Ammonium tri-tert-butoxy­silanethiol­ate

Baranowska, K.; Liadis, K.; Wojnowski, W.

doi:10.1107/S1600536808018370

organic compounds

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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page o1329

doi:10.1107/S1600536808018370

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Ammonium tri-tert-butoxysilanethiolate

Katarzyna Baranowska,^a ^* Ksymena Liadis ^a and Wiesław Wojnowski ^a

^aDepartment of Inorganic Chemistry, Faculty of Chemistry, Gdańsk University of Technology, 11/12 G. Narutowicz Street, 80952 PL Gdańsk, Poland
^*Correspondence e-mail: kasiab29@wp.pl

(Received 13 June 2008; accepted 17 June 2008; online 21 June 2008)

The cations and anions of the title salt, NH₄⁺·C₁₂H₂₇O₃SSi⁻, are linked by N—H⋯S and N—H⋯O hydrogen bonds into a linear chain that runs along the a axis of the monoclinic unit cell. The asymmetric unit contains two cations and two anions.

Related literature

For the synthesis of the thiol reagent, see: Piękoś & Wojnowski (1962 ). For an early study of its ammonium salt, see: Wojnowski (1971 ). For the structures of similar salts and comparison bond distances, see: Baranowska (2007 ); Baranowska, Chojnacki, Becker & Wojnowski (2003 ); Baranowska, Chojnacki, Gosiewska & Wojnowski (2006 ); Baranowska, Chojnacki, Konitz et al. (2006 ); Baranowska, Chojnacki, Wojnowski & Becker (2003 ); Becker et al. (2002 , 2004 ); Chojnacki (2008 ); Dołęga et al. (2008 ); Pladzyk & Baranowska (2007 ). For the graph-set description of hydrogen-bonding patterns, see: Bernstein et al. (1995 ); Etter (1990 ).

Experimental

Crystal data

NH₄⁺·C₁₂H₂₇O₃SSi⁻
M_r = 297.53
Monoclinic, P 2₁ /c
a = 11.9981 (4) Å
b = 12.5580 (5) Å
c = 24.8181 (12) Å
β = 100.336 (4)°
V = 3678.7 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 120 (2) K
0.2 × 0.06 × 0.04 mm

Data collection

Oxford Diffraction KM-4 CCD diffractometer
Absorption correction: none
12272 measured reflections
6433 independent reflections
4509 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.126
S = 1.04
6433 reflections
367 parameters
8 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.71 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯S1ⁱ	0.903 (17)	2.331 (18)	3.223 (2)	170 (2)
N1—H1B⋯S2	0.891 (17)	2.334 (18)	3.215 (2)	169 (3)
N1—H1C⋯S1	0.899 (18)	2.326 (19)	3.219 (3)	172 (3)
N1—H1D⋯O2	0.893 (17)	2.49 (2)	3.059 (3)	122 (2)
N2—H2E⋯S2ⁱⁱ	0.902 (19)	2.38 (2)	3.255 (3)	162 (4)
N2—H2D⋯O3	0.877 (19)	2.01 (2)	2.886 (3)	175 (4)
N2—H2D⋯S1	0.877 (19)	2.95 (4)	3.337 (3)	109 (3)
N2—H2F⋯S2	0.897 (18)	2.435 (19)	3.323 (3)	171 (3)
N2—H2G⋯O5ⁱⁱ	0.867 (18)	2.39 (3)	2.952 (3)	123 (3)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x, -y+1, -z+1.

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808018370/ng2465sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808018370/ng2465Isup2.hkl

checkCIF report

Comment top

Complexes of trialkoxysilanethiols with ammonia were first obtained in 1971 by the reaction of (ⁱPrO)₃SiSH and (^sBuO)₃SiSH (Wojnowski, 1971) with ammonia but no structural data are available.

Amino tri-tert-butoxysilanethiolates show great structural diversity. Structures of isolated dimers, cubans, chains or sheets have been recognized so far. Cubic motifs were characterized for salts of primary amines (Becker, et al., 2004); for secondary amines dimers and/or chains have been found (Baranowska, Chojnacki, Konitz et al., 2006, Baranowska, Chojnacki, Becker & Wojnowski, 2003).

