Synthesis, characterization and protonation reaction of copper and palladium complexes bearing nitrite ligands in O,O-bidentate and N-monodentate bonding fashions

Article abstract of DOI:10.1016/j.ica.2011.06.052

Cu(Ph₂P(o-C₆H₄C(O)H))₂(NO ₂) (3) has been prepared in high yield by treating [Cu(Ph ₂P(o-C₆H₄C(O)H))₂(NCMe)]BF ₄ (2) with [Ph₂PNPPh₂]NO₂ at ambient temperature. The nitrite ligand of 3 is coordinated to the Cu(I) center in an O,O-bidentate mode. Protonation of 3 releases NO molecule, which mimics the reactivity of the Type 2 Cu-NiRs. In contrast, reaction of [Pd(NCMe) ₄](BF₄)₂ and Ph₂P(o-C ₆H₄C(O)H) affords cis-[Pd(Ph₂P(o-C ₆H₄C(O)H))₂](BF₄)₂ (4) with the Pd²⁺ ion chelated by two phosphino-aldehyde moieties. The hemilabile formyl ligands of 4 can be displaced by NO₂^- to produce trans-Pd(Ph₂P(o-C₆H₄C(O)H)) ₂(NO₂)₂ (5), of which the nitrite ligands present an N-monodentate bonding feature. Protonation of 5 with HBF₄, however, regenerates compound 4, likely via elimination of nitrous acid. The structures of 3-5 have been determined by an X-ray diffraction study.

Full text of DOI:10.1016/j.ica.2011.06.052

Inorganica Chimica Acta 376 (2011) 396–400
Contents lists available at ScienceDirect
Inorganica Chimica Acta
journal homepage: www.elsevier.com/locate/ica
Synthesis, characterization and protonation reaction of copper and palladium
complexes bearing nitrite ligands in O,O-bidentate and N-monodentate
bonding fashions
⇑
Chi-Shian Chen, Huei-Fang Dai, Chia-Hsiang Chen, Wen-Yann Yeh
Department of Chemistry, National Sun Yat-Sen University, Kaohsiung 804, Taiwan
a r t i c l e i n f o
a b s t r a c t
Article history:
Cu(Ph P(o-C H C(@O)H)) (NO ) (3) has been prepared in high yield by treating [Cu(Ph P(o-C H C-
2
6
4
2
2
2
6
4
Received 4 March 2011
Received in revised form 21 June 2011
Accepted 30 June 2011
(
2 4 2 2 2
@O)H)) (NCMe)]BF (2) with [Ph PNPPh ]NO at ambient temperature. The nitrite ligand of 3 is coordi-
nated to the Cu(I) center in an O,O-bidentate mode. Protonation of 3 releases NO molecule, which mimics
the reactivity of the Type 2 Cu-NiRs. In contrast, reaction of [Pd(NCMe) ](BF ) and Ph P(o-C H C(@O)H)
4 4 2 2 6 4
Available online 12 July 2011
affords cis-[Pd(Ph
2
P(o-C
6
H
4
C(@O)H))
2
](BF
4
)
2
(4) with the Pd2 ion chelated by two phosphino–aldehyde
+
ꢀ
moieties. The hemilabile formyl ligands of 4 can be displaced by NO
C(@O)H)) (NO
Protonation of 5 with HBF
The structures of 3–5 have been determined by an X-ray diffraction study.
Ó 2011 Elsevier B.V. All rights reserved.
2
2
to produce trans-Pd(Ph P(o-
Keywords:
C
6
H
4
2
2
)
2
(5), of which the nitrite ligands present an N-monodentate bonding feature.
, however, regenerates compound 4, likely via elimination of nitrous acid.
Hemilabile property
Cu(I) nitrite complex
Pd(II) nitrite complex
Denitrification
4
2
1
. Introduction
have been described to have an g -O,O coordination mode [9–
I
ꢀ
1
2], while a few known mononuclear Cu –NO
g -N bonding feature [13–15]. In contrast, examples of O,O-
2
complexes contain
1
Transition metal complexes of nitrogen oxides (NO
x
) contain a
an
class of materials with potential uses as catalysts and oxidants.
coordinated nitrite to the copper(I) ion are quite rare. We recently
prepared the complex (2,6-(Ph P(o-C )CH@N) N)Cu(NO
(1) [16] with the nitrite ligand in an -O,O coordination mode
(Eq. (1)), which evolved NO gas upon protonation to mimic the
reactivity of the Type 2 Cu-NiRs. A related complex (Ph P(o-
OMe)Cu(NO ) showing similar structure and reactivity was
shortly reported by Hsu and coworkers [17]. In this paper we wish
to present new nitrite complexes of Cu(I) and Pd(II) ions and to
compare their structures and chemical reactivity towards protonic
acids.
