metal-organic compounds
Bis[2,4-dibromo-6-(n-propyliminomethyl)phenolato-κ2N,O]cobalt(II)
aCollege of Health Science, Wuhan Institute of Physical Education, Wuhan 430079, People's Republic of China
*Correspondence e-mail: lichunyan2009@yahoo.com.cn
In the title complex, [Co(C10H10Br2NO)2], the CoII atom lies on a twofold rotation axis, the N2O2 units having distorted tetrahedral coordination environments comprising two bidentate chelate 2,4-dibromo-6-(n-propyliminomethyl)phenolate Schiff base ligands [Co—N = 1.989 (3) Å, Co—O = 1.924 (2) Å and O/N—Co—O/N = 94.53 (10)–125.40 (15)°]. In the the molecules are linked via weak intermolecular C—H⋯O hydrogen bonds [3.334 (5) Å] and there are also short inversion-related intermolecular Br⋯Br contacts [3.4263 (6) Å]
Related literature
For related compounds, see: Bermejo et al. (1996); Chen et al. (2007); Li & Wang (2007); Li et al. (2008); Maneiro et al. (2001); Qiu et al. (2007); Yuan et al. (2007). For standard bond-length values, see: Allen et al. (1987).
Experimental
Crystal data
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Data collection: SMART (Bruker, 2000); cell SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXL97 (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Supporting information
https://doi.org/10.1107/S1600536810032162/zs2053sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810032162/zs2053Isup2.hkl
3,5-Dibromosalicylaldehyde (560 mg, 2 mmol) and n-propylamine (118 mg, 2 mmol) were dissolved in methanol (25 ml). The mixture was stirred for 30 min to give an orange solution, which was added to a methanol solution (15 ml) of Co(NO3)2.6H2O (280 mg, 1 mmol). The mixture was stirred for another 20 min at room temperature to give a red solution and then filtered. The filtrate was kept in air for 5 d, forming red blocky crystals. The crystals were isolated, washed three times with distilled water and dried in a vacuum desiccator containing anhydrous CaCl2 (yield 68%). Analysis calculated for C20H20Br4CoN2O2: C 34.37, H 2.88, N 4.01%; found: C 34.17, H 2.90, N 3.99%. IR (KBr, cm-1): 3447, 3062, 2966, 2877, 2359, 1619, 1577, 1504, 1434, 1407, 1307, 1212, 1161, 1095, 1040, 865, 838, 749, 705, 604, 466.
All the H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.93–0.97 Å, and with Uiso(H) = 1.2Ueq(carrier) or 1.5Ueq(methyl groups).
The
adducts of the 3,5-dibromosalicylidene compounds derived from the condensation of 3,5-dibromosalicylaldehyde with various primary are of interest, forming complexes with a large number of transition metals (Chen et al., 2007; Qiu et al., 2007; Maneiro et al., 2001; Bermejo et al., 1996). Recently, mononuclear zinc(II) and nickel(II) compounds of Schiff base ligands derived from the condensation of 3,5-dibromosalicylaldehyde with cyclopropylamine have been structurally characterized (Li & Wang, 2007; Yuan et al., 2007). As an extension of this work, the of the title CoII complex, [C20H20Br4CoN2O2] (I), is reported here.In (I), the CoII atoms have distorted tetrahedral coordination environments with two bidentate Schiff base ligands, derived from the condensation of 3,5-dibromosalicylaldehyde and n-propylamine, acting as chelates through their phenolate O and azomethine N atoms [Co—N 1.989 (3) Å; Co—O 1.924 (2) Å; bond-angle range 94.53 (10)–125.40 (15)°] (Fig. 1). The Co atoms lie on two-fold rotation axes. The C7═N1 bond length of 1.274 (4) Å is somewhat shorter than 1.284 (2) Å observed in the previously reported compound of a Schiff base ligand derived from the condensation of salicylaldehyde with n-propylamine (Li et al., 2008). The angle between the two O1—Co1—N1 planes of the molecule is equal to 84.13°. All bond lengths are within normal ranges (Allen et al., 1987). In the the molecules are linked via weak intermolecular C—H···O hydrogen bonds and there are also short inversion-related inermolecular Br···Br contacts [3.4263 (6) Å] (Fig. 2).
