Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807027183/si2020sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807027183/si2020Isup2.hkl |
CCDC reference: 654727
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.002 Å
- R factor = 0.020
- wR factor = 0.047
- Data-to-parameter ratio = 20.0
checkCIF/PLATON results
No syntax errors found
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 27.46 From the CIF: _reflns_number_total 2143 Count of symmetry unique reflns 1265 Completeness (_total/calc) 169.41% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 878 Fraction of Friedel pairs measured 0.694 Are heavy atom types Z>Si present yes PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1 (2) 1.88
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 0 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
In order to synthesize mixed zinc complexes with isopropyllactate and aminoarenethiolate ligands, the title compound, (I), was formed by disproportionation of the mixed zinc compound.
To a mixture of 2.8 mMol EtZn(SC6H4CMe2NMe2-2) and 2.8 mMol (L)-isopropyllactate was added dry diethyl ether. The reaction mixture was stirred for 1 h. At the bottom of the reaction vessel a sticky solid was deposed. After removal of the clear solution, this solid was dried in vacuo. Yellow, needle shaped crystals for data collection were obtained by recrystallization from C6D6/CDCl3 (ratio 1:1).
All hydrogen atoms were introduced in geometrically idealized positions (C—H = 0.95–0.99 Å) and refined with a riding model. Methyl hydrogen atoms where refined to behave as a rigid rotator using the SHELXL97 (Sheldrick, 1997) command AFIX 137. The isotropic displacement parameters of the hydrogen atoms were constrained with Uiso(H) = 1.2Ueq(C) for H atoms of CH and CH2 moieties and with Uiso(H) = 1.5Ueq(C) for methyl H atoms.
The title compound, (I), crystallizes enantiomerically pure in space group P21212. The absolute structure of the crystal chosen could be determined from the Flack parameter of -0.013 (9) (Flack, 1983). The unit cell consists of two chiral Zn(C9H12NS)2 molecules, in which the ZnII complex appears in the Δ form (Ernst et al., 1967).
The ZnII center occupies a special position, located on a twofold axis at [1/2, 0, z]. The coordination geometry at the ZnII is defined by two monoanionic, S,N-bonded 2-[(dimethylamino)methyl]benzenethiolato ligands (Fig. 1). The ligand coordinates to the metal in a bidentate fashion via the anionic thiolato S1 [Zn1—S1 = 2.2811 (4) Å] and the neutral amino N1 [Zn1—N1 = 2.1129 (14) Å]. These distances compare well with those observed in the related Zn(SC6H4CH(Me)NMe2-2)2 complex reported by Rijnberg et al. (1997), with Zn—S of 2.284 (3) and 2.260 (2) Å, and Zn—N of 2.146 (8) and 2.096 (6) Å.
The four coordinated ZnII atom has a distorted-tetrahedral geometry, which is apparent from the S—Zn—N angles of 101.76 (8) and 102.41 (4)°. This can also be seen from the values for the quadratic elongation of 1.052 and for the angle variance of 168.05 Deg2 (Robinson et al., 1971). A conformational analysis of the ring puckering results in a coefficient of 92.6% for the cosine form of the six membered N1—Zn1—S1—C1—C2—C7 chelate ring (Evans & Boeyens, 1989). Therefore the ring is best described as a boat conformation.
The C1—S1—Zn1 angle of 102.47 (5)° indicates a distorted-tetrahedral geometry of the S atom, the distance C1—S1 is 1.7743 (17)Å and again agrees well with the C—S distance found in the Zn(SC6H4CH(Me)NMe2-2)2 complex with C—S = 1.76 (1)Å (Rijnberg et al., 1997). The geometry of the amino N atom is tetrahedral, with angles ranging from 107.63 (13) [C9—N1—C7] to 111.70 (11)° [C9—N1—Zn1].
There is an intermolecular C—H···π contact of H8C to the C1—C6 aromatic ring (centroid Cg), with H8C···Cgi = 2.96Å [symmetry code (i) 1 - x, -y, z], which connects the molecules into a two dimensional network perpendicular to c (Fig. 2).
