Synthesis and characterization of diaminodithio- and aminotrithiophosphoric acid esters

Article abstract of DOI:10.1080/10426500601160694

The synthesis and characterization of a series of five new diaminodithiophosphoric acid esters (R1R2N)2P(S)SR and five new aminotrithiophosphoric acid esters (R1R2N)P(S)(SR)2 are described. The structure of two of these compounds, the diaminodithio deriva

Full text of DOI:10.1080/10426500601160694

Phosphorus, Sulfur, and Silicon, 182:1233–1244, 2007
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500601160694
Synthesis and Characterization of Diaminodithio-
and Aminotrithiophosphoric Acid Esters
Patrice Marchand
Anca Meffre
Bruno Donnadieu
Laboratoire de Chimie de Coordination du CNRS,
Toulouse Cedex, France
Daniel Taton
Yves Gnanou
Laboratoire de Chimie des Polyme`res Organiques, ENSCPB,
Pessac Cedex, France
Mathias Destarac
´
´
Frederic Leising
Rhodia, Centre de Recherches d’Aubervilliers,
Aubervilliers Cedex, France
Anne-Marie Caminade
Jean-Pierre Majoral
Laboratoire de Chimie de Coordination du CNRS,
Toulouse Cedex, France
The synthesis and characterization of a series of five new diaminodithiophospho-
1
2
ric acid esters (R R N) P(S)SR and five new aminotrithiophosphoric acid esters
2
1
2
(R R N)P(S)(SR) are described. The structure of two of these compounds, the
2
diaminodithio derivative (iPr N) P(S)SCH Ph and the aminotrithio derivative
2
2
2
(iPr N)P(S)(SCH Ph) , has been determined by single crystal X-ray diffraction.
2
2
2
These series of compounds are potentially usable as agents for reversible addition-
fragmentation chain transfer polymerization.
Keywords Aminotrithiophosphoric acid esters; amines; diaminodithiophosphoric acid
esters; reversible addition-fragmentation chain transfer (RAFT) agents; thiols
Received February 14, 2006; accepted October 25, 2006.
Financial support by Rhodia, France, is gratefully acknowledged.
Address correspondence to Anne-Marie Caminade, Laboratoire de Chimie de Coor-
dination du CNRS, 205 route de Narbonne, 31077 Toulouse Cedex 4, France. E-mail:
caminade@lcc-toulouse.fr
1233

1234
P. Marchand et al.
I. INTRODUCTION
Thiocarbonyl thio compounds S C(Z)SR are the most effective agents
for the Reversible Addition-Fragmentation Chain Transfer (RAFT) pro-
cess, which is used to produce narrow polydispersity polymers.1 RAFT
polymerizations are applicable to a wide variety of monomers and re-
action conditions, and afford the possibility to finally control the molec-
ular weight and macromolecular architectures (block copolymers, star
polymers from dendrimers,2 etc.). Both Z and R substituents of the
thiocarbonyl thio compounds have been shown to have a tremendous
importance on the efficiency of the RAFT process.3
Recently, it has been demonstrated by some of us that dithioesters
can be directly generated using tetrathiophosphates;4 whether these
thiophosphates themselves can be considered as RAFT agents or not re-
mained unclear. However, taking into account the analogy often demon-
strated between phosphorus and carbon,5 we decided to synthesize
a series of phosphorus analogs of thiocarbonyl thio compounds, i.e.,
S P(Z1)(Z2)SR, in which the Z1, Z2, and R substituents can be varied.
Obviously, phosphorus derivatives possess one substituent more than
carbon analogs, offering a larger palette of modifications, which should
enable a subtle balance between the effects of Z1, Z2, and R substituents.
We decided to synthesize a large series of compounds in which none, one,
or two of the Z substituents are also SR groups. A brief survey of the
literature concerning these types of compounds shows that cases Z1 =
Z2 = OR, SR, or CR3 are well known; an example of the last two cases
was already reported to be able to control radical polymerizations.6 On
the other hand, examples of such compounds in which Z1 = NR1R2 and
Z2 = SR or Z1 = Z2 = NR1R2 are less known. Here we report the synthe-
sis of all the previously unknown types of compounds, which we have
prepared in view of the search for new RAFT agents; all of them are
amino derivatives.
II. RESULTS AND DISCUSSION
Many dithio or trithio derivatives of phosphorus are synthesized start-
ing from P4S3, P4S10, Davy’s or Lawesson’s reagent, or S PX3, i.e., from
reagents possessing already PS linkages. In first attempts, we tried to
use such reagents for obtaining S P(NR1R2)2SR and S P(NR1R2)(SR)2
derivatives, but in our hands, they did not provide the desired com-
pounds with a sufficiently good yield and purity. On the other hand, PCl3
appears as a more powerful and versatile reagent, particularly when
bulky or poorly reactive substituents are to be used. The first family of

