Crystal structures of amarine and isoamarine and copper(I) coordination chemistry with their allylation products

Article abstract of DOI:10.1016/j.jorganchem.2005.10.040

The crystal structures of amarine (1) and isoamarine (2), important intermediates in the preparation of 1,2-diphenyl-diaminoethane, were successfully determined. Their allylation products, 1,3-diallyl amarine (1)(CH₂CHCH₂)₂

Full text of DOI:10.1016/j.jorganchem.2005.10.040

Journal of Organometallic Chemistry 691 (2006) 1065–1074
www.elsevier.com/locate/jorganchem
Note
Crystal structures of amarine and isoamarine and
copper(I) coordination chemistry with their allylation products
1
1
1
*
Xue-Feng Huang , Yu-Mei Song , Xi-Sen Wang , Jie Pang, Jing-Lin Zuo, Ren-Gen Xiong
Coordination Chemistry Institute, The State Key Laboratory of Coordination Chemistry, Nanjing University, Hankou Road,
Nanjing, Jiangsu 210093, PR China
Received 24 August 2005; received in revised form 13 October 2005; accepted 18 October 2005
Available online 5 December 2005
Abstract
The crystal structures of amarine (1) and isoamarine (2), important intermediates in the preparation of 1,2-diphenyl-diaminoethane,
were successfully determined. Their allylation products, 1,3-diallyl amarine (1)(CH2ACH@CH2)2Br (3) and isoamarine bromide
(2)(CH2ACH@CH2)2Br (4) [the crystal structures of (1)(CH2ACH@CH2)2PF6(3-Br + PF6) and (2)(CH2ACH@CH2)2PF6 (4-Br + PF6)
are also successfully determined to confirm allylation products], react with CuBr to afford (1)2(CH2ACH@CH2)4(Cu2Br4) (5) and
(2)(CH2ACH@CH2)2(Cu2Br3) (6), respectively. Crystal structures of 5 and 6 reveal that 5 is an anion discrete complex without olefin
moiety coordination, and 6 has a 1D infinite chain with olefin moiety coordination as a bridging spacer. The fluorescent emission spectra
of 5 (kemax = 570 nm) and 6 (kemax = 642 nm) were measured, and display a significant difference that can be used for solid state fluo-
rescent sensing them.
ꢀ 2005 Elsevier B.V. All rights reserved.
Keywords: Amarine; Isoamarine; Allylation; Copper(I) olefin complex; Crystal structures; Fluorescent emission
1. Introduction
reported a simplified synthesis of racemic stein from benz-
aldehyde and liquid ammonia, and determined the crystal
structures of hydrobenzamide and protonated amarine by
HCl (meso-2,4,5-triphenyl-2-imidazoline hydrochloride
ethanol solvate). This work revised the structures of the
well known intermediates ‘‘hydrobenzamide’’ and ‘‘ama-
rine’’ (Scheme 1). However, as shown in Scheme 1, the
crystal structure of one of the important intermediates,
‘‘isoamarine (racemic-trans-2,4,5-triphenyl-2-imidazoline)’’
still remains unknown. In addition, there have been no
reports of the chemistry of two intermediates, amarine
and isoamarine, which serve a potential building block
through N atom of imidazoline or its derivatives through
1,3-N atoms allylation. As a part of our studies of the ole-
fin-copper(I) coordination polymers [5], we have deter-
mined the crystal structures of amarine (1) and
isoamarine (2) and carried out the crystal structure deter-
minations of the products of their 1,3-N atom allylation
reactions and the copper(I) coordination chemistry of the
allylation products with bromide anion. Herein, we report
Chiral 1,2-diphenyl-diaminoethane (stilbenediamine,
stein) have been widely used in enantioselective catalysis
as a very useful chelating ligands [1], such as the enantiose-
lective titanium-mediated addition of diethylzinc to alde-
hydes [2a], the V complexes with tetradentate Schiff base
ligands containing optically active stein [2b], and optically
active b-ketoiminato cobalt complexes with optically active
stein as effective Lewis acid catalysts for enantioselective
hetero Diels–Alder reactions [2c]. On the other hand, the
olefin-copper(I) complex with chiral bidentate ligand
(1S,2S)-N,N0-bis-(mesitylmethyl)-1,2-diphenyl-1,2-ethane-
diamine has been used to resolve racemic 1-buten-3-ol [3].
Consequently, the preparation of racemic stein demon-
strates the great importance. Corey and coworkers [4]
*
Corresponding author. Fax: +86 25 83317761/83314502.
E-mail address: xiongrg@netra.nju.edu.cn (R.-G. Xiong).
These authors contributed equally to this work.
