Ammonium O,O′-diethyl dithio­phosphate

Okuniewski, A.; Becker, B.

doi:10.1107/S1600536811022811

organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Pages o1749-o1750

doi:10.1107/S1600536811022811

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Ammonium O,O′-diethyl dithiophosphate

Andrzej Okuniewski ^a and Barbara Becker ^a ^*

^aDepartment of Inorganic Chemistry, Gdansk University of Technology, 11/12 Narutowicza Str., 80-233 Gdańsk, Poland
^*Correspondence e-mail: barbara.becker@pg.gda.pl

(Received 10 June 2011; accepted 13 June 2011; online 18 June 2011)

In the title compound, NH₄⁺·(C₂H₅O)₂PS₂⁻, the ammonium cation is connected by four charge-assisted N—H⋯S hydrogen bonds to four tetrahedral O,O′-diethyl dithiophosphate anions, forming layers parallel to (100). The polar and non-polar constituents of the layers are stacked alternately along [100]. Interlacing of the external ethyl groups through van der Waals interactions combines these layers into a three-dimensional structure.

Related literature

For related structures, see: Chekhlov et al. (1991 ); Chekhlov (2000 ). For applications of O,O′-diethyl dithiophosphate in coordination chemistry, see: Cotero-Villegas et al. (2011 ). For the determination of various ions in analytical chemistry using O,O′-diethyl dithiophosphates, see: Carletto et al. (2009 ); Maltez et al. (2008 ); Pozebon et al. (1998 ); Wu et al. (2006 ). For a description of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

NH₄⁺·C₄H₁₀O₂PS₂⁻
M_r = 203.25
Monoclinic, P 2₁ /c
a = 12.0274 (7) Å
b = 7.2006 (3) Å
c = 12.5690 (7) Å
β = 110.305 (6)°
V = 1020.89 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.63 mm⁻¹
T = 120 K
0.30 × 0.16 × 0.05 mm

Data collection

Oxford Diffraction Xcalibur diffractometer
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ) using a multi-faceted crystal model based on expressions derived by Clark & Reid (1995 )] T_min = 0.856, T_max = 0.969
3955 measured reflections
2004 independent reflections
1579 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.085
S = 1.01
2004 reflections
109 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯S1ⁱ	0.89 (1)	2.43 (1)	3.310 (2)	178 (3)
N1—H4N⋯S1ⁱⁱ	0.88 (1)	2.50 (1)	3.377 (2)	177 (2)
N1—H3N⋯S2ⁱⁱⁱ	0.89 (1)	2.54 (1)	3.409 (2)	169 (2)
N1—H2N⋯S2	0.88 (1)	2.39 (1)	3.2633 (19)	171 (2)
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009 ) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811022811/wm2499sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811022811/wm2499Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811022811/wm2499Isup3.cml

checkCIF report

Comment top

Ammonium O,O'-diethyl dithiophosphate is frequently used as a source of the (C₂H₅O)₂PS₂^- ligand in coordination chemistry (Cotero-Villegas et al., 2011) and in analytical chemistry for determination of various ions, eg. As (Pozebon et al., 1998), Pb (Maltez et al., 2008), Cd (Carletto et al., 2009), Hg (Wu et al., 2006).

There are at least 340 structures deposited in the Cambridge Structural Database (v5.32; Allen, 2008) containing the O,O'-diethyl dithiophosphate moiety, but there are no crystal structure of simple ammonium, sodium or potassium salts reported. Among these structures one can find 328 complexes (including 204 of row 6 family metals, mainly molybdenum compounds), five compounds with complex cations, five simple organic or inorganic compounds and finally two salts of 1,10-diaza-18-crown-6 (Chekhlov, 2000; Chekhlov et al., 1991).

