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Acta Cryst. (2009). E65, m418    [ doi:10.1107/S1600536809009234 ]

{4-Bromo-2-[(2-morpholinoethyl)iminomethyl]phenolato}iodido(methanol)zinc(II)

C.-L. Han

Abstract top

The title compound, [Zn(C13H16BrN2O2)I(CH3OH)], is a new mononuclear zinc(II) complex synthesized by the reaction of equimolar quantities of 5-bromosalicylaldehyde, 2-morpholinoethylamine and ZnI2 in methanol. The Zn atom is four-coordinate in a distorted tetrahedral geometry, binding to a phenolate O and an imine N atom of the Schiff base ligand, the O atom of a methanol molecule and one I- anion. In the crystal structure, adjacent molecules are linked through intermolecular O-H...O hydrogen bonds, forming centrosymmetric dimers.

Comment top

Metal complexes of the Schiff base 4-bromo-2-[(2-morpholinoethylimino)methyl]phenol have not been reported previously. In this paper, the author reports the crystal structure of the title compound, a new mononuclear zinc(II) complex, (I), Fig. 1.

In (I), the Zn atom is four-coordinate in a tetrahedral geometry, with one O and one imine N atoms of a Schiff base ligand, one O atom of a methanol molecule, and one I atom. The tetrahedral geometry is severely distorted, as evidenced by the coordinate bond lengths and angles (Table 1). The bond lengths and angles in this complex are comparable with those in the similar zinc(II) complexes (Ali et al., 2008; You, 2005; Zhu & Yang, 2008). In the crystal structure, adjacent molecules are linked through intermolecular O–H···O hydrogen bonds (Table 2), forming centrosymmetric dimers (Fig. 2).

Related literature top

For the structures of related zinc(II) complexes, see: Ali et al. (2008); You (2005); Zhu & Yang (2008).

Experimental top

Equimolar quantities (1.0 mmol each) of 5-bromosalicyaldehyde, 2-morpholinoethylamine, and ZnI2 were mixed in methanol. The mixture was stirred at reflux for 30 min and filtered. The filtrate was slowly evaporated for a few days, yielding yellow block-like crystals.

