Chalcogenolato-di-thiocarbamato-complexes of zinc: The X-ray single crystal structures of pyridine adducts

Article abstract of DOI:10.1016/S0277-5387(98)00427-6

Novel mixed complexes 2,4,6-Me₃C₆H₂SZnS₂CNEt₂ (1), 2,4,6-Me₃C₆H₂SeZnSe₂CNEt₂ (2) and their pyridine adducts ([Zn(SC₆H₂Me

Full text of DOI:10.1016/S0277-5387(98)00427-6

Polyhedron 18 (1999) 1259–1264
Chalcogenolato-di-thiocarbamato-complexes of zinc:
The X-ray single crystal structures of pyridine adducts
M. Azad Malika, M. Motevallib, Paul O’Briena,
*
aDepartment of Chemistry, Imperial College of Science, Technology and Medicine, South Kensington, London SW7 2AY, UK
bDepartment of Chemistry, Queen Mary and Westfield College, Mile End Road, London E1 4NS, UK
Received 30 September 1998; accepted 23 November 1998
Abstract
Novel mixed complexes 2,4,6-Me3C6H2SZnS2CNEt2 (1), 2,4,6-Me3C6H2SeZnSe2CNEt2 (2) and their pyridine adducts
([Zn(SC6H2Me3-2,4,6)2(C5H5N)2] (3), [Zn(SeC6H2Me3-2,4,6)2(C5H5N)2] (4) and (Et2CNSe2)2Zn.NC5H5 (5) and
(Et2CNS2)2Zn.NC5H5 (6) have been synthesised and characterised. The X-ray single crystal structures of (4), (5) and (6) have been
determined. 1999 Elsevier Science Ltd. All rights reserved.
Keywords: Cadmium complexes; Zinc complexes; Chalcogenides; Pyridine adducts
1. Introduction
2,4,6)2(C5H5N)2] (3), [Zn(SeC6H2Me3-2,4,6)2(C5H5N)2]
(4) and (Et2CNSe2)2Zn.NC5H5 (5) and
Arene-thiolato or -selenolato complexes of cadmium or
zinc are usually crystalline solids with infinite lattices in
which the metal centre is bridged by the chalcogenolato
ligands to give pseudo-tetrahedral co-ordination at the
metal [1–4]. The structures of metal-arene chalcogenalato
complex are strongly influenced by packing arrangements
and the nature of the substituents [5] on the arene-chal-
cogenalato ligands is crucial. The mesityl (2,4,6-tri-
methylphenyl) chalogens form one dimensional chain
structures whereas the related 2,4,6-trimethylphenyl com-
plexes MER2 (M5Cd or Zn; E5S or Se) are polymeric
solids which only dissolve in co-ordinating solvents [6].
Other than for Cd(SR)2 (R5C6H2Me3-2,4,6), which forms
a unstable crystalline pyridine adduct, [Cd(SR)2. (py)2], no
defined pyridine adducts have been obtained [6]. The
bulkier tert-butyl analogue of the mesityl aryl group forms
dimers in the solid state [7] which are air-stable, sublime
under reduced pressure, dissociate to monomers and hence
are useful precursors for film deposition by MOCVD.
We report the synthesis and characterisation of several
novel compounds, derived from these chalcogenides. The
compounds synthesised include: the mixed complexes
2,4,6-Me3C6H2SZnS2CNEt2 (1), 2,4,6-Me3C6H2SeZn-
Se2CNEt2 (2) and their pyridine adducts ([Zn(SC6H2Me3-
(Et2CNS2)2Zn.NC5H5 (6) The X-ray single crystal struc-
tures of (4), (5) and (6) have been determined.
2. Experimental
2.1. Chemicals
Dimethylzinc was supplied by Epichem Ltd. Carbon
disulphide, diethylamine, diethyl ether, toluene, thf were
purchased from Aldrich Chemical Co. Ltd, solvents were
dried (distilled after boiling with sodium metal and ben-
zophenone for two hours under nitrogen) and degassed by
freeze and thawing. This process was repeated three times
before use. Carbon diselenide was prepared using the
literature method [12].
