
O13	0.0444 (14)	0.0422 (19)	0.076 (2)	0.0112 (14)	−0.0082 (16)	−0.014 (2)
O14	0.0414 (14)	0.0468 (19)	0.043 (2)	0.0072 (14)	0.0042 (14)	0.003 (2)
O15	0.055 (2)	0.0285 (13)	0.045 (2)	−0.0078 (14)	−0.001 (2)	0.0030 (14)
O16	0.058 (2)	0.040 (2)	0.0293 (12)	−0.0019 (19)	0.0033 (14)	−0.0009 (14)
O17	0.070 (3)	0.037 (2)	0.066 (3)	0.001 (2)	0.015 (3)	0.001 (2)
O18	0.082 (4)	0.080 (3)	0.047 (3)	−0.024 (3)	0.010 (3)	−0.013 (3)
O19	0.087 (4)	0.044 (3)	0.062 (3)	−0.004 (3)	0.007 (3)	0.001 (2)
O20	0.077 (4)	0.093 (4)	0.051 (3)	0.007 (3)	0.024 (3)	0.007 (3)

Ni1—N3	1.816 (4)	C13—C14	1.344 (7)
Ni1—N2	1.832 (4)	C13—H13B	0.9300
Ni1—O1	1.860 (3)	C14—C15	1.376 (7)
Ni1—O6	1.879 (3)	C14—H14B	0.9299
Ni2—N6	1.811 (4)	C15—C16	1.361 (7)
Ni2—N5	1.823 (4)	C15—N4	1.442 (7)
Ni2—O7	1.839 (4)	C16—C17	1.407 (7)
Ni2—O12	1.891 (3)	C16—H16B	0.9300
Mn1—O14	2.125 (4)	C17—C18	1.431 (7)
Mn1—O13	2.145 (4)	C18—N5	1.277 (6)
Mn1—O15	2.150 (3)	C18—H18A	0.9299
Mn1—O5	2.174 (4)	C19—N5	1.462 (6)
Mn1—O11	2.198 (3)	C19—C20	1.522 (7)
Mn1—O16	2.252 (3)	C19—H19A	0.9701
C1—O1	1.287 (6)	C19—H19B	0.9698
C1—C2	1.421 (7)	C20—N6	1.268 (6)
C1—C6	1.428 (7)	C20—O10	1.271 (6)
C2—C3	1.341 (7)	C21—N6	1.460 (6)
C2—H2A	0.9300	C21—C22	1.506 (7)
C3—C4	1.405 (8)	C21—H21A	0.9701
C3—H3A	0.9300	C21—H21B	0.9701
C4—C5	1.365 (7)	C22—O11	1.243 (6)
C4—N1	1.428 (7)	C22—O12	1.275 (6)
C5—C6	1.381 (7)	N1—O3	1.219 (6)
C5—H5A	0.9300	N1—O2	1.233 (6)
C6—C7	1.449 (7)	N4—O9	1.207 (6)
C7—N2	1.262 (6)	N4—O8	1.248 (5)
C7—H7A	0.9300	O13—H13A	0.8499
C8—N2	1.481 (6)	O13—H13D	0.8501
C8—C9	1.496 (7)	O14—H14A	0.8501
C8—H8A	0.9700	O14—H14D	0.8499
C8—H8B	0.9700	O15—H15B	0.8501
C9—O4	1.249 (6)	O15—H15C	0.8502
C9—N3	1.294 (6)	O16—H16C	0.8497
C10—N3	1.453 (6)	O16—H16D	0.8496
C10—C11	1.512 (7)	O17—H17B	0.8503
C10—H10A	0.9700	O17—H17C	0.8491
C10—H10B	0.9700	O18—H18B	0.8499
C11—O5	1.243 (6)	O18—H18D	0.8500
C11—O6	1.267 (6)	O19—H19C	0.8500
C12—O7	1.296 (6)	O19—H19E	0.8500
C12—C13	1.422 (7)	O20—H20D	0.8499
C12—C17	1.422 (7)	O20—H20A	0.8501
N3—Ni1—N2	85.72 (19)	C13—C14—H14B	119.4
N3—Ni1—O1	177.46 (18)	C15—C14—H14B	119.9
N2—Ni1—O1	96.51 (17)	C16—C15—C14	121.5 (5)
