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Acta Cryst. (2009). E65, m1671    [ doi:10.1107/S1600536809049484 ]

{2,2'-[5-Bromopyridine-2,3-diylbis(nitrilomethylidyne)]diphenolato}chlorido(dimethylformamide)manganese(III)

H. Xie, S. Meng, Y. Zhu and P. Bai

Abstract top

In the title complex, [Mn(C19H12BrN3O2)Cl(C3H7NO)], the MnIII ion is coordinated by two N and two O atoms from the tetradentate Schiff base ligand, one O atom from the dimethylformamide ligand and a Cl anion in a distorted octahedral geometry. In the crystal structure, weak intermolecular C-H...Cl hydrogen bonds link the molecules into centrosymmetric dimers with a short distance of 3.878 (3) Å between the centroids of the aromatic rings.

Comment top

Because of their interesting structures and wide potential applications, the synthesis and structural investigation of Schiff base complexes have been given much attention. Furthermore, these types of complexes play an important part in the development of coordination chemistry as well as inorganic biochemistry, catalysis, optical materials and so on (Li et al., 2008; Fei & Fang, 2008).

The crystal structure of the title compound is shown in Fig. 1. The coordination sphere of the MnIII ion is a slightly distorted octahedron, in which the four equatorial positions are occupied by two N atoms and two O atoms coming from the tetradentate Schiff base ligand, and the two axial ones with a trans conformation are occupied by one Cl ion and one O atom of the coordinated dimethylamine-methoxyl, respectively. The Mn—N, Mn—O and Mn—Cl bond lengths are basically consistant with those corresponding distances in other Mn-Schiff base complexes (Li et al., 2008; Eltayeb et al., 2008a, b). It is worth noting that centrosymmetric dimers with the short distance of 3.878 (3) Å between the centroids of aromatic rings are formed under the help of the weak intermolecular C—H···Cl hydrogen bond interaction (Table 1).

Related literature top

For related structures, see: Li et al. (2008); Eltayeb et al. (2008a,b); Fei & Fang (2008).

Experimental top

The Schiff base ligand was synthesized by condensation of 5-bromo-2,3-diaminopyridine and 2-hydroxy-benzaldehyde with the ratio 1:2 in ethanol. The synthesis of the title complex was carried out by reacting Mn(ClO4)2.6H2O, and the schiff-base ligand (1:1, molar ratio) in methanol. After the stirring process was continued for about one hour at room temperature, the mixture was filtered. The insoluble dark-brown solid was filtered out, dissolved in DMF and layered with ether. After one month, the block dark-brown crystals suitable for X-ray diffraction were obtained with a yield about 50%.

