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Acta Cryst. (2007). E63, m1321    [ doi:10.1107/S1600536807018259 ]

Diaquabis(2,4-dibromo-6-formylphenolato-[kappa]2N,N')zinc(II)

X.-M. Chen, S.-H. Zhang, L.-X. Jin, Z. Liu and Y. Yan

Abstract top

In the title compound, [Zn(C7H3Br2O2)2(H2O)2], the ZnII atom is six-coordinated in a slightly distorted octahedral coordination geometry by four O atoms of two 3,5-dibromo-2-hydroxybenzaldehyde ligands and by two water molecules. The Zn-O bond lengths lie in the range 2.040 (4)-2.121 (4) Å, and the angles subtended at the ZnII atom range from 84.10 (18) to 96.64 (17)°. The molecules are linked into a chain along the a axis by O-H...O and O-H...Br hydrogen bonds.

Comment top

Interest in packing arrangements of halogenated compounds goes back many years to what Schmidt (1964) called the "chloro effect",

wherein the presence of chloro substituents on aromatic compounds frequently results in stacking arrangements with a short (ca 4 Å) crystallographic axis (Cohen et al., 1964; Zordan et al., 2005; Desiraju, 1989). We report here the crystal structure of the title mononuclear zinc(II) complex, Zn(L)2(H2O)2 (I), where LH is 3,5-dibromo-2-hydroxy-benzaldehyde, a dibrominated ligand with two Br atoms accessible at the periphery of each ligand.

The asymmetric unit of (I) contains one unique ZnII centre, two independent L- ligands and two coordinated water molecules (Fig. 1). The ZnII atom is coordinated by four O atoms from two L- ligands and two O atoms from two water molecules, forming slightly distorted octahedral geometry (Table 1). The L- ligand is present in the chelating bidentate mode.

The molecules are linked into a chain along the a axis by O—H···O and O—H···Br hydrogen bonds (Table 2).

Related literature top

A similar cobalt(II) complex also forms a distorted octahedral geometry (Xiao et al., 2002). For related literature, see: Cohen et al. (1964); Desiraju (1989); Schmidt (1964); Zordan et al. (2005).

Experimental top

A solution of taurine (2 mmol, 0.253 g) and caustic potash (2 mmol, 0.112 g) in distilled water (10 ml) was slowly added to a solution of 3,5-dibromo- 2-hydroxy-benzaldehyde (2 mmol, 0.560 g) in ethanol (10 ml). The mixture was stirred for 30 min at room temperature, then the solution was slowly added to a solution of zinc nitrate (1 mmol, 0.297 g) in distilled water (10 ml). The mixture was stirred and refluxed for 4 h at room temperature. Colourless needle-shaped single-crystal of (I) were obtained by slow evaporation at room temperature (yield 68%, based on zinc).

Refinement top

H atoms of the water molecule were located in a difference Fourier map. The O—H distances were normalized to 0.85 Å and the H atoms were allowed to ride during subsequent refinement, with Uiso(H) = 1.5 Ueq(O).