Diaminodithio- and Aminotrithiophosphoric Acid Esters
1235
SCHEME 1
compounds we synthesized using a one-pot process starting from PCl3
belongs to the diaminodithiophosphoric acid ester series (Scheme 1).
The first substitution reaction might be carried out to introduce
either one SR or two NR1R2 substituents. The second possibility ap-
pears as the most suitable, because it leads to relatively stable di-
aminochlorophosphines of type 1. The substituents on nitrogen were
chosen in order to have a maximal diversity with a small number of
compounds. An alkyl (1a),7 an aryl (1c),8 and a cyclic (1d)9 derivative
were obtained using known procedures. These compounds can be either
isolated or used directly in a one-pot process.
The second substitution reaction was carried out at low tempera-
ture with three different thiols: a “linear” alkylthiol, leading to 2a,
2c, and 2d; a functionalized branched alkythiol leading to 2b; and an
arylthiol leading to 2e. It is important to use a strictly stoichiometric
amount of the thiol (or even a slight deficiency) to avoid the replace-
ment of one amino group by the highly nucleophilic thiol. This prob-
lem was not observed in cases d and e, where the cyclic substituent
precluded the breaking of the P N bonds. The reaction was only mon-
itored by 31P NMR, and no attempt was made to isolate these new
tricoordinated phosphorus compounds. Finally, S8 was added to all the

1236
P. Marchand et al.
˚
FIGURE 1 ORTEP drawing of compound 3a. Selected bond lengths (A)
and angles (deg.): S(2)-P(1) 1.948(1); S(1)-P(1) 2.123(1); P(1)-N(1) 1.655(1);
P(1)-N(2) 1.667(1); N(1)-P(1)-N(2) 104.6(1); S(2)-P(1)-S(1) 111.6(1); N(1)-P(1)-
S(1) 106.8(1); N(1)-P(1)-S(2) 113.9(1); N(2)-P(1)-S(1) 101.1(1); N(2)-P(1)-S(2)
117.6(1).
samples, either at r.t. or at −20◦C. The completion of the reactions is
shown again by 31P NMR. The R1, R2, and R substituents had only
a weak influence on δ31P (84–92 ppm); even the chemical shift of the
cyclic derivatives was in the same range. Besides 31P NMR, these com-
pounds were also characterized by 1H and 13C NMR, as well as elemen-
tal analyses. Furthermore, single crystals suitable for X-ray diffraction
studies were obtained for compound 3a from ethanol at −30◦C. The
ORTEP drawing is shown in Figure 1, the crystallographic data are
summarized in Table I. All bond lengths were in the expected range.
However, a slight interaction was detected between the sulphur of the
thiophosphoryl group and a proton of the benzylic group. The distance
. . .
˚
S2 H2a = 2.63(26) A was smaller than the sum of van der Waals
˚
radii (2.8 A). Furthermore, the X-ray structure showed that the acces-
sibility to S2 was relatively hindered by the bulky diisopropylamino
substituents.

