Synthesis, structural characterization and crystal structure of selenium bearing 3-(phenylseleno) propylammonium acetate salt and its cleavage on reaction with mercury(II) and tin(IV) salts

Article abstract of DOI:10.1007/s10870-010-9895-3

3-(Phenylseleno) propylammonium acetate, C₉H ₁₄NSe⁺ C₂H₃O₂ ^-, L¹, the first example of a selenium bearing acetate salt has been synthesized and characterized by spectr

Full text of DOI:10.1007/s10870-010-9895-3

J Chem Crystallogr (2011) 41:391–400
DOI 10.1007/s10870-010-9895-3
ORIGINAL PAPER
Synthesis, Structural Characterization and Crystal Structure
of Selenium Bearing 3-(Phenylseleno) Propylammonium Acetate
Salt and its Cleavage on Reaction with Mercury(II) and Tin(IV)
Salts
•
•
•
Rupali Rastogi S. K. Srivastava R. J. Butcher
J. P. Jasinski
Received: 27 March 2010 / Accepted: 3 September 2010 / Published online: 18 September 2010
Ó Springer Science+Business Media, LLC 2010
Abstract 3-(Phenylseleno) propylammonium acetate, C9
–
groups. In order to elucidate the relationship between salt
H14NSe? C2H3O2 , L1, the first example of a selenium
properties and the nature of the counterion, several studies
have been made [1–8]. Some quaternary ammonium salts
such as those containing alkyl trimethyl, dialkyl dimethyl
and dimethyl benzyl groups exhibit antimicrobial activity.
They play an important role in living organisms and are also
involved in many of the functions in prokaryotic and
eukaryotic cells [9, 10]. Generally, short chain alkyl
ammonium salts show good antimicrobial activity as com-
pared to long chain quaternary ammonium salts which
increase the resistance of microorganisms [11]. In modern
medicinal chemistry, the concept of rational design of drug
salts has emerged with great importance since many of these
drugs show poor aqueous solubility and bioavailability [12,
13]. Chemopreventive activity of selenium in humans is
established by epidemiological studies and human inter-
vention trial [14–16]. Inorganic and organic selenium
compounds have chemopreventive effects in the mammary
gland, colon, lung, pancreas and skin [17] which have been
tested in animal assays laboratories. It has been reported that
chronic feeding of selenium in its inorganic form inhibits
carcinogenesis, but doses [5 ppm selenium are toxic in
animals. Selenomethionine and selenocysteine are naturally
occurring selenium-containing amino acids which show
about the same efficacy as inorganic selenium in cancer
prevention and toxicity [17]. Therefore, as selenium com-
pounds with higher anticarcinogenic efficacy have been
developed, selenium compounds of better tolerance have
become a priority in chemoprevention research. In view of
these observations, we have synthesized the first selenium
bearing ammonium acetate salt, 3-(phenylseleno) propyl-
ammonium acetate, C9H14NSe? C2H3O2- (L1), and exam-
ined its ligation behavior with Hg(ClO4)2, [Hg(PPh3)2]
(ClO4)2, HgCl2 and Ph2SnCl2. Reactions of L1 with these
four different metal salts revealed four new selenium
bearing acetate salt has been synthesized and characterized
by spectroscopic, NMR, DSC and single crystal X-ray
crystallographic techniques. L1 crystallizes with one cation–
anion pair in the asymmetric unit. Reactions of L1 with four
different metal salts revealed four new selenium bearing
compounds (1–4) whose identities are characterized by
spectroscopic and NMR techniques. The crystal structure of
Compound 1, [C9H14NSe]2? [ClO4]–2, whose crystal structure
has been confirmed. It crystallizes with two independent
cation–anion pairs in the asymmetric unit. Both L1 and
Compound 1 display strong N–HꢀꢀꢀO hydrogen bond inter-
molecular interactions which help stabilize crystal packing
in the unit cell.
Keywords Acetic acid ꢀ Organoselenium ꢀ Perchlorate ꢀ
3-(Phenylseleno) propylammonium acetate
Introduction
Biopharmaceutical properties of drugs can be altered by the
formation of salts tend to contain one or more ionizable
R. Rastogi (&) ꢀ S. K. Srivastava
School of Studies in Chemistry, Jiwaji University,
Gwalior, India
e-mail: rastogirupali@ymail.com
R. J. Butcher
Department of Chemistry, Howard University,
Washington, DC 20059, USA
J. P. Jasinski
Department of Chemistry, Keene State College,
229 Main Street, Keene, NH, USA
123

