The molecular structure of the title compound, Cy2P(=S)C(=S)N(H)Ph (Cy is cyclohexyl) or C19H28NPS2, is virtually identical to that found in the previously reported triclinic polymorph. Thus, the conformation about the C-N bond is Z and the dimensions defining the central P(=S)C(=S)NC group in both forms are experimentally equivalent.
Supporting information
CCDC reference: 162815
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.004 Å
- R factor = 0.040
- wR factor = 0.028
- Data-to-parameter ratio = 15.1
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Crystals of the title compound (Ojima et al., 1969) were isolated by slow
evaporation of a CH2Cl2 solution at room temperature (m. p. 382–385 K).
Data collection: MSC/AFC Diffractometer Control Software
(Molecular Structure Corporation, 1996); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1992); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: TEXSAN; molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN.
Crystal data top
C19H28NPS2 | F(000) = 784 |
Mr = 365.53 | Dx = 1.210 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.7107 Å |
a = 10.074 (1) Å | Cell parameters from 25 reflections |
b = 18.139 (2) Å | θ = 11.0–12.2° |
c = 11.3858 (9) Å | µ = 0.35 mm−1 |
β = 105.426 (8)° | T = 293 K |
V = 2005.6 (3) Å3 | Prismatic, yellow |
Z = 4 | 0.25 × 0.20 × 0.15 mm |
Data collection top
Rigaku AFC-7R diffractometer | Rint = 0.025 |
Radiation source: Rigaku rotating anode | θmax = 30.1°, θmin = 2.7° |
Graphite monochromator | h = 0→14 |
ω–2θ scans | k = 0→25 |
6358 measured reflections | l = −16→15 |
6054 independent reflections | 3 standard reflections every 150 reflections |
3143 reflections with I > 2σ(I) | intensity decay: 0.6% |
Refinement top
Refinement on F | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.040 | H-atom parameters constrained |
wR(F2) = 0.028 | w = 1/[σ2(Fo) + 0.004|Fo|2] |
S = 1.69 | (Δ/σ)max < 0.001 |
3143 reflections | Δρmax = 0.21 e Å−3 |
208 parameters | Δρmin = −0.16 e Å−3 |
Crystal data top
C19H28NPS2 | V = 2005.6 (3) Å3 |
Mr = 365.53 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.074 (1) Å | µ = 0.35 mm−1 |
b = 18.139 (2) Å | T = 293 K |
c = 11.3858 (9) Å | 0.25 × 0.20 × 0.15 mm |
β = 105.426 (8)° | |
Data collection top
Rigaku AFC-7R diffractometer | Rint = 0.025 |
6358 measured reflections | 3 standard reflections every 150 reflections |
6054 independent reflections | intensity decay: 0.6% |
3143 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.028 | H-atom parameters constrained |
S = 1.69 | Δρmax = 0.21 e Å−3 |
3143 reflections | Δρmin = −0.16 e Å−3 |
208 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.39714 (8) | 0.20810 (4) | 0.11082 (7) | 0.0586 (2) | |
S2 | 0.28158 (7) | 0.06445 (4) | 0.40850 (6) | 0.0547 (2) | |
P1 | 0.39855 (6) | 0.09220 (3) | 0.30227 (6) | 0.0385 (2) | |
N1 | 0.2560 (2) | 0.21695 (10) | 0.2808 (2) | 0.0435 (6) | |
C1 | 0.3403 (2) | 0.1822 (1) | 0.2265 (2) | 0.0379 (6) | |
C2 | 0.1907 (2) | 0.2870 (1) | 0.2620 (2) | 0.0410 (7) | |