All other H atoms were positioned geometrically and were treated as riding atoms, with C–H = 0.93 Å and Uiso(H) = 1.2 Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids. For clarity, all but water H atoms have been omitted.
[Figure 2] Fig. 2. The crystal packing of (I). Dashed lines indicate hydrogen bonds. C-bound H atoms have been omitted for clarity.
Diaquabis(2,4-dibromo-6-formylphenolato-κ2N,N')zinc(II) top
Crystal data top
[Zn(C7H3Br2O2)2(H2O)2]F(000) = 1248
Mr = 659.23Dx = 2.396 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5376 reflections
a = 7.6486 (15) Åθ = 1–27.5°
b = 28.095 (6) ŵ = 10.12 mm−1
c = 8.6716 (17) ÅT = 293 K
β = 101.25 (3)°Needle, colourless
V = 1827.6 (6) Å30.40 × 0.16 × 0.14 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer		4189 independent reflections
Radiation source: fine-focus sealed tube2577 reflections with I > 2σ(I)
graphiteRint = 0.066
φ and ω scansθmax = 27.6°, θmin = 1.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −9→9
Tmin = 0.107, Tmax = 0.332k = −36→33
12164 measured reflectionsl = −10→11
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)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.127H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0561P)2]
where P = (Fo2 + 2Fc2)/3
4189 reflections(Δ/σ)max = 0.001
226 parametersΔρmax = 0.76 e Å−3
0 restraintsΔρmin = −0.77 e Å−3
Crystal data top
[Zn(C7H3Br2O2)2(H2O)2]V = 1827.6 (6) Å3
Mr = 659.23Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.6486 (15) ŵ = 10.12 mm−1
b = 28.095 (6) ÅT = 293 K
c = 8.6716 (17) Å0.40 × 0.16 × 0.14 mm
β = 101.25 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		4189 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2577 reflections with I > 2σ(I)
Tmin = 0.107, Tmax = 0.332Rint = 0.066
12164 measured reflectionsθmax = 27.6°
Refinement top
R[F2 > 2σ(F2)] = 0.041H-atom parameters constrained
wR(F2) = 0.127Δρmax = 0.76 e Å−3
S = 1.03Δρmin = −0.77 e Å−3
4189 reflectionsAbsolute structure: ?
226 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
Br10.55634 (12)0.25086 (3)0.72223 (10)0.0510 (2)
Br20.38278 (11)0.43461 (3)0.91144 (8)0.0425 (2)
Br3−0.07491 (13)0.72472 (3)0.08867 (13)0.0708 (3)
Br40.23829 (11)0.63158 (3)0.65207 (8)0.0425 (2)
C10.3092 (8)0.3676 (2)0.4757 (7)0.0254 (14)
C20.3114 (8)0.4041 (2)0.5911 (7)0.0223 (13)
C30.3828 (8)0.3896 (2)0.7481 (7)0.0279 (15)
C40.4534 (9)0.3450 (2)0.7876 (8)0.0338 (16)
H40.50170.33770.89180.041*
C50.4518 (10)0.3107 (2)0.6699 (9)0.0357 (17)
C60.3789 (9)0.3217 (2)0.5193 (8)0.0327 (16)
H60.37440.29850.44210.039*
