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Acta Cryst. (2007). E63, m2465    [ doi:10.1107/S1600536807042249 ]

Diaquabromido[N,N'-bis(2-pyridylmethylidene)cyclohexane-1,2-diamine]manganese(II) bromide dibromido[N,N'-bis(2-pyridylmethylidene)cyclohexane-1,2-diamine]manganese(II)

I.-C. Hwang and K. Ha

Abstract top

The crystal structure of the title compound, [MnBr(C18H20N4)(H2O)2]Br·[MnBr2(C18H20N4)], contains two different MnII complexes in the asymmetric unit. In the neutral complex, the Mn2+ ion is six-coordinated in a distorted octahedral environment by four N atoms from the tetradentate ligand N,N'-bis(2-pyridylmethylidene)cyclohexane-1,2-diamine (bpic) and two Br atoms. In the cationic complex, the Mn2+ ion is seven-coordinated in an approximately pentagonal-bipyramidal environment by four N atoms from bpic, one Br atom and two O atoms from water ligands. The compound displays intermolecular O-H...Br hydrogen bonding. There are also intermolecular [pi]-[pi] interactions between adjacent pyridine rings, with centroid-to-centroid distances of 3.604 and 3.680 Å, and with dihedral angles between the ring planes of 4.7 and 5.0°.

Comment top

The crystal structure of the title compound, [MnBr2(C18H20N4)][MnBr(C18H20N4)(H2O)2]Br, consists of two different MnII complexes in an asymmetric unit (Fig. 1). In one neutral complex, Mn2+ ion is six-coordinated in a distorted octahedral environment by four N atoms from the tetradentate ligand N,N'-bis(2-pyridylmethylidene)-1,2-diiminocyclohexane (bpic) occupying equatorial positions and two Br atoms occupying axial positions. Within the equatorial plane, the chelating angles lie in the range of 70.69 (16)–71.98 (16)°. The apical Br1—Mn1—Br2 bond angle is 151.60 (4)°. In the other cation complex, Mn2+ ion is seven-coordinated in an approximately pentagonal bipyramidal structure by four N atoms from bpic, one Br atom and two O atoms from water ligands. The four N atoms and one O atom occupy the equatorial positions, and the Br atom and one O atom lie in the axial positions. Within the equatorial plane, the chelating angles lie in the range of 68.66 (17)–69.23 (16)°. The apical Br3—Mn2—O1 bond angle is 170.10 (10)°. The compound displays intermolecular hydrogen bonds between the O atoms and the Br atoms (Br1, Br4) (Fig. 2). Moreover, there are intermolecular π–π interactions between the adjacent pyridine rings. The distances between Cg1 (the centroid of six-membered ring N1–C5) and Cg4iii [ring N8–C36; symmetry code: (iii) 1 − x, 1 − y, −z], and between Cg2 (ring N4–C18) and Cg3iv [ring N5–C23; symmetry code: (iv) 1 − x, 2 − y, 1 − z] are 3.604 Å and 3.680 Å, repectively, with the respective dihedral angles between the ring planes 4.7° and 5.0°.

Related literature top

For some other Mn(bpic) complexes, see: Lu et al. (2006); Schoumacker et al. (2003).

Experimental top

A solution of MnBr2 (0.37 g, 1.72 mmol) and N,N'-bis(2-pyridylmethylidene)-1,2-diiminocyclohexane (0.50 g, 1.71 mmol) in EtOH (30 ml) was stirred for 1 h at room temparature. After add of diethyl ether to the solution, the formed precipitate was separated by filtration and washed with acetone and dried under vacuum, to give a dark yellow powder (0.45 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from a EtOH solution. MS (FAB): m/z 426, 428 [Mn(bpic)Br+]; IR (KBr): 3376 cm−1 (broad).

Refinement top

H atoms were positioned geometrically and allowed to ride on their respective carrier atoms [C—H = 0.94, 0.98 or 0.99 Å and Uiso(H) = 1.2Ueq(C)]. The H atoms of the water ligands were located from Fourier difference maps, but not refined [Uiso(H) = 0.08 Å2].

