Bis{2,4-dibromo-6-[(2-oxidoethyl­imino)meth­yl]phenolato-κ³O,N,O′}manganese(IV) methanol hemisolvate monohydrate

In the title compound, [Mn(C₉H₇Br₂NO₂)₂]·0.5CH₄O·H₂O, the Mn^IV atom is coordinated in a distorted octa­hedral geometry by two N and four O atoms from two different tridentate 2,4-dibromo-6-[(2-oxidoethyl­imino)meth­yl]phenolate ligands. In the crystal structure, the methanol solvent mol­ecule is disordered over two positions with equal occupancies. The crystal packing reveals a three-dimensional network generated by short Br...Br inter­actions [Br...Br = 3.555 (5)–3.742 (5) Å], and O—H...O and O—H...Br hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.014 Å
Some non-H atoms missing
• Disorder in solvent or counterion
• R factor = 0.051
• wR factor = 0.133
• Data-to-parameter ratio = 14.1

checkCIF/PLATON results

No syntax errors found



Alert level B
ABSTM02_ALERT_3_B  The ratio of Tmax/Tmin expected RT(exp) is > 1.20
            Absorption corrections should be applied.
            Tmin and Tmax expected:      0.311     0.392
            RT(exp) =      1.263
PLAT057_ALERT_3_B Correction for Absorption Required   RT(exp) ...       1.26
PLAT417_ALERT_2_B Short Inter D-H..H-D       H1WA   ..  H5A     ..       1.38 Ang.
PLAT420_ALERT_2_B D-H Without Acceptor       O1W    -   H1WB   ...          ?
PLAT430_ALERT_2_B Short Inter D...A Contact  O2     ..  O4      ..       2.76 Ang.

Alert level C
ABSTY03_ALERT_1_C  The _exptl_absorpt_correction_type has been given as none.
            However values have been given for Tmin and Tmax. Remove
            these if an absorption correction has not been applied.
  From the CIF: _exptl_absorpt_correction_T_min   0.357
  From the CIF: _exptl_absorpt_correction_T_max   0.455
CHEMW01_ALERT_1_C  The difference between the given and expected weight for
            compound is greater 1 mass unit. Check that all hydrogen
            atoms have been taken into account.
CRYSC01_ALERT_1_C The word below has not been recognised as a standard
            identifier.
            deep
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.96
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.84
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O3
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      33.00 Perc.
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...         14
PLAT431_ALERT_2_C Short Inter HL..A Contact  Br3    ..  Br3     ..       3.56 Ang.
PLAT432_ALERT_2_C Short Inter X...Y Contact  O1W    ..  C19     ..       2.98 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H5A    ..  BR1     ..       3.04 Ang.
PLAT481_ALERT_4_C Long D...A H-Bond Reported O5     ..  BR1     ..       3.89 Ang.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          2

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C18.4 H18 Br4 Mn1 N2 O5.5
            Atom count from _chemical_formula_moiety:C18.5 H18 Br4 Mn1 N2 O5.5
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C18.4 H18 Br4 Mn1 N2 O5.5
            Atom count from the _atom_site data:  C18.5 H18 Br4 Mn1 N2 O5.5
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G ALERT: Large difference may be due to a
            symmetry error - see SYMMG tests
           From the CIF: _cell_formula_units_Z   16
           From the CIF: _chemical_formula_sum  C18.4 H18 Br4 Mn1 N2 O5.5
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C        294.40    296.00   -1.60
           H        288.00    288.00    0.00
           Br        64.00     64.00    0.00
           Mn        16.00     16.00    0.00
           N         32.00     32.00    0.00
           O         88.00     88.00    0.00
REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values
           From the CIF: _diffrn_reflns_theta_max           25.99
           From the CIF: _reflns_number_total               4075
           From the CIF: _diffrn_reflns_limit_ max hkl   14.   38.   12.
           From the CIF: _diffrn_reflns_limit_ min hkl  -32.  -38.  -13.
           TEST1: Expected hkl limits for theta max
           Calculated maximum hkl   32.   40.   13.
           Calculated minimum hkl  -32.  -40.  -13.
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           25.99
           From the CIF: _reflns_number_total               4075
           Count of symmetry unique reflns         2503
           Completeness (_total/calc)            162.80%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1572
           Fraction of Friedel pairs measured     0.628
           Are heavy atom types Z>Si present        yes
PLAT033_ALERT_2_G Flack Parameter Value Deviates 2 * su from zero.       0.05
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         20