Diaminodithio- and Aminotrithiophosphoric Acid Esters
1237
TABLE I Crystal Data and Structure Refinement for 3a and 7f
3a
7f
Formula
M. W.
C19H35N2PS2
386.58
C20H28NPS3
409.58
Temperature (K)
Crystal system
Space group
160(2)
Monoclinic
P 21/a
a = 15.4247(12)
b = 9.1409(7)
c = 16.4146(13)
106.382(9)
2220.4(3)
180(2)
Monoclinic
P 21/c
a = 8.754(2)
b = 14.366(2)
c = 17.670(6)
91.61(4)
2221.4(10)
4
˚
a/A
˚
b/A
˚
c/A
β/◦
3
˚
V/A
Z
4
Density (calculated)
Absorption Coeff./mm−1
F(000)
1.156
0.316
840
0.32 × 0.13 × 0.09
2.58 to 26.02
−18 ≤ h ≤ 18
−11 ≤ k ≤ 11
−20 ≤ l ≤ 20
16357
1.225
0.409
872
0.24 × 0.12 × 0.08
2.31 to 24.40
−10 ≤ h ≤ 10
−16 ≤ k ≤ 16
−20 ≤ l ≤ 20
14438
Crystal size/mm3
θ range for data collect./◦
Index ranges
Reflections collected
Independent reflections
Max./min. transmission
Data/restraints/parameters
Goodness-of-fit on F2
4211 [R(int) = 0.0309]
0.9721/09057
4211/0/232
1.028
3612 [R(int) = 0.1485]
0.9680/0.9082
3612/0/230
0.925
Final Rindices [I > 2sigma(I)]
R1 = 0.0304,
wR2 = 0.0743
R1 = 0.0387,
wR2 = 0.0779
R1 = 0.0585,
wR2 = 0.1441
R1 = 0.1106
wR2 = 0.1766
Rindices (all data)
−3
−3
˚
˚
Largest diff. peak and hole
0.306 and −0.282 e. A
0.332 and −0.491 e. A
Obviously, the oxides corresponding to compounds 3 could be ob-
tained by using an oxidant such as H2O2 in the last step instead of
S8. We have carried out the experiment with 2a, to finally isolate ox-
ide 4a (Scheme 2). This compound might serve as a negative probe
SCHEME 2

1238
P. Marchand et al.
for the control of RAFT polymerizations, since carbonylthio derivatives
(O C(Z)SR) have no activity in the RAFT process.
A second series of experiments analogous to those shown in Scheme 1
was then carried out using only one equivalent of amine (instead of two
equivalents). In this case, alkyl (5f) and phenyl (5h, 5j) substituents
were used. These compounds are characterized only by 31P NMR of
the crude product and were directly used in a one-pot process, reacting
with two equivalents of linear or branched thiols at low temperature.
A strictly stoichiometric amount of thiols were needed to minimize the
substitution of the amino groups by thiol. Compounds 6f–6j were not
isolated but were reacted directly with S8 at r.t. to afford compounds
7f–7j (Scheme 3).
SCHEME 3
Compounds 7f–7j were first characterized by 31P NMR; here again,
all the chemical shifts were in the same range (88–100 ppm). Two sig-
nals in a 1/1 ratio were observed for 7g (and also for 6g), corresponding
to two diastereomers due to the presence of two asymmetric carbon
1
atoms. H NMR spectra of all compounds 7, except 7g, indicated, the
presence of diastereotopy for both protons of the CH2 group of the R
substituents. Single crystals suitable for X-ray diffraction studies were
obtained for compound 7f from ethanol at –30◦C. The ORTEP drawing
is shown in Figure 2. All bond lengths were in the expected range and
correlated well with those found for 3a. No interaction was detected
between S3 and the benzyl group in the structure of 7f, and access to
S3 appeared easier than for 3a.
This series of 10 new monoaminotrithio and diaminodithio deriva-
tives of phosphorus pertains to a larger series of thiophosphorus deriva-
tives that have been tested as agents for RAFT polymerizations.10