The CIF check program indicates a high ratio of the maximum and minimum residual density (4.07) in the structure and solvent accessible voids of 79 Å3. All these factors indicate a strong likelihood of disordered solvent molecule MeOH in the structure. However, the solvent molecule could neither be located nor refined, because the highest difference peak (2.85 e Å−3) lies on a special position (0, 0, 0) with the site occupation factor 0.5. The distance between this peak and the nearest atom is 1.433 Å.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. The structure of the title compound with the numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The H atoms are presented as a spheres of arbitrary radius.
[Figure 2] Fig. 2. View of the unit-cell contents of the title compound. Hydrogen-bond interactions are drawn with dashed lines.
Diaquabromido[N,N'-bis(2-pyridylmethylidene)cyclohexane-1,2- diamine]manganese(II) bromide dibromido[N,N'-bis(2-pyridylmethylidene)cyclohexane-1,2-diamine]manganese(II) top
Crystal data top
[MnBr(C18H20N4)(H2O)2]Br·[MnBr2(C18H20N4)]Z = 2
Mr = 1050.27F000 = 1044
Triclinic, P1Dx = 1.706 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 11.8283 (9) ÅCell parameters from 4110 reflections
b = 12.4842 (9) Åθ = 2.2–26.3º
c = 14.1340 (10) ŵ = 4.57 mm−1
α = 97.971 (1)ºT = 243 (2) K
β = 91.017 (1)ºPlate, yellow
γ = 98.036 (1)º0.15 × 0.10 × 0.10 mm
V = 2045.2 (3) Å3
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		8169 independent reflections
Radiation source: fine-focus sealed tube5661 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.019
T = 243(2) Kθmax = 26.4º
φ and ω scansθmin = 1.5º
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		h = −14→13
Tmin = 0.520, Tmax = 0.633k = −15→15
12149 measured reflectionsl = −17→16
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.137  w = 1/[σ2(Fo2) + (0.0737P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
8169 reflectionsΔρmax = 2.85 e Å−3
469 parametersΔρmin = −0.70 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[MnBr(C18H20N4)(H2O)2]Br·[MnBr2(C18H20N4)]γ = 98.036 (1)º
Mr = 1050.27V = 2045.2 (3) Å3
Triclinic, P1Z = 2
a = 11.8283 (9) ÅMo Kα
b = 12.4842 (9) ŵ = 4.57 mm−1
c = 14.1340 (10) ÅT = 243 (2) K
α = 97.971 (1)º0.15 × 0.10 × 0.10 mm
β = 91.017 (1)º
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		8169 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		5661 reflections with I > 2σ(I)
Tmin = 0.520, Tmax = 0.633Rint = 0.019
12149 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.044469 parameters
wR(F2) = 0.137H-atom parameters constrained
S = 1.00Δρmax = 2.85 e Å−3
8169 reflectionsΔρmin = −0.70 e Å−3
Special details top