C3 | 0.2116 (2) | 0.3395 (1) | 0.1811 (2) | 0.0480 (8) | |
C4 | 0.1426 (3) | 0.4062 (1) | 0.1726 (2) | 0.0581 (9) | |
C5 | 0.0542 (3) | 0.4210 (1) | 0.2427 (3) | 0.0632 (9) | |
C6 | 0.0348 (3) | 0.3688 (2) | 0.3238 (3) | 0.067 (1) | |
C7 | 0.1021 (3) | 0.3019 (1) | 0.3345 (2) | 0.0550 (9) | |
C8 | 0.5784 (2) | 0.1064 (1) | 0.3875 (2) | 0.0412 (7) | |
C9 | 0.5899 (3) | 0.1720 (1) | 0.4746 (2) | 0.0519 (8) | |
C10 | 0.7367 (3) | 0.1806 (1) | 0.5543 (2) | 0.0645 (9) | |
C11 | 0.8383 (3) | 0.1882 (1) | 0.4780 (3) | 0.0662 (9) | |
C12 | 0.8283 (3) | 0.1227 (2) | 0.3930 (3) | 0.069 (1) | |
C13 | 0.6824 (3) | 0.1133 (1) | 0.3107 (2) | 0.0572 (9) | |
C14 | 0.3931 (2) | 0.0270 (1) | 0.1799 (2) | 0.0407 (7) | |
C15 | 0.2473 (3) | 0.0170 (1) | 0.0981 (2) | 0.0551 (8) | |
C16 | 0.2462 (3) | −0.0380 (2) | −0.0042 (2) | 0.0664 (10) | |
C17 | 0.3101 (3) | −0.1115 (1) | 0.0461 (3) | 0.0658 (10) | |
C18 | 0.4526 (3) | −0.1022 (1) | 0.1302 (3) | 0.0620 (9) | |
C19 | 0.4538 (3) | −0.0476 (1) | 0.2319 (2) | 0.0525 (8) | |
H1 | 0.2361 | 0.1900 | 0.3435 | 0.0521* | |
H2 | 0.2725 | 0.3301 | 0.1319 | 0.0576* | |
H3 | 0.1568 | 0.4425 | 0.1170 | 0.0697* | |
H4 | 0.0070 | 0.4668 | 0.2353 | 0.0758* | |
H5 | −0.0257 | 0.3788 | 0.3731 | 0.0800* | |
H6 | 0.0881 | 0.2661 | 0.3910 | 0.0660* | |
H7 | 0.6052 | 0.0631 | 0.4383 | 0.0495* | |
H8 | 0.5631 | 0.2166 | 0.4274 | 0.0622* | |
H9 | 0.5287 | 0.1641 | 0.5264 | 0.0622* | |
H10 | 0.7419 | 0.2243 | 0.6044 | 0.0774* | |
H11 | 0.7608 | 0.1376 | 0.6061 | 0.0774* | |
H12 | 0.8183 | 0.2330 | 0.4300 | 0.0795* | |
H13 | 0.9309 | 0.1908 | 0.5315 | 0.0795* | |
H14 | 0.8911 | 0.1302 | 0.3426 | 0.0825* | |
H15 | 0.8542 | 0.0784 | 0.4414 | 0.0825* | |
H16 | 0.6785 | 0.0691 | 0.2619 | 0.0686* | |
H17 | 0.6589 | 0.1558 | 0.2576 | 0.0686* | |
H18 | 0.4499 | 0.0464 | 0.1303 | 0.0488* | |
H19 | 0.1883 | −0.0012 | 0.1466 | 0.0661* | |
H20 | 0.2129 | 0.0642 | 0.0626 | 0.0661* | |
H21 | 0.1517 | −0.0463 | −0.0508 | 0.0797* | |
H22 | 0.2981 | −0.0175 | −0.0570 | 0.0797* | |
H23 | 0.2517 | −0.1347 | 0.0908 | 0.0790* | |
H24 | 0.3157 | −0.1428 | −0.0214 | 0.0790* | |
H25 | 0.4850 | −0.1496 | 0.1660 | 0.0745* | |
H26 | 0.5137 | −0.0844 | 0.0834 | 0.0745* | |
H27 | 0.5479 | −0.0403 | 0.2801 | 0.0630* | |
H28 | 0.3994 | −0.0673 | 0.2833 | 0.0630* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0833 (5) | 0.0449 (4) | 0.0609 (4) | 0.0122 (4) | 0.0422 (4) | 0.0146 (3) |
S2 | 0.0665 (5) | 0.0497 (4) | 0.0583 (4) | 0.0028 (4) | 0.0345 (4) | 0.0140 (3) |
P1 | 0.0460 (4) | 0.0315 (3) | 0.0410 (3) | 0.0029 (3) | 0.0170 (3) | 0.0051 (3) |
N1 | 0.049 (1) | 0.041 (1) | 0.047 (1) | 0.0076 (10) | 0.0221 (10) | 0.0105 (9) |
C1 | 0.041 (1) | 0.033 (1) | 0.041 (1) | 0.003 (1) | 0.013 (1) | 0.004 (1) |
C2 | 0.036 (1) | 0.038 (1) | 0.048 (1) | 0.005 (1) | 0.008 (1) | −0.002 (1) |
C3 | 0.047 (2) | 0.040 (1) | 0.060 (2) | 0.007 (1) | 0.020 (1) | 0.003 (1) |
C4 | 0.060 (2) | 0.038 (1) | 0.075 (2) | 0.006 (1) | 0.015 (2) | 0.005 (1) |
C5 | 0.058 (2) | 0.048 (2) | 0.080 (2) | 0.015 (1) | 0.012 (2) | −0.008 (2) |
