Sodium thio­phenolate N,N,N',N'-tetra­methyl­ethyl­enedi­amine

The title compound, Na⁺·C₆H₅S^-·C₆H₁₆N₂, forms lipophilically wrapped infinite sodium chains along the a axis. Each sodium cation is coordinated by three thio­phenolate S atoms and two N centres of one tetra­methyl­ethyl­enedi­amine molecule.

S1. Comment

Strong phenyl/phenyl interactions stabilize the dimer of tris(phenylthio)methane, even in the gas phase (Bock, Havlas et al., 2000). An attempt to add negative charge by reduction with sodium metal failed due to tris(phenylthio)methane decomposition to thiophenolate, which crystallizes in the presence of a sodium metal mirror and of tetramethylethylenediamine (I) to another lipophilically wrapped polyion aggregate (Bock, Hauck et al., 1995; Bock, Schödel et al., 1995; Bock, Beck et al., 1998; Bock, Heigel & Nagel, 2000; Bock & Heigel, 2000a,b). \sch

The sodium cations form distorted trigonal bipyramides with sulfur centers of the thiophenolates and N centers of tetramethylethylenediamine. The axial positions are occupied by S1, N2 and the equatorial positions by S1A, S1B and N1 [Fig. 1; symmetry codes: (A) -x, 1 - y, -z; (B) 1 - x, 1 - y, -z]. These interatomic contacts agree with the sum of van der waals radii. Nevertheless, the interaction of the sodium cation to S1A and S1B decreases but the geometry of a trigonal bipyramid is well defined (Fig. 1). The sodium cations are connected by Na—S—Na bridges to infinite chains along the a axis with alternate distances Na—Na of 4.132 (1) Å and 4.361 (1) Å (Fig. 2a). The C—S bonding of the thiophenolate has a distance of 1.754 Å, that is in mean band of 1.77 (3) calculated for the distances C—S of 472 crystal structures including thiophenolate registered in the Cambridge Structural Database. The bonding C—S of thiophenolates shows a broad variety in length obviously independent of the cation. Therefore bis(tetra-n-butylammonium)tetrakis(benzenethiolatoiron) containing only iron cations exhibits distances C—S with maximum differences of 0.04 Å in every published crystal structure (Guiodong et al., 1987; Gloux et al., 1987; Excoffon et al., 1991). The lipophilical wrapping by phenyl rings and methyl groups (Fig.2: B) is responsible for the kinetic stability of the polyion aggregate in analogy to the hexameric tetraphenylimidodiphosphate sodium (Bock, Schödel et al., 1995).

Related literature

For related literature, see: Bock & Heigel (2000, 2000); Bock et al. (1998); Bock, Hauck, Näther, Rösch, Staufer & Häberlein (1995); Bock, Havlas, Krenzel & Sievert (2000); Bock, Heigel & Nagel (2000); Bock, Schödel, Havlas & Herrmann (1995); Excoffon et al. (1991); Gloux et al. (1987); Sheldrick (1986, 1997).

S2. Experimental

Preparation and crystallization: From sodium (0.1 g, 4.3 mmol) by gentle heating at 10^-5 mbar a mirror is generated on the wall of a dried Schlenk trap. Addition of tris(phenylthio)methane (100 mg, 0.2 mmol) in aprotic tetramethylethylenediamine (10 ml) produces a yellow solution, which after one day of standing at room temperature is covered with a layer aprotic n-hexane (10 ml). After one week, yellow crystals are collected from the trap wall near the phase border line.

S3. Refinement

Structure determination: The structure was solved with SHELXS86 (Sheldrick, 1986) and refinement accomplished with SHELXL97 (Sheldrick, 1997), molecular graphics: XP (Siemens XTL-PC). Data were corrected for Lorentz and polarization effects. All C, S, N and Na have been refined with anisotropic displacement parameters, all H atoms were located from the difference map and placed on idealized positions using a riding model with distances C—H_phenyl = 0.95 Å, C—H_methylene = 0.99 Å and C—H_methyl = 0.98 Å. The torsion of the methyl H atoms and the isotropic displacement parameters of all H atoms (groupwise for methyl and methylen H atoms) were refined.

Computing details

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTLPC/XP; software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. Coordination sphere of sodium in (I) with 50% probability displacement ellipsoides and atom-numbering scheme. H atoms are drawn as spheres of arbitrary radii.
	Fig. 2. (a) The unit cell viewed along the b axis showing two infinite chains of (I) along the a axis and (b) space-filled drawing of one chain (profile) illustrating the lipophilical wrapping of the polyionic chain inside (sodium: black; sulfur, nitrogen: dark grey; carbon: grey; hydrogen: white).