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>2σ(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 (Å2) top
xyzUiso*/Ueq
Mn10.76129 (7)0.66873 (7)0.07222 (6)0.0291 (2)
Br10.97942 (5)0.75164 (5)0.12675 (4)0.03992 (17)
Br20.56467 (5)0.68502 (6)−0.00236 (4)0.04501 (18)
N10.8298 (4)0.6500 (4)−0.0837 (3)0.0302 (10)
N20.8074 (4)0.5001 (4)0.0341 (3)0.0385 (12)
N30.7153 (4)0.5746 (4)0.1928 (3)0.0358 (11)
N40.7117 (4)0.7889 (4)0.1988 (3)0.0314 (10)
C10.8331 (5)0.7196 (5)−0.1462 (4)0.0418 (15)
H10.81470.7899−0.12600.050*
C20.8623 (5)0.6940 (6)−0.2398 (5)0.0487 (17)
H20.86100.7451−0.28260.058*
C30.8929 (5)0.5949 (5)−0.2694 (4)0.0441 (15)
H30.91430.5764−0.33270.053*
C40.8921 (5)0.5211 (5)−0.2047 (4)0.0376 (14)
H40.91410.4519−0.22260.045*
C50.8588 (4)0.5516 (4)−0.1147 (4)0.0310 (12)
C60.8508 (5)0.4744 (5)−0.0451 (4)0.0370 (14)
H60.87750.4067−0.05940.044*
C70.8060 (7)0.4325 (6)0.1111 (5)0.068 (2)
H70.87900.45930.14780.081*
C80.8103 (6)0.3115 (5)0.0798 (5)0.0511 (17)
H8A0.74840.28200.03230.061*
H8B0.88310.30240.04970.061*
C90.7984 (8)0.2488 (7)0.1641 (6)0.089 (3)
H9A0.77800.17110.13940.107*
H9B0.87340.25770.19710.107*
C100.7176 (8)0.2776 (6)0.2329 (6)0.084 (3)
H10A0.73320.24560.29040.101*
H10B0.64150.24340.20750.101*
C110.7136 (5)0.3963 (5)0.2621 (4)0.0383 (14)
H11A0.77760.42690.30720.046*
H11B0.64250.40550.29490.046*
C120.7199 (7)0.4588 (6)0.1767 (5)0.064 (2)
H120.64780.42880.13980.077*
C130.6838 (4)0.6249 (5)0.2698 (4)0.0324 (13)
H130.66670.58800.32260.039*
C140.6747 (4)0.7403 (5)0.2754 (4)0.0328 (13)
C150.6282 (4)0.7954 (5)0.3528 (4)0.0360 (13)
H150.60350.75930.40440.043*
C160.6186 (5)0.9029 (5)0.3537 (4)0.0411 (15)
H160.58720.94240.40590.049*
C170.6555 (5)0.9524 (5)0.2770 (5)0.0426 (15)
H170.64961.02650.27550.051*
C180.7022 (5)0.8907 (5)0.2007 (4)0.0398 (14)
H180.72780.92540.14840.048*
Mn20.25348 (7)0.76805 (6)0.42552 (6)0.0291 (2)
Br30.42980 (5)0.81252 (5)0.54720 (4)0.03697 (16)
Br40.12914 (5)0.36444 (5)0.52829 (5)0.04494 (18)
N50.1501 (4)0.8781 (4)0.5369 (3)0.0335 (11)
N60.2646 (4)0.9444 (4)0.3879 (3)0.0326 (11)
N70.3127 (4)0.7766 (4)0.2688 (3)0.0364 (11)
N80.3411 (4)0.6112 (4)0.3653 (4)0.0376 (12)
C190.0984 (5)0.8510 (5)0.6154 (4)0.0404 (14)
H190.09380.77830.62730.048*
C200.0512 (5)0.9247 (6)0.6804 (5)0.0453 (15)
H200.01750.90190.73530.054*
C210.0538 (5)1.0317 (5)0.6639 (5)0.0420 (15)
H210.02151.08260.70650.050*
C220.1053 (5)1.0610 (5)0.5828 (4)0.0393 (14)
H220.10741.13260.56850.047*
C230.1544 (4)0.9839 (5)0.5219 (4)0.0332 (13)
C240.2162 (4)1.0140 (5)0.4385 (4)0.0345 (13)
H240.21961.08520.42290.041*
C250.3296 (5)0.9712 (5)0.3049 (4)0.0364 (14)
H250.41170.97530.32240.044*
C260.3135 (5)1.0776 (5)0.2695 (5)0.0504 (17)
H26A0.23261.07700.25300.061*
H26B0.33721.13900.32030.061*
C270.3832 (6)1.0917 (7)0.1833 (6)0.069 (2)
H27A0.37191.16040.16090.083*
H27B0.46441.09620.20110.083*
C280.3511 (7)0.9993 (6)0.1042 (5)0.066 (2)
