metal-organic compounds
Bis[2-({[2-(methylsulfanyl)phenyl]imino}methyl)phenolato-κ2N,O]zinc chloroform disolvate
aDepartment of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung 807, Taiwan, and bDepartment of Chemistry, National Chung Hsing University, Taichung 402, Taiwan
*Correspondence e-mail: hchen@kmu.edu.tw
The monomeric title complex, [Zn(C14H12NOS)2]·2CHCl3 or L2Zn·2CHCl3, where L is the 2-({[2-(methylsulfanyl)phenyl]imino}methyl)phenolate anion, may be obtained by the reaction of LZnEt with benzyl alcohol or by the reaction of two equivalents of LH with ZnEt2 in tetrahydrofuran. The Zn atom, located on a twofold axis, is four-coordinated in a distorted tetrahedral geometry by two O atoms [Zn—O = 1.9472 (19) Å] from the phenolate anions and two imine N atoms [Zn—N = 2.054 (2) Å].
Related literature
For backgroud to poly(lactide) (PLA) and its copolymers, see: Huang et al. (2007). For the use of bulky ligands coordinated to the centre to avoid undesirable transesterification during synthesis by (ROP) of see: Wu et al. (2006). Many complexes with bulky ligands have been designed for this function, incorporating a single site, see: Wu et al. (2006). For the preparation of a series of Zn complexes with N,N,O-tridentate which have great activity in the ROP of see: Chen et al. (2006). For the 2-(2,6-diisopropylphenylimino)methyl)-4-nitrophenolate anion, see: Chisholm et al. (2001).
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2007); cell SAINT (Bruker, 2007); data reduction: SAINT; 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.
Supporting information
10.1107/S1600536812045473/hp2049sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812045473/hp2049Isup2.hkl
To a suspension of LH (4.86 g, 20 mmol) in tetrahydrofuran (15 ml) was added ZnEt2 (1.22 g, 10 mmol). After being stirred for 3 hr, volatile materials were then removed under a vacuum to yield a yellow powder. The powder was washed twice with hexane (30 ml), and a high yellow powder was obtained after filtration. The crystal was obtain in CHCl3 soultion. A colourless crystal was selected from this sample.
X-ray experimental: Data were collected at 173 K on a Siemens SMART PLATFORM equipped with A CCD area detector and a graphite monochromator utilizing MoKaradiation (l= 0.71073 Å).Cell parameters were refined using up to 8192 reflections. A full sphere of data (1850 frames) was collected using the w-scan method (0.3°frame width).The first 50 frames were re-measured at the end of data collection to monitor instrument and crystal stability (maximum correction on I was < 1%).Absorption corrections by integration were applied based on measured indexed crystal faces.
The structure was solved by the
in SHELXTL6, and refined using full-matrix least squares.The non-H atoms were treated anisotropically, whereas the hydrogen atoms were calculated in ideal positions and were riding on their respective carbon atoms.A total of 195 parameters were refined in the final cycle of using 3345 reflections with I > 2 s(I) to yield R1 and wR2 of 4.37% and 12.30%, respectively.Refinement was done using F2.Data collection: APEX2 (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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).Fig. 1. A view of the molecular structure of [L2Zn] with displacement ellipsoids shown at the 20% probability level. | |
Fig. 2. Reaction scheme. |
[Zn(C14H12NOS)2]·2CHCl3 | F(000) = 1600 |
Mr = 788.72 | Dx = 1.537 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 4002 reflections |
