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Acta Cryst. (2009). E65, m225    [ doi:10.1107/S1600536809002104 ]

{6,6'-Dimethoxy-2,2'-[4-bromo-o-phenylenebis(nitrilomethylidyne)]diphenolato}nickel(II) methanol solvate

M.-M. Yu, H. Xu, Q.-Z. Shi, Y.-N. Wei and Z.-X. Li

Abstract top

In the title compound, [Ni(C22H17BrN2O4)]·CH3OH, the NiII ion is in a slightly distorted square-planar geometry involving an N2O2 atom set of the tetradentate Schiff base ligand. The asymmetric unit contains one nickel complex and one methanol solvent molecule. The dihedral angle between the aromatic ring planes of the central aromatic ring and other two aromatic rings are 10.8 (3) and 6.0 (2)°. The crystal structure is stabilized by intermolecular C-H...O and C-H...Br and by intramolecular O-H...O hydrogen bonds.

Comment top

The synthesis and structural investigation of Schiff base complexes have attracted much attention due to their interesting structures and wide potential applications. They play an important role in the development of coordination chemistry as well as inorganic biochemistry, catalysis and optical materials (Aurangzeb et al., 1994; Fun & Kia, 2008; Hulme et al., 1997; Li et al., 2008; Fei & Fang, 2008; Zhang & Janiak, 2001). Here, the synthesis and crystal structure of the title complex (I) are reported.

The molecular structure of title compound is showing in Fig. 1. The dihedral angles between the aromatic ring planes of the middle aromatic ring and other two aromatic rings are 10.8 (3)° and 6.0 (2)°, respectively. The crystal structure, is stabilized by intermolecular C—H···O and C—H···Br and intramolecular O—H···O hydrogen bonds.

Related literature top

For Schiff base complexes in coordination chemistry, inorganic biochemistry, catalysis and optical

materials, see: Aurangzeb et al. (1994); Fun & Kia (2008); Hulme et al. (1997); Li et al. (2008); Fei & Fang (2008); Xia et al. (2007); Zhang & Janiak (2001).

Experimental top

6,6'-Dimethoxy-2,2'-[-4-bromo-o-phenylenebis (nitrilomethylidyne)]diphenol was synthesized according to modified reported methods (Xia, et al., 2007). A mixture of NiCl2.6H2O (1 mmol, 237.7 mg), 6,6'-Dimethoxy-2,2'-[-4-bromo-o-phenylenebis (nitrilomethylidyne)]diphenol (1 mmol, 455.3 mg) in 40 ml methanol and 20 ml water was refluxed for forty minutes. Crystals suitable for X-ray diffraction analysis were obtained by slow evaporation at room temperature for three weeks.

Refinement top

All H atoms were placed in geometrically calculated positions with C—H = 0.96 Å for methyl H atoms, C—H = 0.93 Å for aromatic H atoms and were refined isotropic with Uiso(H) = 1.2Ueq(C) of parent atom using a riding model. H atoms of methanol were constrained to idealized geometries, with C—H = 0.96 Å for methyl H atoms, O—H = 0.82 Å, and with Uiso(H) = 1.2Ueq(C) and 1.5Ueq(O).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (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).