H28A0.39791.01100.04900.079*
H28B0.27070.99620.08440.079*
C290.3693 (6)0.8919 (6)0.1379 (5)0.0551 (18)
H29A0.45050.89320.15370.066*
H29B0.34580.83110.08660.066*
C300.2990 (5)0.8754 (5)0.2262 (4)0.0376 (14)
H300.21720.87160.20760.045*
C310.3557 (5)0.6978 (5)0.2261 (4)0.0422 (15)
H310.37950.69990.16320.051*
C320.3693 (4)0.6028 (5)0.2731 (4)0.0373 (14)
C330.4082 (5)0.5137 (5)0.2263 (5)0.0474 (17)
H330.42600.51040.16150.057*
C340.4213 (5)0.4281 (6)0.2752 (6)0.058 (2)
H340.44550.36430.24380.069*
C350.3987 (5)0.4372 (5)0.3691 (6)0.0561 (19)
H350.41050.38120.40460.067*
C360.3580 (5)0.5294 (5)0.4122 (5)0.0437 (15)
H360.34150.53460.47740.052*
O10.0812 (3)0.7290 (3)0.3424 (3)0.0405 (10)
H1W0.05950.73530.27920.080*
H2W0.01870.70350.36590.080*
O20.1481 (3)0.6340 (3)0.5022 (3)0.0424 (10)
H3W0.15760.56340.50370.080*
H4W0.07670.63110.50190.080*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0353 (5)0.0276 (5)0.0254 (5)0.0090 (4)0.0041 (3)0.0021 (3)
Br10.0350 (3)0.0481 (4)0.0344 (3)0.0081 (3)0.0011 (2)−0.0039 (3)
Br20.0384 (3)0.0614 (4)0.0355 (4)0.0150 (3)−0.0011 (3)0.0000 (3)
N10.033 (2)0.031 (3)0.027 (3)0.006 (2)0.0000 (19)0.005 (2)
N20.054 (3)0.029 (3)0.036 (3)0.012 (2)0.016 (2)0.008 (2)
N30.051 (3)0.031 (3)0.028 (3)0.013 (2)0.006 (2)0.003 (2)
N40.032 (2)0.031 (3)0.031 (3)0.009 (2)0.002 (2)−0.002 (2)
C10.045 (4)0.043 (4)0.040 (4)0.009 (3)0.006 (3)0.012 (3)
C20.051 (4)0.063 (5)0.037 (4)0.004 (3)0.005 (3)0.025 (3)
C30.042 (4)0.061 (4)0.028 (3)0.004 (3)0.006 (3)0.002 (3)
C40.037 (3)0.045 (4)0.030 (3)0.008 (3)0.005 (3)0.000 (3)
C50.030 (3)0.031 (3)0.030 (3)0.003 (2)0.002 (2)0.001 (2)
C60.046 (3)0.029 (3)0.037 (4)0.012 (3)0.010 (3)−0.001 (3)
C70.118 (7)0.042 (4)0.056 (5)0.034 (4)0.041 (5)0.023 (4)
C80.080 (5)0.035 (4)0.044 (4)0.020 (3)0.021 (3)0.011 (3)
C90.148 (9)0.050 (5)0.091 (7)0.047 (5)0.056 (6)0.039 (5)
C100.153 (9)0.041 (4)0.067 (6)0.019 (5)0.039 (6)0.026 (4)
C110.041 (3)0.038 (3)0.037 (4)0.006 (3)0.002 (3)0.010 (3)
C120.119 (6)0.039 (4)0.041 (4)0.029 (4)0.024 (4)0.012 (3)
C130.034 (3)0.039 (3)0.023 (3)0.002 (2)0.002 (2)0.003 (3)
C140.022 (3)0.042 (3)0.031 (3)0.006 (2)−0.002 (2)−0.007 (3)
C150.028 (3)0.044 (4)0.033 (3)0.004 (3)0.000 (2)−0.006 (3)
C160.027 (3)0.051 (4)0.040 (4)0.008 (3)−0.003 (3)−0.012 (3)
C170.036 (3)0.035 (3)0.053 (4)0.013 (3)−0.012 (3)−0.010 (3)
C180.041 (3)0.038 (4)0.039 (4)0.009 (3)−0.001 (3)−0.001 (3)
Mn20.0316 (4)0.0273 (5)0.0282 (5)0.0064 (3)0.0025 (3)0.0012 (4)
Br30.0360 (3)0.0412 (4)0.0322 (3)0.0084 (3)−0.0008 (2)−0.0028 (3)
Br40.0395 (3)0.0471 (4)0.0506 (4)0.0006 (3)−0.0001 (3)0.0213 (3)
N50.034 (3)0.032 (3)0.034 (3)0.007 (2)−0.002 (2)0.000 (2)
N60.028 (2)0.036 (3)0.033 (3)0.002 (2)−0.001 (2)0.006 (2)
N70.032 (3)0.043 (3)0.030 (3)0.001 (2)0.004 (2)−0.004 (2)
N80.035 (3)0.033 (3)0.042 (3)0.005 (2)0.003 (2)−0.006 (2)
C190.043 (3)0.036 (4)0.039 (4)0.003 (3)0.004 (3)0.001 (3)