2.2. Physical measurements
NMR spectra were recorded using a Bruker AM250
pulsed Fourier transform instrument. Infra red spectra were
carried out using Matteson Polaris FT-IR spectrometer as
nujol mulls, mass spectra were recorded by a micromass
Auto-spec-Q using micromass OPUS software. An elec-
tron impact energy of 70 eV at 1027 Torr was used to
initiate mass fragmentation. Melting points were measured
*
Corresponding author. E-mail: p.obrien@ic.ac.uk
0277-5387/99/$ – see front matter
PII: S0277-5387(98)00427-6
1999 Elsevier Science Ltd. All rights reserved.

1260
M. Azad Malik et al. / Polyhedron 18 (1999) 1259–1264
in sealed tubes with an electrothermal melting point
apparatus and are uncorrected. Microanalyses were carried
out by the Imperial College London service.
Atomic co-ordinates, thermal parameters and bond
lengths and angles have been deposited at the Cambridge
Crystallographic Data Center (CCDC).
2.4. Synthesis
2.3. X-ray crystallography
All reactions were performed under dry nitrogen using
standard Schlenck techniques. 2,4,6-Me3C6H2SH, 2,4,6-
Me3C6H2SeH [11,6], CSe2 [12] MeZnS2CNEt2 [13] and
MeZnSe2CNEt2 were prepared as described in the litera-
ture [14].
The structures of compounds (4), (5) and (6) were
determined by single crystal X-ray methods. Measure-
ments were made on a sample mounted in a glass capillary.
The intensity data were collected with a CAD4 diffrac-
tometer in v/2u scan mode with graphite-monochromated
Mo Ka, and corrected for absorption by the empirical
method (c-scan) [8]. The unit cell parameters were de-
termined by a least-squares refinement on diffractometer
angles for automatically centred reflections. The structure
was solved by the heavy-atom method using the SHELX-97
program package [9] and than refined anisotropically (non-
hydrogen atoms) by a full-matrix least-square on F2. All
hydrogen atoms were calculated geometrically (riding
model) using the AFIX command of the SHELX-97 pro-
gram. The program ORTEP-3 for Windows [10] was used for
drawing molecular structures. Crystal data and details of
the intensity measurements and refinements are given in
Table 1.
2.4.1. 2,4,6-Me3C6H2SZnS2CNEt2 (1)
2,4,6-Me3C6H2SH (0.20 g, 1.4 mmol) and
MeZnS2CNEt2 (0.33 g, 1.4 mmol) in toluene (20 cm3)
were stirred and heated at 808C for 0.5 h. The mixture on
concentration gave white powder which was separated by
decanting the solvent. The product, m.p. .2608C (0.40 g,
1.1 mmol, 79%) was insoluble in most organic solvents
and hence could not be recrystallised. (Found: C, 45.38; H,
5.68; N, 3.93; S, 26.42. Calculated: C, 46.08; H, 5.80; N,
3.84; S, 26.36). 1H NMR ([2H6]C6H6), 250 MHz) d (ppm)
1.30 [6H, t, CH3], 3.84 [4H, q, CH2], 1.55 [6H, s, CCH3],
2.24 [3H, s, CCH3], 6.71 [2H, s, C6H2-]. 13C-h1Hj NMR
Table 1
Crystal data and structure refinement
(4)
(5)
(6)
Formula
C28H32N2Se2Zn
619.85
Monoclinic
0.430.330.25
P21/a
16.410(3)
12.425(1)
13.546(2)
90
99.68(2)
90
C15H25N3Se4Zn
628.59
Monoclinic
0.3530.2330.2
P21/c
10.392(5)
32.796(8)
13.186(4)
90
105.41(4)
90
C15H25N3S4Zn
440.99
Monoclinic
0.3030.2530.2
P21/c
10.140(2)
31.794(5)
13.48191)
90
107.17(1)
90
Molecular weight
Crystal system
Crystal size, mm
Space group
˚
a, A
˚
b, A
˚
c, A
a/8
b/8
g/ 8
3
˚
Volume (A )
2722.6(7)
4
1.512
4332(3)
8
1.927
4152.5(2)
8
1.411
Z
Dcalc (g cm23
F(000)
)
1248
2416
1840
Temperature (K)
293(2)
Mo Ka
3.594
293(2)
Mo Ka
7.855
293(2)
Mo Ka
1.58
˚
l, A
m, mm21
20 range (8)
Data/restraints/parameters
Observed
1.52/26.97
5926/0/316
3012
1.72/24.97
7608/0/441
4134
1.28/24.98
7274/0/441
3959
reflections[I.2s(I)]
Refinement method
Full-matrix least
squares on F2
0.878
a50.0569, b50.00
0.0484
Full-matrix least
squares on F2
0.966
a50.1308, b50.00
0.0567
Full-matrix least
squares on F2
1.054
a50.0626, b50.00
0.0497
Goodness of fit on F2
Calculated weightsa
Final Rb
c
Final WR2
0.0.0979
0.1680
0.1194
a w51[s2(F2o)1(aP)21bP] where P5(Fo212F2c )/3.
b R5ouuFou2uFCuu/ouFou.
c
WR25[o[w(F2O2F2C)2]/o[w(F2O)2]]1 / 2
.

