Synthesis, spectroscopic characterization, and structural studies of new Cu(I) and Cu(II) complexes containing organophosphorus ligands, and crystal structures of (Ph3P)2Cu[S2PMe2], (Ph3P)2Cu[(OPPh2)2N], Cu[(OPPh2)2N]2, and Cu[(OPPh2)(SPPh2)N]2

Article abstract of DOI:10.1139/v01-048

The Cu(I) complexes, (Ph₃P)₂CuL (L = [S₂PMe₂]^-, [OSPR₂]^- (R = Me, Ph), [(XPR₂)(YPR′₂)N]^- (X, Y, R, R′ = O, O, Ph, Ph; O, S, Ph, Ph; O, S, OEt, Ph; S, S, Me, Me)) and Cu(II) complexes, CuL₂ (L = [(XPR₂)(YPR′₂)N]^- (X, Y, R, R′ = O, O, Ph, Ph; O, S, Ph, Ph)), have been prepared. The Cu(I) derivatives were characterized by multinuclear NMR spectroscopy and in two cases by X-ray crystallography. (Ph₃P)₂Cu[S₂PMe₂] (1) crystallizes in the orthorhombic space group P2₁2₁2₁ (No. 19) with cell parameters a = 9.782(2), b = 17.808(4), c = 20.216(4) A, V = 3521(6) A³ and Z = 4, and (Ph₃P)₂Cu[(OPPh₂)₂N] (4) in the triclinic space group P1 (No. 2) with cell parameters a = 9.8079(2), b = 12.9141(3), c = 22.5666(5) A, α = 75.714(2), β = 79.465(2), γ = 68.2770(8)°, V = 2559.9(1) A³ and Z = 2. In both cases the phosphorus ligands are bidentate, thus resulting in monomeric molecules that contain tetrahedral CuP₂S₂ and CuP₂O₂ cores. The molecular structures of two of the Cu(II) derivatives were also determined. Cu[(OPPh₂)₂N]₂ (8) and Cu[(OPPh₂)(SPPh₂)N]₂ (9) crystallize in the triclinic space group P1 (No. 2) with cell parameters a = 8.887(2), b = 10.739(2), c = 12.477(3) A, α = 77.61(3), β = 76.15(5), γ = 79.46(3)°, V = 1118.3(4) A³ and Z = 1 for 8, and a = 9.626(2), b = 14.151(3), c = 24.752(5) A, α = 88.23(3), β = 79.93(3), γ = 89.77(3)°, V = 3181(1) A³ and Z = 3 for 9. The molecule of Cu[(OPPh₂)₂N]₂ (8) has a planar CuO₄ core, while in Cu[(OPPh₂)(SPPh₂)N]₂ (9) both planar and tetrahedral copper cores are observed in a ratio of 1:2.

Full text of DOI:10.1139/v01-048

983
Synthesis, spectroscopic characterization, and
structural studies of new Cu(I) and Cu(II)
complexes containing organophosphorus ligands,
and crystal structures of (Ph3P)2Cu[S2PMe2],
(Ph3P)2Cu[(OPPh2)2N], Cu[(OPPh2)2N]2, and
Cu[(OPPh2)(SPPh2)N]2
Anca Silvestru, Adina Rotar, John E. Drake, Michael B. Hursthouse,
Mark E. Light, Sorin I. Farcas, Roland Rösler, and Cristian Silvestru
–
–
–
′
Abstract: The Cu(I) complexes, (Ph3P)2CuL (L = [S2PMe2] , [OSPR2] (R = Me, Ph), [(XPR2)(YPR2 )N] (X, Y, R, R′ =
–
′
O, O, Ph, Ph; O, S, Ph, Ph; O, S, OEt, Ph; S, S, Me, Me)) and Cu(II) complexes, CuL2 (L = [(XPR2)(YPR2 )N] (X,
Y, R, R′ = O, O, Ph, Ph; O, S, Ph, Ph)), have been prepared. The Cu(I) derivatives were characterized by multinuclear
NMR spectroscopy and in two cases by X-ray crystallography. (Ph3P)2Cu[S2PMe2] (1) crystallizes in the orthorhombic
space group P212121 (No. 19) with cell parameters a = 9.782(2), b = 17.808(4), c = 20.216(4) Å, V = 3521(6) Å3 and
Z = 4, and (Ph3P)2Cu[(OPPh2)2N] (4) in the triclinic space group P1 (No. 2) with cell parameters a = 9.8079(2), b =
12.9141(3), c = 22.5666(5) Å, α = 75.714(2), β = 79.465(2), γ = 68.2770(8)°, V = 2559.9(1) Å3 and Z = 2. In both
cases the phosphorus ligands are bidentate, thus resulting in monomeric molecules that contain tetrahedral CuP2S2 and
CuP2O2 cores. The molecular structures of two of the Cu(II) derivatives were also determined. Cu[(OPPh2)2N]2 (8) and
Cu[(OPPh2)(SPPh2)N]2 (9) crystallize in the triclinic space group P1 (No. 2) with cell parameters a = 8.887(2), b =
10.739(2), c = 12.477(3) Å, α = 77.61(3), β = 76.15(5), γ = 79.46(3)°, V = 1118.3(4) Å3 and Z = 1 for 8, and a =
9.626(2), b = 14.151(3), c = 24.752(5) Å, α = 88.23(3), β = 79.93(3), γ = 89.77(3)°, V = 3181(1) Å3 and Z = 3 for 9.
The molecule of Cu[(OPPh2)2N]2 (8) has a planar CuO4 core, while in Cu[(OPPh2)(SPPh2)N]2 (9) both planar and tet-
rahedral copper cores are observed in a ratio of 1:2.
Key words: structure, copper, thiophosphinates, oxo- an9d9t1hio-imidodiphosphinates.
