(Disulfur dinitrido)triphenyl­anti­mony(V)

Slawin, A.M.Z.; Waddell, P.G.; Woollins, J.D.

doi:10.1107/S1600536810009487

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page m418

doi:10.1107/S1600536810009487

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(Disulfur dinitrido)triphenylantimony(V)

Alexandra M. Z. Slawin,^a ^* Paul G. Waddell ^a and J. Derek Woollins ^a

^aDepartment of Chemistry, University of St Andrews, St Andrews KY16 9ST, Scotland
^*Correspondence e-mail: amzs@st-and.ac.uk

(Received 11 March 2010; accepted 12 March 2010; online 17 March 2010)

The title compound, [Sb(C₆H₅)₃(N₂S₂)], contains a molecular entity that is very similar to that of the known polymorph of Sb(S₂N₂)Ph₃ [Kunkel et al. (1997 ). Z. Naturforsch. Teil B, 52, 193–198], differing only in the orientation of the phenyl rings. The bond order in the SNSN unit is S—N=S=N, consisting of one long S—N bond, an intermediate length N=S bond and a short S=N bond.

Related literature

For the polymorph crystallizing in space group P2₁/n, see: Kunkel et al. (1997). For Pt(S₂N₂)(PR₃)₂ complexes with a similar bond order in the SNSN unit, see: Bates et al. (1986 ); Read et al. (2007 ).

Experimental

Crystal data

[Sb(C₆H₅)₃(N₂S₂)]
M_r = 445.20
Monoclinic, C 2/c
a = 16.997 (3) Å
b = 11.587 (2) Å
c = 18.166 (3) Å
β = 99.732 (7)°
V = 3526.3 (11) Å³
Z = 8
Mo Kα radiation
μ = 1.80 mm⁻¹
T = 93 K
0.08 × 0.05 × 0.05 mm

Data collection

Rigaku Mercury70 CCD diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.741, T_max = 0.914
11155 measured reflections
3094 independent reflections
2826 reflections with F² > 2σ(F²)
R_int = 0.053

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.113
S = 1.37
3094 reflections
208 parameters
H-atom parameters constrained
Δρ_max = 3.38 e Å⁻³
Δρ_min = −1.67 e Å⁻³

Table 1
Selected bond lengths (Å)

Sb1—C7	2.098 (6)
Sb1—C1	2.123 (6)
Sb1—C13	2.172 (5)
Sb1—N1	2.180 (5)
Sb1—S2	2.5030 (17)
S1—N1	1.510 (6)
S1—N2	1.589 (6)
S2—N2	1.656 (6)

Data collection: SCXMini (Rigaku, 2006 ); cell refinement: SCXMini; data reduction: SCXMini; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2009 ); software used to prepare material for publication: CrystalStructure.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810009487/jh2136sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810009487/jh2136Isup2.hkl

checkCIF report

Comment top

Previously the title compound has been prepared from tetrasulfurteranitride. The synthesis described here uses a non explosive S—N starting material.

Related literature top

For an isostructural compound, see: Kunkel et al. (1997). For Pt(S₂N₂)(PR₃)₂ complexes [R = ????] with a similar bond order in the SNSN unit, see: Bates et al. (1986); Read et al. (2007).

Experimental top

Liquid ammonia (30 ml) was condensed under nitrogen using an ammonia condenser filled with dry ice and acetone into a dry Schlenk tube in a dry ice/acetone bath. To this, 0.102 g (0.5 mmol) [S₄N₃]Cl was added. After stirring for 30 min s, 0.212 g (0.5 mmol) of triphenylstibenedichloride was added rapidly. The solution was then allowed to warm to room temperature and the ammonia gas blown off under a stream of nitrogen. The residue was placed under vacuum to remove any excess ammonia, before being dissolved in dichloromethane and filtered through celite. The product was precipitated by slow addition of hexane to give a yellow powder. Crystals were grown via slow diffusion of hexane into a solution of the product in dichloromethane.

Computing details top

Data collection: SCXMini (Rigaku, 2006); cell refinement: SCXMini (Rigaku, 2006); data reduction: SCXMini (Rigaku, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2009); software used to prepare material for publication: CrystalStructure (Rigaku, 2009).

