Ammonium O,O-dicyclo­hexyl phosphoro­dithio­ate

The structure of the title compound, NH₄⁺·C₁₂H₂₂O₂PS₂⁻, consists of a polymeric arrangement of ammonium cations and O,O-dicyclohexyl phosphorodithioate anions linked through N—H...O and N—H...S hydrogen bonds. These inter­actions result in the formation of (100) sheets.

S1. Comment

Organodithio derivatives of phosphorus have been widely studied for many years (Larson, 2004; Gray et al., 2004; Ivanov et al., 2000). The corresponding acids and metal complexes of phosphorodithioates (Dtph) have been shown to have many industrial and agricultural applications (Gray et al., 2003, 2004). For example, coordination compounds of transition metals with these ligands are used in agriculture as fungicides. They also function as antioxidants and corrosion inhibitors (Ivanov et al., 2000). Sodium or potassium salts of O,O'-dialkyl phosphorodithioates are used as selective collector reagents of sulfide minerals (Gray et al., 2003, 2004; Ivanov et al., 2000; Larson, 2004). These complexes can be mono-, di- or polynuclear, the choice being mainly determined by the ability of the Dtph ligands to perform terminal, bridging or mixed structural functions (El-Khaldy et al., 2003). Nickel complexes of Dtph ligands are mononuclear, while zinc complexes of the ligands are dinuclear (Gray et al., 2003, 2004; Ivanov et al., 2000).

The crystal structure determination of the title compound, (I) (Fig. 1), was carried out in order to determine the strength of the hydrogen-bond capability between the molecules of the Dtph ligands, and also to establish the local symmetry around the P atom.

The asymmetric unit of (I) contains one cation and one anion. The coordination around the P atom is distorted tetrahedral. Selected bond distances and angles of (I) are compared in Table 1 with those of some previously reported nickel complexes of (I), (II) (Chichang et al., 1987; Taş et al., 2005), and two nickel complexes of related dialkyl phosphorodithioate ligands, (IIIa) and (IIIb) (Gray et al., 2003, 2004). While the P—S bond lengths of (I) are shorter than the corresponding values reported for nickel complexes of (II), (IIIa) and (IIIb), the O—P distances are longer.

The ions in (I) are linked via N—H···O and N—H···S hydrogen bonds (Table 2). Within the selected asymmetric unit, atoms H1A and H1B of the cation act as hydrogen-bond donors to atoms S1 and S2 of the anion. In addition, atoms H1C and H1D at (x, y, z) act as donors to atoms S1 and O2 at (x, 1/2 − y, −1/2 + z) and (1 − x, 1/2 + y, 1/2 − z), respectively (Table 2). These interactions generate R₈⁶(20) and R₂²(6) rings (Bernstein et al., 1995) (Fig. 2). Propagation by translation and inversion of all these rings linking pseudo-tetrahedra then generates (100) sheets (Figs. 2 and 3). The distance between these sheets is 14.406 Å.

S2. Experimental

Ammonium dicyclohexyldithiophosphate was prepared based on the procedure used in the literature (Ma et al., 1995). Phosphorus pentasulfide (0.25 mol, 27.8 g; Acros Organics) and benzene (60 ml) were heated in a water bath at 348–353 K. Cyclohexanol (1 mol, 55 ml; Merck) was added dropwise with stirring and condensing under a nitrogen atmosphere. After refluxing for 3 h with stirring, ammonia gas was bubbled through the hot solution until the gas started to appear from the condenser, during which a white precipitate appeared. The solution was slowly cooled to room temparature. The product was filtered off, rinsed three times with 20 ml of benzene and dried under reduced pressure (yield ca 50%).

S3. Refinement

H atoms of the NH₄⁺ cation were located in a difference map and refined isotropically. All other H atoms were treated as riding, with C—H distances of 0.97–0.98 Å and with U_iso(H) = 1.2U_eq(C)

Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 2005); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. A view of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. Hydrogen-bond (dashed lines) and polyhedral representation of (I), in a view along the (100) axis. Distorted PS2O2 tetrahedra are shaded dark and cyclohexyl groups have been omitted for clarity. Atoms labelled with a hash sign (#) or dollar sign ($) are at the symmetry positions (x, 1/2 − y, −1/2 + z) and (1 − x,1/2 + y,1/2 − z), respectively.
	Fig. 3. Showing how the propagation by translation and inversion of all hydrogen-bond interactions (dashed lines) linking pseudo-tetrahedra generates (200) sheets. The distance between these sheets is 14.406 Å.