C70.2336 (9)0.3744 (3)0.3118 (8)0.0352 (17)
H70.22890.34740.24890.042*
C80.1252 (9)0.5882 (2)0.1838 (8)0.0304 (15)
C90.1785 (8)0.5864 (2)0.3508 (7)0.0247 (14)
C100.1614 (9)0.6300 (2)0.4297 (8)0.0300 (15)
C110.0909 (9)0.6704 (3)0.3535 (9)0.0399 (18)
H110.08020.69790.41030.048*
C120.0361 (10)0.6701 (3)0.1931 (9)0.0393 (18)
C130.0548 (9)0.6299 (3)0.1089 (8)0.0385 (18)
H130.01990.63030.00000.046*
C140.1414 (9)0.5481 (3)0.0829 (8)0.0318 (16)
H140.11590.5544−0.02440.038*
O10.1748 (6)0.41087 (16)0.2442 (5)0.0305 (10)
O20.2526 (6)0.44684 (15)0.5594 (5)0.0303 (10)
O30.1838 (6)0.50740 (17)0.1193 (5)0.0325 (11)
O40.2395 (6)0.54800 (15)0.4281 (5)0.0291 (10)
O1W0.4842 (6)0.47247 (17)0.3266 (5)0.0328 (11)
H1WB0.55310.45410.38880.049*
H1WA0.54340.49770.31900.049*
O2W−0.0665 (6)0.48299 (16)0.3156 (5)0.0291 (10)
H2WA−0.14640.50330.27930.044*
H2WB−0.11360.46390.37190.044*
Zn10.21512 (10)0.47942 (3)0.34528 (8)0.02439 (19)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0589 (5)0.0313 (4)0.0632 (5)0.0112 (4)0.0130 (4)0.0182 (4)
Br20.0587 (5)0.0441 (5)0.0252 (4)−0.0025 (4)0.0089 (3)−0.0051 (3)
Br30.0697 (7)0.0406 (5)0.0988 (8)0.0178 (5)0.0080 (6)0.0331 (5)
Br40.0599 (5)0.0325 (4)0.0371 (4)−0.0081 (4)0.0142 (4)−0.0102 (3)
C10.025 (3)0.024 (3)0.029 (3)0.002 (3)0.009 (3)−0.002 (3)
C20.023 (3)0.018 (3)0.029 (3)−0.002 (2)0.012 (3)−0.001 (3)
C30.025 (4)0.032 (4)0.027 (3)−0.003 (3)0.006 (3)0.002 (3)
C40.035 (4)0.037 (4)0.028 (4)−0.002 (3)0.004 (3)0.008 (3)
C50.041 (4)0.021 (4)0.045 (4)0.005 (3)0.008 (3)0.012 (3)
C60.040 (4)0.021 (4)0.037 (4)0.004 (3)0.008 (3)0.001 (3)
C70.042 (4)0.029 (4)0.033 (4)0.003 (3)0.005 (3)−0.010 (3)
C80.029 (4)0.028 (4)0.031 (4)−0.005 (3)−0.002 (3)0.003 (3)
C90.019 (3)0.023 (3)0.032 (4)−0.002 (3)0.003 (3)0.004 (3)
C100.029 (4)0.028 (4)0.035 (4)−0.001 (3)0.011 (3)−0.002 (3)
C110.035 (4)0.029 (4)0.058 (5)0.000 (3)0.016 (4)0.000 (4)
C120.037 (4)0.027 (4)0.057 (5)0.007 (3)0.014 (4)0.016 (4)
C130.033 (4)0.041 (5)0.036 (4)−0.003 (3)−0.006 (3)0.014 (3)
C140.034 (4)0.038 (4)0.020 (3)0.000 (3)−0.002 (3)0.001 (3)
O10.033 (3)0.029 (3)0.025 (2)0.001 (2)−0.004 (2)−0.002 (2)
O20.044 (3)0.023 (2)0.024 (2)0.005 (2)0.007 (2)−0.0003 (18)
O30.038 (3)0.035 (3)0.023 (2)0.003 (2)0.005 (2)−0.001 (2)
O40.033 (3)0.022 (2)0.029 (2)0.0020 (19)−0.003 (2)0.0015 (19)
O1W0.025 (2)0.036 (3)0.035 (3)0.000 (2)0.000 (2)−0.001 (2)
O2W0.023 (2)0.032 (3)0.032 (2)0.000 (2)0.0040 (19)0.000 (2)
Zn10.0266 (4)0.0229 (4)0.0223 (4)0.0022 (3)0.0015 (3)−0.0017 (3)
Geometric parameters (Å, °) top
Br1—C51.880 (6)C9—O41.308 (7)
Br2—C31.899 (6)C9—C101.420 (9)
Br3—C121.896 (7)C10—C111.370 (10)
