(S)-1,2-Dimethyl-1,1,2-triphenyl-2-(4-piperidiniometh-yl)disilane chloride.

The title compound, C(26)H(34)NSi(2) (+)·Cl(-), shows chirality at silicon. Because of its highly selective synthesis with an e.r. of >99:1 by means of a racemic resolution with mandelic acid, the free disilane is of great importance to the chemistry of highly enanti-omerically enriched lithio-silanes and their trapping products. N-H⋯Cl hydrogen bonding is present between the protonated nitro-gen atom of the piperidino group and the chloride counter-anion. The silicon-silicon distance as well as silicon-carbon and carbon-nitro-gen bond lengths are in the same ranges as in other quaternary, functionalized di- and tetra-silanes.

Related literature

For details of lithio­silanes, see: Lickiss & Smith (1995 ▶); Sekiguchi et al. (2000 ▶); Strohmann et al. (2001 ▶, 2006 ▶); Strohmann & Däschlein (2008a ▶,b ▶); Tamao & Kawachi (1995 ▶). For enanti­o­merically enriched lithio­silanes, see: Colomer & Corriu (1976 ▶); Oestreich et al. (2005 ▶); Omote et al. (2000 ▶); Sommer & Mason (1965 ▶); Strohmann et al. (2007 ▶). For the determination of the absolute configuration of the disilane as the mandelic acid adduct, see: Strohmann et al. (2002 ▶). For related literature on hydro­chlorides of amines, see: Farrugia et al. (2001 ▶).

Experimental

Crystal data

C26H34NSi2 +·Cl−

M = 452.19

Orthorhombic,

a = 10.120 (2) Å

b = 13.289 (3) Å

c = 18.598 (4) Å

V = 2501.3 (9) Å3

Z = 4

Mo Kα radiation

μ = 0.26 mm−1

T = 173 (2) K

0.30 × 0.30 × 0.20 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1999 ▶) T min = 0.926, T max = 0.950

45451 measured reflections

4911 independent reflections

4808 reflections with I > 2σ(I)

R int = 0.077

Refinement

R[F 2 > 2σ(F 2)] = 0.055

wR(F 2) = 0.149

S = 1.05

4911 reflections

277 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.41 e Å−3

Δρmin = −0.34 e Å−3

Absolute structure: Flack (1983 ▶), 2128 Friedel pairs

Flack parameter: 0.08 (10)

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 1999 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536808028808/wm2191sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808028808/wm2191Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C26H34NSi2+·Cl−	F(000) = 968
Mr = 452.19	Dx = 1.201 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 999 reflections
a = 10.120 (2) Å	θ = 1.9–26.0°
b = 13.289 (3) Å	µ = 0.26 mm−1
c = 18.598 (4) Å	T = 173 K
V = 2501.3 (9) Å3	Block, colourless
Z = 4	0.30 × 0.30 × 0.20 mm

Bruker SMART APEX CCD diffractometer	4911 independent reflections
Radiation source: fine-focus sealed tube	4808 reflections with I > 2σ(I)
graphite	Rint = 0.077
ω–scans	θmax = 26.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −12→12
Tmin = 0.926, Tmax = 0.950	k = −16→16
45451 measured reflections	l = −22→22

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.055	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.149	w = 1/[σ2(Fo2) + (0.0402P)2 + 1.4067P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
4911 reflections	Δρmax = 0.41 e Å−3
277 parameters	Δρmin = −0.34 e Å−3
0 restraints	Absolute structure: Flack (1983), 2128 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.08 (10)

