Synthesis of some macrocycles/bicycles from bis(o-formylphenyl) selenide: X-ray crystal structure of bis(o-formylphenyl) selenide and the first 28-membered selenium containing macrocyclic ligand

Article abstract of DOI:10.1016/S0022-328X(00)00830-5

Bis(o-formylphenyl) selenide (7) was synthesized using the ortholithiation methodology. The reaction of o-lithiobenzaldehyde acetal (5) with Se(dtc)₂ (dtc=diethyldithiacarbamate) afforded bis(o-formylphenyl) selenide acetal (6) in good yield. The key starting material 7 was isolated as pale yellow solid upon refluxing 6 with concentrated HCl. The structure of 7 was solved in the monoclinic space group P2/c with cell constants a=8.0170(6) ?, b=8.4514(6) ? and c=17.5289(12) ?, Z=4. The condensation of 7 with diethylenetriamine yielded the novel macrocyclic ligand [C₃₆H₃₈N₆Se₂] 8 via metal-free dimerization. Crystals of 8 are monoclinic, space group C2/c with a=18.732(3) ?, b=8.6515(10) ?, c=22.590(3) ? and Z=4. Hydrogenation of macrocycle 8 provided the corresponding saturated tetraazamacrocycle [C₃₆H₄₆N₆Se₂] (9), protonation of which with HBr afforded [C₃₆H₅₂N₆Se₂Br₆·H₂O] (10). The two novel cryptands [C₅₄H₅₄N₈Se₃] (12) and [C₅₄H₅₄N₈Te₃] (13) were prepared from the reaction of tris(2-aminoethyl)amine (tren) and the chalcogenides (7) and bis(o-formylphenyl) telluride (11) respectively using cesium ion as the template.

Full text of DOI:10.1016/S0022-328X(00)00830-5

Journal of Organometallic Chemistry 623 (2001) 87–94
www.elsevier.nl/locate/jorganchem
Synthesis of some macrocycles/bicycles from bis(o-formylphenyl)
selenide: X-ray crystal structure of bis(o-formylphenyl) selenide
and the first 28-membered selenium containing macrocyclic ligand
Arunashree Panda a, Saija C. Menon a, Harkesh B. Singh a,*, Ray J. Butcher b
a Department of Chemistry, Indian Institute of Technology, Powai, Bombay 400 076, India
b Department of Chemistry, Howard Uni6ersity, Washington, DC 20059, USA
Received 4 July 2000; accepted 19 October 2000
Abstract
Bis(o-formylphenyl) selenide (7) was synthesized using the ortholithiation methodology. The reaction of o-lithiobenzaldehyde
acetal (5) with Se(dtc)2 (dtc=diethyldithiacarbamate) afforded bis(o-formylphenyl) selenide acetal (6) in good yield. The key
starting material 7 was isolated as pale yellow solid upon refluxing 6 with concentrated HCl. The structure of 7 was solved in the
,
,
,
monoclinic space group P2/c with cell constants a=8.0170(6) A, b=8.4514(6) A and c=17.5289(12) A, Z=4. The condensation
of 7 with diethylenetriamine yielded the novel macrocyclic ligand [C36H38N6Se2] 8 via metal-free dimerization. Crystals of 8 are
,
,
,
monoclinic, space group C2/c with a=18.732(3) A, b=8.6515(10) A, c=22.590(3) A and Z=4. Hydrogenation of macrocycle
8 provided the corresponding saturated tetraazamacrocycle [C36H46N6Se2] (9), protonation of which with HBr afforded
[C36H52N6Se2Br6·H2O] (10). The two novel cryptands [C54H54N8Se3] (12) and [C54H54N8Te3] (13) were prepared from the reaction
of tris(2-aminoethyl)amine (tren) and the chalcogenides (7) and bis(o-formylphenyl) telluride (11) respectively using cesium ion as
the template. © 2001 Elsevier Science B.V. All rights reserved.
Keywords: Macrocycle; Cryptands; Selenide; Selenaazamacrocycle; Polyamine; Tetrabromide salt
mainly dealt with homoleptic selenoethers ligands such
as 1,5,9,13-tetraselenacyclohexadecane ([16]aneSe4) [3].
As part of our research into design and synthesis of
novel heavier chalcogenaaza macrocycles, we recently
reported the synthesis and complexation studies of the
first telluraaza macrocyclic Schiff base [4].