Résumé : On a préparé les complexes suivants du Cu(I), (Ph3P)2CuL (L = [S2PMe2]–, [OSPR2]– (R = Me, Ph),
–
′
′
[(XPR2)(YPR2 )N] (X, Y, R, R′ = O, O, Ph, Ph; O, S, Ph, Ph; O, S, OEt, Ph; S, S, Me, Me)) et du Cu(II), CuL2 (L =
–
[(XPR2)(YPR2 )N] (X, Y, R, R′ = O, O, Ph, Ph; O, S, Ph, Ph)). On a caractérisé les dérivés du Cu(I) par spectroscopie
RMN multinucléaire et, dans deux cas, par diffraction des rayons X. Les cristaux de (Ph3P)2Cu[S2PMe2] (1) sont or-
thorhombiques, groupe d’espace P212121 (No. 19) avec a = 9,782(2), b = 17,808(4) et c = 20,216(4) Å, V = 3521(6)
Å3 et Z = 4; ceux du (Ph3P)3Cu[OPPh2)2N] (4) sont tricliniques, groupe d’espace P1 (No. 2) avec a = 9,08079(2), b =
12,9141(3) et c = 22,5666(5) Å, α = 75,714(2), β = 79,465(2) et γ = 68,2770(8)°, V = 2559,9(1) Å3 et Z = 2. Dans les
deux cas, les ligands phosphorés sont bidentates ce qui conduit à des molécules monomères qui comportent des unités
centrales CP2S2 et CP2O2 tétraédriques. On a aussi déterminé les structures moléculaires de deux des dérivés du Cu(II).
Les cristaux de Cu[(OPPh2)2N]2 (8) et de Cu[(OPPh2)(SPPh2)N]2 (9) sont tous les deux tricliniques, groupe d’espace P1
(No. 2) avec a = 8,887(2), b = 10,739(3) et c = 12,477(3) Å, α = 77,61(3), β = 76,15(5) et γ = 79,46(3)°, V =
1118,3(1) Å3 et Z = 1, pour le composé 8, et avec a = 9,626(2), b = 14,151(3) et c = 24,752(5) Å, α = 88,23(3), β =
79,93(3) et γ = 89,77(3)°, V = 3181(1) Å3 et Z = 3, pour le composé 9. La molécule de Cu[(OPPh2)2N]2 (8) comporte
une unité centrale de CuO4 qui est plane alors que dans la molécule de Cu[(OPPh2)(SPPh2)N]2 (9), on observe la
Received August 31, 2000. Published on the NRC Research Press Web site at http://canjchem.nrc.ca on July 11, 2001.
Dedicated to Professor Brian James on the occasion of his 65th birthday.
A. Silvestru, A. Rotar, R. Rösler, and C. Silvestru. Chemistry Department, “Babes-Bolyai” University, RO-3400 Cluj-Napoca,
Romania.
J.E. Drake.1 Chemistry and Biochemistry, University of Windsor, Windsor, ON N9B 3P4, Canada.
M.B. Hursthouse and M.E. Light. Department of Chemistry, University of Southampton, Highfield, Southampton SO17 1BJ, U.K.
S.I. Farcas. Institute for Isotopic and Molecular Technology, RO-3400 Cluj-Napoca 5, P.O. Box 700, Romania.
1Corresponding author (telephone: (519) 253-4232; fax: (519) 973-7098; e-mail: ak4@uwindsor.ca).
Can. J. Chem. 79: 983–991 (2001)
© 2001 NRC Canada
DOI: 10.1139/cjc-79-5/6-983

984
Can. J. Chem. Vol. 79, 2001
présence d’unités de cuivre planes et tétraédriques dans un rapport de 1:2.
Mots clés : structure, cuivre, thiophosphinates, oxo- et thio-imidodiphosphinates.
[Traduit par la Rédaction] Silvestru et al.
and K[(SPMe2)2N] (23). All solvents were dried and dis-
tilled prior to use.
Introduction
Relatively few copper complexes containing both neutral
donors and O,O′-diorganodithiophosphato ligands have been
structurally characterized (1, 2). For Cu(I) derivatives, the
presence of the P-neutral ligand affords tetrahedral
Physical measurements
1
The H, 13C, and 31P NMR spectra were recorded on a
Varian Gemini 300S instrument operating at 299.5, 75.4, and
121.4 MHz, respectively, using solutions in dried CDCl3.
mononuclear (Ph3P)2Cu[S2P(OR)2] (R = Et (3), (OR)2
=
(OCH2)2CMe2 (4)) or dinuclear [(Ph3P)Cu{S2P(OEt)2}]2 (5)
complexes. Polynuclear phosphine adducts of Cu(I) thiolates
have also been reported (6, 7). Recent studies on neutral
Cu(I) thiocarboxylates with triphenylphosphine demonstrate
that complexes of different stoichiometry and structure can
be obtained with small changes in the thio ligand. Thus, for
1
The H and 13C and 31P chemical shifts are reported in ppm
relative to TMS and external H3PO4 85%, respectively. Elec-
tron spin resonance (ESR) measurements were performed at
room temperature on a Radiopan SE/X-2543 9GHz ESR
spectrometer, using a 100 kHz field modulation.
example,
using
1:1:1
stoichiometric
ratios
of
Preparation of (Ph3P)2CuL compounds (1–7)
CuCl:Na[S(O)CR]:PPh3, the thioacetate anion gave the tetra-
mer [Cu{S(O)CMe}(PPh3)]4, while for R = Ph a 4:4:3 com-
plex [Cu4{S(O)CPh}4(PPh3)3] was isolated. Attempts to
prepare a 4:4:3 derivative for R = Me failed; only the
tetrameric complex being isolated. Thioacetate and
thiobenzoate ligands both gave products of 1:1:2
stoichiometry, but for R = Me the complex was a dimer
[Cu{S(O)CMe}(PPh3)2]2, whereas for R = Ph it was a
monomer (8). In the absence of a neutral ligand, a
polynuclear Cu(I) cluster complex, [Cu{S2P(O-i-Pr)2}]4, has
been isolated (9). On the other hand, the use of [(XPR2)2N]–
(X = S, Se) ligands, which are characterized by flexible
XPNPX skeletons and a larger X···X bite, resulted in the
displacement of a coordinated triphenylphosphine, leading to
trigonal, mononuclear Cu(I) complexes, (Ph3P)Cu[(XPR2)2N]
(R = Ph, X = S (10), Se (11)). Reaction of Cu(II) salts with
Typically, stoichiometric amounts of (PPh3)2CuNO3
(0.54 g, 0.83 mmol) and NaS2PMe2·2H2O (0.15 g,
0.81 mmol) were placed in a round-bottom flask and solvent
(CH2Cl2, ca. 20 mL) was added. The reaction mixture was
stirred for 2 h at room temperature, followed by filtration to
remove NaNO3. Concentration under vacuum gave
(Ph3P)2Cu[S2PMe2]
(1),
as
a
colorless
solid.