1
0022-328X/$ - see front matter ꢀ 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2005.10.040

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X.-F. Huang et al. / Journal of Organometallic Chemistry 691 (2006) 1065–1074
NH
Ph
CHO
liq. NH3
H
HN
Ph
N
120˚
Ph
"hydrobenzamide"
"amarine"
O
HO
OH
H2O, NaOH
155˚,45min
Ph
Ph
AcHN
Ph
NHBz
HCl aq
AcN
Ac2O
H2N
Ph
NH2
Ph
HCl
EtOH
HN
Ph
N
N
Ph
Ph
Ph
Ph
"iso-amarine"
Scheme 1.
Ph
are unexceptional and comparable to those in 1 and pro-
tonated 1 [4].
Ph
HN
Ph
N
N
N
The reactions of 1 and 2 with allyl bromide afford 1,3-
diallyl 1 [(1)(CH2ACH@CH2)2Br] (3) and 1,3-diallyl 2
[(2)(CH2ACH@CH2)2Br] (4), respectively, in the presence
of Na2CO3 as shown in Scheme 2. Due to the difficulty
of the formation of single crystals of 3 and 4, we use PF6ꢀ
anion to replace the Brꢀ anion in 3 and 4 successfully to
determine their crystal structures of 3-Br + PF6 and
4-Br + PF6 as shown in Scheme 3.
CH2=CH-CH2Br / Na2CO3
Br
Ph
Ph
Ph
1
3
Ph
Ph
HN
Ph
N
N
N
CH2=CH-CH2Br / Na2CO3
Br
Figs. 1(c) and 2(c) clearly confirms the above-mentioned
diallylation reactions. Meanwhile, the cis- and trans-config-
urations of two phenyl rings in 3 and 4 still remain
unchanged. As expected, the C–C and C–N bond lengths
of 3-Br + PF6 and 4-Br + PF6 (Tables 3 and 4) are unex-
ceptional and comparable to the corresponding 1 and 2.
Furthermore, the solvothermal reactions of 3 and 4 with
CuBr give (1)2(CH2ACH@CH2)4(Cu2Br4) (5) and (2)
(CH2ACH@CH2)2(Cu2Br3) (6), respectively (Scheme 4).
The crystal structure of 5 (Fig. 3) discloses that the olefin
moiety of the allyl group does not take part in the coordi-
nation to Cu(I) probably due to the steric hindrance in
which two phenyl groups and two olefin moieties in 3 are
on the opposite plane of imidazole, and (1)(CH2A CH@
CH2)2 only acts as cation to balance the charge of dimeric
Cu2Br4 anion in which the local coordination environment
around Cu atom can be best described as three-coordinated
planar trigonal. Interestingly, the crystal structure determi-
nation of 6 (Figs. 4 and 5) shows that the olefin moiety of
the allyl group in (2)(CH2ACH@CH2)2(Cu2Br3) partici-
pates in the coordination to Cu(I) to result in the formation
of 1D infinite chain with two different local coordination
geometry Cu atoms probably due to one of two phenyl
rings being in the same plane of imidazole as one of
two olefin moieties which is quite different from that
found in 3 [6]. In one coordination geometry, Cu(I) is in
a slightly distorted tetrahedron defined by two l2-bridging
Br atoms, one terminal Br atom and the olefin moiety
(Fig. 4). In the second coordination geometry, the
Ph
Ph
Ph
2
4
Scheme 2.
the synthesis and crystal structures of amarine (1) and isoa-
marine (2), and their 1,3-N atom allylation products as well
as the fluorescent properties and crystal structures of the
copper(I) complexes with their allylation bromide products
as shown in Scheme 2.
2. Results and discussion
Amarine (1) and isoamarine (2) were prepared according
to the literature reported by Corey et al. Their single crys-
tals were obtained through the evaporation of solvent in air
at room temperature. Crystal structure determination of 1
(Fig. 1(a)) shows that two amarine molecules and one
water co-crystallize together through H-bonds and two
phenyl rings are in cis-configuration, as the meso isomer.
Compared to the crystal structure of the protonated 1,
the 1-N atom of imidazoline in 1 is un-protonated. As
expected, the C–C and C–N bond distances (Table 1) in
amarine are comparable to those found in protonated ama-
rine [4].
The crystal structure of 2 (Fig. 2(a)), different from that
found in 1, reveals that two phenyl rings are trans and 2 is a
racemic mixture. Similar to 1, there is no protonated N
atoms in 2. The C–C and C–N bond lengths (Table 2)

X.-F. Huang et al. / Journal of Organometallic Chemistry 691 (2006) 1065–1074
1067
Fig. 1. (a) Perspective view of amarine (1) molecule. (b) Crystal packing view of 1 along a-axis. (c) Perspective view of 3-Br + PF6 clearly showing two
phenyl rings are cis-mode.