To our knowledge, selenium has not been incorpo-
rated into a macrocyclic Schiff base. The closest exam-
ple would be the nitro-capped cage with an N3Se3
donor set [5]. Other related polyselena macrocycles
include; [6]aneSe2 and [8]aneSe4, the tetraselena-macro-
cycles [16]aneSe4, [14]aneSe4, [12]aneSe4 and hexase-
lena-macrocycle [24]aneSe6 [2a], the selenium
containing cyclophane [2b], novel tetraselenide macro-
cycles [2c,d], cyclic polyselenoether, the selenium
analogs [2e,f] of crown ethers, the host molecule con-
taining the Se–Se bond [2g]. The diselena crown ether
reported by Meunier et al. [2h], tetraselena crown ethers
of three different sizes incorporating several oxygen
atoms in the bridge [2i] are other notable examples.
1. Introduction
The design and synthesis of Schiff-base macrocylic
ligands for the selective coordination of metals has
attracted considerable current interest [1]. There is a
significant activity in the design and synthesis of Schiff
base macrocyclic ligands incorporating additional
donor atoms such as O (oxaaza) and S (thiaaza) [1].
Incorporation of the larger Se and Te would lead to a
change in the size of the cage cavity and hence allow for
some interesting coordination behaviour. In addition,
the greater s-donating ability of Se and Te would
facilitate the complexation of a variety of metal ions.
Surprisingly, there is a paucity of information in the
literature concerning the heavier chalcogen (Se, Te)
analogs, although some homoleptic selenoether macro-
cycles have been reported [2]. Also reports on the
metal-ion complexes of the selenium macrocycles have
* Corresponding author.
0022-328X/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(00)00830-5

88
A. Panda et al. / Journal of Organometallic Chemistry 623 (2001) 87–94
In continuation of our work on selenium [6] and
formylphenyl) selenide acetal (6). Yield=2.6g (68%);
m.p.: 130–132°C; Anal. Found: C, 57.65; H, 4.54;
C18H18O4Se Calc.: C, 57.30; H, 4.81%; 1H-NMR
(CDCl3): l 7.63–7.16 (m, 8H, aromatic-H), 6.14 (s, 2H,
tellurium [4] containing macrocycles, we report in this
paper the synthesis and coordination chemistry of a
novel 28-membered selenium azamacrocyle (Se2N6 sys-
tem) with more donor atoms and also the first example
of a tellurium containing macrobicyclic ligand along
with its selenium analog having E3N8 (E=Te, Se)
donor sets.
Ar–CH
(CDCl3): l 138.53, 134.71, 131.78, 130.04, 127.61,
126.90 (aromatic-C), 103.11 (Ar–CHO2), 65.45
(OCH2–C
H2O); 77Se--NMR (CDCl3): l 321.
6 ), 4.77–4.02 (m, 8H, OCH6 2–CH6 2
O); 13C-NMR
6
6
6
2.2. Preparation of bis(o-formylphenyl) selenide (7)
2. Experimental
Bis(o-formylphenyl) selenide acetal (2.12 g, 5.63
mmol) in CCl4 (10 ml) and methanol (30 ml) mixture
was refluxed with HCl (6 N, 2.2 ml) for 2 h. To this
water (10 ml) was added and the reaction mixture was
further refluxed for 5 min. After cooling, the mixture
was washed with water (3×25 ml). The organic layer
was separated and dried over sodium sulfate. The ex-
cess of CCl4 was distilled off and the product was
precipitated out as pale yellow solid after keeping for
overnight. Yield=1.2 g (74%); m.p.: 124–126°C [lit.
127°C]; IR (KBr): 1706 cm−1; Anal. Found: C, 59.05;
H, 3.46; C14H10O2Se Calc.: C, 58.15; H, 3.49%; 1H-
NMR (CDCl3): l 8.01–7.27 (m, 8H, aromatic-H),
10.28 (s, 2H, aldehydic-H); 13C-NMR (CDCl3): l
Bis(o-formylphenyl) telluride [4a], Se(dtc)2 [7] and
Pd(COD)Cl2 [8] were prepared by reported procedures.