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
Cl	−0.09614 (10)	0.04149 (6)	0.25243 (5)	0.0361 (2)
Si1	0.28622 (9)	0.21087 (7)	0.20801 (5)	0.0249 (2)
Si2	0.40619 (9)	0.23973 (7)	0.10071 (5)	0.0276 (2)
N1	0.0148 (3)	0.2532 (2)	0.25691 (15)	0.0246 (5)
C3	−0.2128 (4)	0.2953 (3)	0.2978 (2)	0.0346 (8)
H3B	−0.2411	0.2241	0.2961	0.042*
H3A	−0.2909	0.3378	0.2876	0.042*
C17	0.4393 (5)	0.0299 (3)	−0.0646 (2)	0.0433 (10)
H17	0.5060	0.0075	−0.0968	0.052*
C8	0.3754 (3)	0.2680 (3)	0.28642 (17)	0.0271 (7)
C2	−0.1098 (3)	0.3132 (3)	0.24077 (19)	0.0309 (7)
H2A	−0.0881	0.3858	0.2387	0.037*
H2B	−0.1452	0.2930	0.1933	0.037*
C16	0.4683 (4)	0.1011 (3)	−0.0121 (2)	0.0374 (9)
H16	0.5559	0.1262	−0.0082	0.045*
C6	0.0655 (3)	0.2780 (3)	0.32978 (17)	0.0297 (7)
H6A	0.0922	0.3496	0.3312	0.036*
H6B	0.1446	0.2366	0.3400	0.036*
C1	0.1159 (3)	0.2715 (2)	0.19928 (16)	0.0273 (7)
H1A	0.1290	0.3452	0.1956	0.033*
H1B	0.0773	0.2489	0.1531	0.033*
C11	0.4933 (4)	0.3529 (4)	0.4090 (2)	0.0456 (10)
H11	0.5315	0.3812	0.4510	0.055*
C18	0.3126 (5)	−0.0077 (3)	−0.0696 (2)	0.0435 (10)
H18	0.2926	−0.0565	−0.1054	0.052*
C19	0.2150 (5)	0.0243 (3)	−0.0237 (2)	0.0466 (10)
H19	0.1282	−0.0025	−0.0273	0.056*
C10	0.4387 (4)	0.4145 (3)	0.3574 (2)	0.0386 (9)
H10	0.4416	0.4855	0.3630	0.046*
C21	0.3634 (3)	0.3622 (3)	0.05534 (19)	0.0302 (7)
C24	0.3080 (4)	0.5453 (3)	−0.0126 (2)	0.0411 (9)
H24	0.2899	0.6077	−0.0355	0.049*
C26	0.3724 (4)	0.3723 (3)	−0.0189 (2)	0.0366 (8)
H26	0.3978	0.3157	−0.0469	0.044*
C23	0.2970 (4)	0.5373 (3)	0.0615 (2)	0.0420 (9)
H23	0.2708	0.5938	0.0894	0.050*
C9	0.3793 (4)	0.3723 (3)	0.29742 (19)	0.0314 (7)
H9	0.3400	0.4154	0.2627	0.038*
C14	0.5853 (4)	0.2419 (3)	0.1259 (2)	0.0397 (8)
H14C	0.6392	0.2482	0.0823	0.060*
H14B	0.6081	0.1794	0.1509	0.060*
H14A	0.6024	0.2994	0.1576	0.060*
C7	0.2688 (4)	0.0726 (3)	0.2230 (2)	0.0357 (8)
H7B	0.3567	0.0420	0.2266	0.054*
H7C	0.2209	0.0426	0.1825	0.054*
H7A	0.2198	0.0607	0.2676	0.054*
C4	−0.1613 (4)	0.3193 (3)	0.3725 (2)	0.0394 (9)
H4A	−0.1416	0.3920	0.3762	0.047*
H4B	−0.2293	0.3024	0.4088	0.047*
C22	0.3244 (4)	0.4466 (3)	0.0945 (2)	0.0363 (8)
H22	0.3166	0.4415	0.1452	0.044*
C12	0.4926 (4)	0.2503 (4)	0.3995 (2)	0.0435 (9)
H12	0.5315	0.2080	0.4348	0.052*
C5	−0.0374 (4)	0.2590 (3)	0.38669 (18)	0.0334 (8)
H5A	−0.0012	0.2774	0.4344	0.040*
H5B	−0.0595	0.1864	0.3876	0.040*
C20	0.2446 (4)	0.0968 (3)	0.0282 (2)	0.0368 (9)
H20	0.1770	0.1196	0.0596	0.044*
C15	0.3720 (4)	0.1364 (3)	0.03482 (18)	0.0314 (8)
C13	0.4352 (4)	0.2081 (3)	0.33837 (18)	0.0338 (8)
H13	0.4369	0.1372	0.3321	0.041*
C25	0.3450 (4)	0.4636 (3)	−0.0533 (2)	0.0434 (9)
H25	0.3518	0.4690	−0.1041	0.052*
H100	−0.007 (5)	0.180 (4)	0.254 (3)	0.050 (12)*