Figures top
[Figure 1] Fig. 1. A view of complex (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme.
[Figure 2] Fig. 2. The crystal packing of title compound, viewed along the a axis. Hydrogen bonds are shown as dashed lines.
{6,6'-Dimethoxy-2,2'-[4-bromo-o- phenylenebis(nitrilomethylidyne)]diphenolato}nickel(II) methanol solvate top
Crystal data top
[Ni(C22H17BrN2O4)]·CH4OZ = 2
Mr = 544.04F(000) = 552
Triclinic, P1Dx = 1.710 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.4991 (12) ÅCell parameters from 4086 reflections
b = 11.8367 (18) Åθ = 1.7–26.0°
c = 12.5428 (19) ŵ = 2.85 mm−1
α = 105.042 (2)°T = 295 K
β = 96.971 (3)°Block, brown
γ = 95.932 (3)°0.12 × 0.08 × 0.04 mm
V = 1056.6 (3) Å3
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer		4086 independent reflections
Radiation source: fine-focus sealed tube3123 reflections with I > 2σ(I)
graphiteRint = 0.018
φ and ω scansθmax = 26.0°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		h = −9→9
Tmin = 0.726, Tmax = 0.895k = −14→12
5680 measured reflectionsl = −13→15
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)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.161H-atom parameters constrained
S = 1.14 w = 1/[σ2(Fo2) + (0.0951P)2 + 0.0167P]
where P = (Fo2 + 2Fc2)/3
4086 reflections(Δ/σ)max = 0.003
291 parametersΔρmax = 0.67 e Å−3
0 restraintsΔρmin = −0.61 e Å−3
Crystal data top
[Ni(C22H17BrN2O4)]·CH4Oγ = 95.932 (3)°
Mr = 544.04V = 1056.6 (3) Å3
Triclinic, P1Z = 2
a = 7.4991 (12) ÅMo Kα radiation
b = 11.8367 (18) ŵ = 2.85 mm−1
c = 12.5428 (19) ÅT = 295 K
α = 105.042 (2)°0.12 × 0.08 × 0.04 mm
β = 96.971 (3)°
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer		4086 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		3123 reflections with I > 2σ(I)
Tmin = 0.726, Tmax = 0.895Rint = 0.018
5680 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.161Δρmax = 0.67 e Å−3
S = 1.14Δρmin = −0.61 e Å−3
4086 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
C30.8652 (7)0.0691 (4)0.3998 (4)0.0510 (12)
H30.8869−0.00850.39120.061*
C40.7842 (7)0.1013 (4)0.3070 (4)0.0471 (11)
C50.7428 (6)0.2142 (4)0.3178 (4)0.0443 (10)
H50.68760.23630.25730.053*
C60.7873 (5)0.2926 (4)0.4224 (3)0.0357 (9)
C10.8774 (6)0.2549 (4)0.5093 (3)0.0370 (9)
C71.0169 (6)0.3214 (4)0.6961 (4)0.0393 (10)
H71.03570.24350.68880.047*
C81.0843 (6)0.4041 (4)0.7991 (4)0.0413 (10)
C91.1868 (7)0.3673 (5)0.8839 (4)0.0521 (12)
H91.20060.28790.87170.063*
C101.2639 (7)0.4443 (5)0.9811 (4)0.0569 (13)
H101.32770.41761.03580.068*
C111.2491 (7)0.5644 (5)1.0008 (4)0.0552 (13)
H111.30350.61741.06830.066*
C121.1539 (7)0.6045 (4)0.9200 (4)0.0477 (11)
C131.0650 (6)0.5251 (4)0.8169 (3)0.0397 (10)
C141.2135 (11)0.8037 (5)1.0330 (5)0.093 (2)
H14B1.34190.80151.04510.139*
H14A1.16050.78421.09300.139*
H14C1.19180.88151.03040.139*
C150.6634 (5)0.4582 (4)0.3866 (3)0.0368 (9)
H150.61450.40890.31620.044*
C160.6301 (5)0.5774 (4)0.4112 (3)0.0371 (9)
C170.5302 (6)0.6144 (5)0.3271 (4)0.0489 (11)
H170.48330.56010.25880.059*
C180.5021 (7)0.7289 (5)0.3451 (4)0.0517 (12)
H180.43820.75270.28830.062*
C190.5680 (6)0.8118 (4)0.4482 (4)0.0503 (12)
H190.54830.89000.45910.060*