Recrystallization from a CH2Cl2–n-hexane mixture gave
crystals suitable for X-ray diffraction studies, yield 70%
2
(0.35 g), mp 185–187°C. 1H NMR δ: 1.77 (d, JP,H
=
3
12.8 Hz, 6H, P-CH3), 7.24 (t, JH,H = 7.2 Hz, 12H,
P(C6H5)3-meta), 7.34 (t, 3JH,H = 7.1 Hz, 6H, P(C6H5)3-para),
3
3
7.45 (dd, JH,H = 8.5, JP,H = 9.2 Hz, 12H, P(C6H5)3-ortho).
13C NMR δ: 31.84 (d, JP,C = 48.2 Hz, P-CH3), 128.40 (d,
1
2JP,C = 8.7 Hz, P(C6H5)3-ortho), 129.44 (P(C6H5)3-para),
134.11 (d, JP,C = 14.6 Hz P(C6H5)3-meta). 31P NMR δ: –4.1
3
′
dithio ligands of the type (SPR2)(SPR2)NH resulted in
(2P, PPh3), 60.7 (1P, PMe2).
In the same fashion the following compounds were pre-
pared:
polynuclear Cu(I) complexes such as trinuclear
′
[Cu{(XPR2)(YPR2)N}]3 (R, R′ = i-Pr, i-Pr; i-Pr, Ph; i-Pr, OPh;
OEt, OPh (12)) or tetranuclear [CuI4{(SPPh2)2N}3][CuICl2]
(R, R′ = Ph, Ph (13, 14)). By contrast, with O,S- and O,O-
(Ph3P)2Cu[OSPMe2] (2): from (PPh3)2CuNO3 (0.46 g,
0.70 mmol) and NaOSPMe2·1.5H2O (0.11 g, 0.69 mmol)
Recrystallization gave colorless crystals, yield 88% (0.44 g),
mp 143–145°C. H NMR δ: 1.54 (d, JP,H = 12.7 Hz, 6H,
P-CH3); 7.32 (m, 30H, P(C6H5)3). 31P NMR δ: –2.7 (2P,
PPh3), 64.1 (1P, PMe2).
phosphorus ligands of the type [OSPR2]– and
–
′
[(OPR2)(YPR2)N] , no Cu(I) complexes have been reported
to date, and only one Cu(II) complex Cu[{OP(OPh)2}2N]2
(15) has been reported. Therefore, we decided to examine
the differences that result in copper complexes using related
ligands when the organic groups and (or) the chalcogens at-
tached to the phosphorus atoms are changed.
We report on the synthesis and spectroscopic characteriza-
tion of new (Ph3P)2CuL and CuL2 complexes of anionic
phosphorus ligands, as well as the crystal and molecular
structures of two Cu(I) derivatives, (Ph3P)2Cu[S2PMe2] and
(Ph3P)2Cu[(OPPh2)2N], along with two Cu(II) derivatives,
Cu[(OPPh2)2N]2 and Cu[(OPPh2)(SPPh2)N]2.
1
2
(Ph3P)2Cu[OSPPh2] (3): from (PPh3)2CuNO3 (0.47 g,
0.72 mmol) and NH4OSPPh2 (0.18 g, 0.71 mmol). Recrystal-
lization gave colorless crystals, yield 98% (0.49 g), mp 148–
1
151°C. H NMR δ: 7.22 (m, 36H, P(C6H5)3, P-C6H5-meta +
3
3
para), 7.75 (dd, JH,H = 6.9, JP,H = 12.6 Hz, 4H, P-C6H5-
ortho). 13C NMR δ: 127.60 (d, JP,C = 12.8 Hz, P-C6H5-
3
2
meta), 128.45 (d, JP,C = 8.5 Hz, P(C6H5)32-ortho), 129.60
(P(C6H5)3-para, P-C6H5-para), 130.80 (d, JP,C = 9.9 Hz,
3
P-C6H5-ortho), 134.00 (d, JP,C = 13.8 Hz, P(C6H5)3-meta).
Experimental
31P NMR δ: –3.8 (2P, PPh3), 55.3 (1P, PPh2).
Materials
Starting materials were prepared according to published
methods: NaS2PMe2·2H2O (16), NaOSPMe2·1.5H2O (17),
(Ph3P)2Cu[(OPPh2)2N] (4): from (PPh3)2CuNO3 (0.38 g,
0.58 mmol) and Na[(OPPh2)2N] (0.26 g, 0.59 mmol).
Recrystallization gave colorless crystals, yield 84%
(0.42 g), mp 168–170°C. 1H NMR δ: 7.15 (m, 42H,
NH4OSPPh2
(18,
19),
Na[(OPPh2)2N]
(20),
K[(OPPh2)(SPPh2)N] (21), K[{OP(OEt)2}(SPPh2)N] (22),
© 2001 NRC Canada

Silvestru et al.
985
P(C6H5)3, P-C6H5-meta + para), 7.68 (dd, 3JH,H = 7.4, 3JP,H
=
=
Preparation of Cu[(OPPh2)(SPPh2)N]2 (9)
3
11.1 Hz, 8H, P-C6H5-ortho). 13C NMR δ: 127.43 (d, JP,C
Stoichiometric amounts of CuCl2·2H2O (0.092 g,
0.54 mmol) and K[(OPPh2)(SPPh2)N] (0.5 g, 1.06 mmol)
were placed in a round-bottom flask and CH2Cl2 (20 mL)
was added. The reaction mixture, which immediately turned
brown, was stirred for 6 h at room temperature before KCl
was filtered off to leave a brown solution. Concentration un-
der vacuum gave Cu[(OPPh2)(SPPh2)N]2 (9) as a dark
brown solid. Recrystallization from a CH2Cl2–n-hexane mix-
ture gave crystals suitable for X-ray diffraction studies, yield
66% (0.33 g), mp 90–91°C. 31P NMR δ: 21.5 (1P), 23.5 (1P,
P(O)Ph2, P(S)Ph2).
12.8 Hz, P-C6H5-meta), 128.17 (P(C6H5)3-ortho), 129.10
2
(P(C6H5)3-para), 129.28 (P-C6H5-para), 131.36 (d, JP,C
=
3
9.2 Hz, P-C6H5-ortho), 134.13 (d, JP,C = 7.8 Hz, P(C6H5)3-
meta). 31P NMR δ: –6.5 (2P, PPh3), 18.9 (2P, PPh2).
