Synthesis, structure and biological activity of some new aroylurea derivatives containing 1,3,4-thiadiazole

Article abstract of DOI:10.1080/10426500701734323

In an extensive search for biologically active aroylurea compounds as plant growth regulators, a series of new N-aroyl-N′-[5-(E)-styryl-1,3,4- thiadiazol-2-yl]ureas have been designed and synthesized. Their structures were characterized by IR, 1H NMR, MS, elemental analysis, and single-crystal X-ray diffraction techniques. The preliminary bioassay showed that some of the title compounds exhibited good plant-growth regulating activity. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/10426500701734323

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Phosphorus, Sulfur, and Silicon
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Synthesis, Structure and
Biological Activity of Some
New Aroylurea Derivatives
Containing 1,3,4-Thiadiazole
Xin-Jian Song a b & Xiao-Hong Tan b
a Key Laboratory of Biological Resources Protection
and Utilization of Hubei Province , Enshi, Hubei, P.
R. China
b School of Chemical and Environmental
Engineering, Hubei Institute for Nationalities ,
Enshi, Hubei, P. R. China
Published online: 24 Jun 2008.
To cite this article: Xin-Jian Song & Xiao-Hong Tan (2008) Synthesis, Structure and
Biological Activity of Some New Aroylurea Derivatives Containing 1,3,4-Thiadiazole,
Phosphorus, Sulfur, and Silicon and the Related Elements, 183:7, 1755-1765, DOI:
10.1080/10426500701734323
To link to this article: http://dx.doi.org/10.1080/10426500701734323
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Phosphorus, Sulfur, and Silicon, 183:1755–1765, 2008
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500701734323
Synthesis, Structure and Biological Activity of Some
New Aroylurea Derivatives Containing 1,3,4-Thiadiazole
Xin-Jian Song1,2 and Xiao-Hong Tan2
1Key Laboratory of Biological Resources Protection and Utilization of
Hubei Province. Enshi, Hubei, P. R. China
2School of Chemical and Environmental Engineering, Hubei Institute
for Nationalities. Enshi, Hubei, P. R. China
In an extensive search for biologically active aroylurea compounds as plant growth
regulators, a series of new N-aroyl-Nꢀ-[5-(E)-styryl-1,3,4-thiadiazol-2-yl]ureas have
1
been designed and synthesized. Their structures were characterized by IR, H NMR,
MS, elemental analysis, and single-crystal X-ray diffraction techniques. The prelim-
inary bioassay showed that some of the title compounds exhibited good plant-growth
regulating activity.
Keywords 1,3,4-thiadiazole; aroylurea; crystal structure; plant growth regulating
activity
INTRODUCTION
Over the last few decades, many efforts have been devoted to the re-
search on aroylurea derivatives because they are known to possess
diverse biological activities, such as insecticidal, fungicidal, herbici-
dal and plant-growth regulating activities.1–4 Some of them have been
widely used in agriculture. The important and multiple biological and
pharmacological properties of 1,3,4-thiadiazole derivatives have also
attracted considerable attention.5–9 Therefore, we think it worthwhile
to investigate the aroylurea derivatives containing 1,3,4-thiadiazole.
Moreover, it has been reported that trans-6-styrylpurine has high
cytokinin activity10,11 among purine derivatives, demonstrating the
Received 29 August 2007; accepted 5 September 2007.
We acknowledge financial support from the Natural Science Foundation of Hubei
Province, China (2007ABA001), and the Scientific Research Project for Excellent
Young & Middle-aged Talent of Hubei Provincial Department of Education (grant No.
Q200729001).
Address correspondence to Xin-Jian Song, School of Chemical and Environmental
Engineering, Hubei Institute for Nationalities, Enshi, Hubei 445000, P. R. China. E-mail:
whxjsong@yahoo.com.cn
1755