N3—Ni1—O6	86.06 (17)	C16—C15—N4	118.5 (5)
N2—Ni1—O6	171.67 (17)	C14—C15—N4	119.9 (5)
O1—Ni1—O6	91.69 (15)	C15—C16—C17	119.8 (5)
N6—Ni2—N5	84.86 (19)	C15—C16—H16B	120.1
N6—Ni2—O7	178.46 (17)	C17—C16—H16B	120.1
N5—Ni2—O7	96.66 (17)	C16—C17—C12	119.3 (5)
N6—Ni2—O12	85.41 (17)	C16—C17—C18	118.5 (5)
N5—Ni2—O12	170.27 (17)	C12—C17—C18	122.2 (5)
O7—Ni2—O12	93.07 (15)	N5—C18—C17	124.3 (5)
O14—Mn1—O13	179.20 (16)	N5—C18—H18A	117.9
O14—Mn1—O15	90.04 (15)	C17—C18—H18A	117.8
O13—Mn1—O15	90.57 (15)	N5—C19—C20	107.8 (4)
O14—Mn1—O5	87.37 (15)	N5—C19—H19A	110.9
O13—Mn1—O5	93.08 (16)	C20—C19—H19A	110.3
O15—Mn1—O5	96.69 (14)	N5—C19—H19B	109.6
O14—Mn1—O11	88.61 (14)	C20—C19—H19B	109.8
O13—Mn1—O11	90.74 (15)	H19A—C19—H19B	108.4
O15—Mn1—O11	175.37 (14)	N6—C20—O10	128.4 (5)
O5—Mn1—O11	87.67 (14)	N6—C20—C19	111.9 (5)
O14—Mn1—O16	90.16 (15)	O10—C20—C19	119.7 (4)
O13—Mn1—O16	89.30 (16)	N6—C21—C22	107.3 (4)
O15—Mn1—O16	91.85 (14)	N6—C21—H21A	110.6
O5—Mn1—O16	171.11 (13)	C22—C21—H21A	110.1
O11—Mn1—O16	83.72 (13)	N6—C21—H21B	110.0
O1—C1—C2	118.8 (5)	C22—C21—H21B	110.4
O1—C1—C6	123.7 (5)	H21A—C21—H21B	108.5
C2—C1—C6	117.5 (5)	O11—C22—O12	124.5 (5)
C3—C2—C1	121.2 (5)	O11—C22—C21	119.5 (5)
C3—C2—H2A	119.4	O12—C22—C21	116.0 (4)
C1—C2—H2A	119.4	O3—N1—O2	121.2 (5)
C2—C3—C4	120.7 (5)	O3—N1—C4	120.2 (5)
C2—C3—H3A	119.7	O2—N1—C4	118.6 (5)
C4—C3—H3A	119.7	C7—N2—C8	119.7 (4)
C5—C4—C3	119.8 (5)	C7—N2—Ni1	127.0 (4)
C5—C4—N1	119.7 (5)	C8—N2—Ni1	113.3 (3)
C3—C4—N1	120.5 (5)	C9—N3—C10	125.0 (4)
C4—C5—C6	121.1 (5)	C9—N3—Ni1	119.4 (4)
C4—C5—H5A	119.5	C10—N3—Ni1	115.6 (3)
C6—C5—H5A	119.5	O9—N4—O8	121.4 (5)
C5—C6—C1	119.7 (5)	O9—N4—C15	120.8 (5)
C5—C6—C7	117.8 (5)	O8—N4—C15	117.8 (4)
C1—C6—C7	122.5 (5)	C18—N5—C19	118.7 (4)
N2—C7—C6	124.2 (5)	C18—N5—Ni2	126.8 (4)
N2—C7—H7A	117.9	C19—N5—Ni2	114.5 (3)
C6—C7—H7A	117.9	C20—N6—C21	123.4 (4)
N2—C8—C9	108.6 (4)	C20—N6—Ni2	120.9 (4)
N2—C8—H8A	110.0	C21—N6—Ni2	115.7 (3)
C9—C8—H8A	110.0	C1—O1—Ni1	126.0 (3)
N2—C8—H8B	110.0	C11—O5—Mn1	144.8 (4)
C9—C8—H8B	110.0	C11—O6—Ni1	114.4 (3)
H8A—C8—H8B	108.4	C12—O7—Ni2	125.9 (3)
O4—C9—N3	127.3 (5)	C22—O11—Mn1	132.6 (4)