(Ph3P)2Cu[(OPPh2)(SPPh2)N] (5): from
(PPh3)2CuNO3
(0.34 g, 0.52 mmol) and K[(OPPh2)(SPPh2)N] (0.24 g,
0.50 mmol). Recrystallization gave colorless crystals, yield
94% (0.47 g), mp 170°C. 1H NMR δ: 7.22 (m, 42H,
P(C6H5)3, P-C6H5-meta + para), 7.59 (ddd, 3JH,H = 7.0, 4JH,H
1.1, 3JP,H = 12.1 Hz, 4H, P(O)-C6H5-ortho), 7.85 (ddd, 3JH,H
=
=
4
3
7.5, JH,H = 1.4, JP,H = 13.5 Hz, 4H, P(S)-C6H5-ortho). 13C
X-ray crystallographic analysis
Colourless, block crystals of (Ph3P)2Cu[S2PMe2] (1) and
3
NMR δ: 127.46 (d, JP,C = 11.4 Hz, P-C6H5-meta), 127.61
(d, JP,C = 10.9 Hz, P-C6H5-meta), 128.21 (d, JP,C = 8.0 Hz,
P(C6H5)3-ortho), 129.04 (P(C6H5)3-para), 129.43 (P-C6H5-
3
2
(Ph3P)2Cu[(OPPh2)2N] (4),
a
blue block crystal of
Cu[(OPPh2)2N]2 (8), and a dark brown block crystal of
Cu[(OPPh2)(SPPh2)N]2 (9) were mounted on glass fibres.
Data for 1, 4, and 8 were collected on an Enraf Nonius
KappaCCD area detector (φ scans and ω scans to fill Ewald
sphere) at the University of Southampton EPSRC National
Crystallography Service. For 9, data collection and process-
ing was carried out by G. Yapp, then at the University of
Windsor, using a Siemens SMART/CCD system. Cell refine-
ment (24) gave cell constants corresponding to orthorhombic
(for 1) and triclinic (for 4, 8, and 9) cells whose dimensions
are given in Table 1, along with other experimental parame-
ters. An absorption correction was applied (25), which re-
sulted in transmission factors ranging from 0.870 to 0.825
for 1, 0.943 to 0.842 for 4, 0.937 to 0.773 for 8, and 0.927 to
0.861 for 9.
2
para), 129.54 (P-C6H5-para), 130.93 (d, JP,C = 10.3 Hz,
2
P(O)-C6H5-ortho), 131.26 (d, JP,C = 9.1 Hz, P(S)-C6H5-
ortho), 134.12 (d, 3JP,C = 15.2 Hz, P(C6H5)3-meta). 31P NMR
δ: –5.7 (2P, PPh3), 18.1 (1P, P(O)Ph2), 30.0 (1P, P(S)Ph2).
(Ph3P)2Cu-[{OP(OEt)2}(SPPh2)N] (6): from (PPh3)2CuNO3
(0.46 g, 0.71 mmol) and K[{OP(OEt)2}(SPPh2)N] (0.29 g,
0.71 mmol). Recrystallization gave colorless crystals, yield
92% (0.46 g), mp 160°C. 1H NMR δ: 1.01 (t, 3JH,H = 6.9 Hz,
3
3
6H, P-O-CH2CH3), 3.67 (dq, JH,H = 6.9, JP,H = 7.1 Hz, 4H,
P-O-CH2CH3), 7.24 (m, 36H, P(C6H5)3, P-C6H5-meta +
3
3
para), 7.90 (dd, JH,H = 7.4, JP,H = 13.4 Hz, 4H, P-C6H5-
ortho). 31P NMR δ: –5.2 (2P, PPh3), 4.4 (1P, P(OEt)2), 34.2
(1P, PPh2).
The structures were solved by direct methods (26). All of
the nonhydrogen atoms were treated anisotropically. Hydro-
gen atoms were included in idealized positions with isotro-
pic thermal parameters set at 1.2 times that of the carbon
atom to which they were attached. The data for 1 and 4 were
of much better quality than that for 8, and the positions of
the higher residual peaks in the latter made no chemical
sense. The final cycle of full-matrix least-squares refinement
(27) was based on 8027 (1), 10601 (4), 3925 (8), and 9164
(9) observed reflections (4949 (1), 6343 (4), 3289 (8), and
7548 (9) for F2 > 4σ(F2)) and 399 (1), 613 (4), 269 (8), and
799 (9) variable parameters and converged (largest parame-
ter shift was 0.001 times its esd). The absolute configuration
parameter for 1 was –0.017(12). Selected distances and bond
angles are given in Tables 2–5 and the molecules are dis-
played in the ORTEP diagrams in Figs. 1–4.2
(Ph3P)2Cu[(SPMe2)2N] (7): from (PPh3)2CuNO3 (0.41 g,
0.63 mmol) and K[(SPMe2)2N] (0.15 g, 0.62 mmol).
Recrystallization gave colorless crystals, yield 80% (0.40 g),
mp 149–152°C. H NMR δ: 1.81 (d, JP,H = 12.0 Hz, 12H,
P-CH3), 7.35 (m, 30H, P(C6H5)3). 31P NMR δ: –2.9 (2P,
PPh3), 40.0 (2P, PMe2).
1
2
Preparation of Cu[(OPPh2)2N]2 (8)
Stoichiometric amounts of CuCl2·2H2O (0.095 g,
0.56 mmol) and K[(OPPh2)2N] (0.51 g, 1.12 mmol) were
placed in a round-bottom flask and solvent (MeOH, ca.
20 mL) was added. The reaction mixture was stirred for 12 h
at room temperature and the solvent was removed to dryness
under vacuum. The blue-greenish residual solid was ex-
tracted twice with CH2Cl2 (ca. 20 mL) to remove KCl and
unreacted starting materials. Concentration of the blue solu-
tion under vacuum then gave Cu[(OPPh2)2N]2 (8) as a blue
solid. Recrystallization from a CH2Cl2–n-hexane mixture
gave crystals suitable for X-ray diffraction studies, yield 72%
(0.36 g), mp 273 to 274°C. ESR (X band): gz = 2.017 ±
0.004, g|| = 2.086 ± 0.004, A = 140 ± 10 Gs, B = 30 ± 10 Gs.
