Crystal structures of four dimeric manganese(II) bromide coordination complexes with various derivatives of pyridine N-oxide

Lynch, S.; Lynch, G.; Lynch, W.E.; Padgett, C.W.

doi:10.1107/S2056989019010557

Crystal structures of four dimeric manganese(II) bromide coordination complexes with various derivatives of pyridine N-oxide

S. Lynch, G. Lynch, W. E. Lynch and C. W. Padgett

The synthesis and crystal structures of four dimeric complexes composed of manganese(II) dibromide, a pyridine N-oxide and solvent molecules are reported. The pyridine N--oxide, 2-methylpyridine N-oxide, 3-methylpyridine N-oxide, and 4-methylpyridine N-oxide complexes all form similar structures with slight differences owing to the substituent group effects.

Keywords: crystal structure; manganese(II) bromide; pyridine N-oxide ligand; complex; offset π-stacking; hydrogen bonding.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989019010557/su5505sup1.cif Contains datablocks Global, II, III, IV, I
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989019010557/su5505Isup2.hkl Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989019010557/su5505IIsup3.hkl Contains datablock II
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989019010557/su5505IIIsup4.hkl Contains datablock III
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989019010557/su5505IVsup5.hkl Contains datablock IV

CCDC references: 1942967; 1942966; 1942965; 1942964

checkCIF report

Key indicators

Structure: I

Single-crystal X-ray study
T = 170 K
Mean (C-C) = 0.007 Å
R factor = 0.043
wR factor = 0.110
Data-to-parameter ratio = 19.2

Structure: II

Single-crystal X-ray study
T = 170 K
Mean (C-C) = 0.007 Å
R factor = 0.037
wR factor = 0.080
Data-to-parameter ratio = 18.5

Structure: III

Single-crystal X-ray study
T = 170 K
Mean (C-C) = 0.008 Å
R factor = 0.040
wR factor = 0.098
Data-to-parameter ratio = 19.2

Structure: IV

Single-crystal X-ray study
T = 170 K
Mean (C-C) = 0.006 Å
R factor = 0.043
wR factor = 0.112
Data-to-parameter ratio = 20.2

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level C
RINTA01_ALERT_3_C  The value of Rint is greater than 0.12
            Rint given   0.178
PLAT341_ALERT_3_C Low Bond Precision on  C-C Bonds ...............    0.00737 Ang.
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600         17 Report
PLAT978_ALERT_2_C Number C-C Bonds with Positive Residual Density.          0 Info

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          3 Note
PLAT020_ALERT_3_G The Value of Rint is Greater Than 0.12 .........      0.178 Report
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          1 Report
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Br1      --Mn1      .        5.2 s.u.
PLAT794_ALERT_5_G Tentative Bond Valency for Mn1       (II)      .       2.21 Info
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          2 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          7 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...         14 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   4 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   8 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 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
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check




Datablock: II


Alert level C
PLAT341_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0065 Ang.
PLAT411_ALERT_2_C Short Inter H...H Contact  H5       ..H9       .       2.14 Ang.
                                                1+x,1+y,1+z  =      1_666 Check
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      2.112 Check
PLAT978_ALERT_2_C Number C-C Bonds with Positive Residual Density.          0 Info

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          6 Note
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          2 Report
PLAT794_ALERT_5_G Tentative Bond Valency for Mn1       (II)      .       2.05 Info
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          4 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         12 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   4 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   5 ALERT level G = General information/check it is not something unexpected

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




Datablock: III



Alert level C
PLAT220_ALERT_2_C Non-Solvent  Resd 1  C   Ueq(max)/Ueq(min) Range        3.8 Ratio
PLAT222_ALERT_3_C Non-Solv.  Resd 1  H   Uiso(max)/Uiso(min) Range        4.9 Ratio
PLAT341_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0076 Ang.
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      2.744 Check
PLAT971_ALERT_2_C Check Calcd Resid. Dens.  0.92A   From Br1             1.63 eA-3
PLAT978_ALERT_2_C Number C-C Bonds with Positive Residual Density.          0 Info

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          3 Note
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          1 Report
PLAT180_ALERT_4_G Check Cell Rounding: # of Values Ending with 0 =          3 Note
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Br1      --Mn1      .        8.0 s.u.
PLAT794_ALERT_5_G Tentative Bond Valency for Mn1       (II)      .       2.22 Info
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          2 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          5 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   6 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   7 ALERT level G = General information/check it is not something unexpected

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




Datablock: IV


Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.22 Report
PLAT341_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0062 Ang.
PLAT971_ALERT_2_C Check Calcd Resid. Dens.  0.95A   From Br2             1.77 eA-3
PLAT971_ALERT_2_C Check Calcd Resid. Dens.  0.91A   From Br1             1.62 eA-3
PLAT978_ALERT_2_C Number C-C Bonds with Positive Residual Density.          0 Info

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          4 Note
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          1 Report
PLAT173_ALERT_4_G The CIF-Embedded .res File Contains DANG Records          2 Report
PLAT794_ALERT_5_G Tentative Bond Valency for Mn1       (II)      .       2.24 Info
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          3 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          2 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   5 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   6 ALERT level G = General information/check it is not something unexpected

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

Computing details top

For all structures, data collection: CrysAlis PRO (Rigaku Oxford Diffraction, 2018); cell refinement: CrysAlis PRO (Rigaku Oxford Diffraction, 2018); data reduction: CrysAlis PRO (Rigaku Oxford Diffraction, 2018); program(s) used to solve structure: ShelXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Bis(µ-pyridine N-oxide)bis[aquadibromido(pyridine N-oxide)manganese(II)] (I) top

Crystal data top

[Mn₂Br₄(C₅H₅NO)₄(H₂O)₂]	F(000) = 820
M_r = 845.95	D_x = 1.940 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.736 (4) Å	Cell parameters from 4250 reflections
b = 15.179 (7) Å	θ = 2.1–27.5°
c = 12.528 (6) Å	µ = 6.43 mm⁻¹
β = 100.055 (4)°	T = 170 K
V = 1448.5 (12) Å³	Prism, colorless
Z = 2	0.5 × 0.5 × 0.2 mm

