Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807018259/ci2359sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807018259/ci2359Isup2.hkl |
CCDC reference: 646605
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.009 Å
- R factor = 0.041
- wR factor = 0.127
- Data-to-parameter ratio = 18.5
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.73 PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ? PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 9 PLAT431_ALERT_2_C Short Inter HL..A Contact Br2 .. O3 .. 3.29 Ang. PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 4
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.731 Tmax scaled 0.243 Tmin scaled 0.078 PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
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).
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).
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).
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).
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).
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.
[Zn(C7H3Br2O2)2(H2O)2] | F(000) = 1248 |
Mr = 659.23 | Dx = 2.396 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5376 reflections |
a = 7.6486 (15) Å | θ = 1–27.5° |
b = 28.095 (6) Å | µ = 10.12 mm−1 |
c = 8.6716 (17) Å | T = 293 K |
β = 101.25 (3)° | Needle, colourless |
V = 1827.6 (6) Å3 | 0.40 × 0.16 × 0.14 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 4189 independent reflections |
Radiation source: fine-focus sealed tube | 2577 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.066 |
φ and ω scans | θmax = 27.6°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→9 |
Tmin = 0.107, Tmax = 0.332 | k = −36→33 |
12164 measured reflections | l = −10→11 |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.127 | H-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 parameters | Δρmax = 0.76 e Å−3 |
0 restraints | Δρmin = −0.77 e Å−3 |
[Zn(C7H3Br2O2)2(H2O)2] | V = 1827.6 (6) Å3 |
Mr = 659.23 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.6486 (15) Å | µ = 10.12 mm−1 |
b = 28.095 (6) Å | T = 293 K |
c = 8.6716 (17) Å | 0.40 × 0.16 × 0.14 mm |
β = 101.25 (3)° |
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 = 0.332 | Rint = 0.066 |
12164 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.76 e Å−3 |
4189 reflections | Δρmin = −0.77 e Å−3 |
226 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 | ||
Br1 | 0.55634 (12) | 0.25086 (3) | 0.72223 (10) | 0.0510 (2) | |
Br2 | 0.38278 (11) | 0.43461 (3) | 0.91144 (8) | 0.0425 (2) | |
Br3 | −0.07491 (13) | 0.72472 (3) | 0.08867 (13) | 0.0708 (3) | |