(I)

Crystal data

Na^+·C6H5S^−·C6H16N2	Z = 2
Mr = 248.36	F(000) = 268
Triclinic, P1	Dx = 1.187 Mg m^−3
a = 5.944 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.200 (2) Å	Cell parameters from 81 reflections
c = 11.899 (2) Å	θ = 8.5–18°
α = 62.58 (1)°	µ = 0.24 mm^−1
β = 87.14 (2)°	T = 180 K
γ = 81.32 (2)°	Block, yellow
V = 694.9 (2) Å^3	0.60 × 0.42 × 0.25 mm

Data collection

Siemens P4 four circle diffractometer	Rint = 0.043
Radiation source: fine-focus sealed tube	θmax = 28.0°, θmin = 1.9°
Graphite monochromator	h = −1→7
θ–2θ scans	k = −13→13
3921 measured reflections	l = −15→15
3066 independent reflections	4 standard reflections every 100 reflections
2636 reflections with I > 2σ(I)	intensity decay: <5%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0459P)^2 + 0.1435P] where P = (Fo^2 + 2Fc^2)/3
3066 reflections	(Δ/σ)max < 0.001
149 parameters	Δρmax = 0.34 e Å^−3
0 restraints	Δρmin = −0.21 e Å^−3

Special details

Experimental. The count of measured symmetry unique reflections to theta 30 is not complete but ratio data parameter 20.6 is quite good.

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
S1	0.28669 (6)	0.36592 (3)	0.00593 (3)	0.02952 (11)
Na1	0.20232 (10)	0.65095 (6)	−0.09001 (5)	0.03402 (15)
C11	0.2423 (2)	0.35842 (13)	−0.13519 (12)	0.0268 (3)
C12	0.0259 (2)	0.38947 (17)	−0.19132 (13)	0.0367 (3)
H12	−0.1018	0.4138	−0.1511	0.044*
C13	−0.0071 (3)	0.38566 (18)	−0.30345 (14)	0.0417 (4)
H13	−0.1563	0.4077	−0.3391	0.050*
C14	0.1739 (3)	0.35034 (17)	−0.36429 (14)	0.0408 (4)
H14	0.1508	0.3478	−0.4415	0.049*
C15	0.3888 (3)	0.31874 (18)	−0.31119 (15)	0.0413 (4)
H15	0.5150	0.2942	−0.3523	0.050*
C16	0.4231 (2)	0.32232 (16)	−0.19853 (13)	0.0336 (3)
H16	0.5729	0.2997	−0.1635	0.040*
N1	0.29374 (19)	0.75373 (12)	−0.32466 (10)	0.0297 (2)
N2	0.16160 (19)	0.90602 (12)	−0.16959 (11)	0.0319 (3)
C1	0.5352 (3)	0.7097 (2)	−0.32441 (17)	0.0511 (5)
H1A	0.5630	0.6109	−0.2929	0.077*
H1B	0.6151	0.7338	−0.2693	0.077*