Data collection top

Rigaku Mini template diffractometer	3305 independent reflections
Radiation source: Sealed Tube	3024 reflections with I > 2σ(I)
Graphite Monochromator monochromator	R_int = 0.178
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 2.1°
profile data from ω–scans	h = −10→10
Absorption correction: multi-scan (REQAB; Rigaku, 1998)	k = −19→19
T_min = 0.066, T_max = 0.114	l = −16→16
15117 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.043	w = 1/[σ²(F_o²) + (0.0191P)² + 0.4786P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.110	(Δ/σ)_max = 0.001
S = 1.13	Δρ_max = 1.43 e Å⁻³
3305 reflections	Δρ_min = −1.15 e Å⁻³
172 parameters	Extinction correction: (SHELXL-2018/1; Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
2 restraints	Extinction coefficient: 0.0140 (11)
Primary atom site location: dual

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	0.88172 (4)	0.48605 (2)	0.66632 (3)	0.02264 (14)
C1	0.4849 (5)	0.3093 (3)	0.3370 (3)	0.0303 (8)
H1	0.363028	0.310997	0.339833	0.036*
Mn1	0.54254 (7)	0.43050 (3)	0.61896 (4)	0.01589 (16)
O1	0.5247 (3)	0.43379 (14)	0.44408 (17)	0.0171 (5)
N1	0.5922 (4)	0.36998 (16)	0.3881 (2)	0.0160 (5)
Br2	0.61302 (5)	0.26431 (2)	0.63521 (3)	0.02396 (15)
N2	0.5951 (4)	0.4668 (2)	0.8619 (2)	0.0250 (6)
O2	0.4813 (4)	0.46894 (19)	0.7689 (2)	0.0296 (6)
C2	0.5520 (6)	0.2438 (3)	0.2796 (4)	0.0403 (10)
H2	0.476706	0.199462	0.243743	0.048*
C3	0.7280 (6)	0.2428 (3)	0.2744 (4)	0.0377 (10)
H3	0.774934	0.198354	0.234356	0.045*
O3	0.2446 (4)	0.40522 (18)	0.5691 (2)	0.0260 (6)
C4	0.8354 (6)	0.3068 (3)	0.3280 (4)	0.0440 (12)
H4	0.957332	0.307435	0.325343	0.053*
C5	0.7628 (5)	0.3702 (3)	0.3855 (4)	0.0339 (9)
H5	0.835724	0.414384	0.423704	0.041*
C6	0.6494 (6)	0.3886 (3)	0.9054 (3)	0.0385 (10)
H6	0.610967	0.335631	0.868308	0.046*
C7	0.7611 (8)	0.3855 (4)	1.0040 (4)	0.0570 (14)
H7	0.800377	0.330116	1.034421	0.068*
C8	0.8162 (7)	0.4620 (5)	1.0588 (4)	0.0627 (17)
H8	0.892059	0.460197	1.127146	0.075*
C9	0.7581 (8)	0.5413 (4)	1.0116 (4)	0.0600 (16)
H9	0.792711	0.594992	1.048066	0.072*
C10	0.6498 (7)	0.5426 (3)	0.9116 (4)	0.0396 (10)
H10	0.613977	0.597312	0.877878	0.048*
H3A	0.214 (6)	0.418 (3)	0.5042 (18)	0.037 (13)*
H3B	0.172 (5)	0.424 (3)	0.606 (4)	0.042 (14)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0170 (2)	0.0266 (2)	0.0235 (2)	−0.00262 (13)	0.00117 (15)	0.00210 (12)
C1	0.0210 (18)	0.030 (2)	0.038 (2)	−0.0009 (15)	−0.0002 (16)	−0.0156 (16)
Mn1	0.0175 (3)	0.0151 (3)	0.0155 (3)	0.00165 (18)	0.0039 (2)	0.00189 (17)
O1	0.0237 (12)	0.0126 (10)	0.0161 (10)	0.0056 (9)	0.0062 (9)	−0.0010 (8)
N1	0.0210 (14)	0.0101 (12)	0.0172 (12)	0.0016 (11)	0.0046 (11)	−0.0037 (10)
Br2	0.0256 (2)	0.0155 (2)	0.0302 (2)	0.00169 (13)	0.00347 (16)	0.00366 (12)
N2	0.0240 (16)	0.0354 (17)	0.0165 (13)	0.0059 (13)	0.0064 (12)	−0.0019 (12)
O2	0.0298 (15)	0.0420 (16)	0.0175 (11)	0.0119 (12)	0.0050 (11)	0.0009 (11)
C2	0.032 (2)	0.031 (2)	0.054 (3)	0.0001 (18)	−0.0029 (19)	−0.025 (2)
C3	0.038 (2)	0.029 (2)	0.047 (2)	0.0010 (18)	0.012 (2)	−0.0200 (18)
O3	0.0220 (13)	0.0305 (14)	0.0263 (13)	0.0033 (11)	0.0063 (11)	0.0089 (11)
C4	0.026 (2)	0.035 (2)	0.077 (3)	−0.0021 (18)	0.025 (2)	−0.023 (2)
C5	0.026 (2)	0.0254 (19)	0.053 (2)	−0.0056 (16)	0.0161 (19)	−0.0176 (17)
C6	0.044 (3)	0.039 (2)	0.030 (2)	0.016 (2)	0.0008 (18)	0.0047 (17)
C7	0.053 (3)	0.084 (4)	0.032 (2)	0.029 (3)	−0.001 (2)	0.012 (2)
C8	0.032 (3)	0.127 (5)	0.027 (2)	0.003 (3)	−0.001 (2)	−0.013 (3)
C9	0.055 (3)	0.085 (4)	0.043 (3)	−0.030 (3)	0.016 (3)	−0.031 (3)
C10	0.047 (3)	0.038 (2)	0.036 (2)	−0.011 (2)	0.014 (2)	−0.0076 (18)

Geometric parameters (Å, º) top

Mn1—Br1	2.7212 (13)	C3—H3	0.9500
C1—H1	0.9500	C3—C4	1.375 (6)
C1—N1	1.327 (5)	O3—H3A	0.829 (19)
C1—C2	1.381 (5)	O3—H3B	0.829 (19)
Mn1—O1	2.172 (2)	C4—H4	0.9500
Mn1—O1ⁱ	2.235 (2)	C4—C5	1.379 (5)
Mn1—Br2	2.5813 (13)	C5—H5	0.9500
Mn1—O2	2.099 (3)	C6—H6	0.9500
Mn1—O3	2.312 (3)	C6—C7	1.380 (7)
O1—N1	1.353 (3)	C7—H7	0.9500
N1—C5	1.326 (5)	C7—C8	1.378 (8)
N2—O2	1.332 (4)	C8—H8	0.9500
N2—C6	1.342 (5)	C8—C9	1.381 (9)
N2—C10	1.342 (5)	C9—H9	0.9500
C2—H2	0.9500	C9—C10	1.381 (8)
C2—C3	1.374 (6)	C10—H10	0.9500

