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Acta Cryst. (2007). E63, m2418-m2419    [ doi:10.1107/S1600536807041037 ]

Bis{2,4-dibromo-6-[(2-oxidoethylimino)methyl]phenolato-[kappa]3O,N,O'}manganese(IV) methanol hemisolvate monohydrate

G.-B. Jiang, S.-H. Zhang and M.-H. Zeng

Abstract top

In the title compound, [Mn(C9H7Br2NO2)2]·0.5CH4O·H2O, the MnIV 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.

Comment top

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 MnIV atom is coordinated by two N and four O atoms from two different tridentate ligands L2− 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···Br2iv = 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 top

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).

Experimental top

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).

Refinement top

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 Uiso(H) = 1.5 Ueq(O). All other H atoms were positioned geometrically and refined as riding, with C–H distances of 0.93–0.97 Å and Uiso(H) = 1.2 Ueq(C).

Computing details top

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 top
[Figure 1] Fig. 1. The asymmetric unit of (I) with displacement ellipsoids drawn at the 30% probability level. Non-solution H atoms have been omitted.
[Figure 2] 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 top
Crystal data top
C18H14Br4MnN2O4·0.5CH4O·H2ODx = 2.010 Mg m−3
Mr = 730.89Mo Kα radiation
λ = 0.71073 Å
Orthorhombic, Fdd2Cell parameters from 4075 reflections
a = 26.286 (4) Åθ = 2.5–26.0º
b = 32.908 (5) ŵ = 7.20 mm−1
c = 11.1681 (17) ÅT = 293 (2) K
V = 9661 (2) Å3Block, deep purple
Z = 160.18 × 0.14 × 0.13 mm
F000 = 5632
Data collection top
Bruker SMART CCD area-detector
diffractometer		4075 independent reflections
Radiation source: fine-focus sealed tube3143 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.029
T = 293(2) Kθmax = 26.0º
φ and ω scansθmin = 2.5º
Absorption correction: multi-scan
SADABS (Sheldrick, 1996)		h = −32→14
Tmin = 0.357, Tmax = 0.455k = −38→38
8149 measured reflectionsl = −13→12
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.051  w = 1/[σ2(Fo2) + (0.0654P)2 + 43.5887P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.133(Δ/σ)max < 0.001
S = 1.05Δρmax = 1.09 e Å−3
4075 reflectionsΔρmin = −0.38 e Å−3
290 parametersExtinction correction: none
20 restraintsAbsolute structure: Flack (1983), 1669 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.045 (19)
Secondary atom site location: difference Fourier map
Crystal data top
C18H14Br4MnN2O4·0.5CH4O·H2OV = 9661 (2) Å3
Mr = 730.89Z = 16
Orthorhombic, Fdd2Mo Kα
a = 26.286 (4) ŵ = 7.20 mm−1
b = 32.908 (5) ÅT = 293 (2) K