Results and discussion
The preparation of the Cu(I) complexes ((Ph3P)2CuL) is
achieved by the reaction of stoichiometric amounts of
2 Supplementary material including the final atomic coordinates and equivalent isotropic thermal parameters for the nonhydrogen atoms,
anisotropic thermal parameters for the nonhydrogen atoms, final fractional coordinates and thermal parameters for hydrogen atoms, and all
bond distances and angles, have been deposited and may be purchased from the Depository of Unpublished Data, Document Delivery,
CISTI, National Research Council of Canada, Ottawa, ON, Canada, K1A 0S2 (http://www.nrc.ca/cisti/irm/unpub_e.shtml). Tables of atomic
coordinates for the structures reported in this paper have also been deposited with the Cambridge Crystallographic Data Centre. Copies of
the data can be obtained, free of charge, on application to the Director, CCDC, 12 Union Road, Cambridge, CB2 1EZ, U.K. (fax: 44-1223-
336033 or e-mail:deposit@ccdc.cam.ac.uk). Structure factor amplitudes are no longer being deposited and may be obtained directly from
the author.
© 2001 NRC Canada

Table 1. Crystal data and structure refinement for (Ph3P)2Cu(S2PMe2) (1), (Ph3P)2Cu[(OPPh2)2N] (4), Cu[(OPPh2)2N]2 (8), and Cu[(OPPh2)(SPPh2)N]2 (9).
1
4
8
9
Empirical formula
C38H36P3S2Cu
C60H50NO2P4Cu
C48H40N2O4P4Cu
C48H40N2O2P4S2Cu
FW
T (°C)
λ (Å)
Crystal system
Space group
713.24
298(2)
0.71073
Orthorhombic
P212121
1004.43
298(2)
0.71073
Triclinic
P1
896.24
298(2)
0.71073
Triclinic
P1
928.36
298(2)
0.71073
Triclinic
P1
a (Å)
b (Å)
c (Å)
α (°)
9.782(2)
17.808(4)
20.216(4)
9.8079(2)
8.887(2)
9.626(2)
12.9141(3)
22.5666(5)
75.714(2)
10.739(2)
12.477(3)
77.61(3)
14.151(3)
24.752(5)
88.23(3)
β (°)
79.465(2)
76.15(3)
79.93(3)
γ (°)
68.2770(8)
2559.9(1)
2
1.303
0.596
79.46(3)
1118.3(4)
1
1.331
0.677
89.77(3)
3318(1)
3
1.394
0.774
Volume (Å–3)
Z
3521.6(1)
4
1.345
0.901
ρcalcd. (g cm–3)
µ (mm–1)
F(000)
1480
1044
463
1437
Crystal size (mm)
θ range for data collection (°)
Limiting indices
0.25 × 0.15 × 0.10
3.05–27.89
–9 ≤ h ≤ 12, –18 ≤ k ≤ 23,
–25 ≤ l ≤ 25
21154
0.30 × 0.15 × 0.10
3.00–27.47
–12 ≤ h ≤ 12, –16 ≤ k ≤ 16,
–22 ≤ l ≤ 28
16010
0.10 × 0.10 × 0.10
3.21–25.03
–10 ≤ h ≤ 10, –12 ≤ k ≤ 12,
–14 ≤ l ≤ 14
9925
0.20 × 0.10 × 0.10
1.64–23.24
–10 ≤ h ≤ 10, –15 ≤ k ≤ 15,
0 ≤ l ≤ 27
9164
Reflections collected
Independent reflections
8028 (Rint = 0.0623)
10601 (Rint = 0.0422)
3925 (Rint = 0.0428)
9164 (Rint = 0.0496)
Max. and min. transmissions
Refinement method
0.870 and 0.825
0.943 and 0.842
0.937 and 0.773
0.9266 and 0.8605
Full-matrix least-squares on F2
8027/0/399
Data/restraints/ parameters
GoF on F2
10601/0/613
1.003
R1 = 0.0499, wR2 = 0.0967
R1 = 0.1048, wR2 = 0.1134
0.412 and –0.419
3925/0/269
1.062
R1 = 0.0702, wR2 = 0.2010
R1 = 0.0806, wR2 = 0.2129
2.305 and –0.477
9164/0/799
1.060
R1 = 0.0423, wR2 = 0.1129
R1 = 0.0538, wR2 = 0.1193
0.708 and –0.312
0.971
Final R indices [F2 > 4σ(F2)]
R indices (all data)
R1 = 0.0455, wR2 = 0.0788
R1 = 0.1059, wR2 = 0.0937
0.220 and –0.279
Largest diff. peak and hole (e Å3)

Silvestru et al.
Table 2. Selected bond lengths (Å) and angles (°) for (PPh3)2CuS2PMe2 (1).
987
Bond lengths (Å)
Cu(1)—P(1)
Cu(1)—S(1)
S(1)—P(3)
2.2718(10)
2.4343(12)
1.997(2)
Cu(1)—P(2)
Cu(1)—S(2)
S(2)—P(3)
2.2796(10)
2.4797(12)
2.000(2)
Bond angles (°)
P(1)-Cu(1)-P(2)
P(2)-Cu(1)-S(1)
P(2)-Cu(1)-S(2)
P(3)-S(1)-Cu(1)
C(1)-P(1)-Cu(1)
C(7)-P(1)-Cu(1)
C(13)-P(1)-Cu(1)
S(1)-P(3)-S(2)
117.09(4)
P(1)-Cu(1)-S(1)
P(1)-Cu(1)-S(2)
S(1)-Cu(1)-S(2)
P(3)-S(2)-Cu(1)
C(19)-P(2)-Cu(1)
C(25)-P(2)-Cu(1)
C(31)-P(2)-C(19)
C(37)-P(3)-C(38)
117.60(4)
114.20(4)
85.07(4)
107.08(4)
111.43(4)
80.75(5)
113.83(11)
112.16(11)
119.02(13)
112.47(7)
79.56(5)
117.34(13)
113.45(11)
103.1(2)
103.7(3)
Table 3. Selected bond lengths (Å) and angles (°) for (Ph3P)2Cu[(OPPh2)2N] (4) and Cu[(OPPh2)2N]2 (8).
