A bent two-coordinate silver(I) complex with 2,2',3,3'-tetra­hydro-4,4'-di­thia-1,1'-binaphyl­idene

The Ag^I complex of 2,2',3,3'-tetra­hydro-4,4'-di­thia-1,1'-binaphyl­idene (ttp) has been synthesized and its molecular structure determined as its PF₆^- salt, i.e. (2,2',3,3'-tetra­hydro-4,4'-di­thia-1,1'-binaphyl­idene)silver(I) hexa­fluoro­phosphate, [Ag(C₁₈H₁₆S₂)]PF₆. The Ag^I ion has a distorted linear geometry comprised of the two S atoms of ttp, with an Ag-S distance of 2.4889 (8) Å and an S-Ag-S angle of 157.48 (4)°; the cation has twofold symmetry. This coordination mode results in the formation of a nine-membered ring.

Key indicators

• Single-crystal X-ray study
• T = 200 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.034
• wR factor = 0.079
• Data-to-parameter ratio = 13.9

checkCIF results

No syntax errors found



ADDSYM reports no extra symmetry

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Computing details

Data collection: D*TREK (Rigaku Corporation, 1991); cell refinement: D*TREK; data reduction: TEXSAN Ver. 1.10 (Molecular Structure Corporation, 1985 & 1999); program(s) used to solve structure: MULTAN88 (Debaerdemaeker et al., 1988); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: TEXSAN Ver. 1.10.

(AgPF6-ttp)

Crystal data

[Ag(C18H16S2)]PF6'	Dx = 1.994 Mg m^−3
Mr = 549.28	Mo Kα radiation, λ = 0.7107 Å
Orthorhombic, Pccn	Cell parameters from 28404 reflections
a = 7.109 (3) Å	θ = 6.3–27.6°
b = 15.014 (2) Å	µ = 1.48 mm^−1
c = 17.139 (2) Å	T = 200 K
V = 1829.4 (8) Å^3	Block, colorless
Z = 4	0.20 × 0.20 × 0.10 mm

Data collection

Quantum CCD/Rigaku AFC8 diffractometer	1777 reflections with I > 2.0σ(I)
ω scans	Rint = 0.039
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	θmax = 27.6°, θmin = 6.3°
Tmin = 0.694, Tmax = 0.863	h = −8→9
28404 measured reflections	k = −18→19
2082 independent reflections	l = −22→22

Refinement

Refinement on F^2	H-atom parameters not refined
R[F^2 > 2σ(F^2)] = 0.034	w = 1/[σ^2(Fo^2) + (0.0266P)^2 + 4.3325P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.079	(Δ/σ)max < 0.001
S = 1.13	Δρmax = 0.88 e Å^−3
1777 reflections	Δρmin = −0.48 e Å^−3
128 parameters

Special details

Refinement. Refinement using reflections with F² > -10.0 σ(F²). 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 (Ų)

	x	y	z	Uiso*/Ueq
Ag(1)	0.7500	0.2500	0.49647 (2)	0.0239 (1)
S(1)	0.8227 (1)	0.09111 (5)	0.46812 (4)	0.0214 (2)
P(1)	1.2500	0.2500	0.58480 (6)	0.0245 (2)
F(1)	1.1204 (4)	0.2910 (2)	0.5183 (2)	0.0623 (7)
F(2)	1.1207 (6)	0.2907 (2)	0.6489 (2)	0.096 (1)
F(3)	1.1306 (3)	0.1605 (1)	0.5841 (1)	0.0449 (5)
C(1)	1.0162 (4)	0.1058 (2)	0.3995 (2)	0.0238 (6)
C(2)	0.9849 (4)	0.1817 (2)	0.3411 (2)	0.0231 (6)
C(3)	0.7793 (4)	0.2074 (2)	0.3324 (2)	0.0185 (5)
C(4)	0.6457 (4)	0.1324 (2)	0.3322 (2)	0.0190 (5)
C(5)	0.5154 (4)	0.1183 (2)	0.2733 (2)	0.0235 (6)
C(6)	0.3971 (4)	0.0451 (2)	0.2755 (2)	0.0270 (6)
C(7)	0.4084 (4)	−0.0152 (2)	0.3363 (2)	0.0267 (6)
C(8)	0.5367 (4)	−0.0023 (2)	0.3961 (2)	0.0233 (6)
C(9)	0.6533 (4)	0.0716 (2)	0.3942 (2)	0.0197 (5)
H(1)	1.1274	0.1181	0.4283	0.0286*
H(2)	1.0320	0.0520	0.3712	0.0286*
H(3)	1.0531	0.2324	0.3584	0.0277*
H(4)	1.0311	0.1634	0.2916	0.0277*
H(5)	0.5073	0.1591	0.2311	0.0282*
H(6)	0.3077	0.0363	0.2350	0.0323*
H(7)	0.3277	−0.0656	0.3372	0.0320*
H(8)	0.5447	−0.0437	0.4379	0.0280*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag(1)	0.0270 (2)	0.0234 (2)	0.0214 (2)	0.0024 (1)	0.0000	0.0000
S(1)	0.0212 (3)	0.0228 (3)	0.0203 (3)	0.0020 (3)	−0.0026 (3)	0.0027 (3)
P(1)	0.0281 (5)	0.0242 (5)	0.0212 (5)	0.0015 (4)	0.0000	0.0000
F(1)	0.049 (1)	0.056 (1)	0.081 (2)	−0.010 (1)	−0.032 (1)	0.024 (1)
F(2)	0.156 (3)	0.044 (1)	0.088 (2)	−0.006 (2)	0.088 (2)	−0.010 (1)
F(3)	0.055 (1)	0.037 (1)	0.043 (1)	−0.0138 (10)	0.009 (1)	0.0010 (9)
C(1)	0.017 (1)	0.027 (1)	0.027 (1)	0.005 (1)	0.000 (1)	0.000 (1)
C(2)	0.019 (1)	0.025 (1)	0.025 (1)	0.004 (1)	0.003 (1)	0.001 (1)
C(3)	0.020 (1)	0.021 (1)	0.015 (1)	0.002 (1)	−0.0003 (10)	−0.0002 (10)
C(4)	0.019 (1)	0.017 (1)	0.021 (1)	0.004 (1)	0.000 (1)	−0.002 (1)
C(5)	0.025 (1)	0.022 (1)	0.023 (1)	0.004 (1)	−0.004 (1)	−0.004 (1)
C(6)	0.022 (1)	0.031 (2)	0.028 (1)	0.003 (1)	−0.004 (1)	−0.011 (1)
C(7)	0.024 (1)	0.024 (1)	0.032 (2)	−0.002 (1)	0.003 (1)	−0.008 (1)
C(8)	0.025 (1)	0.020 (1)	0.025 (1)	0.001 (1)	0.005 (1)	−0.001 (1)
C(9)	0.019 (1)	0.021 (1)	0.020 (1)	0.004 (1)	0.001 (1)	−0.003 (1)