Figures top

Fig. 1. The structure of (1) with displacement ellipsoids drawn at the 50% probability level, hydrogen atoms omitted for clarity.

(Disulfur dinitrido)triphenylantimony(V) top

Crystal data top

[Sb(C₆H₅)₃(N₂S₂)]	F(000) = 1760.00
M_r = 445.20	D_x = 1.677 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: -C 2yc	Cell parameters from 1987 reflections
a = 16.997 (3) Å	θ = 2.1–25.4°
b = 11.587 (2) Å	µ = 1.80 mm⁻¹
c = 18.166 (3) Å	T = 93 K
β = 99.732 (7)°	Prism, yellow
V = 3526.3 (11) Å³	0.08 × 0.05 × 0.05 mm
Z = 8

Data collection top

Rigaku Mercury70 CCD diffractometer	2826 reflections with F² > 2σ(F²)
ω scans	R_int = 0.053
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	θ_max = 25.4°
T_min = 0.741, T_max = 0.914	h = −20→19
11155 measured reflections	k = −8→13
3094 independent reflections	l = −21→16

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.113	H-atom parameters constrained
S = 1.37	w = 1/[σ²(F_o²) + (0.0236P)² + 20.1P] where P = (F_o² + 2F_c²)/3
3094 reflections	(Δ/σ)_max = 0.002
208 parameters	Δρ_max = 3.38 e Å⁻³
0 restraints	Δρ_min = −1.67 e Å⁻³
Primary atom site location: structure-invariant direct methods

Crystal data top

[Sb(C₆H₅)₃(N₂S₂)]	V = 3526.3 (11) Å³
M_r = 445.20	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 16.997 (3) Å	µ = 1.80 mm⁻¹
b = 11.587 (2) Å	T = 93 K
c = 18.166 (3) Å	0.08 × 0.05 × 0.05 mm
β = 99.732 (7)°

Data collection top

Rigaku Mercury70 CCD diffractometer	3094 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2826 reflections with F² > 2σ(F²)
T_min = 0.741, T_max = 0.914	R_int = 0.053
11155 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.113	H-atom parameters constrained
S = 1.37	w = 1/[σ²(F_o²) + (0.0236P)² + 20.1P] where P = (F_o² + 2F_c²)/3
3094 reflections	Δρ_max = 3.38 e Å⁻³
208 parameters	Δρ_min = −1.67 e Å⁻³