The asymmetric unit of (I) consists of two silanethiolate anions and two ammonium cations (Fig.1). The ions are connected via N⁽⁺⁾–H···S^(-) hydrogen bonds, forming an eight-membered ring as R²₄(8) with four donors and two acceptors (Etter, 1990; Bernstein et al., 1995). Similar (thiol-amine)₂ ring formation has been observed in other ammonium salts (Baranowska, Chojnacki, Konitz et al., 2006; Baranowska, Chojnacki, Wojnowski & Becker, 2003). These rings are futher linked by N–H···S and N–H···O hydrogen bonds into chains parallel to the (010) (Fig.2). The application of graph theory to the chain results in a variety of possible hydrogen bonding patterns: the N1–H1C···S1, N1–H1A···S1⁽ⁱ⁾, N1–H1C···S1⁽ⁱ⁾ and N1–H1A···S1 hydrogen bonds form an R²₄(8)ring, the N2–H2E···S2⁽ⁱⁱ⁾, N2–H2F···S2⁽ⁱⁱ⁾, N2–H2F···S2 and N2–H2E···S2 hydrogen bonds form an R²₄(8) ring, the N1–H1C···S1and N1–H1D···O2 hydrogen bonds form an R²₂(6) ring, the N2–H2G···O5⁽ⁱⁱ⁾and N2–H2E···S2⁽ⁱⁱ⁾ hydrogen bonds form an R¹₂(6) ring, the N1–H1B···S2, N2–H2F···S2, N1–H1C···S1 and N2–H2D···S1 hydrogen bonds form an R²₄(8) ring, in which atom N2 acts as a bifurcated donor.

The N···S distances in (I) lie in the range 2.886 (3)–3.340 (3) Å, comparable with values observed in other silanethiolates (Baranowska, Chojnacki, Gosiewska & Wojnowski 2006; Pladzyk & Baranowska, 2007; Dołęga et al., 2008) or aromatic thiolates (Baranowska, Chojnacki, Becker & Wojnowski, 2003; Baranowska, 2007). The length of silicon – sulfur bond is short (2.059 – 2.062 Å) and it is characteristic for ionic silanethiolates (Becker et al., 2002, Chojnacki, 2008). Hydrogen bonds are grouped in " hydrophilic" core, while the organic hydrocarbon groups form "hydrophobic" coat in the crystal. It is a very characteristic motif for many polimeric structures.

Related literature top

For the synthesis of the thiol reagent, see: Piękoś & Wojnowski (1962). For an early study of its ammonium salt, see: Wojnowski (1971). For the structures of similar salts and comparison bond distances, see: Baranowska (2007); Baranowska, Chojnacki, Becker & Wojnowski (2003); Baranowska, Chojnacki, Gosiewska & Wojnowski (2006); Baranowska, Chojnacki, Konitz et al. (2006); Baranowska, Chojnacki, Wojnowski & Becker (2003); Becker et al. (2002, 2004); Chojnacki (2008); Dołęga et al. (2008); Pladzyk & Baranowska (2007). For the graph-set description of hydrogen-bonding patterns, see: Bernstein et al. (1995); Etter (1990).

Experimental top

The substrate (^tBuO)₃SiSH was prepared according to the literature (Piękoś & Wojnowski, 1962).

To the mixture of to tri-tert-butoxysilanethiol (1.9 g; 0.0064 mol) and metallic magnesium (0.084 g; 0.0035 mol) in toluene one drop of concentrated ammonia solution was added. The mixture was stirred and heated at boiling point of toluene for one week. The solution was separated from the metal by filtration. The solvent was removed. The liquid residue was kept in refrigerator (4 °C) for a few days for crystallization. The final product has a form of colourless, crystalline needles.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. A view of the molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. All ^tBu H atoms have been omitted for clarity. Hydrogen bonds are indicated with dashed lines.
	Fig. 2. The chains of molecules of (I) linked by hydrogen bonds. A view direction is parallel to the crystallographic b axis. All ^tBu H atoms have been omitted for clarity. Hydrogen bonds are indicated with dashed lines.