4
8
Bond lengths (Å)
Cu(1)—O(1)
Cu(1)—O(2)
Cu(1)—P(1)
Cu(1)—P(2)
P(3)—O(1)
P(4)—O(2)
P(3)—N(1)
P(4)—N(1)
2.122(2)
2.165(2)
2.2554(7)
2.2449(7)
1.505(2)
1.503(2)
1.586(2)
1.586(2)
Cu(1)—O(1)
Cu(1)—O(2)
P(1)—O(1)
P(2)—O(2)
P(1)—N(1)
P(2)—N(1)
1.917(3)
1.918(3)
1.515(3)
1.508(3)
1.579(3)
1.575(4)
Bond angles (°)
O(1)-Cu(1)-P(1)
O(1)-Cu(1)-P(2)
O(2)-Cu(1)-P(1)
O(2)-Cu(1)-P(2)
P(1)-Cu(1)-P(2)
O(1)-Cu(1)-O(2)
P(3)-O(1)-Cu(1)
O(1)-P(3)-N(1)
P(3)-N(1)-P(4)
O(2)-P(4)-N(1)
P(4)-O(2)-Cu(1)
103.55(5)
O(1)-Cu(1)-O(2)
O(1)-Cu(1)-O(1)′
O(2)-Cu(1)-O(1)′
P(1)-O(1)-Cu(1)
O(1)-P(1)-N(1)
P(1)-N(1)-P(2)
O(2)-P(2)-N(1)
P(2)-O(2)-Cu(1)
94.67(13)
180.0
85.33(13)
131.60(17)
117.35(18)
125.6(2)
109.51(5)
106.91(5)
107.50(5)
126.10(3)
100.32(7)
119.13(11)
118.43(11)
129.5(2)
117.09(19)
132.6(2)
118.56(12)
119.14(10)
Note: Symmetry equivalent position (–x + 2, –y + 1, –z + 2) given by a prime.
(Ph3P)2CuNO3 with the ammonium or alkali salt of the ap-
propriate organophosphorus acid in CH2Cl2 as solvent, in
accord with rxn. [1]
even though similar reaction conditions were used. This sug-
gests that changes in the organic groups and (or) chalcogens
on phosphorus can influence the stoichiometry of the iso-
lated Cu(I) adducts.
[1]
(Ph3P)2CuNO3 + ML → (Ph3P)2CuL + MNO3
The (Ph3P)2CuL derivatives are readily dissolved in chlo-
roform, which is therefore used as the preferred solvent for
1
recording NMR spectra. In all cases, both H and 31P NMR
where L = (S2PMe2) (1), (OSPR2) (R = Me (2), Ph (3)),
[(XPR2)(YPR2)N] (X, Y, R, R′ = O, O, Ph, Ph (4), O, S, Ph,
Ph (5), O, S, OEt, Ph (6), S, S, Me, Me (7)).
′
data are consistent with a 2:1 molar ratio between the neu-
tral and anionic ligands. For (Ph3P)2Cu[OSPR2] (R = Me,
Ph) derivatives, the magnitude of the 31P chemical shifts is
indicative of an O,S-bidentate coordination of the monothio
ligand moieties δ: R = Me, 64.1 (PMe2) (cf. Me2P(S)OMe
94.3 (28), Me2P(O)SMe 45.9 (29)), R = Ph 55.3 (PPh2) (cf.
Ph2P(S)OMe 83.5 (29), Ph2P(O)SMe 42.8 (29)). The 31P
chemical shifts assigned for the phosphorus atoms of the an-
ionic ligand in the spectra of the Cu(I) imidodiphosphinato
All of the compounds are isolated in good yields as crys-
talline colorless solids and X-ray quality crystals are ob-
tained for 1 and 4. In previous reports, the use of
[(XPR2)2N]– (X = S, Se) ligands was found to result in dis-
placement of a coordinated triphenylphosphine and isolation
of trigonal (Ph3P)Cu[(XPR2)2N] (R = Ph, X = S (10), Se
(11)). By contrast, for all reactions (eq. [1]) investigated in
this work, the isolated products are found to preserve two
neutral phosphine ligands coordinated to the metal atom,
′
complexes (Ph3P)2Cu[(XPR2)(YPR2)N], are also consistent
with a chelated ligand. This behavior suggests that tetrahe-
© 2001 NRC Canada

988
Can. J. Chem. Vol. 79, 2001
Table 4. Selected bond lengths (Å) and angles (°) for Cu[(OPPh2)(SPPh2)N]2 (9).
9a
9b
Bond lengths (Å)
Cu(1)—O(1)
Cu(1)—O(2)
Cu(1)—S(1)
Cu(1)—S(2)
P(1)—O(1)
P(1)—N(1)
P(2)—N(1)
P(2)—S(1)
P(3)—O(2)
P(3)—N(2)
P(4)—N(2)
P(4)—S(2)
1.940(2)
1.934(2)
2.2837(11)
2.2931(11)
1.517(2)
1.590(3)
1.590(3)
2.0311(14)
1.518(2)
1.577(3)
1.578(3)
2.0344(14)
Cu(2)—O(3)
Cu(2)—O(3)′
Cu(2)—S(3)
Cu(2)—S(3)′
P(5)—O(3)
P(5)—N(3)
P(6)—N(3)
P(6)—S(3)
1.940(2)
1.940(2)
2.3398(13)
2.3398(13)
1.517(3)
1.583(3)
1.595(3)
2.0216(15)
Bond angles (°)
O(1)-Cu(1)-S(1)
O(1)-Cu(1)-S(2)
O(1)-Cu(1)-O(2)
O(2)-Cu(1)-S(1)
O(2)-Cu(1)-S(2)
S(1)-Cu(1)-S(2)
Cu(1)-O(1)-P(1)
O(1)-P(1)-N(1)
P(1)-N(1)-P(2)
S(1)-P(2)-N(1)
Cu(1)-S(1)-P(2)
Cu(1)-O(2)-P(3)
O(2)-P(3)-N(2)
P(3)-N(2)-P(4)
S(2)-P(4)-N(2)
Cu(1)-S(2)-P(4)
100.12(8)
O(3)-Cu(2)-S(3)
O(3)-Cu(2)-S(3)′
O(3)-Cu(2)-O(3)′
O(3)′-Cu(2)-S(3)
O(3)′Cu(2)-S(3)′
S(3)-Cu(2)-S(3)′
Cu(2)-O(3)-P(5)
O(3)-P(5)-N(3)
P(5)-N(3)-P(6)
S(3)-P(6)-N(3)
Cu(2)-S(3)-P(6)
97.47(8)
82.53(8)
180
82.53(8)
97.47(8)
180
125.37(16)
117.45(15)
120.93(19)
115.43(12)
104.19(5)
149.35(8)
88.91(11)
140.59(8)
100.74(8)
90.76(5)
130.10(15)
117.42(15)
125.53(19)
117.69(12)
106.06(6)
132.82(15)
116.78(15)
132.57(19)
118.91(12)
107.00(5)
Note: Symmetry equivalent position (–x, –y, –z) given by a prime.
dral structures similar to that established in the solid state
for (Ph3P)2Cu[S2PMe2] (1) and (Ph3P)2Cu[(OPPh2)2N] (4)
(see below), are preserved in solution. However, a recent re-
port (8) demonstrates that the nature of the anionic ligand
may result in significant structural modifications so that, in
the solid state, (Ph3P)2Cu[S(O)CPh] is mononuclear with
only a weak intramolecular Cu···O interaction (2.439(2) Å),
while [(Ph3P)2Cu(OSCMe)]2 is dinuclear with different
coordination modes for the monothiocarboxylato moieties
(S-bridging and O,S-bridging).