C6 | 0.055 (2) | 0.072 (2) | 0.077 (2) | 0.020 (2) | 0.025 (2) | −0.008 (2) |
C7 | 0.052 (2) | 0.057 (2) | 0.062 (2) | 0.009 (1) | 0.026 (1) | 0.007 (1) |
C8 | 0.045 (1) | 0.032 (1) | 0.047 (1) | 0.006 (1) | 0.012 (1) | 0.004 (1) |
C9 | 0.059 (2) | 0.042 (2) | 0.053 (2) | 0.005 (1) | 0.012 (1) | −0.006 (1) |
C10 | 0.069 (2) | 0.051 (2) | 0.065 (2) | 0.001 (2) | 0.003 (2) | −0.007 (1) |
C11 | 0.054 (2) | 0.046 (2) | 0.090 (2) | −0.002 (1) | 0.003 (2) | 0.001 (2) |
C12 | 0.048 (2) | 0.063 (2) | 0.096 (2) | 0.000 (1) | 0.022 (2) | −0.009 (2) |
C13 | 0.050 (2) | 0.059 (2) | 0.067 (2) | 0.000 (1) | 0.023 (1) | −0.008 (1) |
C14 | 0.049 (2) | 0.033 (1) | 0.042 (1) | −0.001 (1) | 0.017 (1) | 0.001 (1) |
C15 | 0.058 (2) | 0.045 (2) | 0.059 (2) | 0.000 (1) | 0.010 (1) | −0.001 (1) |
C16 | 0.073 (2) | 0.056 (2) | 0.062 (2) | −0.007 (2) | 0.006 (2) | −0.009 (1) |
C17 | 0.082 (2) | 0.044 (2) | 0.073 (2) | −0.013 (2) | 0.025 (2) | −0.014 (1) |
C18 | 0.075 (2) | 0.038 (1) | 0.075 (2) | 0.001 (1) | 0.025 (2) | −0.008 (1) |
C19 | 0.060 (2) | 0.037 (1) | 0.061 (2) | 0.005 (1) | 0.018 (1) | 0.000 (1) |
Geometric parameters (Å, º) top
S1—C1 | 1.639 (2) | C8—C9 | 1.534 (3) |
S2—P1 | 1.9655 (8) | C8—C13 | 1.538 (3) |
P1—C1 | 1.866 (2) | C9—C10 | 1.524 (3) |
P1—C8 | 1.832 (2) | C10—C11 | 1.514 (4) |
P1—C14 | 1.817 (2) | C11—C12 | 1.518 (4) |
N1—C1 | 1.334 (3) | C12—C13 | 1.528 (3) |
N1—C2 | 1.420 (3) | C14—C15 | 1.527 (3) |
C2—C3 | 1.380 (3) | C14—C19 | 1.537 (3) |
C2—C7 | 1.393 (3) | C15—C16 | 1.532 (3) |
C3—C4 | 1.387 (3) | C16—C17 | 1.524 (4) |
C4—C5 | 1.371 (3) | C17—C18 | 1.509 (4) |
C5—C6 | 1.372 (4) | C18—C19 | 1.522 (3) |
C6—C7 | 1.380 (3) | | |
| | | |
S1···C9i | 3.536 (2) | | |
| | | |
S2—P1—C1 | 110.00 (7) | C12—C11—H12 | 109.2 |
S2—P1—C8 | 112.35 (8) | C12—C11—H13 | 109.2 |
S2—P1—C14 | 113.86 (8) | H12—C11—H13 | 109.5 |
C1—P1—C8 | 105.51 (10) | C11—C12—C13 | 111.6 (2) |
C1—P1—C14 | 105.85 (10) | C11—C12—H14 | 108.9 |
C8—P1—C14 | 108.7 (1) | C11—C12—H15 | 108.9 |
C1—N1—C2 | 132.8 (2) | C13—C12—H14 | 108.9 |
C1—N1—H1 | 113.6 | C13—C12—H15 | 108.9 |
C2—N1—H1 | 113.6 | H14—C12—H15 | 109.5 |
S1—C1—P1 | 119.2 (1) | C8—C13—C12 | 110.5 (2) |
S1—C1—N1 | 129.6 (2) | C8—C13—H16 | 109.2 |
P1—C1—N1 | 111.1 (2) | C8—C13—H17 | 109.2 |
N1—C2—C3 | 124.8 (2) | C12—C13—H16 | 109.2 |
N1—C2—C7 | 115.4 (2) | C12—C13—H17 | 109.2 |
C3—C2—C7 | 119.8 (2) | H16—C13—H17 | 109.5 |
C2—C3—C4 | 119.1 (2) | P1—C14—C15 | 111.9 (2) |
C2—C3—H2 | 120.4 | P1—C14—C19 | 110.5 (2) |
C4—C3—H2 | 120.4 | P1—C14—H18 | 108.0 |
C3—C4—C5 | 121.4 (2) | C15—C14—C19 | 110.5 (2) |
C3—C4—H3 | 119.3 | C15—C14—H18 | 108.0 |
C5—C4—H3 | 119.3 | C19—C14—H18 | 108.0 |
C4—C5—C6 | 119.2 (2) | C14—C15—C16 | 110.6 (2) |
C4—C5—H4 | 120.4 | C14—C15—H19 | 109.2 |
C6—C5—H4 | 120.4 | C14—C15—H20 | 109.2 |
C5—C6—C7 | 120.8 (2) | C16—C15—H19 | 109.2 |
C5—C6—H5 | 119.6 | C16—C15—H20 | 109.2 |
C7—C6—H5 | 119.6 | H19—C15—H20 | 109.5 |
C2—C7—C6 | 119.7 (2) | C15—C16—C17 | 111.6 (2) |
C2—C7—H6 | 120.2 | C15—C16—H21 | 109.0 |