Ammonium tri-tert-butoxysilanethiolate top

Crystal data top

NH₄⁺·C₁₂H₂₇O₃SSi⁻	F(000) = 1312
M_r = 297.53	D_x = 1.074 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7143 reflections
a = 11.9981 (4) Å	θ = 2.0–32.4°
b = 12.5580 (5) Å	µ = 0.24 mm⁻¹
c = 24.8181 (12) Å	T = 120 K
β = 100.336 (4)°	Prism, colourless
V = 3678.7 (3) Å³	0.2 × 0.06 × 0.04 mm
Z = 8

Data collection top

Oxford Diffraction KM-4 CCD diffractometer	4509 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
Detector resolution: 8.1883 pixels mm^-1	θ_max = 25.1°, θ_min = 2.4°
0.75° width ω scans	h = −14→8
12272 measured reflections	k = −14→8
6433 independent reflections	l = −29→29

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.126	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0746P)²] where P = (F_o² + 2F_c²)/3
6433 reflections	(Δ/σ)_max = 0.001
367 parameters	Δρ_max = 0.72 e Å⁻³
8 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

NH₄⁺·C₁₂H₂₇O₃SSi⁻	V = 3678.7 (3) Å³
M_r = 297.53	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.9981 (4) Å	µ = 0.24 mm⁻¹
b = 12.5580 (5) Å	T = 120 K
c = 24.8181 (12) Å	0.2 × 0.06 × 0.04 mm
β = 100.336 (4)°