   0 ALERT level A = In general: serious problem
   5 ALERT level B = Potentially serious problem
  18 ALERT level C = Check and explain
  10 ALERT level G = General alerts; check

  13 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   9 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   6 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

Interest on packing arrangements of halogenated compounds goes back many years to what Schmidt called the 'chloro effect', where the presence of chloro substituents on aromatic compounds frequently results in stacking arrangements with a short (ca 4 Å) crystallographic axis (Cohen et al., 1964; Zordan et al., 2005; Desiraju, 1989). The title compound, (I), contains the dibrominated ligand L^- with two Br atoms accessible at the periphery of each ligand.

In (I) the Mn^IV atom is coordinated by two N and four O atoms from two different tridentate ligands L^2- forming a distorted octahedral geometry (Fig. 1 and Table 1). The shortest Br···Br contacts (Zordan et al., 2005; Zaman et al., 2004; Sarma & Desiraju, 1986) are Br3ⁱ···Br3ⁱⁱ = 3.555 (5) Å, Br3ⁱ···Br4ⁱⁱⁱ = 3.742 (5) Å, and Br4ⁱ···Br2^iv = 3.631 (5) Å, [symmetry codes: (i) 1/2 - x, -1/2 - y, z; (ii) x, -1 + y, z; (iii) 1/4 + x,-1/4 - y, -1/4 + z; (iv) 1/4 - x, -3/4 - y, 1/4 + z]. The molecules of (I) are connected into a 3-D network through short Br···Br interactions, very strong O–H···O hydrogen bond and O–H···Br hydrogen bond (Table 2 and Fig. 2).

Related literature

A similar manganese (II) complex also has a distorted octahedral geometry (Kessissoglou et al., 1986). For related literature, see: Cohen et al. (1964); Zordan et al. (2005); Desiraju (1989); Zaman et al. (2004); Sarma & Desiraju (1986).

S2. Experimental

A solution of 2-amino-ethanol (0.061 g, 1 mmol) and caustic potash (0.112 g, 2 mmol) in methanol (10 ml) was added slowly to a solution of 3,5-dibromo-2-hydroxybenzaldehyde (1 mmol, 0.280 g) in methanol (20 ml). The mixture was stirred for 1 h at 323 K, then added slowly to a solution of MnCl₂ (2 mmol, 0.396 g) in methanol (10 ml). This mixture was stirred and refluxed for 2 h at 323 K. The solution was filtered and the filtrate was left to stand at room temperature. Deep purple suitable for X-ray diffraction were obtained in a yield of 38% (based on manganese).

S3. Refinement

H atoms of the water molecule were located in a difference Fourier map. The O—H distances were normalized to 0.85 Å and the H atoms were allowed to ride on the O atom, with U_iso(H) = 1.5 U_eq(O). All other H atoms were positioned geometrically and refined as riding, with C–H distances of 0.93–0.97 Å and U_iso(H) = 1.2 U_eq(C).

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).

Figures

	Fig. 1. The asymmetric unit of (I) with displacement ellipsoids drawn at the 30% probability level. Non-solution H atoms have been omitted.
	Fig. 2. The 3-D network of (I): dashed lines denote hydrogen bonds and Br···Br interactions. Non-solution H atoms have been omitted.

