Crystal and molecular structures of di-1-adamantylthiophosphinic chloride, p,p-diphenyl-n-benzyl phosphinothioic- and selenoic- amides

Article abstract of DOI:10.1007/s10870-009-9524-1

Synthesis and X-ray structural determination of three phosphorus compounds are reported. (3b) is monoclinic P2(1)/c with a = 11.852(1), b = 12.825(1), c = 12.445(1) A, β = 103.693(1)°; (4a) and (4b) are monoclinic P2(1)/n with a = 12.1422(16), b = 9.0860(

Full text of DOI:10.1007/s10870-009-9524-1

J Chem Crystallogr (2009) 39:530–534
DOI 10.1007/s10870-009-9524-1
ORIGINAL PAPER
Crystal and Molecular Structures of Di-1-
Adamantylthiophosphinic Chloride, P,P-Diphenyl-N-Benzyl
Phosphinothioic- and Selenoic- Amides
´
´
Fernando Rascon-Cruz Æ Sandra Gonzalez-Gallardo Æ
´
´
Miguel A. Mun˜oz-Hernandez Æ Ruben A. Toscano Æ
´
Veronica Garcıa-Montalvo
´
Received: 2 September 2008 / Accepted: 13 February 2009 / Published online: 26 February 2009
Ó Springer Science+Business Media, LLC 2009
Abstract Synthesis and X-ray structural determination of
three phosphorus compounds are reported. (3b) is mono-
clinic P2(1)/c with a = 11.852(1), b = 12.825(1),
and catalyst, and as building blocks of supramolecular
architecture [1–5]. Several efforts have been devoted to
synthesize bulky organophosphine and their derivatives
since the steric protection of the phosphorus atoms could
lead to a kinetic stabilization of reactive systems [6, 7].
During the past decade some simple and efficient synthetic
methods to obtain di-1-adamantylphosphine (1), -chloro-
phosphine (2) and its oxide, sulfide and selenide derivatives
(3) were published [8–11]. In the course of the synthesis of
these type of starting material for phosphorus amino
derivatives as ligand precursors, we obtained di-1-ada-
mantylthiophosphinic chloride in good yield by modifying
the reported -chlorophosphine procedure [8]. In adition, we
synthesized (N-benzylamino) diphenylphosphine sulfide
(4a) and selenide (4b) (see Scheme 1). Here we reported
the crystal structures of these three phosphorus compounds.
˚
c = 12.445(1) A, b = 103.693(1)8; (4a) and (4b) are
monoclinic P2(1)/n with a = 12.1422(16), b = 9.0860(12),
˚
c = 14.845(2) A, b = 96.498(3)8 for (4a), and a =
˚
12.2714(16), b = 9.2812(12), c = 14.800(2) A, b =
97.176(2)8 for (4b). They all exhibit distorted tetrahedral
geometry about the P atom. Ph2P(X)NHC7H7 (X=S (4a) and
X=Se (4b)) show typical P–S and P–Se double bond dis-
tances and P–N single bonds, while P–S bond in
1-Ad2P(S)Cl (3b) is comparable to P–S single bonded
probably due to the largeness of 1-adamantyl groups.
Keywords Phosphorus compounds Á
Chalcogeno phosphoramidate Á
Di-1-adamantylthiophosphinic chloride Á Crystal structures
Results and Discussion
Introduction
The compound 1-Ad2P(S)Cl (3b) was prepared from the
reaction of the di-1-adamantylphosphine (1) with thionyl
chloride in toluene at room temperature, when we were
trying to get 1-Ad2PCl (2) by using SOCl2 instead of
phosgene, which is employed in the procedure described by
Schmutzler to get (2) [8]. The compound was obtained as
mixture of (3a) and (3b) according to the chemical shift of
the two singlet 31P NMR signals observed at 86.53 and
138.45 ppm. The recrystallization with hot ethanol in which
(3a) was not soluble allowed the isolation of (3b) confirmed
by an only signal at 138.45 ppm in the 31P NMR spectrum.
Additionally, we also tried the substitution of phosgene by
oxalyl chloride (C2Cl2O2) following a similar synthetic
procedure but without success. We attempted the reaction of
(3b) with lithium salts of benzylamine, 2-aminothiophenol,
Organophosphines are a very important family of hetero-
atom-containing molecules that serve as synthetic reagents,
ligands or precursor of ligands for coordination complexes
´
´
F. Rascon-Cruz Á S. Gonzalez-Gallardo Á
´
R. A. Toscano Á V. Garcıa-Montalvo (&)
´
Instituto de Quımica, Universidad Nacional Autonoma de
Mexico, Circuito Exterior, Ciudad Universitaria, Mexico DF
´
´
´
´
04510, Mexico
e-mail: vgm@servidor.unam.mx
´
M. A. Mun˜oz-Hernandez
´
´
Centro de Investigaciones Quıımicas, Universidad Autonoma del
Estado de Morelos, Av. Universidad 1001, Col. Chamilpa,
´
Cuernavaca, Morelos 62210, Mexico
123

