Ammonium O,O'-diethyl dithio-phosphate.

In the title compound, NH(4) (+)·(C(2)H(5)O)(2)PS(2) (-), the ammonium cation is connected by four charge-assisted N-H⋯S hydrogen bonds to four tetra-hedral O,O'-diethyl dithio-phosphate anions, forming layers parallel to (100). The polar and non-polar constituents of the layers are stacked alternately along [100]. Inter-lacing of the external ethyl groups through van der Waals inter-actions 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 = 203.25

Monoclinic,

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 ▶) 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[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.085

S = 1.01

2004 reflections

109 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.46 e Å−3

Δρmin = −0.21 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); 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 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811022811/wm2499sup1.cif

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

Supplementary material file. DOI: 10.1107/S1600536811022811/wm2499Isup3.cml

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

NH4+·C4H10O2PS2−	F(000) = 432
Mr = 203.25	Dx = 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

Oxford Diffraction Xcalibur diffractometer	2004 independent reflections
graphite	1579 reflections with I > 2σ(I)
Detector resolution: 8.1883 pixels mm-1	Rint = 0.023
ω scans	θmax = 26.0°, θmin = 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
Tmin = 0.856, Tmax = 0.969	k = −8→8
3955 measured reflections	l = −15→14

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(Fo2) + (0.0521P)2] where P = (Fo2 + 2Fc2)/3
2004 reflections	(Δ/σ)max = 0.001
109 parameters	Δρmax = 0.46 e Å−3
4 restraints	Δρmin = −0.21 e Å−3

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.

	x	y	z	Uiso*/Ueq
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)*

	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)

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)

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)

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) ; (ii) ; (iii) .