M. Azad Malik et al. / Polyhedron 18 (1999) 1259–1264
1261
([2H6]C6H6), 62.9 MHz) d (ppm) 12.09 [CH3], 49.21
[CH2], 26.51 [(CH3)2], 20.72 [CCH3], 128.3 [meta-C],
138.9 [ortho-], 142.2 [ipso-C], 128.4 [para-C], 202.2
[CS2]. IR major bands and tentative assignments) 559, 557
cm21 (y(Zn–S), 987cm21 (y(C=S), 1489 cm21 (y(C=N).
Mass spectrum (m/z): M1 362 [Me3C6H2SZnS2CNEt2],
base peak 116 [SCNEt2], 244 [SZnS2CNEt2], 212
[ZnS2CNEt2], 148 [S2CNEt2], 119 [Me3C6H2], 96 [ZnS],
72 [NEt2], 44 [HNEt].
2.4.2. 2,4,6-Me3C6H2SeZnSe2CNEt2 (2)
A mixture of 2,4,6-Me3C6H2SeH (0.85 g, 4.3 mmol)
and MeZnSe2CNEt2 (1.40 g, 4.3 mmol) in toluene (20
cm3) were stirred and heated at 808C for 0.5 h. On cooling
a yellowish powdery material settled in a yellow solution.
The product was separated by decanting the solvent and
dried under vacuum, m.p. .2608C (1.51 g, 3.0 mmol,
87%). Several attempts to recrystallise from ordinary
organic solvent were unsuccessful as the product was
insoluble in most of them. (Found: C, 33.11; H, 4.13; N,
1
2.86. Calculated: C, 33.26; H, 4.18; N, 2.77). H NMR
([2H6]C6H6), 250 MHz) d (ppm) 1.35 [6H, t, CH3], 3.79
[4H, q, CH2], 1.48 [6H, s, CCH3], 2.20 [3H, s, CCH3],
6.69 [2H, s, C6H2 –]. 13C-h1Hj NMR ([2H6]C6H6), 62.9
MHz) d (ppm) 11.7 [CH3], 52.1 [CH2], 27.2 [(CCH3)2],
19.9 [CCH3], 122.6 [meta-C], 136.5 [ortho-C], 143.1
[ipso-C], 126.7 [para-C], 191.3 [CSe2].
Scheme 1.
4.09;). NMR data: 1H NMR ([2H6]C6H6), 250 MHz) d
(ppm) 2.10 [3H, s, CH3], 2.66 [6H, s, (CH3)2], 6.71 [2H,
s, C6H2 –], 6.37, 6.68, 8.45 [5H, m, NC5H5]. 13C-h1Hj
NMR ([2H6]C6H6), 62.9 MHz) d (ppm) 20.89 [CH3],
27.20 [(CH3)2], 122.0 [meta-C], 134.1 [ortho-C], 142.3
[ipso-C], 133.0 [para-C],, 123.9, 139.2, 149.6 [NC5H5]. IR
(major bands and tentative assignments) 476 cm21 (y(Zn–
Se), 798 cm21 (y(C–Se).
Compound (5) : (Found: C, 28.72; H, 4.0; N, 6.75.
Calculated: C, 28.65; H, 3.98; N, 6.68). 1H NMR
([2H6]C6H6), 250 MHz) d (ppm) 1.23 [6H, t, CH3], 3.95
[4H, q, CH2], 7.43, 7.78, 8.88 [5H, m, NC5H5]. 13C-h1Hj
NMR ([2H6]C6H6), 62.9 MHz) d (ppm) 11.7 [CH3], 52.6
[CH2], 124.6, 138.3, 149.1 [NC5H5], 189.9 [CSe2]. IR
(major bands and tentative assignments) 447 cm21 (y(Zn–
Se), 837 cm21 (y(C–Se), 1508 cm21 (y(C=N).