C200.6611 (6)0.7783 (4)0.5328 (4)0.0395 (10)
C210.6960 (5)0.6590 (4)0.5160 (3)0.0343 (9)
C220.7016 (8)0.9703 (4)0.6604 (4)0.0581 (13)
H22A0.75801.01110.73540.087*
H22B0.57370.97440.65320.087*
H22C0.75361.00670.60910.087*
C230.7099 (11)0.8110 (6)0.8879 (5)0.087 (2)
H23A0.84010.82050.89840.131*
H23B0.66870.81310.95780.131*
H23C0.66850.87390.86070.131*
C20.9109 (5)0.1459 (3)0.4982 (3)0.0303 (8)
H20.96580.12380.55880.036*
N20.7574 (4)0.4124 (3)0.4553 (3)0.0349 (8)
N30.9301 (4)0.3451 (3)0.6101 (3)0.0343 (7)
O10.7893 (4)0.6322 (2)0.5995 (2)0.0385 (7)
O20.9756 (4)0.5679 (3)0.7446 (2)0.0416 (7)
O31.1343 (6)0.7207 (3)0.9303 (3)0.0678 (11)
O40.7307 (5)0.8499 (3)0.6360 (3)0.0501 (8)
O50.6410 (5)0.7031 (3)0.8107 (3)0.0665 (10)
H5'0.68960.69660.75460.100*
Ni10.86214 (7)0.48899 (4)0.60223 (4)0.03314 (19)
Br10.73229 (10)−0.01370 (5)0.16760 (5)0.0796 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C30.053 (3)0.038 (2)0.064 (3)0.013 (2)0.013 (2)0.013 (2)
C40.060 (3)0.037 (2)0.036 (2)0.004 (2)0.003 (2)−0.0015 (19)
C50.051 (3)0.042 (2)0.036 (2)0.006 (2)0.004 (2)0.0065 (19)
C60.034 (2)0.033 (2)0.037 (2)0.0021 (16)0.0070 (18)0.0065 (18)
C10.033 (2)0.038 (2)0.039 (2)0.0048 (17)0.0081 (18)0.0082 (19)
C70.038 (2)0.040 (2)0.044 (2)0.0129 (18)0.0070 (19)0.0136 (19)
C80.039 (2)0.049 (3)0.036 (2)0.0110 (19)0.0031 (19)0.013 (2)
C90.064 (3)0.059 (3)0.042 (3)0.022 (2)0.007 (2)0.023 (2)
C100.059 (3)0.069 (4)0.045 (3)0.023 (3)−0.006 (2)0.021 (3)
C110.052 (3)0.066 (3)0.040 (3)0.004 (2)−0.008 (2)0.009 (2)
C120.052 (3)0.049 (3)0.039 (2)0.006 (2)−0.002 (2)0.012 (2)
C130.039 (2)0.046 (2)0.037 (2)0.0074 (18)0.0071 (18)0.0149 (19)
C140.146 (7)0.053 (4)0.055 (4)−0.014 (4)−0.031 (4)0.006 (3)
C150.033 (2)0.042 (2)0.034 (2)−0.0010 (17)0.0043 (17)0.0092 (18)
C160.029 (2)0.046 (2)0.038 (2)0.0049 (17)0.0049 (17)0.0158 (19)
C170.044 (3)0.062 (3)0.043 (3)0.009 (2)−0.001 (2)0.020 (2)
C180.049 (3)0.066 (3)0.046 (3)0.018 (2)−0.005 (2)0.028 (2)
C190.049 (3)0.048 (3)0.063 (3)0.015 (2)0.008 (2)0.029 (2)
C200.037 (2)0.045 (2)0.041 (2)0.0072 (18)0.0078 (19)0.019 (2)
C210.028 (2)0.040 (2)0.037 (2)0.0026 (16)0.0065 (17)0.0145 (18)
C220.074 (3)0.036 (3)0.066 (3)0.018 (2)0.012 (3)0.014 (2)
C230.119 (6)0.074 (4)0.051 (3)0.021 (4)−0.015 (4)−0.005 (3)
C20.034 (2)0.0273 (19)0.0283 (19)0.0080 (15)0.0012 (16)0.0056 (16)
N20.0321 (17)0.0362 (18)0.0341 (18)0.0026 (14)0.0040 (15)0.0070 (15)
N30.0323 (17)0.0354 (18)0.0341 (18)0.0054 (14)0.0072 (14)0.0067 (15)
O10.0466 (17)0.0355 (15)0.0317 (15)0.0087 (13)−0.0023 (13)0.0092 (12)
O20.0493 (17)0.0393 (16)0.0346 (15)0.0074 (13)−0.0034 (13)0.0116 (13)
O30.100 (3)0.044 (2)0.045 (2)−0.0022 (19)−0.017 (2)0.0069 (16)
O40.066 (2)0.0355 (16)0.0469 (19)0.0123 (15)0.0009 (16)0.0103 (14)
O50.069 (3)0.073 (3)0.048 (2)0.007 (2)0.0067 (18)0.0035 (18)
Ni10.0361 (3)0.0314 (3)0.0302 (3)0.0051 (2)0.0022 (2)0.0068 (2)
Br10.1203 (6)0.0507 (4)0.0512 (4)0.0185 (3)−0.0019 (3)−0.0107 (3)
Geometric parameters (Å, °) top
C3—C21.310 (6)C15—N21.307 (5)
C3—C41.406 (7)C15—C161.419 (6)
C3—H30.9300C15—H150.9300
C4—C51.380 (7)C16—C171.408 (6)
C4—Br11.885 (4)C16—C211.411 (6)
C5—C61.376 (6)C17—C181.358 (7)
C5—H50.9300C17—H170.9300