a = 10.5673 (9) Å | θ = 2.4–25.8° |
b = 21.5085 (19) Å | µ = 1.34 mm−1 |
c = 15.1215 (14) Å | T = 110 K |
β = 97.309 (2)° | Parallelpiped, yellow |
V = 3409.0 (5) Å3 | 0.45 × 0.38 × 0.32 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 3345 independent reflections |
Radiation source: fine-focus sealed tube | 2494 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
Detector resolution: 16.0690 pixels mm-1 | θmax = 26.0°, θmin = 2.2° |
phi and ω scans | h = −12→13 |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | k = −26→23 |
Tmin = 0.381, Tmax = 1.000 | l = −18→10 |
9547 measured reflections |
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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.135 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.090P)2] where P = (Fo2 + 2Fc2)/3 |
3345 reflections | (Δ/σ)max < 0.001 |
195 parameters | Δρmax = 0.50 e Å−3 |
6 restraints | Δρmin = −0.50 e Å−3 |
[Zn(C14H12NOS)2]·2CHCl3 | V = 3409.0 (5) Å3 |
Mr = 788.72 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 10.5673 (9) Å | µ = 1.34 mm−1 |
b = 21.5085 (19) Å | T = 110 K |
c = 15.1215 (14) Å | 0.45 × 0.38 × 0.32 mm |
β = 97.309 (2)° |
Bruker SMART CCD area-detector diffractometer | 3345 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 2494 reflections with I > 2σ(I) |
Tmin = 0.381, Tmax = 1.000 | Rint = 0.037 |
9547 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 6 restraints |
wR(F2) = 0.135 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.50 e Å−3 |
3345 reflections | Δρmin = −0.50 e Å−3 |
195 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 | ||
Zn | 0.0000 | 0.23879 (2) | 0.2500 | 0.0481 (2) | |
S | 0.19745 (7) | 0.19012 (4) | 0.13833 (6) | 0.0531 (2) | |
N | −0.0763 (2) | 0.17983 (10) | 0.15038 (15) | 0.0398 (5) | |
O | −0.12511 (19) | 0.30361 (9) | 0.21523 (16) | 0.0571 (6) | |
C1 | 0.3508 (3) | 0.16784 (19) | 0.1930 (3) | 0.0707 (10) | |
H1A | 0.4055 | 0.2036 | 0.1999 | 0.106* | |
H1B | 0.3874 | 0.1371 | 0.1577 | 0.106* | |
H1C | 0.3419 | 0.1508 | 0.2505 | 0.106* | |
C2 | 0.1132 (3) | 0.11931 (14) | 0.1323 (2) | 0.0482 (7) | |
C3 | 0.1706 (3) | 0.06183 (16) | 0.1214 (2) | 0.0610 (9) | |
H3A | 0.2578 | 0.0599 | 0.1180 | 0.073* | |
C4 | 0.0998 (4) | 0.00797 (16) | 0.1157 (3) | 0.0752 (11) | |
H4A | 0.1393 | −0.0300 | 0.1084 | 0.090* | |
C5 | −0.0301 (4) | 0.01012 (16) | 0.1208 (3) | 0.0751 (11) | |
H5A | −0.0777 | −0.0264 | 0.1174 | 0.090* | |
C6 | −0.0886 (3) | 0.06656 (14) | 0.1308 (2) | 0.0557 (8) | |
H6A | −0.1758 | 0.0680 | 0.1343 | 0.067* | |
C7 | −0.0181 (3) | 0.12148 (13) | 0.13598 (19) | 0.0441 (6) | |
C8 | −0.1873 (3) | 0.19109 (14) | 0.10609 (19) | 0.0447 (7) | |
H8A | −0.2161 | 0.1624 | 0.0621 | 0.054* | |
C9 | −0.2703 (3) | 0.24188 (13) | 0.11654 (19) | 0.0418 (6) | |
C10 | −0.3943 (3) | 0.23780 (16) | 0.0687 (2) | 0.0537 (8) | |
H10A | −0.4142 | 0.2039 | 0.0313 | 0.064* | |
C11 | −0.4851 (3) | 0.28157 (17) | 0.0753 (2) | 0.0608 (9) | |
H11A | −0.5661 | 0.2776 | 0.0436 | 0.073* | |
C12 | −0.4544 (3) | 0.33205 (18) | 0.1302 (3) | 0.0703 (10) | |
H12A | −0.5162 | 0.3621 | 0.1358 | 0.084* | |
C13 | −0.3341 (3) | 0.33914 (15) | 0.1770 (3) | 0.0638 (9) | |
H13A | −0.3163 | 0.3741 | 0.2127 | 0.077* | |
C14 | −0.2387 (3) | 0.29454 (13) | 0.1715 (2) | 0.0463 (7) | |
Cl3 | −0.58113 (11) | −0.07026 (6) | 0.05933 (10) | 0.1060 (4) | |
Cl2 | −0.34051 (11) | −0.13281 (7) | 0.06052 (9) | 0.0998 (4) | |
Cl1 | −0.36432 (13) | −0.03130 (6) | 0.18120 (10) | 0.1029 (4) | |
