Crystal structure of bis-(μ-2-benzoyl-benzoato-κ(2) O:O')bis-[bis-(2,2'-bi-pyridine-κ(2) N,N')manganese(II)] bis-(perchlorate).

The title compound, [Mn2(C6H5COC6H4COO)2(C10H8N2)4](ClO4)2, comprises a centrosymmetric binuclear cation and two perchlorate anions. In the complex cation, two Mn(II) atoms are bridged by two O atoms of two different 2-benzoyl-benzoate ligands, each Mn(II) atom being further coordinated by two 2,2'-bi-pyridine (bipy) ligands in a distorted octa-hedral environment. Within the binuclear mol-ecule, the Mn⋯Mn separation is 4.513 (7) Å. Inter-molecular C-H⋯O and C-H⋯ π inter-actions link the mol-ecules into a three-dimensional network.

Related literature

For applications of inorganic–organic complexes, see: Burd et al. (2012 ▸); FitzGerald et al. (2013 ▸); Huang et al. (2013 ▸); Carrington et al. (2014 ▸); Wu et al. (2005 ▸); Lee et al. (2009 ▸); Li et al. (2014 ▸); Zhou et al. (2013 ▸); Wang et al. (2014 ▸); Hagrman et al. (1999 ▸); Ghosh & Bharadwaj (2004 ▸); Evans et al. (1999 ▸); Maspoch et al. (2007 ▸); Kitagawa & Matsuda (2007 ▸). For manganese complexes with bipyridine, see: Lopes et al. (2011 ▸); Knight et al. (2010 ▸); McCann et al. (1998 ▸); Lumme & Lindell (1988 ▸); Li et al. (2002 ▸, 2011 ▸); Wang et al. (2012 ▸).

Experimental

Crystal data

[Mn2(C14H9O3)2(C10H8N2)4](ClO4)2

M = 1383.94

Monoclinic,

a = 13.348 (4) Å

b = 17.136 (5) Å

c = 14.499 (4) Å

β = 111.321 (10)°

V = 3089.3 (16) Å3

Z = 2

Mo Kα radiation

μ = 0.57 mm−1

T = 296 K

0.27 × 0.23 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▸) T min = 0.857, T max = 0.935

39502 measured reflections

7799 independent reflections

5603 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.130

S = 1.06

6892 reflections

424 parameters

H-atom parameters constrained

Δρmax = 0.52 e Å−3

Δρmin = −0.53 e Å−3

Data collection: APEX2 (Bruker, 2007 ▸); cell refinement: SAINT (Bruker, 2007 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: SHELXTL ( Sheldrick, 2008 ▸); software used to prepare material for publication: WinGX (Farrugia, 2012 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015023671/bg2577sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015023671/bg2577Isup2.hkl

Click here for additional data file.

x y z . DOI: 10.1107/S2056989015023671/bg2577fig1.tif

The mol­ecular structure of the title compound, (displacement ellipsoids are shown at 50% probability levels). Symmetry code: (i) −x + 1, −y, −z + 2.

Click here for additional data file.

c . DOI: 10.1107/S2056989015023671/bg2577fig2.tif

Packing view drawn along the c axis, showing O—H⋯O, C—H⋯C hydrogen bonds and C—H⋯ π, and π–π stacking inter­actions drawn as dotted lines.

CCDC reference: 1014518

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Mn2(C14H9O3)2(C10H8N2)4](ClO4)2	F(000) = 1420
Mr = 1383.94	Dx = 1.488 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 13.348 (4) Å	Cell parameters from 8617 reflections
b = 17.136 (5) Å	θ = 2.5–28.2°
c = 14.499 (4) Å	µ = 0.57 mm−1
β = 111.321 (10)°	T = 296 K
V = 3089.3 (16) Å3	Square, yellow
Z = 2	0.27 × 0.23 × 0.12 mm

Bruker APEXII CCD diffractometer	7799 independent reflections
Radiation source: fine-focus sealed tube	5603 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
phi and ω scans	θmax = 28.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −16→17
Tmin = 0.857, Tmax = 0.935	k = −22→19
39502 measured reflections	l = −19→19

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.130	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.073P)2 + 1.2301P] where P = (Fo2 + 2Fc2)/3
6892 reflections	(Δ/σ)max = 0.002
424 parameters	Δρmax = 0.52 e Å−3
0 restraints	Δρmin = −0.53 e Å−3