	U11	U22	U33	U12	U13	U23
Cl	0.0441 (5)	0.0229 (4)	0.0413 (5)	−0.0063 (4)	−0.0004 (4)	−0.0006 (3)
Si1	0.0270 (5)	0.0232 (4)	0.0246 (4)	−0.0006 (4)	0.0003 (4)	−0.0014 (3)
Si2	0.0272 (5)	0.0288 (4)	0.0269 (4)	0.0008 (4)	0.0010 (4)	−0.0027 (4)
N1	0.0219 (13)	0.0218 (13)	0.0300 (13)	−0.0003 (11)	−0.0012 (11)	−0.0007 (11)
C3	0.0275 (17)	0.0338 (18)	0.0425 (19)	0.0043 (15)	−0.0010 (16)	0.0033 (16)
C17	0.059 (3)	0.040 (2)	0.0312 (18)	0.018 (2)	0.0047 (17)	−0.0007 (16)
C8	0.0232 (16)	0.0319 (18)	0.0263 (14)	−0.0005 (13)	0.0004 (13)	−0.0045 (13)
C2	0.0268 (17)	0.0288 (16)	0.0370 (17)	0.0046 (14)	−0.0029 (15)	0.0047 (14)
C16	0.044 (2)	0.0319 (19)	0.036 (2)	0.0022 (16)	0.0021 (17)	0.0010 (15)
C6	0.0299 (18)	0.0297 (17)	0.0296 (15)	−0.0014 (14)	−0.0039 (13)	0.0027 (14)
C1	0.0310 (17)	0.0254 (16)	0.0254 (15)	−0.0010 (13)	0.0006 (13)	0.0002 (12)
C11	0.035 (2)	0.067 (3)	0.034 (2)	0.003 (2)	−0.0007 (17)	−0.0203 (19)
C18	0.066 (3)	0.037 (2)	0.0277 (17)	0.006 (2)	−0.0085 (19)	−0.0083 (15)
C19	0.046 (2)	0.048 (2)	0.046 (2)	0.000 (2)	−0.0119 (19)	−0.0086 (18)
C10	0.030 (2)	0.040 (2)	0.046 (2)	−0.0015 (16)	0.0077 (16)	−0.0142 (17)
C21	0.0263 (18)	0.0330 (17)	0.0314 (17)	−0.0021 (14)	0.0021 (14)	0.0005 (14)
C24	0.038 (2)	0.035 (2)	0.051 (2)	−0.0022 (17)	−0.0056 (17)	0.0141 (18)
C26	0.036 (2)	0.039 (2)	0.0353 (19)	−0.0011 (16)	−0.0011 (16)	−0.0027 (16)
C23	0.044 (2)	0.0252 (17)	0.057 (2)	−0.0022 (17)	0.0085 (19)	0.0011 (17)
C9	0.0306 (19)	0.0304 (17)	0.0333 (17)	−0.0031 (14)	−0.0030 (15)	0.0015 (15)
C14	0.0336 (19)	0.047 (2)	0.0386 (19)	0.0019 (18)	−0.0008 (16)	−0.0016 (17)
C7	0.046 (2)	0.0242 (16)	0.0369 (18)	−0.0006 (16)	0.0047 (16)	0.0003 (14)
C4	0.035 (2)	0.045 (2)	0.0382 (19)	0.0024 (17)	0.0073 (16)	−0.0065 (17)
C22	0.036 (2)	0.0367 (19)	0.0360 (18)	−0.0055 (16)	0.0053 (15)	0.0010 (16)
C12	0.038 (2)	0.061 (3)	0.0323 (18)	0.0150 (19)	−0.0073 (16)	0.0049 (19)
C5	0.0322 (18)	0.0378 (19)	0.0302 (17)	−0.0004 (15)	0.0056 (14)	−0.0009 (15)
C20	0.036 (2)	0.039 (2)	0.0353 (19)	0.0032 (16)	0.0016 (16)	−0.0080 (15)
C15	0.037 (2)	0.0297 (17)	0.0281 (17)	0.0024 (15)	−0.0028 (14)	0.0009 (13)
C13	0.034 (2)	0.0348 (18)	0.0325 (17)	0.0053 (16)	−0.0001 (14)	0.0002 (15)
C25	0.049 (2)	0.044 (2)	0.0368 (19)	−0.0060 (19)	−0.0076 (18)	0.0085 (18)