coordination geometry around Cu(I) has a planar trigonal
environment defined by one terminal Br atom, one l2-
bridging Br atom and the olefin moiety (Fig. 4). Thus
[(2)(CH2ACH@CH2)2] cation acts as a bi-dentate spacer
to link the two Cu(I) atoms. If [(2)(CH2ACH@CH2)2] cat-
ion can be abbreviated as one straight line, a double infinite
chain was formed in the 1D olefin copper(I) coordination
polymer (6) as shown in Fig. 5(b) [6]. Furthermore, it can
be found from crystal packing view of 6 that the terminal
Table 1
Selected bond lengths (A) and angles (ꢁ) for 1 (amarine)
˚
N(1)–C(10)
N(1)–C(15)
N(2)–C(10)
C(9)–N(4)
1.326(4)
1.472(3)
1.312(4)
1.279(4)
1.567(4)
N(3)–C(20)
N(3)–C(9)
N(2)–C(19)
N(4)–C(21)
C(20)–C(21)
1.458(4)
1.353(3)
1.451(3)
1.475(4)
1.561(4)
C(15)–C(19)
C(10)–N(1)–C(15)
N(1)–C(10)–N(2)
C(8)–C(15)–C(19)
N(2)–C(19)–C(15)
N(4)–C(9)–N(3)
C(9)–N(4)–C(21)
N(3)–C(20)–C(21)
107.3(2)
C(10)–N(2)–C(19)
N(1)–C(15)–C(19)
C(18)–C(19)–C(15)
C(7)–C(20)–C(21)
C(9)–N(3)–C(20)
C(11)–C(21)–C(20)
N(4)–C(21)–C(20)
110.3(3)
115.7(3)
117.3(3)
102.0(2)
115.5(3)
108.3(3)
101.1(2)
104.1(2)
115.9(2)
118.9(2)
108.9(3)
116.6(2)
104.2(2)
˚
Br atom weakly coordinates to a Cu(I) atom (2.984 A) to
result in the formation of 2D network (Fig. 6(b)) [6]. As
expected, two phenyl rings in 5 and 6 are in cis- and
trans-configurations, respectively, from their crystal

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X.-F. Huang et al. / Journal of Organometallic Chemistry 691 (2006) 1065–1074
Fig. 2. (a) Perspective view of isoamarine (2). (b) Crystal packing view of 2 along a-axis. (c) Perspective view of 4-Br + PF6 clearly showing two phenyl
rings are trans-mode.
˚
structure determinations while the C–C and C–N bond dis-
tances are comparable to those in 1 and 2, and unexcep-
tional (Tables 5 and 6). The Cu–Brterminal bond distance
(2.3682 A) are also slightly longer than the corresponding
˚
l2-bridging Cu–Br (2.4388–2.3905 A) in 6. The bond dis-
tances (1.325–1.336 A) of the coordinated olefin moiety
C@C in 6 are slightly longer than the corresponding bond
lengths (1.284 A) of the uncoordinated olefin moiety C@C
˚
˚
(2.444 A) is slightly longer than that of Cu–Brl2-bridging
˚
˚
(2.001 A) in 5. Similarly, the Cu–Brterminal bond lengths

X.-F. Huang et al. / Journal of Organometallic Chemistry 691 (2006) 1065–1074
1069
Table 2
Selected bond lengths (A) and angles (ꢁ) for 2 (isoamarine)
Table 4
Selected bond lengths (A) and angles (ꢁ) for 4-Br + PF6
˚
˚
N3 –C2
N4 –C3
C2 –C4
1.4679(19)
1.3569(19)
1.565(2)
N3 –C3
N4 –C4
1.2874(18)
1.438(2)
P(1)–F(1)
P(1)–F(4)
P(1)–F(5)
N(1)–C(24)
N(1)–C(18)
N(2)–C(20)
1.556(4)
1.567(4)
1.568(4)
1.312(5)
1.491(6)
1.457(6)
P(1)–F(3)
P(1)–F(6)
P(1)–F(2)
N(1)–C(27)
N(2)–C(24)
N(2)–C(22)
1.569(4)
1.570(4)
1.558(4)
1.467(5)
1.311(5)
1.470(5)
C2 –N3 –C3
N3 –C2 –C4
N3 –C3 –N4
C2 –C4 –C10
107.53(11)
105.40(11)
115.51(13)
113.68(12)
C3 –N4 –C4
C4 –C2 –C6
N4 –C4 –C2
110.05(12)
112.44(12)
101.10(11)
F(1)–P(1)–F(3)
F(3)–P(1)–F(4)
F(3)–P(1)–F(6)
F(1)–P(1)–F(5)
F(4)–P(1)–F(5)
F(1)–P(1)–F(2)
F(4)–P(1)–F(2)
F(5)–P(1)–F(2)
C(24)–N(1)–C(18)
C(24)–N(2)–C(20)
C(20)–N(2)–C(22)
90.1(3)
91.3(3)
88.9(3)
89.8(3)
89.3(2)
179.0(3)
88.5(2)
91.2(3)
123.7(4)
125.3(4)
121.3(4)
F(1)–P(1)–F(4)
F(1)–P(1)–F(6)
F(4)–P(1)–F(6)
F(3)–P(1)–F(5)
F(6)–P(1)–F(5)
F(3)–P(1)–F(2)
F(6)–P(1)–F(2)
C(24)–N(1)–C(27)
C(27)–N(1)–C(18)
C(24)–N(2)–C(22)
91.1(2)
90.6(2)
178.3(3)
179.3(3)
90.5(2)
89.0(3)
89.8(2)
111.0(3)
120.0(4)
110.0(3)
Ph
Ph
KPF6
N
N
N
N
Br
PF6
formation of single crystal
Ph
Ph
Ph
Ph
3
3-Br+PF6
Ph
Ph
N
N
N
N
KPF6
Br
PF6
formation of single crystal
Ph
Ph
Ph
Ph
Ph
Ph
4
4-Br+PF6
Br-
N
N+
N
N
2-Butanol
Cu2Br4
+
CuBr
Scheme 3.