The Cu(II) complexes, Cu[(OPPh2)(YPPh2)N]2 (Y = O (8),
S (9)), are obtained by reacting stoichiometric amounts of
CuCl2·2H2O with the potassium salt of the imidodiphosph-
inato acid in organic solvent at room temperature, in accord
with rxn. [2].
symmetry with the strongest interaction for the case when
the magnetic field is parallel to the deformation axis of the
paramagnetic center. For the perpendicular orientation the
splitting is too small and the four lines cannot be separated.
The analysis of the spectrum was carried out with the axially
symmetric spin Hamiltonian, the nuclear quadrupole interac-
tion being neglected. The values of the hyperfine tensor A
and B (parallel and perpendicular components to the
tetragonal axis) and of the g-factors were calculated. The g-
factors are consistent with a |x2 – y2 > ground state of the
paramagnetic ion, while the magnitude of the A value sug-
gests a relatively large electronic density at the Cu nucleus.
The brown crystals of the monothio derivative 9 are
readily soluble in organic solvents, and the 31P NMR spec-
trum of its CDCl3 solution exhibited two broad resonance
signals. A more detailed examination of its spectroscopic
properties, both in solution and the solid state, is being un-
dertaken.
[2]
CuCl2·2H2O + K[(OPPh2)(YPPh2)N] →
Cu[(OPPh2)(YPPh2)N]2 + 2KCl + 2H2O
Blue crystals of the dioxo derivative 8 are also formed di-
rectly in an NMR tube during evaporation in open atmo-
sphere of a CDCl3 solution of (Ph3P)2Cu[(OPPh2)2N] (4)
(m/z 896 (molecular ion), and identical spectroscopic proper-
ties as a pure sample of the same compound). In the EPR
spectrum of 8, the characteristic hyperfine structure for
Cu(II) ions is observed. The hyperfine tensor exhibits axial
Crystal structure of (Ph3P)2Cu[S2PMe2] (1)
The dithiophosphinato derivative (Ph3P)2Cu[S2PMe2] (1),
is monomeric. Its molecular structure is displayed as an
ORTEP diagram (Fig. 1), and important bond distances and
bond angles are given in Table 2. The dithio ligand is essen-
tially isobidentate (Cu(1)—S(1) 2.4343(12), Cu(1)—S(2)
2.4797(12) Å), resulting in approximately tetrahedral
© 2001 NRC Canada

Silvestru et al.
989
Fig. 1. ORTEP plot of the molecule (Ph3P)2Cu(S2PMe2) (1). The
atoms are drawn with 50% probability ellipsoids.
Fig. 3. ORTEP plot of the molecule Cu[(OPPh2)2N]2 (8). The at-
oms are drawn with 50% probability ellipsoids. Carbon atoms of
the phenyl rings other than the ipso atoms and hydrogen atoms
are omitted for clarity. Copper located at –1 symmetry center.
C(13')
C(19')
C(1)
P(1)
P(2')
C(7)
O(2')
O(1)
O(2)
C(19)
N(1')
Cu(1)
O(1')
N(1)
P(1')
P(2)
C(13)
C(7')
C(1')
Fig. 4. ORTEP plot of the molecule Cu[(OPPh2)(SPPh2)N]2 (9)
showing the two copper environments: (a) tetrahedral, with Cu
located at a general position; and (b) square planar, with Cu lo-
cated at –1 symmetry center. The atoms are drawn with 50%
probability ellipsoids. Carbon atoms of the phenyl rings other
than the ipso atoms and hydrogen atoms are omitted for clarity.
Fig. 2. ORTEP plot of the molecule (Ph3P)2Cu[(OPPh2)2N] (4).
The atoms are drawn with 50% probability ellipsoids. Hydrogen
atoms are omitted for clarity.
C(13)
C(19)
P(2)
S(1)
N(1)
S(2)
Cu(1)
C(37)
P(1)
P(4)
C(1)
O(1)
P(3)
O(2)
C(43)
N(2)
C(7)
(a)
C(25)
C(31)
C(61)
CuP2S2 coordination (dihedral angle Cu(1)-P(1)-P(2) –
Cu(1)-S(1)-S(2) 86.9°). The four-membered CuS2P chelate
ring is nonplanar but folded about the S(1)–S(2) axis
(17.3°). The overall molecular structure is very similar to
S(3)
C(49')
O(3')
P(6)
C(55')
that
of
the
related
dithiophosphato
derivative,
P(5')
C(67')
C(67)
(Ph3P)2Cu[S2P(OEt)2] (3). The main difference is in the rela-
tive magnitudes of the phosphorus sulfur bond lengths
(1.997(2), 2.000(2) Å in 1 vs. 1.967(2), 1.973(2) Å), reflect-
ing the nature of the phosphorus ligands, which contain P–C
or P–OC bonds.
N(3)
N(3')
Cu(2)
P(6')
O(3)
C(55)
P(5)
(b)
S(3')
Crystal structure of (Ph3P)2Cu[(OPPh2)2N] (4)
C(61')
The molecular structure of the Cu(I) imidodiphosphinate,
(Ph3P)2Cu[(OPPh2)2N] (4), is displayed as an ORTEP dia-
gram (Fig. 2), and important bond distances and bond angles
C(49)
© 2001 NRC Canada

990
Can. J. Chem. Vol. 79, 2001
are given in Table 3. This mononuclear compound contains
a chelating dioxo ligand (Cu(1)—O(1) 2.122(2), Cu(1)—O(2)
2.165(2) Å), and the resulting tetrahedral CuP2O2 core is
symmetry, also exhibit distorted boat conformations, but
one ring is folded about the P(1)–S(1) axis (dihedral angle
S(1)-Cu(1)-O(1)-P(1) – S(1)-P(2)-N(1)-P(1) 145.2°), while
the other is folded about the Cu(1)–N(2) axis (dihedral angle
Cu(1)-O(2)-P(3)-N(2) – Cu(1)-S(2)-P(4)-N(2) 26.5°). The
P-N-P angles within the two chelate rings in 9a are signifi-
cantly different (125.53(19) and 132.57(19)°); both being
larger than in 9b (120.93(19)°).
characterized by
a dihedral angle Cu(1)-P(1)-P(2) –
Cu(1)-O(1)-O(2) 88.1° close to that observed in 1. The six-
membered CuO2P2N chelate ring displays a twisted boat
conformation being folded about the P(3)–O(2) axis (dihed-
ral angle O(2)-Cu(1)-O(1)-P(3)
– O(2)-P(4)-N(1)-P(3)
29.0°). Similar tetrahedral, mononuclear structures have also
been reported for related β-diketonato derivatives, such as
(R3P)2Cu[(OCCF3)2C] (R = Ph (30), Cy (31)).