For related compounds, see: Bermejo et al. (1996); Chen et al. (2007); Li & Wang (2007); Li et al. (2008); Maneiro et al. (2001); Qiu et al. (2007); Yuan et al. (2007). For standard bond-distance values, see: Allen et al. (1987).
Data collection: SMART (Bruker, 2000); cell
SMART (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXL97 (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).[Co(C10H10Br2NO)2] | F(000) = 1348 |
Mr = 698.91 | Dx = 1.993 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 1806 reflections |
a = 24.3684 (10) Å | θ = 3.3–25.5° |
b = 4.8555 (2) Å | µ = 7.62 mm−1 |
c = 21.8132 (10) Å | T = 296 K |
β = 115.523 (4)° | Block, red |
V = 2329.08 (19) Å3 | 0.32 × 0.22 × 0.20 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 2270 independent reflections |
Radiation source: fine-focus sealed tube | 1657 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
φ and ω scans | θmax = 26.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −29→21 |
Tmin = 0.097, Tmax = 0.218 | k = −5→5 |
6076 measured reflections | l = −26→26 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.065 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0251P)2 + 0.88P] where P = (Fo2 + 2Fc2)/3 |
2270 reflections | (Δ/σ)max < 0.001 |
133 parameters | Δρmax = 0.41 e Å−3 |
0 restraints | Δρmin = −0.50 e Å−3 |
[Co(C10H10Br2NO)2] | V = 2329.08 (19) Å3 |
Mr = 698.91 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 24.3684 (10) Å | µ = 7.62 mm−1 |
b = 4.8555 (2) Å | T = 296 K |
c = 21.8132 (10) Å | 0.32 × 0.22 × 0.20 mm |
β = 115.523 (4)° |
Bruker SMART CCD area-detector diffractometer | 2270 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 1657 reflections with I > 2σ(I) |
Tmin = 0.097, Tmax = 0.218 | Rint = 0.036 |
6076 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.065 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.41 e Å−3 |
2270 reflections | Δρmin = −0.50 e Å−3 |
133 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Co1 | 0.0000 | 0.31955 (14) | 0.7500 | 0.03770 (18) | |
Br1 | 0.028614 (18) | 0.79002 (8) | 0.569909 (19) | 0.05211 (14) | |
Br2 | 0.232643 (17) | 0.11525 (10) | 0.62503 (2) | 0.06655 (17) | |
N1 | 0.07574 (11) | 0.1053 (6) | 0.80081 (13) | 0.0385 (7) | |
O1 | 0.03028 (9) | 0.5013 (5) | 0.69236 (11) | 0.0413 (6) | |
C1 | 0.11919 (14) | 0.2181 (7) | 0.72164 (16) | 0.0369 (8) | |
C2 | 0.07618 (13) | 0.4180 (7) | 0.68171 (16) | 0.0341 (8) | |
C3 | 0.08482 (14) | 0.5258 (7) | 0.62579 (16) | 0.0368 (8) | |
C4 | 0.13048 (15) | 0.4419 (8) | 0.60975 (18) | 0.0440 (9) | |
H4 | 0.1343 | 0.5164 | 0.5725 | 0.053* | |
C5 | 0.17107 (15) | 0.2444 (8) | 0.64965 (19) | 0.0437 (9) | |
C6 | 0.16661 (15) | 0.1351 (8) | 0.70498 (18) | 0.0468 (9) | |
H6 | 0.1949 | 0.0056 | 0.7318 | 0.056* | |
C7 | 0.11686 (14) | 0.0829 (7) | 0.77979 (17) | 0.0415 (9) | |
H7 | 0.1491 | −0.0336 | 0.8046 | 0.050* | |
C8 | 0.08417 (17) | −0.0483 (8) | 0.86238 (18) | 0.0516 (10) | |