Cl—H100	2.05 (5)	C18—H18	0.9500
Si1—C7	1.867 (4)	C19—C20	1.397 (6)
Si1—C8	1.876 (3)	C19—H19	0.9500
Si1—C1	1.910 (3)	C10—C9	1.386 (5)
Si1—Si2	2.3672 (13)	C10—H10	0.9500
Si2—C14	1.873 (4)	C21—C26	1.390 (5)
Si2—C15	1.873 (4)	C21—C22	1.393 (5)
Si2—C21	1.884 (4)	C24—C25	1.375 (6)
N1—C6	1.486 (4)	C24—C23	1.388 (6)
N1—C1	1.502 (4)	C24—H24	0.9500
N1—C2	1.521 (4)	C26—C25	1.400 (6)
N1—H100	1.00 (5)	C26—H26	0.9500
C3—C2	1.506 (5)	C23—C22	1.381 (6)
C3—C4	1.518 (5)	C23—H23	0.9500
C3—H3B	0.9900	C9—H9	0.9500
C3—H3A	0.9900	C14—H14C	0.9800
C17—C18	1.379 (7)	C14—H14B	0.9800
C17—C16	1.392 (6)	C14—H14A	0.9800
C17—H17	0.9500	C7—H7B	0.9800
C8—C13	1.391 (5)	C7—H7C	0.9800
C8—C9	1.402 (5)	C7—H7A	0.9800
C2—H2A	0.9900	C4—C5	1.511 (5)
C2—H2B	0.9900	C4—H4A	0.9900
C16—C15	1.389 (5)	C4—H4B	0.9900
C16—H16	0.9500	C22—H22	0.9500
C6—C5	1.506 (5)	C12—C13	1.395 (5)
C6—H6A	0.9900	C12—H12	0.9500
C6—H6B	0.9900	C5—H5A	0.9900
C1—H1A	0.9900	C5—H5B	0.9900
C1—H1B	0.9900	C20—C15	1.398 (5)
C11—C12	1.374 (7)	C20—H20	0.9500
C11—C10	1.377 (6)	C13—H13	0.9500
C11—H11	0.9500	C25—H25	0.9500
C18—C19	1.374 (6)	N1—Cl	3.031 (3)
C7—Si1—C8	109.16 (17)	C11—C10—H10	120.2
C7—Si1—C1	110.05 (17)	C9—C10—H10	120.2
C8—Si1—C1	109.24 (14)	C26—C21—C22	117.4 (3)
C7—Si1—Si2	109.48 (13)	C26—C21—Si2	120.9 (3)
C8—Si1—Si2	110.06 (11)	C22—C21—Si2	121.7 (3)
C1—Si1—Si2	108.84 (10)	C25—C24—C23	120.5 (4)
C14—Si2—C15	110.72 (17)	C25—C24—H24	119.7
C14—Si2—C21	108.73 (17)	C23—C24—H24	119.7
C15—Si2—C21	107.34 (15)	C21—C26—C25	121.6 (4)
C14—Si2—Si1	106.77 (13)	C21—C26—H26	119.2
C15—Si2—Si1	109.76 (12)	C25—C26—H26	119.2
C21—Si2—Si1	113.55 (12)	C22—C23—C24	119.4 (4)
C6—N1—C1	112.3 (2)	C22—C23—H23	120.3
C6—N1—C2	110.5 (3)	C24—C23—H23	120.3
C1—N1—C2	109.8 (2)	C10—C9—C8	122.0 (3)
C6—N1—H100	110 (3)	C10—C9—H9	119.0
C1—N1—H100	105 (3)	C8—C9—H9	119.0