∆
Ph
Ph
Ph
Ph
2
3
5
Table 3
Ph
Ph
˚
Br
Selected bond lengths (A) and angles (ꢁ) for 3-Br + PF6
CuBr
2-Butanol
N
N
N
N
CuBr
P(1)–F(5)
P(1)–F(6)
P(1)–F(2)
N(2)–C(26)
N(2)–C(22)
N(1)–C(25)
1.464(5)
1.471(5)
1.553(4)
1.330(5)
1.470(5)
1.465(5)
P(1)–F(3)
P(1)–F(4)
P(1)–F(1)
N(2)–C(12)
N(1)–C(26)
1.469(5)
1.505(6)
1.563(4)
1.472(6)
1.301(5)
+
∆
CuBr2
Ph
Ph
Ph
Ph
6
4
Scheme 4.
F(5)–P(1)–F(3)
F(3)–P(1)–F(6)
F(3)–P(1)–F(4)
F(5)–P(1)–F(2)
F(6)–P(1)–F(2)
F(5)–P(1)–F(1)
F(6)–P(1)–F(1)
F(2)–P(1)–F(1)
C(26)–N(2)–C(22)
C(26)–N(1)–C(25)
C(25)–N(1)–C(18)
88.9(6)
176.2(6)
91.8(5)
87.1(3)
90.6(3)
92.0(3)
89.0(3)
179.0(3)
109.9(3)
111.1(3)
121.3(3)
F(5)–P(1)–F(6)
F(5)–P(1)–F(4)
F(6)–P(1)–F(4)
F(3)–P(1)–F(2)
F(4)–P(1)–F(2)
F(3)–P(1)–F(1)
F(4)–P(1)–F(1)
C(26)–N(2)–C(12)
C(12)–N(2)–C(22)
C(26)–N(1)–C(18)
94.8(6)
178.8(4)
84.5(5)
89.0(3)
93.9(3)
91.4(3)
86.9(3)
125.3(4)
120.4(4)
127.3(4)
The luminescent spectra of 5 and 6 in the solid state at
room temperature are shown in Fig. 7 with a maximum
emission peak at ca. 570 nm (kex = 363 nm) and 642 nm
(kex = 363 nm), respectively. The emission spectrum of
the former (strong yellow-green fluorescent emission) is
similar to those found in Cu4I4(pyridine)4 (kemax = 580 nm)
[8], [Cu(3,40-bipyridine)(Br)]n (kemax = 580 nm) [9] and
[Cu(3-PYA)]n as well as {[(2-PYA)Cu(I)]n(H2O)}n (kemax
=
580 nm, PYA = pyridylacrylate) [5]. Thus, the emission at
580 nm in 5 has been tentatively assigned to MLCT
(metal-to-ligand charge transfer) since the fluorescent emis-
sion of the free ligand (3) is observed at about 470 nm. In
addition, the shorter luminescent lifetime of 5 (ca.