J Chem Crystallogr (2009) 39:530–534
531
X
P
X
P
H
H
Cl
N
P
P
Cl
X
S (4a)
1
2
X
O (3a)
S (3b)
Se (3c)
Se (4b)
Scheme 1 Phosphorus compounds
Ph2P(E)NH2 (E=O, S) and ammonia, in THF or toluene, at
low and at reflux temperature. In all the cases we recovered
the starting materials.
The procedure for getting (N-benzylamino)diphenyl-
phosphine sulfide (4a) and selenide (4b) was not carried
out in one-pot reaction as Dehghanpour et al. have reported
recently [12], but in two steps. First the Ph2PNHC7H7 was
obtained and then the oxidation with either sulfur or sele-
nium was performed to get pure compounds, as it has been
informed for analogous compounds [13, 14].
The molecular structures in crystalline solid state of (3b),
(4a) and (4b) were determined by single crystal X-ray dif-
fraction analysis. The ORTEP diagrams of the molecules
along with the atom numbering are depicted in Fig. 1 and 2.
Relevant bond lengths and angles are given in Table 1.
The molecules of the title compounds, 1-Ad2P(S)Cl (3b),
Ph2P(S)NHC7H7 (4a), Ph2P(Se)NHC7H7 (4b), exhibit dis-
torted tetrahedral geometry about the P atom. The
arrangement is constituted of two C atoms from the organic
sustituents (phenyl groups for (4a) and (4b), 1-adamatyl
groups for (3b)), the chalcogen atom (S for (3b) and (4a), Se
for (4b)), and either N atom from the N-benzylamine group
in (4a) and (4b) or Cl atom for (3b). The angles at P in the
Fig. 2 Molecular structures of Ph2P(S)NHC7H7 (4a), Ph2P(Se)
NHC7H7 (4b) with thermal ellipsoids at 50% probability level
Fig. 1 Molecular structure of
1-Ad2P(S)Cl (3b) with thermal
ellipsoids at 30% probability
level
123