Br4 | 0.23829 (11) | 0.63158 (3) | 0.65207 (8) | 0.0425 (2) | |
C1 | 0.3092 (8) | 0.3676 (2) | 0.4757 (7) | 0.0254 (14) | |
C2 | 0.3114 (8) | 0.4041 (2) | 0.5911 (7) | 0.0223 (13) | |
C3 | 0.3828 (8) | 0.3896 (2) | 0.7481 (7) | 0.0279 (15) | |
C4 | 0.4534 (9) | 0.3450 (2) | 0.7876 (8) | 0.0338 (16) | |
H4 | 0.5017 | 0.3377 | 0.8918 | 0.041* | |
C5 | 0.4518 (10) | 0.3107 (2) | 0.6699 (9) | 0.0357 (17) | |
C6 | 0.3789 (9) | 0.3217 (2) | 0.5193 (8) | 0.0327 (16) | |
H6 | 0.3744 | 0.2985 | 0.4421 | 0.039* | |
C7 | 0.2336 (9) | 0.3744 (3) | 0.3118 (8) | 0.0352 (17) | |
H7 | 0.2289 | 0.3474 | 0.2489 | 0.042* | |
C8 | 0.1252 (9) | 0.5882 (2) | 0.1838 (8) | 0.0304 (15) | |
C9 | 0.1785 (8) | 0.5864 (2) | 0.3508 (7) | 0.0247 (14) | |
C10 | 0.1614 (9) | 0.6300 (2) | 0.4297 (8) | 0.0300 (15) | |
C11 | 0.0909 (9) | 0.6704 (3) | 0.3535 (9) | 0.0399 (18) | |
H11 | 0.0802 | 0.6979 | 0.4103 | 0.048* | |
C12 | 0.0361 (10) | 0.6701 (3) | 0.1931 (9) | 0.0393 (18) | |
C13 | 0.0548 (9) | 0.6299 (3) | 0.1089 (8) | 0.0385 (18) | |
H13 | 0.0199 | 0.6303 | 0.0000 | 0.046* | |
C14 | 0.1414 (9) | 0.5481 (3) | 0.0829 (8) | 0.0318 (16) | |
H14 | 0.1159 | 0.5544 | −0.0244 | 0.038* | |
O1 | 0.1748 (6) | 0.41087 (16) | 0.2442 (5) | 0.0305 (10) | |
O2 | 0.2526 (6) | 0.44684 (15) | 0.5594 (5) | 0.0303 (10) | |
O3 | 0.1838 (6) | 0.50740 (17) | 0.1193 (5) | 0.0325 (11) | |
O4 | 0.2395 (6) | 0.54800 (15) | 0.4281 (5) | 0.0291 (10) | |
O1W | 0.4842 (6) | 0.47247 (17) | 0.3266 (5) | 0.0328 (11) | |
H1WB | 0.5531 | 0.4541 | 0.3888 | 0.049* | |
H1WA | 0.5434 | 0.4977 | 0.3190 | 0.049* | |
O2W | −0.0665 (6) | 0.48299 (16) | 0.3156 (5) | 0.0291 (10) | |
H2WA | −0.1464 | 0.5033 | 0.2793 | 0.044* | |
H2WB | −0.1136 | 0.4639 | 0.3719 | 0.044* | |
Zn1 | 0.21512 (10) | 0.47942 (3) | 0.34528 (8) | 0.02439 (19) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0589 (5) | 0.0313 (4) | 0.0632 (5) | 0.0112 (4) | 0.0130 (4) | 0.0182 (4) |
Br2 | 0.0587 (5) | 0.0441 (5) | 0.0252 (4) | −0.0025 (4) | 0.0089 (3) | −0.0051 (3) |
Br3 | 0.0697 (7) | 0.0406 (5) | 0.0988 (8) | 0.0178 (5) | 0.0080 (6) | 0.0331 (5) |
Br4 | 0.0599 (5) | 0.0325 (4) | 0.0371 (4) | −0.0081 (4) | 0.0142 (4) | −0.0102 (3) |
C1 | 0.025 (3) | 0.024 (3) | 0.029 (3) | 0.002 (3) | 0.009 (3) | −0.002 (3) |
C2 | 0.023 (3) | 0.018 (3) | 0.029 (3) | −0.002 (2) | 0.012 (3) | −0.001 (3) |
C3 | 0.025 (4) | 0.032 (4) | 0.027 (3) | −0.003 (3) | 0.006 (3) | 0.002 (3) |
C4 | 0.035 (4) | 0.037 (4) | 0.028 (4) | −0.002 (3) | 0.004 (3) | 0.008 (3) |
C5 | 0.041 (4) | 0.021 (4) | 0.045 (4) | 0.005 (3) | 0.008 (3) | 0.012 (3) |
