Morpholinium dimorpholinidodi­thio­phosphate

It was planned to sythesize morpholinedi­thio­monometa­phospho­ryl morpholinide by reaction of pyridine­di­thio­monometa­phospho­ryl chloride with 4-(trimethylsilyl)morpholine. But due to traces of water the title compound was formed as by-product, (I).

S1. Experimental

A solution of 4-(trimethylsilyl)morpholine in benzene was slowly dropped to a suspension of pyridinedithiomonometaphosphoryl chloride in benzene. After one hour stirring at 333 K, the solid product was filtrated and washed with benzene. For the studied crystal of a ΔF² based absorption correction was carried out. The calculation was done with ABSCOR (Stoe & Cie, 1997), a modification of DIFABS (Walker & Stuart, 1983). In contrary of DIFABS, ABSCOR loads F² values instead of F values.

Computing details

Data collection: IPDS2.75 (Stoe & Cie, 1997); cell refinement: IPDS2.75 (Stoe & Cie, 1997); data reduction: IPDS2.75 (Stoe & Cie, 1997); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: XSTEP (Stoe & Cie, 1997); software used to prepare material for publication: SHELXL93 (Sheldrick, 1993).

Morpholinium-dimorpholidodithiophosphate

Crystal data

C4H10NO^+·C8H16N2O2PS2^−	F(000) = 380
Mr = 355.45	Dx = 1.389 Mg m^−3
Triclinic, P1	Melting point: 353 (decomposition) K
a = 7.355 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.291 (3) Å	Cell parameters from 4803 reflections
c = 14.374 (5) Å	θ = 2.6–25.0°
α = 95.78 (4)°	µ = 0.42 mm^−1
β = 98.68 (4)°	T = 180 K
γ = 98.51 (4)°	Prism, colorless
V = 850.1 (5) Å^3	0.41 × 0.20 × 0.19 mm
Z = 2

Data collection

Stoe IPDS diffractometer	2881 independent reflections
Radiation source: fine-focus sealed X-ray tube	1833 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.101
Detector resolution: 6.667 pixels mm^-1	θmax = 25.2°, θmin = 2.5°
ϕ–oscill., ϕ–incr. = 1.5°; 147 exposures scans	h = −8→8
Absorption correction: part of the refinement model (ΔF) see Experimental	k = −10→10
Tmin = 0.847, Tmax = 0.925	l = −17→17
6844 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.057	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.137	Calculated w = 1/[σ^2(Fo^2) + (0.0823P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.90	(Δ/σ)max = 0.012
2876 reflections	Δρmax = 0.54 e Å^−3
197 parameters	Δρmin = −0.46 e Å^−3
0 restraints	Extinction correction: SHELXL93, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0033 (29)