Data collection top

Oxford Diffraction KM-4 CCD diffractometer	4509 reflections with I > 2σ(I)
12272 measured reflections	R_int = 0.028
6433 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	8 restraints
wR(F²) = 0.126	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.72 e Å⁻³
6433 reflections	Δρ_min = −0.38 e Å⁻³
367 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.42331 (5)	0.53353 (5)	0.58655 (3)	0.02431 (17)
Si1	0.42375 (6)	0.37946 (6)	0.61491 (3)	0.01975 (18)
O1	0.49073 (14)	0.35757 (14)	0.67658 (7)	0.0264 (4)
O2	0.47413 (14)	0.29078 (13)	0.57685 (7)	0.0236 (4)
O3	0.28781 (14)	0.34803 (14)	0.60815 (7)	0.0234 (4)
C1	0.5191 (2)	0.4195 (3)	0.72592 (12)	0.0377 (7)
C2	0.4156 (3)	0.4800 (3)	0.73596 (13)	0.0554 (10)
H2A	0.3533	0.43	0.7369	0.083*
H2B	0.3932	0.5318	0.7064	0.083*
H2C	0.4334	0.5176	0.7711	0.083*
C3	0.6160 (3)	0.4934 (4)	0.72026 (16)	0.0703 (12)
H3A	0.5911	0.5443	0.6906	0.105*
H3B	0.6797	0.4516	0.7118	0.105*
H3C	0.64	0.5321	0.7547	0.105*
C4	0.5552 (3)	0.3381 (3)	0.77117 (12)	0.0550 (10)
H4A	0.4924	0.2889	0.7727	0.082*
H4B	0.5757	0.3749	0.8064	0.082*
H4C	0.6207	0.298	0.7635	0.082*
C5	0.5858 (2)	0.2435 (2)	0.58098 (11)	0.0273 (6)
C6	0.5803 (2)	0.1793 (2)	0.52880 (12)	0.0351 (7)
H6A	0.5641	0.2269	0.4971	0.053*
H6B	0.5202	0.1258	0.5265	0.053*
H6C	0.6531	0.1437	0.5291	0.053*
C7	0.6098 (3)	0.1701 (3)	0.63015 (12)	0.0424 (8)
H7A	0.6108	0.2115	0.6637	0.064*
H7B	0.6835	0.1357	0.6314	0.064*
H7C	0.5505	0.1156	0.6272	0.064*
C8	0.6743 (2)	0.3297 (2)	0.58404 (15)	0.0450 (9)
H8A	0.6592	0.3729	0.5506	0.067*
H8B	0.7495	0.2972	0.5876	0.067*
H8C	0.6715	0.3751	0.6159	0.067*
C9	0.2329 (2)	0.2472 (2)	0.61567 (12)	0.0317 (7)
C10	0.2878 (3)	0.1914 (3)	0.66557 (15)	0.0667 (12)
H10A	0.3677	0.1788	0.6638	0.1*
H10B	0.2497	0.1232	0.6684	0.1*
H10C	0.2825	0.2352	0.6977	0.1*
C11	0.2340 (3)	0.1800 (3)	0.56391 (15)	0.0600 (10)
H11A	0.2038	0.2223	0.5314	0.09*
H11B	0.187	0.1165	0.5649	0.09*
H11C	0.3119	0.1585	0.5625	0.09*
C12	0.1101 (3)	0.2741 (3)	0.6167 (2)	0.0734 (13)
H12A	0.0763	0.3086	0.5822	0.11*
H12B	0.1061	0.3224	0.6473	0.11*
H12C	0.0684	0.2086	0.6213	0.11*
S2	0.10838 (5)	0.46097 (5)	0.41794 (3)	0.02520 (18)
Si2	0.05808 (6)	0.31006 (6)	0.39125 (3)	0.02122 (18)
O4	0.02593 (15)	0.29638 (15)	0.32505 (7)	0.0286 (4)
O5	−0.05329 (15)	0.28237 (14)	0.41883 (8)	0.0311 (5)
O6	0.15294 (16)	0.21879 (15)	0.41046 (7)	0.0348 (5)
C13	−0.0289 (2)	0.3627 (3)	0.28096 (11)	0.0349 (7)
C14	0.0582 (3)	0.4383 (3)	0.26532 (14)	0.0525 (10)
H14A	0.0894	0.4827	0.2969	0.079*
H14B	0.0223	0.4838	0.2351	0.079*
H14C	0.1194	0.3973	0.2538	0.079*
C15	−0.1263 (3)	0.4238 (3)	0.29753 (13)	0.0468 (9)
H15A	−0.0971	0.4715	0.3281	0.07*
H15B	−0.1803	0.3737	0.3088	0.07*
H15C	−0.1645	0.4659	0.2664	0.07*
C16	−0.0726 (3)	0.2868 (3)	0.23444 (13)	0.0578 (10)
H16A	−0.1298	0.2397	0.2453	0.087*
H16B	−0.0096	0.244	0.226	0.087*
H16C	−0.1065	0.3276	0.202	0.087*
C17	−0.1164 (3)	0.1842 (2)	0.42078 (12)	0.0354 (7)
C18	−0.1311 (3)	0.1229 (3)	0.36650 (16)	0.0608 (10)
H18A	−0.1662	0.1694	0.3365	0.091*
H18B	−0.1796	0.0607	0.3684	0.091*
H18C	−0.0568	0.0993	0.3599	0.091*
C19	−0.0602 (4)	0.1198 (3)	0.4673 (2)	0.1000 (19)
H19A	0.0185	0.1064	0.4636	0.15*
H19B	−0.1002	0.0518	0.4678	0.15*
H19C	−0.0616	0.1582	0.5016	0.15*
C20	−0.2341 (3)	0.2171 (3)	0.4273 (2)	0.0743 (13)
H20A	−0.2662	0.2647	0.3972	0.111*
H20B	−0.2305	0.2544	0.4623	0.111*
H20C	−0.2819	0.1538	0.4267	0.111*
C21	0.2338 (2)	0.1648 (2)	0.38299 (12)	0.0357 (7)
C22	0.1726 (3)	0.0832 (3)	0.34325 (14)	0.0484 (9)