s = 1.02 ns) in the solid state suggests its emission should
be fluorescent emission. Interestingly, the emission spec-
trum of the later (6, strong red fluorescent emission) is
similar to that found in {[bpy](4-hpya)Cu(I)}(BF4)n
in 5. Furthermore, the C–C bond distance for the coordi-
nated olefin moiety 6 is slightly shorter than that
found in [Cu2Cl2(C5H8)] (C5H8 = 2-methylbutadiene)
˚
(1.358(7) A), [7c] [CuCl-(C5H8O)] (C5H8O = 1-penten-3-
˚
one) (1.383(8) A) [7a] and [CuCl(C4H6O2)] (C4H6O2 =
˚
methylpropenoate) (1.370(8) A) [6b] as well as {Cu(4-
˚
VPY)Cl}n (4-VPY = 4-vinylpyridine) (1.364(4) A) [5d]. It
is interesting to note that the C–C bond lengths of the coor-
dinated olefin in the two copper(I) p-complexes Cu4Cl4L
(bpy = 2,20-bipryridine,
acid) with a maximum at ca. 647 nm (kexc = 250 nm). A
clearly bathochromic shift occurs in relative to
[Cu4I4(py)] (kemax = 580 nm), [Cu(3,4-bpyBr)] (kemax
580 nm) and 5 (kemax = 580 nm) which is probably due to
p-back-donation from the filled metal dp orbital to the
vacant antibonding p* orbital of the coordinated olefin
4-hpya = trans-4-pyridylacrilic
˚
˚
(1.33(2) A) and Cu4Br4L (1.34(2) A) (L = C7H8, 1,4-penta-
diene) containing a Cu4X4 cubane core are almost
comparable to those found in 6 [7e], and the Cu–C bond
6
=
˚
distances in Cu4Cl4L (2.10(1)–2.06(1) A) and Cu4Br4L
˚
(2.05(1)–2.10(1) A) are also similar to those found in 6
˚
(2.082(8)–2.134(7) A).

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X.-F. Huang et al. / Journal of Organometallic Chemistry 691 (2006) 1065–1074
Fig. 3. (a) Perspective view of (1)2(CH2ACH@CH2)4(Cu2Br4) (5). (b) Crystal packing of 5 along b-axis.
Fig. 4. Perspective of asymmetric unit of (2)(CH2ACH@CH2)2(Cu2Br3) (6).

X.-F. Huang et al. / Journal of Organometallic Chemistry 691 (2006) 1065–1074
1071
Fig. 5. (a) 1D chain representation of (2)(CH2ACH@CH2)2(Cu2Br3) (6). (b) Simplified 1D chain representation of (2)(CH2ACH@CH2)2(Cu2Br3) in which
cation is abbreviated as a straight line.
[5a]. In addition, because the short lifetime (ca. s = 1.50 ns)
and free ligand maximum emission peak being ca. 480 nm,
the emission of 6 at 642 nm could be assigned to MLCT.
Thus, the significant difference of fluorescent emission peak
between Cu(I) complex without olefin moiety coordination
and Cu(I) olefin coordination polymer has been observed
and probably can be used for fluorescent sensing to dis-
criminate two types of Cu(I) complexes.
In conclusion, we have successfully determined the crys-
tal structures of amarine and isoamarine, intermediates in
the preparation of 1,2-diphenyl-diaminoethane as well as
their 1,-3-diallyation products. The coordination chemistry
of Cu(I) with 1,3-diallylation amarine and isoamarine as
ligands makes them useful in supramolecular chemistry
as building blocks and solid state fluorescent sensing.
3.2. Preparation of 3
A mixture of 1 (1.49 g, 5 mmol), allyl bromide (1.21 g,
10 mmol) and Na2CO3 (0.265 g, 2.5 mmol) in anhydrous
CH2Cl2 (20 mL) were refluxed for 24 h. After cooling, the
solution was filtered. The filtrate was concentrated under
reduced pressure to give 3 with a yield of ca. 45% based
on amarine. IR data (cmꢀ1): 3462(s), 3403(s), 3029(m),
2923(m), 2357(w), 1591(m), 1562(s), 1492(m), 1455(m),
1416(m), 1361(w), 1339(w), 1317(m), 1281(w), 1254(m),
1158(w), 1081(w), 1027(w), 993(m), 934(m), 790(m),
753(w), 700(s), 552(w), 514(w). m/z = 379.4. 1H NMR
(500 MHz, CDCl3) d 2.67 (N+CH2), d 3.38 (NCH2), d
3.67 (N+CHaPh), d 4.51 (NCHbPh), d 4.70 (@CH2),
d 5.68 (N+CH2CH@CH2), d 6.04 (NCH2CH@CH2), d
6.74–7.35 (15H, 3 · Ph). 13C NMR (500 MHz, CDCl3)
d 49.7 (N+CH2), d 50.1 (NCH2), d 68.7 (N+CHaPh), d
78.3 (NCHbPh), d 121.2 (NCH2CH@CH2), d 122.4 (N+
3. Experimental
3.1. The preparation of amarine (1) and isoamarine (2)
CH2CH@CH2), d 128.7–130.4 (18C,3 · Ph), d 131.6
(NCH2CH@CH2), d 133.3 (N+CH2CH@CH2), d 167
(PhC@N).
Compounds 1 and 2 were prepared from benzaldehye
via hydrobenzamide according to the methods in the liter-
atures reported by Corey et al. IR (cmꢀ1) for 1: 3269(s),
3058(m), 3027(m), 2926(m), 1616(s), 1567(m), 1506(m),
1453(s), 1363(w), 1327(m) 1281(m), 1256(m), 1182(w),
1118(w), 1074(w), 1028(m), 1000(w), 922(m), 864(w),
744(s), 698(s), 576(m), 511(w); IR (cmꢀ1) for 2: 3148(s),
3060(m), 3027(s), 2886(m), 1597(s), 1565(s), 1509(s),
1471(s), 1362(w), 1337(m), 1273(m), 1192(m), 1125(w),
1073(w),1022(m), 986(w), 922(w), 847(w), 757(s), 696(s),
643(m), 606(m), 536(m), 511(w).