In the crystal structure of the title compound, the asymmetric unit consists of one ammonium cation and one tetrahedral O,O'-diethyl dithiophosphate anion (Fig. 1). The P—S distances are 1.9720 (8) Å and 1.9753 (8) Å. These values are slightly lower than the mean value of 1.9872 (25) Å calculated for the 340 compounds deposited in the CSD. Each ammonium cation is connected by four N—H···S hydrogen bonds to four O,O'-diethyl dithiophosphate anions. This way three structural ring motifs are formed: two of them are centrosymmetric – R²₄(8), R⁴₄(12), and one is not – R³₄(10) (Fig. 2.) Hydrogen bonding interactions are summarized in Tab. 1.

The connected ions form layers parallel to the (100) plane. Each layer has an hydrophilic interior, where heteroatoms and hydrogen bonds can be found, and an hydrophobic exterior formed by the ethyl groups (Fig. 3). These layers interact with each other by van der Waals forces forming a three-dimensional crystal structure.

Related literature top

For related structures, see: Chekhlov et al. (1991); Chekhlov (2000). For applications of O,O'-diethyl dithiophosphate in coordination chemistry, see: Cotero-Villegas et al. (2011). For determination of various ions in analytical chemistry using O,O'-diethyl dithiophosphates, see: Carletto et al. (2009); Maltez et al. (2008); Pozebon et al. (1998); Wu et al. (2006). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

1 g of commercially available ammonium O,O'-diethyl dithiophosphate was dissolved in 5 ml of acetone and left to evaporate slowly. After one week colourless crystals suitable for single-crystal X-ray diffraction analysis were collected.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of NH₄⁺.(C₂H₅O)₂PS₂^-, with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Hydrogen bond pattern found in the structure of NH₄⁺.(C₂H₅O)₂PS₂^-, with R²₄(8), R⁴₄(12) and R³₄(10) structural motifs depicted. Hydrogen bonds are marked with dashed lines.
	Fig. 3. Layers of NH₄⁺.(C₂H₅O)₂PS₂^- projected down [001] (a)) and [010] (b)). Hydrogen bonds are marked with dashed lines, with hydrogen atoms omitted for clarity.

Ammonium O,O'-diethyl dithiophosphate top

Crystal data top

NH₄⁺·C₄H₁₀O₂PS₂⁻	F(000) = 432
M_r = 203.25	D_x = 1.322 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 438(1) K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 12.0274 (7) Å	Cell parameters from 2402 reflections
b = 7.2006 (3) Å	θ = 2.8–28.4°
c = 12.5690 (7) Å	µ = 0.63 mm⁻¹
β = 110.305 (6)°	T = 120 K
V = 1020.89 (9) Å³	Plate, colourless
Z = 4	0.30 × 0.16 × 0.05 mm

Data collection top

Oxford Diffraction Xcalibur diffractometer	2004 independent reflections
Graphite monochromator	1579 reflections with I > 2σ(I)
Detector resolution: 8.1883 pixels mm^-1	R_int = 0.023
ω scans	θ_max = 26.0°, θ_min = 3.3°
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2010) using a multi-faceted crystal model based on expressions derived by Clark & Reid (1995)]	h = −14→12
T_min = 0.856, T_max = 0.969	k = −8→8
3955 measured reflections	l = −15→14

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0521P)²] where P = (F_o² + 2F_c²)/3
2004 reflections	(Δ/σ)_max = 0.001
109 parameters	Δρ_max = 0.46 e Å⁻³
4 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

NH₄⁺·C₄H₁₀O₂PS₂⁻	V = 1020.89 (9) Å³
M_r = 203.25	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.0274 (7) Å	µ = 0.63 mm⁻¹
b = 7.2006 (3) Å	T = 120 K
c = 12.5690 (7) Å	0.30 × 0.16 × 0.05 mm
β = 110.305 (6)°