ꢀ
The triatomic nitrite anion (NO
isoelectronic with other species, such as allyl anion and SO
2
), with 18 valence electrons, is
. It be-
2
6
H
g
4
2
C H
5 3
2
)
2
2
haves as an ambidentate ligand that may coordinate in two or
more ways through oxygen and/or nitrogen atoms [1–3]. The ni-
trite O,O-bidentate binding mode has been determined crystallo-
graphically for the nitrite adducts of the copper containing nitrite
reductases (Cu-NiRs) [4,5] that catalyze the reduction of nitrite to
nitric oxide (NO), a key step in denitrification [6–8]. Several mono-
2
C H
6 4
2
II
ꢀ
nuclear Cu –NO
2
complexes with biomimetic ancillary ligands
N
N
N
N
Ph P
N
N
2
+
Cu
PPh
Ph
2
2
Ph2
+
Ph
P
P
+
2 NO2
2
2
ð1Þ
P
Cu
Ph2
P
Cu
N
N
N
O
O
N
1
⇑
Corresponding author. Fax: +886 7 5253908.
E-mail address: wenyann@mail.nsysu.edu.tw (W.-Y. Yeh).
0
020-1693/$ - see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2011.06.052

C.-S. Chen et al. / Inorganica Chimica Acta 376 (2011) 396–400
397
H
Ph
Ph
P
O
Ph
Ph
RT
O
P
+
BF4
[
Cu(NCMe) ]BF4
+
2
4
MeCN
Cu
H
P
Ph
Ph
O
H
2
RT
[
PPN] NO2
H
O
Ph
Ph
CH CO H
3
2
O
P
P
Cu(OAc)2
+
NO(g)
N
Cu
Ph
Ph
RT
O
O
H
3
Scheme 1. Synthesis and protonation reaction of 3.
2
. Results and discussion
2
(NO ) (3) was obtained in 80% yield after crystallization from
1
dichloromethane/diethyl ether (Scheme 1). The H NMR spectrum
presents the aldehyde proton resonance at 9.89 ppm which is only
Ph
can bind transition metals in an
18–21]. It was previously revealed that the Cu(I) complex [Cu(Ph2-
P(o-C C(@O)H)) (NCMe)]BF (2) [22] can undergo facial substi-
2 6 4
P(o-C H C(@O)H) is a versatile bifunctional molecule which
1
2
3
31
1
g
-P,
g
-P,O or
g
-P,CO feature
slightly deviated from 2 (9.74 ppm), while the
P{ H} NMR
[
spectrum shows an upfield shift for the phosphine ligand at –
0.45 ppm compared to 2 (0.47 pm).
6
H
4
2
4
tution reactions with the labile acetonitrile ligand displaced by
phosphines or pyridine derivatives [23]. Likewise, treating 2 with
The ORTEP diagram for 3 is displayed in Fig. 1, with the selected
bond distances and angles summarized in Table 1. Compound 3
shows a pseudotetrahedral Cu(I) center linked to two phosphine
groups and one nitrite species. There is a crystallographic symme-
try imposed on the molecule. The Cu–P1 distance 2.2342(7) Å and
the P1–Cu1–P1A angle 123.03(4)° are comparable to those found
for 1 (av. 2.261 Å and 129.86(4)°). The Cu, O1, N1 and O1A atoms
are coplanar to give a dihedral angle of 80.3(1)° with the P1–Cu–
P1A plane. On the covalent model the O,O-coordinated nitrite is a
equal molar of [PPN]NO
ature produced yellow precipitates, from which a slightly air-
sensitive, yellow crystalline solid of Cu(Ph P(o-C C(@O)H))
2
2
in acetonitrile solvent at ambient temper-
2
H
6 4
4
e ligand, giving rise to a 18-electron Cu(I) complex. The nitrite li-
gand is bonded to the copper ion symmetrically with Cu–O1
.195(2) Å, N1–O1 1.249(3) Å, O1–Cu–O1A 56.8(1)° and O1–N1–
2
O1A 113.2(4)°, while the long CuꢁꢁꢁN1 distance of 2.62 Å indicates
no interaction between the two atoms. In contrast, the nitrite li-
gand of 1 presents an asymmetric chelating mode with a more
acute O–Cu–O bite-angle (50.3(2)°),
a flatter O–N–O angle
(
128.7(6)°), a shorter N–O distance (av. 1.022 Å), and a weak inter-
action between the Cu and N atoms (2.40 Å) [16].