H22A	0.1192	0.1196	0.3146	0.073*
H22B	0.1311	0.0338	0.363	0.073*
H22C	0.2279	0.0436	0.3265	0.073*
C23	0.3137 (3)	0.1104 (3)	0.42870 (14)	0.0545 (10)
H23A	0.3499	0.164	0.4548	0.082*
H23B	0.3719	0.0719	0.4134	0.082*
H23C	0.2712	0.0602	0.4475	0.082*
C24	0.2952 (3)	0.2437 (3)	0.35263 (13)	0.0482 (9)
H24A	0.2411	0.2768	0.3231	0.072*
H24B	0.3539	0.2065	0.337	0.072*
H24C	0.3305	0.2988	0.3781	0.072*
N1	0.36606 (19)	0.40699 (19)	0.47213 (10)	0.0245 (5)
H1A	0.419 (2)	0.423 (2)	0.4515 (10)	0.038*
H1B	0.2948 (16)	0.414 (2)	0.4546 (11)	0.038*
H1C	0.380 (3)	0.449 (2)	0.5020 (10)	0.048*
H1D	0.379 (2)	0.3393 (15)	0.4824 (11)	0.026*
N2	0.1426 (2)	0.5109 (2)	0.55138 (11)	0.0333 (6)
H2E	0.071 (2)	0.503 (4)	0.5577 (19)	0.113*
H2D	0.185 (3)	0.463 (3)	0.5707 (16)	0.09*
H2F	0.137 (3)	0.490 (3)	0.5165 (8)	0.047*
H2G	0.166 (3)	0.5762 (17)	0.5557 (15)	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0224 (3)	0.0208 (3)	0.0313 (4)	−0.0013 (3)	0.0089 (3)	0.0004 (3)
Si1	0.0197 (4)	0.0211 (4)	0.0188 (4)	−0.0014 (3)	0.0044 (3)	0.0005 (3)
O1	0.0250 (9)	0.0321 (10)	0.0209 (10)	0.0016 (8)	0.0012 (8)	−0.0008 (8)
O2	0.0231 (9)	0.0238 (10)	0.0237 (10)	0.0039 (8)	0.0038 (8)	0.0002 (8)
O3	0.0214 (9)	0.0242 (10)	0.0249 (10)	−0.0036 (8)	0.0047 (8)	0.0026 (8)
C1	0.0325 (16)	0.055 (2)	0.0232 (15)	−0.0012 (15)	−0.0011 (13)	−0.0124 (15)
C2	0.066 (2)	0.069 (3)	0.0322 (18)	0.020 (2)	0.0104 (17)	−0.0167 (18)
C3	0.063 (2)	0.088 (3)	0.053 (2)	−0.036 (2)	−0.0059 (19)	−0.026 (2)
C4	0.047 (2)	0.091 (3)	0.0240 (17)	0.013 (2)	−0.0014 (15)	−0.0020 (18)
C5	0.0262 (14)	0.0211 (14)	0.0352 (16)	0.0072 (12)	0.0071 (12)	0.0045 (13)
C6	0.0375 (16)	0.0343 (17)	0.0347 (17)	0.0114 (14)	0.0097 (14)	0.0008 (14)
C7	0.054 (2)	0.0396 (19)	0.0324 (17)	0.0204 (16)	0.0039 (15)	0.0047 (15)
C8	0.0272 (16)	0.0332 (18)	0.076 (3)	0.0023 (14)	0.0138 (16)	−0.0061 (17)
C9	0.0296 (15)	0.0264 (16)	0.0399 (17)	−0.0114 (13)	0.0086 (13)	0.0069 (14)
C10	0.073 (3)	0.063 (2)	0.057 (2)	−0.033 (2)	−0.008 (2)	0.030 (2)
C11	0.072 (3)	0.049 (2)	0.060 (2)	−0.028 (2)	0.015 (2)	−0.0103 (19)
C12	0.0363 (19)	0.051 (2)	0.137 (4)	−0.0139 (18)	0.027 (2)	0.021 (3)
S2	0.0219 (3)	0.0236 (4)	0.0301 (4)	0.0002 (3)	0.0046 (3)	−0.0017 (3)
Si2	0.0227 (4)	0.0215 (4)	0.0199 (4)	0.0040 (3)	0.0049 (3)	−0.0008 (3)
O4	0.0289 (10)	0.0335 (11)	0.0208 (10)	0.0077 (9)	−0.0026 (8)	−0.0002 (9)
O5	0.0376 (11)	0.0216 (10)	0.0378 (12)	−0.0063 (9)	0.0168 (9)	−0.0036 (9)
O6	0.0428 (12)	0.0355 (12)	0.0250 (10)	0.0195 (10)	0.0032 (9)	−0.0034 (9)
C13	0.0307 (15)	0.0506 (19)	0.0217 (15)	0.0130 (14)	0.0006 (12)	0.0056 (14)
C14	0.0428 (19)	0.077 (3)	0.0389 (19)	0.0078 (18)	0.0116 (16)	0.0254 (19)
C15	0.0415 (18)	0.064 (2)	0.0351 (18)	0.0239 (17)	0.0062 (15)	0.0184 (17)
C16	0.059 (2)	0.083 (3)	0.0257 (17)	0.013 (2)	−0.0085 (16)	−0.0033 (18)
C17	0.0470 (18)	0.0211 (15)	0.0411 (18)	−0.0124 (13)	0.0158 (15)	−0.0007 (13)
C18	0.060 (2)	0.055 (2)	0.069 (3)	−0.0186 (19)	0.017 (2)	−0.021 (2)
C19	0.119 (4)	0.060 (3)	0.095 (4)	−0.049 (3)	−0.050 (3)	0.049 (3)
C20	0.064 (2)	0.051 (2)	0.119 (4)	−0.020 (2)	0.047 (3)	−0.004 (2)
C21	0.0326 (16)	0.0345 (17)	0.0359 (17)	0.0169 (14)	−0.0052 (13)	−0.0168 (14)
C22	0.0457 (19)	0.047 (2)	0.049 (2)	0.0105 (16)	−0.0014 (16)	−0.0230 (17)
C23	0.056 (2)	0.042 (2)	0.055 (2)	0.0265 (17)	−0.0198 (17)	−0.0226 (17)
C24	0.0380 (18)	0.062 (2)	0.046 (2)	0.0076 (17)	0.0101 (15)	−0.0189 (18)
N1	0.0226 (12)	0.0240 (12)	0.0279 (13)	0.0002 (11)	0.0069 (10)	0.0001 (11)
N2	0.0261 (13)	0.0430 (16)	0.0310 (14)	0.0058 (12)	0.0058 (11)	−0.0021 (13)