3.3. Preparation of 4
The procedure was identical to that used for 3 with a
yield of ca. 35% based on isoamarine. IR data (cmꢀ1):
3423(s), 3031(m), 2924(m), 2357(w), 1732(w), 1561(s),
1489(w), 1447(m), 1421(m), 1338(m), 1277(m), 1224(w),
1076(w), 994(m), 929(m), 832(w), 757(m), 702(s), 550(w).
m/z = 379.4. 1H NMR (500 MHz, CDCl3)
(N+CH2), d 3.43 (NCH2), d 3.59 (N+CHaPh), d 4.40
d 2.39

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X.-F. Huang et al. / Journal of Organometallic Chemistry 691 (2006) 1065–1074
Fig. 6. (a) 2D network representation of (2)(CH2ACH@CH2)2(Cu2Br3) (6) through weak Cu–Br interaction (red line). (b) Simplified 2D representation of
(2)(CH2ACH@CH2)2(Cu2Br3) (6) in which each 1D chain is connected by weak Cu–Br interaction and (2)(CH2ACH@CH2)2(Cu2Br3) is abbreviated as a
straight line. (For interpretation of the reference to colour in this figure, the reader is referred to the web version of this article.)
(NCHbPh), d 4.60 (@CH2), d 5.20 (CH@), d 6.99–7.27
Table 5
(15H,3 · Ph). 13C NMR (500 MHz, CDCl3)
d 49.7
˚
Selected bond lengths (A) and angles (ꢁ) for 5
(N+CH2), d 50.1 (NCH2), d 73.2 (N+CHaPh), d 78.3
(NCHbPh), d 121.1 (NCH2CH@CH2), d 122.2 (N+CH2-
CH@CH2), d 129.3–130.0 (18C,3 · Ph), d 133.2 (NCH2-
CH@CH2), d 134.0 (N+CH2CH@CH2), d 167 (PhC@N).
Br(1)–Cu(1)
C(27)–N(1)
C(27)–N(2)
C(26)–C(21)
C(9)–C(1)
2.4222(9) Br(2)–Cu(1)
2.2968(8)
1.478(5)
1.478(5)
2.7842(13)
1.284(2)
1.311(5)
1.321(5)
1.576(6)
N(1)–C(26)
N(2)–C(21)
Cu(1)–Cu(1)#1
1.117(12) C(7)–C(2)
69.75(3) Br(2)–Cu(1)–Br(1)
Br(1)–Cu(1)–Br(1)#1 110.25(3)
Cu(1)–Br(1)–Cu(1)#1
Br(2)–Cu(1)–Br(1)#1 124.19(4)
125.56(3)
3.4. Synthesis of 3-Br + PF6
N(1)–C(27)–N(2)
N(1)–C(26)–C(21)
N(2)–C(21)–C(26)
C(25)–C(26)–C(21)
C(22)–N(1)–C(26)
112.9(4)
101.1(3)
101.7(3)
114.0(4)
120.8(4)
C(27)–N(1)–C(26)
C(27)–N(2)–C(21)
C(18)–C(21)–C(26)
C(6)–N(2)–C(21)
111.3(3)
110.4(4)
114.2(3)
121.6(4)
The mixture of 3 and KPF6 in the solution of ethanol
evaporates at the room temperature for three days to afford
block-colorless single crystals. IR data (cmꢀ1): 3444(w),
3073(w), 1646(w), 1570(s), 1495(m), 1487(m), 1455(m),
1420(m), 1345(m), 1316(m), 1252(m), 1184(w), 1164(w),
Symmetry transformations used to generate equivalent atoms: #1
ꢀx + 1,ꢀy,ꢀz + 1.

X.-F. Huang et al. / Journal of Organometallic Chemistry 691 (2006) 1065–1074
1073
Table 6
Selected bond lengths (A) and angles (ꢁ) for 6
Anal. Calc. for C54H54Br4N4Cu2 (5): C, 53.79; H, 4.51; N,
4.65. Found: C, 53.54; H, 4.62; N, 4.57%. IR spectrum
(KBr, cmꢀ1): (KBr, cmꢀ1): 3425(br, w), 3084(w), 3059(w),
3048(w), 2935(w), 2909(w), 1640(w), 1608(w), 16591(s),
1568(s), 1485(m), 1454(s), 1433(w), 1419(w), 1348(w),
1337(w), 1318(w), 1289(w), 1258(m), 1228(w), 1207(w),
1155(w), 1081(w), 1027 (w), 927(w), 1026(w), 993 (m),
926(m), 860(w), 789(s), 770(w), 754(w), 720(w), 698(s),
633(w), 614(w), 582(w), 547(w), 511 (w), 460(w), 424(w).