Air sensitive reactions were carried out under an inert
atmosphere. Solvents were purified by standard tech-
niques and were freshly distilled prior to use. Diethylen-
etriamine was reagent grade and was distilled prior to
use. Tris(2-aminoethyl)amine (Aldrich) was used as re-
ceived. Melting points were recorded in capillary tubes
and are uncorrected. IR spectra were recorded as KBr
pellets on a Nicolet Impact 400 FTIR spectrometer
(4000–400 cm−1). 1H- (299.94 MHz), 13C- (75.42
MHz), and 77Se-NMR (57.22 MHz) NMR spectra were
recorded on a Varian VXR 300S spectrometer at the
indicated frequencies. Chemical shifts cited were refer-
enced to TMS (1H, 13C) as internal, Me2Se (77Se) as
external reference. Elemental analyses were performed
on a Carlo-Erba model 1106 elemental analyzer. Mass
spectra were recorded at room temperature (r.t.) on a
JEOL D-300 (EI/CI) mass spectrometer. Fast atom
bombardment (FAB) mass spectra were recorded at r.t.
on a JEOL SX 102 DA-6000 mass spectrometer/data
system using xenon (6 kV, 10 mV) as the bombarding
gas. The acceleration voltage was 10 kV and m-ni-
trobenzyl alcohol was used as the matrix with positive-
ion detection. In case of isotopic patterns the value
given is for the most intense peak.
193.48 (Ar–C6 HO), 136.06, 135.81, 134.93, 134.63,
132.75, 128.28 (aromatic-C); 77Se-NMR (CDCl3): l
393.
2.3. Synthesis of bis(diphenylselenide)BISDIEN Schiff
base (8)
A solution of bis(o-formylphenyl) selenide (0.15 g,
0.5 mmol) in acetonitrile (100 ml) was added to a
stirred solution of diethylenetriamine (0.052 g, 0.5
mmol) in CH3CN (100 ml) over a period of 1 h. The
mixture was stirred overnight and the precipitated
white powder was filtered off, washed with acetonitrile
and recrystallized from CHCl3/CH3CN: Yield=0.16g
2.1. Preparation of bis(o-formylphenyl) selenide acetal
(6)
(84%); m.p. 172–174°C; IR (KBr): 1639, 1584 cm−1
,
(wCꢀN stretching); Anal Found: C, 60.88; H, 5.22; N,
11.88; C36H38N6Se2 Calc.: C, 60.67; H, 5.37; N, 11.79%;
MS (FAB): m/z 713(M+), 460, 358, 307, 289, 154, 136,
120, 107, 89, 63; 77Se-NMR (CDCl3): l 387.9, 387.5,
335.6, 329.8, 328.5.
To a solution of ethylene acetal of o-bromobenzalde-
hyde (4.7 g, 20.5 mol) in dry ether (100 ml) taken in a
three-necked (250 ml) flask fitted with rubber septum
and nitrogen gas inlet was added dropwise with stirring
a 1.6 M solution of n-butyllithium (14 ml, 22.4 mmol)
over a period of 5 min at r.t. The mixture was stirred
for additional 5 min to get a cloudy white slurry. Then
Se(dtc)2 (3.86g, 10.3 mmol) was added under a brisk
flow of nitrogen in small portions. After stirring for 1 h
at r.t. the solution was poured into ice water (500 ml)
and extracted with diethyl ether (3×50 ml). The ether
solution was dried over anhydrous sodium sulfate and
concentrated in vacuo. The residue was kept aside
overnight to get colorless crystals of bis(o-
2.4. Synthesis of bis(diphenylselenide)BISDIEN (9)
To a suspension of 8 (0.29 g, 0.4 mmol) in ethanol
NaBH4 was added in excess in small portions and the
reaction mixture was stirred for 3 h at r.t. Excess
ethanol was removed under reduced pressure. To the
residue, water (50 ml) was added and the product was
extracted with dichloromethane. Yield=0.17 g (61%);
185–187°C; IR (KBr): 3320 cm−1 (NH stretching),
1728, 1664 cm−1 (NH bending); Anal Found: C, 59.79;

A. Panda et al. / Journal of Organometallic Chemistry 623 (2001) 87–94
89
H, 6.49; N, 11.38 C36H46N6Se2 Calc.: C, 60.00; H, 6.43;
2.6.2. Synthesis of 13
N, 11.66%; MS (FAB): m/z 723 (M+), 635, 362, 259;
77Se-NMR (CDCl3): l 328.