c = 11.1681 (17) Å0.18 × 0.14 × 0.13 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		4075 independent reflections
Absorption correction: multi-scan
SADABS (Sheldrick, 1996)		3143 reflections with I > 2σ(I)
Tmin = 0.357, Tmax = 0.455Rint = 0.029
8149 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.051H-atom parameters constrained
wR(F2) = 0.133  w = 1/[σ2(Fo2) + (0.0654P)2 + 43.5887P]
where P = (Fo2 + 2Fc2)/3
S = 1.05Δρmax = 1.09 e Å−3
4075 reflectionsΔρmin = −0.38 e Å−3
290 parametersAbsolute structure: Flack (1983), 1669 Friedel pairs
20 restraintsFlack parameter: 0.045 (19)
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 > 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 (Å2) top
xyzUiso*/UeqOcc. (<1)
Mn10.04388 (5)0.25185 (4)0.55027 (13)0.0418 (3)
Br10.14995 (5)0.31726 (4)0.25588 (13)0.0797 (4)
Br20.21088 (5)0.16499 (5)0.07739 (14)0.1024 (5)
Br30.18568 (5)0.26672 (3)0.84250 (12)0.0769 (4)
Br40.09302 (5)0.40746 (4)1.02880 (13)0.0909 (5)
C10.1120 (3)0.2418 (3)0.3450 (9)0.045 (2)
C20.1451 (4)0.2600 (3)0.2601 (11)0.063 (3)
C30.1729 (4)0.2370 (4)0.1815 (12)0.074 (3)
H30.19390.24930.12530.089*
C40.1690 (5)0.1956 (4)0.1872 (11)0.073 (3)
C50.1366 (3)0.1763 (3)0.2602 (10)0.058 (3)
H50.13230.14830.25430.070*
C60.1091 (3)0.1988 (3)0.3463 (9)0.048 (2)
C70.0781 (3)0.1767 (3)0.4321 (10)0.049 (2)
H70.07560.14870.42380.059*
C80.0263 (4)0.1681 (3)0.6026 (11)0.062 (3)
H8A0.04810.16060.66900.075*
H8B0.01420.14350.56420.075*
C9−0.0180 (3)0.1932 (3)0.6464 (11)0.059 (3)
H9A−0.04440.19440.58570.071*
H9B−0.03230.18130.71830.071*
C100.0955 (3)0.3013 (3)0.7461 (9)0.046 (2)
C110.1330 (4)0.3063 (3)0.8315 (10)0.059 (3)
C120.1339 (4)0.3363 (3)0.9175 (8)0.052 (2)
H120.15920.33750.97580.062*
C130.0937 (4)0.3656 (3)0.9116 (10)0.061 (3)
C140.0584 (3)0.3634 (3)0.8245 (9)0.051 (2)
H140.03340.38340.82020.061*
C150.0581 (3)0.3327 (3)0.7422 (8)0.045 (2)
C160.0194 (3)0.3353 (3)0.6506 (9)0.046 (2)
H16−0.00190.35790.65360.055*
C17−0.0327 (4)0.3176 (3)0.4826 (10)0.063 (3)
H17A−0.05750.33470.52240.075*
H17B−0.02070.33170.41170.075*
C18−0.0569 (3)0.2783 (3)0.4473 (10)0.057 (3)
H18A−0.07510.26710.51530.069*
H18B−0.08130.28310.38380.069*
N10.0543 (2)0.1932 (2)0.5168 (8)0.0453 (17)
N20.0111 (3)0.3096 (2)0.5650 (7)0.0466 (17)
O10.0876 (2)0.26594 (18)0.4206 (6)0.0494 (15)
O20.0007 (2)0.23280 (19)0.6711 (6)0.0564 (17)
O30.0963 (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−0.03830.46570.71500.121*0.50
C190.0282 (5)0.4748 (6)0.759 (2)0.068 (6)0.50
H19A0.03780.49530.70220.102*0.50
H19B0.03880.44870.73050.102*0.50
H19C0.04440.48030.83460.102*0.50
O1W−0.0549 (6)0.4146 (5)0.7965 (13)0.172 (6)
H1WA−0.05720.44030.80210.257*
H1WB−0.08570.41110.77600.257*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0489 (6)0.0388 (7)0.0378 (7)0.0059 (6)−0.0051 (6)−0.0072 (6)