C200.038 (3)0.058 (4)0.037 (4)0.005 (3)0.005 (3)0.000 (3)
C210.033 (3)0.041 (4)0.047 (4)0.010 (3)−0.001 (3)−0.013 (3)
C220.037 (3)0.033 (3)0.046 (4)0.014 (3)−0.013 (3)−0.007 (3)
C230.030 (3)0.032 (3)0.037 (3)0.009 (2)−0.006 (2)−0.001 (3)
C240.030 (3)0.030 (3)0.043 (4)0.002 (2)−0.006 (3)0.006 (3)
C250.030 (3)0.042 (4)0.039 (4)0.004 (3)−0.001 (3)0.013 (3)
C260.042 (4)0.053 (4)0.061 (5)0.004 (3)0.004 (3)0.029 (4)
C270.048 (4)0.086 (6)0.086 (6)0.011 (4)0.007 (4)0.056 (5)
C280.079 (5)0.079 (6)0.041 (4)0.000 (4)0.010 (4)0.025 (4)
C290.055 (4)0.075 (5)0.031 (4)0.000 (4)0.005 (3)0.007 (3)
C300.034 (3)0.049 (4)0.029 (3)0.001 (3)−0.001 (2)0.008 (3)
C310.034 (3)0.056 (4)0.031 (3)0.000 (3)0.005 (3)−0.007 (3)
C320.027 (3)0.039 (4)0.039 (4)−0.002 (2)−0.001 (3)−0.012 (3)
C330.030 (3)0.048 (4)0.056 (4)0.003 (3)0.007 (3)−0.022 (3)
C340.035 (4)0.041 (4)0.088 (6)0.006 (3)0.009 (4)−0.021 (4)
C350.041 (4)0.035 (4)0.090 (6)0.003 (3)0.002 (4)0.006 (4)
C360.040 (3)0.034 (4)0.056 (4)0.008 (3)0.005 (3)0.001 (3)
O10.037 (2)0.049 (3)0.034 (2)−0.0017 (19)0.0005 (17)0.0084 (19)
O20.038 (2)0.034 (2)0.058 (3)0.0068 (18)0.004 (2)0.011 (2)
Geometric parameters (Å, °) top
Mn1—N32.234 (4)Mn2—N72.346 (5)
Mn1—N22.245 (5)Mn2—N82.403 (5)
Mn1—N42.309 (4)Mn2—N52.408 (5)
Mn1—N12.354 (4)Mn2—Br32.6268 (10)
Mn1—Br22.5818 (10)N5—C191.338 (7)
Mn1—Br12.6988 (10)N5—C231.361 (7)
N1—C11.320 (7)N6—C241.256 (7)
N1—C51.339 (7)N6—C251.465 (7)
N2—C61.259 (7)N7—C311.256 (7)
N2—C71.466 (8)N7—C301.473 (7)
N3—C131.268 (7)N8—C361.327 (7)
N3—C121.441 (8)N8—C321.345 (7)
N4—C181.289 (7)C19—C201.389 (8)
N4—C141.363 (7)C19—H190.9400
C1—C21.379 (9)C20—C211.384 (9)
C1—H10.9400C20—H200.9400
C2—C31.350 (9)C21—C221.377 (8)
C2—H20.9400C21—H210.9400
C3—C41.384 (8)C22—C231.395 (8)
C3—H30.9400C22—H220.9400
C4—C51.358 (7)C23—C241.464 (8)
C4—H40.9400C24—H240.9400
C5—C61.466 (7)C25—C301.515 (8)
C6—H60.9400C25—C261.517 (8)
C7—C121.431 (9)C25—H250.9900
C7—C81.522 (9)C26—C271.501 (9)
C7—H70.9900C26—H26A0.9800
C8—C91.513 (9)C26—H26B0.9800
C8—H8A0.9800C27—C281.493 (11)
C8—H8B0.9800C27—H27A0.9800
C9—C101.421 (10)C27—H27B0.9800
C9—H9A0.9800C28—C291.524 (9)
C9—H9B0.9800C28—H28A0.9800
C10—C111.490 (9)C28—H28B0.9800
C10—H10A0.9800C29—C301.534 (8)
C10—H10B0.9800C29—H29A0.9800
C11—C121.523 (8)C29—H29B0.9800
C11—H11A0.9800C30—H300.9900
C11—H11B0.9800C31—C321.463 (9)
C12—H120.9900C31—H310.9400
C13—C141.450 (8)C32—C331.356 (8)
C13—H130.9400C33—C341.374 (10)
C14—C151.375 (7)C33—H330.9400
C15—C161.361 (8)C34—C351.351 (10)
C15—H150.9400C34—H340.9400
C16—C171.369 (8)C35—C361.379 (9)
C16—H160.9400C35—H350.9400
C17—C181.405 (8)C36—H360.9400
C17—H170.9400O1—H1W0.942
C18—H180.9400O1—H2W0.855
Mn2—O12.291 (4)O2—H3W0.907
Mn2—N62.322 (4)O2—H4W0.840
Mn2—O22.344 (4)
N3—Mn1—N271.68 (16)O1—Mn2—N8100.81 (15)
N3—Mn1—N471.98 (16)N6—Mn2—N8134.05 (16)
N2—Mn1—N4142.60 (17)O2—Mn2—N879.55 (15)