Yield=0.19g (79%); m.p. 222–224°C; IR (KBr):
1636 cm−1 (wCꢀN stretching); Anal Found: C, 53.93; H,
4.45: N, 9.47 C54H54N8Te3 Calc.: C, 54.15; H, 4.54; N,
9.35%; MS (FAB): m/z 1195 (M+), 663, 490, 418, 320,
2.5. Synthesis of bis(diphenylselenide)BISDIEN
hydrobromide salt (10)
287, 232; 1H-NMR (CDCl3): l 8.40 (s, 6H, CH
6
ꢀN),
7.99–7.05 (m, 24H, aromatic-H), 3.52 (t, CꢀN–CH2
12H), 2.69 (t, N–CH2–CH2, 12H).
6
,
The crude reduced Schiff base (9) (0.36 g, 0.5 mmol)
was treated with HBr (48%) and ethanol. The precipi-
tated salt (10) was filtered off, washed with ethanol
followed by ether. Yield=0.48 g (80%); m.p. 278–
280°C; IR(KBr): 1637–1578, 1446 cm−1 (NH bending);
Anal Found: C, 34.84, H, 4.32, N, 6.53;
C36H52N6Se2Br6.H2O Calc.: C, 35.32, H, 4.45, N,
6.86%; MS (FAB): m/z 745 (M+–6Br−+H2O), 723
(M+–6Br−), 587, 413, 176, 154, 136, 107, 91, 77;
77Se-NMR (CDCl3): l 323.
6
3. Results and discussion
For the preparation of the selenium containing pre-
cursor bis(o-formylphenyl) selenide (7), easily available
and inexpensive o-bromotoluene (1) was used as the
starting material.
o-Bromobenzaldehyde (3) was prepared following
the reported procedure (Scheme 1) [9].
2.6. General procedure for the synthesis of cryptands
n-Butyllithium was added to o-bromobenzaldehyde
acetal (4) in ether at room temperature as reported by
Piette and Renson [10] and stirred for 15 min to get
o-lithiobenzaldehyde acetal (5) as a cloudy white slurry.
Subsequently Se(dtc)2 was added and the reaction mix-
ture stirred for 1 h at room temperature. The reaction
mixture was extracted with ether. On evaporation of
the solvent, bis(o-formylphenyl) selenide acetal (6) sep-
arated out as a white solid in 68% yield. Deprotection
of the aldehydic group was performed by refluxing the
acetal with concentrated HCl and bis(aldehyde) 7 was
found as pale yellow solid in 74% yield. Interestingly
Syper et al. [11] have reported the isolation of bis(o-
formylphenyl) selenide as a by-product in 6% yield
while preparing bis(o-formylphenyl) diselenide by react-
ing lithium diselenide with o-chlorobenzaldehyde. They
The bis(o-formylphenyl) selenide/telluride (0.6 mmol)
in methanol was added dropwise to the solution of
tris(2-aminoethyl)amine (tren) (0.058 g, 0.4 mmol) and
CsCl (0.034 g, 0.2 mmol) in methanol at r.t. over a
period of 1 h. The mixture was allowed to stir for
overnight and the yellow precipitate was filtered and
washed with methanol.
2.6.1. Synthesis of 12
Yield=0.19 g (90%); m.p. 218–220°C; IR (KBr):
1644 cm−1 (wCꢀN stretching); Anal Found: C, 61.48; H,
5.29; N, 10.76 C54H54N8Se3 Calc.: C, 61.66; H, 5.17; N,
10.65%; MS (FAB): m/z 1054 (M+), 671, 534, 460, 401,
370, 307, 273, 258, 245, 226, 155, 120, 91, 65, 39, 31;
1H-NMR (CDCl3): l 8.36 (s, 6H, CHꢀN), 7.82–7.11
1
have characterized 7 by IR and H-NMR study only.
(m, 24H, aromatic-H), 3.57 (t, CꢀN–CH2
6 , 12H), 2.76
The novel 28-membered macrocycle 8 was obtained
by the condensation of bis(o-formylphenyl) selenide
and diethylenetriamine in acetonitrile in the absence of
any templating cation and was isolated in good yield
(Scheme 2). Secondary intramolecular Se···N co-ordina-
tion (vide infra) plays an important role in the forma-
tion of the macrocycle by reducing the unfavourable
lone pair–lone pair interaction between nitrogen atoms
in the ring. The ligand is fairly soluble in CHCl3 and
CH2Cl2 but insoluble in polar solvent like MeOH and
(CH3)2SO; it could be recrystallized from CHCl3/
MeCN (1:1). Reduction with NaBH4 in ethanol under
reflux conditions afforded 9 in good yield. The proto-
nated derivative 10 was obtained in quantitative yield
by treatment of 9 with 48% hydrobromic acid.