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

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

	x	y	z	Uiso*/Ueq
Mn1	0.33958 (2)	0.022476 (15)	1.01401 (2)	0.03203 (11)
C29	0.54535 (17)	0.19533 (12)	0.76826 (15)	0.0413 (5)
Cl2	0.81581 (7)	0.02743 (3)	0.63743 (5)	0.0627 (2)
O1	0.58328 (12)	0.08588 (7)	0.93327 (10)	0.0384 (3)
O3	0.72438 (13)	0.22041 (12)	0.87465 (14)	0.0610 (5)
O2	0.47457 (14)	0.08637 (9)	1.01711 (15)	0.0590 (5)
O6	0.8226 (2)	−0.04173 (14)	0.6922 (2)	0.0967 (8)
O5	0.8838 (3)	0.02323 (14)	0.5845 (3)	0.1155 (11)
O4	0.8379 (3)	0.09348 (15)	0.69834 (19)	0.1176 (11)
N1	0.18370 (14)	−0.03974 (10)	0.99225 (14)	0.0414 (4)
N2	0.27238 (15)	−0.01610 (10)	0.85656 (13)	0.0398 (4)
N3	0.35547 (14)	0.07990 (10)	1.15558 (13)	0.0400 (4)
N4	0.24957 (16)	0.13976 (10)	0.97526 (14)	0.0472 (4)
O7	0.7095 (3)	0.0362 (2)	0.5656 (3)	0.1379 (13)
C5	0.13050 (17)	−0.06874 (12)	0.90196 (17)	0.0437 (5)
C4	0.0383 (2)	−0.11325 (18)	0.8835 (3)	0.0711 (8)
H4	0.0008	−0.1328	0.8205	0.085*
C3	0.0035 (2)	−0.1279 (2)	0.9606 (3)	0.0837 (10)
H3	−0.0576	−0.1581	0.9499	0.100*
C2	0.0580 (2)	−0.09852 (18)	1.0515 (3)	0.0691 (8)
H2	0.0354	−0.1081	1.1039	0.083*
C1	0.1471 (2)	−0.05439 (15)	1.0643 (2)	0.0532 (6)
H1	0.1841	−0.0335	1.1267	0.064*
C6	0.17701 (17)	−0.05233 (12)	0.82610 (16)	0.0421 (5)
C10	0.3191 (2)	−0.00160 (14)	0.79121 (17)	0.0498 (5)
H10	0.3855	0.0235	0.8131	0.060*
C9	0.2740 (3)	−0.02187 (15)	0.69354 (18)	0.0609 (7)
H9	0.3091	−0.0116	0.6499	0.073*
C8	0.1752 (3)	−0.05798 (18)	0.6619 (2)	0.0698 (8)
H8	0.1417	−0.0719	0.5957	0.084*
C7	0.1266 (2)	−0.07322 (16)	0.72797 (19)	0.0632 (7)
H7	0.0598	−0.0976	0.7071	0.076*
C21	0.53450 (15)	0.11944 (10)	0.98092 (14)	0.0343 (4)
C22	0.55033 (15)	0.20527 (10)	0.99784 (14)	0.0332 (4)
C27	0.59429 (15)	0.25089 (10)	0.94292 (14)	0.0345 (4)
C28	0.62929 (17)	0.21976 (11)	0.86348 (16)	0.0405 (5)
C30	0.5765 (2)	0.15888 (15)	0.69870 (18)	0.0555 (6)
H30	0.6490	0.1492	0.7118	0.067*
C31	0.5003 (3)	0.1367 (2)	0.6095 (2)	0.0731 (8)
H31	0.5215	0.1117	0.5627	0.088*
C32	0.3929 (3)	0.1511 (2)	0.5893 (2)	0.0808 (9)
H32	0.3419	0.1354	0.5291	0.097*
C33	0.3611 (2)	0.1883 (2)	0.6571 (2)	0.0726 (8)
H33	0.2887	0.1993	0.6426	0.087*
C34	0.4369 (2)	0.20974 (15)	0.74772 (17)	0.0528 (6)
H34	0.4152	0.2338	0.7949	0.063*
C26	0.60483 (18)	0.33052 (12)	0.96073 (18)	0.0482 (5)
H26	0.6345	0.3616	0.9246	0.058*
C25	0.5722 (2)	0.36409 (12)	1.0307 (2)	0.0574 (7)
H25	0.5779	0.4178	1.0403	0.069*
C24	0.5313 (2)	0.31917 (14)	1.0867 (2)	0.0575 (6)
H24	0.5107	0.3418	1.1353	0.069*
C23	0.52106 (18)	0.23995 (13)	1.07001 (17)	0.0458 (5)
H23	0.4938	0.2092	1.1083	0.055*
C15	0.32092 (17)	0.15410 (12)	1.15152 (16)	0.0414 (5)
C16	0.26552 (17)	0.18769 (12)	1.05165 (17)	0.0429 (5)
C20	0.2014 (3)	0.16810 (16)	0.8851 (2)	0.0727 (8)
H20	0.1894	0.1346	0.8317	0.087*
C19	0.1679 (3)	0.24425 (19)	0.8656 (2)	0.0846 (10)
H19	0.1345	0.2619	0.8009	0.102*
C18	0.1850 (3)	0.29259 (16)	0.9434 (2)	0.0740 (8)
H18	0.1639	0.3446	0.9329	0.089*
C17	0.2335 (2)	0.26480 (14)	1.0375 (2)	0.0582 (6)
H17	0.2447	0.2975	1.0916	0.070*
C14	0.3385 (2)	0.19644 (15)	1.23753 (19)	0.0583 (6)
H14	0.3142	0.2476	1.2344	0.070*
C13	0.3920 (3)	0.16196 (18)	1.3268 (2)	0.0692 (8)
H13	0.4037	0.1895	1.3850	0.083*
C12	0.4285 (3)	0.08675 (17)	1.33073 (19)	0.0643 (7)
H12	0.4660	0.0627	1.3910	0.077*
C11	0.4078 (2)	0.04829 (14)	1.24293 (17)	0.0519 (5)
H11	0.4319	−0.0028	1.2450	0.062*