C6 | 0.040 (4) | 0.021 (4) | 0.037 (4) | 0.004 (3) | 0.008 (3) | 0.001 (3) |
C7 | 0.042 (4) | 0.029 (4) | 0.033 (4) | 0.003 (3) | 0.005 (3) | −0.010 (3) |
C8 | 0.029 (4) | 0.028 (4) | 0.031 (4) | −0.005 (3) | −0.002 (3) | 0.003 (3) |
C9 | 0.019 (3) | 0.023 (3) | 0.032 (4) | −0.002 (3) | 0.003 (3) | 0.004 (3) |
C10 | 0.029 (4) | 0.028 (4) | 0.035 (4) | −0.001 (3) | 0.011 (3) | −0.002 (3) |
C11 | 0.035 (4) | 0.029 (4) | 0.058 (5) | 0.000 (3) | 0.016 (4) | 0.000 (4) |
C12 | 0.037 (4) | 0.027 (4) | 0.057 (5) | 0.007 (3) | 0.014 (4) | 0.016 (4) |
C13 | 0.033 (4) | 0.041 (5) | 0.036 (4) | −0.003 (3) | −0.006 (3) | 0.014 (3) |
C14 | 0.034 (4) | 0.038 (4) | 0.020 (3) | 0.000 (3) | −0.002 (3) | 0.001 (3) |
O1 | 0.033 (3) | 0.029 (3) | 0.025 (2) | 0.001 (2) | −0.004 (2) | −0.002 (2) |
O2 | 0.044 (3) | 0.023 (2) | 0.024 (2) | 0.005 (2) | 0.007 (2) | −0.0003 (18) |
O3 | 0.038 (3) | 0.035 (3) | 0.023 (2) | 0.003 (2) | 0.005 (2) | −0.001 (2) |
O4 | 0.033 (3) | 0.022 (2) | 0.029 (2) | 0.0020 (19) | −0.003 (2) | 0.0015 (19) |
O1W | 0.025 (2) | 0.036 (3) | 0.035 (3) | 0.000 (2) | 0.000 (2) | −0.001 (2) |
O2W | 0.023 (2) | 0.032 (3) | 0.032 (2) | 0.000 (2) | 0.0040 (19) | 0.000 (2) |
Zn1 | 0.0266 (4) | 0.0229 (4) | 0.0223 (4) | 0.0022 (3) | 0.0015 (3) | −0.0017 (3) |
Br1—C5 | 1.880 (6) | C9—O4 | 1.308 (7) |
Br2—C3 | 1.899 (6) | C9—C10 | 1.420 (9) |
Br3—C12 | 1.896 (7) | C10—C11 | 1.370 (10) |
Br4—C10 | 1.904 (7) | C11—C12 | 1.372 (10) |
C1—C6 | 1.418 (9) | C11—H11 | 0.93 |
C1—C2 | 1.431 (8) | C12—C13 | 1.369 (11) |
C1—C7 | 1.439 (9) | C13—H13 | 0.93 |
C2—O2 | 1.292 (7) | C14—O3 | 1.214 (8) |
C2—C3 | 1.424 (8) | C14—H14 | 0.93 |
C3—C4 | 1.383 (9) | O1—Zn1 | 2.114 (4) |
C4—C5 | 1.401 (10) | O2—Zn1 | 2.040 (4) |
C4—H4 | 0.93 | O3—Zn1 | 2.081 (4) |
C5—C6 | 1.353 (9) | O4—Zn1 | 2.052 (4) |
C6—H6 | 0.93 | O1W—Zn1 | 2.105 (4) |
C7—O1 | 1.223 (8) | O1W—H1WB | 0.85 |
C7—H7 | 0.93 | O1W—H1WA | 0.85 |
C8—C13 | 1.394 (9) | O2W—Zn1 | 2.121 (4) |
C8—C9 | 1.426 (9) | O2W—H2WA | 0.85 |
C8—C14 | 1.447 (9) | O2W—H2WB | 0.85 |
C6—C1—C2 | 120.9 (6) | C13—C12—Br3 | 119.8 (6) |
C6—C1—C7 | 116.2 (6) | C11—C12—Br3 | 120.0 (6) |
C2—C1—C7 | 122.9 (6) | C12—C13—C8 | 121.0 (7) |
O2—C2—C3 | 121.4 (5) | C12—C13—H13 | 119.5 |
O2—C2—C1 | 124.2 (6) | C8—C13—H13 | 119.5 |
C3—C2—C1 | 114.4 (6) | O3—C14—C8 | 128.8 (6) |
C4—C3—C2 | 123.7 (6) | O3—C14—H14 | 115.6 |
C4—C3—Br2 | 118.4 (5) | C8—C14—H14 | 115.6 |
C2—C3—Br2 | 117.9 (5) | C7—O1—Zn1 | 123.7 (4) |
C3—C4—C5 | 119.7 (6) | C2—O2—Zn1 | 126.3 (4) |
C3—C4—H4 | 120.2 | C14—O3—Zn1 | 125.2 (4) |
C5—C4—H4 | 120.2 | C9—O4—Zn1 | 126.6 (4) |
C6—C5—C4 | 119.4 (6) | Zn1—O1W—H1WB | 120.1 |