Bis{2,4-dibromo-6-[(2-oxidoethylimino)methyl]phenolato-κ³O,N,O'}manganese(IV) methanol hemisolvate monohydrate

Crystal data

C18H14Br4MnN2O4·0.5CH4O·H2O	Dx = 2.010 Mg m^−3
Mr = 730.89	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Fdd2	Cell parameters from 4075 reflections
a = 26.286 (4) Å	θ = 2.5–26.0°
b = 32.908 (5) Å	µ = 7.20 mm^−1
c = 11.1681 (17) Å	T = 293 K
V = 9661 (2) Å^3	Block, deep purple
Z = 16	0.18 × 0.14 × 0.13 mm
F(000) = 5632

Data collection

Bruker SMART CCD area-detector diffractometer	4075 independent reflections
Radiation source: fine-focus sealed tube	3143 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
φ and ω scans	θmax = 26.0°, θmin = 2.5°
Absorption correction: multi-scan SADABS (Sheldrick, 1996)	h = −32→14
Tmin = 0.357, Tmax = 0.455	k = −38→38
8149 measured reflections	l = −13→12

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.051	H-atom parameters constrained
wR(F^2) = 0.133	w = 1/[σ^2(Fo^2) + (0.0654P)^2 + 43.5887P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
4075 reflections	Δρmax = 1.09 e Å^−3
290 parameters	Δρmin = −0.39 e Å^−3
20 restraints	Absolute structure: Flack (1983), 1669 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.045 (19)

