Pyridinium di­hydrogenmono­thio­phosphate

By reaction of pyridine di­thio­monometa­phospho­ryl fluoride with ethyl­di­phenyl­phosphine in the presence of traces of water, we isolated crystals of the title compound, (I). In the structure of this salt, two kinds of hydrogen bonds were detected. They link N-H (part of the cation), as well as one O-H group (part of the anion), to the phospho­ryl O atom of the anion. The donor-acceptor distances are 2.654 (1) and 2.568 (1) Å, respectively. The P-O and P-S bond lengths are 1.514 (2) and 1.967 (1) Å, respectively, which fall therefore in the range of a 1.5-fold bond.

S1. Experimental

According to Fluck et al. (1973), a solution of ethyldiphenylphosphine in benzene was slowly dropped into a suspension of pyridine-dithiomonometaphosphoryl fluoride in benzene with stirring. After 1 h, the solid product was filtered and recrystallized from a solution in benzene/acetonitrile.

S2. Refinement

For the studied crystal, a ΔF²-based absorption correction was carried out. The calculation made with ABSCOR (Stoe & Cie, 1997), a modification of DIFABS (Walker & Stuart, 1983). Unlike DIFABS, ABSCOR works with F² values instead of F. All H atoms were refined [C—H 0.89 (2)–0.91 (2) Å].

Computing details

Data collection: IPDS2.87 (Stoe & Cie, 1997); cell refinement: IPDS2.87 (Stoe & Cie, 1997); data reduction: IPDS2.87 (Stoe & Cie, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XSTEP-2.18 (Stoe & Cie, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Pyridinium-dihydrohenmonothiophosphate

Crystal data

C5H6N^+·H2PSO3^−	F(000) = 400
Mr = 193.15	Dx = 1.612 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 6.7837 (13) Å	Cell parameters from 1775 reflections
b = 9.0268 (11) Å	θ = 2.5–25.0°
c = 13.237 (2) Å	µ = 0.56 mm^−1
β = 101.02 (2)°	T = 180 K
V = 795.7 (2) Å^3	Plate, yellow
Z = 4	0.40 × 0.28 × 0.12 mm

Data collection

Stoe IPDS diffractometer	1540 independent reflections
Radiation source: fine-focus sealed X-ray tube	1260 reflections with I > 2σ(I)
Planar graphite monochromator	Rint = 0.038
Detector resolution: 6.667 pixels mm^-1	θmax = 26.0°, θmin = 2.8°
ϕ–oscill., ϕ–incr. = 1.5°, 133 exposures scans	h = −8→8
Absorption correction: part of the refinement model (ΔF) see _publ_section_exptl_prep	k = −11→10
Tmin = 0.806, Tmax = 0.935	l = −16→16
4980 measured reflections

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)] = 0.029	Hydrogen site location: difference Fourier map
wR(F^2) = 0.077	All H-atom parameters refined
S = 1.04	Calculated w = 1/[σ^2(Fo^2) + (0.0472P)^2] where P = (Fo^2 + 2Fc^2)/3
1538 reflections	(Δ/σ)max = 0.001
126 parameters	Δρmax = 0.34 e Å^−3
0 restraints	Δρmin = −0.35 e Å^−3

Special details

Experimental. During data collection the crystal was in cold N₂ gas of the Cryostream Cooler (Oxford Cryosystems, 1992) mounted on a ϕ-axis diffractometer supplied with an area detector.