N1—C1—H1	120.3	C3—C2—C1	119.9 (4)
N1—C1—C2	119.4 (4)	C3—C2—H2	120.1
C2—C1—H1	120.3	C2—C3—H3	120.4
O1—Mn1—Br1	95.84 (7)	C2—C3—C4	119.2 (3)
O1ⁱ—Mn1—Br1	87.00 (7)	C4—C3—H3	120.4
O1—Mn1—O1ⁱ	69.66 (9)	Mn1—O3—H3A	109 (3)
O1—Mn1—Br2	94.44 (6)	Mn1—O3—H3B	122 (4)
O1ⁱ—Mn1—Br2	164.07 (6)	H3A—O3—H3B	111 (5)
O1ⁱ—Mn1—O3	84.14 (10)	C3—C4—H4	120.6
O1—Mn1—O3	81.19 (9)	C3—C4—C5	118.8 (4)
Br2—Mn1—Br1	95.93 (3)	C5—C4—H4	120.6
O2—Mn1—Br1	94.50 (9)	N1—C5—C4	120.6 (4)
O2—Mn1—O1ⁱ	89.15 (10)	N1—C5—H5	119.7
O2—Mn1—O1	155.81 (10)	C4—C5—H5	119.7
O2—Mn1—Br2	106.17 (8)	N2—C6—H6	120.1
O2—Mn1—O3	85.28 (11)	N2—C6—C7	119.8 (5)
O3—Mn1—Br1	171.14 (7)	C7—C6—H6	120.1
O3—Mn1—Br2	92.63 (7)	C6—C7—H7	119.7
Mn1—O1—Mn1ⁱ	110.34 (9)	C8—C7—C6	120.5 (5)
N1—O1—Mn1	122.99 (18)	C8—C7—H7	119.7
N1—O1—Mn1ⁱ	124.32 (17)	C7—C8—H8	120.9
C1—N1—O1	118.8 (3)	C7—C8—C9	118.2 (5)
C5—N1—C1	122.1 (3)	C9—C8—H8	120.9
C5—N1—O1	119.1 (3)	C8—C9—H9	119.9
O2—N2—C6	119.2 (3)	C10—C9—C8	120.1 (5)
O2—N2—C10	119.4 (4)	C10—C9—H9	119.9
C6—N2—C10	121.3 (4)	N2—C10—C9	120.0 (5)
N2—O2—Mn1	123.9 (2)	N2—C10—H10	120.0
C1—C2—H2	120.1	C9—C10—H10	120.0

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···Br1ⁱ	0.83 (2)	2.58 (2)	3.372 (3)	159 (4)
O3—H3B···Br1ⁱⁱ	0.84 (4)	2.66 (4)	3.473 (4)	163 (4)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, y, z.

Bis(µ-2-methylpyridine N-oxide)bis[diaquadibromidomanganese(II)]–2-methylpyridine N-oxide (1/2) (II) top

Crystal data top

[Mn₂Br₄(C₆H₇NO)₂(H₂O)₄]·2C₆H₇NO	Z = 1
M_r = 938.09	F(000) = 462
Triclinic, P1	D_x = 1.858 Mg m⁻³
a = 8.9560 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.7922 (9) Å	Cell parameters from 4291 reflections
c = 10.2945 (8) Å	θ = 2.3–33.2°
α = 110.048 (8)°	µ = 5.57 mm⁻¹
β = 90.336 (7)°	T = 170 K
γ = 98.052 (7)°	Block, clear light yellow
V = 838.34 (13) Å³	0.2 × 0.2 × 0.1 mm

Data collection top

Rigaku XtaLAB mini diffractometer	3838 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	2931 reflections with I > 2σ(I)
Graphite Monochromator monochromator	R_int = 0.053
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 2.1°
profile data from ω–scans	h = −11→11
Absorption correction: multi-scan (CrysAlisPro; Rigaku Oxford Diffraction, 2018)	k = −12→12
T_min = 0.580, T_max = 1.000	l = −13→13
8918 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.080	w = 1/[σ²(F_o²) + (0.0319P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.001
3838 reflections	Δρ_max = 0.72 e Å⁻³
208 parameters	Δρ_min = −0.61 e Å⁻³
4 restraints