It has been demonstrated that protonation of compound 1
evolves NO gas that mimics the reactivity of biological denitrifica-
2 2
tion process. Comparably, treatment of a CH Cl solution of 3 with
glacial acetic acid (HOAc) at ambient temperature under dinitro-
gen resulted in an immediate color change from yellow to green.
Analysis of the head-space gas by a GC analyzer indicated that
NO had been generated (85%). This reaction was concomitant with
+
oxidation of the Cu ion, leading to decomposition of 3 to release
Fig. 1. Molecular structure of
3 with 30% probability ellipsoids. The phenyl
hydrogen atoms have been artificially omitted for clarity.
2 6 4 2
Ph P(o-C H C(@O)H) ligand and produce Cu(OAc) . On the basis
of the mechanisms proposed in the literature [24], the reaction
presumably proceeds via nitrite protonation and dehydration to af-
II
Table 1
ford a [Cu NO] intermediate, followed by release of NO gas. A Cu(II)
Selected bond distances (Å) and bond angles (°) for 3.
complex coordinated by a NO ligand was recently reported by Hay-
4
ton and coworkers [25]. The reaction of 3 and HBF also evolved
NO gas, likely through the same pathways.
Cu–P1
N1–O1
O1–N1–O1A
P1–Cu–O1
O1–Cu–O1A
2.2342(7)
1.249(3)
113.2(4)
110.45(9)
56.8(1)
Cu–O1
C19–O2
P1–Cu–P1A
P1–Cu–O1A
O2–C19–C18
2.195(2)
1.206(4)
123.03(4)
119.33(8)
125.8(3)
It is of interest to compare the coordination chemistry of
P(o-C C(@O)H) and nitrite ligands bonded to a square planar
metal center. Thus, reaction of [Pd(NCMe) ](BF with two
Ph
2
6 4
H
4
4 2
)

3
98
C.-S. Chen et al. / Inorganica Chimica Acta 376 (2011) 396–400
Ph
Ph
P
PPh2
RT
Ph
Ph
2+
[
Pd(NCMe) ] (BF )
H
4
2
4 2
2
2 BF4
O
Pd
P
H
O
O
4
2
[PPN] NO2
H
Ph
P
O
RT
2 HNO2
Ph
N
O
O
2 HBF4
Pd
O
Ph
Ph
H
N
P
O
O
5
H
Scheme 2. Synthesis of 4 and 5.
ꢀ
1
equivalents of Ph
methane solvent at room temperature to result in a solution color
change from yellow to orange, and an air-stable, yellow crystalline
2
P(o-C
6
H
4
C(@O)H) was carried out in dichloro-
by ca. 60 cm compared with the uncoordinated formyl moiety
1
in 3. The H resonance for the aldehyde protons is recorded at
9.86 ppm, the phosphine groups display one sharp P resonance
at 41.42 ppm, and the C resonance for the formyl carbons is ob-
served at 200.2 ppm. These spectral data indicate that the two
2 6 4
Ph P(o-C H C(@O)H) ligands are coordinated to the Pd(II) ion sym-
3
1
1
3
solid of cis-[Pd(Ph
2
P(o-C
6
H
4
C(@O)H))
2
](BF
4
)
2
(4) was obtained in
8
5% yield by adding diethyl ether (Scheme 2). The ESI mass spec-
106
11
trum displays the ion peak at m/z 773 ( Pd, B) corresponding
ꢀ
+
to the [M–BF
4
]
fragment. The IR spectrum in KBr disc presents
metrically and only one geometric isomer is afforded.
ꢀ1
the C@O stretching frequency at 1633 cm , which is red-shifted
The ORTEP diagram for the cationic part of 4 is illustrated in
Fig. 2(a), and the selected bond distances and angles are summa-
rized in Table 2. There is a crystallographic symmetry imposed
on the complex. The Pd(II) ion is chelated by two (Ph
2
P(o-
C H
6
4
C(@O)H)) ligands to display a distorted square planar geom-
2
etry. The two phosphorus atoms are in the cis-position with the
bond length Pd–P1 2.237(1) Å. The formyl moieties are coordinated
to the Pd(II) ion in a
O1 2.106(4) Å and the bite-angle P1–Pd–O1A 90.5(1)°. The PdP
segment is not planar, where the O1 and O1A atoms are deviated
from the PdP plane oppositely by 0.45 Å (Fig. 2(b)), and the inter-
r-fashion through the oxygen atom, with Pd–
2 2
O
2
ligand angles P1–Pd–P1A 97.34(7)° and O1–Pd–O1A 84.6(2)° are
ca. 7° away from the idealized 90°, presumably due to steric repul-
ˆ
sions between the PO groups.
