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Acta Cryst. (2007). E63, m2365    [ doi:10.1107/S1600536807039815 ]

Aquachlorido{4,4'-dibromo-2,2'-[propane-1,3-diylbis(nitrilomethylidyne)]diphenolato}manganese(III)

I.-C. Hwang and K. Ha

Abstract top

In the title complex, [Mn(C17H14Br2N2O2)Cl(H2O)], the MnIII ion is six-coordinated by the tetradentate N,N'-bis(5-bromosalicylidene)-1,3-diiminopropane dianion (Brsalpn), Cl and water ligands in a distorted octahedral geometry. The complexes are assembled through intermolecular hydrogen bonds and [pi]-[pi] interactions (the centroid-centroid distance is 3.844 Å and the dihedral angle between the ring planes is 13.5°) along the c axis.

Comment top

In the title complex, Mn3+ ion is six-coordinated by two N and two O atoms from the tetradentate ligand, N,N'-bis(5-bromosalicylidene)-1,3- diiminopropane dianion (Brsalpn), occupying the four equatorial positions, one Cl atom and one O atom from water ligand in the axial positions (Fig.1). The coordination environment around the Mn centre is distorted octahedral. Within the equatorial plane, the chelating angles lie in the range of 90.68 (10)°–92.70 (11)° and the O1—Mn—O2 bond angle is 85.46 (9)°. The apical O3w—Mn—Cl bond angle is 170.43 (10)° (Table 1). The Mn—N bond lengths (2.039 (3) and 2.009 (3) Å) are longer than the Mn—O bond (1.894 (2) and 1.882 (2) Å), but the bond distance between the Mn atom and the O atom of the water ligand is considerably long with 2.342 (4) Å. The compound displays the intermolecular hydrogen bonds between the O atom of the water and the O atom of the chelate ligand or Cl anion (Table 2). Moreover, there are intermolecular π-π interactions between the adjacent benzene rings. For Cg1 (the centroid of six-membered ring C1–C6) and Cg2i (ring C12–C17; symmetry code i: 1 − x, 1 − y, 1 − z), the centroid-centroid distance is 3.844 Å and the dihedral angle between the ring planes is 13.5°. The compounds are assembled through these hydrogen-bonding and π-π interactions along the c axis (Fig. 2).

Related literature top

For related literature, see: Mitra et al. (2006).

Experimental top

Mn(CH3COO)3·2H2O (0.50 g, 1.86 mmol), NaCl (0.11 g, 1.88 mmol) and N,N'-bis(5-bromosalicylidene)-1,3-diiminopropane (H2Brsalpn; 0.83 g, 1.89 mmol) in EtOH (70 ml) and H2O (3 ml) were stirred for 3 h at room temparature and then filtered. The solvent was removed, the residue washed with water and acetone, and dried under vacuum, to give a dark green powder (0.76 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from a MeOH solution. MS (FAB): m/z 491, 493, 495 (Mn(Brsalpn)+); IR (KBr): 3358 cm−1 (broad).

Refinement top

H atoms were positioned geometrically and allowed to ride on their respective carrier atoms [C—H = 0.93 (sp2) or 0.97 Å (sp3) and Uiso(H) = 1.2Ueq(C)]. The H atoms of the water ligand were localized from Fourier difference maps and refined with isotropic thermal parameters.