H1C	0.5912	0.7545	−0.4108	0.077*
C2	0.1784 (3)	0.7152 (2)	−0.40627 (15)	0.0460 (4)
H2A	0.0133	0.7365	−0.4013	0.069*
H2B	0.2196	0.6174	−0.3782	0.069*
H2C	0.2251	0.7657	−0.4939	0.069*
C3	0.2412 (3)	0.90096 (16)	−0.37395 (13)	0.0387 (3)
H3A	0.0768	0.9288	−0.3961	0.046*
H3B	0.3261	0.9451	−0.4528	0.046*
C4	0.2984 (3)	0.95221 (17)	−0.28344 (15)	0.0400 (3)
H4A	0.4613	0.9212	−0.2582	0.048*
H4B	0.2750	1.0528	−0.3276	0.048*
C5	−0.0746 (3)	0.97054 (19)	−0.19733 (18)	0.0469 (4)
H5A	−0.1594	0.9402	−0.1185	0.070*
H5B	−0.1427	0.9454	−0.2553	0.070*
H5C	−0.0806	1.0695	−0.2368	0.070*
C6	0.2568 (3)	0.94047 (18)	−0.07953 (16)	0.0426 (4)
H6A	0.1688	0.9080	−0.0018	0.064*
H6B	0.2499	1.0393	−0.1167	0.064*
H6C	0.4156	0.8973	−0.0596	0.064*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.03234 (17)	0.02730 (19)	0.02845 (17)	−0.00377 (12)	−0.00031 (11)	−0.01245 (13)
Na1	0.0476 (3)	0.0251 (3)	0.0265 (3)	−0.0068 (2)	0.0074 (2)	−0.0097 (2)
C11	0.0286 (6)	0.0231 (6)	0.0272 (6)	−0.0084 (5)	0.0024 (5)	−0.0089 (5)
C12	0.0271 (6)	0.0461 (9)	0.0323 (7)	−0.0075 (6)	0.0030 (5)	−0.0138 (6)
C13	0.0349 (7)	0.0528 (10)	0.0349 (7)	−0.0151 (7)	−0.0028 (6)	−0.0152 (7)
C14	0.0508 (9)	0.0438 (9)	0.0345 (7)	−0.0179 (7)	0.0014 (6)	−0.0204 (7)
C15	0.0429 (8)	0.0475 (10)	0.0417 (8)	−0.0086 (7)	0.0079 (6)	−0.0276 (7)
C16	0.0289 (6)	0.0379 (8)	0.0361 (7)	−0.0051 (6)	0.0015 (5)	−0.0186 (6)
N1	0.0328 (6)	0.0296 (6)	0.0258 (5)	−0.0080 (5)	0.0032 (4)	−0.0111 (4)
N2	0.0305 (6)	0.0285 (6)	0.0371 (6)	−0.0066 (5)	0.0047 (4)	−0.0150 (5)
C1	0.0363 (8)	0.0733 (13)	0.0458 (9)	0.0054 (8)	−0.0032 (6)	−0.0326 (9)
C2	0.0461 (9)	0.0585 (11)	0.0413 (8)	−0.0185 (8)	0.0023 (7)	−0.0264 (8)
C3	0.0460 (8)	0.0326 (8)	0.0298 (7)	−0.0091 (6)	0.0026 (6)	−0.0070 (6)
C4	0.0443 (8)	0.0353 (8)	0.0429 (8)	−0.0186 (6)	0.0131 (6)	−0.0175 (6)
C5	0.0325 (7)	0.0429 (9)	0.0638 (10)	−0.0036 (6)	−0.0004 (7)	−0.0236 (8)
C6	0.0448 (8)	0.0396 (9)	0.0476 (8)	−0.0011 (7)	−0.0040 (7)	−0.0245 (7)