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 5 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
C1	0.3807 (6)	0.7024 (6)	−0.0077 (3)	0.0279 (11)
H1A	0.4038 (6)	0.7728 (6)	−0.0578 (3)	0.031*
H1B	0.3887 (6)	0.5880 (6)	−0.0318 (3)	0.031*
C2	0.5232 (7)	0.7604 (5)	0.0800 (3)	0.0281 (11)
H2A	0.5023 (7)	0.6864 (5)	0.1286 (3)	0.031*
H2B	0.6494 (7)	0.7561 (5)	0.0649 (3)	0.031*
C3	0.3345 (7)	0.9294 (6)	0.1427 (3)	0.0318 (12)
H3A	0.3298 (7)	1.0424 (6)	0.1708 (3)	0.035*
H3B	0.3148 (7)	0.8549 (6)	0.1912 (3)	0.035*
C4	0.1824 (7)	0.8797 (6)	0.0587 (3)	0.0319 (12)
H4A	0.0596 (7)	0.8822 (6)	0.0785 (3)	0.035*
H4B	0.1972 (7)	0.9572 (6)	0.0112 (3)	0.035*
C5	−0.1688 (7)	0.2335 (6)	0.2542 (3)	0.0326 (12)
H5A	−0.1575 (7)	0.1420 (6)	0.2067 (3)	0.036*
H5B	−0.2481 (7)	0.3051 (6)	0.2222 (3)	0.036*
C6	−0.2569 (7)	0.1664 (7)	0.3329 (3)	0.0363 (13)
H6A	−0.2754 (7)	0.2588 (7)	0.3778 (3)	0.040*
H6B	−0.3809 (7)	0.1009 (7)	0.3061 (3)	0.040*
C7	0.0343 (7)	0.1578 (6)	0.4214 (3)	0.0347 (12)
H7A	0.1114 (7)	0.0866 (6)	0.4553 (3)	0.038*
H7B	0.0215 (7)	0.2505 (6)	0.4677 (3)	0.038*
C8	0.1300 (7)	0.2234 (6)	0.3434 (3)	0.0322 (12)
H8A	0.2540 (7)	0.2879 (6)	0.3711 (3)	0.035*
H8B	0.1481 (7)	0.1307 (6)	0.2985 (3)	0.035*
C9	0.4807 (6)	0.5411 (6)	0.3253 (3)	0.0283 (11)
H9A	0.5144 (6)	0.4922 (6)	0.2658 (3)	0.031*
H9B	0.4887 (6)	0.4611 (6)	0.3718 (3)	0.031*
C10	0.6138 (7)	0.6978 (7)	0.3637 (3)	0.0379 (13)
H10A	0.7418 (7)	0.6731 (7)	0.3790 (3)	0.042*
H10B	0.6131 (7)	0.7739 (7)	0.3148 (3)	0.042*
C11	0.3818 (7)	0.8179 (6)	0.4260 (3)	0.0322 (12)
H11A	0.3818 (7)	0.8940 (6)	0.3772 (3)	0.035*
H11B	0.3492 (7)	0.8750 (6)	0.4836 (3)	0.035*
C12	0.2385 (7)	0.6657 (6)	0.3899 (3)	0.0284 (11)
H12A	0.2312 (7)	0.5935 (6)	0.4405 (3)	0.031*
H12B	0.1143 (7)	0.6972 (6)	0.3724 (3)	0.031*
N1	0.1929 (6)	0.7106 (5)	0.0165 (3)	0.0267 (10)
H1NA	0.107 (7)	0.681 (6)	−0.034 (4)	0.029*
H2NA	0.166 (7)	0.637 (6)	0.054 (3)	0.029*
N2	0.0156 (5)	0.3277 (4)	0.2929 (2)	0.0243 (9)
N3	0.2900 (5)	0.5767 (4)	0.3067 (2)	0.0209 (8)
O1	0.5127 (5)	0.9238 (4)	0.1169 (2)	0.0314 (8)
O2	−0.1455 (5)	0.0657 (4)	0.3828 (2)	0.0416 (10)
O3	0.5615 (5)	0.7751 (4)	0.4478 (2)	0.0409 (10)
P1	0.1177 (2)	0.46109 (13)	0.22869 (7)	0.0186 (3)
S1	0.2258 (2)	0.34968 (14)	0.12451 (7)	0.0250 (3)
S2	−0.0695 (2)	0.59723 (14)	0.18240 (8)	0.0261 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.025 (3)	0.028 (3)	0.028 (2)	0.003 (2)	0.000 (2)	−0.001 (2)
C2	0.023 (3)	0.025 (3)	0.031 (2)	0.000 (2)	−0.005 (2)	0.000 (2)
C3	0.038 (3)	0.025 (3)	0.029 (3)	0.004 (2)	0.000 (2)	−0.003 (2)
C4	0.027 (3)	0.030 (3)	0.039 (3)	0.009 (2)	−0.001 (2)	0.008 (2)
C5	0.027 (3)	0.037 (3)	0.025 (2)	−0.013 (2)	−0.005 (2)	0.006 (2)
C6	0.022 (3)	0.049 (3)	0.034 (3)	−0.009 (2)	−0.001 (2)	0.017 (2)
C7	0.028 (3)	0.036 (3)	0.036 (3)	−0.005 (2)	−0.003 (2)	0.016 (2)
C8	0.020 (3)	0.038 (3)	0.042 (3)	0.002 (2)	0.003 (2)	0.021 (2)
C9	0.019 (3)	0.033 (3)	0.030 (2)	0.002 (2)	−0.001 (2)	0.002 (2)
C10	0.017 (3)	0.057 (4)	0.032 (3)	−0.011 (2)	−0.001 (2)	−0.001 (2)
C11	0.031 (3)	0.030 (3)	0.031 (3)	−0.006 (2)	0.005 (2)	−0.004 (2)
C12	0.026 (3)	0.033 (3)	0.021 (2)	−0.004 (2)	0.001 (2)	−0.004 (2)
N1	0.023 (2)	0.026 (2)	0.025 (2)	−0.007 (2)	−0.006 (2)	0.009 (2)
N2	0.015 (2)	0.030 (2)	0.024 (2)	−0.006 (2)	−0.004 (2)	0.008 (2)
N3	0.015 (2)	0.025 (2)	0.019 (2)	−0.0020 (14)	−0.0016 (15)	−0.0022 (15)
O1	0.030 (2)	0.024 (2)	0.032 (2)	−0.0073 (14)	−0.0051 (15)	0.0011 (14)
O2	0.038 (2)	0.040 (2)	0.039 (2)	−0.016 (2)	−0.003 (2)	0.019 (2)
O3	0.031 (2)	0.047 (2)	0.032 (2)	−0.015 (2)	−0.003 (2)	−0.009 (2)
P1	0.0179 (6)	0.0185 (6)	0.0162 (5)	−0.0039 (4)	−0.0013 (4)	0.0036 (4)
S1	0.0257 (7)	0.0255 (6)	0.0214 (6)	0.0001 (5)	0.0016 (5)	0.0008 (4)
S2	0.0234 (7)	0.0262 (6)	0.0275 (6)	0.0035 (5)	−0.0016 (5)	0.0076 (5)