1756
X.-J. Song and X.-H. Tan
amino group is not essential for the promotion of all kinds of cytokinin
effects; whereas cis-6-styrylpurine is only weakly active.11,12 Based
upon this point, the trans-styryl group could be assumed as bioactive
substructure for plant-growth regulating activity.
In view of these, and as a continuation of our search for biologi-
cally active compounds, we synthesized a series of N-aroyl-Nꢀ-[5-(E)-
styryl-1,3,4-thiadiazol-2-yl]urea for evaluating their plant-growth reg-
ulating activities, focusing mainly on the auxin activity and cytokinin
activity.
RESULTS AND DISCUSSION
Synthesis and Characterization
2-Amino-5-(E)-styryl-1,3,4-thiadiazole 1 was synthesized through the
dehydration-cyclization of trans-cinnamic acid and thiosemicarbazide
in the presence of phosphorous oxychloride, which was used as ef-
fective dehydrating agent (Scheme 1). Thus, the amino-substituted
1,3,4-thiadiazole heterocycle was conveniently prepared by one-step
procedure; meanwhile, the trans-styryl group was simply introduced
to 1,3,4-thiadiazole ring at 5-position. The required aroyl isocyanates
2 were obtained by treating substituted benzamide with an excess
of oxalyl chloride in anhydrous 1,2-dichloroethane (DCE), was used
without further purification after removing the remaining oxalyl chlo-
ride by distillation under reduced pressure, then reacted directly
with 2-amino-5-styryl-1,3,4-thiadiazole to prepare the corresponding
aroylureas (Scheme 2). This general method involves the advantages
of readily available starting material, simple operation and good
yield.
S
N
N
POCl3
COOH
+
H2NNHCNH2
NH2
S
O
O
1
SCHEME 1
The structures of the title compounds 3a–3j were confirmed by IR,
1H NMR, elemental analysis, and mass spectroscopy. The IR spectra
showed the existence of the two secondary amino groups (two broadened
bands in the region of 3300–3100 cm–1) and two carbonyl groups (two
strong and sharp peaks in the range of 1725–1660 cm−1), which are typ-
ical for the aroylurea structure. NMR spectra exhibited two broad sin-
glet peaks at δ = 11.80–12.30 and 11.55–11.75 ppm characteristic of two

Aroylurea Derivatives Containing 1,3,4-Thiadiazole
1757
O
C
O
C
(COCl)2
Ar
NH2
Ar
N
C
O
DCE, reflux
2
O
O
C
N
N
1 + 2
Ar
C
NH
NH
S
3
Ar = C6H5 (a);
2-ClC6H4 (b);
4-BrC6H4 (f);
4-CH3OC6H4 (j)
3-ClC6H4 (c);
4-ClC6H4 (d);
3-CH3C6H4 (h);
2-BrC6H4 (e);
4-CH3C6H4 (i);
SCHEME 2
2-CH3C6H4 (g);
N–H groups, whichever signal was located downfield could be assigned
to the N H group bonded to thiadiazole ring owing to the occurrence
of intramolecular hydrogen bonding together with the strong electron-
drawing effect of the thiadiazole heterocycle. The vinyl protons were
sandwiched among so many aromatic hydrogens that their signals
were indecipherable. However, the signals from vinyl protons in in-
termediate 1 were distinguishable, appearing at δ 7.34 and 7.06 ppm
as doublet with J = 16.4 Hz, which suggested that the styryl moi-
ety assumes a trans-configuration, as further proved by X-ray diffrac-
tion analysis (see Figure 1). In addition, the EI mass spectra gave
the anticipated molecular ion peaks. It is apparent that all the spec-
troscopic data for the title compounds are in accordance with their
structures.
Crystal Structure Analysis
The crystallographic data for 3i are summarized in Table I, and the
selected bond lengths and angles are listed in Table II. The molecular
FIGURE 1 Molecular structure of compound 3i with the atomic labeling.

1758
X.-J. Song and X.-H. Tan
TABLE I Crystallographic Data and Parameters for 3i
Empirical formula
Formula weight
Crystal system
Space group
C19H16N4O2S
364.42
Triclinic
P1
Unit cell dimensions
a = 6.8929(8) A
α = 81.328(2)◦
˚
˚
b = 10.8007(13) A
β = 77.906(2)◦
˚
c = 12.4114(15) A
γ = 73.700(2)◦
3
˚
Volume
Z
863.01(18) A
2
Density (calculated)
Absorption coefficient
F(000)
θ range for data collection
Index ranges
Reflections collected
Independent reflections
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I > 2σ (I)]
R indices (all data)
Large diff. peak and hole
1.402 Mg·m−3
–1
0.209 mm
380
1.69 to 20.81◦
−6 ≤ h ≤ 6, −10 ≤ k ≤ 10, −12 ≤ l ≤ 12
3750
1796 [Rint = 0.0304]
1796/0/237
1.053
R = 0.0509, wR2 = 0.1160
R1 = 0.0689, wR2 = 0.1358
1
−3
˚
0.180 and −0.180 e·A
structure and the packing diagram of 3i are depicted in Figures 1 and
2, respectively.
In the molecule of 3i, all of the C N distances (Table II) are be-
˚
tween the normal C N double bond (1.27 A) and C N single bond
FIGURE 2 Packing diagram of compound 3i approximately along a axis, show-
ing the H-bonding (dashed lines) and π -π stacking interactions.