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.97900 (4)	0.80035 (4)	0.74971 (4)	0.02737 (11)
O1	1.0009 (3)	0.4219 (3)	0.5880 (2)	0.0216 (5)
C1	0.9673 (4)	0.2520 (4)	0.7046 (4)	0.0271 (8)
Mn1	0.82268 (6)	0.55061 (6)	0.56887 (5)	0.02123 (13)
N1	1.0302 (3)	0.3845 (3)	0.6999 (3)	0.0219 (6)
Br2	0.62884 (4)	0.49697 (4)	0.74319 (4)	0.03065 (11)
C2	1.0052 (4)	0.2179 (4)	0.8211 (4)	0.0304 (9)
H2	0.962787	0.125920	0.827065	0.037*
O3	0.7281 (3)	0.3472 (3)	0.3927 (3)	0.0267 (6)
H3A	0.647 (3)	0.288 (4)	0.388 (4)	0.043 (13)*
H3B	0.799 (3)	0.297 (4)	0.359 (4)	0.036 (12)*
C3	1.1028 (5)	0.3150 (4)	0.9273 (4)	0.0329 (9)
H3	1.127202	0.290351	1.005596	0.039*
C4	1.1643 (5)	0.4487 (5)	0.9180 (4)	0.0368 (10)
H4	1.231315	0.517477	0.990012	0.044*
O4	0.6790 (3)	0.6595 (3)	0.4807 (3)	0.0268 (6)
H4A	0.642 (6)	0.726 (4)	0.542 (4)	0.09 (2)*
H4B	0.614 (5)	0.614 (6)	0.417 (4)	0.10 (2)*
C5	1.1269 (4)	0.4809 (4)	0.8023 (4)	0.0320 (9)
H5	1.169778	0.571996	0.794612	0.038*
C6	0.8633 (5)	0.1536 (4)	0.5885 (4)	0.0377 (10)
H6A	0.769395	0.194740	0.589890	0.057*
H6B	0.840725	0.056545	0.597618	0.057*
H6C	0.910470	0.144060	0.500794	0.057*
N2	0.4507 (3)	0.0303 (3)	0.2438 (3)	0.0262 (7)
O2	0.4865 (3)	0.1344 (3)	0.3682 (3)	0.0288 (6)
C7	0.5133 (4)	−0.0960 (4)	0.2104 (4)	0.0292 (9)
C8	0.4748 (6)	−0.2028 (5)	0.0806 (4)	0.0455 (12)
H8	0.518213	−0.290783	0.054919	0.055*
C9	0.3744 (6)	−0.1829 (6)	−0.0117 (5)	0.0544 (14)
H9	0.349499	−0.256046	−0.100515	0.065*
C10	0.3105 (5)	−0.0539 (6)	0.0278 (5)	0.0516 (13)
H10	0.238985	−0.039227	−0.032830	0.062*
C11	0.3517 (4)	0.0509 (5)	0.1542 (4)	0.0378 (10)
H11	0.310341	0.140125	0.180201	0.045*
C12	0.6228 (5)	−0.1073 (4)	0.3143 (4)	0.0383 (10)
H12A	0.713697	−0.035107	0.324504	0.057*
H12B	0.650204	−0.206492	0.283156	0.057*
H12C	0.576598	−0.087782	0.403703	0.057*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0266 (2)	0.0235 (2)	0.0261 (2)	0.00076 (15)	0.00103 (15)	0.00222 (15)
O1	0.0243 (13)	0.0249 (13)	0.0179 (12)	0.0027 (11)	−0.0006 (10)	0.0110 (10)
C1	0.0272 (19)	0.024 (2)	0.028 (2)	0.0024 (16)	0.0022 (16)	0.0072 (16)
Mn1	0.0213 (3)	0.0217 (3)	0.0198 (3)	0.0016 (2)	−0.0009 (2)	0.0067 (2)
N1	0.0236 (15)	0.0223 (16)	0.0203 (15)	0.0014 (13)	0.0008 (13)	0.0088 (13)
Br2	0.0294 (2)	0.0379 (2)	0.0225 (2)	−0.00298 (17)	0.00138 (16)	0.01083 (17)
C2	0.040 (2)	0.026 (2)	0.031 (2)	0.0067 (18)	0.0077 (18)	0.0170 (18)
O3	0.0247 (14)	0.0246 (14)	0.0269 (14)	−0.0001 (12)	0.0010 (12)	0.0055 (12)
C3	0.040 (2)	0.039 (2)	0.027 (2)	0.0095 (19)	0.0009 (18)	0.0198 (19)
C4	0.041 (2)	0.041 (2)	0.025 (2)	−0.002 (2)	−0.0076 (18)	0.0103 (19)
O4	0.0305 (15)	0.0269 (15)	0.0228 (15)	0.0069 (13)	−0.0031 (13)	0.0074 (12)
C5	0.035 (2)	0.028 (2)	0.030 (2)	−0.0046 (18)	−0.0073 (18)	0.0099 (17)
C6	0.046 (3)	0.029 (2)	0.035 (2)	−0.0069 (19)	−0.003 (2)	0.0126 (19)
N2	0.0229 (16)	0.0293 (18)	0.0237 (16)	−0.0054 (14)	0.0025 (13)	0.0096 (14)
O2	0.0316 (14)	0.0243 (14)	0.0255 (14)	0.0036 (12)	0.0051 (12)	0.0024 (11)
C7	0.038 (2)	0.024 (2)	0.0230 (19)	−0.0034 (17)	0.0049 (17)	0.0080 (16)
C8	0.068 (3)	0.028 (2)	0.030 (2)	−0.012 (2)	0.005 (2)	0.0046 (19)
C9	0.062 (3)	0.057 (3)	0.027 (2)	−0.036 (3)	−0.005 (2)	0.009 (2)
C10	0.032 (2)	0.088 (4)	0.036 (3)	−0.017 (3)	−0.008 (2)	0.033 (3)
C11	0.0185 (19)	0.059 (3)	0.042 (3)	0.0064 (19)	0.0035 (18)	0.024 (2)
C12	0.054 (3)	0.035 (2)	0.030 (2)	0.018 (2)	0.007 (2)	0.0113 (19)

Geometric parameters (Å, º) top

Mn1—Br1	2.7009 (7)	O4—H4B	0.83 (2)
Mn1—O1	2.214 (2)	C5—H5	0.9500
O1—Mn1ⁱ	2.321 (2)	C6—H6A	0.9800
O1—N1	1.358 (3)	C6—H6B	0.9800
C1—N1	1.357 (4)	C6—H6C	0.9800
C1—C2	1.402 (5)	N2—O2	1.338 (4)
C1—C6	1.473 (5)	N2—C7	1.366 (5)
Mn1—Br2	2.6340 (7)	N2—C11	1.359 (5)
Mn1—O3	2.237 (3)	C7—C8	1.390 (5)
Mn1—O4	2.157 (3)	C7—C12	1.490 (5)
N1—C5	1.353 (5)	C8—H8	0.9500
C2—H2	0.9500	C8—C9	1.384 (7)
C2—C3	1.381 (5)	C9—H9	0.9500
O3—H3A	0.852 (19)	C9—C10	1.394 (7)
O3—H3B	0.857 (19)	C10—H10	0.9500
C3—H3	0.9500	C10—C11	1.362 (6)
C3—C4	1.383 (5)	C11—H11	0.9500
C4—H4	0.9500	C12—H12A	0.9800
C4—C5	1.382 (5)	C12—H12B	0.9800
O4—H4A	0.846 (19)	C12—H12C	0.9800