Geometric parameters (Å, º)

S1—C11	1.7542 (14)	C12—C13	1.379 (2)
S1—Na1	2.8219 (8)	C13—C14	1.377 (2)
S1—Na1^i	3.0310 (8)	C14—C15	1.376 (2)
S1—Na1^ii	3.1966 (8)	C15—C16	1.385 (2)
Na1—N2	2.5375 (14)	N1—C1	1.445 (2)
Na1—N1	2.5482 (13)	N1—C3	1.460 (2)
Na1—S1^i	3.0310 (8)	N1—C2	1.4634 (19)
Na1—S1^ii	3.1966 (8)	N2—C5	1.4570 (19)
Na1—Na1^i	4.1323 (12)	N2—C6	1.458 (2)
C11—C16	1.3983 (19)	N2—C4	1.4613 (18)
C11—C12	1.3994 (18)	C3—C4	1.506 (2)
C11—S1—Na1	98.21 (5)	C16—C11—S1	121.47 (10)
C11—S1—Na1^i	95.56 (4)	C12—C11—S1	122.18 (11)
Na1—S1—Na1^i	89.751 (18)	C13—C12—C11	121.85 (14)
C11—S1—Na1^ii	118.28 (4)	C14—C13—C12	120.72 (14)
Na1—S1—Na1^ii	92.662 (19)	C15—C14—C13	118.82 (14)
Na1^i—S1—Na1^ii	145.28 (2)	C14—C15—C16	120.78 (14)
N2—Na1—N1	73.60 (4)	C15—C16—C11	121.50 (13)
N2—Na1—S1	174.95 (4)	C1—N1—C3	111.97 (13)
N1—Na1—S1	106.93 (3)	C1—N1—C2	108.35 (13)
N2—Na1—S1^i	93.77 (3)	C3—N1—C2	108.11 (12)
N1—Na1—S1^i	120.38 (3)	C1—N1—Na1	103.32 (9)
S1—Na1—S1^i	90.249 (18)	C3—N1—Na1	106.29 (9)
N2—Na1—S1^ii	87.62 (3)	C2—N1—Na1	118.81 (9)
N1—Na1—S1^ii	93.31 (3)	C5—N2—C6	108.55 (13)
S1—Na1—S1^ii	87.338 (19)	C5—N2—C4	111.76 (13)
S1^i—Na1—S1^ii	145.28 (2)	C6—N2—C4	108.64 (12)
N2—Na1—Na1^i	136.76 (4)	C5—N2—Na1	112.35 (10)
N1—Na1—Na1^i	124.73 (4)	C6—N2—Na1	111.95 (9)
S1—Na1—Na1^i	47.179 (15)	C4—N2—Na1	103.50 (9)
S1^i—Na1—Na1^i	43.070 (14)	N1—C3—C4	114.21 (12)
S1^ii—Na1—Na1^i	124.83 (2)	N2—C4—C3	113.28 (12)
C16—C11—C12	116.35 (13)
C11—S1—Na1—N2	−121.6 (4)	N2—Na1—N1—C3	−7.31 (9)
Na1^i—S1—Na1—N2	142.8 (4)	S1—Na1—N1—C3	177.94 (8)
Na1^ii—S1—Na1—N2	−2.6 (4)	S1^i—Na1—N1—C3	77.35 (9)
C11—S1—Na1—N1	−26.41 (5)	S1^ii—Na1—N1—C3	−93.84 (9)
Na1^i—S1—Na1—N1	−122.00 (4)	Na1^i—Na1—N1—C3	128.74 (9)
Na1^ii—S1—Na1—N1	92.66 (3)	N2—Na1—N1—C2	−129.34 (12)
C11—S1—Na1—S1^i	95.59 (4)	S1—Na1—N1—C2	55.91 (12)
Na1^i—S1—Na1—S1^i	0.0	S1^i—Na1—N1—C2	−44.67 (12)
Na1^ii—S1—Na1—S1^i	−145.35 (2)	S1^ii—Na1—N1—C2	144.13 (11)
C11—S1—Na1—S1^ii	−119.07 (4)	Na1^i—Na1—N1—C2	6.72 (13)
Na1^i—S1—Na1—S1^ii	145.35 (2)	N1—Na1—N2—C5	98.91 (11)
Na1^ii—S1—Na1—S1^ii	0.0	S1—Na1—N2—C5	−164.4 (4)
C11—S1—Na1—Na1^i	95.59 (4)	S1^i—Na1—N2—C5	−21.68 (11)
Na1^ii—S1—Na1—Na1^i	−145.35 (2)	S1^ii—Na1—N2—C5	−166.93 (11)
Na1—S1—C11—C16	108.64 (12)	Na1^i—Na1—N2—C5	−24.73 (13)
Na1^i—S1—C11—C16	−160.81 (11)	N1—Na1—N2—C6	−138.63 (10)
Na1^ii—S1—C11—C16	11.12 (14)	S1—Na1—N2—C6	−41.9 (4)
Na1—S1—C11—C12	−70.63 (12)	S1^i—Na1—N2—C6	100.78 (9)
Na1^i—S1—C11—C12	19.93 (12)	S1^ii—Na1—N2—C6	−44.47 (9)
Na1^ii—S1—C11—C12	−168.15 (10)	Na1^i—Na1—N2—C6	97.73 (10)
C16—C11—C12—C13	−0.5 (2)	N1—Na1—N2—C4	−21.81 (9)
S1—C11—C12—C13	178.83 (13)	S1—Na1—N2—C4	74.9 (4)
C11—C12—C13—C14	0.2 (3)	S1^i—Na1—N2—C4	−142.40 (9)
C12—C13—C14—C15	0.0 (3)	S1^ii—Na1—N2—C4	72.35 (9)
C13—C14—C15—C16	0.0 (3)	Na1^i—Na1—N2—C4	−145.45 (8)
C14—C15—C16—C11	−0.3 (3)	C1—N1—C3—C4	−75.09 (16)
C12—C11—C16—C15	0.5 (2)	C2—N1—C3—C4	165.63 (13)
S1—C11—C16—C15	−178.82 (12)	Na1—N1—C3—C4	37.04 (14)
N2—Na1—N1—C1	110.71 (11)	C5—N2—C4—C3	−70.22 (18)
S1—Na1—N1—C1	−64.05 (11)	C6—N2—C4—C3	170.03 (13)
S1^i—Na1—N1—C1	−164.63 (10)	Na1—N2—C4—C3	50.90 (14)
S1^ii—Na1—N1—C1	24.17 (11)	N1—C3—C4—N2	−65.32 (18)
Na1^i—Na1—N1—C1	−113.24 (11)

Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1, −y+1, −z.