Special details

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Mn1	0.04388 (5)	0.25185 (4)	0.55027 (13)	0.0418 (3)
Br1	0.14995 (5)	0.31726 (4)	0.25588 (13)	0.0797 (4)
Br2	0.21088 (5)	0.16499 (5)	0.07739 (14)	0.1024 (5)
Br3	0.18568 (5)	0.26672 (3)	0.84250 (12)	0.0769 (4)
Br4	0.09302 (5)	0.40746 (4)	1.02880 (13)	0.0909 (5)
C1	0.1120 (3)	0.2418 (3)	0.3450 (9)	0.045 (2)
C2	0.1451 (4)	0.2600 (3)	0.2601 (11)	0.063 (3)
C3	0.1729 (4)	0.2370 (4)	0.1815 (12)	0.074 (3)
H3	0.1939	0.2493	0.1253	0.089*
C4	0.1690 (5)	0.1956 (4)	0.1872 (11)	0.073 (3)
C5	0.1366 (3)	0.1763 (3)	0.2602 (10)	0.058 (3)
H5	0.1323	0.1483	0.2543	0.070*
C6	0.1091 (3)	0.1988 (3)	0.3463 (9)	0.048 (2)
C7	0.0781 (3)	0.1767 (3)	0.4321 (10)	0.049 (2)
H7	0.0756	0.1487	0.4238	0.059*
C8	0.0263 (4)	0.1681 (3)	0.6026 (11)	0.062 (3)
H8A	0.0481	0.1606	0.6690	0.075*
H8B	0.0142	0.1435	0.5642	0.075*
C9	−0.0180 (3)	0.1932 (3)	0.6464 (11)	0.059 (3)
H9A	−0.0444	0.1944	0.5857	0.071*
H9B	−0.0323	0.1813	0.7183	0.071*
C10	0.0955 (3)	0.3013 (3)	0.7461 (9)	0.046 (2)
C11	0.1330 (4)	0.3063 (3)	0.8315 (10)	0.059 (3)
C12	0.1339 (4)	0.3363 (3)	0.9175 (8)	0.052 (2)
H12	0.1592	0.3375	0.9758	0.062*
C13	0.0937 (4)	0.3656 (3)	0.9116 (10)	0.061 (3)
C14	0.0584 (3)	0.3634 (3)	0.8245 (9)	0.051 (2)
H14	0.0334	0.3834	0.8202	0.061*
C15	0.0581 (3)	0.3327 (3)	0.7422 (8)	0.045 (2)
C16	0.0194 (3)	0.3353 (3)	0.6506 (9)	0.046 (2)
H16	−0.0019	0.3579	0.6536	0.055*
C17	−0.0327 (4)	0.3176 (3)	0.4826 (10)	0.063 (3)
H17A	−0.0575	0.3347	0.5224	0.075*
H17B	−0.0207	0.3317	0.4117	0.075*
C18	−0.0569 (3)	0.2783 (3)	0.4473 (10)	0.057 (3)
H18A	−0.0751	0.2671	0.5153	0.069*
H18B	−0.0813	0.2831	0.3838	0.069*
N1	0.0543 (2)	0.1932 (2)	0.5168 (8)	0.0453 (17)
N2	0.0111 (3)	0.3096 (2)	0.5650 (7)	0.0466 (17)
O1	0.0876 (2)	0.26594 (18)	0.4206 (6)	0.0494 (15)
O2	0.0007 (2)	0.23280 (19)	0.6711 (6)	0.0564 (17)
O3	0.0963 (3)	0.2718 (2)	0.6697 (7)	0.0630 (19)
O4	−0.0208 (2)	0.2505 (2)	0.4085 (6)	0.0536 (16)
O5	−0.0213 (4)	0.4752 (5)	0.7733 (17)	0.081 (4)	0.50
H5A	−0.0383	0.4657	0.7150	0.121*	0.50
C19	0.0282 (5)	0.4748 (6)	0.759 (2)	0.068 (6)	0.50
H19A	0.0378	0.4953	0.7022	0.102*	0.50
H19B	0.0388	0.4487	0.7305	0.102*	0.50
H19C	0.0444	0.4803	0.8346	0.102*	0.50
O1W	−0.0549 (6)	0.4146 (5)	0.7965 (13)	0.172 (6)