Geometric parameters (Å, º)

C1—N1	1.484 (6)	C7—H7B	0.99
C1—C2	1.500 (6)	C8—N2	1.463 (6)
C1—H1A	0.99	C8—H8A	0.99
C1—H1B	0.99	C8—H8B	0.99
C2—O1	1.421 (5)	C9—N3	1.466 (6)
C2—H2A	0.99	C9—C10	1.505 (6)
C2—H2B	0.99	C9—H9A	0.99
C3—O1	1.420 (6)	C9—H9B	0.99
C3—C4	1.495 (6)	C10—O3	1.441 (6)
C3—H3A	0.99	C10—H10A	0.99
C3—H3B	0.99	C10—H10B	0.99
C4—N1	1.487 (6)	C11—O3	1.417 (6)
C4—H4A	0.99	C11—C12	1.511 (6)
C4—H4B	0.99	C11—H11A	0.99
C5—N2	1.459 (5)	C11—H11B	0.99
C5—C6	1.500 (6)	C12—N3	1.470 (6)
C5—H5A	0.99	C12—H12A	0.99
C5—H5B	0.99	C12—H12B	0.99
C6—O2	1.424 (6)	N1—H1NA	0.87 (5)
C6—H6A	0.99	N1—H2NA	0.88 (5)
C6—H6B	0.99	N2—P1	1.676 (4)
C7—O2	1.426 (5)	N3—P1	1.667 (3)
C7—C8	1.516 (7)	P1—S2	1.987 (2)
C7—H7A	0.99	P1—S1	2.006 (2)
N1—C1—C2	108.5 (4)	H8A—C8—H8B	108.2
N1—C1—H1A	110.0 (2)	N3—C9—C10	109.5 (4)
C2—C1—H1A	110.0 (3)	N3—C9—H9A	109.8 (2)
N1—C1—H1B	110.0 (2)	C10—C9—H9A	109.8 (3)
C2—C1—H1B	110.0 (3)	N3—C9—H9B	109.8 (2)
H1A—C1—H1B	108.4	C10—C9—H9B	109.8 (3)
O1—C2—C1	111.1 (4)	H9A—C9—H9B	108.2
O1—C2—H2A	109.4 (2)	O3—C10—C9	110.6 (4)
C1—C2—H2A	109.4 (3)	O3—C10—H10A	109.5 (3)
O1—C2—H2B	109.4 (2)	C9—C10—H10A	109.5 (3)
C1—C2—H2B	109.4 (3)	O3—C10—H10B	109.5 (3)
H2A—C2—H2B	108.0	C9—C10—H10B	109.5 (3)
O1—C3—C4	111.3 (4)	H10A—C10—H10B	108.1
O1—C3—H3A	109.4 (2)	O3—C11—C12	110.3 (4)
C4—C3—H3A	109.4 (3)	O3—C11—H11A	109.6 (2)
O1—C3—H3B	109.4 (2)	C12—C11—H11A	109.6 (3)
C4—C3—H3B	109.4 (3)	O3—C11—H11B	109.6 (2)
H3A—C3—H3B	108.0	C12—C11—H11B	109.6 (3)
N1—C4—C3	108.7 (4)	H11A—C11—H11B	108.1
N1—C4—H4A	110.0 (3)	N3—C12—C11	109.9 (4)
C3—C4—H4A	110.0 (3)	N3—C12—H12A	109.7 (2)
N1—C4—H4B	110.0 (3)	C11—C12—H12A	109.7 (3)
C3—C4—H4B	110.0 (3)	N3—C12—H12B	109.7 (2)