Br10.0789 (7)0.0729 (8)0.0871 (9)−0.0109 (6)0.0038 (6)0.0148 (7)
Br20.0957 (9)0.1375 (13)0.0739 (10)0.0320 (8)0.0151 (7)−0.0354 (9)
Br30.0814 (7)0.0637 (7)0.0855 (9)0.0061 (6)−0.0389 (6)−0.0095 (6)
Br40.0996 (8)0.0844 (8)0.0886 (11)−0.0175 (7)0.0070 (7)−0.0550 (8)
C10.040 (4)0.055 (6)0.041 (5)0.003 (4)−0.003 (4)−0.017 (5)
C20.080 (7)0.062 (6)0.046 (7)0.002 (5)−0.002 (5)0.004 (5)
C30.061 (6)0.108 (11)0.054 (8)−0.008 (6)−0.013 (5)0.003 (7)
C40.085 (8)0.092 (9)0.043 (7)0.018 (7)−0.013 (6)−0.026 (6)
C50.050 (5)0.075 (7)0.049 (6)0.012 (5)0.008 (5)−0.020 (6)
C60.035 (4)0.060 (6)0.050 (6)0.001 (4)0.003 (4)−0.013 (5)
C70.056 (5)0.029 (5)0.063 (7)0.008 (4)−0.003 (5)−0.011 (5)
C80.069 (6)0.059 (6)0.059 (7)−0.012 (5)0.002 (5)0.003 (5)
C90.048 (5)0.062 (7)0.067 (7)−0.008 (5)−0.004 (5)0.010 (5)
C100.050 (5)0.032 (5)0.055 (6)−0.006 (4)−0.001 (4)−0.001 (4)
C110.077 (6)0.041 (5)0.058 (7)−0.005 (4)−0.012 (5)−0.002 (5)
C120.065 (6)0.052 (6)0.039 (6)−0.018 (5)−0.007 (4)−0.012 (4)
C130.064 (6)0.068 (7)0.050 (6)−0.019 (5)0.010 (5)−0.028 (5)
C140.056 (5)0.047 (5)0.050 (6)0.006 (4)0.009 (4)−0.011 (4)
C150.054 (5)0.037 (5)0.043 (6)−0.012 (4)0.009 (4)−0.010 (4)
C160.058 (5)0.034 (5)0.045 (6)0.006 (4)0.000 (4)0.003 (4)
C170.072 (6)0.061 (7)0.056 (7)0.023 (5)−0.018 (5)−0.003 (5)
C180.043 (5)0.080 (7)0.050 (6)0.008 (5)−0.002 (4)0.001 (5)
N10.034 (3)0.051 (4)0.050 (5)0.000 (3)−0.005 (3)−0.005 (4)
N20.054 (4)0.044 (4)0.042 (5)0.009 (3)−0.009 (3)−0.004 (4)
O10.044 (3)0.047 (4)0.057 (4)0.002 (3)0.006 (3)0.001 (3)
O20.071 (4)0.055 (4)0.043 (4)0.008 (3)−0.004 (3)−0.005 (3)
O30.074 (4)0.054 (4)0.061 (5)0.013 (3)−0.020 (3)−0.028 (4)
O40.049 (3)0.057 (4)0.055 (4)0.012 (3)−0.009 (3)−0.007 (3)
O50.057 (7)0.105 (10)0.080 (11)0.003 (7)−0.002 (8)0.013 (9)
C190.042 (9)0.074 (11)0.088 (14)0.019 (8)0.050 (9)0.032 (11)
O1W0.214 (12)0.196 (12)0.105 (11)−0.067 (10)0.020 (9)0.009 (9)
Geometric parameters (Å, °) top
Mn1—O21.871 (7)C9—H9B0.9700
Mn1—O11.906 (7)C10—O31.292 (11)
Mn1—N11.984 (7)C10—C111.381 (14)
Mn1—O32.027 (7)C10—C151.426 (12)
Mn1—N22.094 (7)C11—C121.377 (14)
Mn1—O42.324 (6)C12—C131.432 (14)
Br1—C21.888 (10)C12—H120.9300
Br2—C41.931 (11)C13—C141.348 (14)
Br3—C111.905 (10)C14—C151.367 (13)
Br4—C131.900 (9)C14—H140.9300
C1—O11.326 (10)C15—C161.446 (13)
C1—C61.415 (13)C16—N21.295 (12)
C1—C21.419 (15)C16—H160.9300
C2—C31.370 (17)C17—C181.494 (14)
C3—C41.368 (18)C17—N21.496 (12)
C3—H30.9300C17—H17A0.9700
C4—C51.339 (17)C17—H17B0.9700
C5—C61.414 (13)C18—O41.388 (11)
C5—H50.9300C18—H18A0.9700
C6—C71.453 (14)C18—H18B0.9700
C7—N11.257 (12)O5—C191.312 (9)
C7—H70.9300O5—H5A0.8501
C8—N11.464 (13)C19—H19A0.9600
C8—C91.508 (14)C19—H19B0.9600
