Bis{2-[(dimethyl­amino-κN)­meth­yl]­benzene­thiol­ato-κS}zinc(II)

In the title compound, [Zn(C₉H₁₂NS)₂], the Zn^II center is located on a twofold rotation axis and is coordinated in a distorted tetra­hedral environment in a bidentate fashion by anionic thiol­ate S and neutral amino N atoms of two 2-[(dimethyl­amino)methyl]benzene­thiol­ate ligands. All the mol­ecules are in the Δ form. The chosen crystal can thus be considered enanti­omerically pure. Inter­molecular C—H...π contacts connect the mol­ecules into a two-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.020
• wR factor = 0.047
• Data-to-parameter ratio = 20.0

checkCIF/PLATON results

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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

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S1. Comment

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 Zn^II complex appears in the Δ form (Ernst et al., 1967).

The Zn^II center occupies a special position, located on a twofold axis at [1/2, 0, z]. The coordination geometry at the Zn^II 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 Zn^II 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).

Related literature

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).

S2. Experimental

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).

S3. Refinement

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 U_iso(H) = 1.2U_eq(C) for H atoms of CH and CH₂ moieties and with U_iso(H) = 1.5U_eq(C) for methyl H atoms.

Computing details

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.

Figures

	Fig. 1. : Displacement ellipsoid plot and atomic numbering scheme of (I). Ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) 1 - x, -y, z]
	Fig. 2. : C—H···π interaction in (I), view along the crystallographic c axis. The C—H···π contacts are shown as dashed lines. [Symmetry codes: (i) 1 - x, -y, z; (ii) x - 1/2, 1/2 - y, 1 - z; (iii) 1/2 + x, 1/2 - y, -z; (iv) 1/2 - x, 1/2 + y, -z; (v) 1 - x, 1 - y, z; (vi) 3/2 - x, 1/2 + y, 1 - z; (vii) x, 1 + y, z]

Bis{2-[(dimethylamino-κN)methyl]benzenethiolato-κS}zinc(II)

Crystal data

[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) Å^3	Needle, yellow
Z = 2	0.36 × 0.12 × 0.09 mm

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.020	H-atom parameters constrained
wR(F^2) = 0.047	w = 1/[σ^2(Fo^2) + (0.0182P)^2 + 0.1166P] where P = (Fo^2 + 2Fc^2)/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)

Special details

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 (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

Zn1—N1^i	2.1128 (14)	C4—C5	1.378 (3)
Zn1—N1	2.1129 (14)	C4—H4	0.9500
Zn1—S1^i	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
N1^i—Zn1—N1	119.76 (8)	C4—C5—C6	120.53 (17)
N1^i—Zn1—S1^i	101.23 (4)	C4—C5—H5	119.7
N1—Zn1—S1^i	102.41 (4)	C6—C5—H5	119.7
N1^i—Zn1—S1	102.41 (4)	C5—C6—C1	121.03 (17)
N1—Zn1—S1	101.24 (4)	C5—C6—H6	119.5
S1^i—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
N1^i—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)
S1^i—Zn1—S1—C1	88.32 (5)	S1—C1—C2—C7	4.3 (2)
N1^i—Zn1—N1—C8	−141.01 (12)	C1—C2—C3—C4	−0.6 (3)
S1^i—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)
N1^i—Zn1—N1—C9	−20.77 (10)	C3—C4—C5—C6	0.9 (3)
S1^i—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)
N1^i—Zn1—N1—C7	98.41 (10)	S1—C1—C6—C5	−179.50 (13)
S1^i—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.