	U11	U22	U33	U12	U13	U23
Mn1	0.0380 (2)	0.02841 (15)	0.03140 (17)	−0.00411 (10)	0.01470 (14)	−0.00338 (10)
C29	0.0429 (12)	0.0437 (10)	0.0358 (10)	−0.0035 (9)	0.0128 (9)	0.0106 (8)
Cl2	0.0910 (5)	0.0447 (3)	0.0708 (4)	0.0073 (3)	0.0514 (4)	0.0037 (3)
O1	0.0505 (8)	0.0298 (6)	0.0389 (7)	−0.0006 (5)	0.0210 (7)	0.0029 (5)
O3	0.0359 (9)	0.0848 (12)	0.0638 (11)	−0.0114 (8)	0.0201 (8)	0.0015 (9)
O2	0.0678 (11)	0.0397 (8)	0.0887 (13)	−0.0165 (7)	0.0512 (10)	−0.0046 (8)
O6	0.128 (2)	0.0668 (13)	0.115 (2)	0.0097 (13)	0.0686 (18)	0.0332 (13)
O5	0.175 (3)	0.0781 (16)	0.152 (3)	−0.0089 (16)	0.129 (2)	−0.0082 (15)
O4	0.210 (3)	0.0697 (14)	0.0783 (16)	0.0250 (18)	0.0579 (19)	−0.0091 (12)
N1	0.0359 (9)	0.0427 (9)	0.0473 (10)	−0.0031 (7)	0.0169 (8)	0.0002 (7)
N2	0.0420 (10)	0.0413 (9)	0.0346 (9)	−0.0044 (7)	0.0120 (8)	−0.0055 (7)
N3	0.0481 (10)	0.0393 (8)	0.0378 (9)	−0.0056 (7)	0.0218 (8)	−0.0049 (7)
N4	0.0536 (11)	0.0409 (9)	0.0429 (10)	0.0056 (8)	0.0126 (9)	−0.0018 (7)
O7	0.120 (3)	0.123 (3)	0.142 (3)	0.0136 (19)	0.013 (2)	0.034 (2)
C5	0.0329 (11)	0.0396 (10)	0.0555 (13)	−0.0022 (8)	0.0125 (10)	−0.0052 (9)
C4	0.0506 (16)	0.0759 (18)	0.086 (2)	−0.0242 (13)	0.0244 (15)	−0.0266 (16)
C3	0.0553 (17)	0.087 (2)	0.122 (3)	−0.0286 (16)	0.0489 (19)	−0.017 (2)
C2	0.0595 (17)	0.0725 (17)	0.090 (2)	−0.0093 (14)	0.0452 (16)	0.0057 (16)
C1	0.0487 (14)	0.0593 (13)	0.0579 (14)	−0.0031 (11)	0.0270 (12)	0.0045 (11)
C6	0.0390 (12)	0.0381 (9)	0.0424 (11)	0.0001 (8)	0.0070 (9)	−0.0054 (8)
C10	0.0581 (15)	0.0540 (12)	0.0395 (12)	−0.0075 (11)	0.0201 (11)	−0.0048 (10)
C9	0.085 (2)	0.0630 (15)	0.0367 (12)	0.0011 (13)	0.0250 (13)	−0.0026 (10)
C8	0.085 (2)	0.0727 (17)	0.0381 (13)	−0.0082 (15)	0.0055 (14)	−0.0109 (12)
C7	0.0603 (17)	0.0682 (16)	0.0460 (14)	−0.0132 (13)	0.0015 (12)	−0.0122 (12)
C21	0.0346 (10)	0.0295 (8)	0.0374 (10)	−0.0036 (7)	0.0114 (8)	0.0032 (7)
C22	0.0283 (10)	0.0300 (8)	0.0379 (10)	−0.0024 (7)	0.0079 (8)	0.0013 (7)
C27	0.0266 (10)	0.0309 (8)	0.0380 (10)	−0.0040 (7)	0.0021 (8)	0.0051 (7)
C28	0.0374 (12)	0.0392 (10)	0.0447 (11)	−0.0051 (8)	0.0148 (9)	0.0096 (8)
C30	0.0577 (15)	0.0670 (15)	0.0441 (13)	0.0021 (12)	0.0212 (12)	0.0096 (11)
C31	0.087 (2)	0.092 (2)	0.0400 (14)	−0.0023 (17)	0.0229 (14)	−0.0025 (13)
C32	0.076 (2)	0.115 (3)	0.0374 (14)	−0.0142 (19)	0.0036 (14)	−0.0023 (15)
C33	0.0487 (16)	0.108 (2)	0.0479 (15)	−0.0024 (15)	0.0013 (13)	0.0014 (15)
C34	0.0447 (14)	0.0673 (14)	0.0421 (12)	−0.0022 (11)	0.0107 (11)	0.0028 (10)
C26	0.0432 (13)	0.0321 (9)	0.0561 (13)	−0.0058 (8)	0.0024 (11)	0.0081 (9)
C25	0.0527 (14)	0.0301 (9)	0.0729 (17)	−0.0001 (9)	0.0031 (13)	−0.0062 (10)
C24	0.0546 (15)	0.0498 (12)	0.0620 (15)	0.0069 (11)	0.0140 (13)	−0.0188 (11)
C23	0.0443 (12)	0.0448 (11)	0.0495 (12)	−0.0028 (9)	0.0185 (10)	−0.0051 (9)
C15	0.0415 (12)	0.0402 (10)	0.0489 (12)	−0.0055 (8)	0.0240 (10)	−0.0084 (8)
C16	0.0404 (12)	0.0387 (10)	0.0523 (12)	−0.0016 (8)	0.0202 (10)	−0.0053 (9)
C20	0.094 (2)	0.0569 (15)	0.0504 (15)	0.0180 (14)	0.0065 (15)	0.0008 (12)
C19	0.103 (3)	0.0684 (18)	0.0653 (19)	0.0278 (17)	0.0095 (18)	0.0171 (15)
C18	0.084 (2)	0.0457 (13)	0.084 (2)	0.0187 (13)	0.0202 (17)	0.0108 (13)
C17	0.0617 (16)	0.0423 (11)	0.0729 (17)	0.0050 (10)	0.0272 (14)	−0.0063 (11)
C14	0.0686 (17)	0.0554 (13)	0.0563 (15)	0.0002 (12)	0.0292 (13)	−0.0174 (11)
C13	0.089 (2)	0.0789 (18)	0.0464 (14)	−0.0084 (15)	0.0320 (14)	−0.0218 (13)
C12	0.083 (2)	0.0711 (17)	0.0387 (13)	−0.0101 (14)	0.0221 (13)	−0.0029 (11)
C11	0.0677 (16)	0.0490 (11)	0.0409 (12)	−0.0048 (11)	0.0221 (11)	0.0031 (9)

Mn1—O2	2.0949 (16)	C8—H8	0.9300
Mn1—O1i	2.1260 (14)	C7—H7	0.9300
Mn1—N3	2.2158 (17)	C21—C22	1.493 (2)
Mn1—N2	2.2281 (18)	C22—C23	1.378 (3)
Mn1—N1	2.2555 (18)	C22—C27	1.389 (3)
Mn1—N4	2.3037 (19)	C27—C26	1.386 (3)
C29—C30	1.373 (3)	C27—C28	1.490 (3)
C29—C34	1.390 (3)	C30—C31	1.377 (4)
C29—C28	1.487 (3)	C30—H30	0.9300
Cl2—O5	1.386 (3)	C31—C32	1.377 (5)
Cl2—O4	1.400 (3)	C31—H31	0.9300
Cl2—O6	1.411 (2)	C32—C33	1.364 (5)
Cl2—O7	1.430 (3)	C32—H32	0.9300
O1—C21	1.249 (2)	C33—C34	1.385 (4)
O1—Mn1i	2.1260 (14)	C33—H33	0.9300
O3—C28	1.220 (3)	C34—H34	0.9300
O2—C21	1.242 (2)	C26—C25	1.368 (4)
N1—C1	1.329 (3)	C26—H26	0.9300
N1—C5	1.338 (3)	C25—C24	1.368 (4)
N2—C10	1.334 (3)	C25—H25	0.9300
N2—C6	1.339 (3)	C24—C23	1.377 (3)
N3—C11	1.320 (3)	C24—H24	0.9300
N3—C15	1.346 (3)	C23—H23	0.9300
N4—C20	1.322 (3)	C15—C14	1.387 (3)
N4—C16	1.332 (3)	C15—C16	1.482 (3)
C5—C4	1.388 (3)	C16—C17	1.381 (3)
C5—C6	1.473 (3)	C20—C19	1.375 (4)
C4—C3	1.381 (5)	C20—H20	0.9300
C4—H4	0.9300	C19—C18	1.351 (5)
C3—C2	1.349 (5)	C19—H19	0.9300
C3—H3	0.9300	C18—C17	1.366 (4)
C2—C1	1.363 (4)	C18—H18	0.9300
C2—H2	0.9300	C17—H17	0.9300
C1—H1	0.9300	C14—C13	1.364 (4)
C6—C7	1.382 (3)	C14—H14	0.9300
C10—C9	1.367 (3)	C13—C12	1.371 (4)
C10—H10	0.9300	C13—H13	0.9300
C9—C8	1.376 (4)	C12—C11	1.370 (3)
C9—H9	0.9300	C12—H12	0.9300
C8—C7	1.364 (4)	C11—H11	0.9300
O2—Mn1—O1i	98.53 (7)	O2—C21—C22	117.04 (18)
O2—Mn1—N3	87.49 (7)	O1—C21—C22	118.25 (16)
O1i—Mn1—N3	100.61 (6)	C23—C22—C27	119.23 (18)
O2—Mn1—N2	101.52 (7)	C23—C22—C21	119.16 (18)
O1i—Mn1—N2	94.08 (6)	C27—C22—C21	121.61 (18)
N3—Mn1—N2	161.48 (7)	C26—C27—C22	118.8 (2)
O2—Mn1—N1	172.97 (7)	C26—C27—C28	117.20 (19)
O1i—Mn1—N1	86.51 (6)	C22—C27—C28	123.93 (16)
N3—Mn1—N1	96.45 (7)	O3—C28—C29	121.5 (2)
N2—Mn1—N1	73.10 (7)	O3—C28—C27	119.8 (2)
O2—Mn1—N4	85.27 (7)	C29—C28—C27	118.44 (18)
O1i—Mn1—N4	172.33 (6)	C29—C30—C31	119.9 (3)
N3—Mn1—N4	72.80 (7)	C29—C30—H30	120.1
N2—Mn1—N4	91.66 (7)	C31—C30—H30	120.1
N1—Mn1—N4	90.31 (7)	C30—C31—C32	120.5 (3)
C30—C29—C34	119.6 (2)	C30—C31—H31	119.8
C30—C29—C28	118.9 (2)	C32—C31—H31	119.8
C34—C29—C28	121.6 (2)	C33—C32—C31	120.2 (3)
O5—Cl2—O4	111.14 (19)	C33—C32—H32	119.9
O5—Cl2—O6	110.27 (16)	C31—C32—H32	119.9
O4—Cl2—O6	111.62 (18)	C32—C33—C34	119.8 (3)
O5—Cl2—O7	106.2 (2)	C32—C33—H33	120.1
O4—Cl2—O7	107.5 (2)	C34—C33—H33	120.1
O6—Cl2—O7	110.0 (2)	C33—C34—C29	120.1 (2)
C21—O1—Mn1i	119.02 (12)	C33—C34—H34	120.0
C21—O2—Mn1	155.61 (17)	C29—C34—H34	120.0
