New organophosphorus ligands with SPNSO skeleton and their copper(I) complexes. Crystal and molecular structures of (SPPh2)(O2SPh)NH, [(Ph3P)2Cu{(SPPh2)(O2SMe)N}] and [(Ph3P)2Cu{(SPPh2)(O2SC6H4Me-4)N}] · 0.5C6H5CH3

Article abstract of DOI:10.1016/j.ica.2007.07.023

The new phosphorus ligand (SPPh₂)(O₂SPh)NH (1) was prepared by reacting Li[HN(S)PPh₂] and PhSO₂Cl and was easily converted into its potassium salt, K[(SPPh₂)(O₂SPh)N] (2), by treatment with t-BuOK. Copper(I) complexes, [(Ph₃P)₂Cu{(SPPh₂)(O₂SR)N}] [R = Me (3), Ph (4), C₆H₄Me-4 (5)], were obtained from (Ph₃P)₂CuNO₃ and the potassium salt of the corresponding acid in a 1:1 molar ratio. All compounds were characterized by multinuclear (¹H, ¹³C, ³¹P) NMR spectroscopy. The molecular structures of the free acid 1, as well as of complexes 3 and 5 · 0.5C₆H₅CH₃, were established by single-crystal X-ray diffraction. The acidic proton in 1 is attached to nitrogen and the molecular units are associated through intermolecular S = O?H-N hydrogen bonding [H?O 2.098 A?], resulting in dimeric units. For the copper complexes, monomeric structures with bidentate [(SPPh₂)(O₂SR)N]^- ligands were found.

Full text of DOI:10.1016/j.ica.2007.07.023

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Inorganica Chimica Acta 361 (2008) 255–261
www.elsevier.com/locate/ica
New organophosphorus ligands with SPNSO skeleton and
their copper(I) complexes
Crystal and molecular structures of (SPPh2)(O2SPh)NH,
[(Ph3P)2Cu{(SPPh2)(O2SMe)N}] and [(Ph3P)2Cu{(SPPh2)
(O2SC6H4Me-4)N}] Æ 0.5C6H5CH3
a
a
a,
*
Alexandra Pop , Adina Rotar , Ciprian Rat b,1, Anca Silvestru
a
Faculty of Chemistry and Chemical Engineering, ‘‘Babes-Bolyai’’ University, RO-400028 Cluj-Napoca, Romania
b
Institut fu¨r Anorganische und Physikalische Chemie, Universita¨t Bremen, D-28534 Bremen, Germany
Received 28 April 2007; received in revised form 20 July 2007; accepted 25 July 2007
Available online 3 August 2007
Abstract
The new phosphorus ligand (SPPh2)(O2SPh)NH (1) was prepared by reacting Li[HN(S)PPh2] and PhSO2Cl and was easily converted
into its potassium salt, K[(SPPh2)(O2SPh)N] (2), by treatment with t-BuOK. Copper(I) complexes, [(Ph3P)2Cu{(SPPh2)(O2SR)N}]
[R = Me (3), Ph (4), C6H4Me-4 (5)], were obtained from (Ph3P)2CuNO3 and the potassium salt of the corresponding acid in a 1:1 molar
ratio. All compounds were characterized by multinuclear (1H, 13C, 31P) NMR spectroscopy. The molecular structures of the free acid 1,
as well as of complexes 3 and 5 Æ 0.5C6H5CH3, were established by single-crystal X-ray diffraction. The acidic proton in 1 is attached to
˚
nitrogen and the molecular units are associated through intermolecular S = Oꢀ ꢀ ꢀH–N hydrogen bonding [Hꢀ ꢀ ꢀO 2.098 A], resulting in
dimeric units. For the copper complexes, monomeric structures with bidentate [(SPPh2)(O2SR)N]ꢁ ligands were found.
ꢀ 2007 Elsevier B.V. All rights reserved.
Keywords: Thiophosphorus ligands; Copper complexes; X-ray crystal structures
1. Introduction
Copper complexes containing ½ðXPR2ÞðYPR02ÞNꢂꢁ
ligands raised considerable interest as structural model
compounds for the active sites in copper-containing
enzymes and proteins [4–6], compounds with nonlinear
optical properties [7] or precursors for solid state materials
[8]. Mononuclear copper(I) and copper(II) complexes with
chelating O,O-, O,S- or S,S-ligands were described and
they display different structures, i.e. trigonal [(Ph3P)Cu
{(XPPh2)2N}] (X = S [9], Se [10]), or tetrahedral [(Ph3P)2
Cu{(XPR2)2N}] (R = Me, X = S; R = Ph, X = O) [11],
and [Cu{(XPR2)(YPR2)N}2] (R = Ph, X = Y = O; R =
Ph, X = S, Y = O) [11], [Cu{{OP(OPh)2}2N}2] [12].