Diaminodithio- and Aminotrithiophosphoric Acid Esters
1239
˚
FIGURE 2 ORTEP drawing of compound 7f. Selected bond lengths (A) and
angles (deg.): P(1)-S(3) 1.940(2); P(1)-S(1) 2.103(2); P(1)-S(2) 2.105(2); P(1)-N(1)
1.643(4); S(3)-P(1)-S(1) 112.2(1); S(3)-P(1)-S(2) 114.5(1); S(2)-P(1)-S(1) 100.6(1);
N(1)-P(1)-S(3) 118.2(1); N(1)–P(1)-S(2) 102.4(2); N(1)-P(1)-S(1) 107.1(2).
III. EXPERIMENTAL
All manipulations were carried out using standard high vacuum and
dry-argon techniques. 1H, 13C, and 31P NMR spectra were recorded
with Bruker AC 200, AC 250, or DPX 300 spectrometers. References
for NMR chemical shifts are 85% H3PO4 for 31P and SiMe4 for 1H
and 13C. The assignment of the 13C NMR signals has been done us-
ing J
experiments. Solvents were dried and distilled prior to use
mod
(THF over sodium/benzophenone, CH2Cl2 over phosphorus pentoxide)
and degassed when phosphines were used.
a. Procedure for Preparation of Compounds 3
The diaminochlorophosphines 1a,c,d were prepared from PCl3 and the
corresponding amine; they were either isolated or used crudely. A slight

1240
P. Marchand et al.
deficiency of thiol (0.95 equiv.) was added dropwise to a solution of
1a,c,d (1 equiv.) and NEt3 (0.95 equiv.) either in THF at −78◦C or in
CH2Cl2 (30 mL per g of 1a,c,d in both cases) at −50◦C. The resulting
mixture was allowed to reach r.t. overnight; then it was cooled again
at −20◦C, and a slight excess of S8 (1.1 equiv.) was added. The reac-
tion needed 2 to 72 h to go to completion. After filtration, the solution
was poured into the same volume of aqueous HCl (10%) and then ex-
tracted with diethylether (five times the amount of water). The organic
phases were recovered and washed with a saturated solution of K2CO3
or Na2CO3 (same amount of water as previously), dried over MgSO4,
filtered, and evaporated to dryness. Compounds 3a, 3d, and 3e were
obtained as crystalline white powders; compounds 3b and 3c were ob-
tained as thick pale yellow oils. The yields that follow are the overall
yields from PCl3.
1
3a: (50% yield) 31P{ H} NMR (CDCl3): 84.5; 1H NMR (CDCl3): 1.33
3
3
(d, J = 6.9 Hz, 12H, CH3), 1.42 (d, J = 6.9 Hz, 12H, CH3), 3.84
HH
HH
(sept of d, 3 J
=
3 J = 6.9 Hz, 4H, CH), 4.17 (d, J = 9.5 Hz, 2H,
3
HH
PH
PH
CH2), 7.34 (m, 5H, C6H5); 13C{ H} NMR (CDCl3): 22.4 (s, CH3), 23.5 (s,
1
CH3), 38.5 (s, CH2), 47.2 (d, 2 J = 4.7 Hz, CH), 127.0 (s, CAr), 128.3
PC
(s, CAr), 129.2 (s, CAr), 137.2 (d,3 J = 9.8 Hz, Ci ); anal. calcd. for
PC
Ar
C19H35N2PS2 (386.6): C, 59.03; H, 9.13; N, 7.25; found: C, 59.12; H,
9.17; N, 7.14.
3b: (48% yield): 31P{ H} NMR (CDCl3): 84.6; 1H NMR (CDCl3): 1.26
1
(m, 27H, CH3), 1.55 (d, 3 J = 7.2 Hz, 3H, CH3CHS), 3.77 (sept of d,
HH
3 J
=
3 J = 6.7 Hz, 4H, CHN), 4.16 (m, 3H, CH2O, CHS); 13C{ H}
1
HH
PH
NMR (CDCl3): 14.1 (s, CH3CH2O), 20.2 (d, 3 J = 3.8 Hz, CH3CHS),
PC
22.4 (d, 3 J = 4.3 Hz, CH3CHN), 23.6 (d,3 J = 3.3 Hz, CH3CHN), 45.7
PC
PC
(s, CHS), 47.4 (d, 2 J = 3.8 Hz, CHN), 47.5 (d, 2 J = 3.9 Hz, CHN),
PC
PC
61.1 (s, CH2O), 173.1 (s, CO2Et).
3c: (55% yield): 31P{ H} NMR (CDCl3): 91.1; 1H NMR (CDCl3): 3.12
1
(d, 3 J = 11.9 Hz, 6H, CH3N), 3.97 (d, 3 J = 13.2 Hz, 2H, CH2S), 7.32
PH
PH
(m, 15H, HAr); 13C{ H} NMR (CDCl3): 38.6 (s, CH2S), 39.6 (d, 2 J = 4.7
1
Hz, CH3N), 126.3 (s, CpArN), 127.3 (s, CAprC), 127.7 (d, 3 J =P4C.0 Hz,
PC
CoArN), 128.5 (s, CAo rC), 128.8 (s, CAmrN), 129.2 (s, CmArC), 137.5 (d, 3 J = 2.0
PC
Hz, CiArC), 145.1 (d, J = 2.8 Hz, Ci ); anal. calcd for C21H23N2PS2
2
PC
ArN
(398.5): C, 63.29; H, 5.82; N, 7.03; found: C, 63.43; H, 5.94; N, 6.91.
3d: (48% yield): 31P{ H} NMR (CDCl3): 91.8; 1H NMR (CDCl3): 2.56
1
3
3
(d, J = 13.5 Hz, 6H, CH3N), 3.1 (m, 4H, CH2N), 3.9 (d, J = 15.1
PH
PH
Hz, 2H, CH2S), 7.3 (m, 5H, Ph); 13C{ H} NMR (CDCl3): 31.4 (d,
1
2 J = 7.1 Hz, CH3), 38.9 (s, CH2S), 48.3 (d, 2 J = 7.0 Hz, CH2N),
PC
PC
127.4 (s, CAr), 128.5 (s, CAr), 128.8 (s, CAr), 138.2 (s, CiAr); anal. calcd
for C11H17N2PS2 (272.4): C, 48.51; H, 6.29; N, 10.29; found: C, 48.59; H,
6.35; N, 10.22.