C30 | −0.4421 (3) | −0.09453 (17) | 0.1255 (3) | 0.0655 (9) | |
H30A | −0.4660 | −0.1238 | 0.1702 | 0.079* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn | 0.0422 (3) | 0.0320 (3) | 0.0641 (4) | 0.000 | −0.0162 (2) | 0.000 |
S | 0.0397 (4) | 0.0542 (5) | 0.0646 (5) | −0.0025 (3) | 0.0033 (3) | 0.0053 (4) |
N | 0.0338 (10) | 0.0403 (12) | 0.0442 (13) | 0.0013 (9) | 0.0003 (9) | −0.0022 (10) |
O | 0.0470 (11) | 0.0355 (10) | 0.0823 (16) | 0.0041 (9) | −0.0174 (11) | 0.0007 (10) |
C1 | 0.0438 (17) | 0.089 (3) | 0.077 (2) | 0.0010 (17) | −0.0032 (17) | −0.001 (2) |
C2 | 0.0471 (15) | 0.0475 (16) | 0.0490 (17) | 0.0050 (13) | 0.0027 (13) | 0.0027 (14) |
C3 | 0.0593 (18) | 0.0548 (19) | 0.070 (2) | 0.0158 (15) | 0.0132 (17) | −0.0005 (17) |
C4 | 0.087 (3) | 0.0436 (18) | 0.096 (3) | 0.0141 (17) | 0.017 (2) | −0.0066 (19) |
C5 | 0.079 (2) | 0.0471 (19) | 0.099 (3) | −0.0049 (17) | 0.014 (2) | −0.0124 (19) |
C6 | 0.0514 (16) | 0.0443 (16) | 0.071 (2) | −0.0049 (13) | 0.0061 (15) | −0.0082 (15) |
C7 | 0.0439 (14) | 0.0431 (15) | 0.0444 (16) | 0.0025 (12) | 0.0026 (12) | −0.0018 (13) |
C8 | 0.0398 (14) | 0.0494 (16) | 0.0431 (16) | −0.0029 (12) | −0.0011 (12) | −0.0026 (13) |
C9 | 0.0357 (13) | 0.0474 (15) | 0.0413 (15) | 0.0026 (11) | 0.0015 (11) | 0.0066 (12) |
C10 | 0.0425 (16) | 0.0648 (19) | 0.0514 (18) | −0.0019 (13) | −0.0037 (13) | 0.0026 (15) |
C11 | 0.0344 (15) | 0.075 (2) | 0.069 (2) | 0.0045 (15) | −0.0078 (14) | 0.0192 (19) |
C12 | 0.0478 (17) | 0.064 (2) | 0.098 (3) | 0.0205 (16) | 0.0038 (18) | 0.019 (2) |
C13 | 0.0557 (18) | 0.0471 (17) | 0.085 (3) | 0.0122 (15) | −0.0055 (17) | 0.0012 (17) |
C14 | 0.0398 (14) | 0.0406 (15) | 0.0562 (18) | 0.0013 (12) | −0.0031 (13) | 0.0105 (13) |
Cl3 | 0.0805 (7) | 0.0978 (9) | 0.1336 (11) | 0.0076 (6) | −0.0101 (7) | −0.0009 (8) |
Cl2 | 0.0855 (7) | 0.1220 (10) | 0.0938 (8) | 0.0107 (7) | 0.0185 (6) | −0.0140 (7) |
Cl1 | 0.1125 (9) | 0.0812 (7) | 0.1130 (10) | −0.0309 (6) | 0.0068 (8) | −0.0142 (7) |
C30 | 0.068 (2) | 0.059 (2) | 0.071 (2) | −0.0078 (16) | 0.0122 (17) | 0.0078 (18) |
Zn—O | 1.9472 (19) | C5—H5A | 0.9300 |
Zn—Oi | 1.9472 (19) | C6—C7 | 1.393 (4) |
Zn—Ni | 2.054 (2) | C6—H6A | 0.9300 |
Zn—N | 2.054 (2) | C8—C9 | 1.422 (4) |
S—C2 | 1.761 (3) | C8—H8A | 0.9300 |
S—C1 | 1.788 (3) | C9—C10 | 1.417 (4) |
N—C8 | 1.297 (3) | C9—C14 | 1.420 (4) |
N—C7 | 1.427 (3) | C10—C11 | 1.357 (5) |
O—C14 | 1.309 (3) | C10—H10A | 0.9300 |
C1—H1A | 0.9600 | C11—C12 | 1.380 (5) |
C1—H1B | 0.9600 | C11—H11A | 0.9300 |
C1—H1C | 0.9600 | C12—C13 | 1.382 (5) |
C2—C3 | 1.396 (4) | C12—H12A | 0.9300 |
C2—C7 | 1.396 (4) | C13—C14 | 1.402 (4) |
C3—C4 | 1.376 (5) | C13—H13A | 0.9300 |
C3—H3A | 0.9300 | Cl3—C30 | 1.748 (4) |
C4—C5 | 1.385 (5) | Cl2—C30 | 1.751 (4) |
C4—H4A | 0.9300 | Cl1—C30 | 1.749 (4) |
C5—C6 | 1.380 (5) | C30—H30A | 0.9800 |
O—Zn—Oi | 88.54 (11) | C7—C6—H6A | 119.7 |
O—Zn—Ni | 146.08 (10) | C6—C7—C2 | 119.8 (3) |
Oi—Zn—Ni | 93.12 (9) | C6—C7—N | 121.1 (3) |
O—Zn—N | 93.12 (9) | C2—C7—N | 119.0 (2) |
Oi—Zn—N | 146.08 (10) | N—C8—C9 | 128.0 (3) |
Ni—Zn—N | 103.74 (12) | N—C8—H8A | 116.0 |
C2—S—C1 | 102.40 (16) | C9—C8—H8A | 116.0 |
C8—N—C7 | 117.7 (2) | C10—C9—C14 | 118.8 (3) |
C8—N—Zn | 120.54 (19) | C10—C9—C8 | 116.0 (3) |
C7—N—Zn | 121.25 (16) | C14—C9—C8 | 125.1 (2) |
C14—O—Zn | 125.24 (17) | C11—C10—C9 | 122.4 (3) |
S—C1—H1A | 109.5 | C11—C10—H10A | 118.8 |
S—C1—H1B | 109.5 | C9—C10—H10A | 118.8 |
H1A—C1—H1B | 109.5 | C10—C11—C12 | 118.4 (3) |
S—C1—H1C | 109.5 | C10—C11—H11A | 120.8 |
H1A—C1—H1C | 109.5 | C12—C11—H11A | 120.8 |