O1—Mn1—O1ⁱ	74.40 (9)	Mn1—O4—H4A	112 (4)
Mn1—O1—Mn1ⁱ	105.60 (9)	Mn1—O4—H4B	123 (4)
N1—O1—Mn1	125.53 (19)	H4A—O4—H4B	110 (5)
N1—O1—Mn1ⁱ	124.62 (18)	N1—C5—C4	121.0 (3)
N1—C1—C2	117.5 (3)	N1—C5—H5	119.5
N1—C1—C6	118.5 (3)	C4—C5—H5	119.5
C2—C1—C6	124.1 (3)	C1—C6—H6A	109.5
O1—Mn1—Br1	91.54 (6)	C1—C6—H6B	109.5
O1ⁱ—Mn1—Br1	85.90 (6)	C1—C6—H6C	109.5
O1—Mn1—Br2	101.36 (6)	H6A—C6—H6B	109.5
O1ⁱ—Mn1—Br2	175.09 (6)	H6A—C6—H6C	109.5
O1—Mn1—O3	84.60 (9)	H6B—C6—H6C	109.5
Br2—Mn1—Br1	96.79 (2)	O2—N2—C7	119.0 (3)
O3—Mn1—Br1	169.21 (8)	O2—N2—C11	119.7 (3)
O3—Mn1—O1ⁱ	83.36 (9)	C11—N2—C7	121.3 (3)
O3—Mn1—Br2	93.85 (7)	N2—C7—C8	118.2 (4)
O4—Mn1—Br1	95.42 (8)	N2—C7—C12	117.4 (3)
O4—Mn1—O1ⁱ	87.70 (9)	C8—C7—C12	124.4 (4)
O4—Mn1—O1	160.29 (10)	C7—C8—H8	119.5
O4—Mn1—Br2	96.11 (8)	C9—C8—C7	121.1 (5)
O4—Mn1—O3	85.19 (10)	C9—C8—H8	119.5
C1—N1—O1	120.1 (3)	C8—C9—H9	120.5
C5—N1—O1	117.8 (3)	C8—C9—C10	118.9 (4)
C5—N1—C1	122.0 (3)	C10—C9—H9	120.5
C1—C2—H2	119.2	C9—C10—H10	120.4
C3—C2—C1	121.5 (3)	C11—C10—C9	119.3 (4)
C3—C2—H2	119.2	C11—C10—H10	120.4
Mn1—O3—H3A	128 (3)	N2—C11—C10	121.2 (4)
Mn1—O3—H3B	110 (3)	N2—C11—H11	119.4
H3A—O3—H3B	109 (4)	C10—C11—H11	119.4
C2—C3—H3	120.5	C7—C12—H12A	109.5
C2—C3—C4	119.0 (3)	C7—C12—H12B	109.5
C4—C3—H3	120.5	C7—C12—H12C	109.5
C3—C4—H4	120.5	H12A—C12—H12B	109.5
C5—C4—C3	119.0 (4)	H12A—C12—H12C	109.5
C5—C4—H4	120.5	H12B—C12—H12C	109.5

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O2	0.85 (2)	1.89 (2)	2.731 (4)	171 (4)
O3—H3B···Br1ⁱ	0.86 (2)	2.44 (2)	3.282 (3)	168 (4)
O4—H4A···O2ⁱⁱ	0.85 (2)	1.91 (3)	2.721 (4)	161 (5)
O4—H4B···Br2ⁱⁱ	0.83 (4)	2.59 (4)	3.403 (3)	167 (4)

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+1, −z+1.

Bis(µ-3-methylpyridine N-oxide)bis[aquadibromido(3-methylpyridine N-oxide)manganese(II)] (III) top

Crystal data top

[Mn₂Br₄(C₆H₇NO)₄(H₂O)₂]	Z = 1
M_r = 902.05	F(000) = 442
Triclinic, P1	D_x = 1.859 Mg m⁻³
a = 7.6354 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.9700 (8) Å	Cell parameters from 4991 reflections
c = 11.898 (1) Å	θ = 2.2–33.1°
α = 111.980 (7)°	µ = 5.79 mm⁻¹
β = 100.360 (6)°	T = 170 K
γ = 97.737 (6)°	Plate, clear light yellow
V = 805.71 (12) Å³	0.45 × 0.4 × 0.2 mm

Data collection top

Rigaku XtaLAB mini diffractometer	3672 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	2875 reflections with I > 2σ(I)
Graphite Monochromator monochromator	R_int = 0.036
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 1.9°
profile data from ω–scans	h = −9→9
Absorption correction: multi-scan (CrysAlisPro; Rigaku Oxford Diffraction, 2018)	k = −12→12
T_min = 0.319, T_max = 1.000	l = −15→15
8460 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.098	w = 1/[σ²(F_o²) + (0.0461P)² + 0.5922P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
3672 reflections	Δρ_max = 1.66 e Å⁻³
191 parameters	Δρ_min = −0.84 e Å⁻³
2 restraints