2
Compound 4 reacted with [PPN]NO in acetonitrile solution at
ambient temperature to yield an air-stable, yellow solid product
in 90% yield, which is insoluble in common organic solvents,
making its characterization by solution NMR spectroscopy
5
Fig. 2. (a) Molecular structure of
coordination environment of the Pd atom. The BF
4
with 30% probability ellipsoids, and (b)
ꢀ
4
counter anions and phenyl
hydrogen atoms have been artificially omitted for clarity.
Table 2
Selected bond distances (Å) and bond angles (°) for 4.
Pd–P1
C19–O1
P1–Pd–P1A
P1–Pd–O1A
Pd–O1–C19
C2A–C19–O1
2.237(1)
1.211(6)
97.34(7)
90.5(1)
133.3(3)
128.2(5)
Pd–O1
2.106(4)
P1–Pd–O1
O1–Pd–O1A
Pd–P1–C1
165.3(1)
84.6(2)
108.5(2)
Fig. 3. Molecular structure of
5 with 30% probability ellipsoids. The phenyl
hydrogen atoms have been artificially omitted for clarity.

C.-S. Chen et al. / Inorganica Chimica Acta 376 (2011) 396–400
399
Table 3
recorded on a Jasco FT/IR-4100 IR spectrometer. NMR spectra were
obtained on a Varian Unity INOVA-500 spectrometer. Matrix-
assisted laser desorption ionization (MALDI) and electrospray ion-
ization (ESI) mass spectra were recorded on a Bruker Microflex-LT
and a Waters ZQ-4000 mass spectrometer, respectively. Elemental
analyses were performed at the National Science Council Regional
Instrumentation Center at National Chen-Kung University, Tainan,
Taiwan. Gas chromatography experiments were performed by
using a Varian CP-3800, with a Porpak Q column (6 ft, 20 mL/min
flow rate, 30 °C, dinitrogen carrier gas) and a TCD detector. Nitric
oxide (NO) quantitation was performed by calibrating detector re-
Selected bond distances (Å) and bond angles (°) for 5.
Pd1–P1
N1–O1
C19–O3
P1–Pd1–P1A
N1–Pd1–N1A
O1–N1–Pd1
C18–C19–O3
2.370(1)
1.233(5)
1.206(6)
180.0
180.0(3)
120.0(3)
125.7(5)
Pd1–N1
N1–O2
2.014(4)
1.238(5)
P1–Pd1–N1
O1–N1–O2
O2–N1–Pd1
89.5(1)
120.7(4)
119.3(4)
unachievable. The elementary analysis agrees with the formulation
Pd(Ph P(o-C C(@O)H)) (NO , while the IR spectrum in KBr disc
2
6
H
4
2
2 2
)
ꢀ
1
sponse with known concentrations of NO mixed with N ; molar
presents the carbonyl stretching at 1682 cm , suggesting uncoor-
dination of the aldehyde groups. Crystals of 5 found suitable for an
X-ray diffraction study were obtained by direct diffusion of an ace-
2
quantities were calculated using the ideal gas equation.
3.2. Preparation of 3
tonitrile solution of [PNN]NO
2
into a dichloromethane solution of
4
. There are two independent but structurally similar complexes
[
Cu(Ph
2
P(o-C
6 4 2 4
H C(@O)H)) (NCMe)]BF (2) (50 mg, 0.065 mmol),
in the asymmetric unit for 5, with both bearing a crystallographic
center of symmetry. One ORTEP diagram is illustrated in Fig. 3, and
the selected bond distances and angles are summarized in Table 3.