N3—Mn1—N1142.22 (16)N7—Mn2—N868.79 (17)
N2—Mn1—N170.69 (16)O1—Mn2—N583.30 (15)
N4—Mn1—N1145.68 (16)N6—Mn2—N569.23 (16)
N3—Mn1—Br2102.99 (12)O2—Mn2—N578.73 (14)
N2—Mn1—Br2111.61 (14)N7—Mn2—N5134.79 (16)
N4—Mn1—Br284.99 (11)N8—Mn2—N5156.11 (16)
N1—Mn1—Br287.70 (11)O1—Mn2—Br3170.10 (10)
N3—Mn1—Br199.48 (13)N6—Mn2—Br395.07 (11)
N2—Mn1—Br191.76 (13)O2—Mn2—Br397.15 (11)
N4—Mn1—Br185.68 (11)N7—Mn2—Br3110.61 (12)
N1—Mn1—Br185.05 (11)N8—Mn2—Br384.23 (12)
Br2—Mn1—Br1151.60 (4)N5—Mn2—Br388.70 (11)
C1—N1—C5116.7 (5)C19—N5—C23116.6 (5)
C1—N1—Mn1128.4 (4)C19—N5—Mn2128.2 (4)
C5—N1—Mn1114.6 (3)C23—N5—Mn2114.9 (4)
C6—N2—C7122.4 (5)C24—N6—C25121.7 (5)
C6—N2—Mn1119.7 (4)C24—N6—Mn2120.0 (4)
C7—N2—Mn1116.8 (4)C25—N6—Mn2118.3 (3)
C13—N3—C12124.0 (5)C31—N7—C30123.4 (5)
C13—N3—Mn1118.6 (4)C31—N7—Mn2118.6 (4)
C12—N3—Mn1117.4 (4)C30—N7—Mn2118.0 (3)
C18—N4—C14117.6 (5)C36—N8—C32117.2 (5)
C18—N4—Mn1128.0 (4)C36—N8—Mn2126.4 (4)
C14—N4—Mn1113.9 (3)C32—N8—Mn2116.2 (4)
N1—C1—C2122.9 (6)N5—C19—C20123.4 (6)
N1—C1—H1118.5N5—C19—H19118.3
C2—C1—H1118.5C20—C19—H19118.3
C3—C2—C1119.5 (6)C21—C20—C19119.8 (6)
C3—C2—H2120.3C21—C20—H20120.1
C1—C2—H2120.3C19—C20—H20120.1
C2—C3—C4118.6 (6)C22—C21—C20117.7 (6)
C2—C3—H3120.7C22—C21—H21121.1
C4—C3—H3120.7C20—C21—H21121.1
C5—C4—C3118.2 (6)C21—C22—C23119.7 (6)
C5—C4—H4120.9C21—C22—H22120.2
C3—C4—H4120.9C23—C22—H22120.2
N1—C5—C4124.0 (5)N5—C23—C22122.8 (5)
N1—C5—C6115.8 (5)N5—C23—C24116.1 (5)
C4—C5—C6120.2 (5)C22—C23—C24121.1 (5)
N2—C6—C5118.9 (5)N6—C24—C23119.7 (5)
N2—C6—H6120.5N6—C24—H24120.1
C5—C6—H6120.5C23—C24—H24120.1
C12—C7—N2109.7 (6)N6—C25—C30106.7 (4)
C12—C7—C8116.5 (6)N6—C25—C26116.5 (5)
N2—C7—C8115.7 (6)C30—C25—C26110.7 (5)
C12—C7—H7104.5N6—C25—H25107.5
N2—C7—H7104.5C30—C25—H25107.5
C8—C7—H7104.5C26—C25—H25107.5
C9—C8—C7110.9 (6)C27—C26—C25110.0 (6)
C9—C8—H8A109.5C27—C26—H26A109.7
C7—C8—H8A109.5C25—C26—H26A109.7
C9—C8—H8B109.5C27—C26—H26B109.7
C7—C8—H8B109.5C25—C26—H26B109.7
H8A—C8—H8B108.1H26A—C26—H26B108.2
C10—C9—C8117.2 (6)C28—C27—C26111.7 (6)
C10—C9—H9A108.0C28—C27—H27A109.3
C8—C9—H9A108.0C26—C27—H27A109.3
C10—C9—H9B108.0C28—C27—H27B109.3
C8—C9—H9B108.0C26—C27—H27B109.3
H9A—C9—H9B107.2H27A—C27—H27B107.9
C9—C10—C11117.2 (6)C27—C28—C29109.8 (6)
C9—C10—H10A108.0C27—C28—H28A109.7
C11—C10—H10A108.0C29—C28—H28A109.7
C9—C10—H10B108.0C27—C28—H28B109.7
C11—C10—H10B108.0C29—C28—H28B109.7
H10A—C10—H10B107.2H28A—C28—H28B108.2
C10—C11—C12111.9 (6)C28—C29—C30109.7 (6)
C10—C11—H11A109.2C28—C29—H29A109.7
C12—C11—H11A109.2C30—C29—H29A109.7
C10—C11—H11B109.2C28—C29—H29B109.7
C12—C11—H11B109.2C30—C29—H29B109.7
H11A—C11—H11B107.9H29A—C29—H29B108.2
C7—C12—N3111.6 (6)N7—C30—C25106.3 (4)
C7—C12—C11114.3 (6)N7—C30—C29115.4 (5)
N3—C12—C11118.8 (6)C25—C30—C29110.8 (5)
C7—C12—H12103.3N7—C30—H30108.0
N3—C12—H12103.3C25—C30—H30108.0
C11—C12—H12103.3C29—C30—H30108.0
N3—C13—C14119.0 (5)N7—C31—C32120.8 (5)