A related structure was reported by Rijnberg et al. (1997). For related literature concerning the geometrical features see: Ernst et al. (1967); Evans & Boeyens (1989); Robinson et al. (1971).
Data collection: COLLECT (Nonius, 1999); cell refinement: HKL-2000 (Otwinowski & Minor, (1997); data reduction: HKL-2000; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: manual editing of the SHELXL97 output.
[Zn(C9H12NS)2] | F(000) = 416 |
Mr = 397.88 | Dx = 1.416 Mg m−3 |
Orthorhombic, P21212 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2 2ab | Cell parameters from 10982 reflections |
a = 10.1731 (2) Å | θ = 1.0–27.5° |
b = 14.1431 (2) Å | µ = 1.54 mm−1 |
c = 6.4862 (1) Å | T = 150 K |
V = 933.23 (3) Å3 | Needle, yellow |
Z = 2 | 0.36 × 0.12 × 0.09 mm |
Nonius KappaCCD diffractometer | 2143 independent reflections |
Radiation source: rotating anode | 2001 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
φ and ω scans | θmax = 27.5°, θmin = 2.5° |
Absorption correction: multi-scan (MULABS routine of PLATON; Spek, 2003) | h = −12→13 |
Tmin = 0.82, Tmax = 0.87 | k = −12→18 |
11294 measured reflections | l = −8→8 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.020 | H-atom parameters constrained |
wR(F2) = 0.047 | w = 1/[σ2(Fo2) + (0.0182P)2 + 0.1166P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.001 |
2143 reflections | Δρmax = 0.20 e Å−3 |
107 parameters | Δρmin = −0.18 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 880 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.013 (9) |
[Zn(C9H12NS)2] | V = 933.23 (3) Å3 |
Mr = 397.88 | Z = 2 |
Orthorhombic, P21212 | Mo Kα radiation |
a = 10.1731 (2) Å | µ = 1.54 mm−1 |
b = 14.1431 (2) Å | T = 150 K |
c = 6.4862 (1) Å | 0.36 × 0.12 × 0.09 mm |
Nonius KappaCCD diffractometer | 2143 independent reflections |
Absorption correction: multi-scan (MULABS routine of PLATON; Spek, 2003) | 2001 reflections with I > 2σ(I) |
Tmin = 0.82, Tmax = 0.87 | Rint = 0.037 |
11294 measured reflections |
R[F2 > 2σ(F2)] = 0.020 | H-atom parameters constrained |
wR(F2) = 0.047 | Δρmax = 0.20 e Å−3 |
S = 1.06 | Δρmin = −0.18 e Å−3 |
2143 reflections | Absolute structure: Flack (1983), 880 Friedel pairs |
107 parameters | Absolute structure parameter: −0.013 (9) |
0 restraints |
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 | ||
Zn1 | 0.5000 | 0.0000 | 0.11091 (3) | 0.02267 (8) | |
S1 | 0.34728 (4) | 0.09804 (3) | 0.25447 (7) | 0.02740 (10) | |
N1 | 0.61791 (13) | 0.09749 (11) | −0.0526 (2) | 0.0260 (3) | |
C1 | 0.43649 (15) | 0.20488 (12) | 0.2857 (2) | 0.0232 (3) | |
C2 | 0.52665 (15) | 0.23934 (12) | 0.1408 (2) | 0.0256 (4) | |
C3 | 0.59119 (17) | 0.32491 (12) | 0.1791 (3) | 0.0331 (4) | |
H3 | 0.6530 | 0.3480 | 0.0816 | 0.040* | |