H1WA	−0.0572	0.4403	0.8021	0.257*
H1WB	−0.0857	0.4111	0.7760	0.257*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0489 (6)	0.0388 (7)	0.0378 (7)	0.0059 (6)	−0.0051 (6)	−0.0072 (6)
Br1	0.0789 (7)	0.0729 (8)	0.0871 (9)	−0.0109 (6)	0.0038 (6)	0.0148 (7)
Br2	0.0957 (9)	0.1375 (13)	0.0739 (10)	0.0320 (8)	0.0151 (7)	−0.0354 (9)
Br3	0.0814 (7)	0.0637 (7)	0.0855 (9)	0.0061 (6)	−0.0389 (6)	−0.0095 (6)
Br4	0.0996 (8)	0.0844 (8)	0.0886 (11)	−0.0175 (7)	0.0070 (7)	−0.0550 (8)
C1	0.040 (4)	0.055 (6)	0.041 (5)	0.003 (4)	−0.003 (4)	−0.017 (5)
C2	0.080 (7)	0.062 (6)	0.046 (7)	0.002 (5)	−0.002 (5)	0.004 (5)
C3	0.061 (6)	0.108 (11)	0.054 (8)	−0.008 (6)	−0.013 (5)	0.003 (7)
C4	0.085 (8)	0.092 (9)	0.043 (7)	0.018 (7)	−0.013 (6)	−0.026 (6)
C5	0.050 (5)	0.075 (7)	0.049 (6)	0.012 (5)	0.008 (5)	−0.020 (6)
C6	0.035 (4)	0.060 (6)	0.050 (6)	0.001 (4)	0.003 (4)	−0.013 (5)
C7	0.056 (5)	0.029 (5)	0.063 (7)	0.008 (4)	−0.003 (5)	−0.011 (5)
C8	0.069 (6)	0.059 (6)	0.059 (7)	−0.012 (5)	0.002 (5)	0.003 (5)
C9	0.048 (5)	0.062 (7)	0.067 (7)	−0.008 (5)	−0.004 (5)	0.010 (5)
C10	0.050 (5)	0.032 (5)	0.055 (6)	−0.006 (4)	−0.001 (4)	−0.001 (4)
C11	0.077 (6)	0.041 (5)	0.058 (7)	−0.005 (4)	−0.012 (5)	−0.002 (5)
C12	0.065 (6)	0.052 (6)	0.039 (6)	−0.018 (5)	−0.007 (4)	−0.012 (4)
C13	0.064 (6)	0.068 (7)	0.050 (6)	−0.019 (5)	0.010 (5)	−0.028 (5)
C14	0.056 (5)	0.047 (5)	0.050 (6)	0.006 (4)	0.009 (4)	−0.011 (4)
C15	0.054 (5)	0.037 (5)	0.043 (6)	−0.012 (4)	0.009 (4)	−0.010 (4)
C16	0.058 (5)	0.034 (5)	0.045 (6)	0.006 (4)	0.000 (4)	0.003 (4)
C17	0.072 (6)	0.061 (7)	0.056 (7)	0.023 (5)	−0.018 (5)	−0.003 (5)
C18	0.043 (5)	0.080 (7)	0.050 (6)	0.008 (5)	−0.002 (4)	0.001 (5)
N1	0.034 (3)	0.051 (4)	0.050 (5)	0.000 (3)	−0.005 (3)	−0.005 (4)
N2	0.054 (4)	0.044 (4)	0.042 (5)	0.009 (3)	−0.009 (3)	−0.004 (4)
O1	0.044 (3)	0.047 (4)	0.057 (4)	0.002 (3)	0.006 (3)	0.001 (3)
O2	0.071 (4)	0.055 (4)	0.043 (4)	0.008 (3)	−0.004 (3)	−0.005 (3)
O3	0.074 (4)	0.054 (4)	0.061 (5)	0.013 (3)	−0.020 (3)	−0.028 (4)
O4	0.049 (3)	0.057 (4)	0.055 (4)	0.012 (3)	−0.009 (3)	−0.007 (3)
O5	0.057 (7)	0.105 (10)	0.080 (11)	0.003 (7)	−0.002 (8)	0.013 (9)
C19	0.042 (9)	0.074 (11)	0.088 (14)	0.019 (8)	0.050 (9)	0.032 (11)
O1W	0.214 (12)	0.196 (12)	0.105 (11)	−0.067 (10)	0.020 (9)	0.009 (9)