C2—N1—H100	109 (3)	Si2—C14—H14C	109.5
C2—C3—C4	112.0 (3)	Si2—C14—H14B	109.5
C2—C3—H3B	109.2	H14C—C14—H14B	109.5
C4—C3—H3B	109.2	Si2—C14—H14A	109.5
C2—C3—H3A	109.2	H14C—C14—H14A	109.5
C4—C3—H3A	109.2	H14B—C14—H14A	109.5
H3B—C3—H3A	107.9	Si1—C7—H7B	109.5
C18—C17—C16	119.4 (4)	Si1—C7—H7C	109.5
C18—C17—H17	120.3	H7B—C7—H7C	109.5
C16—C17—H17	120.3	Si1—C7—H7A	109.5
C13—C8—C9	116.9 (3)	H7B—C7—H7A	109.5
C13—C8—Si1	121.2 (3)	H7C—C7—H7A	109.5
C9—C8—Si1	121.8 (3)	C5—C4—C3	109.5 (3)
C3—C2—N1	110.6 (3)	C5—C4—H4A	109.8
C3—C2—H2A	109.5	C3—C4—H4A	109.8
N1—C2—H2A	109.5	C5—C4—H4B	109.8
C3—C2—H2B	109.5	C3—C4—H4B	109.8
N1—C2—H2B	109.5	H4A—C4—H4B	108.2
H2A—C2—H2B	108.1	C23—C22—C21	121.9 (4)
C15—C16—C17	121.5 (4)	C23—C22—H22	119.1
C15—C16—H16	119.3	C21—C22—H22	119.1
C17—C16—H16	119.3	C11—C12—C13	120.4 (4)
N1—C6—C5	111.4 (3)	C11—C12—H12	119.8
N1—C6—H6A	109.3	C13—C12—H12	119.8
C5—C6—H6A	109.3	C6—C5—C4	111.2 (3)
N1—C6—H6B	109.3	C6—C5—H5A	109.4
C5—C6—H6B	109.3	C4—C5—H5A	109.4
H6A—C6—H6B	108.0	C6—C5—H5B	109.4
N1—C1—Si1	119.1 (2)	C4—C5—H5B	109.4
N1—C1—H1A	107.5	H5A—C5—H5B	108.0
Si1—C1—H1A	107.5	C19—C20—C15	121.2 (4)
N1—C1—H1B	107.5	C19—C20—H20	119.4
Si1—C1—H1B	107.5	C15—C20—H20	119.4
H1A—C1—H1B	107.0	C16—C15—C20	117.7 (3)
C12—C11—C10	119.9 (4)	C16—C15—Si2	121.9 (3)
C12—C11—H11	120.1	C20—C15—Si2	120.3 (3)
C10—C11—H11	120.1	C8—C13—C12	121.1 (4)
C19—C18—C17	121.0 (4)	C8—C13—H13	119.4
C19—C18—H18	119.5	C12—C13—H13	119.4
C17—C18—H18	119.5	C24—C25—C26	119.1 (4)
C18—C19—C20	119.3 (4)	C24—C25—H25	120.4
C18—C19—H19	120.4	C26—C25—H25	120.4
C20—C19—H19	120.4	N1—H100—Cl	166.1 (41)
C11—C10—C9	119.6 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H100···Cl	1.00 (5)	2.05 (5)	3.031 (3)	166 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H100⋯Cl	1.00 (5)	2.05 (5)	3.031 (3)	166 (4)