Ammonium O,O-dicyclohexyl phosphorodithioate

Crystal data

NH4^+·C12H22O2PS2^−	F(000) = 672
Mr = 311.43	Dx = 1.275 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 18994 reflections
a = 15.0755 (11) Å	θ = 1.9–27.6°
b = 10.6965 (5) Å	µ = 0.42 mm^−1
c = 10.5305 (7) Å	T = 293 K
β = 107.123 (5)°	Shapeless, colourless
V = 1622.83 (18) Å^3	0.57 × 0.37 × 0.17 mm
Z = 4

Data collection

Stoe IPDS 2 diffractometer	3723 independent reflections
Radiation source: fine-focus sealed tube	2862 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
Detector resolution: 6.67 pixels mm^-1	θmax = 27.6°, θmin = 2.4°
ω scans	h = −19→19
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −13→13
Tmin = 0.832, Tmax = 0.934	l = −13→13
18994 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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0576P)^2 + 0.213P] where P = (Fo^2 + 2Fc^2)/3
3723 reflections	(Δ/σ)max < 0.001
179 parameters	Δρmax = 0.22 e Å^−3
0 restraints	Δρmin = −0.33 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.19349 (13)	0.08614 (17)	0.02949 (17)	0.0461 (4)
H1	0.2422	0.1194	−0.0054	0.055*
C2	0.13353 (18)	−0.0026 (2)	−0.0695 (2)	0.0634 (6)
H2A	0.0893	−0.0417	−0.0312	0.076*
H2B	0.1719	−0.0679	−0.0897	0.076*
C3	0.0812 (2)	0.0649 (3)	−0.1978 (2)	0.0772 (7)
H3A	0.1251	0.0930	−0.2429	0.093*
H3B	0.0387	0.0068	−0.2561	0.093*
C4	0.02762 (16)	0.1750 (2)	−0.1716 (2)	0.0695 (6)
H4A	0.0013	0.2204	−0.2539	0.083*
H4B	−0.0232	0.1456	−0.1405	0.083*
C5	0.0872 (2)	0.2612 (2)	−0.0707 (3)	0.0823 (7)
H5A	0.0491	0.3275	−0.0515	0.099*
H5B	0.1331	0.2993	−0.1065	0.099*
C6	0.13629 (18)	0.1924 (2)	0.0575 (2)	0.0717 (6)
H6A	0.1762	0.2500	0.1199	0.086*
H6B	0.0907	0.1600	0.0975	0.086*
C7	0.29386 (13)	−0.04311 (17)	0.44176 (17)	0.0456 (4)
H7	0.2674	0.0413	0.4298	0.055*
C8	0.21714 (19)	−0.1375 (3)	0.4107 (2)	0.0763 (7)
H8A	0.2431	−0.2208	0.4139	0.092*
H8B	0.1764	−0.1234	0.3216	0.092*
C9	0.1616 (2)	−0.1282 (3)	0.5099 (3)	0.0832 (8)
H9A	0.1311	−0.0475	0.5011	0.100*
H9B	0.1141	−0.1924	0.4908	0.100*
C10	0.2226 (2)	−0.1437 (2)	0.6475 (3)	0.0820 (8)
H10A	0.2491	−0.2270	0.6583	0.098*
H10B	0.1862	−0.1344	0.7091	0.098*