Compound 5 consists of a regular square planar structure where
the Pd1 atom is surrounded by two phosphine ligands in the
trans-position and two nitrite ligands which replace the ligation
of the hemilabile formyl groups. The nitrite ligands present an
g
where the nitrogen atom retains an sp hybridization to give the
bond angles O1–N1–O2 120.7(4)°, O1–N1–Pd1 120.0(3)° and O2–
N1–Pd1 119.3(4)°. The NO
PdN plane, giving a dihedral angle of 76.4(5)°. It is noteworthy
that the Pd1–P1 distance (2.370(1) Å) is 0.13 Å longer than that
found in 4. The lengthening of the Pd–P bonds from 4 to 5 is likely
a consequence of isomerization, and the greater trans influence of
the phosphorous donor with respect to the formyl group.
[
PPN]NO
2
(38 mg, 0.068 mmol) and acetonitrile (10 ml) were
placed in a 25 ml Schlenk tube under dinitrogen. The solution was
stirred at room temperature for 4 h to produce a yellow solid. The
solid was filtered, dissolved in 10 ml dichloromethane, and carefully
layered with 30 ml diethyl ether to afford a slightly air-sensitive,
yellow crystalline solid of Cu(Ph
2 6 4 2 2
P(o-C H C(@O)H)) (NO ) (3;
6
3
+
1
3
6 mg, 0.052 mmol, 80%). MS (MALDI) m/z 659 ( Cu; M ꢀNO),
-N bonding feature with the bond length Pd1–N1 2.014(4) Å,
+
ꢀ1
1
2
643 (M ꢀNO ). IR (KBr) 1697 (C@O) cm
.
2 2
H NMR (CD Cl ,
2
2
J
2
(
4 °C): 9.89 (s, 2H, CHO), 7.82 (d, JH–H = 7 Hz, 2H, C
H–H = 7 Hz, 2H, C ), 7.50 (t, JH–H = 8 Hz, 2H, C ), 7.41–7.28 (m,
), 6.93 (d, JH–H = 8 Hz, 2H, C ) ppm. P{ H} NMR
, 24 °C): ꢀ0.45 (s) ppm. Anal. Calc. for C38 30CuNO : C,
6.13; H, 4.38; N, 2.03. Found: C, 65.99; H, 4.50; N, 2.07%.
6 4
H ), 7.61 (t,
H
6 4
6 4
H
2
plane is not perpendicular to the
3
1
1
0H, C
Cl
H
6 5
6 4
H
2 2
P
CD
2
2
H
4 2
P
6
3
3 2
.3. Reaction of 3 and CH CO H
I
ꢀ
Several known mononuclear Cu –NO
2
complexes carrying out
1
A solution of compound 3 (10 mg, 0.014 mmol) in CH2Cl2
the denitrification reaction contain an
1
of 5 can produce NO gas. The reaction of 5 and HBF occurred in
dichloromethane at ambient temperature, however, leading to
the regeneration of compound 4 in 84% after purification. There
was no evidence for the generation of NO, and nitrous acid is likely
the product formed. It is apparent that Pd(II) ion is not able to re-
duce the protonated nitrite species under acidic conditions. Inter-
estingly, interconversion of 5–4 is accomplished by stereospecific
isomerism of the two phosphines ligands from a trans to a cis form.
g
-N bonding feature [13–
(
0.5 ml) was prepared in a small vial capped with a rubber septum
under dinitrogen. A degassed solution of CH COOH (2 l) in CH Cl
0.05 ml) was then introduced with a syringe at room temperature.
The solution color changed immediately from yellow to brown.
Analysis of the head-space gas by GC indicated that nitric oxide
NO) was generated (0.11 mmol, 85%).
.4. Preparation of 4
Ph P(o-C H C(@O)H) (70 mg, 0.241 mmol), [Pd(NCMe) ](BF )
4 2
5]. It is therefore of interest to investigate whether protonation
3
l
2
2
4
(
(
3
I
ꢀ
In summary, we have prepared a new Cu –NO
2
complex 3
2
6
4
4
(
50 mg, 0.113 mmol) and dichloromethane (15 ml) were placed
bearing an O,O-bidentate mode. Protonation of 3 to evolve NO
in a 25 ml Schlenk tube under dinitrogen. The mixture was stirred
at room temperature for 3 h, resulting a solution color change from
yellow to orange. Diethyl ether (30 ml) was then slowly added into
the solution to produce an air-stable, yellow crystalline solid of cis-
gas is of interest within the context of the chemistry of the biolog-
ical denitrification process. The square planar Pd(II) complexes 4
ꢀ
and 5 containing Ph
2
P(o-C
6
4
H C(@O)H) and NO
2
ligands are syn-
thesized and structurally characterized for comparison. Proton-
ation of 5, however, regenerates 4 likely by eliminating nitrous
acid. Compound 4 displays hemilabile coordination properties
with prospects for applications in catalysis.