Refinement top

H atoms were placed in calcluated positions (C—H 0.93-0.96 Å), and were refined as riding atoms, with Uiso(H) = 1.2-1.5Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: SHELXTL (Sheldrick, 2008b); software used to prepare material for publication: SHELXTL (Sheldrick, 2008b).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. All H-atoms are omitted for clarity.
{2,2'-[5-Bromopyridine-2,3-diylbis(nitrilomethylidyne)]diphenolato} chlorido(dimethylformamide)manganese(III) top
Crystal data top
[Mn(C19H12BrN3O2)Cl(C3H7NO)]F(000) = 1120
Mr = 557.71Dx = 1.653 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2012 reflections
a = 13.2834 (11) Åθ = 2.1–26.7°
b = 15.4971 (13) ŵ = 2.52 mm−1
c = 12.2314 (11) ÅT = 293 K
β = 117.143 (1)°Block, dark-brown
V = 2240.6 (3) Å30.31 × 0.21 × 0.19 mm
Z = 4
Data collection top
Bruker APEXII CCD area-detector
diffractometer		3945 independent reflections
Radiation source: fine-focus sealed tube3238 reflections with I > 2σ(I)
graphiteRint = 0.022
φ and ω scansθmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008a)		h = −15→15
Tmin = 0.508, Tmax = 0.646k = −13→18
10906 measured reflectionsl = −14→13
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0643P)2 + 1.7733P]
where P = (Fo2 + 2Fc2)/3
3945 reflections(Δ/σ)max = 0.001
291 parametersΔρmax = 1.30 e Å−3
0 restraintsΔρmin = −0.52 e Å−3
Crystal data top
[Mn(C19H12BrN3O2)Cl(C3H7NO)]V = 2240.6 (3) Å3
Mr = 557.71Z = 4
Monoclinic, P21/cMo Kα radiation
a = 13.2834 (11) ŵ = 2.52 mm−1
b = 15.4971 (13) ÅT = 293 K
c = 12.2314 (11) Å0.31 × 0.21 × 0.19 mm
β = 117.143 (1)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer		3945 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008a)		3238 reflections with I > 2σ(I)
Tmin = 0.508, Tmax = 0.646Rint = 0.022
10906 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.039H-atom parameters constrained
wR(F2) = 0.116Δρmax = 1.30 e Å−3
S = 1.06Δρmin = −0.52 e Å−3
3945 reflectionsAbsolute structure: ?
291 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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*/Ueq
Br10.45611 (4)0.63147 (3)0.36373 (4)0.06441 (17)
Mn10.81172 (4)0.45734 (3)0.12690 (5)0.03870 (16)
Cl10.68097 (8)0.34011 (7)0.05359 (10)0.0587 (3)
O10.9460 (2)0.38529 (17)0.1822 (2)0.0521 (6)
O20.7824 (2)0.49890 (18)−0.0267 (2)0.0518 (6)
O30.9317 (2)0.56444 (18)0.2006 (3)0.0567 (7)
N10.8278 (2)0.45131 (18)0.3010 (3)0.0423 (7)
N20.6755 (2)0.54058 (18)0.1157 (3)0.0418 (7)
N30.7332 (3)0.4802 (2)0.4180 (3)0.0516 (8)
N41.0806 (3)0.6366 (2)0.1995 (3)0.0503 (8)
C10.7383 (3)0.4907 (2)0.3157 (3)0.0418 (8)
C20.6585 (3)0.5396 (2)0.2180 (3)0.0401 (8)
C30.5713 (3)0.5821 (2)0.2312 (3)0.0459 (8)
H30.51750.61510.16810.055*
C40.5694 (3)0.5727 (2)0.3378 (4)0.0482 (9)
C50.6486 (3)0.5208 (3)0.4285 (4)0.0530 (9)
H50.64280.51350.50090.064*
C61.0097 (3)0.3730 (2)0.3939 (4)0.0455 (9)
C71.0197 (3)0.3568 (2)0.2899 (4)0.0455 (9)
C81.1146 (3)0.3060 (3)0.3007 (4)0.0550 (10)
H81.12280.29510.23040.066*
C91.1925 (3)0.2733 (3)0.4095 (5)0.0618 (11)
H91.25190.23990.41250.074*
C101.1839 (3)0.2892 (3)0.5137 (4)0.0623 (11)
H101.23720.26750.58880.075*
C111.0937 (3)0.3385 (3)0.5056 (4)0.0559 (10)
H111.08810.34960.57740.067*
C120.9159 (3)0.4184 (2)0.3953 (3)0.0463 (8)