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.36280 (5)	0.42105 (5)	0.13651 (4)	0.03458 (13)
C1	0.4906 (7)	0.7816 (7)	0.4116 (5)	0.0544 (14)
H1	0.509132	0.827435	0.356286	0.065*
N1	0.3196 (5)	0.7177 (4)	0.4046 (3)	0.0383 (9)
Mn1	0.04801 (8)	0.51611 (7)	0.16098 (5)	0.02659 (16)
O1	0.1816 (4)	0.7175 (4)	0.3187 (3)	0.0418 (8)
O2	0.0827 (3)	0.6326 (3)	0.0380 (3)	0.0295 (6)
C2	0.6381 (7)	0.7822 (7)	0.4963 (5)	0.0606 (16)
Br2	−0.07392 (6)	0.33641 (5)	0.25163 (4)	0.03571 (14)
N2	0.1876 (4)	0.7681 (4)	0.0757 (3)	0.0254 (7)
C3	0.6062 (7)	0.7148 (6)	0.5770 (5)	0.0520 (13)
H3	0.705412	0.710037	0.635284	0.062*
O3	−0.2115 (4)	0.5986 (4)	0.1560 (3)	0.0360 (7)
H3A	−0.304 (4)	0.546 (5)	0.159 (4)	0.045 (15)*
H3B	−0.237 (7)	0.594 (6)	0.082 (3)	0.065 (18)*
C4	0.4293 (7)	0.6553 (6)	0.5712 (5)	0.0489 (12)
H4	0.406617	0.612501	0.627790	0.059*
C5	0.2857 (6)	0.6573 (5)	0.4846 (4)	0.0391 (10)
H5	0.163976	0.616659	0.481113	0.047*
C6	0.8283 (9)	0.8554 (11)	0.5025 (7)	0.110 (3)
H6A	0.848206	0.962978	0.548807	0.165*
H6B	0.841882	0.833305	0.417405	0.165*
H6C	0.918146	0.817490	0.545184	0.165*
C7	0.3693 (5)	0.7876 (4)	0.1021 (4)	0.0287 (9)
H7	0.422698	0.704972	0.095217	0.034*
C8	0.4801 (5)	0.9247 (5)	0.1391 (4)	0.0317 (9)
C9	0.3993 (6)	1.0418 (5)	0.1454 (4)	0.0369 (10)
H9	0.472406	1.136963	0.166642	0.044*
C10	0.2119 (6)	1.0206 (5)	0.1206 (5)	0.0425 (11)
H10	0.155519	1.101679	0.127690	0.051*
C11	0.1069 (6)	0.8811 (5)	0.0856 (4)	0.0376 (10)
H11	−0.022312	0.865462	0.068630	0.045*
C12	0.6838 (6)	0.9463 (6)	0.1743 (6)	0.0583 (15)
H12A	0.727982	0.988271	0.265702	0.087*
H12B	0.739282	1.014307	0.142149	0.087*
H12C	0.717356	0.850553	0.138142	0.087*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0214 (2)	0.0436 (3)	0.0499 (3)	0.00744 (18)	0.00730 (17)	0.0319 (2)
C1	0.044 (3)	0.076 (4)	0.044 (3)	−0.004 (3)	0.009 (2)	0.031 (3)
N1	0.036 (2)	0.043 (2)	0.032 (2)	0.0035 (18)	0.0039 (16)	0.0153 (18)
Mn1	0.0209 (3)	0.0312 (3)	0.0304 (3)	−0.0003 (2)	0.0023 (2)	0.0195 (3)
O1	0.0405 (18)	0.0424 (19)	0.0391 (18)	0.0021 (15)	−0.0031 (14)	0.0214 (16)
O2	0.0230 (13)	0.0309 (15)	0.0352 (16)	−0.0048 (12)	0.0013 (11)	0.0207 (13)
C2	0.041 (3)	0.084 (4)	0.044 (3)	0.003 (3)	0.006 (2)	0.017 (3)
Br2	0.0330 (2)	0.0405 (3)	0.0419 (3)	0.00105 (19)	0.00990 (18)	0.0280 (2)
N2	0.0225 (16)	0.0287 (18)	0.0282 (17)	0.0018 (14)	0.0054 (13)	0.0169 (15)
C3	0.046 (3)	0.064 (4)	0.035 (3)	0.012 (3)	0.002 (2)	0.011 (3)
O3	0.0261 (16)	0.0437 (19)	0.047 (2)	0.0063 (14)	0.0113 (14)	0.0273 (17)
C4	0.051 (3)	0.057 (3)	0.039 (3)	0.009 (3)	0.008 (2)	0.022 (3)
C5	0.041 (2)	0.043 (3)	0.032 (2)	0.003 (2)	0.0093 (19)	0.015 (2)
C6	0.043 (4)	0.180 (9)	0.095 (6)	−0.025 (5)	0.007 (3)	0.064 (6)
C7	0.0226 (19)	0.025 (2)	0.040 (2)	0.0041 (17)	0.0054 (17)	0.0168 (19)
C8	0.028 (2)	0.029 (2)	0.040 (2)	0.0042 (18)	0.0103 (18)	0.017 (2)
C9	0.044 (3)	0.026 (2)	0.037 (2)	0.000 (2)	0.006 (2)	0.014 (2)
C10	0.045 (3)	0.028 (2)	0.055 (3)	0.013 (2)	0.005 (2)	0.019 (2)
C11	0.029 (2)	0.043 (3)	0.048 (3)	0.016 (2)	0.0118 (19)	0.023 (2)
C12	0.029 (2)	0.048 (3)	0.100 (5)	0.002 (2)	0.017 (3)	0.034 (3)

Geometric parameters (Å, º) top

Mn1—Br1	2.7237 (7)	O3—H3B	0.844 (19)
C1—H1	0.9500	C4—H4	0.9500
C1—N1	1.347 (6)	C4—C5	1.370 (6)
C1—C2	1.368 (7)	C5—H5	0.9500
N1—O1	1.328 (4)	C6—H6A	0.9800
N1—C5	1.346 (6)	C6—H6B	0.9800
Mn1—O1	2.129 (3)	C6—H6C	0.9800
Mn1—O2	2.211 (3)	C7—H7	0.9500
Mn1—O2ⁱ	2.219 (3)	C7—C8	1.372 (6)
Mn1—Br2	2.5687 (7)	C8—C9	1.377 (6)
Mn1—O3	2.245 (3)	C8—C12	1.499 (6)
O2—N2	1.339 (4)	C9—H9	0.9500
C2—C3	1.399 (8)	C9—C10	1.377 (6)
C2—C6	1.511 (8)	C10—H10	0.9500
N2—C7	1.336 (5)	C10—C11	1.377 (6)
N2—C11	1.332 (5)	C11—H11	0.9500
C3—H3	0.9500	C12—H12A	0.9800
C3—C4	1.379 (7)	C12—H12B	0.9800
O3—H3A	0.834 (19)	C12—H12C	0.9800

N1—C1—H1	119.2	Mn1—O3—H3B	101 (4)
N1—C1—C2	121.6 (5)	H3A—O3—H3B	104 (5)
C2—C1—H1	119.2	C3—C4—H4	119.7
O1—N1—C1	119.2 (4)	C5—C4—C3	120.7 (5)
O1—N1—C5	119.5 (4)	C5—C4—H4	119.7
C5—N1—C1	121.3 (4)	N1—C5—C4	119.1 (4)
O1—Mn1—Br1	93.86 (9)	N1—C5—H5	120.4
O1—Mn1—O2ⁱ	157.76 (11)	C4—C5—H5	120.4
O1—Mn1—O2	88.94 (11)	C2—C6—H6A	109.5
O1—Mn1—Br2	105.48 (9)	C2—C6—H6B	109.5
O1—Mn1—O3	88.95 (12)	C2—C6—H6C	109.5
O2—Mn1—Br1	91.19 (7)	H6A—C6—H6B	109.5
O2ⁱ—Mn1—Br1	89.84 (8)	H6A—C6—H6C	109.5
O2—Mn1—O2ⁱ	69.05 (11)	H6B—C6—H6C	109.5
O2ⁱ—Mn1—Br2	95.91 (7)	N2—C7—H7	119.4
O2—Mn1—Br2	163.39 (7)	N2—C7—C8	121.2 (4)
O2—Mn1—O3	81.25 (11)	C8—C7—H7	119.4
O2ⁱ—Mn1—O3	84.75 (11)	C7—C8—C9	118.3 (4)
Br2—Mn1—Br1	95.91 (2)	C7—C8—C12	120.6 (4)
O3—Mn1—Br1	171.89 (8)	C9—C8—C12	121.1 (4)
O3—Mn1—Br2	90.65 (8)	C8—C9—H9	120.1
N1—O1—Mn1	119.7 (3)	C8—C9—C10	119.8 (4)
Mn1—O2—Mn1ⁱ	110.95 (11)	C10—C9—H9	120.1
N2—O2—Mn1ⁱ	123.8 (2)	C9—C10—H10	120.2
N2—O2—Mn1	124.7 (2)	C11—C10—C9	119.6 (4)
C1—C2—C3	117.8 (5)	C11—C10—H10	120.2
C1—C2—C6	120.5 (6)	N2—C11—C10	119.6 (4)
C3—C2—C6	121.7 (5)	N2—C11—H11	120.2
C7—N2—O2	119.9 (3)	C10—C11—H11	120.2
C11—N2—O2	118.7 (3)	C8—C12—H12A	109.5
C11—N2—C7	121.5 (4)	C8—C12—H12B	109.5
C2—C3—H3	120.3	C8—C12—H12C	109.5
C4—C3—C2	119.4 (5)	H12A—C12—H12B	109.5
C4—C3—H3	120.3	H12A—C12—H12C	109.5
Mn1—O3—H3A	118 (3)	H12B—C12—H12C	109.5

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···Br1ⁱⁱ	0.83 (2)	2.60 (2)	3.410 (3)	164 (4)
O3—H3B···Br1ⁱ	0.84 (2)	2.55 (2)	3.386 (3)	172 (5)

Symmetry codes: (i) −x, −y+1, −z; (ii) x−1, y, z.