Geometric parameters (Å, º)

Mn1—O2	1.871 (7)	C9—H9B	0.9700
Mn1—O1	1.906 (7)	C10—O3	1.292 (11)
Mn1—N1	1.984 (7)	C10—C11	1.381 (14)
Mn1—O3	2.027 (7)	C10—C15	1.426 (12)
Mn1—N2	2.094 (7)	C11—C12	1.377 (14)
Mn1—O4	2.324 (6)	C12—C13	1.432 (14)
Br1—C2	1.888 (10)	C12—H12	0.9300
Br2—C4	1.931 (11)	C13—C14	1.348 (14)
Br3—C11	1.905 (10)	C14—C15	1.367 (13)
Br4—C13	1.900 (9)	C14—H14	0.9300
C1—O1	1.326 (10)	C15—C16	1.446 (13)
C1—C6	1.415 (13)	C16—N2	1.295 (12)
C1—C2	1.419 (15)	C16—H16	0.9300
C2—C3	1.370 (17)	C17—C18	1.494 (14)
C3—C4	1.368 (18)	C17—N2	1.496 (12)
C3—H3	0.9300	C17—H17A	0.9700
C4—C5	1.339 (17)	C17—H17B	0.9700
C5—C6	1.414 (13)	C18—O4	1.388 (11)
C5—H5	0.9300	C18—H18A	0.9700
C6—C7	1.453 (14)	C18—H18B	0.9700
C7—N1	1.257 (12)	O5—C19	1.312 (9)
C7—H7	0.9300	O5—H5A	0.8501
C8—N1	1.464 (13)	C19—H19A	0.9600
C8—C9	1.508 (14)	C19—H19B	0.9600
C8—H8A	0.9700	C19—H19C	0.9600
C8—H8B	0.9700	O1W—H1WA	0.8500
C9—O2	1.419 (11)	O1W—H1WB	0.8500
C9—H9A	0.9700
O2—Mn1—O1	174.3 (3)	H9A—C9—H9B	108.5
O2—Mn1—N1	83.9 (3)	O3—C10—C11	122.4 (8)
O1—Mn1—N1	90.6 (3)	O3—C10—C15	122.2 (8)
O2—Mn1—O3	92.7 (3)	C11—C10—C15	115.2 (8)
O1—Mn1—O3	90.6 (3)	C12—C11—C10	125.5 (9)
N1—Mn1—O3	110.2 (3)	C12—C11—Br3	115.6 (8)
O2—Mn1—N2	89.9 (3)	C10—C11—Br3	118.7 (7)
O1—Mn1—N2	95.0 (3)	C11—C12—C13	115.9 (8)
N1—Mn1—N2	162.6 (3)	C11—C12—H12	122.0
O3—Mn1—N2	86.2 (3)	C13—C12—H12	122.0
O2—Mn1—O4	92.3 (3)	C14—C13—C12	120.4 (8)
O1—Mn1—O4	85.9 (3)	C14—C13—Br4	122.0 (8)
N1—Mn1—O4	87.3 (3)	C12—C13—Br4	117.6 (7)
O3—Mn1—O4	162.2 (3)	C13—C14—C15	121.9 (9)
N2—Mn1—O4	76.7 (3)	C13—C14—H14	119.0
O1—C1—C6	124.4 (9)	C15—C14—H14	119.0
O1—C1—C2	117.9 (8)	C14—C15—C10	120.8 (8)
C6—C1—C2	117.6 (8)	C14—C15—C16	115.7 (8)
C3—C2—C1	121.4 (10)	C10—C15—C16	123.5 (8)
C3—C2—Br1	119.9 (9)	N2—C16—C15	126.9 (8)
C1—C2—Br1	118.7 (8)	N2—C16—H16	116.5
C4—C3—C2	118.7 (12)	C15—C16—H16	116.5
C4—C3—H3	120.6	C18—C17—N2	109.8 (7)
C2—C3—H3	120.6	C18—C17—H17A	109.7
C5—C4—C3	123.2 (11)	N2—C17—H17A	109.7
C5—C4—Br2	120.1 (9)	C18—C17—H17B	109.7
C3—C4—Br2	116.6 (10)	N2—C17—H17B	109.7
C4—C5—C6	119.4 (10)	H17A—C17—H17B	108.2
C4—C5—H5	120.3	O4—C18—C17	111.2 (7)
C6—C5—H5	120.3	O4—C18—H18A	109.4
C5—C6—C1	119.2 (9)	C17—C18—H18A	109.4
C5—C6—C7	118.3 (9)	O4—C18—H18B	109.4
C1—C6—C7	122.5 (8)	C17—C18—H18B	109.4
N1—C7—C6	124.0 (8)	H18A—C18—H18B	108.0
N1—C7—H7	118.0	C7—N1—C8	119.9 (8)
C6—C7—H7	118.0	C7—N1—Mn1	129.1 (7)
N1—C8—C9	107.0 (8)	C8—N1—Mn1	110.8 (6)
N1—C8—H8A	110.3	C16—N2—C17	118.0 (7)
C9—C8—H8A	110.3	C16—N2—Mn1	125.6 (6)
N1—C8—H8B	110.3	C17—N2—Mn1	115.3 (6)
C9—C8—H8B	110.3	C1—O1—Mn1	129.1 (6)
H8A—C8—H8B	108.6	C9—O2—Mn1	112.2 (6)
O2—C9—C8	107.3 (7)	C10—O3—Mn1	131.9 (6)
O2—C9—H9A	110.3	C18—O4—Mn1	105.9 (5)
C8—C9—H9A	110.3	C19—O5—H5A	115.3
O2—C9—H9B	110.3	H1WA—O1W—H1WB	94.9
C8—C9—H9B	110.3

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···Br1^i	0.85	3.04	3.893 (18)	179
O1W—H1WA···O5	0.85	1.52	2.19 (2)	134

Symmetry code: (i) x−1/4, −y+3/4, z+1/4.