H120.91770.42520.47170.056*
C130.6144 (3)0.5898 (2)−0.0885 (3)0.0432 (8)
C140.7045 (3)0.5503 (2)−0.1064 (3)0.0450 (8)
C150.7093 (4)0.5706 (3)−0.2114 (4)0.0555 (10)
H150.76760.5487−0.22540.067*
C160.6292 (4)0.6232 (3)−0.2976 (4)0.0620 (11)
H160.63490.6356−0.36890.074*
C170.5388 (4)0.6590 (3)−0.2831 (4)0.0605 (11)
H170.48530.6937−0.34380.073*
C180.5322 (3)0.6420 (3)−0.1807 (4)0.0528 (9)
H180.47280.6645−0.16930.063*
C190.6052 (3)0.5823 (2)0.0182 (3)0.0418 (8)
H190.54380.60910.02130.050*
C200.9824 (3)0.5958 (3)0.1477 (4)0.0518 (9)
H200.94840.59020.06270.062*
C211.1408 (4)0.6469 (4)0.3284 (4)0.0799 (14)
H21A1.10980.69460.35320.120*
H21B1.21910.65790.35150.120*
H21C1.13440.59520.36800.120*
C221.1358 (4)0.6716 (3)0.1327 (4)0.0620 (11)
H22A1.08570.66870.04620.093*
H22B1.20300.63900.15080.093*
H22C1.15580.73070.15620.093*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0571 (3)0.0792 (3)0.0650 (3)0.0171 (2)0.0349 (2)0.0026 (2)
Mn10.0317 (3)0.0426 (3)0.0388 (3)0.0076 (2)0.0134 (2)0.0029 (2)
Cl10.0422 (5)0.0516 (5)0.0713 (7)0.0020 (4)0.0165 (5)−0.0049 (5)
O10.0397 (14)0.0642 (17)0.0499 (15)0.0126 (12)0.0184 (12)0.0036 (12)
O20.0499 (15)0.0583 (16)0.0463 (14)0.0128 (13)0.0212 (12)0.0064 (12)
O30.0516 (15)0.0600 (17)0.0592 (17)−0.0085 (13)0.0259 (14)−0.0013 (13)
N10.0373 (15)0.0417 (16)0.0448 (16)0.0038 (12)0.0161 (13)0.0031 (13)
N20.0378 (15)0.0421 (16)0.0402 (16)0.0030 (12)0.0133 (13)0.0013 (12)
N30.0526 (19)0.061 (2)0.0447 (18)0.0090 (16)0.0252 (15)0.0067 (14)
N40.0459 (18)0.0497 (18)0.057 (2)0.0010 (14)0.0248 (16)0.0029 (14)
C10.0361 (18)0.0406 (19)0.047 (2)0.0007 (15)0.0179 (16)−0.0015 (15)
C20.0362 (18)0.0412 (18)0.0413 (19)−0.0008 (14)0.0163 (15)−0.0027 (14)
C30.0387 (19)0.045 (2)0.047 (2)0.0038 (16)0.0134 (16)0.0002 (16)
C40.042 (2)0.051 (2)0.055 (2)0.0018 (16)0.0245 (18)−0.0021 (17)
C50.057 (2)0.057 (2)0.050 (2)0.0087 (19)0.0292 (19)0.0052 (18)
C60.0330 (18)0.045 (2)0.052 (2)0.0016 (14)0.0131 (16)0.0069 (16)
C70.0298 (17)0.0419 (19)0.058 (2)0.0004 (14)0.0142 (17)0.0061 (16)
C80.044 (2)0.049 (2)0.073 (3)0.0061 (17)0.028 (2)0.0050 (19)
C90.033 (2)0.054 (2)0.089 (3)0.0102 (17)0.020 (2)0.014 (2)
C100.039 (2)0.060 (3)0.070 (3)0.0065 (18)0.009 (2)0.019 (2)
C110.043 (2)0.059 (2)0.053 (2)−0.0006 (18)0.0110 (18)0.0064 (19)
C120.042 (2)0.049 (2)0.044 (2)0.0027 (16)0.0164 (17)0.0019 (16)
C130.0367 (18)0.0402 (19)0.0426 (19)−0.0040 (15)0.0094 (15)0.0022 (15)
C140.0415 (19)0.046 (2)0.0420 (19)−0.0066 (16)0.0139 (16)−0.0031 (15)
C150.056 (2)0.063 (3)0.051 (2)−0.004 (2)0.027 (2)−0.0019 (19)
C160.064 (3)0.071 (3)0.045 (2)−0.006 (2)0.020 (2)0.0082 (19)
C170.059 (3)0.063 (3)0.048 (2)0.004 (2)0.014 (2)0.0117 (19)
C180.046 (2)0.056 (2)0.050 (2)0.0023 (17)0.0159 (18)0.0049 (18)
C190.0339 (17)0.0390 (18)0.049 (2)0.0023 (15)0.0159 (16)0.0002 (15)
C200.049 (2)0.053 (2)0.050 (2)0.0000 (18)0.0201 (19)0.0005 (18)
C210.067 (3)0.105 (4)0.062 (3)−0.029 (3)0.024 (2)−0.006 (3)
C220.060 (3)0.063 (3)0.077 (3)0.002 (2)0.043 (2)0.008 (2)
Geometric parameters (Å, °) top
Br1—C41.906 (4)C7—C81.441 (5)
Mn1—O21.851 (3)C8—C91.357 (6)
Mn1—O11.945 (2)C8—H80.9300
Mn1—N12.043 (3)C9—C101.352 (6)
Mn1—N22.175 (3)C9—H90.9300
Mn1—O32.190 (3)C10—C111.387 (6)
Mn1—Cl12.3875 (11)C10—H100.9300
O1—C71.308 (4)C11—H110.9300
O2—C141.317 (4)C12—H120.9300