Geometric parameters (Å, º) top

S1—Si1	2.0586 (10)	O4—C13	1.437 (3)
Si1—O1	1.6194 (18)	O5—C17	1.452 (3)
Si1—O2	1.6439 (18)	O6—C21	1.450 (3)
Si1—O3	1.6570 (17)	C13—C14	1.514 (4)
O1—C1	1.439 (3)	C13—C15	1.515 (4)
O2—C5	1.452 (3)	C13—C16	1.516 (4)
O3—C9	1.454 (3)	C14—H14A	0.98
C1—C3	1.514 (5)	C14—H14B	0.98
C1—C2	1.514 (4)	C14—H14C	0.98
C1—C4	1.523 (5)	C15—H15A	0.98
C2—H2A	0.98	C15—H15B	0.98
C2—H2B	0.98	C15—H15C	0.98
C2—H2C	0.98	C16—H16A	0.98
C3—H3A	0.98	C16—H16B	0.98
C3—H3B	0.98	C16—H16C	0.98
C3—H3C	0.98	C17—C19	1.471 (5)
C4—H4A	0.98	C17—C20	1.507 (4)
C4—H4B	0.98	C17—C18	1.534 (4)
C4—H4C	0.98	C18—H18A	0.98
C5—C8	1.509 (4)	C18—H18B	0.98
C5—C7	1.515 (4)	C18—H18C	0.98
C5—C6	1.517 (4)	C19—H19A	0.98
C6—H6A	0.98	C19—H19B	0.98
C6—H6B	0.98	C19—H19C	0.98
C6—H6C	0.98	C20—H20A	0.98
C7—H7A	0.98	C20—H20B	0.98
C7—H7B	0.98	C20—H20C	0.98
C7—H7C	0.98	C21—C23	1.511 (4)
C8—H8A	0.98	C21—C24	1.514 (5)
C8—H8B	0.98	C21—C22	1.517 (4)
C8—H8C	0.98	C22—H22A	0.98
C9—C10	1.472 (4)	C22—H22B	0.98
C9—C12	1.517 (4)	C22—H22C	0.98
C9—C11	1.539 (4)	C23—H23A	0.98
C10—H10A	0.98	C23—H23B	0.98
C10—H10B	0.98	C23—H23C	0.98
C10—H10C	0.98	C24—H24A	0.98
C11—H11A	0.98	C24—H24B	0.98
C11—H11B	0.98	C24—H24C	0.98
C11—H11C	0.98	N1—H1A	0.903 (17)
C12—H12A	0.98	N1—H1B	0.891 (17)
C12—H12B	0.98	N1—H1C	0.899 (18)
C12—H12C	0.98	N1—H1D	0.893 (17)
S2—Si2	2.0619 (10)	N2—H2E	0.902 (19)
Si2—O6	1.6253 (19)	N2—H2D	0.877 (19)
Si2—O4	1.6279 (19)	N2—H2F	0.897 (18)
Si2—O5	1.6440 (18)	N2—H2G	0.867 (18)