C4 | 0.56685 (18) | 0.37667 (13) | 0.3565 (3) | 0.0382 (5) | |
H4 | 0.6122 | 0.4343 | 0.3814 | 0.046* | |
C5 | 0.47595 (18) | 0.34349 (13) | 0.4964 (3) | 0.0351 (4) | |
H5 | 0.4577 | 0.3789 | 0.6175 | 0.042* | |
C6 | 0.41102 (17) | 0.25888 (13) | 0.4619 (3) | 0.0291 (4) | |
H6 | 0.3482 | 0.2372 | 0.5594 | 0.035* | |
C7 | 0.54904 (17) | 0.19101 (13) | −0.0639 (2) | 0.0294 (4) | |
H7A | 0.4628 | 0.1815 | −0.1314 | 0.035* | |
H7B | 0.6012 | 0.2338 | −0.1528 | 0.035* | |
C8 | 0.74530 (16) | 0.10835 (13) | 0.0541 (3) | 0.0344 (4) | |
H8A | 0.7935 | 0.0484 | 0.0491 | 0.052* | |
H8B | 0.7300 | 0.1261 | 0.1981 | 0.052* | |
H8C | 0.7970 | 0.1577 | −0.0142 | 0.052* | |
C9 | 0.6432 (2) | 0.06543 (15) | −0.2681 (3) | 0.0419 (5) | |
H9A | 0.7097 | 0.1063 | −0.3315 | 0.063* | |
H9B | 0.5615 | 0.0690 | −0.3479 | 0.063* | |
H9C | 0.6749 | 0.0000 | −0.2664 | 0.063* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.01809 (12) | 0.02763 (14) | 0.02228 (12) | −0.00127 (13) | 0.000 | 0.000 |
S1 | 0.0215 (2) | 0.0304 (2) | 0.0303 (2) | −0.00084 (18) | 0.00561 (18) | −0.00021 (19) |
N1 | 0.0218 (7) | 0.0309 (8) | 0.0253 (7) | −0.0020 (6) | 0.0054 (5) | 0.0016 (6) |
C1 | 0.0199 (7) | 0.0251 (9) | 0.0245 (8) | 0.0039 (7) | −0.0040 (6) | 0.0046 (7) |
C2 | 0.0217 (9) | 0.0271 (9) | 0.0282 (8) | 0.0037 (7) | −0.0020 (6) | 0.0056 (7) |
C3 | 0.0252 (9) | 0.0305 (11) | 0.0435 (10) | 0.0017 (8) | 0.0024 (7) | 0.0086 (9) |
C4 | 0.0308 (10) | 0.0285 (10) | 0.0552 (12) | −0.0001 (8) | −0.0053 (9) | −0.0055 (9) |
C5 | 0.0356 (12) | 0.0327 (10) | 0.0370 (10) | 0.0066 (8) | −0.0043 (8) | −0.0059 (8) |
C6 | 0.0271 (9) | 0.0335 (10) | 0.0267 (8) | 0.0074 (8) | −0.0020 (7) | 0.0021 (8) |
C7 | 0.0281 (8) | 0.0348 (10) | 0.0255 (9) | 0.0012 (8) | 0.0025 (7) | 0.0100 (7) |
C8 | 0.0195 (8) | 0.0350 (11) | 0.0487 (11) | −0.0043 (8) | −0.0013 (8) | 0.0065 (9) |
C9 | 0.0400 (11) | 0.0532 (13) | 0.0325 (10) | −0.0058 (10) | 0.0172 (9) | −0.0035 (9) |
Zn1—N1i | 2.1128 (14) | C4—C5 | 1.378 (3) |
Zn1—N1 | 2.1129 (14) | C4—H4 | 0.9500 |
Zn1—S1i | 2.2811 (4) | C5—C6 | 1.385 (2) |
Zn1—S1 | 2.2811 (4) | C5—H5 | 0.9500 |
S1—C1 | 1.7743 (17) | C6—H6 | 0.9500 |
N1—C8 | 1.477 (2) | C7—H7A | 0.9900 |
N1—C9 | 1.492 (2) | C7—H7B | 0.9900 |
N1—C7 | 1.499 (2) | C8—H8A | 0.9800 |
C1—C6 | 1.398 (2) | C8—H8B | 0.9800 |
C1—C2 | 1.401 (2) | C8—H8C | 0.9800 |
C2—C3 | 1.399 (2) | C9—H9A | 0.9800 |
C2—C7 | 1.510 (2) | C9—H9B | 0.9800 |
C3—C4 | 1.386 (2) | C9—H9C | 0.9800 |
C3—H3 | 0.9500 | ||
N1i—Zn1—N1 | 119.76 (8) | C4—C5—C6 | 120.53 (17) |
N1i—Zn1—S1i | 101.23 (4) | C4—C5—H5 | 119.7 |
N1—Zn1—S1i | 102.41 (4) | C6—C5—H5 | 119.7 |
N1i—Zn1—S1 | 102.41 (4) | C5—C6—C1 | 121.03 (17) |
N1—Zn1—S1 | 101.24 (4) | C5—C6—H6 | 119.5 |