392
J Chem Crystallogr (2011) 41:391–400
bearing compounds (1–4) whose identities are characterized
by spectroscopic and NMR techniques. The crystal struc-
tures of L1 and compound [3-(phenylseleno) propylammo-
nium]2(ClO4)2 (1), have been characterized by single crystal
X-ray crystallography.
ethanolic solution of 3-(phenylseleno) propylamine
(2.16 g, 10 mmol), Scheme 1. The mixture was stirred for
4–5 h at 60–70 °C and the reaction extract was monitored
by TLC. The solvent was evaporated under reduced pres-
sure while the crude product was separated by TLC (hex-
ane:chloroform) (9:1) mixture to yield the pure ligand.
Yellow crystals suitable for X-ray analysis were obtained.
Yield 85–90%, M.P. 76 °C, Calc: %C (48.18), %H
(6.24) %N (5.10), Found: %C (48.62) %H (7.45) %N
Experimental
Reagents and Techniques
(5.51). IR spectrum: m
1566, m
1371, m N–H
as C O
sC O
3370–3280, d N–H 1643, m Se–C 468 cm-1; ESI mass
m/z = 292 for [M ? H2O], 216 for [M–CH3COOH] as
Diphenyl diselenide [18], diphenyltin dichloride, [19] and
3-(phenylseleno) propylamine [20] were prepared accord-
ing to the published procedures. Triphenylphosphine was
obtained from Sigma–Aldrich. Selenium powder, acetic acid
and sodium borohydride were purchased from CDH (India).
The C, H and N analysis were carried out with an Ele-
mentar Vario EL III analyser. 1H and 13C-NMR spectra were
recorded with a JEOL AL300 FT NMR spectrometer at 300
and 75.45 MHz, respectively, using CDCl3, MeOH as sol-
vents. ESI mass spectra were recorded on a MICROMASS
QUARTTRO II mass spectrometer. Samples (dissolved in
suitable solvents) were introduced into the ESI source
through a syringe pump at the rate of 5 ll per min. The ESI
capillary was set at 3.5 kV with the cone voltage at 40 V. IR
spectra in the range of 4000–400 cm-1 were recorded with a
Shimadzu Prestige 21 FT IR spectrometer as KBr pellets.
The DSC thermograms were recorded on a Perkin Elmer
Differential Scanning Calorimeter, model DSC 823e, using
an Alumina sample pan. The melting points, determined in
open capillary, were reported as found directly.
1
base peak. H-NMR: Ar–H 7.24–7.50 (m, 5H), NH3 4.09
(s, 3H), N–CH2 2.94 (t, 2H, JH–H 7.2 Hz), Se–CH2 2.87
(t, 2H, JH–H 7.2 Hz), CH2, CH3 1.86–1.95 ppm (5H, m).
13C-NMR: C=O 178.38, Se–Cipso 129.49, o to Se 132.82, m
to Se 129.13, p to Se 127.10, N–CH2 39.44, CH2 29.19,
Se–CH2 24.26, CH3 23.95 ppm.
Reaction of Hg(ClO4)2 with L1 (1)
Mercuric chloride (0.271 g, 1 mmol) was dissolved in
5 mL of methanol and stirred for 0.5 h with a solution of
AgClO4 (0.414 g, 2 mmol) made in 5 mL of methanol.
The resulting AgCl was filtered off through Whatman filter
paper and the filtrate was mixed with a solution of L1
(0.274 g, 1 mmol) which was further stirred for 4–5 h. A
cream color precipitate was washed with 10 mL pet. ether,
yielded cream colored crystals suitable for X-ray analysis,
Scheme 2. Yield: 75%, M.P. 50 °C, Calc: %C (34.36), %H
(4.48) %N (4.45), Found: %C (34.82) %H (4.90) %N
(5.91). IR spectrum: m N–H 3390–3310, d N–H 1577,
m Se–C 464 cm-1, m(ClO4) 1089, 626; 1H-NMR: Ar–H
7.20–7.64 (m, 5H), NH3 4.97 (s, 3H), N–CH2 3.07 (s, 2H),
Se–CH2 2.90 (s, 2H), CH2 2.04 ppm (2H, s). 13C-NMR:
Se–Cipso 130.85, o to Se 133.32, m to Se 129.30, p to Se
127.28, N–CH2 40.80, CH2 27.32, Se–CH2 23.90 ppm. A
proposed path for the formation of compound 1 by cleav-
age with Hg(ClO4)2 is shown in Scheme 3.
Preparations
Synthesis of 3-(Phenylseleno) Propylammonium
Acetate Salt (L1)
L1 was prepared by adding 20 mL of an ethanolic solution
of acetic acid (0.57 g, 10 mmol) to the same volume of an
+
-
Se
Se
Se Na
-NaCl
NaBH4,N2 atm
EtOH
+
Cl
NH
2.HCl
Se
NH2
O
60-70 OC
C
+
-
+
Se
NH
3 CH3COO
Se
NH2
Stirred in EtOH
HO
CH3
L1
Scheme 1 Synthetic scheme and chemical structure of L1
123