Data collection top

Oxford Diffraction Xcalibur diffractometer	2004 independent reflections
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2010) using a multi-faceted crystal model based on expressions derived by Clark & Reid (1995)]	1579 reflections with I > 2σ(I)
T_min = 0.856, T_max = 0.969	R_int = 0.023
3955 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	4 restraints
wR(F²) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.46 e Å⁻³
2004 reflections	Δρ_min = −0.21 e Å⁻³
109 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
C1	0.3199 (2)	0.5211 (3)	0.2964 (2)	0.0326 (5)
H1A	0.2982	0.4906	0.3635	0.039*
H1B	0.265	0.6179	0.2517	0.039*
C2	0.4451 (2)	0.5890 (4)	0.3330 (3)	0.0511 (7)
H2A	0.4984	0.493	0.3783	0.077*
H2B	0.4529	0.7018	0.3788	0.077*
H2C	0.466	0.6169	0.266	0.077*
C3	0.3169 (2)	0.0606 (4)	0.3984 (2)	0.0392 (6)
H3A	0.369	0.1581	0.4457	0.047*
H3B	0.36	−0.0022	0.3543	0.047*
C4	0.2849 (3)	−0.0763 (4)	0.4717 (2)	0.0425 (7)
H4A	0.2426	−0.0129	0.5152	0.064*
H4B	0.3572	−0.1334	0.524	0.064*
H4C	0.234	−0.1727	0.4242	0.064*
O1	0.31244 (13)	0.35602 (19)	0.22740 (13)	0.0281 (4)
O2	0.20831 (13)	0.1435 (2)	0.32198 (12)	0.0278 (4)
P1	0.20257 (5)	0.21895 (8)	0.20040 (5)	0.02272 (16)
S1	0.23286 (5)	0.02043 (8)	0.10585 (5)	0.03012 (17)
S2	0.04716 (5)	0.34439 (8)	0.13990 (4)	0.02542 (16)
N1	0.0076 (2)	0.3099 (3)	0.38320 (17)	0.0284 (4)
H1N	−0.0563 (17)	0.369 (4)	0.385 (2)	0.053 (8)*
H2N	0.020 (2)	0.333 (4)	0.3191 (14)	0.047 (8)*
H3N	−0.010 (3)	0.1909 (16)	0.385 (2)	0.052 (9)*
H4N	0.0644 (18)	0.357 (3)	0.4414 (15)	0.047 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0318 (13)	0.0262 (11)	0.0376 (13)	−0.0028 (10)	0.0093 (10)	−0.0092 (10)
C2	0.0360 (15)	0.0437 (15)	0.0672 (19)	−0.0085 (13)	0.0101 (14)	−0.0231 (15)
C3	0.0281 (13)	0.0406 (14)	0.0387 (14)	0.0043 (12)	−0.0015 (11)	0.0107 (12)
C4	0.0528 (17)	0.0459 (15)	0.0302 (13)	0.0196 (14)	0.0162 (12)	0.0099 (12)
O1	0.0263 (8)	0.0254 (8)	0.0348 (8)	−0.0061 (7)	0.0133 (7)	−0.0074 (7)
O2	0.0250 (8)	0.0333 (8)	0.0231 (7)	0.0047 (7)	0.0061 (6)	0.0067 (7)
P1	0.0227 (3)	0.0229 (3)	0.0233 (3)	−0.0008 (2)	0.0088 (2)	−0.0015 (2)
S1	0.0256 (3)	0.0295 (3)	0.0370 (3)	−0.0010 (2)	0.0131 (3)	−0.0097 (3)
S2	0.0263 (3)	0.0297 (3)	0.0202 (3)	0.0051 (2)	0.0080 (2)	0.0011 (2)
N1	0.0328 (12)	0.0313 (12)	0.0244 (10)	0.0047 (10)	0.0141 (9)	0.0026 (9)