S1i—Zn1—S1 | 131.82 (2) | C1—C6—H6 | 119.5 |
C1—S1—Zn1 | 102.47 (5) | N1—C7—C2 | 115.27 (13) |
C8—N1—C9 | 108.61 (14) | N1—C7—H7A | 108.5 |
C8—N1—C7 | 109.96 (14) | C2—C7—H7A | 108.5 |
C9—N1—C7 | 107.63 (13) | N1—C7—H7B | 108.5 |
C8—N1—Zn1 | 109.33 (11) | C2—C7—H7B | 108.5 |
C9—N1—Zn1 | 111.70 (11) | H7A—C7—H7B | 107.5 |
C7—N1—Zn1 | 109.58 (10) | N1—C8—H8A | 109.5 |
C6—C1—C2 | 118.66 (16) | N1—C8—H8B | 109.5 |
C6—C1—S1 | 117.63 (13) | H8A—C8—H8B | 109.5 |
C2—C1—S1 | 123.67 (13) | N1—C8—H8C | 109.5 |
C3—C2—C1 | 119.26 (15) | H8A—C8—H8C | 109.5 |
C3—C2—C7 | 118.49 (15) | H8B—C8—H8C | 109.5 |
C1—C2—C7 | 122.08 (15) | N1—C9—H9A | 109.5 |
C4—C3—C2 | 121.38 (17) | N1—C9—H9B | 109.5 |
C4—C3—H3 | 119.3 | H9A—C9—H9B | 109.5 |
C2—C3—H3 | 119.3 | N1—C9—H9C | 109.5 |
C5—C4—C3 | 119.12 (18) | H9A—C9—H9C | 109.5 |
C5—C4—H4 | 120.4 | H9B—C9—H9C | 109.5 |
C3—C4—H4 | 120.4 | ||
N1i—Zn1—S1—C1 | −154.00 (7) | S1—C1—C2—C3 | 179.43 (12) |
N1—Zn1—S1—C1 | −29.82 (7) | C6—C1—C2—C7 | −173.28 (15) |
S1i—Zn1—S1—C1 | 88.32 (5) | S1—C1—C2—C7 | 4.3 (2) |
N1i—Zn1—N1—C8 | −141.01 (12) | C1—C2—C3—C4 | −0.6 (3) |
S1i—Zn1—N1—C8 | −30.18 (11) | C7—C2—C3—C4 | 174.74 (15) |
S1—Zn1—N1—C8 | 107.53 (11) | C2—C3—C4—C5 | −0.8 (3) |
N1i—Zn1—N1—C9 | −20.77 (10) | C3—C4—C5—C6 | 0.9 (3) |
S1i—Zn1—N1—C9 | 90.06 (12) | C4—C5—C6—C1 | 0.4 (3) |
S1—Zn1—N1—C9 | −132.23 (11) | C2—C1—C6—C5 | −1.8 (2) |
N1i—Zn1—N1—C7 | 98.41 (10) | S1—C1—C6—C5 | −179.50 (13) |
S1i—Zn1—N1—C7 | −150.76 (10) | C8—N1—C7—C2 | −56.26 (18) |
S1—Zn1—N1—C7 | −13.05 (10) | C9—N1—C7—C2 | −174.41 (15) |
Zn1—S1—C1—C6 | −143.07 (11) | Zn1—N1—C7—C2 | 63.93 (16) |
Zn1—S1—C1—C2 | 39.38 (14) | C3—C2—C7—N1 | 114.67 (17) |
C6—C1—C2—C3 | 1.9 (2) | C1—C2—C7—N1 | −70.1 (2) |
Symmetry code: (i) −x+1, −y, z. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C9H12NS)2] |
Mr | 397.88 |
Crystal system, space group | Orthorhombic, P21212 |
Temperature (K) | 150 |
a, b, c (Å) | 10.1731 (2), 14.1431 (2), 6.4862 (1) |
V (Å3) | 933.23 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.54 |
Crystal size (mm) | 0.36 × 0.12 × 0.09 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | Multi-scan (MULABS routine of PLATON; Spek, 2003) |
Tmin, Tmax | 0.82, 0.87 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11294, 2143, 2001 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.020, 0.047, 1.06 |
No. of reflections | 2143 |
No. of parameters | 107 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.20, −0.18 |
Absolute structure | Flack (1983), 880 Friedel pairs |
Absolute structure parameter | −0.013 (9) |
Computer programs: COLLECT (Nonius, 1999), HKL-2000 (Otwinowski & Minor, (1997), HKL-2000, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), manual editing of the SHELXL97 output.