Aroylurea Derivatives Containing 1,3,4-Thiadiazole
1759
◦
˚
TABLE II Selected Bond Lengths (A) and Bond Angles ( ) for 3i
Bond lengths
C(1)–C(2)
C(5)–C(8)
O(1)–C(8)
O(2)–C(9)
N(1)–C(8)
N(1)–C(9)
N(2)–C(9)
N(2)–C(10)
1.512(6)
1.483(6)
1.226(5)
1.218(4)
1.372(5)
1.397(5)
1.344(5)
1.364(5)
S(1)–C(10)
S(1)–C(11)
N(3)–C(10)
N(3)–N(4)
N(4)–C(11)
C(11)–C(12)
C(12)–C(13)
C(13)–C(14)
1.724(4)
1.740(4)
1.308(5)
1.374(5)
1.293(5)
1.460(6)
1.293(6)
1.463(6)
Bond angles
O(1)–C(8)–N(1)
O(1)–C(8)–C(5)
N(1)–C(8)–C(5)
C(8)–N(1)–C(9)
O(2)–C(9)–N(1)
O(2)–C(9)–N(2)
N(2)–C(9)–N(1)
C(9)–N(2)–C(10)
N(2)–C(10)–S(1)
N(3)–C(10)–N(2)
119.9(4)
121.3(4)
118.8(4)
127.8(3)
121.6(4)
123.1(4)
115.3(4)
125.6(3)
125.6(3)
119.8(4)
N(3)–C(10)–S(1)
C(10)–S(1)–C(11)
C(10)–N(3)–N(4)
C(11)–N(4)–N(3)
N(4)–C(11)–S(1)
N(4)–C(11)–C(12)
C(12)–C(11)–S(1)
C(11)–C(12)–C(13)
C(12)–C(13)–C(14)
C(13)–C(14)–C(15)
114.6(3)
86.2(2)
112.1(3)
112.8(4)
114.3(3)
121.0(4)
124.7(4)
127.6(5)
127.7(5)
123.4(5)
2
˚
(1.47 A), indicating all the N atoms are characterized by sp hybridiza-
tion in part. The whole molecule is nearly coplanar except for the
methyl H atoms, the dihedral angles formed by the thiadiazole ring
with the methylbenzene and vinylbenzene moieties being only 7.7(2)◦
and 9.9(2)◦, respectively.
The X-ray diffraction analysis revealed that the urea linkage unit
O(1) C(8) N(1) C(9) N(2) H(2) adopts the most stable conformation
due to the presence of an intramolecular N–H· · ·O hydrogen bond to
give a planar six-membered ring. As shown in Figure 2 and Table III,
intermolecular N–H· · ·O hydrogen bonds link pairs of neighboring
molecules into centrosymmetric dimers, which can be described as
graph-set motifs of R2(8).13 In addition, intermolecular π-π stacking
2
interactions between thiadiazole and vinylbenzene rings were also ob-
served. Obviously, these various non-covalent inter- and intramolecular
◦
˚
TABLE III Hydrogen-Bonding Geometry (A, ) for Compound 3i
D–H· · ·A
d(D–H)
d(H· · ·A)
d(D· · ·A)
D–H· · ·A Symmetry code
N(1)–H(1)· · ·O(2)
N(2)–H(2)· · ·O(1)
0.86
0.86
2.15
1.86
2.986(4)
2.556(4)
163
137
–x+1, –y, –z+1