C6—C5—Br1 | 120.9 (5) | Zn1—O1W—H1WA | 118.3 |
C4—C5—Br1 | 119.7 (5) | H1WB—O1W—H1WA | 106.3 |
C5—C6—C1 | 121.9 (6) | Zn1—O2W—H2WA | 135.8 |
C5—C6—H6 | 119.1 | Zn1—O2W—H2WB | 115.8 |
C1—C6—H6 | 119.1 | H2WA—O2W—H2WB | 106.3 |
O1—C7—C1 | 128.6 (6) | O2—Zn1—O4 | 96.64 (17) |
O1—C7—H7 | 115.7 | O2—Zn1—O3 | 175.22 (18) |
C1—C7—H7 | 115.7 | O4—Zn1—O3 | 87.75 (18) |
C13—C8—C9 | 120.8 (6) | O2—Zn1—O1W | 93.58 (19) |
C13—C8—C14 | 116.3 (6) | O4—Zn1—O1W | 95.20 (18) |
C9—C8—C14 | 123.0 (6) | O3—Zn1—O1W | 84.10 (18) |
O4—C9—C10 | 121.4 (6) | O2—Zn1—O1 | 87.25 (17) |
O4—C9—C8 | 123.6 (6) | O4—Zn1—O1 | 175.34 (17) |
C10—C9—C8 | 115.0 (6) | O3—Zn1—O1 | 88.45 (18) |
C11—C10—C9 | 123.1 (6) | O1W—Zn1—O1 | 87.10 (17) |
C11—C10—Br4 | 118.9 (5) | O2—Zn1—O2W | 95.20 (18) |
C9—C10—Br4 | 118.0 (5) | O4—Zn1—O2W | 91.08 (17) |
C10—C11—C12 | 119.9 (7) | O3—Zn1—O2W | 86.59 (18) |
C10—C11—H11 | 120.0 | O1W—Zn1—O2W | 168.55 (17) |
C12—C11—H11 | 120.0 | O1—Zn1—O2W | 85.99 (17) |
C13—C12—C11 | 120.1 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WB···O4i | 0.85 | 2.01 | 2.751 (6) | 144 |
O1W—H1WA···O2i | 0.85 | 2.31 | 3.065 (6) | 148 |
O2W—H2WA···O2ii | 0.85 | 2.24 | 2.773 (6) | 121 |
O2W—H2WB···O4ii | 0.85 | 2.17 | 2.932 (6) | 149 |
O1W—H1WA···Br2i | 0.85 | 2.89 | 3.596 (5) | 141 |
O2W—H2WA···Br2ii | 0.85 | 2.81 | 3.637 (5) | 166 |
O2W—H2WB···Br4ii | 0.85 | 2.84 | 3.509 (5) | 137 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C7H3Br2O2)2(H2O)2] |
Mr | 659.23 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 7.6486 (15), 28.095 (6), 8.6716 (17) |
β (°) | 101.25 (3) |
V (Å3) | 1827.6 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 10.12 |
Crystal size (mm) | 0.40 × 0.16 × 0.14 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.107, 0.332 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12164, 4189, 2577 |
Rint | 0.066 |
(sin θ/λ)max (Å−1) | 0.651 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.127, 1.03 |
No. of reflections | 4189 |
No. of parameters | 226 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.76, −0.77 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WB···O4i | 0.85 | 2.01 | 2.751 (6) | 144 |
O1W—H1WA···O2i | 0.85 | 2.31 | 3.065 (6) | 148 |
O2W—H2WA···O2ii | 0.85 | 2.24 | 2.773 (6) | 121 |
O2W—H2WB···O4ii | 0.85 | 2.17 | 2.932 (6) | 149 |
O1W—H1WA···Br2i | 0.85 | 2.89 | 3.596 (5) | 141 |
O2W—H2WA···Br2ii | 0.85 | 2.81 | 3.637 (5) | 166 |
O2W—H2WB···Br4ii | 0.85 | 2.84 | 3.509 (5) | 137 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1. |
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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).