˚
Br(1)–Cu(5)
Br(2)–Cu(4)#1
Br(3)–Cu(5)
Cu(5)–C(24)
N(1)–C(3)
2.4204(13) Br(1)–Cu(4)
2.3905(15) C(16)–Cu(4)#3
2.3682(15) Cu(4)–C(21)#2
2.4388(14)
2.134(7)
2.131(7)
2.082(8)
1.317(9)
1.323(10)
1.541(10)
1.336(11)
Cu(5)–C(9)
N(1)–C(7)
N(2)–C(4)
C(16)–C(21)
2.114(8)
1.479(10)
1.478(10)
1.325(12)
N(2)–C(3)
C(4)–C(7)
C(9)–C(24)
Cu(5)–Br(1)–Cu(4)
Cu(4)#1–Br(2)–Cu(4)
Br(2)#1–Cu(4)–Br(1) 111.85(5)
139.30(5)
75.64(5)
Br(1)–Cu(4)–Br(2)
Br(3)–Cu(5)–Br(1)
Br(2)#1–Cu(4)–Br(2) 104.36(5)
101.71(5)
113.73(6)
3.7. Synthesis of 6
C(3)–N(1)–C(11)
C(3)–N(2)–C(34)
N(1)–C(3)–N(2)
N(2)–C(4)–C(7)
C(5)–C(4)–C(7)
128.0(7)
128.0(7)
111.7(7)
101.3(6)
112.2(6)
C(3)–N(1)–C(7)
C(3)–N(2)–C(4)
N(2)–C(4)–C(5)
C(10)–C(7)–C(4)
110.4(6)
110.3(6)
116.0(6)
112.3(6)
Hydrothermal treatment of CuBr (2.0 mmol, 0.287 g)
and 4 (1.0 mmol, 0.456 g) over 4 days at 60–70 ꢁC yielded
yellow block crystalline 6 (0.332 g, ca. 55.4% based on 4).
Anal. Calc. for C27H27N2Cu2Br3 (6): C, 43.35; H, 3.65;
N, 3.75. Found: C, 43.18; H, 3.49; N 3.68%. IR spectrum
(KBr, cmꢀ1): 3448(br, w), 3084(w), 3059(w), 3032(w),
3007(w), 2977(w), 2940(w), 2909(w), 1970(w), 1900(w),
1833(w), 1780(w), 1736(w), 1685(w), 1642(w), 1600(w),
1586(m), 1548(s), 1530(s), 1495(w), 1482(w), 1454(m),
1400(m), 1354(w), 1322(w), 1314(w), 1271(m), 1221(m),
1189(m), 1162(w), 1105(w), 1085(w), 1026(w), 1001(w),
971(w), 920 (m), 832(m), 780(m), 757(s), 701(s), 641(w),
615(w), 556(w), 516(w), 473(w), 449(w), 412(w).
Symmetry transformations used to generate equivalent atoms: #1
ꢀx + 2,ꢀy + 1,ꢀz, #2 x + 1,y ꢀ 1,z, #3 x ꢀ 1,y + 1,z.
2.5
2.0
1.5
1.0
0.5
0.0
3.8. Crystal data for 1
ꢀ
C42H38N4O, triclinic, space group, P1, Mr = 614.76,
˚
a = 11.791(3),
b = 12.232(3),
c = 14.151(4) A;
a =
3
˚
66.775(4), b = 81.245(5), c = 64.868(5)ꢁ, V = 1697.8(7) A ,
Z = 2, Dc = 1.203 Mg/m3, l = 0.073 mmꢀ1, S = 0.972,
˚
R1 = 0.0623, wR2 = 0.1689, T = 293 K, k = 0.71073 A.
500
550
600
650
700
750
Wavelength(nm)
3.9. Crystal data for 2
Fig. 7. The fluorescent emission spectra of (1)2(CH2ACH@CH2)4(Cu2Br4)
(5) and (2)(CH2ACH@CH2)2(Cu2Br3) (6) at the solid state.
C21H18N2, monoclinic, space group, P2(1)/c, Mr =
298.37, a = 12.1743(18), b = 13.303(2), c = 10.1640
3
˚
˚
(16) A; b = 92.876(4)ꢁ, V = 1644.1(4) A , Z = 4, Dc =
1121(w), 1098(w), 1081(w), 1027(w), 999(m), 934(s),
850(vs), 841(vs), 830(vs), 789(w), 698(m), 557(m).
1.205 Mg/m3, l = 0.071 mmꢀ1
, S = 1.13, R1 = 0.0746,
˚
wR2 = 0.2291, T = 293 K, k = 0.71073 A.