A few polynuclear copper(I) complexes with bimetallic
triconnective ligand units were also reported, i.e. neutral
trinuclear ½CufðXPR2ÞðYPR02ÞNgꢂ3 (R, R0 = Pri, Ph; OEt,
OPh, OC6H4But-2; X = Y = S, Se [8,13,14]), ionic tetranu-
Tetraorganodichalcogenoimidodiphosphinato anions,
½ðXPR2ÞðYPR02ÞNꢂꢁ (X, Y = O, S, Se; R, R0 = alkyl, aryl,
OR), are proved to be versatile ligands towards Main
Group or transition metals [1–3]. Usually they behave as
bidentate moieties, generating six-membered carbon-free
metallacycles (A). However, due to the high flexibility of
the XPNPY skeleton, other coordination patterns were
also observed [1–3].
*
Corresponding author. Tel.: +40 264 593833; fax: +40 264 590818.
E-mail address: ancas@chem.ubbcluj.ro (A. Silvestru).
Tel.: +49 421 218 2266; fax: +49 421 218 4042.
1
0020-1693/$ - see front matter ꢀ 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2007.07.023

256
A. Pop et al. / Inorganica Chimica Acta 361 (2008) 255–261
H
N
H
N
R
R'
R
R'
R
R'
N
R
P
P
R'
O
S
S
O
R
P
S
O
X
Y
O
O
X
O
M
A
B
C
clear [Cu4{(SPPh2)2N}3][X] (X = [CuCl2]ꢁ [15,16], [BF4]ꢁ
[17], [I3]ꢁ [18]) or [Cu4{(SePPh2)2N}3][BF4]ꢁ [17], and neu-
tral tetranuclear [Cu{(OPMe2)(SPPh2)N}]4 [19].
2.2. Syntheses
2.2.1. Preparation of (SPPh2)(O2SPh)NH (1)
Bis(organosulfonyl)imides, (O2SR)(O2SR0)NH (B),
have also attracted some interest as ligands towards metal
centres [20]. Only two copper(II) complexes with such
ligands are structurally characterized by X-ray diffraction
studies, i.e. [Cu(L)4{(O2SMe)2N}2] (L = H2O [21], pyri-
dine [22]), and they display polymeric networks built by
hydrogen bonding. However, the ligands act as monoden-
tate units towards the metal centre and the octahedral
coordination sphere is completed by water or pyridine
molecules.
We previously reported the synthesis and spectroscopic
characterization of two members of a new class of organo-
phosphorus ligands of type C, i.e. (SPPh2)(O2SR)NH
[R = Me, C6H4Me-4], along with their alkali metal (Li,
Na, K) salts [20]. Here we report on the synthesis and
spectroscopic characterization of a new member of this ser-
ies of ligands and its potassium salt, i.e. (SPPh2)(O2SPh)
NH (1) and K[(SPPh2)(O2SPh)N] (2), as well as on the cop-
per(I) complexes of type [(Ph3P)2Cu{(SPPh2)(O2SR)N}]
[R = Me (3), Ph (4), C6H4Me-4 (5)]. The molecular struc-
tures of 1, 3 and 5 Æ 0.5C6H5CH3 are also reported.
A solution of n-BuLi in n-hexane (8.375 mL 1.6 M,
0.0134 mol) was added dropwise at room temperature to
a stirred solution of Ph2P(S)NH2 (6.246 g, 0.0268 mol)
in 100 mL of anhydrous tetrahydrofurane, under an
argon atmosphere. The reaction mixture was stirred for
2 h. Then a solution of PhSO2Cl (1.75 mL, 0.0134 mol)
in 50 mL of anhydrous tetrahydrofurane was added drop-
wise. The reaction mixture was stirred for 12 h and then
the solvent was removed under vacuum. Toluene
(50 mL) was added to the resulting oily product and the
obtained suspension was treated with water (200 mL).
From the organic phase the solvent was removed under
vacuum and half of the initial Ph2P(S)NH2 was recovered
(3.12 g). The aqueous phase was treated with HCl 0.5 N
(50 mL) and the resulting colourless solid product was
separated by suction filtration and dried under vacuum.
Recrystallisation from a chloroform/n-hexane mixture
(1/4, v/v) gave the title compound as a microcrystalline
1
solid. Yield: 2.52 g (54%), m.p. 170–172 ꢁC. H NMR: d
6.50s,br [1H, NH], 7.32t [2H, P-C6H5-para, 3J(HH)
8.0 Hz], 7.41dt [4H, P-C6H5-meta, 3J(HH) 8.0, 4J(PH)
3.6 Hz], 7.51m [3H, S-C6H5-meta+para], 7.58d [2H,
3
2. Experimental
S-C6H5-ortho, J(HH) 7.3 Hz], 7.87dd [4H, P-C6H5-ortho,
3
3J(PH) 14.6, J(HH) 7.2 Hz]. 13C NMR: d 127.12s [Cm,
3
2.1. General methods
S-C6H5], 128.44d [Cm, P-C6H5, J(PC) 14.1 Hz], 128.78s
[Co, S-C6H5], 132.05d [Ci, 1J(PC) 100.0 Hz], 132.10d
[Co, P-C6H5, 2J(PC) 12.3 Hz], 132.44d [Cp, P-C6H5,
4J(PC) 3.2 Hz], 133.07s [Cp, S-C6H5], 140.76s [Ci,
S-C6H5]. 31P NMR: d 53.9s.