Special details top

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Sb(1)	0.22035 (2)	0.02024 (4)	0.064344 (19)	0.0189
S(1)	0.39390 (10)	0.02791 (16)	0.16524 (9)	0.0317
S(2)	0.34568 (10)	0.05730 (17)	0.01298 (9)	0.0326
N(1)	0.3060 (3)	0.0161 (5)	0.1682 (3)	0.0320
N(2)	0.4187 (4)	0.0478 (6)	0.0857 (3)	0.0402
C(1)	0.1547 (4)	0.1472 (5)	0.1125 (3)	0.0176
C(2)	0.1924 (4)	0.2490 (5)	0.1401 (3)	0.0187
C(3)	0.1493 (4)	0.3314 (6)	0.1715 (3)	0.0245
C(4)	0.0709 (4)	0.3115 (6)	0.1773 (3)	0.0283
C(5)	0.0330 (4)	0.2102 (6)	0.1503 (3)	0.0299
C(6)	0.0750 (4)	0.1279 (6)	0.1179 (3)	0.0242
C(7)	0.1724 (4)	−0.1403 (5)	0.0867 (3)	0.0210
C(8)	0.1975 (4)	−0.1975 (6)	0.1561 (4)	0.0266
C(9)	0.1631 (4)	−0.2976 (6)	0.1714 (4)	0.0327
C(10)	0.1015 (4)	−0.3454 (6)	0.1208 (4)	0.0312
C(11)	0.0752 (4)	−0.2915 (6)	0.0538 (4)	0.0319
C(12)	0.1128 (4)	−0.1908 (5)	0.0364 (3)	0.0223
C(13)	0.1639 (4)	0.0371 (5)	−0.0517 (3)	0.0192
C(14)	0.1094 (4)	0.1244 (5)	−0.0747 (3)	0.0202
C(15)	0.0780 (4)	0.1359 (6)	−0.1512 (3)	0.0266
C(16)	0.1023 (4)	0.0618 (6)	−0.2029 (3)	0.0271
C(17)	0.1570 (4)	−0.0245 (6)	−0.1798 (3)	0.0295
C(18)	0.1880 (4)	−0.0367 (6)	−0.1046 (3)	0.0257
H(2)	0.2471	0.2616	0.1374	0.022*
H(3)	0.1740	0.4020	0.1890	0.029*
H(4)	0.0423	0.3678	0.2002	0.034*
H(5)	−0.0214	0.1976	0.1540	0.036*
H(6)	0.0496	0.0583	0.0992	0.029*
H(8)	0.2388	−0.1649	0.1919	0.032*
H(9)	0.1813	−0.3358	0.2174	0.039*
H(10)	0.0774	−0.4155	0.1325	0.037*
H(11)	0.0319	−0.3226	0.0197	0.038*
H(12)	0.0970	−0.1563	−0.0113	0.027*
H(14)	0.0934	0.1758	−0.0393	0.024*
H(15)	0.0400	0.1946	−0.1674	0.032*
H(16)	0.0813	0.0705	−0.2545	0.033*
H(17)	0.1734	−0.0753	−0.2154	0.035*
H(18)	0.2259	−0.0957	−0.0889	0.031*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sb(1)	0.0204	0.0206	0.0152	0.0039	0.0013	−0.0005
S(1)	0.0231	0.0360	0.0332	−0.0013	−0.0035	0.0030
S(2)	0.0245	0.0462	0.0280	−0.0055	0.0072	0.0023
N(1)	0.0291	0.0398	0.0255	−0.0014	0.0001	0.0023
N(2)	0.0266	0.0576	0.0363	−0.0008	0.0053	0.0008
C(1)	0.0186	0.0233	0.0114	0.0019	0.0040	0.0012
C(2)	0.0136	0.0234	0.0201	−0.0021	0.0057	0.0017
C(3)	0.0273	0.0242	0.0207	0.0028	0.0004	−0.0023
C(4)	0.0345	0.0328	0.0179	0.0122	0.0050	−0.0038
C(5)	0.0143	0.0493	0.0275	0.0021	0.0077	−0.0031
C(6)	0.0216	0.0289	0.0230	−0.0016	0.0062	−0.0022
C(7)	0.0199	0.0203	0.0240	0.0014	0.0072	0.0010
C(8)	0.0213	0.0191	0.0362	0.0045	−0.0043	−0.0004
C(9)	0.0301	0.0348	0.0339	0.0066	0.0076	0.0102
C(10)	0.0240	0.0273	0.0458	0.0019	0.0160	0.0052
C(11)	0.0248	0.0270	0.0446	−0.0052	0.0075	−0.0039
C(12)	0.0307	0.0186	0.0167	−0.0061	0.0010	0.0043
C(13)	0.0203	0.0188	0.0180	−0.0018	0.0017	0.0019
C(14)	0.0174	0.0243	0.0184	−0.0010	0.0014	0.0010
C(15)	0.0213	0.0313	0.0255	0.0030	−0.0013	0.0053
C(16)	0.0246	0.0411	0.0141	−0.0056	−0.0009	0.0033
C(17)	0.0236	0.0429	0.0220	−0.0054	0.0037	−0.0067
C(18)	0.0235	0.0358	0.0178	0.0051	0.0029	−0.0016