C11	0.2999 (2)	−0.0476 (3)	0.6792 (2)	0.0822 (8)
H11A	0.3402	−0.0611	0.7687	0.099*
H11B	0.2736	0.0356	0.6751	0.099*
C12	0.35679 (18)	−0.0570 (3)	0.5804 (2)	0.0732 (6)
H12A	0.4037	0.0081	0.5987	0.088*
H12B	0.3880	−0.1373	0.5900	0.088*
N1	0.50436 (17)	0.2441 (2)	0.0963 (2)	0.0630 (5)
H1A	0.465 (2)	0.269 (3)	0.011 (4)	0.098 (9)*
H1B	0.544 (3)	0.295 (3)	0.121 (3)	0.105 (11)*
H1C	0.476 (3)	0.254 (4)	0.149 (4)	0.121 (14)*
H1D	0.504 (3)	0.159 (5)	0.101 (5)	0.171 (18)*
O1	0.23556 (9)	0.01628 (12)	0.15060 (12)	0.0481 (3)
O2	0.34894 (9)	−0.06271 (12)	0.34951 (12)	0.0494 (3)
P1	0.34298 (3)	0.03059 (4)	0.22883 (4)	0.04401 (13)
S1	0.36910 (4)	0.20511 (5)	0.29114 (5)	0.05616 (15)
S2	0.42263 (4)	−0.04177 (5)	0.12986 (5)	0.05971 (16)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0449 (9)	0.0486 (9)	0.0450 (9)	−0.0002 (7)	0.0135 (7)	0.0058 (7)
C2	0.0823 (16)	0.0540 (11)	0.0474 (10)	0.0015 (10)	0.0089 (10)	−0.0039 (8)
C3	0.0921 (18)	0.0815 (16)	0.0471 (11)	0.0026 (13)	0.0034 (11)	0.0007 (10)
C4	0.0549 (12)	0.0821 (15)	0.0635 (13)	0.0041 (11)	0.0051 (10)	0.0161 (11)
C5	0.0736 (16)	0.0617 (14)	0.0964 (18)	0.0177 (12)	0.0019 (14)	0.0041 (13)
C6	0.0670 (14)	0.0681 (14)	0.0679 (13)	0.0149 (11)	0.0014 (11)	−0.0169 (11)
C7	0.0481 (10)	0.0476 (9)	0.0422 (8)	0.0012 (7)	0.0149 (7)	0.0024 (7)
C8	0.0784 (16)	0.0992 (18)	0.0583 (12)	−0.0373 (14)	0.0310 (12)	−0.0177 (12)
C9	0.0894 (18)	0.0996 (19)	0.0742 (15)	−0.0315 (15)	0.0453 (14)	−0.0106 (14)
C10	0.133 (2)	0.0603 (13)	0.0763 (15)	0.0193 (14)	0.0674 (17)	0.0188 (11)
C11	0.0900 (19)	0.114 (2)	0.0409 (10)	0.0194 (16)	0.0160 (11)	−0.0020 (12)
C12	0.0671 (14)	0.1016 (19)	0.0454 (10)	0.0066 (13)	0.0080 (10)	0.0033 (11)
N1	0.0659 (12)	0.0646 (12)	0.0563 (11)	−0.0171 (10)	0.0142 (10)	0.0031 (9)
O1	0.0458 (7)	0.0536 (7)	0.0436 (6)	−0.0032 (5)	0.0114 (5)	0.0062 (5)
O2	0.0517 (7)	0.0526 (7)	0.0470 (6)	0.0072 (6)	0.0192 (6)	0.0097 (5)
P1	0.0446 (3)	0.0460 (3)	0.0417 (2)	−0.00129 (18)	0.01313 (19)	0.00304 (17)
S1	0.0638 (3)	0.0495 (3)	0.0518 (3)	−0.0074 (2)	0.0119 (2)	−0.0020 (2)
S2	0.0618 (3)	0.0624 (3)	0.0629 (3)	0.0022 (2)	0.0308 (3)	−0.0016 (2)