Starting materials, i.e. Ph2P(S)NH2 [23], K[(SPPh2)(O2S-
R)N] (R = Me, C6H4Me-4) [20] and (Ph3P)2CuNO3 [24],
were prepared according to the literature methods. Other
reagents including BunLi, PhSO2Cl, Ph3P and Cu(NO3)2
were purchased from Aldrich and used without further
purification. All manipulations involving air sensitive
compounds were carried out under vacuum or argon using
Schlenk techniques. Solvents were dried and distilled prior
to use. Solutions in dry CDCl3 (1, 3–5) or DMSO-d6 (2) were
used for NMR studies. The 1H-, 13C- and 2D-NMR spectra
were recorded on a BRUKER DRX 400 instrument operat-
ing at 400.13 and 100.61 MHz, while 31P NMR spectra were
recorded on a BRUKER 300 Avance instrument operating
at 121.4 MHz. The chemical shifts are reported in d units
(ppm) relative to the residual peak of the deuterated solvent
2.2.2. Preparation of K[(SPPh2)(O2SPh)N] (2)
A reaction mixture of (SPPh2)(O2SPh)NH (1.12 g,
3 mmol) and ButOK (0.336 g, 3 mmol) in 100 mL of anhy-
drous diethyl ether was stirred at room temperature
for 24 h. The resulting solid was separated by filtration and
then dried under vacuum. The title compound was obtained
as a white powder. Yield: 1.12 g (92%), m.p. 224–225 ꢁC.
1H NMR: d 7.31m (9H, P-C6H5-meta+para + S-C6H5-
meta+para), 7.84m (6H, P-C6H5-ortho + S-C6H5-ortho).
13C NMR: d 126.05s (Cm, S-C6H5), 127.55d [Cm, P-C6H5,
3J(PC) 12.3 Hz], 127.74s (Co, S-C6H5), 129.46s (Cp,
S-C6H5), 129.59d [Cp, P-C6H5, 4J(PC) 2.6 Hz], 130.79d
(ref. CHCl3: 1H 7.26, 13C 77.0 ppm; DMSO-d6: 1H 2.50, 13
C
39.43 ppm) and H3PO4 85%. The 1H and 13C chemical shifts
were assigned based on 2D experiments using standard
BRUKER XWIN-NMR pulse sequences.
[Co, P-C6H5, J(PC) 10.7 Hz], 141.27d [Ci, P-C6H5, J(PC)
105.9 Hz], 148.42s (Ci, S-C6H5). 31P NMR: d 36.9s [1J(PC)
105.7 Hz].
2
1

A. Pop et al. / Inorganica Chimica Acta 361 (2008) 255–261
257
2.2.3. Preparation of [(Ph3P)2Cu{(SPPh2)(O2SMe)N}] (3)
Stoichiometric amounts of (Ph3P)2CuNO3 (0.362 g,
0.56 mmol) and K[(SPPh2)(O2SMe)N] (0.195 g, 0.56 mmol)
were placed in a round-bottom flask and CH2Cl2 (50 mL)
was added. The reaction mixture was stirred for 6 h at room
temperature. KNO3 was removed by filtration and the solvent
was evaporated under reduced pressure. Recrystallization
from a CH2Cl2/n-hexane mixture resulted in a colourless
microcrystalline product. Yield: 0.28 g (56%), m.p. 210 ꢁC.
1H NMR: d 2.22s (3H, CH3), 7.13m [12H, P(C6H5)3-ortho],
7.30m [24H, P(C6H5)3-meta+para + P-C6H5-meta+para],
7.84dd [4H, P-C6H5-ortho, 3J(PH) 13.7, 3J(HH) 6.9 Hz].
and (Ph3P)2Cu[(SPPh2)(O2SC6H4Me-4)N] Æ 0.5C6H5CH3
(5 Æ 0.5C6H5CH3) were obtained from chloroform/n-hexane
mixtures (1/4 v/v) (for compounds 1 and 3) and toluene,
respectively.
Colourless, block crystals of 1, 3 and 5 Æ 0.5C6H5CH3
were attached with epoxy glue on cryoloops. Data collection
and processing were carried out on a Bruker SMART APEX sys-
tem (Babes-Bolyai University, Cluj-Napoca) using graphite-
˚
monochromated Mo Ka radiation (k = 0.71073 A). Details
of the crystal structure determination and refinement are
given in Table 1.