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J Chem Crystallogr (2009) 39:530–534
˚
˚
NHÁÁÁS length being 2.596 A and the N–HÁÁÁS angle being
Table 1 Selected bond lengths [A] and bond angles [°] of
1-Ad2P(S)Cl (3b), Ph2P(S)NHC7H7 (4a), Ph2P(Se)NHC7H7 (4b)
178.18 similar to those detected in HN(SPiPr2)(SePPh2)
˚
[17], and SÁÁÁH(Ph) contact of 2.84 A. There are also weak
3b E=S
4a E=S
4b E=Se
˚
SeÁÁÁH(Ph) intermolecular contact of 2.90 and 3.05 A
P(1)-E(1)
2.012(4) 1.9578(6)
2.072(5)
2.1120(6)
in (4b).
P(1)-S(1B)
P(1)-C(1)
1.858(2)
1.864(2)
1.975(5)
1.960(4)
1.803(1)
1.816(2)
1.812(2)
1.809(2)
P(1)-C(7) (4)/C(11) (3b)
P(1)-Cl(1)
Experimental
P(1)-Cl(1B)
Chemicals of commercial grade were purchased from
Aldrich and were used as supplied. The 1-Ad2PH (1) and
1-Ad2P(O)Cl (3a) were prepared according the methods
described by Schmutzler et al. [9, 10]. 31P (121 MHz)
NMR (CDCl3) spectra were recorded on a Jeol Eclipse ?
300 spectrometer (external reference H3PO4 85%). The
entire characterization of 3b [8], (4a) and (4b) [12] was
published somewhere else. The procedure for (4a) and (4b)
was also different to that reported in [12].
P(1)-N(1)
1.6516(17)
1.468(2)
1.665(1)
1.471(3)
107.3(1)
110.71(7)
113.45(8)
N(1)-C(13)
C(1)-P(1)-C(7) (4)/C(11) (3b)
E(1) –P(1)-C(1)
117.53(9) 107.32(8)
106.07(8) 113.23(6)
E(1) –P(1)-C(7) (4)/C(11) (3b) 105.32(9) 110.50(6)
S(1B)-P(1)-C(1)
S(1B)-P(1)-C(11)
E(1)-P(1)-Cl(1)
S(1B)-P(1)-Cl(1B)
C(1)-P(1)-Cl(1)
C(11)-P(1)-Cl(1)
C(1)-P(1)-Cl(1B)
C(11)-P(1)-Cl(1B)
N(1)-P(1)-C(1)
N(1)-P(1)-C(7)
N(1)-P(1)-E(1)
102.70(9)
102.4(1)
113.70(6)
111.07(8)
108.23(9)
106.24(9)
109.57(8)
112.75(9)
1-Ad2P(S)Cl (3b): 2.7 mL (18.2 mmol) of 1,8-di-
aza[5.4.0]undec-7-en (DBU) were added under stirring to a
solution of 4.6 g (15.2 mmol) of 1 in 100 mL toluene, then
1.6 mL of SOCl2 were slowly added to the mixture. An
immediate change of color to yellow was detected. After
10 h of stirring the color has changed to a brown-orange
and some dark oil was detected. The mixture was separated
and the toluene was pumped off. The solid obtained was a
mixture of (3a) and (3b) that was recrystallized with hot
ethanol to get pure (3b). Yield 63.3%, m.p. 220°C (lit.
226°C), 31P (121 MHz) NMR (CDCl3) d = 138.95 (s)ppm
(lit. 138.97 ppm [8]).
102.01(8)
103.87(8)
118.88(6)
104.2(1)
101.61(9)
118.43(7)
chalcogeno phosphoramidate compounds are within the
range of 102.01(8) to 118.88(6) where the largest angles
correspond to N(1)-P(1)-E(1) (118.88(6) for (4a) and
118.43(7) for (4b)), while in (3b) they vary from 102.43(10)
to 117.53(9) with the largest angle being that between the
two 1-adamantyl groups (C(1)-P(1)-C(11)) as expected. A
quite similar configuration was observed in the molecular
structure of the analogous di-1-adamantyl phosphinic acid
(3a) [8]. The P–S, P-Se, and P–N bond lengths in (4a) and
(4b) agree with P–S and P–Se [15–18] double bonds and
P–N single bonds distances known from the literature.
However, the P–S bonds in the Chlorothiophosphine
Ph2P(S)NHC7H7 (4a): n-Butyllithium (1 mL of 2 M
solution in hexane, 0.43 mmol) was added at 0 °C to a stirred
solution of benzylamine (2.2 mL, 0.02 mol) in THF. After
1 h of reflux, the THF was pumped off and 25 mL of toluene
was poured to the solid. A solution of chlorodiphenylphos-
phine (3.6 mL, 0.03 mol) in toluene (10 mL) was then added
dropwise to this mixture followed by 1 h reflux. The
resulting LiCl was filtered off. The filtrate containing
Ph2PNHC7H7 and 0.02 mol of sulfur were refluxed 2 h.
Evaporation to a volume that induced crystallization fol-
lowed by refrigeration afforded a precipitate that was washed
with cyclohexane to give pure (4a). m.p. 106–107 °C (lit 98–
99 °C [12]), 31P NMR (CDCl3) d = 60.45 (s) ppm (lit.
(CD3)2CO) 59.35 ppm [12]), yield 75%.
˚
(3b) (2.012(4) and 2.072(5) A) are lengthened with respect
to the thiophosphoramidate (4a), where the P–S bond was
˚
1.9578(6) A. These long P–S bonds are comparable to those
observed for P–S single bonded species such as [Ph3PSPh]
[ClO4] and [Ph3PSCH2C6H5][ClO4], which have bond
˚