H8A | 0.1148 | −0.1894 | 0.8712 | 0.062* | |
H8B | 0.0464 | −0.1385 | 0.8552 | 0.062* | |
C9 | 0.10364 (16) | 0.1417 (9) | 0.92354 (18) | 0.0559 (11) | |
H9A | 0.0750 | 0.2931 | 0.9127 | 0.067* | |
H9B | 0.1023 | 0.0408 | 0.9612 | 0.067* | |
C10 | 0.16709 (18) | 0.2569 (10) | 0.9451 (2) | 0.0746 (14) | |
H10A | 0.1958 | 0.1081 | 0.9567 | 0.112* | |
H10B | 0.1772 | 0.3744 | 0.9838 | 0.112* | |
H10C | 0.1685 | 0.3610 | 0.9083 | 0.112* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0308 (3) | 0.0523 (4) | 0.0343 (4) | 0.000 | 0.0181 (3) | 0.000 |
Br1 | 0.0656 (3) | 0.0533 (3) | 0.0443 (2) | 0.0123 (2) | 0.03017 (19) | 0.01239 (19) |
Br2 | 0.0498 (2) | 0.0945 (4) | 0.0726 (3) | 0.0031 (2) | 0.0427 (2) | −0.0139 (3) |
N1 | 0.0333 (15) | 0.0490 (19) | 0.0339 (16) | −0.0022 (14) | 0.0150 (12) | 0.0031 (14) |
O1 | 0.0377 (12) | 0.0517 (16) | 0.0424 (13) | 0.0080 (11) | 0.0247 (11) | 0.0090 (12) |
C1 | 0.0351 (18) | 0.044 (2) | 0.0357 (19) | −0.0021 (16) | 0.0191 (15) | −0.0042 (16) |
C2 | 0.0324 (17) | 0.038 (2) | 0.0349 (19) | −0.0042 (16) | 0.0176 (15) | −0.0035 (16) |
C3 | 0.0448 (19) | 0.035 (2) | 0.0363 (19) | −0.0020 (16) | 0.0230 (16) | −0.0034 (16) |
C4 | 0.050 (2) | 0.050 (2) | 0.042 (2) | −0.0075 (19) | 0.0297 (18) | −0.0053 (18) |
C5 | 0.0372 (19) | 0.056 (3) | 0.049 (2) | −0.0048 (18) | 0.0285 (17) | −0.0104 (19) |
C6 | 0.0334 (19) | 0.061 (3) | 0.045 (2) | 0.0065 (18) | 0.0156 (16) | 0.0001 (19) |
C7 | 0.0323 (18) | 0.049 (2) | 0.042 (2) | 0.0064 (16) | 0.0147 (16) | 0.0080 (17) |
C8 | 0.050 (2) | 0.060 (3) | 0.047 (2) | −0.003 (2) | 0.0231 (18) | 0.015 (2) |
C9 | 0.046 (2) | 0.088 (3) | 0.037 (2) | −0.006 (2) | 0.0215 (17) | 0.010 (2) |
C10 | 0.053 (3) | 0.112 (4) | 0.051 (3) | −0.016 (3) | 0.015 (2) | 0.002 (3) |
Co1—O1i | 1.924 (2) | C4—C5 | 1.383 (5) |
Co1—O1 | 1.924 (2) | C4—H4 | 0.9300 |
Co1—N1i | 1.989 (3) | C5—C6 | 1.365 (5) |
Co1—N1 | 1.989 (3) | C6—H6 | 0.9300 |
Br1—C3 | 1.889 (3) | C7—H7 | 0.9300 |
Br2—C5 | 1.905 (3) | C8—C9 | 1.520 (5) |
N1—C7 | 1.274 (4) | C8—H8A | 0.9700 |
N1—C8 | 1.471 (4) | C8—H8B | 0.9700 |
O1—C2 | 1.301 (3) | C9—C10 | 1.516 (5) |
C1—C6 | 1.411 (5) | C9—H9A | 0.9700 |
C1—C2 | 1.419 (4) | C9—H9B | 0.9700 |
C1—C7 | 1.451 (4) | C10—H10A | 0.9600 |
C2—C3 | 1.424 (4) | C10—H10B | 0.9600 |
C3—C4 | 1.365 (4) | C10—H10C | 0.9600 |
O1i—Co1—O1 | 125.40 (15) | C5—C6—C1 | 120.2 (3) |
O1i—Co1—N1i | 94.53 (10) | C5—C6—H6 | 119.9 |
O1—Co1—N1i | 113.63 (10) | C1—C6—H6 | 119.9 |
O1i—Co1—N1 | 113.64 (10) | N1—C7—C1 | 127.5 (3) |
O1—Co1—N1 | 94.53 (10) | N1—C7—H7 | 116.2 |
N1i—Co1—N1 | 116.90 (16) | C1—C7—H7 | 116.2 |
C7—N1—C8 | 117.6 (3) | N1—C8—C9 | 111.2 (3) |
C7—N1—Co1 | 122.0 (2) | N1—C8—H8A | 109.4 |
C8—N1—Co1 | 120.3 (2) | C9—C8—H8A | 109.4 |
C2—O1—Co1 | 125.1 (2) | N1—C8—H8B | 109.4 |
C6—C1—C2 | 120.5 (3) | C9—C8—H8B | 109.4 |
C6—C1—C7 | 116.1 (3) | H8A—C8—H8B | 108.0 |
C2—C1—C7 | 123.3 (3) | C10—C9—C8 | 112.8 (3) |
O1—C2—C1 | 124.6 (3) | C10—C9—H9A | 109.0 |
O1—C2—C3 | 119.6 (3) | C8—C9—H9A | 109.0 |