The structures were solved by direct methods [25] and
refined using SHELX-97 [26]. All of the non-hydrogen atoms
were treated anisotropically. The hydrogen atom attached
to nitrogen in 1 was located from the difference map. The
other hydrogen atoms were included in idealized positions
with isotropic thermal parameters set at 1.2 times that of
the carbon atom to which they were attached, except the
methyl protons for which the isotropic thermal parameters
were set at 1.5. The drawings were created with the Dia-
mond program [27]. The presence of the disordered toluene
molecule in 5, which is only isotropically refined, and the
disorder of some phenyl groups attached to phosphorus
explain the high R1 value for 5.
3
13C NMR: d 43.21s (CH3), 127.85d [Cm, P-C6H5, J(PC)
13.2 Hz], 128.28d [Co, P(C6H5)3, 2J(PC) 8.6 Hz], 129.30s
[Cp, P(C6H5)3], 130.37d [Cp, P-C6H5, 4J(PC) 3.0 Hz],
130.98d [Co, P-C6H5, 2J(PC) 11.2 Hz], 133.52d [Ci,
1
3
P(C6H5)3, J(PC) 23.8 Hz], 133.94d [Cm, P(C6H5)3, J(PC)
14.8 Hz], 137.92d [Ci, P-C6H5, 1J(PC) 108.3 Hz]. 31P NMR:
d ꢁ5.3s,br [P(C6H5)3], 33.4s,br (P-C6H5).
Compounds
4
and
5
were prepared similarly:
[(Ph3P)2Cu{(SPPh2)(O2SPh)N}] (4), from (Ph3P)2CuNO3
(0.362 g, 0.56 mmol) and K[(SPPh2)(O2SPh)N] (0.229 g,
0.56 mmol). Yield: 0.4 g (73%), m.p. 178–180 ꢁC. 1H
3
NMR: d 6.82t [2H, S-C6H5-meta, J(HH) 7.7 Hz], 7.06t
[1H, S-C6H5-para, 3J(HH) 7.5 Hz], 7.24m [38H,
P(C6H5)3 + P-C6H5-meta+para + S-C6H5-ortho], 7.66dd
[4H, P-C6H5-ortho, 3J(PH) 13.8, 3J(HH) 7.1 Hz]. 13C
NMR: d 125.93s (Cm, S-C6H5), 127.53s (Co, S-C6H5),
127.58d [Cm, P-C6H5, 3J(PC) 13.3 Hz], 128.26d [Co,
3. Results and discussion
3.1. Preparation and solution NMR characterization
3
P(C6H5)3, J(PC) 8.3 Hz], 129.24s [Cp, P(C6H5)3], 129.52s
Compound 1 was prepared as previously described for
the methyl and para-tolyl substituted analogues, i.e. by
reacting the lithiated amide, Li[HN(S)PPh2], with phen-
ylsulfonyl chloride, PhSO2Cl, in anhydrous tetrahydrofu-
rane, followed by the treatment of the reaction mixture
with an aqueous HCl solution [20].
The potassium salt of 1, K[(SPPh2)(O2SPh)N] (2), was
prepared by reacting the free acid with ButOK, in anhy-
drous diethyl ether (Scheme 1):
(Cp, S-C6H5), 130.02d [Cp, P-C6H5, 4J(PC) 2.8 Hz],
130.92d [Co, P-C6H5, 2J(PC) 11.3 Hz], 133.61d [Ci,
P(C6H5)3, 1J(PC) 23.0 Hz], 133.97d [Cm, P(C6H5)3,
3J(PC) 14.7 Hz], 137.26d [Ci, P-C6H5, 1J(PC) 108.7 Hz],
145.44s (Ci, S-C6H5). 31P NMR: d ꢁ5.4s,br. [P(C6H5)3],
32.6s (P-C6H5).
[(Ph3P)2Cu{(SPPh2)(O2SC6H4Me-4)N}] (5) from (Ph3P)2
CuNO3 (0.362 g, 0.56 mmol) and K[(SPPh2)(O2 SC6H4Me-
4)N] (0.238 g, 0.56 mmol). Yield: 0.37 g (68%), m.p. 183 ꢁC.
1H NMR: d 2.20s (3H, CH3), 6.68d [2H, C6H4-meta,
3J(HH) 7.5 Hz], 7.26 m [38H, P(C6H5)3 + P-C6H5-meta+par-
a + C6H4-ortho], 7.70dd [4H, P-C6H5-ortho, 3J(PH) 13.7,
3J(HH) 7.3 Hz]. 13C NMR: d 21.21s (CH3), 126.04s [Cm,
The copper(I) complexes were obtained by salt metath-
esis reactions between (Ph3P)2CuNO3 and the potassium
salt of the appropriate acid (Scheme 2):
All compounds described in this paper are colourless,
crystalline solids. The free acid 1 and copper(I) complexes
3–5 are soluble in common organic solvents, while potas-
sium salt 2 is soluble only in strong polar solvents, such
as DMSO. All compounds were characterized by solution
multinuclear NMR spectroscopy. The molecular structures
of 1 as well as of complexes 3 and 5 Æ 0.5C6H5CH3 were
established by single-crystal X-ray diffraction.