N3—C13—H13120.5N7—C31—H31119.6
C14—C13—H13120.5C32—C31—H31119.6
N4—C14—C15122.6 (5)N8—C32—C33123.0 (6)
N4—C14—C13116.1 (5)N8—C32—C31115.2 (5)
C15—C14—C13121.3 (5)C33—C32—C31121.9 (6)
C16—C15—C14119.2 (6)C32—C33—C34119.0 (6)
C16—C15—H15120.4C32—C33—H33120.5
C14—C15—H15120.4C34—C33—H33120.5
C15—C16—C17118.6 (6)C35—C34—C33118.9 (6)
C15—C16—H16120.7C35—C34—H34120.6
C17—C16—H16120.7C33—C34—H34120.6
C16—C17—C18118.9 (6)C34—C35—C36119.3 (7)
C16—C17—H17120.5C34—C35—H35120.3
C18—C17—H17120.5C36—C35—H35120.3
N4—C18—C17123.1 (6)N8—C36—C35122.5 (6)
N4—C18—H18118.4N8—C36—H36118.7
C17—C18—H18118.4C35—C36—H36118.7
O1—Mn2—N687.55 (15)Mn2—O1—H1W132.4
O1—Mn2—O275.62 (14)Mn2—O1—H2W124.1
N6—Mn2—O2145.34 (14)H1W—O1—H2W103.6
O1—Mn2—N779.24 (15)Mn2—O2—H3W130.0
N6—Mn2—N768.66 (17)Mn2—O2—H4W118.0
O2—Mn2—N7134.59 (16)H3W—O2—H4W102.6
N3—Mn1—N1—C1168.5 (4)N8—Mn2—N5—C19−6.7 (7)
N2—Mn1—N1—C1174.0 (5)Br3—Mn2—N5—C19−79.2 (5)
N4—Mn1—N1—C1−17.5 (6)O1—Mn2—N5—C23−91.6 (4)
Br2—Mn1—N1—C160.1 (5)N6—Mn2—N5—C23−1.7 (4)
Br1—Mn1—N1—C1−92.4 (5)O2—Mn2—N5—C23−168.2 (4)
N3—Mn1—N1—C5−4.7 (5)N7—Mn2—N5—C23−24.0 (5)
N2—Mn1—N1—C50.8 (4)N8—Mn2—N5—C23166.8 (4)
N4—Mn1—N1—C5169.3 (3)Br3—Mn2—N5—C2394.3 (4)
Br2—Mn1—N1—C5−113.1 (4)O1—Mn2—N6—C2484.1 (4)
Br1—Mn1—N1—C594.4 (4)O2—Mn2—N6—C2424.1 (6)
N3—Mn1—N2—C6179.6 (5)N7—Mn2—N6—C24163.5 (5)
N4—Mn1—N2—C6−166.2 (4)N8—Mn2—N6—C24−173.2 (4)
N1—Mn1—N2—C63.1 (5)N5—Mn2—N6—C240.4 (4)
Br2—Mn1—N2—C682.5 (5)Br3—Mn2—N6—C24−86.3 (4)
Br1—Mn1—N2—C6−81.0 (5)O1—Mn2—N6—C25−96.3 (4)
N3—Mn1—N2—C7−12.1 (5)O2—Mn2—N6—C25−156.4 (3)
N4—Mn1—N2—C72.1 (6)N7—Mn2—N6—C25−16.9 (4)
N1—Mn1—N2—C7171.4 (5)N8—Mn2—N6—C256.4 (5)
Br2—Mn1—N2—C7−109.2 (5)N5—Mn2—N6—C25180.0 (4)
Br1—Mn1—N2—C787.3 (5)Br3—Mn2—N6—C2593.3 (4)
N2—Mn1—N3—C13171.8 (5)O1—Mn2—N7—C31−103.1 (4)
N4—Mn1—N3—C130.8 (4)N6—Mn2—N7—C31165.3 (5)
N1—Mn1—N3—C13177.2 (4)O2—Mn2—N7—C31−46.0 (5)
Br2—Mn1—N3—C13−79.5 (4)N8—Mn2—N7—C313.0 (4)
Br1—Mn1—N3—C1383.1 (4)N5—Mn2—N7—C31−172.3 (4)
N2—Mn1—N3—C12−10.2 (5)Br3—Mn2—N7—C3177.9 (4)
N4—Mn1—N3—C12178.8 (5)O1—Mn2—N7—C3077.8 (4)
N1—Mn1—N3—C12−4.8 (6)N6—Mn2—N7—C30−13.7 (4)
Br2—Mn1—N3—C1298.6 (5)O2—Mn2—N7—C30135.0 (4)
Br1—Mn1—N3—C12−98.9 (5)N8—Mn2—N7—C30−176.0 (4)
N3—Mn1—N4—C18−175.0 (5)N5—Mn2—N7—C308.7 (5)
N2—Mn1—N4—C18170.8 (4)Br3—Mn2—N7—C30−101.1 (4)
N1—Mn1—N4—C188.9 (6)O1—Mn2—N8—C36−107.4 (5)
Br2—Mn1—N4—C18−69.6 (5)N6—Mn2—N8—C36155.4 (4)
Br1—Mn1—N4—C1883.6 (5)O2—Mn2—N8—C36−34.4 (5)
N3—Mn1—N4—C14−3.9 (3)N7—Mn2—N8—C36178.7 (5)
N2—Mn1—N4—C14−18.1 (5)N5—Mn2—N8—C36−9.5 (7)
N1—Mn1—N4—C14180.0 (3)Br3—Mn2—N8—C3664.0 (5)
Br2—Mn1—N4—C14101.5 (3)O1—Mn2—N8—C3268.2 (4)
Br1—Mn1—N4—C14−105.3 (3)N6—Mn2—N8—C32−28.9 (5)
C5—N1—C1—C21.3 (8)O2—Mn2—N8—C32141.2 (4)
Mn1—N1—C1—C2−171.8 (4)N7—Mn2—N8—C32−5.6 (4)
N1—C1—C2—C3−2.3 (10)N5—Mn2—N8—C32166.1 (4)
C1—C2—C3—C41.0 (9)Br3—Mn2—N8—C32−120.4 (4)
C2—C3—C4—C51.0 (9)C23—N5—C19—C20−0.4 (8)
C1—N1—C5—C40.9 (8)Mn2—N5—C19—C20173.0 (4)