C1—C2—C3 | 115.8 (3) | C10—C9—H9B | 109.0 |
C4—C3—C2 | 123.2 (3) | C8—C9—H9B | 109.0 |
C4—C3—Br1 | 118.8 (3) | H9A—C9—H9B | 107.8 |
C2—C3—Br1 | 117.9 (2) | C9—C10—H10A | 109.5 |
C3—C4—C5 | 119.1 (3) | C9—C10—H10B | 109.5 |
C3—C4—H4 | 120.4 | H10A—C10—H10B | 109.5 |
C5—C4—H4 | 120.4 | C9—C10—H10C | 109.5 |
C6—C5—C4 | 121.2 (3) | H10A—C10—H10C | 109.5 |
C6—C5—Br2 | 119.6 (3) | H10B—C10—H10C | 109.5 |
C4—C5—Br2 | 119.2 (3) |
Symmetry code: (i) −x, y, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Co(C10H10Br2NO)2] |
Mr | 698.91 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 296 |
a, b, c (Å) | 24.3684 (10), 4.8555 (2), 21.8132 (10) |
β (°) | 115.523 (4) |
V (Å3) | 2329.08 (19) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 7.62 |
Crystal size (mm) | 0.32 × 0.22 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.097, 0.218 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6076, 2270, 1657 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.065, 1.00 |
No. of reflections | 2270 |
No. of parameters | 133 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.41, −0.50 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
This work was supported by the Education Office of Hubei Province (grant No. D20104104).
References
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The Lewis base adducts of the 3,5-dibromosalicylidene compounds derived from the condensation of 3,5-dibromosalicylaldehyde with various primary amines are of interest, forming complexes with a large number of transition metals (Chen et al., 2007; Qiu et al., 2007; Maneiro et al., 2001; Bermejo et al., 1996). Recently, mononuclear zinc(II) and nickel(II) compounds of Schiff base ligands derived from the condensation of 3,5-dibromosalicylaldehyde with cyclopropylamine have been structurally characterized (Li & Wang, 2007; Yuan et al., 2007). As an extension of this work, the crystal structure of the title CoII complex, [C20H20Br4CoN2O2] (I), is reported here.
In (I), the CoII atoms have distorted tetrahedral coordination environments with two bidentate Schiff base ligands, derived from the condensation of 3,5-dibromosalicylaldehyde and n-propylamine, acting as chelates through their phenolate O and azomethine N atoms [Co—N 1.989 (3) Å; Co—O 1.924 (2) Å; bond-angle range 94.53 (10)–125.40 (15)°] (Fig. 1). The Co atoms lie on two-fold rotation axes. The C7═N1 bond length of 1.274 (4) Å is somewhat shorter than 1.284 (2) Å observed in the previously reported compound of a Schiff base ligand derived from the condensation of salicylaldehyde with n-propylamine (Li et al., 2008). The angle between the two O1—Co1—N1 planes of the molecule is equal to 84.13°. All bond lengths are within normal ranges (Allen et al., 1987). In the crystal structure, the molecules are linked via weak intermolecular C—H···O hydrogen bonds and there are also short inversion-related inermolecular Br···Br contacts [3.4263 (6) Å] (Fig. 2).