Diaminodithio- and Aminotrithiophosphoric Acid Esters
1241
1
3e: (50% yield): 31P{ H} NMR (CDCl3): 85.0; 1H NMR (CDCl3): 2.42
3
(m, 2H, CH2), 2.78 (d, J = 12.7 Hz, 6H, CH3N), 2.98 (m, 2H, CH2),
PH
1
2
7.4 (m, 5H, Ph); 13C{ H} NMR (CDCl3): 31.2 (d, J = 7.9 Hz, CH3),
PC
47.8 (d, 2 J = 7.0 Hz, CH2N), 128.8 (s, CAr), 128.9 (s, CAr), 129.1 (s,
PC
CAr), 135.2 (s, Ci ); anal. calcd for C10H15N2PS2 (258.3): C, 46.49; H,
5.85; N, 10.84. foAurnd; C, 46.55; H, 5.89; N, 10.78.
b. Synthesis of Compound 4a
To a crude solution of 2a (0.50 g) in THF (10 mL) cooled at −20◦C was
added an excess of H2O2 (30% in water) instead of S8. Compound 4a
was isolated as colorless oil in 72% yield after a work-up analogous to
that used for compounds 3.
1
1
3
4a: 31P{ H} NMR (CDCl3): 36.7; H NMR (CDCl3): 1.27 (d, J
=
HH
3
7.1 Hz, 12H, CH3), 1.31 (d, J = 7.1 Hz, 12H, CH3), 3.59 (sept of d,
HH
3 J = J = 7.1 Hz, 4H, CH), 4.02 (d, 3 J = 8.8 Hz, 2H, CH2), 7.34
3
HH
PH
PH
(m, 5H, Ph); 13C{ H} NMR (CDCl3): 22.9 (s, CH3), 23.8 (s, CH3), 30.6
1
(s, CH2), 46.7 (d, 2 J = 4.6 Hz, CH), 126.9 (s, CAr), 128.4 (s, CAr), 129.2
PC
(s, CAr), 137.5 (d,3 J = 9.7 Hz, Ci ).
PC
Ar
c. Procedure for Preparation of Compounds 7
Compounds 7 were synthesized by the same method as compounds 3,
but two equivalents of thiol were used instead of one. Compounds 7f
and 7h were obtained as crystalline white powders; 7g, 7i, and 7j were
obtained as thick pale yellow oils. The yields that follow are the overall
yields from PCl3.
1
7f: (62% yield): 31P{ H} NMR (CDCl3): 89.9; 1H NMR (CDCl3): 1.29
3
(d, 3 J = 6.9 Hz, 12H, CH3), 3.94 (sept. of d, 3 J = J = 6.9 Hz,
HH
HH
PH
2H, CH3CH), 4.20 (dd, 2 J
=
3 J = 12.0 Hz, 2H, CH2), 4.26 (dd,
HH
PH
2 J
=
3 J = 12.0 Hz, 2H, CH2), 7.32 (m, 10H, Ph); 13C{ H} NMR
1
HH
PH
(CDCl3): 22.9 (d, 3 J = 9.0 Hz, CH3), 39.2 (d, 2 J = 3.1 Hz, CH2), 49.3
PC
PC
(d, 2 J = 3.1 Hz, CH), 127.5 (s, CAr), 128.7 (s, CAr), 129.4 (s, CAr), 137.0
PC
(d, 3 J = 4.5 Hz, Ci ); anal. calcd for C20H28NPS3 (409.6): C, 58.64; H,
PC
6.89; N, 3.42; foundA: rC, 58.67; H, 6.90; N, 3.40.
7g: Two diastereomers in a 1:1 ratio (45% yield): 31P{ H} NMR
1
1
(CDCl3): 88.2 (s), 88.6 (s); H NMR (CDCl3): 1.25 (m, 6H, CH3CH2O),
1.32 (m, 12H, CH3CHN), 1.57 (dd, 3 J = 7.3 Hz, 4 J = 0.7 Hz, 3H,
HH
PH
CH3CHS), 1.58 (d, 3 J = 7.2 Hz, 3H, CH3CHS), 3.89 (m, 4H, CHN,
HH
CHS), 4.18 (m, 4H, CH2O).
7h: (52% yield): 31P{ H} NMR (CDCl3): 92.8; 1H NMR (CDCl3): 4.09
1
(dd, 2 J = J = 13.0 Hz, 2H, CH2), 4.19 (dd, 2 J = J = 13.0 Hz,
3
3
HH
PH
HH
PH