Compound (6): (Found: C, 41.23; H, 5.73; N, 9.71.
Calculated: C, 40.87; H, 5.68; N, 9.54;). 1H NMR
([2H6]C6H6), 250 MHz) d (ppm) 1.29 [6H, t, CH3], 3.87
[4H, q, CH2], 7.45, 7.84, 8.98 [5H, m, NC5H5]. 13C-h1Hj
NMR ([2H6]C6H6), 62.9 MHz) d (ppm) 12.1 [CH3], 49.1
[CH2], 124.4, 137.8, 149.5 [NC5H5], 203.3 [CS2]. IR
(major bands and tentative assignments) 463 cm21 (y(Zn–
S), 973 cm21 (y(C–S), 1510 cm21 (y(C=N).
IR (major bands and tentative assignments) 472, 503
cm21 (y(Zn–Se), 850 cm21 (y(C=Se), 1503 cm21
(y(C=N).
Mass
spectrum
(m/z):
M1
507
[Me3C6H2SeZnSe2CNEt2], base peak 44 [HNEt], 388
[SeZnSe2CNEt2], 308[ZnSe2CNEt2], 244 [Se2CNEt2],
119 [Me3C6H2], 144 [ZnSe], 72 [NEt2].
2.4.3. 2,4,6-Me3C6H2SNC5H5 (3) and 2,4,6-
Me3C6H2SeNC5H5 (4), (Et2CNSe2 )2Zn.NC5H5 (5) and
(Et2CNS2 )2Zn.NC5H5 (6)
All four compounds were prepared by the reaction of
compounds (1) or (2) with an excess of pyridine. The
mixture was heated to obtain a clear solution, concentrated
under vacuum, and left in the fridge to crystallise. Crys-
talline products were obtained for all compounds, (Scheme
1).
Compound (3): m.p. 2558C (decomp.), 89%, (Found: C,
56.06; H, 5.39; N, 4.89; S, 10.90. Calculated: C, 56.86; H,
5.45; N, 4.78; S, 10.84). NMR data: 1H NMR
([2H6]C6H6), 250 MHz) d (ppm) 2.11 [3H, s, CH3], 2.66
[6H, s, (CH3)2], 6.71 [2H, s, C6H2 –], 6.39, 6.72, 8.45 [5H,
m, NC5H5]. 13C-h1Hj NMR ([2H6]C6H6), 62.9 MHz) d
(ppm) 21.1 [CH3], 27.4 [(CH3)2], 128.0 [meta-C], 131.5
[ortho-C], 142.8 [ipso-C], 133.2 [para-C], 124.5, 138.0,
149.3 [NC5H5]. IR (major bands and tentative assign-
ments) 557 cm21 (y(Zn–S), 866 cm21 (y(C–S).
Compound (4): m.p. 2458C (decomp.), 67% (Found: C,
47.98; H, 4.64; N, 4.15. Calculated: C, 49.08; H, 4.71; N,
3. Results and discussion
3.1. Structure of [Zn(SeC6H2Me3-2,4,6)2(C5H5N)2 ] (4)
The structure of the pyridine adduct (4) was determined

1262
M. Azad Malik et al. / Polyhedron 18 (1999) 1259–1264
Table 2
˚
Selected bond lengths [A] and angles [8]
Compound (4)
Zn(1)–N(1)
Zn(1)–N(2)
2.112(4)
2.125(3)
Zn(1)–Se(2)
Zn(1)–Se(1)
Se(1)–C(20)
2.3768(9)
2.3775(8)
1.926(4)
Se(2)–C(11)
1.925(4)
N(1)–Zn(1)–N(2)
N(1)–Zn(1)–Se(2)
N(2)–Zn(1)–Se(2)
N(1)–Zn(1)–Se(1)
N(2)–Zn(1)–Se(1)
Se(2)–Zn(1)–Se(1)
93.94(14)
110.61(12)
100.92(10)
106.82(13)
108.18(10)
130.16(3)
Compound (5)
Zn(1)–N(1)
Zn(1)–Se(2)
Zn(1)–Se(3)
Zn(1)–Se(1)
2.054(10)
2.430(2)
2.4329(19)
2.737(2)
2.749(2)
112.2(3)
109.8(3)
137.89(8)
96.4(3)
75.84(6)
102.44(7)
94.0(3)
98.14(7)
75.95(6)
169.34(7)
Zn(1)–Se(4)
N(1)–Zn(1)–Se(2)
N(1)–Zn(1)–Se(3)
Se(2)–Zn(1)–Se(3)
N(1)–Zn(1)–Se(1)
Se(2)–Zn(1)–Se(1)
Se(3)–Zn(1)–Se(1)
N(1)–Zn(1)–Se(4)
Se(2)–Zn(1)–Se(4)
Se(3)–Zn(1)–Se(4)
Se(1)–Zn(1)–Se(4)
Fig. 1. The molecular structure of [Zn(SeC6H2Me3-2,4,6)2(C6H5N)2].