C6—C11.406 (6)C18—C191.401 (7)
C6—N21.419 (5)C18—H180.9300
C1—C21.316 (6)C19—C201.366 (6)
C1—N31.409 (5)C19—H190.9300
C7—N31.301 (5)C20—O41.357 (5)
C7—C81.402 (6)C20—C211.429 (6)
C7—H70.9300C21—O11.315 (5)
C8—C131.417 (6)C22—O41.423 (5)
C8—C91.423 (6)C22—H22A0.9600
C9—C101.339 (7)C22—H22B0.9600
C9—H90.9300C22—H22C0.9600
C10—C111.397 (7)C23—O51.392 (7)
C10—H100.9300C23—H23A0.9600
C11—C121.381 (6)C23—H23B0.9600
C11—H110.9300C23—H23C0.9600
C12—O31.373 (6)C2—H20.9300
C12—C131.425 (6)N2—Ni11.862 (3)
C13—O21.299 (5)N3—Ni11.851 (3)
C14—O31.419 (6)O1—Ni11.841 (3)
C14—H14B0.9600O2—Ni11.840 (3)
C14—H14A0.9600O5—H5'0.8200
C14—H14C0.9600
C2—C3—C4121.5 (4)C18—C17—C16120.4 (4)
C2—C3—H3119.3C18—C17—H17119.8
C4—C3—H3119.3C16—C17—H17119.8
C5—C4—C3120.8 (4)C17—C18—C19120.9 (4)
C5—C4—Br1120.8 (4)C17—C18—H18119.6
C3—C4—Br1118.4 (4)C19—C18—H18119.6
C6—C5—C4116.7 (4)C20—C19—C18120.4 (4)
C6—C5—H5121.6C20—C19—H19119.8
C4—C5—H5121.6C18—C19—H19119.8
C5—C6—C1118.7 (4)O4—C20—C19125.8 (4)
C5—C6—N2127.6 (4)O4—C20—C21114.0 (4)
C1—C6—N2113.7 (3)C19—C20—C21120.2 (4)
C2—C1—C6123.6 (4)O1—C21—C16123.9 (4)
C2—C1—N3122.6 (4)O1—C21—C20117.6 (4)
C6—C1—N3113.9 (4)C16—C21—C20118.5 (4)
N3—C7—C8125.1 (4)O4—C22—H22A109.5
N3—C7—H7117.4O4—C22—H22B109.5
C8—C7—H7117.4H22A—C22—H22B109.5
C7—C8—C13121.2 (4)O4—C22—H22C109.5
C7—C8—C9119.1 (4)H22A—C22—H22C109.5
C13—C8—C9119.5 (4)H22B—C22—H22C109.5
C10—C9—C8121.5 (5)O5—C23—H23A109.5
C10—C9—H9119.3O5—C23—H23B109.5
C8—C9—H9119.3H23A—C23—H23B109.5
C9—C10—C11120.5 (4)O5—C23—H23C109.5
C9—C10—H10119.7H23A—C23—H23C109.5
C11—C10—H10119.7H23B—C23—H23C109.5
C12—C11—C10120.0 (5)C3—C2—C1118.5 (4)
C12—C11—H11120.0C3—C2—H2120.7
C10—C11—H11120.0C1—C2—H2120.7
O3—C12—C11124.5 (4)C15—N2—C6121.1 (3)
O3—C12—C13114.2 (4)C15—N2—Ni1126.4 (3)
C11—C12—C13121.3 (5)C6—N2—Ni1112.5 (3)
O2—C13—C8124.3 (4)C7—N3—C1119.6 (4)
O2—C13—C12118.5 (4)C7—N3—Ni1127.2 (3)
C8—C13—C12117.2 (4)C1—N3—Ni1113.2 (3)
O3—C14—H14B109.5C21—O1—Ni1127.9 (3)
O3—C14—H14A109.5C13—O2—Ni1128.0 (3)
H14B—C14—H14A109.5C12—O3—C14116.9 (4)
O3—C14—H14C109.5C20—O4—C22117.9 (4)
H14B—C14—H14C109.5C23—O5—H5'109.5
H14A—C14—H14C109.5O2—Ni1—O184.82 (12)
N2—C15—C16125.1 (4)O2—Ni1—N393.97 (14)
N2—C15—H15117.5O1—Ni1—N3177.54 (13)
C16—C15—H15117.5O2—Ni1—N2177.07 (14)
C17—C16—C21119.7 (4)O1—Ni1—N294.73 (14)
C17—C16—C15118.3 (4)N3—Ni1—N286.59 (15)
C21—C16—C15122.0 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O5—H5'···O10.822.152.952 (4)165
C15—H15···O5i0.932.373.203 (5)149
C23—H23B···Br1ii0.962.843.556 (6)133
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y+1, z+1.
Table 1
Selected geometric parameters (Å, °) top
N2—Ni11.862 (3)O1—Ni11.841 (3)
N3—Ni11.851 (3)O2—Ni11.840 (3)
O2—Ni1—O184.82 (12)O1—Ni1—N294.73 (14)
O2—Ni1—N393.97 (14)N3—Ni1—N286.59 (15)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O5—H5'···O10.822.152.952 (4)165
C15—H15···O5i0.932.373.203 (5)149
C23—H23B···Br1ii0.962.843.556 (6)133
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y+1, z+1.
Acknowledgements top

This work was supported by the Natural Science Foundation of China (No. 50873093).

references
References top

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