C6—C7—H6 | 120.2 | C15—C16—H22 | 109.0 |
P1—C8—C9 | 110.2 (2) | C17—C16—H21 | 108.9 |
P1—C8—C13 | 116.0 (2) | C17—C16—H22 | 108.9 |
P1—C8—H7 | 106.3 | H21—C16—H22 | 109.5 |
C9—C8—C13 | 111.0 (2) | C16—C17—C18 | 112.1 (2) |
C9—C8—H7 | 106.3 | C16—C17—H23 | 108.8 |
C13—C8—H7 | 106.3 | C16—C17—H24 | 108.8 |
C8—C9—C10 | 111.0 (2) | C18—C17—H23 | 108.8 |
C8—C9—H8 | 109.1 | C18—C17—H24 | 108.8 |
C8—C9—H9 | 109.1 | H23—C17—H24 | 109.5 |
C10—C9—H8 | 109.1 | C17—C18—C19 | 111.7 (2) |
C10—C9—H9 | 109.1 | C17—C18—H25 | 108.9 |
H8—C9—H9 | 109.5 | C17—C18—H26 | 108.9 |
C9—C10—C11 | 111.4 (2) | C19—C18—H25 | 108.9 |
C9—C10—H10 | 109.0 | C19—C18—H26 | 108.9 |
C9—C10—H11 | 109.0 | H25—C18—H26 | 109.5 |
C11—C10—H10 | 109.0 | C14—C19—C18 | 111.0 (2) |
C11—C10—H11 | 109.0 | C14—C19—H27 | 109.1 |
H10—C10—H11 | 109.5 | C14—C19—H28 | 109.1 |
C10—C11—C12 | 110.7 (2) | C18—C19—H27 | 109.1 |
C10—C11—H12 | 109.2 | C18—C19—H28 | 109.1 |
C10—C11—H13 | 109.2 | H27—C19—H28 | 109.5 |
Symmetry code: (i) x, −y+1/2, z−1/2. |
Experimental details
Crystal data |
Chemical formula | C19H28NPS2 |
Mr | 365.53 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 10.074 (1), 18.139 (2), 11.3858 (9) |
β (°) | 105.426 (8) |
V (Å3) | 2005.6 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.35 |
Crystal size (mm) | 0.25 × 0.20 × 0.15 |
|
Data collection |
Diffractometer | Rigaku AFC-7R diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6358, 6054, 3143 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.706 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.028, 1.69 |
No. of reflections | 3143 |
No. of parameters | 208 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.16 |
Compounds of the general formula R2P(Y)C(═S)N(H)R' (where R, R' = alkyl or aryl, and Y = 0, O, S or Se) are known to adopt of a variety of coordination modes in both their neutral and deprotonated forms (Siasios & Tiekink, 1996a,b; Horn et al., 2000). Consequently, systematic structural studies have been conducted on these ligands (Cowan et al., 1984; Siasios & Tiekink, 1994, 1995a,b). The structure of the title compound, Cy2P(═S)C(═S)N(H)Ph, (I), represents a second polymorph, a triclinic form having been determined previously (Siasios & Tiekink, 1994).
The key geometric parameters defining the P(S)C(S)NC chromphore [e.g. P1—S2 1.9655 (8) Å, C1—S1 1.639 (2) Å, P1—C1 1.866 (2) Å, N1—C1 1.334 (3) Å and S2—P1—C1—S1 - 166.1 (1)°] are equal within experimental error to those in the triclinic form (Siasios & Tiekink, 1994). The major difference between the polymorphs is found in the relative orientations of the cyclohexyl rings. Thus, whilst the P(S)C(S)N(H)Ph portions of the molecules are essentially superimposable in the two forms, the cyclohexyl groups are not. Referring to Fig. 1, it can be seen that the methine H atom bound to C8 is directed towards the same side of the molecule as S2, and the C14 H atom is directed towards the same side as the S1 atom. Opposite orientations are observed in the triclinic form (Siasios & Tiekink, 1994).