3
C6H4], 127.63d [Cm, P-C6H5, J(PC) 13.3 Hz], 128.26d [Co,
3
P(C6H5)3, J(PC) 8.0 Hz], 129.08s [Cp, P(C6H5)3], 130.14d
4
2
[Cp, P-C6H5, J(PC) 1.8 Hz], 131.07d [Co, P-C6H5, J(PC)
3
11.3 Hz], 133.91d [Cm, P(C6H5)3, J(PC) 15.7 Hz], 134.34d
[Ci, P(C6H5)3, 1J(PC) 15.8 Hz], 136.84d [Ci, P-C6H5, 1J(PC)
107.8 Hz], 140.10s, 142,15s [Ci/Cp, C6H4], the resonance for
the Co carbon of the 4-MeC6H4 group is overlapped by the
resonance at d 127.63 ppm. 31P NMR: d ꢁ5.5s [P(C6H5)3],
33.0s,br (P-C6H5).
1
The H and 13C NMR resonances for all compounds
were assigned using 2D NMR experiments. For the phenyl
groups attached to phosphorus the 1H and 13C NMR spec-
tra showed resonances with the expected pattern due to the
proton–proton, phosphorus–proton and phosphorus–car-
bon couplings, respectively. A broad resonance was
2.3. Crystal structure determination of compounds 1, 3 and 5
1
X-ray quality crystals for (SPPh2)(O2SMe)NH (1) and
the copper(I) complexes (Ph3P)2Cu[(SPPh2)(O2SMe)N] (3)
observed in the H NMR spectrum of the free acid at d
6.50 ppm, which was assigned to the NH proton.

258
A. Pop et al. / Inorganica Chimica Acta 361 (2008) 255–261
Table 1
Crystallographic data for (SPPh2)(O2SPh)NH (1), (Ph3P)2Cu[(SPPh2)(O2SMe)N] (3) and (Ph3P)2Cu[(SPPh2)(O2SC6H4Me-4)N] Æ 0.5C6H5CH3
(5 Æ 0.5C6H5CH3)
Compound
1
3
5 Æ 0.5C6H5CH3
Empirical formula
Formula weight
Crystal size (mm)
Temperature (K)
Crystal system
Space group
C18H16NO2PS2
373.41
0.37 · 0.18 · 0.09
297(2)
monoclinic
P2(1)/c
13.7684(13)
14.6365(14)
9.5460(9)
90.00
108.633(2)
90.00
1822.9(3)
4
1.361
0.390
C49H43CuNO2P3S2
898.41
0.40 · 0.28 · 0.14
297(2)
monoclinic
P2(1)/c
17.7203(11)
12.2740(7)
21.1994(13)
90.00
110.3450(10)
90.00
4323.2(5)
4
C117H102Cu2N2O4P6S4
2041.15
0.34 · 0.25 · 0.12
293(2)
triclinic
ꢀ
P1
˚
a (A)
12.573(2)
13.041(2)
19.091(3)
86.215(3)
74.532(3)
63.601(3)
2697.3(7)
1
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
3
˚
V (A )
Z
Dcalc (Mg mꢁ3
)
1.380
0.754
1864
1.257
0.613
1062
l (mmꢁ1
F(000)
)
776
h Range for data collections (ꢁ)
Maximum, minimum transmission
Reflections collected
1.56–26.37
0.9658, 0.8693
14435
1.85–26.02
0.9018, 0.7524
33303
1.11–26.37
0.9301, 0.8187
29005
Independent reflections [Rint
Refinement method
]
3717 [0.0425]
8519 [0.0609]
full-matrix least-squares on F2
8519/0/524
1.164
R1 = 0.0631, wR2 = 0.1317
R1 = 0.0780, wR2 = 0.1383
0.594, ꢁ0.329
10964 [0.0524]
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I > 2r(I)]
R indices (all data)
3717/1/221
1.170
R1 = 0.0717, wR2 = 0.1495
R1 = 0.0884, wR2 = 0.1578
0.423, ꢁ0.265
10964/6/587
1.103
R1 = 0.1045, wR2 = 0.2862
R1 = 0.1269, wR2 = 0.3028
3.481, ꢁ0.984
ꢁ3
˚
Final K-map (e A
)
Et2O
Scheme 1.
(SPPh2)(O2SPh)NH + ButOK
K[(SPPh2)(O2SPh)N] + ButOH
(Ph3P)2CuNO3 + K[(SPPh2)(O2SR)N]
[(Ph3P)2Cu{(SPPh2)(O2SR)N}] + KNO3
R = Me (3), Ph (4), C6H4Me-4 (5)
Scheme 2.
The 31P NMR spectra of the free acid and its potassium
salt exhibit, as expected, a single 31P resonance. The loss of
the acidic proton is reflected for the alkali metal salt in a
significant shift of the 31P resonance to higher field. The
31P NMR spectra of the copper complexes exhibit two res-
onances, one corresponding to the Ph2P(S) moiety and the
other for the Ph3P ligands coordinated to the metal centre,
thus consistent with their equivalence at the NMR time
scale.