H1B—C1—H1C | 109.5 | C13—C12—C11 | 121.7 (3) |
C3—C2—C7 | 118.9 (3) | C13—C12—H12A | 119.2 |
C3—C2—S | 123.2 (2) | C11—C12—H12A | 119.2 |
C7—C2—S | 117.9 (2) | C12—C13—C14 | 121.0 (3) |
C4—C3—C2 | 120.8 (3) | C12—C13—H13A | 119.5 |
C4—C3—H3A | 119.6 | C14—C13—H13A | 119.5 |
C2—C3—H3A | 119.6 | O—C14—C13 | 119.2 (3) |
C3—C4—C5 | 120.2 (3) | O—C14—C9 | 123.2 (3) |
C3—C4—H4A | 119.9 | C13—C14—C9 | 117.6 (3) |
C5—C4—H4A | 119.9 | Cl1—C30—Cl2 | 110.6 (2) |
C6—C5—C4 | 119.8 (3) | Cl1—C30—Cl3 | 110.7 (2) |
C6—C5—H5A | 120.1 | Cl2—C30—Cl3 | 110.5 (2) |
C4—C5—H5A | 120.1 | Cl1—C30—H30A | 108.3 |
C5—C6—C7 | 120.6 (3) | Cl2—C30—H30A | 108.3 |
C5—C6—H6A | 119.7 | Cl3—C30—H30A | 108.3 |
Symmetry code: (i) −x, y, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C14H12NOS)2]·2CHCl3 |
Mr | 788.72 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 110 |
a, b, c (Å) | 10.5673 (9), 21.5085 (19), 15.1215 (14) |
β (°) | 97.309 (2) |
V (Å3) | 3409.0 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.34 |
Crystal size (mm) | 0.45 × 0.38 × 0.32 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.381, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9547, 3345, 2494 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.135, 1.01 |
No. of reflections | 3345 |
No. of parameters | 195 |
No. of restraints | 6 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.50, −0.50 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
Financial support from the National Science Council of the Republic of China is gratefully appreciated. Helpful comments from the reviewers are also greatly appreciated.
References
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Because of their potential applications in many fields, poly(lactide) (PLA) and its copolymers have been investigated intensively (Huang et al., 2007). Ring-opening polymerization (ROP) of lactides is the major method used to synthesize these polymers. In these processes, undesirable transesterification reaction is the drawback but it can be lessened by using bulky ligands coordinated to the active metal centre (Wu et al., 2006). A lot of complexes with bulky ligands have been designed for this function, incorporating a single active metal site (Wu et al., 2006). Lin group have prepared a series of Zn complexes with NNO-tridentate Schiff base supported (Chen et al., 2006) which have great activity in the ROP of lactides. Recently, we have prepared NOS– tridentate Schiff base ligand (2-(((2-methylthiophenyl)methylimino)methyl)phenol) and its Zn complex. During these studies, it has been observed that LZnEt, where L is the (2-(((2-methylthiophenyl)methylimino)methyl)phenolate anion (C14H12NOS), reacts with benzyl alcohol to give L2Zn, (I) because of disproportionation. It seems that the sulfur atom can not stabilize Zn atom to form Zn alkoxide complex. L2Zn can also be prepared by the reaction of 2 equal LH with ZnEt2 in tetrahydrofuran. In the solid state, complex (I) shows a monomeric structure in which Zn atom are tetracoordinated and the geometry around Zn, resemble distorted tetrahedral with N—Zn—O(1), O(1)—Zn—O(1 A), and N—Zn—N(0 A) bond angles of 93.13 (9)o, 88.57 (11)o, and 103.73 (12)o. The distances of Zn—O and Zn—N are 1.9472 (18) and 2.054 (2) Å. A closely comparable conformation has been observed for the L'2Zn, where L' are the 2-(2,6-diisopropylphenylimino)methyl)-4-nitrophenolate anion (Chisholm et al., 2001) and 2-(2-dimethylaminoethylimino)methyl)-4-bromophenolate anion (Chen et al., 2006).