3.5. Synthesis of 4-Br + PF6
3.10. Crystal data for 3-Br + PF6
The mixture of 4 and KPF6 in the solution of ethanol
evaporates at the room temperature for four days to afford
block-colorless single crystals. IR data (cmꢀ1): 3421(w),
3035(w), 1647(w), 1565(s), 1486(w), 1454(m), 1417(m),
1355(m), 1336(m), 1277(m), 1230(w), 1203(w), 1133(w),
1076(w), 1031(w), 992(m), 839(vs), 755(s), 699(s), 639(w),
557(s).
C27H27F6N2P, monoclinic, space group, P2(1)/n, Mr =
˚
524.48, a = 11.344(3), b = 15.858(4), c = 14.717(4) A;
3
˚
a = 90, b = 90.494(5), c = 90ꢁ, V = 2647.5(13) A , Z = 4,
Dc = 1.316 Mg/m3, l = 0.164 mmꢀ1
0.0972, wR2 = 0.2883, T = 293 K, k = 0.71073 A.
,
S = 1.289, R1 =
˚
3.11. Crystal data for 4-Br + PF6
3.6. Synthesis of 5
C27H27F6N2P, monoclinic, space group, Cc, Mr =
˚
524.48, a = 14.856(2), b = 10.8075(16), c = 15.652(2) A;
3
˚
Hydrothermal treatment of CuBr (2.0 mmol, 0.287 g)
and 3 (1.0 mmol, 0.456 g) over four days at 60–70 ꢁC yielded
yellow block crystalline 5 (0.380 g, ca. 63.4% based on 3).
a = 90, b = 93.123(3), c = 90ꢁ, V = 2509.3(6) A , Z = 4,
Dc = 1.388 Mg/m3, l = 0.173 mmꢀ1
0.0629, wR2 = 0.1379, T = 293 K, k = 0.71073 A.
,
S = 0.810, R1 =
˚

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X.-F. Huang et al. / Journal of Organometallic Chemistry 691 (2006) 1065–1074
(d) J. Zhang, R.-G. Xiong, X.-T. Chen, Z. Xue, S.-M. Peng, X.-Z.
3.12. Crystal data for 5
You, Organometallics 21 (2002) 225;
(e) X. Xue, X.-S. Wang, R.-G. Xiong, B.F. Abrahams, X.-Z. You, C.-
M. Che, Angew. Chem., Int. Ed. 41 (2002) 2944;
(f) Z.-R. Qu, Z.-F. Chen, J. Zhang, R.-G. Xiong, B.F. Abrahams, Z.
Xue, Organometallics 22 (2003) 2814;
(g) Y.-R. Xie, X.-S. Wang, H. Zhao, J. Zhang, L.-H. Wang, C.-Y.
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4396;
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(2005) 208.
C54H54Br4N4Cu2, monoclinic, space group, P2(1)/n,
Mr = 1205.73,
a = 10.3420(13),
b = 16.483(2),
c =
˚
15.825(2) A; a = 90, b = 106.998(3), c = 90ꢁ, V = 2579.7
3
3
(6) A , Z = 2, Dc = 1.552 Mg/m , l = 3.961 mmꢀ1, S =
˚
0.971, R1 = 0.0487, wR2 = 0.1401, T = 293 K, k =
˚
0.71073 A.
3.13. Crystal data for 6
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(b) K.A. Hirsch, S.R. Wilson, J.S. Moore, Chem. Eur. J. 3 (1997)
765;
C27H27N2Cu2Br3, monoclinic, space group, P2(1)/n, Mr
= 746.32, a = 11.3900(12), b = 9.5579(10), c = 24.582(3)
3
˚
˚
A, a = 90, b = 101.621(3), c = 90ꢁ, V = 2621.3(5) A , Z =
(c) C. Janiak, Angew. Chem., Int. Ed. 36 (1997) 1431;
(d) O.M. Yaghi, H. Li, C. Davis, D. Richardson, T.L. Groy, Acc.
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4, Dc = 1.891 Mg/m3, l = 6.215 mmꢀ1, S = 1.214, R1=
˚
0.0793, wR2 = 0.1912, T = 293 K, k = 0.71073 A.
4. Supporting information available
Crystallographic CIF (excluding structure factors) and
tables of atomic coordinates, thermal parameters, bond
distances and angles for 1, 2, 3-Br + PF6, 4-Br + PF6, 5
and 6.
(k) S. Masaoka, D. Tanaka, Y. Nankanishi, S. Kitagawa, Angew.
Chem., Int. Ed. 43 (2004) 2530.
Acknowledgements
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This work supported by The Major State Basic Re-
search Development Program (Grant No. G2000077500),
Distinguished Young Scholar Funds to XRG (No.
20225103) from the Natural Science Foundation of China,
Nos. 20490214 and 20471029 as well as BK2003204.
(f) M. Hakansson, K. Wettstrom, S. Jagner, J. Organomet. Chem. 421
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