1242
P. Marchand et al.
1
2H, CH2), 7.37 (m, 20H, Ar); 13C{ H} NMR (CDCl3): 39.8 (d, 2 J = 3.7
PC
Hz, SCH2), 127.0 (s, CAr), 127.6 (s, CAr), 128.7 (s, CAr), 129.1 (s, CAr),
129.2 (s, CAr), 129.4 (s, CAr), 136.3 (d, 3 J = 7.3 Hz, CAi rCH2), 143.5 (bs,
PC
CiArN); Anal. Calcd for C26H24NPS3 (477.76): C, 65.38; H, 5.06; N, 2.93.
found; C, 65.46; H, 5.11; N, 2.88.
7i: (51% yield): 31P{ H} NMR (CDCl3): 93.8; 1H NMR (CDCl3): 3.71
1
(s, 6H, CH3O), 3.76 (m, 4H, SCH2), 7.28 (m, 6H, Ar), 7.53 (m, 4H, Ar).
7j: (25% yield): 31P{ H} NMR (CDCl3): 100.4; 1H NMR (CDCl3): 4.07
1
(dd, 2 JHH= J = 11.0 Hz, 2H, CH2Ph), 4.13 (dd, 2 J
=
3 J = 11.0
3
PH
HH
PH
Hz, 2H, CH2Ph), 6.96 (d, 3 J = 7.8 Hz, 2H, Ar), 7.30 (m, 15H, Ar), 8.1
HH
(d, 3 J = 7.8 Hz, 2H, Ar).
HH
d. X-Ray Structure Determination for Compounds 3a and 7f
Measurements were carried out on a one-circle IPDS STOE x-ray
˚
diffractometer system (Mo-radiation, λ = 0.71073 A, 50 KV/30 mA
power). The data were collected at low temperature at T = 160(2) K
and 180(2) K for 3a and 7f, respectively. Frames were integrated with
the aid of STOE, X-RED, Data Reduction for STADI4 and IPDS, Re-
vision 1.08, STOE software.11
For 3a a total of 100 frames were collected for a hemisphere of re-
flections. Based on a monoclinic crystal system, the integrated frames
yielded a total of 16,357 reflections at a maximum 2θ angle of 52.04◦ of
which 4211 were independent reflections (Rint = 0.0309, Rsig = 0.0224,
completeness = 96.3%) and 3,559 (84.5%) reflections were greater
than 2σ(I). Absorption corrections were applied (absorption coefficient
µ = 0.316 mm−1; max/min transmission 0.9721 and 0.9057) using the
DIFABS program.12
For 7f a total of 150 frames were collected for a hemisphere of re-
flections. Based on a monoclinic crystal system, the integrated frames
yielded a total of 14,438 reflections collected at a maximum 2θ angle
of 48.80o (3612 independent reflections, Rint = 0.1485, Rsig = 0.1101,
completeness = 98.6 %) and 2025 (56.06) reflections were found greater
than 2σ(I). Absorption corrections were applied (absorption coefficient
µ = 0.409 mm−1; max/min transmission = 0.9680 and 0.9082) using
the DIFABS program.12
Structures were solved by using direct methods, with the aid of
SIR9213 and refined by full-matrix least-squares procedures on F2 us-
ing SHELXL-97 included in the WinGX programs version 1.64 04.14
For all compounds, direct methods of phase determination followed
by subsequent Fourier cycles of refinement led to an electron density
map, from which most of the non-hydrogen atoms were identified. With