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: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. The structure of the title complex. Displacement ellipsoids are drawn at the 50% probability level. H atoms at C atoms have been omitted for clarity.
[Figure 2] Fig. 2. View of the unit-cell contents of the title complex. Hydrogen-bond interactions are drawn with dashed lines.
Aquachlorido{4,4'-dibromo-2,2'-[propane-1,3- diylbis(nitrilomethylidyne)]diphenolato}manganese(III) top
Crystal data top
[Mn(C17H14Br2N2O2)Cl(H2O)]F000 = 1072
Mr = 546.53Dx = 1.939 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2295 reflections
a = 13.2369 (14) Åθ = 2.5–23.9º
b = 10.2666 (11) ŵ = 5.14 mm−1
c = 13.8635 (15) ÅT = 293 (2) K
β = 96.434 (2)ºPlate, green
V = 1872.2 (3) Å30.12 × 0.10 × 0.10 mm
Z = 4
Data collection top
Bruker SMART 1000 CCD
diffractometer		3263 independent reflections
Radiation source: fine-focus sealed tube2153 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.035
T = 293(2) Kθmax = 25.0º
φ and ω scansθmin = 1.6º
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		h = −15→7
Tmin = 0.448, Tmax = 0.598k = −11→12
10208 measured reflectionsl = −16→14
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)] = 0.034H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.062  w = 1/[σ2(Fo2) + (0.0243P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.84(Δ/σ)max = 0.001
3263 reflectionsΔρmax = 0.73 e Å−3
243 parametersΔρmin = −0.63 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Mn(C17H14Br2N2O2)Cl(H2O)]V = 1872.2 (3) Å3
Mr = 546.53Z = 4
Monoclinic, P21/cMo Kα
a = 13.2369 (14) ŵ = 5.14 mm−1
b = 10.2666 (11) ÅT = 293 (2) K
c = 13.8635 (15) Å0.12 × 0.10 × 0.10 mm
β = 96.434 (2)º
Data collection top
Bruker SMART 1000 CCD
diffractometer		3263 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		2153 reflections with I > 2σ(I)
Tmin = 0.448, Tmax = 0.598Rint = 0.035
10208 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.034243 parameters
wR(F2) = 0.062H atoms treated by a mixture of
independent and constrained refinement
S = 0.84Δρmax = 0.73 e Å−3
3263 reflectionsΔρmin = −0.63 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 > 2sigma(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
Mn0.40515 (4)0.33233 (5)0.37376 (4)0.02959 (16)
Br1−0.06136 (4)0.73006 (5)0.33024 (4)0.07213 (19)
Br20.94384 (3)0.14805 (5)0.41859 (4)0.06350 (17)
Cl0.33221 (7)0.31177 (9)0.19346 (7)0.0414 (3)
O10.36286 (17)0.5071 (2)0.38667 (19)0.0353 (7)
O20.53279 (17)0.4039 (2)0.35665 (18)0.0351 (7)
O3W0.4692 (3)0.3130 (4)0.5376 (3)0.0461 (9)