Mn1—N1—C5—C4175.0 (4)N5—C19—C20—C211.7 (9)
C1—N1—C5—C6−178.0 (5)C19—C20—C21—C22−0.8 (9)
Mn1—N1—C5—C6−4.0 (6)C20—C21—C22—C23−1.3 (8)
C3—C4—C5—N1−2.1 (8)C19—N5—C23—C22−1.7 (8)
C3—C4—C5—C6176.8 (5)Mn2—N5—C23—C22−176.0 (4)
C7—N2—C6—C5−174.0 (6)C19—N5—C23—C24177.0 (5)
Mn1—N2—C6—C5−6.4 (7)Mn2—N5—C23—C242.7 (6)
N1—C5—C6—N26.9 (8)C21—C22—C23—N52.6 (8)
C4—C5—C6—N2−172.0 (6)C21—C22—C23—C24−176.0 (5)
C6—N2—C7—C12−159.9 (7)C25—N6—C24—C23−178.7 (5)
Mn1—N2—C7—C1232.1 (9)Mn2—N6—C24—C230.9 (7)
C6—N2—C7—C8−25.6 (10)N5—C23—C24—N6−2.5 (8)
Mn1—N2—C7—C8166.4 (5)C22—C23—C24—N6176.3 (5)
C12—C7—C8—C9−44.1 (10)C24—N6—C25—C30−137.7 (5)
N2—C7—C8—C9−175.2 (7)Mn2—N6—C25—C3042.7 (5)
C7—C8—C9—C1040.7 (12)C24—N6—C25—C26−13.6 (8)
C8—C9—C10—C11−42.9 (13)Mn2—N6—C25—C26166.9 (4)
C9—C10—C11—C1243.4 (11)N6—C25—C26—C27−178.6 (6)
N2—C7—C12—N3−39.5 (10)C30—C25—C26—C27−56.6 (7)
C8—C7—C12—N3−173.4 (6)C25—C26—C27—C2858.7 (8)
N2—C7—C12—C11−177.8 (6)C26—C27—C28—C29−59.5 (8)
C8—C7—C12—C1148.3 (10)C27—C28—C29—C3057.6 (8)
C13—N3—C12—C7−150.9 (7)C31—N7—C30—C25−139.5 (5)
Mn1—N3—C12—C731.2 (9)Mn2—N7—C30—C2539.5 (5)
C13—N3—C12—C11−14.7 (10)C31—N7—C30—C29−16.2 (8)
Mn1—N3—C12—C11167.4 (5)Mn2—N7—C30—C29162.7 (4)
C10—C11—C12—C7−45.7 (10)N6—C25—C30—N7−49.9 (5)
C10—C11—C12—N3179.1 (7)C26—C25—C30—N7−177.6 (4)
C12—N3—C13—C14−175.5 (6)N6—C25—C30—C29−176.0 (5)
Mn1—N3—C13—C142.4 (7)C26—C25—C30—C2956.3 (6)
C18—N4—C14—C150.2 (8)C28—C29—C30—N7−177.4 (5)
Mn1—N4—C14—C15−171.8 (4)C28—C29—C30—C25−56.6 (7)
C18—N4—C14—C13178.5 (5)C30—N7—C31—C32178.7 (5)
Mn1—N4—C14—C136.4 (6)Mn2—N7—C31—C32−0.3 (7)
N3—C13—C14—N4−6.0 (7)C36—N8—C32—C333.1 (8)
N3—C13—C14—C15172.2 (5)Mn2—N8—C32—C33−172.9 (4)
N4—C14—C15—C16−0.1 (8)C36—N8—C32—C31−176.4 (5)
C13—C14—C15—C16−178.2 (5)Mn2—N8—C32—C317.5 (6)
C14—C15—C16—C170.1 (8)N7—C31—C32—N8−5.0 (8)
C15—C16—C17—C18−0.2 (8)N7—C31—C32—C33175.4 (5)
C14—N4—C18—C17−0.4 (8)N8—C32—C33—C34−0.9 (9)
Mn1—N4—C18—C17170.4 (4)C31—C32—C33—C34178.7 (5)
C16—C17—C18—N40.4 (9)C32—C33—C34—C35−2.3 (9)
O1—Mn2—N5—C1994.9 (5)C33—C34—C35—C363.1 (10)
N6—Mn2—N5—C19−175.2 (5)C32—N8—C36—C35−2.3 (8)
O2—Mn2—N5—C1918.3 (5)Mn2—N8—C36—C35173.4 (4)
N7—Mn2—N5—C19162.5 (4)C34—C35—C36—N8−0.8 (10)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1W···Br1i0.9422.383.320 (4)172.3
O1—H2W···Br4ii0.8552.463.291 (4)165.0
O2—H3W···Br40.9072.533.413 (4)163.8
O2—H4W···Br4ii0.8402.473.303 (4)169.2
Symmetry codes: (i) x−1, y, z; (ii) −x, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1W···Br1i0.9422.383.320 (4)172.3
O1—H2W···Br4ii0.8552.463.291 (4)165.0
O2—H3W···Br40.9072.533.413 (4)163.8
O2—H4W···Br4ii0.8402.473.303 (4)169.2
Symmetry codes: (i) x−1, y, z; (ii) −x, −y+1, −z+1.
Acknowledgements top

This research was supported in part by the BK21 programme from the Ministry of Education and Human Resources Development, Republic of Korea.

references
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