lengths of 2.074(2) and 2.050(1) A [19], respectively. Also
Ph2P(Se)NHC7H7 (4b):
A similar procedure was
followed to get Ph2PNHC7H7. Then, a mixture of
Ph2PNHC7H7 and 0.02 mol of gray selenium was refluxed
for 2 h. After removal of the residual selenium by filtration,
the solvent was pumped off and ethanol (3–4 mL) was added
to give a solid that was filtered and washed with cold ethanol,
m. p. 104 °C (lit 94–95 °C [12]), 31P NMR (CDCl3)
d = 58.48 s (1JP-Se = 751.79 Hz) ppm (lit. 59.10 ppm
(CD3)2CO) (1JP-Se = 756.39 Hz) [12]), yield 61%.
a slightly lengthening of the P–C bonds is observed when
comparing with those in N-benzylaminophosphine sulfide
(4a) and selenide (4b) (Table 1). Similar long P–C and
P–chalcogen bonds were also detected in 1-Ad2P(O)Cl (3a)
˚
(P–O 1.504(2) A and av. P–C 1.84.5 A) [8].
˚
In (4a) there are weak N–HÁÁÁS and SÁÁÁH(Ph) interactions
between two neighboring molecules, with the calculated
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J Chem Crystallogr (2009) 39:530–534
533
Table 2 Crystal data, summary of intensity data collection and structure refinement
Compound
3b
4a
4b
Empirical formula
M [g/mol]
C20H30ClPS
368.92
C19H18NPS
323.37
C19H17NPSe
369.27
Data collected K
Crystal size (mm)
Crystal system
Space group
294(2)
100(2)
100(2)
0.396 9 0.256 9 0.158
Monoclinic
P2(1)/c
0.33 9 0.27 9 0.18
Monoclinic
P2(1)/n
12.142(1)
9.086(1)
14.845(2)
90
0.41 9 0.37 9 0.32
Monoclinic
P2(1)/n
˚
a (A)
11.852(1)
12.825(1)
12.445(1)
90
12.271(1)
9.281(1)
14.800(2)
90
˚
b (A)
˚
c (A)
a (°)
b (°)
c (°)
Z
103.693(1)
90
96.498(3)
90
97.176(2)
90
4
4
4
3
˚
V (A )
828.0(3)
1.333
1,627.3(4)
1.320
1,672.4(4)
1.467
qcalc (Mg m-3
l (mm-1
)
)
0.407
0.293
2.336
Abs. correction
F(000)
Analytical
792
–
SADABS [20]
748
680
h range, deg
Index range
1.77–25.36
2.30–28.27
2.30–28.21
-14 B h B 14, -15 B k B 15,
-14 B l B 14
-8 B hB16, -9 B kB11,
-17 B lB11
-15 B hB12, -12 B kB7,
-12 B lB19
Reflections collected
Unique reflections, Rint
Data/restraints/parameters
GOF
15,172
5,662
6,468
3,362; 0.0418
3,362/0/209
1.015
2,841, 0.0198
2,841/0/203
1.063
3,769, 0.0227
3,769/0/199
1.057
R1, wR2 [I [ 2r(I)]
R1, wR2 (all data)
0.0461; 0.1146
0.0571; 0.1201
0.540 and -0.238
0.0367, 0.0947
0.0414, 0.0976
0.356 and -0.266
0.0362, 0.0978
0.0406, 0.1001
1.263 and -0.582
-3
)
˚
Large residuals (e A
X-ray Crystallographic Study
the case of (3b) intensities were corrected for absorption
using analytical methods. In addition, positional disorder of
sulfur and chloride atoms for 3b was refined. The best
model was obtained with occupancies of 0.503(4) for S1
and Cl1 and 0.497(4) for S1B and Cl1B.
Suitable single crystals for (3b) were grown by allowing a
layer of n-hexane to diffuse slowly into a concentrated
solution in CH2Cl2, while those of (4a) and (4b) were
obtained from concentrated ethanolic solutions of each of
them. The intensity data were collected on a Bruker Smart
Apex CCD diffractometer in the x scan mode using
graphite monochromated Mo-Ka radiation (k = 0.71073
Supplementary Material
CCDC 700801—700803 contains the supplementary
crystallographic data for this paper. These data can be
obtained free of charge via http://www.ccdc.cam.ac.uk/
data_request/cif, by e-mailing data_request@ccdc.cam.ac.
uk or by contacting The Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax
?44(0)1223-336033.
˚
A). Cell refinement and data reduction were carried out
with the use of the program SAINT, the program SADABS
was employed to make incident beam and decay correc-
tions in the SAINT-Plus v. 6.23c suite [20]. The structures
were refined using the software package SHELXTL vers.
6.10 [21]. Crystal data along with intensity collection
details are summarized in Table 2. All of the non-hydrogen
atoms were refined anisotropically. The positions of the
hydrogen atoms were allowed to ride on the parent carbon
atom with a common isotropic displacement parameter. In
Acknowledgments This research was supported by CONACyT
(Project 40620-F). FRC fully acknowledges a scholarship from
CONACyT
123

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