1760
X.-J. Song and X.-H. Tan
TABLE IV The Plant Growth Regulating Activities of
Compounds 3a–3j
Compd.
Auxin activity (%)
Cytokinin activity (%)
3a
3b
3c
3d
3e
3f
3g
3h
3i
21.3
19.5
15.8
17.3
22.8
16.4
14.0
10.5
24.6
15.1
28.7
25.2
32.7
35.4
45.1
16.6
37.9
29.1
47.5
39.2
27.6
3j
IAA
KT
51.5
interactions, such as hydrogen-bonding and π-π stacking, played a fun-
damental role in forming a three-dimensional supramolecular organi-
zation in the solid state.
Plant-Growth Regulating Activities
The plant-growth regulating activities of compounds 3a–3j were evalu-
ated according to a previously reported method.14 The auxin activity
was tested in terms of the elongation of wheat coleoptile, where β-
indolylacetic acid (called IAA for short) was used as reference compound
for comparison; while the cytokinin activity was investigated by means
of cucumber cotyledon enlargement bioassay, in which kinetin (KT) was
used as reference compound. All investigated compounds were tested
at the concentration of 10 ppm. The data for the bioassays are out-
lined in Table IV. It is evident from the results that all title compounds
displayed moderate-to-good cytokinin activity and an auxin activity to
some extent. The substituents in aromatic phenyl ring had some effects
on activity. Excitingly, compounds 3d and 3h exhibited considerably
high cytokinin activity towards cucumber cotyledon, giving promotive
percentages of 45.1 and 47.5%, respectively, but remained less active
than kinetin. Overall, we would conclude that the aroylurea group, be-
sides the 1,3,4-thiadiazole heterocycle and attached trans-styryl group,
could exert beneficial effects on such good biological activity.
EXPERIMENTAL
All chemicals used for the preparations were of analytical grade. Sol-
vents were dried by standard methods and distilled prior to use.

Aroylurea Derivatives Containing 1,3,4-Thiadiazole
1761
1H NMR spectra were obtained on a Varian Mercury Plus-400 MHz
Spectrometer with TMS as internal standard and DMSO-d6 as the
solvent. IR spectra were recorded in the range 4000–400 cm−1 on a
Nicolet NEXUS 470 FT-IR spectrophotometer, using KBr pellets. Ele-
mental analysis was performed by a Vario EL III analyzer. MS spec-
tra were recorded with a Finnigan Trace MS 2000 organic mass spec-
trometer using the electron ionization (EI) method. Melting points were
measured with an X-4 microscopic melting-point apparatus and uncor-
rected.
Synthesis of 2-Amino-5-(E)-styryl-1,3,4-thiadiazole 1
To a mixture of trans-cinnamic acid (14.82 g, 0.1 mol), thiosemicar-
bazide (9.11 g, 0.1 mol) and 100 mL of 1,4-dioxane was dropwise added
phosphorous oxychloride (15.33 g, 0.1 mol) with stirring. The resulting
slurry was heated slowly to gentle reflux with rapid evolution of hydro-
gen chloride gas, and the refluxing continued for about 3.5 h until the
gas evolution ceased. The dioxane was evaporated off under reduced
pressure and then 80 mL of cold water was added to the residue. The
pH of the solution was adjusted to 8.0–9.0 with 40% sodium hydroxide,
and a solid precipitate formed. The solid precipitate was filtered off,
washed with water, air dried, and then recrystallized from ethanol to
give 2-amino-5-(E)-styryl-1,3,4-thiadiazole 1 in 74% yield as pale yel-
low solid. M.p. 235–236◦C; 1H NMR (400 MHz, DMSO-d6): δ7.64 (d, 2H,
J = 7.2 Hz, Ar-H), 7.43 (s, 1H, NH2), 7.39 (t, 2H, J = 7.4 Hz, Ar-H), 7.34
(d, 1H, J = 16.4 Hz, CH ), 7.31 (t, 1H, J = 7.2 Hz, Ar-H), 7.06 (d, 1H,
J= 16.4 Hz, CH ); Anal. calcd for C10H9N3S: C 59.09; H 4.46; N 20.67.
Found: C 58.93; H 4.58; N 20.86.
General Synthetic Procedure for Target Compounds 3
To a stirred suspension of substituted benzamide (10 mmol) in 8 mL
of anhydrous 1,2-dichloroethane (DCE), 10 mL of fresh distilled oxalyl
chloride was added with cooling on a ice-bath and stirring. The reaction
mixture was stirred for 3 h, while maintaining the temperature within
45–55◦C; it was then refluxed under N2 until the evolution of hydro-
gen chloride gas ceased. The solvent and the remaining oxalyl chloride
was removed by distillation at reduced pressure, the crude aroyl iso-
cyanate 2 was thus obtained without further isolation. Then the solu-
tion of intermediate 1 (1.83 g, 9 mmol) in 30 mL of dry acetonitrile was
added dropwise to the corresponding aroyl isocyanate 2. The mixture
was stirred for 3–4 h at room temperature. The progress of the reactions
was monitored by TLC. The solvent was removed by evaporation under