O1—Si1—O2	104.88 (9)	C13—O4—Si2	134.46 (17)
O1—Si1—O3	111.58 (9)	C17—O5—Si2	131.38 (17)
O2—Si1—O3	103.72 (9)	C21—O6—Si2	133.17 (18)
O1—Si1—S1	116.94 (8)	O4—C13—C14	108.4 (2)
O2—Si1—S1	114.76 (7)	O4—C13—C15	110.9 (2)
O3—Si1—S1	104.31 (7)	C14—C13—C15	110.7 (3)
C1—O1—Si1	135.56 (18)	O4—C13—C16	105.3 (3)
C5—O2—Si1	131.79 (16)	C14—C13—C16	111.0 (3)
C9—O3—Si1	130.88 (16)	C15—C13—C16	110.3 (3)
O1—C1—C3	108.7 (3)	C13—C14—H14A	109.5
O1—C1—C2	109.6 (2)	C13—C14—H14B	109.5
C3—C1—C2	112.0 (3)	H14A—C14—H14B	109.5
O1—C1—C4	104.9 (3)	C13—C14—H14C	109.5
C3—C1—C4	111.0 (3)	H14A—C14—H14C	109.5
C2—C1—C4	110.4 (3)	H14B—C14—H14C	109.5
C1—C2—H2A	109.5	C13—C15—H15A	109.5
C1—C2—H2B	109.5	C13—C15—H15B	109.5
H2A—C2—H2B	109.5	H15A—C15—H15B	109.5
C1—C2—H2C	109.5	C13—C15—H15C	109.5
H2A—C2—H2C	109.5	H15A—C15—H15C	109.5
H2B—C2—H2C	109.5	H15B—C15—H15C	109.5
C1—C3—H3A	109.5	C13—C16—H16A	109.5
C1—C3—H3B	109.5	C13—C16—H16B	109.5
H3A—C3—H3B	109.5	H16A—C16—H16B	109.5
C1—C3—H3C	109.5	C13—C16—H16C	109.5
H3A—C3—H3C	109.5	H16A—C16—H16C	109.5
H3B—C3—H3C	109.5	H16B—C16—H16C	109.5
C1—C4—H4A	109.5	O5—C17—C19	109.0 (3)
C1—C4—H4B	109.5	O5—C17—C20	106.0 (2)
H4A—C4—H4B	109.5	C19—C17—C20	111.8 (4)
C1—C4—H4C	109.5	O5—C17—C18	112.1 (2)
H4A—C4—H4C	109.5	C19—C17—C18	112.2 (3)
H4B—C4—H4C	109.5	C20—C17—C18	105.7 (3)
O2—C5—C8	110.0 (2)	C17—C18—H18A	109.5
O2—C5—C7	110.2 (2)	C17—C18—H18B	109.5
C8—C5—C7	111.5 (3)	H18A—C18—H18B	109.5
O2—C5—C6	105.0 (2)	C17—C18—H18C	109.5
C8—C5—C6	110.3 (2)	H18A—C18—H18C	109.5
C7—C5—C6	109.7 (2)	H18B—C18—H18C	109.5
C5—C6—H6A	109.5	C17—C19—H19A	109.5
C5—C6—H6B	109.5	C17—C19—H19B	109.5
H6A—C6—H6B	109.5	H19A—C19—H19B	109.5
C5—C6—H6C	109.5	C17—C19—H19C	109.5
H6A—C6—H6C	109.5	H19A—C19—H19C	109.5
H6B—C6—H6C	109.5	H19B—C19—H19C	109.5
C5—C7—H7A	109.5	C17—C20—H20A	109.5
C5—C7—H7B	109.5	C17—C20—H20B	109.5
H7A—C7—H7B	109.5	H20A—C20—H20B	109.5
C5—C7—H7C	109.5	C17—C20—H20C	109.5
H7A—C7—H7C	109.5	H20A—C20—H20C	109.5
H7B—C7—H7C	109.5	H20B—C20—H20C	109.5
C5—C8—H8A	109.5	O6—C21—C23	104.3 (2)
C5—C8—H8B	109.5	O6—C21—C24	110.7 (2)
H8A—C8—H8B	109.5	C23—C21—C24	111.6 (3)
C5—C8—H8C	109.5	O6—C21—C22	109.6 (2)
H8A—C8—H8C	109.5	C23—C21—C22	110.6 (3)
H8B—C8—H8C	109.5	C24—C21—C22	109.9 (3)
O3—C9—C10	112.2 (2)	C21—C22—H22A	109.5
O3—C9—C12	105.8 (2)	C21—C22—H22B	109.5
C10—C9—C12	112.4 (3)	H22A—C22—H22B	109.5
O3—C9—C11	107.4 (2)	C21—C22—H22C	109.5
C10—C9—C11	111.8 (3)	H22A—C22—H22C	109.5
C12—C9—C11	106.9 (3)	H22B—C22—H22C	109.5
C9—C10—H10A	109.5	C21—C23—H23A	109.5
C9—C10—H10B	109.5	C21—C23—H23B	109.5
H10A—C10—H10B	109.5	H23A—C23—H23B	109.5
C9—C10—H10C	109.5	C21—C23—H23C	109.5
H10A—C10—H10C	109.5	H23A—C23—H23C	109.5
H10B—C10—H10C	109.5	H23B—C23—H23C	109.5
C9—C11—H11A	109.5	C21—C24—H24A	109.5
C9—C11—H11B	109.5	C21—C24—H24B	109.5
H11A—C11—H11B	109.5	H24A—C24—H24B	109.5
C9—C11—H11C	109.5	C21—C24—H24C	109.5
H11A—C11—H11C	109.5	H24A—C24—H24C	109.5
H11B—C11—H11C	109.5	H24B—C24—H24C	109.5
C9—C12—H12A	109.5	H1A—N1—H1B	114 (3)
C9—C12—H12B	109.5	H1A—N1—H1C	107 (3)
H12A—C12—H12B	109.5	H1B—N1—H1C	112 (3)
C9—C12—H12C	109.5	H1A—N1—H1D	106 (2)
H12A—C12—H12C	109.5	H1B—N1—H1D	110 (3)
H12B—C12—H12C	109.5	H1C—N1—H1D	109 (3)
O6—Si2—O4	104.38 (10)	H2E—N2—H2D	108 (4)
O6—Si2—O5	107.90 (11)	H2E—N2—H2F	103 (4)
O4—Si2—O5	109.56 (10)	H2D—N2—H2F	105 (3)
O6—Si2—S2	113.87 (8)	H2E—N2—H2G	113 (4)
O4—Si2—S2	115.08 (8)	H2D—N2—H2G	116 (4)
O5—Si2—S2	105.88 (7)	H2F—N2—H2G	111 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S1ⁱ	0.90 (2)	2.33 (2)	3.223 (2)	170 (2)
N1—H1B···S2	0.89 (2)	2.33 (2)	3.215 (2)	169 (3)
N1—H1C···S1	0.90 (2)	2.33 (2)	3.219 (3)	172 (3)
N1—H1D···O2	0.89 (2)	2.49 (2)	3.059 (3)	122 (2)
N2—H2E···S2ⁱⁱ	0.90 (2)	2.38 (2)	3.255 (3)	162 (4)
N2—H2D···O3	0.88 (2)	2.01 (2)	2.886 (3)	175 (4)
N2—H2D···S1	0.88 (2)	2.95 (4)	3.337 (3)	109 (3)
N2—H2F···S2	0.90 (2)	2.44 (2)	3.323 (3)	171 (3)
N2—H2G···O5ⁱⁱ	0.87 (2)	2.39 (3)	2.952 (3)	123 (3)