Geometric parameters (Å, º) top

Sb1—C7	2.098 (6)	C8—C9	1.350 (9)
Sb1—C1	2.123 (6)	C8—H8	0.9500
Sb1—C13	2.172 (5)	C9—C10	1.387 (10)
Sb1—N1	2.180 (5)	C9—H9	0.9500
Sb1—S2	2.5030 (17)	C10—C11	1.375 (9)
S1—N1	1.510 (6)	C10—H10	0.9500
S1—N2	1.589 (6)	C11—C12	1.392 (9)
S2—N2	1.656 (6)	C11—H11	0.9500
C1—C6	1.392 (8)	C12—H12	0.9500
C1—C2	1.395 (8)	C13—C14	1.387 (8)
C2—C3	1.383 (8)	C13—C18	1.398 (8)
C2—H2	0.9500	C14—C15	1.407 (8)
C3—C4	1.374 (9)	C14—H14	0.9500
C3—H3	0.9500	C15—C16	1.387 (9)
C4—C5	1.388 (10)	C15—H15	0.9500
C4—H4	0.9500	C16—C17	1.381 (10)
C5—C6	1.382 (9)	C16—H16	0.9500
C5—H5	0.9500	C17—C18	1.385 (8)
C6—H6	0.9500	C17—H17	0.9500
C7—C12	1.375 (9)	C18—H18	0.9500
C7—C8	1.425 (8)

C7—Sb1—C1	106.6 (2)	C8—C7—Sb1	121.1 (5)
C7—Sb1—C13	98.3 (2)	C9—C8—C7	120.5 (6)
C1—Sb1—C13	99.3 (2)	C9—C8—H8	119.8
C7—Sb1—N1	92.2 (2)	C7—C8—H8	119.8
C1—Sb1—N1	88.8 (2)	C8—C9—C10	120.8 (6)
C13—Sb1—N1	164.3 (2)	C8—C9—H9	119.6
C7—Sb1—S2	127.40 (17)	C10—C9—H9	119.6
C1—Sb1—S2	125.09 (17)	C11—C10—C9	120.1 (7)
C13—Sb1—S2	83.53 (16)	C11—C10—H10	120.0
N1—Sb1—S2	80.79 (15)	C9—C10—H10	120.0
N1—S1—N2	117.5 (3)	C10—C11—C12	119.3 (6)
N2—S2—Sb1	105.2 (2)	C10—C11—H11	120.3
S1—N1—Sb1	119.2 (3)	C12—C11—H11	120.3
S1—N2—S2	117.1 (4)	C7—C12—C11	121.4 (6)
C6—C1—C2	120.3 (5)	C7—C12—H12	119.3
C6—C1—Sb1	120.2 (4)	C11—C12—H12	119.3
C2—C1—Sb1	119.5 (4)	C14—C13—C18	119.8 (5)
C3—C2—C1	119.2 (6)	C14—C13—Sb1	121.4 (4)
C3—C2—H2	120.4	C18—C13—Sb1	118.7 (4)
C1—C2—H2	120.4	C13—C14—C15	119.3 (6)
C4—C3—C2	120.3 (6)	C13—C14—H14	120.4
C4—C3—H3	119.8	C15—C14—H14	120.4
C2—C3—H3	119.8	C16—C15—C14	120.2 (6)
C3—C4—C5	120.9 (6)	C16—C15—H15	119.9
C3—C4—H4	119.6	C14—C15—H15	119.9
C5—C4—H4	119.6	C17—C16—C15	120.3 (5)
C6—C5—C4	119.5 (6)	C17—C16—H16	119.8
C6—C5—H5	120.3	C15—C16—H16	119.8
C4—C5—H5	120.3	C16—C17—C18	119.8 (6)
C5—C6—C1	119.8 (6)	C16—C17—H17	120.1
C5—C6—H6	120.1	C18—C17—H17	120.1
C1—C6—H6	120.1	C17—C18—C13	120.6 (6)
C12—C7—C8	117.8 (6)	C17—C18—H18	119.7
C12—C7—Sb1	121.0 (4)	C13—C18—H18	119.7