Bis(µ-4-methylpyridine N-oxide)bis[dibromidomethanol(4-methylpyridine N-oxide)manganese(II)] (IV) top

Crystal data top

[Mn₂Br₄(C₆H₇NO)₄(CH₄O)₂]	F(000) = 916
M_r = 930.11	D_x = 1.790 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 13.5384 (7) Å	Cell parameters from 9251 reflections
b = 9.5354 (4) Å	θ = 2.0–33.1°
c = 13.7292 (7) Å	µ = 5.40 mm⁻¹
β = 103.112 (5)°	T = 170 K
V = 1726.15 (15) Å³	Prism, clear light brown
Z = 2	0.4 × 0.4 × 0.4 mm

Data collection top

Rigaku XtaLAB mini diffractometer	3964 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	3175 reflections with I > 2σ(I)
Graphite Monochromator monochromator	R_int = 0.061
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 1.9°
profile data from ω–scans	h = −17→17
Absorption correction: multi-scan (CrysAlisPro; Rigaku Oxford Diffraction, 2018)	k = −12→12
T_min = 0.659, T_max = 1.000	l = −17→17
17754 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.112	w = 1/[σ²(F_o²) + (0.0665P)² + 0.0317P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
3964 reflections	Δρ_max = 1.64 e Å⁻³
196 parameters	Δρ_min = −0.74 e Å⁻³
3 restraints

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.55122 (3)	0.55895 (4)	0.73950 (3)	0.02951 (13)
Mn1	0.42974 (4)	0.62247 (6)	0.55858 (4)	0.02011 (15)
N1	0.4741 (3)	0.9181 (3)	0.6510 (2)	0.0243 (7)
C1	0.4328 (3)	0.8828 (4)	0.7272 (3)	0.0266 (9)
H1	0.390399	0.802474	0.722371	0.032*
O1	0.4550 (2)	0.8416 (3)	0.56661 (19)	0.0283 (6)
O2	0.4393 (2)	0.4023 (3)	0.5134 (2)	0.0219 (6)
N2	0.3727 (2)	0.3013 (3)	0.5239 (2)	0.0209 (7)
C2	0.4519 (3)	0.9632 (4)	0.8130 (3)	0.0275 (9)
H2	0.422582	0.937169	0.866939	0.033*
Br2	0.25806 (3)	0.60062 (4)	0.60914 (3)	0.03081 (13)
C3	0.5128 (3)	1.0806 (4)	0.8220 (3)	0.0292 (9)
O3	0.3548 (2)	0.6580 (3)	0.3987 (2)	0.0297 (6)
H3	0.3793 (18)	0.613 (4)	0.3550 (13)	0.045*
C4	0.5541 (3)	1.1132 (4)	0.7408 (3)	0.0279 (9)
H4	0.596641	1.193074	0.743893	0.033*
C5	0.5341 (3)	1.0312 (4)	0.6560 (3)	0.0269 (9)
H5	0.562828	1.054615	0.601121	0.032*
C6	0.5321 (4)	1.1692 (5)	0.9149 (3)	0.0417 (11)
H6A	0.476217	1.157376	0.948694	0.063*
H6B	0.536834	1.267992	0.896711	0.063*
H6C	0.595831	1.140083	0.959757	0.063*
C7	0.3259 (3)	0.2277 (4)	0.4442 (3)	0.0256 (8)
H7	0.339610	0.246866	0.380646	0.031*
C8	0.2582 (3)	0.1247 (4)	0.4535 (3)	0.0305 (9)
H8	0.226450	0.071416	0.396473	0.037*
C9	0.2353 (3)	0.0971 (4)	0.5451 (4)	0.0318 (10)
C10	0.2848 (3)	0.1774 (4)	0.6253 (3)	0.0294 (9)
H10	0.270434	0.162602	0.689092	0.035*
C11	0.3542 (3)	0.2781 (4)	0.6148 (3)	0.0255 (8)
H11	0.388719	0.330637	0.671008	0.031*
C12	0.1594 (4)	−0.0123 (5)	0.5565 (4)	0.0475 (13)
H12A	0.105685	−0.016658	0.495319	0.071*
H12B	0.129842	0.011844	0.613227	0.071*
H12C	0.193117	−0.103673	0.568581	0.071*
C13	0.2496 (4)	0.6767 (8)	0.3550 (4)	0.069 (2)
H13A	0.241626	0.735075	0.294999	0.103*
H13B	0.216868	0.722797	0.403254	0.103*
H13C	0.217904	0.585124	0.336828	0.103*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0332 (2)	0.0303 (2)	0.0229 (2)	0.00096 (17)	0.00200 (17)	−0.00194 (16)
Mn1	0.0218 (3)	0.0170 (3)	0.0229 (3)	−0.0003 (2)	0.0080 (2)	−0.0004 (2)
N1	0.0301 (18)	0.0184 (16)	0.0254 (17)	0.0024 (13)	0.0085 (15)	−0.0013 (13)
C1	0.032 (2)	0.021 (2)	0.030 (2)	−0.0061 (16)	0.0127 (19)	−0.0017 (16)
O1	0.0437 (17)	0.0190 (14)	0.0245 (14)	−0.0034 (12)	0.0125 (13)	−0.0045 (11)
O2	0.0236 (13)	0.0171 (13)	0.0271 (14)	−0.0053 (10)	0.0103 (12)	−0.0032 (11)
N2	0.0189 (15)	0.0168 (16)	0.0291 (17)	0.0001 (12)	0.0098 (14)	0.0013 (13)
C2	0.031 (2)	0.029 (2)	0.025 (2)	0.0034 (17)	0.0130 (18)	0.0010 (17)
Br2	0.0271 (2)	0.0298 (2)	0.0401 (3)	−0.00056 (16)	0.01705 (19)	−0.00008 (18)
C3	0.027 (2)	0.030 (2)	0.030 (2)	0.0036 (17)	0.0038 (18)	−0.0032 (17)
O3	0.0291 (15)	0.0340 (16)	0.0247 (14)	0.0083 (13)	0.0035 (13)	−0.0007 (12)
C4	0.029 (2)	0.024 (2)	0.031 (2)	−0.0017 (16)	0.0069 (18)	0.0002 (16)
C5	0.030 (2)	0.023 (2)	0.029 (2)	0.0012 (17)	0.0090 (18)	0.0051 (16)
C6	0.047 (3)	0.043 (3)	0.035 (2)	−0.010 (2)	0.008 (2)	−0.009 (2)
C7	0.025 (2)	0.027 (2)	0.0239 (19)	−0.0003 (16)	0.0035 (17)	−0.0041 (16)
C8	0.027 (2)	0.024 (2)	0.038 (2)	−0.0039 (17)	0.0029 (19)	−0.0064 (18)
C9	0.023 (2)	0.020 (2)	0.052 (3)	0.0039 (16)	0.009 (2)	0.0052 (19)
C10	0.034 (2)	0.023 (2)	0.033 (2)	0.0035 (17)	0.0102 (19)	0.0090 (17)
C11	0.030 (2)	0.023 (2)	0.0239 (18)	0.0032 (16)	0.0065 (17)	0.0020 (16)
C12	0.044 (3)	0.031 (3)	0.068 (4)	−0.009 (2)	0.015 (3)	0.010 (2)
C13	0.030 (3)	0.136 (6)	0.037 (3)	0.012 (3)	−0.001 (2)	0.014 (3)