Diaminodithio- and Aminotrithiophosphoric Acid Esters
1243
subsequent isotropic refinement, all of the non-hydrogen atoms were
identified. Atomic coordinates, isotropic, and anisotropic displacement
parameters of all the non-hydrogen atoms were refined by means of a
full matrix least-squares procedure on F2. The hydrogen atoms were
included in the refinement in calculated positions, riding on the carbon
atoms to which they were attached, except concerning compound 3a, for
which the two hydrogen atoms labelled H2a and H2b connected to the
C(2) atom were isotropically refined. Drawings of molecules were real-
ized with the aid of ORTEP32.15 Atomic scattering factors were taken
from international tables for x-ray crystallography.16
For 3a the refinement converged at R1 = 0.0304 and wR2 = 0.0743,
with intensity I > 2σ(I). The largest peak/hole in the final difference
map was 0.306 and −0.282 e.A−3. For 7f the final values were R1 =
˚
0.0585 and wR2 = 0.1441, with intensity I > σ(I). The largest peak/hole
−3
˚
in the final difference map was 0.332 and −0.491e.A
.
d.1. Supplementary Data
Crystallographic data for both structures reported in this arti-
cle have been deposited with the Cambridge Crystallographic Data
Centre and allocated the deposition number CCDC 295416 (3a) and
295417 (7f). Copies of the data can be obtained free of charge via
www.ccdc.cam.uk/data request/cif.
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