O4—C9—C8	119.8 (5)	C22—O12—Ni2	115.6 (3)
N3—C9—C8	112.9 (5)	Mn1—O13—H13A	108.7
N3—C10—C11	106.1 (4)	Mn1—O13—H13D	109.1
N3—C10—H10A	110.5	H13A—O13—H13D	109.5
C11—C10—H10A	110.5	Mn1—O14—H14A	109.1
N3—C10—H10B	110.5	Mn1—O14—H14D	109.2
C11—C10—H10B	110.5	H14A—O14—H14D	109.5
H10A—C10—H10B	108.7	Mn1—O15—H15B	109.2
O5—C11—O6	122.2 (5)	Mn1—O15—H15C	109.2
O5—C11—C10	119.9 (5)	H15B—O15—H15C	109.5
O6—C11—C10	117.8 (5)	Mn1—O16—H16C	109.1
O7—C12—C13	118.1 (5)	Mn1—O16—H16D	109.4
O7—C12—C17	124.1 (5)	H16C—O16—H16D	109.5
C13—C12—C17	117.8 (5)	H17B—O17—H17C	109.5
C14—C13—C12	120.9 (5)	H18B—O18—H18D	109.5
C14—C13—H13B	119.2	H19C—O19—H19E	109.5
C12—C13—H13B	119.8	H20D—O20—H20A	109.5
C13—C14—C15	120.8 (5)

D—H···A	D—H	H···A	D···A	D—H···A
O13—H13A···O17i	0.85	2.36	2.723 (5)	106
O13—H13D···O4ii	0.85	1.85	2.681 (5)	165
O14—H14A···O10iii	0.85	1.90	2.679 (5)	151
O14—H14D···O4iv	0.85	2.08	2.586 (5)	118
O15—H15B···O17	0.85	2.06	2.826 (6)	150
O15—H15C···O10v	0.85	1.98	2.607 (5)	130
O16—H16C···O12	0.85	2.27	2.737 (5)	115
O16—H16D···O20i	0.85	2.37	2.887 (6)	119
O17—H17B···O6iii	0.85	2.52	3.257 (5)	145
O17—H17C···O11iii	0.85	2.34	3.168 (5)	166
O18—H18B···O8vi	0.85	2.31	3.039 (6)	145
O18—H18D···O19	0.85	2.10	2.710 (6)	128
O19—H19C···O6iii	0.85	2.56	3.087 (5)	121
O19—H19E···O1iii	0.85	2.47	2.867 (5)	109
O20—H20A···O2vii	0.85	2.14	2.938 (6)	156
O20—H20D···O19	0.85	2.29	2.713 (6)	111

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O13—H13A⋯O17i	0.85	2.36	2.723 (5)	106
O13—H13D⋯O4ii	0.85	1.85	2.681 (5)	165
O14—H14A⋯O10iii	0.85	1.90	2.679 (5)	151
O14—H14D⋯O4iv	0.85	2.08	2.586 (5)	118
O15—H15B⋯O17	0.85	2.06	2.826 (6)	150
O15—H15C⋯O10v	0.85	1.98	2.607 (5)	130
O16—H16C⋯O12	0.85	2.27	2.737 (5)	115
O16—H16D⋯O20i	0.85	2.37	2.887 (6)	119
O17—H17B⋯O6iii	0.85	2.52	3.257 (5)	145
O17—H17C⋯O11iii	0.85	2.34	3.168 (5)	166
O18—H18B⋯O8vi	0.85	2.31	3.039 (6)	145
O18—H18D⋯O19	0.85	2.10	2.710 (6)	128
O19—H19C⋯O6iii	0.85	2.56	3.087 (5)	121
O19—H19E⋯O1iii	0.85	2.47	2.867 (5)	109
O20—H20A⋯O2vii	0.85	2.14	2.938 (6)	156
O20—H20D⋯O19	0.85	2.29	2.713 (6)	111

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .