Bis(benzo[h]quinolin-10-olato-κ2N,O)bromidomanganese(III)

Papa, V.; Spannenberg, A.; Beller, M.; Junge, K.

doi:10.1107/S2414314620015709

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 5| Part 12| December 2020| x201570

https://doi.org/10.1107/S2414314620015709

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Bis(benzo[h]quinolin-10-olato-κ²N,O)bromidomanganese(III)

Veronica Papa,^a Anke Spannenberg,^a Matthias Beller ^a and Kathrin Junge ^a ^*

^aLeibniz-Institut für Katalyse e. V., Albert-Einstein-Str. 29a, 18059 Rostock, Germany
^*Correspondence e-mail: kathrin.junge@catalysis.de

Edited by M. Weil, Vienna University of Technology, Austria (Received 14 November 2020; accepted 30 November 2020; online 4 December 2020)

The title compound, [MnBr(C₁₃H₈NO)₂], consists of a manganese(III) atom, which is coordinated by one bromido and two benzo[h]quinolin-10-olato ligands. The Mn^III complex exhibits a distorted square-pyramidal coordination geometry with the Br ligand in the apical position. Neighbouring complexes are held together by π–π interactions and weak C—H⋯Br hydrogen bonds.

Keywords: crystal structure; manganese; benzo[h]quinolin-10-olate; π–π-stacking.

CCDC reference: 2047278

Structure description

Recently, we described the chemoselective reduction of quinolines and related N-heterocycles by molecular hydrogen, using a simple Mn^I complex [Mn(CO)₅Br] (Papa et al., 2020 ). During the mechanistic studies of this catalytic reaction, several manganese compounds starting from [Mn(CO)₅Br] and different N-heteroarenes were prepared and characterized by spectroscopic methods. In this context, the title compound was synthesized and structurally determined by single-crystal X-ray diffraction. The molecular structure consists of a manganese(III) atom coordinated by one bromido and two bidentate benzo[h]quinolin-10-olato ligands (Fig. 1). The coordination environment around the Mn^III atom is best described as distorted square-pyramidal with the Br ligand in the apical position (τ = 0.35, with τ = 0 for an ideal square pyramid and τ = 1 for an ideal trigonal bypramid; Addison et al., 1984 ). The deviation from planarity in the strained benzo[h]quinolin-10-olato ligands can be derived from the torsion angles N1—C13—C12—C11 of 10.0 (3)° and N2—C26—C25—C24 of 11.0 (3)°.

Figure 1
Molecular structure of the title compound with atom labelling and displacement ellipsoids drawn at the 50% probability level.

In the crystal structure, π–π stacking interactions along the crystallographic b axis are observed between N1/C1–C4/C13 and between the C7–C12 rings, respectively (Fig. 2), with centroid-to-centroid distances Cg(N1/C1–C4/C13)⋯Cgⁱ(N1/C1–C4/C13) = 3.6804 (14) Å [symmetry code: (i) 1 − x, 2 − y, 1 − z], ring slippage = 1.42 Å, and Cg(C7–C12)⋯Cgⁱⁱ(C7–C12) = 3.6194 (16) Å [symmetry code: (ii) = 2 − x, 1 − y, 1 − z], ring slippage 1.33 Å. Neighbouring molecules are also linked along the a axis by π–π stacking interactions between the aromatic ring systems N2/C14–C20/C25/C26 (Fig. 2) with centroid-to-centroid distances Cg(N2/C14–C20/C25/C26)⋯Cgⁱⁱⁱ(N2/C14–C20/C25/C26) = 3.6310 (11) Å [symmetry code: (iii) =1 − x, 1 − y, 2 − z], ring slippage = 1.06 Å, and Cg(N2/C14–C20/C25/C26)⋯Cg^iv(N2/C14–C20/C25/C26) = 3.8165 (11) Å, [symmetry code: (iv) 2 − x, 1 − y, 2 − z], ring slippage 1.85 Å. Additionally, in the solid state weak intermolecular C—H⋯Br interactions are observed (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯Br1ⁱ	0.95	3.03	3.674 (2)	126
C2—H2⋯Br1ⁱ	0.95	2.96	3.626 (3)	128
Symmetry code: (i) .

Figure 2
Packing diagram of the title compound along the a axis. Displacement ellipsoids are drawn at the 50% probability level. For clarity H atoms have been omitted. The alternating pattern of π–π stacking interactions between N1/C1–C4/C13 rings as well as between C7–C12 rings is shown with dotted lines.

The crystal structure of a dimeric indium complex containing two benzo[h]quinolin-10-olato units has been reported by Wu et al. (1999 ). In addition, the crystal structure of 10-hydroxybenzo[h]quinoline has been described by Kubicki et al. (1995 ).

Synthesis and crystallization

A mixture of solutions containing [Mn(CO)₅Br] (0.02 mmol) and 10-hydroxybenzo[h]quinoline (0.5 mmol) in dry THF (2 ml) was stirred at 393 K for 18 h. The solvent was slowly removed in air giving dark-brown crystals after two weeks. Oxidation from Mn^I in the starting material to Mn^III in the product was mediated by atmospheric oxygen. Yield: 5.23 mg (50%); LCMS (m/z, pos): calculated for [C₂₆H₁₆BrMnN₂O₂] 521; found [M − Br]⁺ 443.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Seven outlier reflections were ignored during the refinement using the OMIT instruction.

Table 2
Experimental details

Crystal data
Chemical formula	[MnBr(C₁₃H₈NO)₂]
M_r	523.26
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	150
a, b, c (Å)	7.3303 (5), 10.5266 (7), 13.8432 (10)
α, β, γ (°)	76.9612 (18), 78.8220 (18), 72.0364 (18)
V (Å³)	980.97 (12)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	2.74
Crystal size (mm)	0.41 × 0.23 × 0.13

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.40, 0.72
No. of measured, independent and observed [I > 2σ(I)] reflections	42556, 6093, 5110
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.719

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.114, 1.10
No. of reflections	6093
No. of parameters	289
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.96, −0.44
Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2013 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2018/3 (Sheldrick, 2015 ), XP in SHELXTL (Sheldrick, 2015), Mercury (Macrae et al., 2020 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 2047278

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314620015709/wm4143sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314620015709/wm4143Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: XP in SHELXTL (Sheldrick, 2015) and Mercury (Macrae et al., 2020); software used to prepare material for publication: publCIF (Westrip, 2010).

Bis(benzo[h]quinolin-10-olato-κ²N,O)bromidomanganese(III) top

Crystal data top

[MnBr(C₁₃H₈NO)₂]	Z = 2
M_r = 523.26	F(000) = 524
Triclinic, P1	D_x = 1.771 Mg m⁻³
a = 7.3303 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.5266 (7) Å	Cell parameters from 9946 reflections
c = 13.8432 (10) Å	θ = 2.3–30.7°
α = 76.9612 (18)°	µ = 2.74 mm⁻¹
β = 78.8220 (18)°	T = 150 K
γ = 72.0364 (18)°	Prism, brown
V = 980.97 (12) Å³	0.41 × 0.23 × 0.13 mm

Data collection top

Bruker APEXII CCD diffractometer	6093 independent reflections
Radiation source: fine-focus sealed tube	5110 reflections with I > 2σ(I)
Detector resolution: 8.3333 pixels mm^-1	R_int = 0.036
ω scans	θ_max = 30.7°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −10→10
T_min = 0.40, T_max = 0.72	k = −15→15
42556 measured reflections	l = −19→19

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.114	w = 1/[σ²(F_o²) + (0.0649P)² + 0.8212P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max = 0.001
6093 reflections	Δρ_max = 0.96 e Å⁻³
289 parameters	Δρ_min = −0.44 e Å⁻³

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.86544 (3)	0.86413 (2)	0.75405 (2)	0.02263 (8)
C1	0.3671 (3)	0.8124 (2)	0.63030 (17)	0.0194 (4)
H1	0.300222	0.800888	0.696278	0.023*
C2	0.2593 (4)	0.8771 (3)	0.55156 (18)	0.0217 (5)
H2	0.121977	0.905678	0.563390	0.026*
C3	0.3551 (4)	0.8984 (3)	0.45723 (18)	0.0217 (5)
H3	0.284870	0.945580	0.402862	0.026*
C4	0.5574 (4)	0.8506 (2)	0.44051 (17)	0.0192 (4)
C5	0.6605 (4)	0.8746 (3)	0.34209 (18)	0.0239 (5)
H5	0.591514	0.924163	0.287706	0.029*
C6	0.8552 (4)	0.8272 (3)	0.32630 (18)	0.0245 (5)
H6	0.922096	0.848863	0.261538	0.029*
C7	0.9628 (4)	0.7450 (2)	0.40491 (17)	0.0206 (4)
C8	1.1609 (4)	0.6838 (3)	0.38329 (19)	0.0239 (5)
H8	1.225262	0.704000	0.317627	0.029*
C9	1.2636 (4)	0.5947 (3)	0.45581 (19)	0.0256 (5)
H9	1.397247	0.551630	0.439627	0.031*
C10	1.1717 (4)	0.5675 (3)	0.55334 (18)	0.0230 (5)
H10	1.243939	0.506170	0.603124	0.028*
C11	0.9763 (3)	0.6288 (2)	0.57866 (17)	0.0179 (4)
C12	0.8661 (3)	0.7198 (2)	0.50432 (16)	0.0172 (4)
C13	0.6599 (3)	0.7784 (2)	0.52252 (16)	0.0163 (4)
C14	0.8677 (3)	0.4264 (2)	0.85999 (17)	0.0185 (4)
H14	0.905836	0.409618	0.793397	0.022*
C15	0.9360 (3)	0.3231 (2)	0.93801 (18)	0.0200 (4)
H15	1.015414	0.236871	0.924909	0.024*
C16	0.8865 (3)	0.3481 (2)	1.03367 (17)	0.0193 (4)
H16	0.935733	0.280183	1.087564	0.023*
C17	0.7636 (3)	0.4735 (2)	1.05221 (16)	0.0171 (4)
C18	0.7158 (3)	0.5039 (3)	1.15135 (17)	0.0209 (4)
H18	0.766023	0.437282	1.205665	0.025*
C19	0.6004 (4)	0.6261 (3)	1.16818 (17)	0.0216 (4)
H19	0.576532	0.646090	1.233820	0.026*
C20	0.5124 (3)	0.7270 (2)	1.08935 (17)	0.0188 (4)
C21	0.3829 (4)	0.8493 (3)	1.11064 (18)	0.0225 (5)
H21	0.360503	0.868322	1.176527	0.027*
C22	0.2875 (4)	0.9428 (3)	1.03660 (19)	0.0245 (5)
H22	0.199403	1.025525	1.051751	0.029*
C23	0.3201 (4)	0.9160 (2)	0.93963 (18)	0.0221 (5)
H23	0.251384	0.979792	0.889550	0.027*
C24	0.4518 (3)	0.7971 (2)	0.91527 (16)	0.0171 (4)
C25	0.5548 (3)	0.7003 (2)	0.98981 (16)	0.0160 (4)
C26	0.6900 (3)	0.5732 (2)	0.97060 (16)	0.0155 (4)
Mn1	0.69313 (5)	0.69516 (4)	0.74703 (2)	0.01740 (9)
N1	0.5603 (3)	0.76591 (19)	0.61740 (14)	0.0166 (3)
N2	0.7511 (3)	0.54816 (19)	0.87462 (14)	0.0162 (3)
O1	0.8970 (3)	0.59267 (18)	0.67213 (12)	0.0215 (3)
O2	0.4684 (2)	0.77507 (17)	0.82180 (12)	0.0196 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.02412 (13)	0.02379 (13)	0.01929 (12)	−0.00630 (9)	−0.00649 (9)	0.00014 (9)
C1	0.0198 (10)	0.0235 (11)	0.0154 (10)	−0.0071 (9)	−0.0062 (8)	0.0002 (8)
C2	0.0196 (11)	0.0251 (11)	0.0206 (11)	−0.0057 (9)	−0.0080 (9)	−0.0009 (9)
C3	0.0240 (11)	0.0238 (11)	0.0179 (10)	−0.0060 (9)	−0.0109 (9)	0.0014 (8)
C4	0.0260 (11)	0.0174 (10)	0.0149 (10)	−0.0062 (8)	−0.0074 (8)	−0.0002 (8)
C5	0.0315 (13)	0.0254 (11)	0.0140 (10)	−0.0077 (10)	−0.0073 (9)	0.0017 (9)
C6	0.0321 (13)	0.0264 (12)	0.0135 (10)	−0.0085 (10)	−0.0031 (9)	−0.0001 (9)
C7	0.0258 (11)	0.0211 (10)	0.0168 (10)	−0.0088 (9)	−0.0027 (9)	−0.0039 (8)
C8	0.0248 (12)	0.0286 (12)	0.0188 (11)	−0.0091 (10)	0.0004 (9)	−0.0058 (9)
C9	0.0205 (11)	0.0316 (13)	0.0232 (12)	−0.0049 (10)	0.0001 (9)	−0.0076 (10)
C10	0.0226 (11)	0.0250 (11)	0.0191 (11)	−0.0008 (9)	−0.0052 (9)	−0.0052 (9)
C11	0.0204 (10)	0.0177 (10)	0.0153 (9)	−0.0026 (8)	−0.0039 (8)	−0.0045 (8)
C12	0.0211 (10)	0.0150 (9)	0.0154 (10)	−0.0049 (8)	−0.0035 (8)	−0.0019 (7)
C13	0.0205 (10)	0.0144 (9)	0.0141 (9)	−0.0052 (8)	−0.0043 (8)	−0.0006 (7)
C14	0.0206 (10)	0.0173 (10)	0.0168 (10)	−0.0056 (8)	−0.0044 (8)	0.0006 (8)
C15	0.0185 (10)	0.0157 (10)	0.0230 (11)	−0.0042 (8)	−0.0044 (8)	0.0028 (8)
C16	0.0169 (10)	0.0203 (10)	0.0183 (10)	−0.0057 (8)	−0.0064 (8)	0.0055 (8)
C17	0.0143 (9)	0.0209 (10)	0.0159 (9)	−0.0074 (8)	−0.0044 (8)	0.0027 (8)
C18	0.0191 (10)	0.0284 (12)	0.0147 (10)	−0.0092 (9)	−0.0055 (8)	0.0036 (8)
C19	0.0202 (10)	0.0308 (12)	0.0143 (10)	−0.0086 (9)	−0.0031 (8)	−0.0022 (9)
C20	0.0184 (10)	0.0234 (11)	0.0164 (10)	−0.0083 (8)	−0.0037 (8)	−0.0026 (8)
C21	0.0251 (11)	0.0253 (11)	0.0184 (10)	−0.0088 (9)	−0.0006 (9)	−0.0056 (9)
C22	0.0277 (12)	0.0185 (11)	0.0233 (12)	−0.0034 (9)	0.0016 (9)	−0.0040 (9)
C23	0.0240 (11)	0.0183 (10)	0.0187 (11)	−0.0025 (9)	−0.0008 (9)	0.0009 (8)
C24	0.0156 (9)	0.0187 (10)	0.0149 (9)	−0.0049 (8)	−0.0008 (8)	0.0005 (8)
C25	0.0136 (9)	0.0184 (10)	0.0154 (9)	−0.0049 (8)	−0.0027 (7)	−0.0003 (8)
C26	0.0135 (9)	0.0194 (10)	0.0146 (9)	−0.0074 (8)	−0.0044 (7)	0.0011 (8)
Mn1	0.01791 (17)	0.01906 (17)	0.01235 (16)	−0.00190 (13)	−0.00333 (12)	−0.00042 (12)
N1	0.0190 (9)	0.0171 (8)	0.0132 (8)	−0.0050 (7)	−0.0057 (7)	0.0013 (6)
N2	0.0171 (8)	0.0163 (8)	0.0151 (8)	−0.0049 (7)	−0.0052 (7)	0.0002 (7)
O1	0.0232 (8)	0.0224 (8)	0.0126 (7)	0.0019 (6)	−0.0026 (6)	−0.0018 (6)
O2	0.0177 (7)	0.0226 (8)	0.0134 (7)	−0.0006 (6)	−0.0018 (6)	−0.0003 (6)

Geometric parameters (Å, º) top

Br1—Mn1	2.5060 (5)	C14—H14	0.9500
C1—N1	1.338 (3)	C15—C16	1.366 (3)
C1—C2	1.394 (3)	C15—H15	0.9500
C1—H1	0.9500	C16—C17	1.397 (3)
C2—C3	1.363 (3)	C16—H16	0.9500
C2—H2	0.9500	C17—C26	1.422 (3)
C3—C4	1.401 (3)	C17—C18	1.432 (3)
C3—H3	0.9500	C18—C19	1.346 (4)
C4—C13	1.421 (3)	C18—H18	0.9500
C4—C5	1.433 (3)	C19—C20	1.436 (3)
C5—C6	1.350 (4)	C19—H19	0.9500
C5—H5	0.9500	C20—C21	1.398 (3)
C6—C7	1.429 (3)	C20—C25	1.424 (3)
C6—H6	0.9500	C21—C22	1.381 (4)
C7—C8	1.398 (4)	C21—H21	0.9500
C7—C12	1.428 (3)	C22—C23	1.394 (4)
C8—C9	1.373 (4)	C22—H22	0.9500
C8—H8	0.9500	C23—C24	1.389 (3)
C9—C10	1.397 (4)	C23—H23	0.9500
C9—H9	0.9500	C24—O2	1.341 (3)
C10—C11	1.388 (3)	C24—C25	1.424 (3)
C10—H10	0.9500	C25—C26	1.444 (3)
C11—O1	1.334 (3)	C26—N2	1.375 (3)
C11—C12	1.425 (3)	Mn1—O2	1.8356 (17)
C12—C13	1.441 (3)	Mn1—O1	1.8389 (17)
C13—N1	1.373 (3)	Mn1—N2	2.0849 (19)
C14—N2	1.337 (3)	Mn1—N1	2.0858 (18)
C14—C15	1.394 (3)

N1—C1—C2	123.1 (2)	C16—C17—C26	119.1 (2)
N1—C1—H1	118.4	C16—C17—C18	120.9 (2)
C2—C1—H1	118.4	C26—C17—C18	119.9 (2)
C3—C2—C1	118.6 (2)	C19—C18—C17	120.5 (2)
C3—C2—H2	120.7	C19—C18—H18	119.7
C1—C2—H2	120.7	C17—C18—H18	119.7
C2—C3—C4	120.0 (2)	C18—C19—C20	121.6 (2)
C2—C3—H3	120.0	C18—C19—H19	119.2
C4—C3—H3	120.0	C20—C19—H19	119.2
C3—C4—C13	119.2 (2)	C21—C20—C25	120.3 (2)
C3—C4—C5	120.6 (2)	C21—C20—C19	120.2 (2)
C13—C4—C5	120.1 (2)	C25—C20—C19	119.5 (2)
C6—C5—C4	120.3 (2)	C22—C21—C20	120.5 (2)
C6—C5—H5	119.8	C22—C21—H21	119.8
C4—C5—H5	119.8	C20—C21—H21	119.8
C5—C6—C7	121.4 (2)	C21—C22—C23	120.1 (2)
C5—C6—H6	119.3	C21—C22—H22	119.9
C7—C6—H6	119.3	C23—C22—H22	119.9
C8—C7—C12	120.1 (2)	C24—C23—C22	120.9 (2)
C8—C7—C6	119.8 (2)	C24—C23—H23	119.6
C12—C7—C6	120.0 (2)	C22—C23—H23	119.6
C9—C8—C7	120.8 (2)	O2—C24—C23	117.5 (2)
C9—C8—H8	119.6	O2—C24—C25	122.3 (2)
C7—C8—H8	119.6	C23—C24—C25	120.1 (2)
C8—C9—C10	120.0 (2)	C24—C25—C20	118.0 (2)
C8—C9—H9	120.0	C24—C25—C26	123.1 (2)
C10—C9—H9	120.0	C20—C25—C26	118.7 (2)
C11—C10—C9	121.0 (2)	N2—C26—C17	119.6 (2)
C11—C10—H10	119.5	N2—C26—C25	121.04 (19)
C9—C10—H10	119.5	C17—C26—C25	119.4 (2)
O1—C11—C10	117.4 (2)	O2—Mn1—O1	170.00 (9)
O1—C11—C12	122.6 (2)	O2—Mn1—N2	86.73 (7)
C10—C11—C12	119.9 (2)	O1—Mn1—N2	90.35 (8)
C11—C12—C7	118.1 (2)	O2—Mn1—N1	90.70 (8)
C11—C12—C13	123.2 (2)	O1—Mn1—N1	86.90 (8)
C7—C12—C13	118.5 (2)	N2—Mn1—N1	149.10 (8)
N1—C13—C4	119.3 (2)	O2—Mn1—Br1	95.03 (6)
N1—C13—C12	121.41 (19)	O1—Mn1—Br1	94.96 (6)
C4—C13—C12	119.3 (2)	N2—Mn1—Br1	104.39 (5)
N2—C14—C15	123.0 (2)	N1—Mn1—Br1	106.51 (6)
N2—C14—H14	118.5	C1—N1—C13	119.53 (19)
C15—C14—H14	118.5	C1—N1—Mn1	116.41 (15)
C16—C15—C14	118.7 (2)	C13—N1—Mn1	123.77 (15)
C16—C15—H15	120.6	C14—N2—C26	119.37 (19)
C14—C15—H15	120.6	C14—N2—Mn1	116.60 (15)
C15—C16—C17	120.0 (2)	C26—N2—Mn1	123.79 (15)
C15—C16—H16	120.0	C11—O1—Mn1	128.18 (15)
C17—C16—H16	120.0	C24—O2—Mn1	126.02 (15)

N1—C1—C2—C3	−2.4 (4)	C20—C21—C22—C23	−0.2 (4)
C1—C2—C3—C4	2.6 (4)	C21—C22—C23—C24	−1.6 (4)
C2—C3—C4—C13	0.9 (4)	C22—C23—C24—O2	176.7 (2)
C2—C3—C4—C5	−178.7 (2)	C22—C23—C24—C25	0.4 (4)
C3—C4—C5—C6	−179.4 (2)	O2—C24—C25—C20	−173.6 (2)
C13—C4—C5—C6	1.0 (4)	C23—C24—C25—C20	2.5 (3)
C4—C5—C6—C7	4.0 (4)	O2—C24—C25—C26	2.2 (3)
C5—C6—C7—C8	172.1 (3)	C23—C24—C25—C26	178.4 (2)
C5—C6—C7—C12	−4.7 (4)	C21—C20—C25—C24	−4.3 (3)
C12—C7—C8—C9	2.6 (4)	C19—C20—C25—C24	174.4 (2)
C6—C7—C8—C9	−174.1 (2)	C21—C20—C25—C26	179.7 (2)
C7—C8—C9—C10	−2.0 (4)	C19—C20—C25—C26	−1.6 (3)
C8—C9—C10—C11	0.3 (4)	C16—C17—C26—N2	−4.5 (3)
C9—C10—C11—O1	176.9 (2)	C18—C17—C26—N2	173.8 (2)
C9—C10—C11—C12	0.7 (4)	C16—C17—C26—C25	176.7 (2)
O1—C11—C12—C7	−176.1 (2)	C18—C17—C26—C25	−5.0 (3)
C10—C11—C12—C7	0.0 (3)	C24—C25—C26—N2	11.0 (3)
O1—C11—C12—C13	−1.5 (3)	C20—C25—C26—N2	−173.3 (2)
C10—C11—C12—C13	174.6 (2)	C24—C25—C26—C17	−170.3 (2)
C8—C7—C12—C11	−1.6 (3)	C20—C25—C26—C17	5.5 (3)
C6—C7—C12—C11	175.1 (2)	C2—C1—N1—C13	−1.6 (3)
C8—C7—C12—C13	−176.4 (2)	C2—C1—N1—Mn1	172.44 (19)
C6—C7—C12—C13	0.3 (3)	C4—C13—N1—C1	5.2 (3)
C3—C4—C13—N1	−4.9 (3)	C12—C13—N1—C1	−174.8 (2)
C5—C4—C13—N1	174.7 (2)	C4—C13—N1—Mn1	−168.38 (16)
C3—C4—C13—C12	175.1 (2)	C12—C13—N1—Mn1	11.6 (3)
C5—C4—C13—C12	−5.3 (3)	C15—C14—N2—C26	−1.8 (3)
C11—C12—C13—N1	10.0 (3)	C15—C14—N2—Mn1	172.88 (18)
C7—C12—C13—N1	−175.5 (2)	C17—C26—N2—C14	5.0 (3)
C11—C12—C13—C4	−170.0 (2)	C25—C26—N2—C14	−176.2 (2)
C7—C12—C13—C4	4.5 (3)	C17—C26—N2—Mn1	−169.30 (15)
N2—C14—C15—C16	−2.0 (4)	C25—C26—N2—Mn1	9.5 (3)
C14—C15—C16—C17	2.5 (3)	C10—C11—O1—Mn1	150.17 (19)
C15—C16—C17—C26	0.7 (3)	C12—C11—O1—Mn1	−33.7 (3)
C15—C16—C17—C18	−177.5 (2)	N2—Mn1—O1—C11	−169.3 (2)
C16—C17—C18—C19	178.6 (2)	N1—Mn1—O1—C11	41.5 (2)
C26—C17—C18—C19	0.4 (3)	Br1—Mn1—O1—C11	−64.8 (2)
C17—C18—C19—C20	3.6 (4)	C23—C24—O2—Mn1	143.34 (18)
C18—C19—C20—C21	175.7 (2)	C25—C24—O2—Mn1	−40.4 (3)
C18—C19—C20—C25	−3.0 (3)	N2—Mn1—O2—C24	45.79 (18)
C25—C20—C21—C22	3.2 (4)	N1—Mn1—O2—C24	−165.02 (18)
C19—C20—C21—C22	−175.5 (2)	Br1—Mn1—O2—C24	−58.38 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···Br1ⁱ	0.95	3.03	3.674 (2)	126
C2—H2···Br1ⁱ	0.95	2.96	3.626 (3)	128

Symmetry code: (i) x−1, y, z.

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