by single crystal X-ray diffraction methods. The molecular
structure is shown in Fig. 1 and selected bond distances
and angles are given in Table 2. The structure is based on
monomeric units where the zinc atom is four co-ordinated
through two nitrogen atoms of pyridine and two selenium
atoms of the mesitylselenolato group. The co-ordination
can be defined as distorted tetrahedral. Zn–N bond dis-
tances in adducts such as Me2Zn[(CH2NMe)3]2 [15,16]
Compound (6)
Zn(1)–N(1)
Zn(1)–S(3)
Zn(1)–S(1)
Zn(1)–S(2)
2.072(4)
2.3561(17)
2.3691(17)
2.5292(17)
2.5566(18)
109.32(14)
110.38(14)
140.28(7)
96.53(14)
102.90(6)
73.72(6)
Zn(1)–S(4)
N(1)–Zn(1)–S(3)
N(1)–Zn(1)–S(1)
S(3)–Zn(1)–S(1)
N(1)–Zn(1)–S(2)
S(3)–Zn(1)–S(2)
S(1)–Zn(1)–S(2)
N(1)–Zn(1)–S(4)
S(3)–Zn(1)–S(4)
S(1)–Zn(1)–S(4)
S(2)–Zn(1)–S(4)
˚
(2.410(4)
A),
Me2Zn[(Me2N(CH2)2NMe2]2
[17]
˚
˚
(2.260(8) A), [Me2N(CH2)3]Zn [18] (2.307(4) A),
˚
(Me3CCH2)2Zn[Me2N(CH2)2NMe2]2 [17] (2.411(4) A),
[(Et2NCO2)2Zn(Me2NCH2)2] [19] (2.208(9), 2.179(6)
˚
A), are much larger than those observed in this structure
95.63(14)
73.37(6)
101.51(6)
167.84(6)
˚
(2.112(4), 2.125(3) A). The bond distances in other
˚
adducts e.g. C5H5N.Zn[S2CNMe2]2 [20] (2.079 (9) A),
[(CNS)ZnS2CNMe2)2]2
[21]
(1.954(9)
A),
˚
˚
[(Et2NCO2)3MeZn2 NC5H5)2] [19] (2.057(6) A), [2,4,6-
˚
CF3(C6H2)Se]ZnHN(SiMe3)2
[22]
(2.070(4)
A),
˚
[Zn2(C10N2H8)h(i-C4H9)2NCS2j4] [23] (2.076(5) A),
i
2
˚
˚
2.368(8)A). Se–Zn–Se angle (130.16(3)8) is very close to
and [(Me PrNCS )2ZnNC5H5] [24] (2.067(2) A) are
slightly shorter but are comparable in
that reported for Zn(SeBu3C6H2-2,4,6)2.(OSC4H8) [26].
i
2
˚
[(Me PrNCS )2ZnMe2N(CH2)2NMe2] [24] (2.137(5) A).