Zn1—N1 | 2.1129 (14) | S1—C1 | 1.7743 (17) |
Zn1—S1 | 2.2811 (4) | ||
N1i—Zn1—N1 | 119.76 (8) | S1i—Zn1—S1 | 131.82 (2) |
N1—Zn1—S1i | 102.41 (4) | C1—S1—Zn1 | 102.47 (5) |
N1—Zn1—S1 | 101.24 (4) |
Symmetry code: (i) −x+1, −y, z. |
X—H···Cg | X—H | H···Cg | X···Cg | X—H···Cg |
C8—H8C···Cgi | 0.98 | 2.96 | 3.8324 (19) | 149 |
Cg is the centroid of the C1–C6 aromatic ring. [Symmetry code: (i) 1-x, -y, z] |
The title compound, (I), crystallizes enantiomerically pure in space group P21212. The absolute structure of the crystal chosen could be determined from the Flack parameter of -0.013 (9) (Flack, 1983). The unit cell consists of two chiral Zn(C9H12NS)2 molecules, in which the ZnII complex appears in the Δ form (Ernst et al., 1967).
The ZnII center occupies a special position, located on a twofold axis at [1/2, 0, z]. The coordination geometry at the ZnII is defined by two monoanionic, S,N-bonded 2-[(dimethylamino)methyl]benzenethiolato ligands (Fig. 1). The ligand coordinates to the metal in a bidentate fashion via the anionic thiolato S1 [Zn1—S1 = 2.2811 (4) Å] and the neutral amino N1 [Zn1—N1 = 2.1129 (14) Å]. These distances compare well with those observed in the related Zn(SC6H4CH(Me)NMe2-2)2 complex reported by Rijnberg et al. (1997), with Zn—S of 2.284 (3) and 2.260 (2) Å, and Zn—N of 2.146 (8) and 2.096 (6) Å.
The four coordinated ZnII atom has a distorted-tetrahedral geometry, which is apparent from the S—Zn—N angles of 101.76 (8) and 102.41 (4)°. This can also be seen from the values for the quadratic elongation of 1.052 and for the angle variance of 168.05 Deg2 (Robinson et al., 1971). A conformational analysis of the ring puckering results in a coefficient of 92.6% for the cosine form of the six membered N1—Zn1—S1—C1—C2—C7 chelate ring (Evans & Boeyens, 1989). Therefore the ring is best described as a boat conformation.
The C1—S1—Zn1 angle of 102.47 (5)° indicates a distorted-tetrahedral geometry of the S atom, the distance C1—S1 is 1.7743 (17)Å and again agrees well with the C—S distance found in the Zn(SC6H4CH(Me)NMe2-2)2 complex with C—S = 1.76 (1)Å (Rijnberg et al., 1997). The geometry of the amino N atom is tetrahedral, with angles ranging from 107.63 (13) [C9—N1—C7] to 111.70 (11)° [C9—N1—Zn1].
There is an intermolecular C—H···π contact of H8C to the C1—C6 aromatic ring (centroid Cg), with H8C···Cgi = 2.96Å [symmetry code (i) 1 - x, -y, z], which connects the molecules into a two dimensional network perpendicular to c (Fig. 2).