Table 2
˚
Important interatomic distances (A) and angles (ꢁ) for (SPPh2)(O2SPh)NH
(1)
S(1)–O(1)
S(1)–O(2)
S(1)–N(1)
S(1)–C(1)
1.422(2)
1.429(2)
1.634(3)
1.750(4)
P(1)–S(2)
1.9291(13)
P(1)–N(1)
P(1)–C(7)
P(1)–C(13)
1.702(3)
1.803(4)
1.806(4)
N(1)–H(1)
N(1)ꢀ ꢀ ꢀO(20)a
0.844(18)
2.443
H(1)ꢀ ꢀ ꢀO(20)a
2.098
O(1)–S(1)–O(2)
O(1)–S(1)–N(1)
O(2)–S(1)–N(1)
O(1)–S(1)–C(1)
O(2)–S(1)–C(1)
N(1)–S(1)–C(1)
H(1)–N(1)–S(1)
H(1)–N(1)–P(1)
a
119.32(15)
107.13(15)
105.60(14)
109.40(17)
107.59(17)
107.18(16)
111(2)
N(1)–P(1)–S(2)
C(7)–P(1)–S(2)
C(13)–P(1)–S(2)
C(7)–P(1)–C(13)
N(1)–P(1)–C(7)
N(1)–P(1)–C(13)
S(1)–N(1)–P(1)
N(1)–H(1)ꢀ ꢀ ꢀO(20)a
116.00(12)
114.10(12)
113.91(14)
108.36(18)
104.89(15)
98.06(15)
126.02(17)
165.5
3.2. Crystal and molecular structure of 1
Selected bond distances and angles for the free acid
(SPPh2)(O2SPh)NH (1) are listed in Table 2, and the
ORTEP diagram with the corresponding atom numbering
scheme is displayed in Fig. 1.
The compound presents similar features as its previously
described analogues substituted with methyl or para-tolyl
120(2)
Symmetry equivalent positions (1 ꢁ x, ꢁy, 1 ꢁ z) given by a prime.

A. Pop et al. / Inorganica Chimica Acta 361 (2008) 255–261
259
Table 3
Torsion angles (ꢁ) for the S@P–N–S(@O)2 skeleton in (SPPh2)(O2SPh)NH
(1)
O(1)S(1)N(1)P(1)
O(2)S(1)N(1)P(1)
31.7
159.9
S(2)P(1)N(1)S(1)
C(1)S(1)N(1)P(1)
51.2
–85.6
The S@P–N–S(@O)2 skeleton in 1 is similar to those
described for the related (SPPh2)(O2SR)NH [20], as
reflected by the torsion angles (Table 3). The conformation
of the S@P(C)2–N–S–C(@O)2 fragment can be described
by the S(2)P(1)N(1)S(1) and C(1)S(1)N(1)P(1) torsion
angles; with assignment of the terms syn and anti for angles
of 0 and 180ꢁ, the extreme conformations being syn–syn
(D) and syn–anti (E) (Scheme 3). Thus, for compound 1 a
conformation close to syn–syn can be considered [the devi-
ations of the S(2) and C(1) atoms from the P(1)N(1)S(1)
Fig. 1. ORTEP plot of (SPPh2)(O2SPh)NH (1). The atoms are drawn with
30% probability ellipsoids.
˚
plane being ꢁ1.3518/ꢁ1.6666 A]. Similar syn–syn confor-
mations were assigned for the previously described deriva-
tives, (SPPh2)(O2SR)NH (R = Me,0 C6H4Me-4) [20].
˚
groups, (SPPh2)(O2SMe)NH and (SPPh2)(O2SC6H4Me-
4)NH [20]. The acidic proton is attached to nitrogen
Intermolecular N(1)–H(1)ꢀ ꢀ ꢀO(2 ) interactions [2.098 A]
˚
were observed [RvdW (H,O) = 2.60 A] [37] resulting in
˚
˚
˚
[N(1)-H(1) 0.844(18) A in 1 versus 0.72(2) A in the methyl
dimer associations (Fig. 2), as was also found for
˚
derivative or 0.86(2) A in the p-tolyl substituted acid], thus
(SPPh2)(O2SC6H4Me-4)NH [Hꢀ ꢀ ꢀO 2.03(2) A] [20] or
˚
consistent with the solution NMR data. A similar behav-
ior was observed for the related tetraorganodichalcogenoi-
midodiphosphinic acids, ðXPR2ÞðYPR0 ÞNH [1], and
bis(organosulfonyl)imides, (O2SR)(O2SR02)NH [28–34].
In the molecular unit the P–N–S system is angular [S(1)–
N(1)–P(1) 126.02(17)ꢁ in 1; cf. (SPPh2)(O2SR)NH [20]:
126.4(1)ꢁ (R = Me), 126.95(8)ꢁ (R = C6H4Me-4)]. The
phosphorus–sulfur distance [P(1)–S(2) 1.9291(13) in 1; cf.