Br4—C101.904 (7)C11—C121.372 (10)
C1—C61.418 (9)C11—H110.93
C1—C21.431 (8)C12—C131.369 (11)
C1—C71.439 (9)C13—H130.93
C2—O21.292 (7)C14—O31.214 (8)
C2—C31.424 (8)C14—H140.93
C3—C41.383 (9)O1—Zn12.114 (4)
C4—C51.401 (10)O2—Zn12.040 (4)
C4—H40.93O3—Zn12.081 (4)
C5—C61.353 (9)O4—Zn12.052 (4)
C6—H60.93O1W—Zn12.105 (4)
C7—O11.223 (8)O1W—H1WB0.85
C7—H70.93O1W—H1WA0.85
C8—C131.394 (9)O2W—Zn12.121 (4)
C8—C91.426 (9)O2W—H2WA0.85
C8—C141.447 (9)O2W—H2WB0.85
C6—C1—C2120.9 (6)C13—C12—Br3119.8 (6)
C6—C1—C7116.2 (6)C11—C12—Br3120.0 (6)
C2—C1—C7122.9 (6)C12—C13—C8121.0 (7)
O2—C2—C3121.4 (5)C12—C13—H13119.5
O2—C2—C1124.2 (6)C8—C13—H13119.5
C3—C2—C1114.4 (6)O3—C14—C8128.8 (6)
C4—C3—C2123.7 (6)O3—C14—H14115.6
C4—C3—Br2118.4 (5)C8—C14—H14115.6
C2—C3—Br2117.9 (5)C7—O1—Zn1123.7 (4)
C3—C4—C5119.7 (6)C2—O2—Zn1126.3 (4)
C3—C4—H4120.2C14—O3—Zn1125.2 (4)
C5—C4—H4120.2C9—O4—Zn1126.6 (4)
C6—C5—C4119.4 (6)Zn1—O1W—H1WB120.1
C6—C5—Br1120.9 (5)Zn1—O1W—H1WA118.3
C4—C5—Br1119.7 (5)H1WB—O1W—H1WA106.3
C5—C6—C1121.9 (6)Zn1—O2W—H2WA135.8
C5—C6—H6119.1Zn1—O2W—H2WB115.8
C1—C6—H6119.1H2WA—O2W—H2WB106.3
O1—C7—C1128.6 (6)O2—Zn1—O496.64 (17)
O1—C7—H7115.7O2—Zn1—O3175.22 (18)
C1—C7—H7115.7O4—Zn1—O387.75 (18)
C13—C8—C9120.8 (6)O2—Zn1—O1W93.58 (19)
C13—C8—C14116.3 (6)O4—Zn1—O1W95.20 (18)
C9—C8—C14123.0 (6)O3—Zn1—O1W84.10 (18)
O4—C9—C10121.4 (6)O2—Zn1—O187.25 (17)
O4—C9—C8123.6 (6)O4—Zn1—O1175.34 (17)
C10—C9—C8115.0 (6)O3—Zn1—O188.45 (18)
C11—C10—C9123.1 (6)O1W—Zn1—O187.10 (17)
C11—C10—Br4118.9 (5)O2—Zn1—O2W95.20 (18)
C9—C10—Br4118.0 (5)O4—Zn1—O2W91.08 (17)
C10—C11—C12119.9 (7)O3—Zn1—O2W86.59 (18)
C10—C11—H11120.0O1W—Zn1—O2W168.55 (17)
C12—C11—H11120.0O1—Zn1—O2W85.99 (17)
C13—C12—C11120.1 (7)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WB···O4i0.852.012.751 (6)144
O1W—H1WA···O2i0.852.313.065 (6)148
O2W—H2WA···O2ii0.852.242.773 (6)121
O2W—H2WB···O4ii0.852.172.932 (6)149
O1W—H1WA···Br2i0.852.893.596 (5)141
O2W—H2WA···Br2ii0.852.813.637 (5)166
O2W—H2WB···Br4ii0.852.843.509 (5)137
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WB···O4i0.852.012.751 (6)144
O1W—H1WA···O2i0.852.313.065 (6)148
O2W—H2WA···O2ii0.852.242.773 (6)121
O2W—H2WB···O4ii0.852.172.932 (6)149
O1W—H1WA···Br2i0.852.893.596 (5)141
O2W—H2WA···Br2ii0.852.813.637 (5)166
O2W—H2WB···Br4ii0.852.843.509 (5)137
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1.
Acknowledgements top

We acknowledge financial support by Key Laboratory of Non-Ferrous Metal Materials and New Processing Technology, Ministry of Education, China.

references
References top

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