Geometric parameters (Å, º) top

Mn1—Br1	2.7181 (7)	C4—C5	1.377 (6)
Mn1—O1	2.116 (3)	C5—H5	0.9500
Mn1—O2	2.201 (2)	C6—H6A	0.9800
Mn1—O2ⁱ	2.230 (3)	C6—H6B	0.9800
Mn1—Br2	2.5806 (7)	C6—H6C	0.9800
Mn1—O3	2.225 (3)	C7—H7	0.9500
N1—C1	1.336 (5)	C7—C8	1.370 (6)
N1—O1	1.344 (4)	C8—H8	0.9500
N1—C5	1.343 (5)	C8—C9	1.387 (6)
C1—H1	0.9500	C9—C10	1.382 (6)
C1—C2	1.379 (6)	C9—C12	1.497 (6)
O2—N2	1.349 (4)	C10—H10	0.9500
N2—C7	1.333 (5)	C10—C11	1.373 (5)
N2—C11	1.345 (5)	C11—H11	0.9500
C2—H2	0.9500	C12—H12A	0.9800
C2—C3	1.379 (6)	C12—H12B	0.9800
C3—C4	1.390 (6)	C12—H12C	0.9800
C3—C6	1.502 (6)	C13—H13A	0.9800
O3—H3	0.861 (9)	C13—H13B	0.9800
O3—C13	1.426 (6)	C13—H13C	0.9800
C4—H4	0.9500

O1—Mn1—Br1	96.62 (8)	C5—C4—C3	120.9 (4)
O1—Mn1—O2	159.59 (11)	C5—C4—H4	119.6
O1—Mn1—O2ⁱ	89.55 (10)	N1—C5—C4	120.0 (4)
O1—Mn1—Br2	102.17 (8)	N1—C5—H5	120.0
O1—Mn1—O3	86.17 (11)	C4—C5—H5	120.0
O2ⁱ—Mn1—Br1	90.24 (7)	C3—C6—H6A	109.5
O2—Mn1—Br1	89.03 (7)	C3—C6—H6B	109.5
O2—Mn1—O2ⁱ	70.77 (11)	C3—C6—H6C	109.5
O2—Mn1—Br2	96.47 (7)	H6A—C6—H6B	109.5
O2ⁱ—Mn1—Br2	165.02 (7)	H6A—C6—H6C	109.5
O2—Mn1—O3	84.83 (10)	H6B—C6—H6C	109.5
Br2—Mn1—Br1	97.55 (2)	N2—C7—H7	119.8
O3—Mn1—Br1	168.90 (8)	N2—C7—C8	120.3 (4)
O3—Mn1—O2ⁱ	79.01 (10)	C8—C7—H7	119.8
O3—Mn1—Br2	92.34 (8)	C7—C8—H8	119.6
C1—N1—O1	120.4 (3)	C7—C8—C9	120.8 (4)
C1—N1—C5	121.2 (3)	C9—C8—H8	119.6
C5—N1—O1	118.4 (3)	C8—C9—C12	121.8 (4)
N1—C1—H1	120.1	C10—C9—C8	116.7 (4)
N1—C1—C2	119.8 (4)	C10—C9—C12	121.5 (4)
C2—C1—H1	120.1	C9—C10—H10	119.2
N1—O1—Mn1	125.3 (2)	C11—C10—C9	121.5 (4)
Mn1—O2—Mn1ⁱ	109.23 (11)	C11—C10—H10	119.2
N2—O2—Mn1ⁱ	126.1 (2)	N2—C11—C10	119.2 (4)
N2—O2—Mn1	124.6 (2)	N2—C11—H11	120.4
C7—N2—O2	119.5 (3)	C10—C11—H11	120.4
C7—N2—C11	121.4 (3)	C9—C12—H12A	109.5
C11—N2—O2	119.1 (3)	C9—C12—H12B	109.5
C1—C2—H2	119.3	C9—C12—H12C	109.5
C3—C2—C1	121.4 (4)	H12A—C12—H12B	109.5
C3—C2—H2	119.3	H12A—C12—H12C	109.5
C2—C3—C4	116.8 (4)	H12B—C12—H12C	109.5
C2—C3—C6	121.2 (4)	O3—C13—H13A	109.5
C4—C3—C6	122.0 (4)	O3—C13—H13B	109.5
Mn1—O3—H3	116.8 (15)	O3—C13—H13C	109.5
C13—O3—Mn1	128.5 (3)	H13A—C13—H13B	109.5
C13—O3—H3	105.9 (15)	H13A—C13—H13C	109.5
C3—C4—H4	119.6	H13B—C13—H13C	109.5

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···Br1ⁱ	0.86 (1)	2.41 (2)	3.255 (3)	166 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

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