Refinement top

H3A was located from a difference Fourier map and refined isotropically, with the O–H distance restrained to 0.85 (1) Å, and with Uiso(H) values fixed at 0.08 Å2. The other H atoms were placed in idealized positions and constrained to ride on their parent atoms with C–H distances of 0.93–0.97 Å, and with Uiso(H) set at 1.2 or 1.5Ueq(C).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The structure of the complex, showing 30% probability displacement ellipsoids and the atom-numbering scheme.
[Figure 2] Fig. 2. The crystal packing of (I) showing the formation of centrosymmetric dimers. Hydrogen bonds are shown as dashed lines.
{4-Bromo-2-[(2-morpholinoethyl)iminomethyl]phenolato}iodido(methanol)zinc(II) top
Crystal data top
[Zn(C13H16BrN2O2)I(CH4O)]F(000) = 1040
Mr = 536.50Dx = 1.951 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3128 reflections
a = 7.747 (2) Åθ = 2.6–25.8°
b = 24.977 (3) ŵ = 5.24 mm−1
c = 9.598 (2) ÅT = 298 K
β = 100.497 (4)°Block, yellow
V = 1826.1 (6) Å30.30 × 0.30 × 0.28 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer		3928 independent reflections
Radiation source: fine-focus sealed tube2994 reflections with I > 2σ(I)
graphiteRint = 0.038
ω scansθmax = 27.0°, θmin = 1.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −9→9
Tmin = 0.217, Tmax = 0.231k = −30→31
12877 measured reflectionsl = −12→12
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)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.096H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0385P)2 + 2.0556P]
where P = (Fo2 + 2Fc2)/3
3928 reflections(Δ/σ)max < 0.001
203 parametersΔρmax = 0.96 e Å−3
1 restraintΔρmin = −0.71 e Å−3
Crystal data top
[Zn(C13H16BrN2O2)I(CH4O)]V = 1826.1 (6) Å3
Mr = 536.50Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.747 (2) ŵ = 5.24 mm−1
b = 24.977 (3) ÅT = 298 K
c = 9.598 (2) Å0.30 × 0.30 × 0.28 mm
β = 100.497 (4)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		3928 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2994 reflections with I > 2σ(I)
Tmin = 0.217, Tmax = 0.231Rint = 0.038
12877 measured reflectionsθmax = 27.0°
Refinement top
R[F2 > 2σ(F2)] = 0.040H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.096Δρmax = 0.96 e Å−3
S = 1.03Δρmin = −0.71 e Å−3
3928 reflectionsAbsolute structure: ?
203 parametersFlack parameter: ?
1 restraintRogers 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
Zn10.50584 (7)0.55343 (2)0.28004 (5)0.03432 (14)
I10.17781 (4)0.568293 (16)0.25354 (4)0.05466 (14)
Br11.05025 (10)0.31501 (2)0.17245 (8)0.0752 (2)
O10.5139 (4)0.47117 (12)0.3133 (3)0.0403 (8)
O20.6023 (12)0.73465 (19)0.4160 (5)0.119 (3)
O30.6375 (4)0.56560 (12)0.4796 (3)0.0370 (7)
N10.6591 (4)0.54528 (13)0.1329 (4)0.0276 (7)
N20.5630 (5)0.65133 (14)0.2055 (4)0.0381 (9)
C10.7471 (6)0.45205 (16)0.1873 (4)0.0298 (9)
C20.6310 (6)0.43807 (17)0.2793 (5)0.0340 (10)
C30.6426 (7)0.38546 (18)0.3320 (5)0.0464 (13)
H30.56490.37470.38990.056*
C40.7640 (8)0.34916 (19)0.3017 (5)0.0502 (13)
H40.76910.31480.33960.060*
C50.8782 (7)0.36454 (18)0.2139 (5)0.0409 (11)
C60.8706 (6)0.41432 (18)0.1569 (5)0.0364 (10)
H60.94770.42370.09720.044*
C70.7474 (6)0.50294 (17)0.1163 (4)0.0310 (9)
H70.82090.50540.05010.037*
C80.6873 (6)0.59135 (17)0.0431 (5)0.0366 (10)
H8A0.67220.5799−0.05490.044*
H8B0.80660.60440.07130.044*
C90.5603 (6)0.63595 (17)0.0561 (4)0.0346 (10)
H9A0.58970.66690.00410.042*
H9B0.44260.62470.01370.042*
C100.4279 (9)0.6926 (2)0.2083 (6)0.0645 (18)
H10A0.31260.67750.17410.077*
H10B0.44580.72190.14640.077*
C110.4376 (14)0.7133 (3)0.3593 (8)0.099 (3)
H11A0.34890.74070.35930.118*
H11B0.41180.68420.41920.118*
C120.7298 (13)0.6951 (3)0.4179 (7)0.100 (3)
H12A0.70500.66560.47690.119*
H12B0.84380.70970.45920.119*
C130.7348 (9)0.6746 (2)0.2692 (6)0.0619 (16)
H13A0.76290.70380.21060.074*
H13B0.82560.64760.27350.074*
C140.8215 (7)0.5553 (2)0.5089 (6)0.0561 (14)
H14A0.84230.51830.49080.084*
H14B0.86730.56330.60640.084*
H14C0.87880.57730.44920.084*
H3A0.592 (8)0.554 (2)0.547 (4)0.080*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0288 (3)0.0448 (3)0.0309 (3)0.0064 (2)0.0093 (2)−0.0008 (2)
I10.02973 (19)0.0787 (3)0.0568 (2)0.00815 (16)0.01119 (16)0.01217 (18)
Br10.0901 (5)0.0545 (4)0.0895 (5)0.0392 (3)0.0386 (4)0.0100 (3)