O3—C201.227 (5)C13—C191.371 (5)
N1—C121.315 (4)C13—C181.412 (5)
N1—C11.419 (4)C13—C141.447 (5)
N2—C191.302 (4)C14—C151.352 (5)
N2—C21.369 (4)C15—C161.372 (6)
N3—C11.294 (5)C15—H150.9300
N3—C51.344 (5)C16—C171.404 (6)
N4—C201.323 (5)C16—H160.9300
N4—C211.414 (6)C17—C181.322 (6)
N4—C221.431 (5)C17—H170.9300
C1—C21.404 (5)C18—H180.9300
C2—C31.404 (5)C19—H190.9300
C3—C41.324 (5)C20—H200.9300
C3—H30.9300C21—H21A0.9600
C4—C51.385 (5)C21—H21B0.9600
C5—H50.9300C21—H21C0.9600
C6—C71.362 (5)C22—H22A0.9600
C6—C111.416 (5)C22—H22B0.9600
C6—C121.438 (5)C22—H22C0.9600
O2—Mn1—O1106.71 (11)C9—C8—H8118.8
O2—Mn1—N1161.27 (12)C7—C8—H8118.8
O1—Mn1—N188.18 (11)C10—C9—C8120.2 (4)
O2—Mn1—N286.90 (11)C10—C9—H9119.9
O1—Mn1—N2165.18 (11)C8—C9—H9119.9
N1—Mn1—N277.35 (11)C9—C10—C11118.3 (4)
O2—Mn1—O386.03 (11)C9—C10—H10120.8
O1—Mn1—O384.97 (11)C11—C10—H10120.8
N1—Mn1—O383.99 (11)C10—C11—C6123.5 (4)
N2—Mn1—O390.27 (11)C10—C11—H11118.3
O2—Mn1—Cl195.93 (9)C6—C11—H11118.3
O1—Mn1—Cl195.06 (9)N1—C12—C6127.6 (3)
N1—Mn1—Cl193.95 (9)N1—C12—H12116.2
N2—Mn1—Cl189.19 (8)C6—C12—H12116.2
O3—Mn1—Cl1177.93 (8)C19—C13—C18115.9 (3)
C7—O1—Mn1133.6 (2)C19—C13—C14123.2 (3)
C14—O2—Mn1133.8 (2)C18—C13—C14120.8 (3)
C20—O3—Mn1123.7 (3)O2—C14—C15118.8 (4)
C12—N1—C1121.2 (3)O2—C14—C13124.6 (3)
C12—N1—Mn1124.0 (2)C15—C14—C13116.5 (3)
C1—N1—Mn1114.7 (2)C14—C15—C16120.8 (4)
C19—N2—C2119.6 (3)C14—C15—H15119.6
C19—N2—Mn1125.5 (2)C16—C15—H15119.6
C2—N2—Mn1114.5 (2)C15—C16—C17123.1 (4)
C1—N3—C5116.6 (3)C15—C16—H16118.4
C20—N4—C21121.4 (4)C17—C16—H16118.4
C20—N4—C22123.9 (4)C18—C17—C16118.0 (4)
C21—N4—C22114.7 (4)C18—C17—H17121.0
N3—C1—C2122.6 (3)C16—C17—H17121.0
N3—C1—N1119.0 (3)C17—C18—C13120.7 (4)
C2—C1—N1118.4 (3)C17—C18—H18119.7
N2—C2—C1114.1 (3)C13—C18—H18119.7
N2—C2—C3126.0 (3)N2—C19—C13125.1 (3)
C1—C2—C3119.9 (3)N2—C19—H19117.4
C4—C3—C2116.7 (3)C13—C19—H19117.4
C4—C3—H3121.7O3—C20—N4126.5 (4)
C2—C3—H3121.7O3—C20—H20116.7
C3—C4—C5120.3 (3)N4—C20—H20116.7
C3—C4—Br1118.9 (3)N4—C21—H21A109.5
C5—C4—Br1120.9 (3)N4—C21—H21B109.5
N3—C5—C4123.9 (4)H21A—C21—H21B109.5
N3—C5—H5118.1N4—C21—H21C109.5
C4—C5—H5118.1H21A—C21—H21C109.5
C7—C6—C11117.6 (3)H21B—C21—H21C109.5
C7—C6—C12123.7 (3)N4—C22—H22A109.5
C11—C6—C12118.6 (4)N4—C22—H22B109.5
O1—C7—C6122.2 (3)H22A—C22—H22B109.5
O1—C7—C8119.9 (4)N4—C22—H22C109.5
C6—C7—C8118.0 (3)H22A—C22—H22C109.5
C9—C8—C7122.5 (4)H22B—C22—H22C109.5
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C19—H19···Cl1i0.932.813.691 (2)159
Symmetry codes: (i) −x+1, −y+1, −z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C19—H19···Cl1i0.932.813.691 (2)159
Symmetry codes: (i) −x+1, −y+1, −z.
references
References top

Bruker (2001). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2004). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.

Eltayeb, N. E., Teoh, S. G., Chantrapromma, S., Fun, H.-K. & Adnan, R. (2008a). Acta Cryst. E64, m124–m125.

Eltayeb, N. E., Teoh, S. G., Chantrapromma, S., Fun, H.-K. & Adnan, R. (2008b). Acta Cryst. E64, m670–m671.

Li, C. H., Huang, K. L., Dou, J. M., Chi, Y. N., Xu, Y. Q., Shen, L., Wang, D. Q. & Hu, C. W. (2008). CrystEngComm, 8, 3141–3143.

Fei, L. & Fang, Z. (2008). Acta Cryst. E64, m406–m407.

Sheldrick, G. M. (2008a). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008b). Acta Cryst. A64, 112–122.