H3A0.497 (4)0.368 (4)0.556 (4)0.07 (2)*
H3B0.441 (4)0.282 (5)0.577 (4)0.12 (3)*
N10.2690 (2)0.2666 (3)0.4099 (2)0.0294 (8)
N20.4567 (2)0.1510 (2)0.3550 (2)0.0299 (8)
C10.2688 (3)0.5545 (3)0.3745 (3)0.0327 (10)
C20.2529 (3)0.6879 (4)0.3601 (3)0.0410 (11)
H20.30870.74260.35850.049*
C30.1571 (3)0.7398 (4)0.3481 (3)0.0506 (12)
H30.14860.82910.33930.061*
C40.0723 (3)0.6597 (4)0.3491 (3)0.0497 (12)
C50.0858 (3)0.5299 (4)0.3645 (3)0.0475 (11)
H50.02940.47620.36610.057*
C60.1836 (3)0.4754 (4)0.3779 (3)0.0358 (10)
C70.1904 (3)0.3399 (3)0.4022 (3)0.0368 (10)
H70.12990.30010.41390.044*
C80.2479 (3)0.1309 (3)0.4385 (3)0.0455 (12)
H8A0.22930.13230.50420.055*
H8B0.18950.09950.39650.055*
C90.3307 (3)0.0379 (4)0.4349 (4)0.0604 (15)
H9A0.3033−0.04910.44070.072*
H9B0.37990.05240.49110.072*
C100.3850 (3)0.0414 (3)0.3472 (3)0.0418 (11)
H10A0.4215−0.03960.34130.050*
H10B0.33660.05160.28970.050*
C110.5502 (3)0.1228 (3)0.3483 (3)0.0333 (10)
H110.56450.03710.33260.040*
C120.6348 (3)0.2111 (3)0.3627 (3)0.0304 (9)
C130.7313 (3)0.1549 (4)0.3738 (3)0.0384 (10)
H130.73850.06530.36720.046*
C140.8149 (3)0.2313 (4)0.3943 (3)0.0391 (10)
C150.8056 (3)0.3657 (4)0.3990 (3)0.0418 (11)
H150.86330.41730.41120.050*
C160.7113 (3)0.4223 (3)0.3856 (3)0.0358 (10)
H160.70590.51260.38800.043*
C170.6227 (3)0.3467 (3)0.3683 (3)0.0311 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn0.0280 (3)0.0247 (3)0.0364 (4)−0.0021 (2)0.0049 (3)−0.0010 (3)
Br10.0565 (3)0.0848 (4)0.0714 (4)0.0366 (3)−0.0093 (3)−0.0064 (3)
Br20.0318 (3)0.0806 (4)0.0771 (4)0.0098 (2)0.0022 (2)−0.0028 (3)
Cl0.0484 (6)0.0408 (6)0.0344 (7)−0.0017 (4)0.0020 (5)0.0012 (5)
O10.0310 (15)0.0251 (14)0.051 (2)−0.0002 (11)0.0073 (13)−0.0034 (12)
O20.0283 (14)0.0278 (14)0.050 (2)−0.0007 (11)0.0073 (13)0.0013 (12)
O3W0.050 (2)0.044 (2)0.042 (2)−0.0127 (16)−0.0021 (17)−0.0044 (17)
N10.0314 (18)0.0261 (18)0.031 (2)−0.0011 (14)0.0062 (15)0.0004 (14)
N20.0300 (18)0.0226 (17)0.037 (2)−0.0051 (13)0.0015 (15)−0.0036 (14)
C10.045 (3)0.028 (2)0.025 (3)0.0051 (18)0.0042 (19)−0.0048 (18)
C20.051 (3)0.035 (3)0.037 (3)−0.0011 (19)0.007 (2)−0.004 (2)
C30.072 (3)0.039 (3)0.041 (3)0.021 (2)0.009 (2)0.001 (2)
C40.039 (3)0.060 (3)0.049 (3)0.014 (2)−0.001 (2)−0.006 (2)
C50.036 (2)0.051 (3)0.055 (4)0.001 (2)0.001 (2)−0.006 (2)
C60.032 (2)0.035 (2)0.040 (3)0.0033 (18)0.0002 (19)−0.0054 (19)
C70.029 (2)0.040 (2)0.042 (3)−0.0068 (18)0.0073 (19)−0.003 (2)
C80.049 (3)0.031 (2)0.058 (4)−0.0046 (19)0.013 (2)0.006 (2)
C90.064 (3)0.033 (3)0.088 (5)−0.008 (2)0.028 (3)0.007 (2)
C100.042 (2)0.031 (2)0.054 (3)−0.0095 (18)0.010 (2)−0.011 (2)