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

Experimental details

Crystal data
Chemical formula	NH₄⁺·C₁₂H₂₇O₃SSi⁻
M_r	297.53
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	120
a, b, c (Å)	11.9981 (4), 12.5580 (5), 24.8181 (12)
β (°)	100.336 (4)
V (Å³)	3678.7 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.24
Crystal size (mm)	0.2 × 0.06 × 0.04

Data collection
Diffractometer	Oxford Diffraction KM-4 CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	12272, 6433, 4509
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.126, 1.04
No. of reflections	6433
No. of parameters	367
No. of restraints	8
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.72, −0.38

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S1ⁱ	0.903 (17)	2.331 (18)	3.223 (2)	170 (2)
N1—H1B···S2	0.891 (17)	2.334 (18)	3.215 (2)	169 (3)
N1—H1C···S1	0.899 (18)	2.326 (19)	3.219 (3)	172 (3)
N1—H1D···O2	0.893 (17)	2.49 (2)	3.059 (3)	122 (2)
N2—H2E···S2ⁱⁱ	0.902 (19)	2.38 (2)	3.255 (3)	162 (4)
N2—H2D···O3	0.877 (19)	2.01 (2)	2.886 (3)	175 (4)
N2—H2D···S1	0.877 (19)	2.95 (4)	3.337 (3)	109 (3)
N2—H2F···S2	0.897 (18)	2.435 (19)	3.323 (3)	171 (3)
N2—H2G···O5ⁱⁱ	0.867 (18)	2.39 (3)	2.952 (3)	123 (3)

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

Acknowledgements

The work was undertaken with financial support from the Polish State Committee, grant No. 3 T09A 12028.

References

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