1762
X.-J. Song and X.-H. Tan
reduced pressure, and the residue was recrystallized from ethanol/DMF
to afford white crystals 3a–3j with m.p. >300◦C.
Compound 3a
Yield: 81%; 1H NMR (400 MHz, DMSO-d6): δ 12.10 (s, 1H, NH), 11.65
(s, 1H, NH), 7.32–8.06 (m, 12H, Ar-H and CH CH); IR (KBr, ν in cm−1):
3233, 3138 (N H), 1713, 1670 (C O), 1635 (C C), 1595 (C N), 966
(trans CH CH); Anal. calcd for C18H14N4O2S: C 61.70; H 4.03; N 15.99.
Found: C 61.54; H 4.15; N 16.07; EI-MS (%): m/z 350 (M+, 68), 228 (100),
202 (96), 121 (45), 105 (80).
Compound 3b
Yield: 69%; 1H NMR (400 MHz, DMSO-d6): δ 11.80 (s, 1H, NH), 11.74
(s, 1H, NH), 7.35–7.74 (m, 11H, Ar-H and CH CH); IR (KBr, ν in cm−1):
3241, 3155 (N H), 1725, 1679 (C O), 1636 (C C), 1593 (C N), 962
(trans CH CH); Anal. calcd for C18H13ClN4O2S: C 56.18; H 3.40; N
14.56. Found: C 56.06; H 3.31; N 14.28; EI-MS (%): m/z 384 (M+, 4), 349
(3), 228 (100), 202 (57), 155 (17), 139 (74), 111(32).
Compound 3c
Yield: 74%; 1H NMR (400 MHz, DMSO-d6): δ 12.04 (s, 1H, NH), 11.72
(s, 1H, NH), 7.37–8.09 (m, 11H, Ar-H and CH CH); IR (KBr, ν in cm−1):
3236, 3142 (N H), 1717, 1697 (C O), 1635 (C C), 1591 (C N), 969
(trans CH CH); Anal. calcd for C18H13ClN4O2S: C 56.18; H 3.40; N
14.56. Found: C 56.39; H 3.52; N 14.70; EI-MS (%): m/z 384 (M+, 3), 228
(80), 202 (100), 155 (19), 139 (85), 111(46).
Compound 3d
Yield: 77%; 1H NMR (400 MHz, DMSO-d6): δ 12.09 (s, 1H, NH), 11.71
(s, 1H, NH), 7.37–8.06 (m, 11H, Ar–H and CH CH); IR (KBr, ν in cm−1):
3230, 3133 (N–H), 1698, 1682 (C O), 1637 (C C), 1596 (C N), 971
(trans CH CH); Anal. calcd for C18H13ClN4O2S: C 56.18; H 3.40; N
14.56. Found: C 56.34; H 3.27; N 14.45; EI-MS (%): m/z 384 (M+, 5), 228
(31), 202 (100), 155 (6), 139 (48), 111(49).
Compound 3e
Yield: 70%; 1H NMR (400 MHz, DMSO-d6): δ 11.81 (s, 1H, NH), 11.74
(s, 1H, NH), 7.37–7.76 (m, 11H, Ar-H and CH CH); IR (KBr, ν in cm−1):
3243, 3145 (N H), 1724, 1678 (C O), 1639 (C C), 1587 (C N), 962
(trans CH CH); Anal. calcd for C18H13BrN4O2S: C 50.36; H 3.05; N
13.05. Found: C 50.23; H 3.16; N 13.19; EI-MS (%): m/z 428 (M+, 3), 228
(100), 202 (53), 199 (23), 183 (59), 155(27).