C8—H8A0.9700C19—H19C0.9600
C8—H8B0.9700O1W—H1WA0.8500
C9—O21.419 (11)O1W—H1WB0.8500
C9—H9A0.9700
O2—Mn1—O1174.3 (3)H9A—C9—H9B108.5
O2—Mn1—N183.9 (3)O3—C10—C11122.4 (8)
O1—Mn1—N190.6 (3)O3—C10—C15122.2 (8)
O2—Mn1—O392.7 (3)C11—C10—C15115.2 (8)
O1—Mn1—O390.6 (3)C12—C11—C10125.5 (9)
N1—Mn1—O3110.2 (3)C12—C11—Br3115.6 (8)
O2—Mn1—N289.9 (3)C10—C11—Br3118.7 (7)
O1—Mn1—N295.0 (3)C11—C12—C13115.9 (8)
N1—Mn1—N2162.6 (3)C11—C12—H12122.0
O3—Mn1—N286.2 (3)C13—C12—H12122.0
O2—Mn1—O492.3 (3)C14—C13—C12120.4 (8)
O1—Mn1—O485.9 (3)C14—C13—Br4122.0 (8)
N1—Mn1—O487.3 (3)C12—C13—Br4117.6 (7)
O3—Mn1—O4162.2 (3)C13—C14—C15121.9 (9)
N2—Mn1—O476.7 (3)C13—C14—H14119.0
O1—C1—C6124.4 (9)C15—C14—H14119.0
O1—C1—C2117.9 (8)C14—C15—C10120.8 (8)
C6—C1—C2117.6 (8)C14—C15—C16115.7 (8)
C3—C2—C1121.4 (10)C10—C15—C16123.5 (8)
C3—C2—Br1119.9 (9)N2—C16—C15126.9 (8)
C1—C2—Br1118.7 (8)N2—C16—H16116.5
C4—C3—C2118.7 (12)C15—C16—H16116.5
C4—C3—H3120.6C18—C17—N2109.8 (7)
C2—C3—H3120.6C18—C17—H17A109.7
C5—C4—C3123.2 (11)N2—C17—H17A109.7
C5—C4—Br2120.1 (9)C18—C17—H17B109.7
C3—C4—Br2116.6 (10)N2—C17—H17B109.7
C4—C5—C6119.4 (10)H17A—C17—H17B108.2
C4—C5—H5120.3O4—C18—C17111.2 (7)
C6—C5—H5120.3O4—C18—H18A109.4
C5—C6—C1119.2 (9)C17—C18—H18A109.4
C5—C6—C7118.3 (9)O4—C18—H18B109.4
C1—C6—C7122.5 (8)C17—C18—H18B109.4
N1—C7—C6124.0 (8)H18A—C18—H18B108.0
N1—C7—H7118.0C7—N1—C8119.9 (8)
C6—C7—H7118.0C7—N1—Mn1129.1 (7)
N1—C8—C9107.0 (8)C8—N1—Mn1110.8 (6)
N1—C8—H8A110.3C16—N2—C17118.0 (7)
C9—C8—H8A110.3C16—N2—Mn1125.6 (6)
N1—C8—H8B110.3C17—N2—Mn1115.3 (6)
C9—C8—H8B110.3C1—O1—Mn1129.1 (6)
H8A—C8—H8B108.6C9—O2—Mn1112.2 (6)
O2—C9—C8107.3 (7)C10—O3—Mn1131.9 (6)
O2—C9—H9A110.3C18—O4—Mn1105.9 (5)
C8—C9—H9A110.3C19—O5—H5A115.3
O2—C9—H9B110.3H1WA—O1W—H1WB94.9
C8—C9—H9B110.3
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O5—H5A···Br1i0.853.043.893 (18)179
O1W—H1WA···O50.851.522.19 (2)134
Symmetry codes: (i) x−1/4, −y+3/4, z+1/4.
Table 1
Selected geometric parameters (Å, °) top
Mn1—O21.871 (7)Mn1—O32.027 (7)
Mn1—O11.906 (7)Mn1—N22.094 (7)
Mn1—N11.984 (7)Mn1—O42.324 (6)
O2—Mn1—O1174.3 (3)N1—Mn1—N2162.6 (3)
O2—Mn1—N183.9 (3)O3—Mn1—N286.2 (3)
O1—Mn1—N190.6 (3)O2—Mn1—O492.3 (3)
O2—Mn1—O392.7 (3)O1—Mn1—O485.9 (3)
O1—Mn1—O390.6 (3)N1—Mn1—O487.3 (3)
N1—Mn1—O3110.2 (3)O3—Mn1—O4162.2 (3)
O2—Mn1—N289.9 (3)N2—Mn1—O476.7 (3)
O1—Mn1—N295.0 (3)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O5—H5A···Br1i0.853.043.893 (18)179
O1W—H1WA···O50.851.522.19 (2)134
Symmetry codes: (i) x−1/4, −y+3/4, z+1/4.
Acknowledgements top

We acknowledge financial support by the NSFC (Nos. 30460153, 20561001) and the Natural Science Foundation of Guangxi Province (No. 0447019).

references
References top

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