(O2SC6H4Me-4)2NH [Hꢀ ꢀ ꢀO 2.05(2) A] [33].
C
O
C
N
N
C
C
O
C
P
S
P
S
˚
O
O
S
C
S
(SPPh2)(O2SR)NH [20]: 1.9284(7) A (R = Me), 1.9326(8)
˚
A (R = C6H4Me-4)] and the phosphorus–nitrogen bond
syn
syn
syn
anti
˚
[P(1)–N(1) 1.702(3) A in 1; cf. (SPPh2)(O2SR)NH [20]:
D
E
˚
˚
1.708(2) A (R = Me), 1.703(1) A (R = C6H4Me-4)] are typ-
Scheme 3.
ical for double P@S and single P–N bonds [cf. Ph2P(@S)–
˚
N@P(–SMe)Ph2 [35]: P@S 1.954(1) A, P–S 2.071(1), P@N
˚
˚
1.562(2) A, P–N 1.610(2) A; (O2SMe)2N–PMe2 = S [36]:
˚
P@S 1.943(1), P–N 1.777(2) A]. For the N–SO2Ph moiety
of the molecular unit the sulfur–nitrogen and sulfur–oxy-
˚
gen distances [S(1)–N(1) 1.634(3) A; S(1)–O(1)/S(1)–O(2)
˚
1.422(2)/1.429(2) A] are consistent with single S–N and
double S@O bonds and very similar to those found in the
related (SPPh2)(O2SR)NH [S–N/S–O/S–O 1.634(1)/
˚
1.4267(1)/1.428(1) A (R = Me); 1.641(1)/1.429(1)/1.446(1)
˚
A (R = C6H4Me-4)] [20], or in bis(organosulfonyl)imides
˚
[(O2SMe)2NH [30]: S–N 1.647(2)/1.656(1) A, S–O 1.428
˚
(2)–1.435(1) A; (O2SC6H4Me-4)2NH [33]: S–N 1.645(2)/
˚
˚
1.666(2) A, S–O 1.420(1)–1.431(1) A]. However, the
sum of the angles at the nitrogen atom is close to 360ꢁ
P
[
(Nangles) 356.8ꢁ] with N(1) slightly displaced from the
˚
P(1)/H(1)/S(1) plane (0.1312 A for 1, versus ꢁ0.159 and
˚
0.095 A for (SPPh2)(O2SMe)NH and (SPPh2)(O2SC6
H4Me-4)NH, respectively [20]), thus suggesting a consider-
able sp2 character as was also noted for the imidodiphos-
phinic acids [1].
Fig. 2. Dimer association through Oꢀ ꢀ ꢀH bonding in (SPPh2)(O2SPh)NH
(1). Hydrogen atoms, except for those attached to nitrogen, are omitted
for clarity.

260
A. Pop et al. / Inorganica Chimica Acta 361 (2008) 255–261
Table 4
˚
Important interatomic distances (A) and angles (ꢁ) for (Ph3P)2Cu[(SP-
Ph2)(O2SMe)N] (3) and (Ph3P)2Cu[(SPPh2)(O2SC6H4Me-4)N] Æ 0.5C6H5
CH3 (5 Æ 0.5C6H5CH3)
3
5 Æ 0.5C6H5CH3
Cu(1)–O(1)
Cu(1)–S(1)
Cu(1)–P(2)
Cu(1)–P(3)
P(1)–S(1)
P(1)–N(1)
2.188(2)
2.160(4)
2.3761(18)
2.2827(17)
2.2816(18)
1.995(2)
2.3912(11)
2.2684(10)
2.2769(10)
1.9886(14)
1.602(3)
1.605(6)
S(2)–N(1)
1.552(3)
1.558(6)
S(2)–O(1)
1.445(3)
1.465(5)
S(2)–O(2)
1.432(3)
1.435(5)
O(1)–Cu(1)–S(1)
O(1)–Cu(1)–P(2)
O(1)–Cu(1)–P(3)
P(2)–Cu(1)–P(3)
P(2)–Cu(1)–S(1)
P(3)–Cu(1)–S(1)
S(2)–N(1)–P(1)
S(2)–O(1)–Cu(1)
P(1)–S(1)–Cu(1)
N(1)–P(1)–S(1)
O(2)–S(2)–O(1)
O(2)–S(2)–N(1)
O(1)–S(2)–N(1)
101.69(7)
115.45(8)
101.91(8)
125.74(4)
104.69(4)
104.49(4)
130.2(2)
129.90(15)
105.62(5)
119.05(13)
112.51(19)
114.6(2)
100.00(13)
102.10(14)
100.60(14)
124.57(7)
119.34(7)
105.29(7)
128.0(4)
131.7(3)
105.06(8)
118.9(2)
Fig. 3. ORTEP plot of (Ph3P)2Cu[(SPPh2)(O2SMe)N] (3). The atoms are
drawn with 30% probability ellipsoids. Hydrogen atoms are omitted for
clarity.