(t, N–CH
6
2–CH2–, 12H); 77Se-NMR (CDCl3): l 397.
The two macrocyclic cryptands (12, 13) could be
conveniently synthesized from [2+3] condensation of
tris(2-aminoethyl)amine (tren) with bis(2-formylphenyl)
chalcogenides (7 and 11 [4a]) at room temperature
using cesium ions as the template in methanol in 90 and
79% yield, respectively (Scheme 3). Isolation of crystals
Scheme 1.

90
A. Panda et al. / Journal of Organometallic Chemistry 623 (2001) 87–94
Scheme 2. (i) NH2CH2CH2NHCH2CH2NH2, MeCN, room temperature; (ii) NaBH4, EtOH, reflux; (iii) 48% HBr, EtOH.
Scheme 3.
suitable for X-ray analysis has so far proved elusive.
Also, due to poor solubility of 12 and 13 in common
organic solvents, all attempts towards coordination of
12 and 13 with common metal ions or reduction with
NaBH4/methanol/ethanol and LiAlH4/THF have
proved futile.
These compounds were characterized by elemental
analysis, IR, NMR (1H, 13C and 77Se) and mass spec-
troscopic studies. That the macrocyclization had oc-
curred was evidenced by the presence of an imine band
in the IR and the absence of carbonyl and amine
stretching frequencies, together with the absence of a
1
–C(H)ꢀO proton in the H-NMR spectra of the ligand
8. The w(CꢀO) frequency for the selenide 7 was ob-
served at 1706 cm−1. The w(CꢀN) vibrational frequency
of the macrocycle 8 was observed at 1639 cm−1 and its
mass spectrum showed the molecular ion peak at m/z
1
713 as base peak. The H-NMR spectra of 6–9, 12 and

A. Panda et al. / Journal of Organometallic Chemistry 623 (2001) 87–94
91
13 were recorded in CDCl3. A singlet at 6.14 ppm
8.36 and 8.40 ppm, respectively. The 77Se-NMR shows
a single signal for 12 at 397 ppm and thus implies the
similar environment around both the selenium atoms.
The 125Te-NMR of 13 could not be recorded due to its
poor solubility. In the case of cryptand 12, the molecu-
lar ion peak at m/z 1054 was observed as the base peak
(Fig. 1). For the cryptand 13 a low intensity peak was
observed for the molecular ion peak at m/z 1195.
corresponding to Ar–CH
6
protons and multiplets at
4.40 ppm for OCH2–CH2
6
6 O protons were observed in
1
the H-NMR spectrum of 6. For the compound 7 a
singlet for the aldehydic protons was observed at 10.28
1
ppm. The H-NMR spectra of 8–10 were complex. In
particular though the macrocycle 8 gave satisfactory
1
elemental analysis and mass spectral data, its H-NMR
and 77Se-NMR spectra were complex. The 77Se-NMR
displayed several signals. This is probably due to a ring
contraction of the macrocyclic cavity of the Schiff base,
often leading to the stabilization of metal-free ligands.
This generally, occurs when there is a group such as
NH or OH available for addition to the imine bond.
The attack of the amine function (NH) to the imine
group of the open Schiff base macrocycle 8 results in a
decrease of the ring size (28–22) and formation of
isomers 8a and 8b [12]. Also, formation of the 10-Se-3
selane (vide infra) system by intramolecular N“Se
coordination might lead to a different environment for
the two selenium atoms in 8, 8a and 8b. In the case of
compound 9 the disappearance of the w(CꢀN) absorp-
tion in IR confirmed the reduction of the CHꢀN bond.