O10.046 (2)0.0353 (17)0.0463 (19)0.0053 (14)0.0257 (17)0.0043 (14)
O20.253 (9)0.041 (3)0.068 (3)−0.004 (4)0.044 (4)−0.013 (2)
O30.0370 (18)0.0466 (19)0.0286 (16)−0.0013 (14)0.0093 (14)0.0038 (14)
N10.0282 (19)0.0265 (18)0.0288 (18)0.0003 (14)0.0067 (15)0.0010 (14)
N20.053 (3)0.0282 (19)0.037 (2)0.0047 (17)0.0179 (19)0.0044 (15)
C10.032 (2)0.030 (2)0.027 (2)0.0010 (18)0.0060 (19)−0.0024 (17)
C20.038 (3)0.035 (2)0.030 (2)−0.0023 (19)0.008 (2)−0.0002 (18)
C30.066 (4)0.036 (3)0.044 (3)0.004 (2)0.027 (3)0.007 (2)
C40.075 (4)0.029 (2)0.048 (3)0.005 (2)0.014 (3)0.005 (2)
C50.046 (3)0.038 (3)0.040 (3)0.012 (2)0.010 (2)−0.005 (2)
C60.037 (3)0.037 (2)0.037 (2)0.004 (2)0.013 (2)−0.0018 (19)
C70.029 (2)0.038 (2)0.027 (2)−0.0031 (19)0.0084 (18)−0.0034 (18)
C80.042 (3)0.034 (2)0.036 (2)0.000 (2)0.015 (2)0.0049 (19)
C90.038 (3)0.033 (2)0.033 (2)0.0041 (19)0.009 (2)0.0095 (18)
C100.107 (5)0.039 (3)0.057 (3)0.030 (3)0.041 (4)0.017 (2)
C110.174 (10)0.065 (5)0.073 (5)0.055 (5)0.064 (6)0.022 (4)
C120.196 (10)0.046 (4)0.051 (4)−0.041 (5)0.007 (5)−0.009 (3)
C130.087 (5)0.046 (3)0.053 (3)−0.026 (3)0.013 (3)−0.005 (2)
C140.040 (3)0.075 (4)0.050 (3)−0.008 (3)0.001 (3)0.017 (3)
Geometric parameters (Å, °) top
Zn1—N12.014 (3)C4—H40.9300
Zn1—O32.023 (3)C5—C61.355 (6)
Zn1—O12.078 (3)C6—H60.9300
Zn1—I12.5346 (9)C7—H70.9300
Br1—C51.913 (4)C8—C91.507 (6)
O1—C21.311 (5)C8—H8A0.9700
O2—C121.394 (10)C8—H8B0.9700
O2—C111.398 (11)C9—H9A0.9700
O3—C141.425 (6)C9—H9B0.9700
O3—H3A0.84 (5)C10—C111.528 (9)
N1—C71.285 (5)C10—H10A0.9700
N1—C81.478 (5)C10—H10B0.9700
N2—C101.472 (6)C11—H11A0.9700
N2—C131.478 (7)C11—H11B0.9700
N2—C91.481 (5)C12—C131.525 (8)
C1—C61.411 (6)C12—H12A0.9700
C1—C21.414 (6)C12—H12B0.9700
C1—C71.442 (6)C13—H13A0.9700
C2—C31.405 (6)C13—H13B0.9700
C3—C41.375 (7)C14—H14A0.9600
C3—H30.9300C14—H14B0.9600
C4—C51.383 (7)C14—H14C0.9600
N1—Zn1—O3114.78 (13)C9—C8—H8A109.4
N1—Zn1—O190.15 (12)N1—C8—H8B109.4
O3—Zn1—O190.42 (13)C9—C8—H8B109.4
N1—Zn1—I1130.76 (10)H8A—C8—H8B108.0
O3—Zn1—I1113.36 (9)N2—C9—C8112.2 (4)
O1—Zn1—I199.31 (9)N2—C9—H9A109.2
C2—O1—Zn1126.0 (3)C8—C9—H9A109.2
C12—O2—C11109.3 (5)N2—C9—H9B109.2
C14—O3—Zn1118.2 (3)C8—C9—H9B109.2
C14—O3—H3A109 (4)H9A—C9—H9B107.9
Zn1—O3—H3A118 (4)N2—C10—C11110.1 (5)
C7—N1—C8115.5 (3)N2—C10—H10A109.6
C7—N1—Zn1124.4 (3)C11—C10—H10A109.6
C8—N1—Zn1119.9 (3)N2—C10—H10B109.6
C10—N2—C13107.9 (4)C11—C10—H10B109.6
C10—N2—C9108.4 (4)H10A—C10—H10B108.2
C13—N2—C9110.8 (4)O2—C11—C10112.5 (6)
C6—C1—C2119.8 (4)O2—C11—H11A109.1
C6—C1—C7115.6 (4)C10—C11—H11A109.1
C2—C1—C7124.6 (4)O2—C11—H11B109.1
O1—C2—C3120.1 (4)C10—C11—H11B109.1
O1—C2—C1123.2 (4)H11A—C11—H11B107.8
C3—C2—C1116.7 (4)O2—C12—C13111.4 (6)
C4—C3—C2122.8 (4)O2—C12—H12A109.4
C4—C3—H3118.6C13—C12—H12A109.4
C2—C3—H3118.6O2—C12—H12B109.4
C3—C4—C5118.9 (4)C13—C12—H12B109.4
C3—C4—H4120.5H12A—C12—H12B108.0
C5—C4—H4120.5N2—C13—C12110.2 (6)
C6—C5—C4121.0 (4)N2—C13—H13A109.6
C6—C5—Br1119.3 (4)C12—C13—H13A109.6
C4—C5—Br1119.6 (4)N2—C13—H13B109.6
C5—C6—C1120.7 (4)C12—C13—H13B109.6
C5—C6—H6119.7H13A—C13—H13B108.1
C1—C6—H6119.7O3—C14—H14A109.5
N1—C7—C1128.3 (4)O3—C14—H14B109.5
N1—C7—H7115.8H14A—C14—H14B109.5
C1—C7—H7115.8O3—C14—H14C109.5
N1—C8—C9111.1 (3)H14A—C14—H14C109.5
N1—C8—H8A109.4H14B—C14—H14C109.5
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···O1i0.84 (5)1.81 (5)2.649 (4)178 (7)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Table 1
Selected geometric parameters (Å, °) top
Zn1—N12.014 (3)Zn1—O12.078 (3)
Zn1—O32.023 (3)Zn1—I12.5346 (9)
N1—Zn1—O3114.78 (13)N1—Zn1—I1130.76 (10)
N1—Zn1—O190.15 (12)O3—Zn1—I1113.36 (9)
O3—Zn1—O190.42 (13)O1—Zn1—I199.31 (9)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···O1i0.84 (5)1.81 (5)2.649 (4)178 (7)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Acknowledgements top

The author acknowledges a research grant from Qiqihar University.

references
References top

Ali, H. M., Mohamed Mustafa, M. I., Rizal, M. R. & Ng, S. W. (2008). Acta Cryst. E64, m718–m719.

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Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

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

You, Z.-L. (2005). Acta Cryst. E61, m1571–m1573.

Zhu, X.-W. & Yang, X.-Z. (2008). Acta Cryst. E64, m1090–m1091.