112.9(3)
114.6(3)
112.9(3)
113.07(17)
3.3. Crystal and molecular structure of 3 and
5 Æ 0.5C6H5CH3
The molecular structures of compounds
3 and
hedral CuP2SO cores. The Cu–S distances [Cu(1)–S(1)
2.3912(11) in 3 and 2.3761(18) in 5 Æ 0.5C6H5CH3] are
longer than those observed for related copper(I) derivative
5 Æ 0.5C6H5CH3 are displayed in Figs. 3 and 4, respectively,
while relevant bond distances and angles are given in
Table 4.
Both complexes exhibit monomeric structures, with a
chelating S,O-ligand unit and two Ph3P groups coordi-
nated to the metal centre, thus resulting in distorted tetra-
˚
[(Ph3P)Cu{(SPPh2)2N}] [Cu–S(1) 2.215(2) A, Cu–S(2)
˚
2.258(2) A] [9]. The Cu–O bonds [Cu(1)–O(1) 2.188(2) in
3 and 2.160(4) in 5 Æ 0.5C6H5CH3] are of same strength as
observed for the tetrahedral [(PPh3)2Cu{(O2PPh2)N}]
˚
˚
[Cu–O(1) 2.122(2) A, Cu–O(2) 2.165(2) A] [11], but much
shorter than in the octahedral complexes of type
˚
[Cu(L)4{(O2SMe)2N}2] (L = H2O, Cu–O 2.325 A [21],
˚
and L = pyridine, Cu–O 2.545 A [22]), where the
[(MeSO2)2N]ꢁ ligands act as monodentate moieties.
˚
The phosphorus–sulfur [P(1)–S(1) 1.9886(14) A in 3 and
1.995(2) A in 5 Æ 0.5C6H5CH3] and the phosphorus–nitro-
gen distances [P(1)–N(1) 1.602(3) A in 3 and 1.605(6) A
in 5 Æ 0.5C6H5CH3] are of an intermediate magnitude
between double and single bonds, respectively [cf. the typ-
ical double P@S and single P–N bonds are P(1)–S(2)
˚
˚
˚
˚
1.9284(7)/P(1)–N(1) 1.708(2) A in (SPPh2)(O2SMe)NH,
and P(1)–S(2) 1.9326(8)/P(1)–N(1) 1.703(1)
˚
A
in
(SPPh2)(O2SC6H4Me-4)NH, respectively] [20]. For the
N–SO2Ph moiety of the molecular unit the sulfur–nitrogen
and sulfur–oxygen distances [S(2)–N(1), S(2)–O(1)/S(2)–
˚
O(2) 1.552(3), 1.445(3)/1.432(3) A for 3, and 1.558(6),
˚
1.465(5)/1.435(5) A for 5 Æ 0.5C6H5CH3] are again consis-
tent with intermediate values between the single and double
sulfur–nitrogen and sulfur–oxygen bonds, respectively [cf.
the single S–N and double S@O bonds in the correspond-
ing free acids, i.e. (SPPh2)(O2SMe)NH – S(1)–N(1), S(1)–
Fig.
4. ORTEP
plot
of
(Ph3P)2Cu[(SPPh2)(O2SC6H4Me-
4)N] Æ 0.5C6H5CH3 (5 Æ 0.5C6H5CH3). The atoms are drawn with 30%
probability ellipsoids. Hydrogen atoms and the toluene molecule are
omitted for clarity.
˚
O(1)/S(1)–O(2): 1.634(2), 1.427(1) and 1.428(1) A; (SPPh2)
(O2SC6H4Me-4)NH
– S(1)–N(1), S(1)–O(1)/S(1)–O(2):

A. Pop et al. / Inorganica Chimica Acta 361 (2008) 255–261
261
˚
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bonds of a ligand unit in these copper(I) complexes,
although only one of the oxygens is involved in coordina-
tion to the metal centre.
The six-membered CuOS(SP)N ring exhibits a twisted
chair conformation in 3 and a boat conformation in
5 Æ 0.5C6H5CH3, folded along the P(1)–S(2) and O(1)–S(1)
axes, respectively, with the nitrogen and copper atoms at
˚
˚
ꢁ0.479 and 0.123 A in 3 and 0.512 and 0.470 A in
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Acknowledgements
Financial support from the Ministry of Education and
Research of Romania (CERES, Research Project No. 4-
62/2004) is greatly appreciated. We warmly acknowledge
the assistance of Dr. Calin Deleanu in the 2D NMR exper-
iments and of Dr. Richard Varga (the NATIONAL CEN-
TER FOR X-RAY DIFFRACTION, ‘‘Babes-Bolyai’’
University, Cluj-Napoca, Romania) in the solid state struc-
ture determinations.
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CCDC 637071, 637072, and 637073 contain the supple-
mentary crystallographic data for 1, 3 and 5 Æ 0.5C6H5CH3.
These data can be obtained free of charge via http://
www.ccdc.cam.ac.uk/conts/retrieving.html, or from the
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-
mail: deposit@ccdc.cam.ac.uk.
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