For the macrocyclic polyamine ligand the molecular ion
peak was observed as a base peak at m/z 723. The
77Se-NMR spectrum shows a single peak at 328 ppm,
which confirmed the identical environment around both
the selenium atoms. No molecular ion peak was ob-
served for 10. But the highest recorded peak at m/z 745
was equivalent to [10·H2O–6Br−]. The preliminary
identification of the macrobicyclic ligand was estab-
lished from IR spectra. The IR spectra of 12 and 13 do
not show any peaks corresponding to the amino and
carbonyl groups. The medium intensity band at 1644
and 1636 cm−1 for 12 and 13 were assignable to the
w(CꢀN) stretching frequency. The azomethine proton
signal for the Schiff base 12 and 13 were observed at
3.1. Crystal structure of compound 7
An ORTEP view of 7 is shown in Fig. 2. The selected
bond angles and distances are given in Table 1. The
crystal structure involves packing of four molecules in
the unit cell. The bond configuration around the Se
atom is V shaped and the angle C(1A)–Se–C(1B) is
97.84(9)°. The Se–C(1A) and Se–C(1B) bond distances
,
,
of 1.921(2) A and 1.936(2) A, respectively, are slightly
longer than the sum of the Pauling covalent radii 1.91
,
A. This value is also comparable to the Se–C bond
distances in bis[2-(dimethylaminomethyl)phenyl] sele-
,
nide [1.941(3) and 1.953(3) A] [13]. The Se···O(1A)
,
distance 2.806 A is higher than the sum of the single
,
bond covalent radii for selenium (1.17 A) and oxygen
(0.66 A) but considerably shorter than the sum of the
van der Waals radii 3.4 A. This distance is higher than
the Se···O bond distance in (phenylseleno)iminoquinone
,
,
,
[2.476 A] [14] but shorter than the Se···O(mean) dis-
,
tance (2.977 A) in the diselenide bearing a methoxy
substituent ortho to the selenium [15]. The other oxygen
atom is away from the Se atom and thus not coordi-
nated. The O(1A)–Se–C(1B) bond angle is 166.5°
which means the O(1A)–Se bond is roughly trans to the
Se–C(1B) bond. This may be due to the weak interac-
tion between oxygen and selenium. The intermolecular
,
Se···Se distance (4.141 A) is slightly greater than the
sum of the van der Waals radii of selenium atoms.
Fig. 1. FAB mass spectrum of 12.

92
A. Panda et al. / Journal of Organometallic Chemistry 623 (2001) 87–94
Fig. 2. Crystal structure of 7.
3.2. Crystal structure of compound 8
4. Conclusions
The key starting material bis(o-formylphenyl)selenide
was prepared by using ortholithiation methodology.
[2+2] Cyclocondensation of the bis(aldehyde) with
diethylenetriamine afforded the novel selenaaza macro-
cyclic ligand. Reduction of this Schiff base with an
X-ray diffraction determinations of 8 show that the
compound crystallizes in a centrosymmetric space
group C2/c and there are four molecular units in the
unit cell. A selection of bond lengths and bond angles is
given in Tables 2 and 3 in accordance with the number-
ing system given in Fig. 3. The structure shows that this
macrocycle has a 28-membered cavity.
Table 1
,
Significant bond lengths (A) and angles (°) for 7
,
The Se–C(1B) distance (1.931(3) A) is slightly higher
than the sum of the Pauling single bond covalent radii
Se–C(1A)
O(1A)–C(7A)
Se–O(1A)
1.921(2)
1.209(3)
2.806
Se–C(1B)
O(1B)–C(7B)
C(1A)–Se–C(1B)
1.936(2)
1.200(3)
97.84(9)
2
,
for selenium (1.17 A) and sp hybridized carbon (0.74
,
A). This bond distance can be comparable to the
Se(2A)–C(12A) bond length (1.933(8) A) in 1-
(methylselanyl)-8-(phenylselanyl)naphthalene [16].