Geometric parameters (Å, º) top

C1—O1	1.456 (3)	C4—H4A	0.98
C1—C2	1.495 (3)	C4—H4B	0.98
C1—H1A	0.99	C4—H4C	0.98
C1—H1B	0.99	O1—P1	1.5888 (15)
C2—H2A	0.98	O2—P1	1.6005 (14)
C2—H2B	0.98	P1—S1	1.9720 (8)
C2—H2C	0.98	P1—S2	1.9753 (8)
C3—O2	1.454 (3)	N1—H1N	0.886 (10)
C3—C4	1.489 (3)	N1—H2N	0.884 (10)
C3—H3A	0.99	N1—H3N	0.885 (10)
C3—H3B	0.99	N1—H4N	0.879 (10)

O1—C1—C2	107.3 (2)	C3—C4—H4B	109.5
O1—C1—H1A	110.2	H4A—C4—H4B	109.5
C2—C1—H1A	110.2	C3—C4—H4C	109.5
O1—C1—H1B	110.2	H4A—C4—H4C	109.5
C2—C1—H1B	110.2	H4B—C4—H4C	109.5
H1A—C1—H1B	108.5	C1—O1—P1	120.63 (14)
C1—C2—H2A	109.5	C3—O2—P1	120.07 (15)
C1—C2—H2B	109.5	O1—P1—O2	104.47 (8)
H2A—C2—H2B	109.5	O1—P1—S1	105.37 (6)
C1—C2—H2C	109.5	O2—P1—S1	111.94 (6)
H2A—C2—H2C	109.5	O1—P1—S2	113.83 (6)
H2B—C2—H2C	109.5	O2—P1—S2	104.14 (6)
O2—C3—C4	108.3 (2)	S1—P1—S2	116.59 (4)
O2—C3—H3A	110	H1N—N1—H2N	111 (2)
C4—C3—H3A	110	H1N—N1—H3N	104 (3)
O2—C3—H3B	110	H2N—N1—H3N	109 (2)
C4—C3—H3B	110	H1N—N1—H4N	103 (2)
H3A—C3—H3B	108.4	H2N—N1—H4N	111 (3)
C3—C4—H4A	109.5	H3N—N1—H4N	118 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···S1ⁱ	0.89 (1)	2.43 (1)	3.310 (2)	178 (3)
N1—H4N···S1ⁱⁱ	0.88 (1)	2.50 (1)	3.377 (2)	177 (2)
N1—H3N···S2ⁱⁱⁱ	0.89 (1)	2.54 (1)	3.409 (2)	169 (2)
N1—H2N···S2	0.88 (1)	2.39 (1)	3.2633 (19)	171 (2)

Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) x, −y+1/2, z+1/2; (iii) −x, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	NH₄⁺·C₄H₁₀O₂PS₂⁻
M_r	203.25
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	120
a, b, c (Å)	12.0274 (7), 7.2006 (3), 12.5690 (7)
β (°)	110.305 (6)
V (Å³)	1020.89 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.63
Crystal size (mm)	0.30 × 0.16 × 0.05

Data collection
Diffractometer	Oxford Diffraction Xcalibur diffractometer
Absorption correction	Analytical [CrysAlis PRO (Oxford Diffraction, 2010) using a multi-faceted crystal model based on expressions derived by Clark & Reid (1995)]
T_min, T_max	0.856, 0.969
No. of measured, independent and observed [I > 2σ(I)] reflections	3955, 2004, 1579
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.085, 1.01
No. of reflections	2004
No. of parameters	109
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.21

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2008), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···S1ⁱ	0.886 (10)	2.425 (10)	3.310 (2)	178 (3)
N1—H4N···S1ⁱⁱ	0.879 (10)	2.499 (10)	3.377 (2)	177 (2)
N1—H3N···S2ⁱⁱⁱ	0.885 (10)	2.536 (11)	3.409 (2)	169 (2)
N1—H2N···S2	0.884 (10)	2.387 (11)	3.2633 (19)	171 (2)

Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) x, −y+1/2, z+1/2; (iii) −x, y−1/2, −z+1/2.

Acknowledgements

Financial support from the Polish Ministry of Science and Higher Education (project No. N N204 543339) is gratefully acknowledged.

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