[
Pd(Ph
2 6 4 2 4 2
P(o-C H C(@O)H)) ](BF ) (4; 83 mg, 0.096 mmol, 85%). MS
1
06
11
ꢀ +
ꢀ1
(
ESI) m/z 773 ( Pd, B; [MꢀBF
4
] ). IR (KBr) 1633 (C@O) cm
, 24 °C): 9.86 (d, JP–H = 12 Hz, 2H, CHO), 8.40 (s,
), 7.97 (t, JH–H = 7 Hz, 2H, C ), 7.87 (t, JH–H = 7 Hz, 2H,
), 7.17 (t, H–H = 7 Hz, 2H,
, 24 °C): 200.2 (br, CHO), 143.9,
.
1
2 2
H NMR (CD Cl
2
C
C
1
6
H, C H
4
6 4
H
6
H
H
4
), 7.58–7.33 (m, 20H,
) ppm. C{ H} NMR (CD
C
Cl
6
H
5
J
1
3
1
3
. Experimental
6
4
2
2
6 4
39.6, 136.3, 135.1, 135.0, 134.9, 134.8, 134.5, 124.7, 122.0 (C H ,
3
1
1
3.1. General methods
C
6
5 2 2
H ) ppm. P{ H} NMR (CD Cl , 24 °C): 41.42 (s) ppm. Anal. Calc.
for C38 Pd: C, 53.03; H, 3.51. Found: C, 53.05; H, 3.76%.
30 2 8 2 2
H B F O P
All manipulations were carried out under an atmosphere of
purified dinitrogen with standard Schlenk techniques. [Cu(Ph
P(o-C C(@O)H)) (NCMe)]BF (2) [22] and [Pd(NCMe) ](BF
26] were prepared as described in the literature. Ph
C(@O)H), [PPN]NO (PPN = Ph PNPPh ), glacial acetic acid
HOAc) and HBF (6.79 M in diethyl ether) were purchased from
2
-
3.5. Preparation of 5
Compound
0.086 mmol) and acetonitrile (20 ml) were placed in a 25 ml
Schlenk tube under dinitrogen. The solution was stirred at room
temperature for 24 h to result in a yellow solid. The solid was
washed with acetonitrile and dried under vacuum to afford
6
H
4
2
4
4
4
)
2
[
C
(
2
P(o-
4
(35 mg, 0.041 mmol), [PNN]NO
2
(50 mg,
H
6 4
2
2
2
4
Aldrich. Solvents were dried over appropriate reagents under dini-
trogen and distilled immediately before use. Infrared spectra were

4
00
C.-S. Chen et al. / Inorganica Chimica Acta 376 (2011) 396–400
Table 4
package. The data collection and refinement parameters are pre-
sented in Table 4.
Crystallographic data for compounds 3–5.
3
4
5
Formula
C
38
H
30CuNO
4
P
2
C
38
H
30
B
2
F
8
O
2
P
2
Pd
C
38
H
30
N
2
O
6
P
2
Pd
Acknowledgments
Formula weight
Crystal system
Space group
a (Å)
b (Å)
c (Å)
690.11
monoclinic
C2/c
18.5424(4)
9.6591(3)
19.5864(5)
90
115.741(1)
90
3159.87(14)
200(2)
860.58
orthorhombic
Fdd2
10.4760(3)
22.6070(6)
30.8640(9)
90
90
90
7309.5(4)
293(2)
8
778.98
triclinic
P1ꢀ
10.5165(8)
11.2661(9)
16.0018(12)
88.654(4)
83.326(4)
62.762(4)
1673.3(2)
200(2)
We are grateful for support of this work by the National Science
Council of Taiwan and thank Mr. Ting-Shen Kuo (National Taiwan
Normal University, Taipei) for X-ray diffraction analysis.
a
(°)
b (°)
(°)
Appendix A. Supplementary material
c
3
U (Å )
T (K)
Z
CCDC 809400, 809401, 809402 contain the supplementary crys-
tallographic data for compounds 3, 4, and 5, respectively. These
data can be obtained free of charge from The Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.ica.2011.06.052.
4
2
ꢀ
l
(mm 1
)
0.836
0.0317, 0.1343
1.266
0.670
0.0368, 0.0982
1.075
0.702
0.0478, 0.1160
1.021
Final R
1
/wR
2
Goodness-of-fit
(
GOF) on F2
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P(o-C
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[
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