The Cu—O, P—O, P—S, and P—N bond distances in the
two independent molecules are similar (Table 4), but the
Cu—S bond distances in the square-planar core of 9b
(2.3398(13) Å) are significantly longer than in the tetrahe-
dral core of 9a (2.2837(11), 2.2931(1) Å) or in the trans-
Cu[(OCPh)(SCNEt2)CH]2 complex (trans-isomer 2.254(1) Å,
cis-isomer 2.236(2), 2.244(2) Å).
Crystal structure of Cu[(OPPh2)2N]2 (8)
The crystal of the Cu(II) complex 8 contains discrete mol-
ecules of Cu[(OPPh2)2N]2 displayed as an ORTEP diagram
in Fig. 3. Both imidodiphosphinato ligands act as chelating
units, leading to a distorted square planar CuO4 core, with
trans-O-Cu-O angles of 180° and endocyclic-O-Cu-O angles
(94.67(13)°) larger than exocyclic (85.33 (13)°). Not only is
the CuO4 core planar (dihedral angle Cu(1)-O(1)-O(2) –
Cu(1)-O(1′)-O(2′) 0°), but the whole spiro-bicyclic system is
almost planar (deviations from the CuO4 plane: P(1) –0.136,
P(2) 0.076, N(1) –0.002 Å). The quasi-planarity of the six-
membered CuO2P2N ring in 8 is in strong contrast to the
twisted boat conformation observed in 4, pointing out the
high flexibility of the OPNPO skeleton. The Cu—O bond
distances are considerably shorter in 8 (1.917(3), 1.918(3) Å)
than in 4 (2.122(2), 2.165(2) Å), while the P—O and P—N
distances are similar as are the O-P-N angles. However, the
P-N-P and Cu-O-P angles are larger in 8 than in 4 (ca. 4 and
13°, respectively, (Table 3)), which is presumably required
to achieve the planarity of the chelate ring. The overall
structure is similar to that of the related derivative,
Cu[{OP(OPh)2}2N]2 (15), indicating that at least in this
case, replacement of phenoxy by phenyl groups on phospho-
rus atoms does not result in significant structural changes.
Concluding comments
Previous reports have indicated that ligands such as
[(XPPh2)2N]– (X = S, Se) tend to displace coordinated
triphenylphosphine resulting in the isolation of trigonal
(Ph3P)Cu[(XPR2)2N] species. By contrast, monomeric, tetra-
hedral Cu(I) complexes of the type (Ph3P)2CuL (L =
[(XPR2)(YPR′2)N]– (X, Y, R, R′ = O, O, Ph, Ph; O, S, Ph,
Ph; O, S, OEt, Ph, S, S, Me, Me)), [S2PMe2]–, [OSPR2]– (R =
Me, Ph) are formed by treatment of (Ph3P)2CuNO3 with
salts of the appropriate organophosphorus acid, regardless of
the nature of the organophosphorus ligands. The presence of
a tetrahedral CuIX4 core is confirmed by the X-ray structures
of (Ph3P)2Cu[S2PMe2] (1) and (Ph3P)2Cu[(OPPh2)2N] (4),
and NMR studies indicate that the tetrahedral coordination
environment at the Cu(I) atom is also preserved in solution.
For related Cu(II) complexes, Cu[(OPPh2)2N]2 (8) has the
expected planar CuO4 core but, remarkably, the whole spiro-
bicyclic system is almost planar. Even more surprising is the
existence of copper in both planar and tetrahedral environ-
ments in the case of the monothio derivative
Cu[(OPPh2)(SPPh2)N]2 (9), with the planar and tetrahedral
molecules being in a ratio of 1:2.
Crystal structure of Cu[(OPPh2)(SPPh2)N]2 (9)
The most interesting feature of the solid state structure of
the monothio derivative, Cu[(OPPh2)(SPPh2)N]2 (9), is the
presence of both tetrahedral (a) and square-planar (b) copper
environments in a 2:1 ratio, as displayed as an ORTEP dia-
gram in Fig. 4. Important bond distances and bond angles
are given in Table 4.
The conformations of the six-membered CuOXP2N (X =
O, S) rings differ considerably in 1, 4, and 8, providing fur-
ther evidence of the high flexibility of the OPNPX skeleton.
Acknowledgment
The copper atom is in a special position in the square-
planar molecule (Fig. 9b) to give the trans-CuO2S2 core
(O(3)-Cu(2)-O(3′) and S(3)-Cu(2)-S(3′) of 180°) with the
endocyclic O(3)-Cu(2)-S(3) angle (97.47(8)°) again larger
than the exocyclic O(3)-Cu(2)-S(3′) (82.53(8)°). A similar
coordination geometry is found in one of the two independ-
ent molecules of Cu[(OCPh)(SCNEt2)CH]2 (32) in which
the crystals contain one molecule with a trans-arrangement
of the square-planar CuO2S2 core and a second molecule
with a cis-arrangement of the chalcogen atoms around the
metal center. In contrast to the dioxo derivative 8, the six-
membered CuOSP2N ring in 9b exhibits a twisted boat con-
formation which is folded about the P(6)–O(3) axis (dihedral
angle O(3)-Cu(2)-S(3)-P(6) – O(3)-P(5)-N(3)-P(6) 44.3°).
The other molecule (Fig. 9a) exhibits tetrahedral distor-
tion, with a dihedral angle Cu(1)-O(1)-S(1) – Cu(1)-O(2)-S(2)
of 46.51°. The two CuOSP2N rings, which are not related by
J.E.D. wishes to thank the Natural Sciences and Engi-
neering Research Council of Canada (NSERC) for financial
support. M.B.H. thanks the U.K. Engineering and Physical
Sciences Research Council for support of the X-ray facilities
at Southampton.
References
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