C1—N1—C5	118.9 (2)	C25—C26—C27	120.9 (2)
C1—N1—Mn1	124.31 (16)	C25—C26—H26	119.5
C5—N1—Mn1	116.55 (14)	C27—C26—H26	119.5
C10—N2—C6	119.11 (19)	C24—C25—C26	120.4 (2)
C10—N2—Mn1	123.68 (15)	C24—C25—H25	119.8
C6—N2—Mn1	117.12 (14)	C26—C25—H25	119.8
C11—N3—C15	118.87 (19)	C25—C24—C23	119.1 (2)
C11—N3—Mn1	123.07 (15)	C25—C24—H24	120.4
C15—N3—Mn1	117.58 (14)	C23—C24—H24	120.4
C20—N4—C16	118.0 (2)	C24—C23—C22	121.4 (2)
C20—N4—Mn1	125.78 (17)	C24—C23—H23	119.3
C16—N4—Mn1	115.06 (14)	C22—C23—H23	119.3
N1—C5—C4	120.7 (2)	N3—C15—C14	120.8 (2)
N1—C5—C6	116.23 (18)	N3—C15—C16	116.79 (18)
C4—C5—C6	123.0 (2)	C14—C15—C16	122.4 (2)
C3—C4—C5	118.6 (3)	N4—C16—C17	121.3 (2)
C3—C4—H4	120.7	N4—C16—C15	116.42 (18)
C5—C4—H4	120.7	C17—C16—C15	122.3 (2)
C2—C3—C4	120.1 (3)	N4—C20—C19	123.8 (3)
C2—C3—H3	119.9	N4—C20—H20	118.1
C4—C3—H3	119.9	C19—C20—H20	118.1
C3—C2—C1	118.3 (3)	C18—C19—C20	117.8 (3)
C3—C2—H2	120.8	C18—C19—H19	121.1
C1—C2—H2	120.8	C20—C19—H19	121.1
N1—C1—C2	123.3 (3)	C19—C18—C17	119.7 (2)
N1—C1—H1	118.4	C19—C18—H18	120.1
C2—C1—H1	118.4	C17—C18—H18	120.1
N2—C6—C7	120.6 (2)	C18—C17—C16	119.3 (2)
N2—C6—C5	116.77 (19)	C18—C17—H17	120.3
C7—C6—C5	122.7 (2)	C16—C17—H17	120.3
N2—C10—C9	123.0 (2)	C13—C14—C15	119.0 (2)
N2—C10—H10	118.5	C13—C14—H14	120.5
C9—C10—H10	118.5	C15—C14—H14	120.5
C10—C9—C8	117.9 (3)	C14—C13—C12	120.1 (2)
C10—C9—H9	121.1	C14—C13—H13	119.9
C8—C9—H9	121.1	C12—C13—H13	119.9
C7—C8—C9	119.7 (2)	C11—C12—C13	117.7 (3)
C7—C8—H8	120.2	C11—C12—H12	121.2
C9—C8—H8	120.2	C13—C12—H12	121.2
C8—C7—C6	119.7 (3)	N3—C11—C12	123.5 (2)
C8—C7—H7	120.1	N3—C11—H11	118.2
C6—C7—H7	120.1	C12—C11—H11	118.2
O2—C21—O1	124.70 (17)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O5ii	0.93	2.65	3.420 (4)	141
C26—H26···O6iii	0.93	2.58	3.494 (4)	168
C17—H17···O4iv	0.93	2.46	3.304 (4)	152
C18—H18···O7iv	0.93	2.72	3.382 (5)	129
C33—H33···Cg7iv	0.93	2.93	3.793 (3)	146

Table 1

Selected bond lengths (Å)

Mn1—O2	2.0949 (16)
Mn1—O1i	2.1260 (14)
Mn1—N3	2.2158 (17)
Mn1—N2	2.2281 (18)
Mn1—N1	2.2555 (18)
Mn1—N4	2.3037 (19)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

Cg7 is the centroid of the C22–C27 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯O5ii	0.93	2.65	3.420 (4)	141
C26—H26⋯O6iii	0.93	2.58	3.494 (4)	168
C17—H17⋯O4iv	0.93	2.46	3.304 (4)	152
C18—H18⋯O7iv	0.93	2.72	3.382 (5)	129
C33—H33⋯Cg7iv	0.93	2.93	3.793 (3)	146

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