˚
The Zn–Se distance (2.377(9), 2.378(8) A) is shorter
3.2. Structures of (Et2CNSe2 )2Zn.NC5H5 (5) and
(Et2CNS2 )2Zn.NC5H5 (6)
than those reported for selenocarbamates such as
˚
MeZnSe2CNEt2 [14], (2.581(4), 2.467(3), 2.634(3) A),
˚
EtZnSe2CNEt2 [14], (2.590(9), 2.484(8), 2.617(3) A),
Compounds (5) and (6) are isostructural and the struc-
ture of both compounds (5) and (6) is based on monomeric
molecular units [Zn(E2CNEt2)2.Py] (E5S, Se) in which
each zinc atom is five co-ordinate through two diseleno- or
dithio-carbamato which chelate through sulphur (6) or
selenium (5) atoms and an additive bond from nitrogen
˚
MeZnCdSe2CNEt2 [14], (2.682(4), 2.575(4), 2.742(4) A),
˚
and Zn(Se2CNEt2)2 [25], (2.57, 2.45, 2.44, 2.49 A),
slightly longer than that of Zn(SeBu3C6H2-
2,4,6)2.(OSC4H8) [25] (2.313(3) A) and is close to that in
[2,4,6-CF3(C6H2)Se]ZnHN(SiMe3)2 [22] (2.350(8),
˚

M. Azad Malik et al. / Polyhedron 18 (1999) 1259–1264
1263
atom of pyridine. The co-ordination is close to trigonal
bipyramidal. There are two unsymmetrical molecular units
in a unit cell in each of these structures. The structure of
compound (6) is shown in Fig. 2 and the selected bond
distances and angles are given in Table 2.
for the ethyl protons (singlets with different intensity) of
the aryl group and only one signal (a singlet) at lower field
corresponding to equivalent aryl protons. The 13C NMR
appear as nine line spectra as expected (see Section 2). The
1H NMR and 13C NMR spectra of pyridine adducts ((3)
and (4)) and (5) and (6) give spectra as expected. Infra red
spectra showed clear bands for C–E and Zn–E (E5S, Se)
in all compounds. Compounds (1) and (2) were further
characterised by mass spectrometry. Section 2 shows the
assignment of all major peaks to different fragments. Both
compounds show a similar trend in their fragmentation
behaviour.
˚
˚
The Zn–N bond distance (2.054(1) A (5), 2.072(4) A
(6) in both structures is very similar and is close to those
˚
in C5H5N.Zn[S2CNMe2]2 [20] (2.079 (9) A),
˚
[(Et2NCO2)3MeZn2 NC5H5)2] [19] (2.057(6) A), [2,4,6-
˚
CF3(C6H2)Se]ZnHN(SiMe3)2
[22]
(2.070(4)
A),
˚
[Zn2(C10N2H8)h(i-C4H9)2NCS2j4] [23] (2.076(5) A), and
i
2
˚
[(Me PrNCS )2ZnNC5H5] [24] (2.067(2) A). These dis-
tances are much shorter than other adducts [15–18] formed
through nitrogen co-ordination. The Zn–Se bond distances
in compound (5), as usual, encompass short and long
Supplementary material
˚
bonds (2.430(2), 2.433(1), 2.737(2), 2.749(2) A). The
Complete bond lengths and angles, coordinates and
displacement parameters have been deposited at the Cam-
bridge Crystallographic Data Centre. Supplementary data
are available from the CCDC, 12 Union Road, Cambridge
CB2 1EZ, UK on request, quoting the deposition numbers
for compound (4)–103201; compound (5)–103199; and
compound (6)–103200.
shorter Zn–Se distances are close to those reported for
˚
bis(di-ethyl-di-selenocarbamato)zinc [28] (2.45, 2.44A) but
˚
the longer distances (2.49, 2.57 A) are considerably longer
in compound (5). These bond lengths are also longer than
those observed in MeZnSe2CNEt2 [14], (2.581(4),
˚
2.467(3), 2.634(3) A), EtZnSe2CNEt2 [14], (2.590(9),
˚
2.484(8), 2.617(3) A), MeZnCdSe2CNEt2 [14], (2.682(4),
˚
2.575(4),
2.742(4)
A),
[2,4,6-CF3(C6H2)Se]-
˚
ZnHN(SiMe3)2 [22] (2.350(8), 2.368(8)A) and Zn(SeBu3-
C6H2-2,4,6)2.(OSC4H8) [26] (2.313(3) A). But the Zn–S
Acknowledgements
˚
bond distances in compound (6) (2.356(1), 2.369(1),
2.529(1), 2.556(1) A) show a small variation as compared
POB thanks the EPSRC for grants supporting work on
single molecule precursors for chalcogenides. POB is the
Sumitomo/STS Professor of Materials Chemistry and the
Royal Society Amersham International Research Fellow
(1997/98).
˚
to those in EtZnS2CNEt2 [27] (2.481(7), 2.375(9), 2.509(9)
˚
˚
A)andMeZnS2CNEt2 [13](2.512(4), 2.501(4), 2.370(3)A).
3.3. Spectroscopic studies
1
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