H4A—C4—H4B	108.3	C11—C12—H12B	109.7 (3)
N2—C5—C6	109.5 (3)	H12A—C12—H12B	108.2
N2—C5—H5A	109.8 (3)	C1—N1—C4	110.6 (4)
C6—C5—H5A	109.8 (3)	C1—N1—H1NA	110 (3)
N2—C5—H5B	109.8 (2)	C4—N1—H1NA	110 (3)
C6—C5—H5B	109.8 (3)	C1—N1—H2NA	110 (3)
H5A—C5—H5B	108.2	C4—N1—H2NA	112 (3)
O2—C6—C5	112.0 (4)	H1NA—N1—H2NA	104 (4)
O2—C6—H6A	109.2 (3)	C5—N2—C8	109.6 (4)
C5—C6—H6A	109.2 (3)	C5—N2—P1	119.3 (3)
O2—C6—H6B	109.2 (2)	C8—N2—P1	118.3 (3)
C5—C6—H6B	109.2 (2)	C9—N3—C12	112.4 (3)
H6A—C6—H6B	107.9	C9—N3—P1	124.1 (3)
O2—C7—C8	110.5 (4)	C12—N3—P1	117.2 (3)
O2—C7—H7A	109.5 (2)	C3—O1—C2	109.7 (3)
C8—C7—H7A	109.5 (3)	C6—O2—C7	110.0 (3)
O2—C7—H7B	109.5 (3)	C11—O3—C10	110.2 (4)
C8—C7—H7B	109.5 (3)	N3—P1—N2	104.0 (2)
H7A—C7—H7B	108.1	N3—P1—S2	109.93 (15)
N2—C8—C7	109.6 (4)	N2—P1—S2	107.3 (2)
N2—C8—H8A	109.8 (2)	N3—P1—S1	109.2 (2)
C7—C8—H8A	109.8 (2)	N2—P1—S1	112.6 (2)
N2—C8—H8B	109.8 (3)	S2—P1—S1	113.43 (7)
C7—C8—H8B	109.8 (3)
N1—C1—C2—O1	−58.8 (5)	C1—C2—O1—C3	61.6 (5)
O1—C3—C4—N1	58.4 (5)	C5—C6—O2—C7	58.5 (5)
N2—C5—C6—O2	−57.9 (6)	C8—C7—O2—C6	−58.5 (6)
O2—C7—C8—N2	58.9 (5)	C12—C11—O3—C10	61.5 (5)
N3—C9—C10—O3	56.6 (5)	C9—C10—O3—C11	−61.8 (5)
O3—C11—C12—N3	−57.0 (5)	C9—N3—P1—N2	91.7 (4)
C2—C1—N1—C4	56.0 (5)	C12—N3—P1—N2	−58.2 (4)
C3—C4—N1—C1	−55.9 (5)	C9—N3—P1—S2	−153.7 (3)
C6—C5—N2—C8	57.2 (6)	C12—N3—P1—S2	56.4 (3)
C6—C5—N2—P1	−161.9 (4)	C9—N3—P1—S1	−28.7 (4)
C7—C8—N2—C5	−58.0 (5)	C12—N3—P1—S1	−178.6 (3)
C7—C8—N2—P1	160.6 (3)	C5—N2—P1—N3	164.8 (4)
C10—C9—N3—C12	−53.3 (5)	C8—N2—P1—N3	−57.5 (4)
C10—C9—N3—P1	155.5 (3)	C5—N2—P1—S2	48.4 (4)
C11—C12—N3—C9	53.5 (5)	C8—N2—P1—S2	−174.0 (3)
C11—C12—N3—P1	−153.2 (3)	C5—N2—P1—S1	−77.1 (4)
C4—C3—O1—C2	−61.4 (5)	C8—N2—P1—S1	60.5 (4)