Aroylurea Derivatives Containing 1,3,4-Thiadiazole
1763
Compound 3f
Yield: 75%; 1H NMR (400 MHz, DMSO-d6): δ 12.09 (s, 1H, NH), 11.71
(s, 1H, NH), 7.35–7.98 (m, 11H, Ar-H and CH CH); IR (KBr, ν in cm−1):
3210, 3147 (N H), 1697, 1681 (C O), 1628 (C C), 1589 (C N), 959
(trans CH CH); Anal. calcd for C18H13BrN4O2S: C 50.36; H 3.05; N
13.05. Found: C 50.45; H 2.91; N 13.22; EI-MS (%): m/z 428 (M+, 7), 228
(46), 202 (100), 199 (12), 183 (71), 155(58).
Compound 3g
Yield: 68%; 1H NMR (400 MHz, DMSO-d6): δ 12.02 (s, 1H, NH), 11.61
(s, 1H, NH), 7.31–7.74 (m, 11H, Ar-H and CH CH), 2.44 (s, 3H, CH3);
IR (KBr, ν in cm−1): 3220, 3111 (N H), 1699, 1686 (C O), 1631 (C C),
1590 (C N), 957 (trans CH CH); Anal. calcd for C19H16N4O2S: C 62.62;
H 4.43; N 15.37. Found: C 62.74; H 4.30; N 15.21; EI-MS (%): m/z 364
(M+, 9), 228 (64), 202 (100), 135 (15), 119(76), 91(71).
Compound 3h
Yield: 73%; 1H NMR (400 MHz, DMSO-d6): δ 12.18 (s, 1H, NH), 11.61
(s, 1H, NH), 7.37–7.88 (m, 11H, Ar–H and CH CH), 2.41 (s, 3H, CH3);
IR (KBr, ν in cm−1): 3245, 3144 (N–H), 1705, 1673 (C O), 1633 (C C),
1589 (C N), 962 (trans CH CH); Anal. calcd for C19H16N4O2S: C 62.62;
H 4.43; N 15.37. Found: C 62.49; H 4.52; N 15.56; EI-MS (%): m/z 364
(M+, 4), 228 (43), 202 (100), 135 (6), 119(62), 91(48).
Compound 3i
Yield: 76%; 1H NMR (400 MHz, DMSO-d6): δ 12.22 (s, 1H, NH), 11.59
(s, 1H, NH), 7.37–7.97 (m, 11H, Ar–H and CH CH), 2.42 (s, 3H, CH3);
IR (KBr, ν in cm−1): 3276, 3146 (N–H), 1693, 1661 (C O), 1634 (C C),
1590 (C N), 958 (trans CH CH); Anal. calcd for C19H16N4O2S: C 62.62;
H 4.43; N 15.37. Found: C 62.50; H 4.29; N 15.28; EI-MS (%): m/z 364
(M+, 4), 228 (59), 202 (94), 135 (14), 119(100), 91(60).
Compound 3j
Yield: 79%; 1H NMR (400 MHz, DMSO-d6): δ 12.30 (s, 1H, NH), 11.55
(s, 1H, NH), 7.09–8.09 (m, 11H, Ar–H and CH CH), 3.87 (s, 3H, OCH3);
IR (KBr, ν in cm−1): 3290, 3139 (N–H), 1691, 1670 (C O), 1630 (C C),
1589 (C N), 958 (trans CH CH); Anal. calcd for C19H16N4O3S: C 59.99;
H 4.24; N 14.73. Found: C 60.14; H 4.07; N 14.85; EI-MS (%): m/z 380
(M+, 3), 228 (42), 202 (85), 151 (11), 135 (100), 107(12).

1764
X.-J. Song and X.-H. Tan
X-Ray Crystallography of Compound 3i
A colorless single crystal of compound 3i with dimensions of 0.20 ×
0.01 × 0.01 mm3 was selected and mounted on a BRUKER SMART
APEX-CCD diffractometer equipped with a graphite-monochromated
˚
Mo Kα (λ = 0.71073 A) radiation. The intensity data were collected by
using a ψ-ω scan mode at 298(2) K. Absorption correction was not ap-
plied. The structure was solved by direct methods with SHELXS-9715
and expanded using Fourier difference techniques. All non-hydrogen
atoms were refined anisotropically, and the hydrogen atoms were
added according to theoretical models. Structural refinement was car-
ried out by full-matrix least-squares techniques on F2 with SHELXL-
97.16 The θmax for data collection is only 21 degrees, maybe indicat-
ing the diffracting power of the crystal was weak due to small crystal
size.
SUPPLEMENTARY MATERIAL
Crystallographic data for 3i have been deposited with the Cambridge
Crystallographic Data Center (Deposition No. CCDC-656228). These
data can be obtained free of charge by contacting the CCDC, 12 Union
Road, Cambridge CB2 1EZ, UK (fax: +44-1223-336033; e-mail: de-
posit@ccdc.cam.ac.uk).
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