C7—Sb1—S2—N2	−81.8 (3)	S2—Sb1—C7—C12	−97.6 (5)
C1—Sb1—S2—N2	85.8 (3)	C1—Sb1—C7—C8	−83.7 (5)
C13—Sb1—S2—N2	−177.4 (3)	C13—Sb1—C7—C8	174.0 (5)
N1—Sb1—S2—N2	3.8 (3)	N1—Sb1—C7—C8	5.7 (5)
N2—S1—N1—Sb1	2.4 (5)	S2—Sb1—C7—C8	85.8 (5)
C7—Sb1—N1—S1	124.0 (4)	C12—C7—C8—C9	−0.4 (9)
C1—Sb1—N1—S1	−129.4 (4)	Sb1—C7—C8—C9	176.4 (5)
C13—Sb1—N1—S1	−8.1 (11)	C7—C8—C9—C10	−1.5 (10)
S2—Sb1—N1—S1	−3.6 (3)	C8—C9—C10—C11	0.7 (10)
N1—S1—N2—S2	1.6 (6)	C9—C10—C11—C12	2.1 (10)
Sb1—S2—N2—S1	−3.9 (5)	C8—C7—C12—C11	3.2 (10)
C7—Sb1—C1—C6	−30.4 (5)	Sb1—C7—C12—C11	−173.6 (5)
C13—Sb1—C1—C6	71.2 (5)	C10—C11—C12—C7	−4.1 (10)
N1—Sb1—C1—C6	−122.3 (5)	C7—Sb1—C13—C14	115.8 (5)
S2—Sb1—C1—C6	159.8 (4)	C1—Sb1—C13—C14	7.3 (5)
C7—Sb1—C1—C2	148.3 (4)	N1—Sb1—C13—C14	−112.8 (8)
C13—Sb1—C1—C2	−110.0 (4)	S2—Sb1—C13—C14	−117.3 (5)
N1—Sb1—C1—C2	56.4 (4)	C7—Sb1—C13—C18	−69.1 (5)
S2—Sb1—C1—C2	−21.5 (5)	C1—Sb1—C13—C18	−177.6 (5)
C6—C1—C2—C3	−1.2 (8)	N1—Sb1—C13—C18	62.3 (10)
Sb1—C1—C2—C3	−180.0 (4)	S2—Sb1—C13—C18	57.9 (5)
C1—C2—C3—C4	1.9 (9)	C18—C13—C14—C15	1.2 (9)
C2—C3—C4—C5	−1.7 (9)	Sb1—C13—C14—C15	176.2 (4)
C3—C4—C5—C6	0.8 (9)	C13—C14—C15—C16	−1.0 (9)
C4—C5—C6—C1	−0.1 (9)	C14—C15—C16—C17	0.6 (10)
C2—C1—C6—C5	0.3 (9)	C15—C16—C17—C18	−0.3 (10)
Sb1—C1—C6—C5	179.1 (4)	C16—C17—C18—C13	0.5 (10)
C1—Sb1—C7—C12	93.0 (5)	C14—C13—C18—C17	−0.9 (10)
C13—Sb1—C7—C12	−9.4 (6)	Sb1—C13—C18—C17	−176.1 (5)
N1—Sb1—C7—C12	−177.6 (5)

Experimental details

Crystal data
Chemical formula	[Sb(C₆H₅)₃(N₂S₂)]
M_r	445.20
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	93
a, b, c (Å)	16.997 (3), 11.587 (2), 18.166 (3)
β (°)	99.732 (7)
V (Å³)	3526.3 (11)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.80
Crystal size (mm)	0.08 × 0.05 × 0.05

Data collection
Diffractometer	Rigaku Mercury70 CCD diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.741, 0.914
No. of measured, independent and observed [F² > 2σ(F²)] reflections	11155, 3094, 2826
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.113, 1.37
No. of reflections	3094
No. of parameters	208
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0236P)² + 20.1P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	3.38, −1.67

Computer programs: SCXMini (Rigaku, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), CrystalStructure (Rigaku, 2009).

Selected bond lengths (Å) top

Sb1—C7	2.098 (6)	Sb1—S2	2.5030 (17)
Sb1—C1	2.123 (6)	S1—N1	1.510 (6)
Sb1—C13	2.172 (5)	S1—N2	1.589 (6)
Sb1—N1	2.180 (5)	S2—N2	1.656 (6)

References

Bates, P. A., Hursthouse, M. B., Kelly, P. F. & Woollins, J. D. (1986). J. Chem. Soc. Dalton Trans. pp. 2367–2370. CSD CrossRef Google Scholar
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Kunkel, F., Harms, K., Kang, H. C., Massa, W. & Dehnicke, K. (1997). Z. Naturforsch. Teil B, 52, 193–198. CAS Google Scholar
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