Geometric parameters (Å, º)

Ag(1)—S(1)	2.4889 (8)	C(1)—C(2)	1.533 (4)
Ag(1)—S(1)^i	2.4889 (8)	C(2)—C(3)	1.519 (4)
S(1)—C(1)	1.823 (3)	C(3)—C(3)^i	1.346 (5)
S(1)—C(9)	1.773 (3)	C(3)—C(4)	1.473 (4)
P(1)—F(1)	1.590 (3)	C(4)—C(5)	1.387 (4)
P(1)—F(1)^ii	1.590 (3)	C(4)—C(9)	1.402 (4)
P(1)—F(2)	1.557 (4)	C(5)—C(6)	1.383 (4)
P(1)—F(2)^ii	1.557 (4)	C(6)—C(7)	1.384 (4)
P(1)—F(3)	1.589 (2)	C(7)—C(8)	1.385 (4)
P(1)—F(3)^ii	1.589 (2)	C(8)—C(9)	1.385 (4)
F(1)···C(8)^iii	3.484 (4)	F(3)···C(8)^vi	3.369 (4)
F(2)···C(8)^iii	3.257 (4)	F(3)···C(5)^v	3.463 (4)
F(2)···C(7)^iii	3.292 (4)	C(1)···C(7)^vii	3.499 (4)
F(2)···C(2)^iv	3.458 (4)	C(1)···C(6)^vii	3.561 (4)
F(2)···C(5)^v	3.490 (4)
S(1)—Ag(1)—S(1)^i	157.48 (4)	C(1)—C(2)—C(3)	113.1 (2)
Ag(1)—S(1)—C(1)	99.59 (10)	C(2)—C(3)—C(3)^i	122.6 (3)
Ag(1)—S(1)—C(9)	99.04 (9)	C(2)—C(3)—C(4)	115.2 (2)
C(1)—S(1)—C(9)	94.1 (1)	C(3)—C(3)^i—C(4)^i	121.8 (3)
F(1)—P(1)—F(1)^ii	88.3 (2)	C(3)—C(4)—C(5)	123.3 (3)
F(1)—P(1)—F(2)	90.7 (2)	C(3)—C(4)—C(9)	118.1 (2)
F(1)—P(1)—F(2)^ii	179.0 (2)	C(5)—C(4)—C(9)	118.5 (3)
F(1)—P(1)—F(3)	90.7 (1)	C(4)—C(5)—C(6)	120.5 (3)
F(1)—P(1)—F(3)^ii	88.7 (1)	C(5)—C(6)—C(7)	120.3 (3)
F(2)—P(1)—F(2)^ii	90.2 (3)	C(6)—C(7)—C(8)	120.3 (3)
F(2)—P(1)—F(3)	91.3 (1)	C(7)—C(8)—C(9)	119.2 (3)
F(2)—P(1)—F(3)^ii	89.4 (1)	S(1)—C(9)—C(4)	117.4 (2)
F(3)—P(1)—F(3)^ii	179.1 (2)	S(1)—C(9)—C(8)	121.5 (2)
S(1)—C(1)—C(2)	113.7 (2)	C(4)—C(9)—C(8)	121.1 (3)

Symmetry codes: (i) −x+3/2, −y+1/2, z; (ii) −x+5/2, −y+1/2, z; (iii) x+1/2, y+1/2, −z+1; (iv) x, −y+1/2, z+1/2; (v) −x+3/2, y, z+1/2; (vi) −x+2, −y, −z+1; (vii) x+1, y, z.