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 on F² for ALL reflections except for 2 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating R-factors 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
C2	0.2976 (3)	1.1222 (2)	1.04011 (14)	0.0223 (4)
H2	0.309 (3)	1.214 (2)	1.0178 (15)	0.028 (5)*
C3	0.3346 (3)	1.0828 (2)	1.14227 (14)	0.0238 (4)
H3	0.381 (3)	1.152 (2)	1.1909 (16)	0.027 (5)*
C4	0.3066 (2)	0.9365 (2)	1.16783 (14)	0.0237 (4)
H4	0.337 (3)	0.912 (2)	1.2350 (17)	0.026 (5)*
C5	0.2420 (3)	0.8338 (2)	1.09145 (14)	0.0231 (4)
H5	0.218 (3)	0.739 (2)	1.1057 (15)	0.022 (5)*
C6	0.2090 (2)	0.8782 (2)	0.99048 (14)	0.0207 (4)
H6	0.163 (3)	0.817 (2)	0.9381 (16)	0.024 (5)*
P1	0.13611 (6)	1.00598 (4)	0.68966 (3)	0.01481 (15)
S1	0.31967 (6)	0.99166 (5)	0.59164 (3)	0.02010 (15)
N1	0.2376 (2)	1.0202 (2)	0.96762 (12)	0.0191 (3)
H1N	0.213 (3)	1.050 (3)	0.9044 (19)	0.032 (6)*
O1	0.1059 (2)	0.85400 (13)	0.74198 (10)	0.0236 (3)
H1Y	0.1897 (19)	0.7923 (6)	0.7282 (13)	0.026*
O2	−0.0836 (2)	1.0518 (2)	0.63523 (9)	0.0274 (3)
H2Y	−0.1075 (11)	1.0184 (19)	0.5749 (5)	0.030*
O3	0.1920 (2)	1.11798 (13)	0.77550 (9)	0.0209 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C2	0.0226 (8)	0.0212 (9)	0.0228 (9)	0.0007 (7)	0.0036 (7)	0.0015 (8)
C3	0.0241 (9)	0.0281 (11)	0.0184 (9)	−0.0008 (7)	0.0018 (7)	−0.0050 (8)
C4	0.0214 (8)	0.0356 (11)	0.0143 (9)	0.0049 (8)	0.0040 (7)	0.0037 (8)
C5	0.0233 (9)	0.0217 (10)	0.0245 (9)	0.0025 (7)	0.0047 (7)	0.0059 (8)
C6	0.0205 (8)	0.0226 (9)	0.0186 (9)	0.0009 (7)	0.0028 (7)	−0.0047 (8)
P1	0.0208 (2)	0.0118 (3)	0.0111 (2)	0.00026 (15)	0.0013 (2)	−0.0010 (2)
S1	0.0233 (2)	0.0231 (3)	0.0140 (2)	−0.0012 (2)	0.0038 (2)	−0.0012 (2)
N1	0.0192 (7)	0.0257 (8)	0.0125 (7)	0.0029 (6)	0.0030 (5)	0.0018 (6)
O1	0.0320 (7)	0.0137 (6)	0.0286 (7)	0.0017 (5)	0.0142 (5)	0.0017 (5)
O2	0.0264 (6)	0.0388 (8)	0.0154 (6)	0.0102 (6)	0.0002 (5)	−0.0049 (6)
O3	0.0335 (7)	0.0166 (6)	0.0122 (6)	−0.0048 (5)	0.0033 (5)	−0.0028 (5)

Geometric parameters (Å, º)

C2—N1	1.336 (2)	C6—N1	1.339 (2)
C2—C3	1.374 (3)	C6—H6	0.90 (2)
C2—H2	0.89 (2)	P1—O3	1.5141 (12)
C3—C4	1.385 (3)	P1—O1	1.5678 (12)
C3—H3	0.91 (2)	P1—O2	1.5816 (13)
C4—C5	1.380 (3)	P1—S1	1.9669 (7)
C4—H4	0.90 (2)	N1—H1N	0.86 (2)
C5—C6	1.372 (3)	O1—H1Y	0.84
C5—H5	0.90 (2)	O2—H2Y	0.84
N1—C2—C3	120.1 (2)	N1—C6—H6	117.4 (13)
N1—C2—H2	116.0 (13)	C5—C6—H6	122.8 (13)
C3—C2—H2	123.9 (13)	O3—P1—O1	106.73 (7)
C2—C3—C4	118.6 (2)	O3—P1—O2	104.26 (7)
C2—C3—H3	119.6 (13)	O1—P1—O2	103.82 (7)
C4—C3—H3	121.7 (13)	O3—P1—S1	116.08 (5)
C5—C4—C3	120.1 (2)	O1—P1—S1	112.74 (5)
C5—C4—H4	122.4 (14)	O2—P1—S1	112.15 (5)
C3—C4—H4	117.5 (14)	C2—N1—C6	122.3 (2)
C6—C5—C4	119.1 (2)	C2—N1—H1N	117.2 (16)
C6—C5—H5	118.7 (13)	C6—N1—H1N	120.5 (16)
C4—C5—H5	122.1 (12)	P1—O1—H1Y	109.47 (5)
N1—C6—C5	119.7 (2)	P1—O2—H2Y	109.47 (5)
N1—C2—C3—C4	−0.6 (2)	C4—C5—C6—N1	−0.8 (2)
C2—C3—C4—C5	−0.3 (2)	C3—C2—N1—C6	0.8 (2)
C3—C4—C5—C6	0.9 (2)	C5—C6—N1—C2	−0.1 (2)