C110.039 (2)0.024 (2)0.037 (3)0.0029 (17)0.0061 (19)0.0012 (18)
C120.031 (2)0.029 (2)0.032 (3)−0.0002 (16)0.0055 (18)0.0019 (17)
C130.037 (2)0.036 (2)0.042 (3)0.0010 (19)0.007 (2)0.000 (2)
C140.026 (2)0.056 (3)0.035 (3)0.0068 (19)0.0042 (18)0.003 (2)
C150.031 (2)0.060 (3)0.035 (3)−0.013 (2)0.0048 (19)−0.006 (2)
C160.035 (2)0.037 (2)0.036 (3)−0.0066 (18)0.0069 (19)−0.0008 (19)
C170.031 (2)0.037 (2)0.027 (3)−0.0028 (18)0.0086 (18)0.0012 (18)
Geometric parameters (Å, °) top
Mn—O21.882 (2)C5—C61.403 (5)
Mn—O11.894 (2)C5—H50.9300
Mn—N22.009 (3)C6—C71.431 (5)
Mn—N12.039 (3)C7—H70.9300
Mn—O3W2.342 (4)C8—C91.458 (5)
Mn—Cl2.5852 (13)C8—H8A0.9700
Br1—C41.901 (4)C8—H8B0.9700
Br2—C141.905 (4)C9—C101.481 (5)
O1—C11.330 (4)C9—H9A0.9700
O2—C171.321 (4)C9—H9B0.9700
O3W—H3A0.71 (4)C10—H10A0.9700
O3W—H3B0.76 (5)C10—H10B0.9700
N1—C71.279 (4)C11—C121.438 (5)
N1—C81.483 (4)C11—H110.9300
N2—C111.285 (4)C12—C131.394 (5)
N2—C101.468 (4)C12—C171.405 (4)
C1—C61.394 (5)C13—C141.360 (5)
C1—C21.397 (5)C13—H130.9300
C2—C31.368 (5)C14—C151.387 (5)
C2—H20.9300C15—C161.370 (5)
C3—C41.394 (5)C15—H150.9300
C3—H30.9300C16—C171.405 (5)
C4—C51.358 (5)C16—H160.9300
O2—Mn—O185.46 (9)C5—C6—C7116.8 (3)
O2—Mn—N291.32 (10)N1—C7—C6128.4 (3)
O1—Mn—N2176.42 (10)N1—C7—H7115.8
O2—Mn—N1172.37 (11)C6—C7—H7115.8
O1—Mn—N190.68 (10)C9—C8—N1116.2 (3)
N2—Mn—N192.70 (11)C9—C8—H8A108.2
O2—Mn—O3W85.58 (13)N1—C8—H8A108.2
O1—Mn—O3W93.86 (12)C9—C8—H8B108.2
N2—Mn—O3W87.45 (12)N1—C8—H8B108.2
N1—Mn—O3W88.12 (13)H8A—C8—H8B107.4
O2—Mn—Cl98.82 (8)C8—C9—C10116.6 (4)
O1—Mn—Cl94.96 (9)C8—C9—H9A108.1
N2—Mn—Cl83.97 (9)C10—C9—H9A108.1
N1—Mn—Cl88.05 (9)C8—C9—H9B108.1
O3W—Mn—Cl170.43 (10)C10—C9—H9B108.1
C1—O1—Mn128.1 (2)H9A—C9—H9B107.3
C17—O2—Mn128.3 (2)N2—C10—C9109.1 (3)
Mn—O3W—H3A114 (4)N2—C10—H10A109.9
Mn—O3W—H3B125 (5)C9—C10—H10A109.9
H3A—O3W—H3B111 (6)N2—C10—H10B109.9
C7—N1—C8113.6 (3)C9—C10—H10B109.9
C7—N1—Mn121.2 (2)H10A—C10—H10B108.3
C8—N1—Mn125.1 (2)N2—C11—C12126.1 (3)
C11—N2—C10116.2 (3)N2—C11—H11116.9
C11—N2—Mn124.2 (2)C12—C11—H11116.9
C10—N2—Mn119.6 (2)C13—C12—C17120.9 (3)
O1—C1—C6122.1 (3)C13—C12—C11116.4 (3)
O1—C1—C2120.0 (3)C17—C12—C11122.7 (3)
C6—C1—C2117.9 (3)C14—C13—C12119.9 (4)
C3—C2—C1121.4 (4)C14—C13—H13120.1
C3—C2—H2119.3C12—C13—H13120.1
C1—C2—H2119.3C13—C14—C15120.6 (3)
C2—C3—C4120.4 (4)C13—C14—Br2118.0 (3)
C2—C3—H3119.8C15—C14—Br2121.4 (3)
C4—C3—H3119.8C16—C15—C14120.0 (3)
C5—C4—C3119.2 (4)C16—C15—H15120.0
C5—C4—Br1119.9 (3)C14—C15—H15120.0
C3—C4—Br1120.8 (3)C15—C16—C17121.2 (4)
C4—C5—C6121.0 (4)C15—C16—H16119.4
C4—C5—H5119.5C17—C16—H16119.4
C6—C5—H5119.5O2—C17—C12122.8 (3)
C1—C6—C5120.0 (4)O2—C17—C16119.9 (3)