,
C(2A)–C(1A)–Se
C(2B)–C(1B)–Se
121.20(17) C(6A)–C(1A)–Se
118.95(16) C(6B)–C(1B)–Se
120.28(15)
121.63(17)
,
However, the Se–C(1A) bond distance (1.949(3) A) is
longer than Se–C(1B) distance. This may be due to the
fact that Se–C(1A) is trans to the weakly coordinated
nitrogen atom. In this case, out of the four nitrogens of
the azomethine groups, only two are coordinating to
the selenium atoms as the other two are away from the
selenium atoms. The solid-state geometry of the
molecule indicates the presence of only one attractive
Se···N interaction per selenium atom, i.e. it corresponds
to the structure of 10-Se-3 selane. The geometry around
the selenium atom is T-shaped. The intramolecular
O(1B)–C(7B)–C(6B) 124.6(3)
O(1A)–C(7A)–C(6A) 124.8(2)
Table 2
Significant bond lengths (A) and angles (°) for 8
,
Se–C(1B)c1
Se–C(1A)
N(2)–C(9B)
N(1B)–C(7B)
C(1B)–Sec1
1.931(3) N(1A)–C(7A)
1.949(3) N(1A)–C(8A)
1.461(4) N(2)–C(9A)
1.260(4) N(1B)–C(8B)
1.931(3)
1.258(4)
1.460(5)
1.463(4)
1.458(4)
,
Se···N(1BA) distance of 2.814 A is remarkably shorter
C(1B)c1–Se–C(1A)
C(9B)–N(2)–C(9A)
C(6A)–C(1A)–Se
97.54(13) C(7A)–N(1A)–C(8A) 117.8(3)
,
than the sum of the van der Waals radii (3.5 A) of the
112.3(3) C(2A)–C(1A)–Se
117.7(2)
117.3(3)
122.3(2) C(7B)–N(1B)–C(8B)
two elements. The transannular Se···Se(A) distance
N(1A)–C(7A)–C(6A) 123.0(3) N(1A)–C(8A)–C(9A) 111.0(3)
,
(4.177 A) is slightly longer than the sum of van der
N(2)–C(9A)–C(8A)
110.8(3) N(2)–C(9B)–C(8B)
112.2(3)
119.9(2)
112.2(3)
,
Waals radii (4 A). Deviation of N(1BA) from the
C(2B)–C(1B)–Sec1 121.1(2) C(6B)–C(1B)–Sec1
C(1A)–Se–C(1BA) plane is 0.1882°. The C(1B)–Se(1)–
C(1A) angle for this macrocycle is 97.54(13)°.
N(1B)–C(7B)–C(6B) 124.2(3) N(1B)–C(8B)–C(9B)

A. Panda et al. / Journal of Organometallic Chemistry 623 (2001) 87–94
93
Table 3
isotropic thermal parameters and full listings of bond
lengths and bond angles for the structure reported in
this paper have been deposited with the Cambridge
Crystallographic Data Centre. Copies of this informa-
tion may be obtained free of charge from the Director,
CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK
(fax: +44-1223-336033; e-mail: deposit@ccdc.cam.
ac.uk or http://www.ccdc.cam.ac.uk).
Crystal data and structure refinement for 7 and 8
7
8
Empirical formula
Fw
Crystal system
Space group
C14H10O2Se C36H38N6Se2
289.18
Monoclinic
P2/c
712.64
Monoclinic
C2/c
Unit cell dimensions
,
a (A)
8.0170(6)
8.4514(6)
17.5289(12)
90
93.6860(10)
90
1185.21(15)
4
1.621
18.732(3)
8.6515(10)
22.590(3)
90
113.376(8)
90
3360.5(8)
4
1.409
,
b (A)
,
c (A)
h (°)
i (°)
g (°)
V (A )
Acknowledgements
We are grateful to the Department of Science and
Technology (DST), New Delhi and Board of Research
in Nuclear Sciences (BRNS), Department of Atomic
Energy, Bombay for funding this work. Additional help
from the Regional Sophisticated Instrumentation centre
(RSIC), Indian Institute of Technology (IIT), Bombay
for the 300 MHz NMR spectroscopy, RSIC, CDRI
Lucknow for the mass recording facility and Tata
Institute of Fundamental Research (TIFR), Bombay
for the 500 MHz NMR spectroscopy is gratefully ac-
knowledged. R.J.B. wishes to acknowledge the DOD-
ONR program for funds to upgrade the diffractometer.
3
,
Z
Dcalc (Mg m−3
)
Temperature (K)
208(2)
0.71073
3.153
293(2)
0.71073
2.235
,
u (A)
Absorption coefficient (mm−1
Observed reflections [I\2|]
Final R(F) [I\2|] a
)
2898
3815
0.0298
0.0641
2898/0/164
1.030
0.0416
0.0899
3813/0/221
1.038
wR(F2) indices [I\2|]
Data/restraints/parameters
Goodness-of-fit on F2
a Definitions: R(F0)=ꢀꢁꢁF0ꢁ−ꢁFcꢁꢁ/ꢀꢁF0ꢁ and wR(F02)={ꢀ[w(F20−
Fc2)2]/ꢀ[w(Fc2)2}1/2
.
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