Geometric parameters (Å, º)

C1—O1	1.453 (2)	C8—C9	1.522 (3)
C1—C2	1.500 (3)	C8—H8A	0.9700
C1—C6	1.507 (3)	C8—H8B	0.9700
C1—H1	0.9800	C9—C10	1.478 (4)
C2—C3	1.530 (3)	C9—H9A	0.9700
C2—H2A	0.9700	C9—H9B	0.9700
C2—H2B	0.9700	C10—C11	1.516 (4)
C3—C4	1.499 (4)	C10—H10A	0.9700
C3—H3A	0.9700	C10—H10B	0.9700
C3—H3B	0.9700	C11—C12	1.534 (3)
C4—C5	1.492 (4)	C11—H11A	0.9700
C4—H4A	0.9700	C11—H11B	0.9700
C4—H4B	0.9700	C12—H12A	0.9700
C5—C6	1.524 (4)	C12—H12B	0.9700
C5—H5A	0.9700	N1—H1A	0.96 (4)
C5—H5B	0.9700	N1—H1B	0.80 (4)
C6—H6A	0.9700	N1—H1C	0.80 (5)
C6—H6B	0.9700	N1—H1D	0.91 (6)
C7—O2	1.467 (2)	O1—P1	1.5935 (13)
C7—C12	1.496 (3)	O2—P1	1.5974 (12)
C7—C8	1.497 (3)	P1—S2	1.9657 (7)
C7—H7	0.9800	P1—S1	1.9795 (7)
O1—C1—C2	107.60 (15)	C7—C8—H8A	109.5
O1—C1—C6	110.07 (16)	C9—C8—H8A	109.5
C2—C1—C6	110.53 (18)	C7—C8—H8B	109.5
O1—C1—H1	109.5	C9—C8—H8B	109.5
C2—C1—H1	109.5	H8A—C8—H8B	108.1
C6—C1—H1	109.5	C10—C9—C8	110.9 (2)
C1—C2—C3	111.33 (19)	C10—C9—H9A	109.5
C1—C2—H2A	109.4	C8—C9—H9A	109.5
C3—C2—H2A	109.4	C10—C9—H9B	109.5
C1—C2—H2B	109.4	C8—C9—H9B	109.5
C3—C2—H2B	109.4	H9A—C9—H9B	108.0
H2A—C2—H2B	108.0	C9—C10—C11	110.8 (2)
C4—C3—C2	111.94 (19)	C9—C10—H10A	109.5
C4—C3—H3A	109.2	C11—C10—H10A	109.5
C2—C3—H3A	109.2	C9—C10—H10B	109.5
C4—C3—H3B	109.2	C11—C10—H10B	109.5
C2—C3—H3B	109.2	H10A—C10—H10B	108.1
H3A—C3—H3B	107.9	C10—C11—C12	110.7 (2)
C5—C4—C3	111.9 (2)	C10—C11—H11A	109.5
C5—C4—H4A	109.2	C12—C11—H11A	109.5
C3—C4—H4A	109.2	C10—C11—H11B	109.5
C5—C4—H4B	109.2	C12—C11—H11B	109.5
C3—C4—H4B	109.2	H11A—C11—H11B	108.1
H4A—C4—H4B	107.9	C7—C12—C11	109.5 (2)
C4—C5—C6	111.4 (2)	C7—C12—H12A	109.8
C4—C5—H5A	109.3	C11—C12—H12A	109.8
C6—C5—H5A	109.3	C7—C12—H12B	109.8
C4—C5—H5B	109.3	C11—C12—H12B	109.8
C6—C5—H5B	109.3	H12A—C12—H12B	108.2
H5A—C5—H5B	108.0	H1A—N1—H1B	109 (3)
C1—C6—C5	110.4 (2)	H1A—N1—H1C	108 (3)
C1—C6—H6A	109.6	H1B—N1—H1C	100 (3)
C5—C6—H6A	109.6	H1A—N1—H1D	108 (3)
C1—C6—H6B	109.6	H1B—N1—H1D	133 (4)
C5—C6—H6B	109.6	H1C—N1—H1D	95 (3)
H6A—C6—H6B	108.1	C1—O1—P1	121.26 (11)
O2—C7—C12	108.19 (16)	C7—O2—P1	121.82 (11)
O2—C7—C8	108.09 (15)	O1—P1—O2	99.31 (7)
C12—C7—C8	111.91 (19)	O1—P1—S2	112.00 (5)
O2—C7—H7	109.5	O2—P1—S2	106.01 (5)
C12—C7—H7	109.5	O1—P1—S1	109.55 (6)
C8—C7—H7	109.5	O2—P1—S1	111.50 (6)
C7—C8—C9	110.60 (19)	S2—P1—S1	117.00 (3)
O1—C1—C2—C3	176.32 (19)	O2—C7—C12—C11	−175.5 (2)
C6—C1—C2—C3	56.1 (3)	C8—C7—C12—C11	−56.5 (3)
C1—C2—C3—C4	−53.5 (3)	C10—C11—C12—C7	56.1 (3)
C2—C3—C4—C5	52.6 (3)	C2—C1—O1—P1	134.98 (15)
C3—C4—C5—C6	−54.6 (3)	C6—C1—O1—P1	−104.52 (17)
O1—C1—C6—C5	−176.54 (19)	C12—C7—O2—P1	−132.44 (17)
C2—C1—C6—C5	−57.8 (3)	C8—C7—O2—P1	106.18 (18)
C4—C5—C6—C1	57.1 (3)	C1—O1—P1—O2	179.15 (13)
O2—C7—C8—C9	175.8 (2)	C1—O1—P1—S2	−69.28 (13)
C12—C7—C8—C9	56.8 (3)	C1—O1—P1—S1	62.26 (13)
C7—C8—C9—C10	−56.6 (3)	C7—O2—P1—O1	−60.22 (14)
C8—C9—C10—C11	57.1 (3)	C7—O2—P1—S2	−176.45 (12)
C9—C10—C11—C12	−57.3 (3)	C7—O2—P1—S1	55.19 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S1^i	0.96 (4)	2.36 (4)	3.305 (2)	171 (3)
N1—H1B···O2^ii	0.80 (4)	2.17 (4)	2.957 (3)	169 (3)
N1—H1C···S1	0.80 (5)	2.56 (5)	3.318 (3)	159 (4)
N1—H1D···S2	0.91 (6)	2.54 (6)	3.354 (2)	149 (4)

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