C1—C6—C7123.0 (3)C12—C17—C16117.3 (3)
O2—Mn—O1—C1158.8 (3)C2—C1—C6—C51.6 (6)
N1—Mn—O1—C1−27.8 (3)O1—C1—C6—C75.1 (6)
O3W—Mn—O1—C1−116.0 (3)C2—C1—C6—C7−173.3 (4)
Cl—Mn—O1—C160.3 (3)C4—C5—C6—C1−0.7 (6)
O1—Mn—O2—C17159.2 (3)C4—C5—C6—C7174.5 (4)
N2—Mn—O2—C17−22.4 (3)C8—N1—C7—C6178.8 (4)
O3W—Mn—O2—C1764.9 (3)Mn—N1—C7—C6−6.2 (6)
Cl—Mn—O2—C17−106.5 (3)C1—C6—C7—N1−11.3 (7)
O1—Mn—N1—C720.3 (3)C5—C6—C7—N1173.6 (4)
N2—Mn—N1—C7−158.5 (3)C7—N1—C8—C9171.4 (4)
O3W—Mn—N1—C7114.2 (3)Mn—N1—C8—C9−3.4 (5)
Cl—Mn—N1—C7−74.6 (3)N1—C8—C9—C10−45.4 (5)
O1—Mn—N1—C8−165.2 (3)C11—N2—C10—C9123.7 (4)
N2—Mn—N1—C816.0 (3)Mn—N2—C10—C9−57.0 (4)
O3W—Mn—N1—C8−71.4 (3)C8—C9—C10—N278.4 (5)
Cl—Mn—N1—C899.9 (3)C10—N2—C11—C12−173.9 (4)
O2—Mn—N2—C117.4 (3)Mn—N2—C11—C126.8 (5)
N1—Mn—N2—C11−166.1 (3)N2—C11—C12—C13165.8 (4)
O3W—Mn—N2—C11−78.1 (3)N2—C11—C12—C17−12.4 (6)
Cl—Mn—N2—C11106.1 (3)C17—C12—C13—C142.7 (6)
O2—Mn—N2—C10−171.9 (3)C11—C12—C13—C14−175.5 (4)
N1—Mn—N2—C1014.6 (3)C12—C13—C14—C15−3.6 (6)
O3W—Mn—N2—C10102.6 (3)C12—C13—C14—Br2175.2 (3)
Cl—Mn—N2—C10−73.1 (3)C13—C14—C15—C161.8 (6)
Mn—O1—C1—C619.6 (5)Br2—C14—C15—C16−176.9 (3)
Mn—O1—C1—C2−162.0 (3)C14—C15—C16—C170.8 (6)
O1—C1—C2—C3−179.5 (4)Mn—O2—C17—C1223.2 (5)
C6—C1—C2—C3−0.9 (6)Mn—O2—C17—C16−157.8 (3)
C1—C2—C3—C4−0.7 (6)C13—C12—C17—O2178.9 (3)
C2—C3—C4—C51.6 (7)C11—C12—C17—O2−3.0 (6)
C2—C3—C4—Br1−178.8 (3)C13—C12—C17—C16−0.1 (5)
C3—C4—C5—C6−0.9 (7)C11—C12—C17—C16178.0 (3)
Br1—C4—C5—C6179.5 (3)C15—C16—C17—O2179.3 (3)
O1—C1—C6—C5−179.9 (4)C15—C16—C17—C12−1.7 (6)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3W—H3A···O1i0.71 (4)2.31 (5)2.989 (4)159 (5)
O3W—H3B···Clii0.76 (5)2.48 (5)3.236 (4)174 (6)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+1/2, z+1/2.
Selected geometric parameters (Å, °) top
Mn—O21.882 (2)Mn—N12.039 (3)
Mn—O11.894 (2)Mn—O3W2.342 (4)
Mn—N22.009 (3)Mn—Cl2.5852 (13)
O2—Mn—O185.46 (9)N2—Mn—N192.70 (11)
O2—Mn—N291.32 (10)O3W—Mn—Cl170.43 (10)
O1—Mn—N190.68 (10)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3W—H3A···O1i0.71 (4)2.31 (5)2.989 (4)159 (5)
O3W—H3B···Clii0.76 (5)2.48 (5)3.236 (4)174 (6)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+1/2, z+1/2.
Acknowledgements top

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

references
References top

Bruker (2000). SADABS (Version 2.03), SMART (Version 5.618) and SAINT (Version 6.02a). Bruker AXS Inc., Madison, Wisconsin, USA.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?.

Mitra, K., Biswas, S., Lucas, C. R. & Adhikary, B. (2006). Inorg. Chim. Acta, 359, 1997–2003.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.