J Chem Crystallogr (2011) 41:391–400
393
-
(ClO4)2
1
r.t.
+
Se
NH3
Hg(ClO4)2
MeOH
2
r.t.
2
(ClO4)2
.Hg(PPh3)2
NH2
Se
[Hg(PPH3)2](ClO4)2
MeOH
2
1 +
L
r.t.
HgCl2
3
.HgCl
NH2
Se
MeOH
2
4
r.t.
MeOH
.(C6H5)2SnCl2
Se
NH2
(C6H5)2SnCl2
Scheme 2 Synthetic scheme and chemical structure of Compounds 1–4
Scheme 3 Synthetic scheme
and chemical structure of
Compound 1
-
3
+
+
-
Hg(OCOCH3)2
+
2
Se
NH3 ClO
Se
NH3
2
O
CH3COO
+
Hg(ClO4)2
(1)
Reaction of [Hg(PPh3)2](ClO4)2 with L1 (2)
(4.90) %N (1.91). IR spectrum: m N–H 3240–3120, d N–H
1558, m C–N 1207, m Se–C 464 cm-1, m(ClO4) 1118, 630;
1H-NMR: Ar–H 6.70–7.41 (m, 35H), NH2 ? CH2 2.04
(s, 4H), N–CH2 3.21 (s, 2H), Se–CH2 2.87 (t, 2H, JH–H
6.9 Hz); 13C-NMR: Se–Cipso 130.97, o to Se 132.69, m to
Se 129.29, p to Se 127.11, Ca 132.22, Cb 128.7 Cc 131.91,
Cd 129.21, N–CH2 39.96, CH2 27.81, Se–CH2 23.83 ppm.
[HgCl2(PPh3)2] (0.595 g, 1 mmol) was dissolved in chlo-
roform and stirred under N2 atm. for 0.5 h, with a solution
of AgClO4 (0.3 g, 1.46 mmol) in methanol (5 mL). The
resulting AgCl was filtered through Whatman filter paper.
The filtrate was mixed with a solution of L1 (0.375 g,
0.73 mmol) in dichloromethane (10 mL) and stirred for
2 h. The solvent evaporated on a rotary evaporator under
reduced pressure. The reaction extract was purified through
a TLC (hexane:ethanol) (9:1) mixture. Yield 70%, Calc:
%C (50.22), %H (4.03) %N (1.30), Found: %C (50.52) %H
Reaction of HgCl2 with L1 (3)
A mixture of L1 (0.274 g, 1 mmol) and mercuric chloride
(0.271 g, 1 mmol) in methanol 5 mL was stirred at room
123

394
J Chem Crystallogr (2011) 41:391–400
temperature for 5 h. The resultant cream colored precipi-
tate was filtered, washed with pet. ether and dried in vacuo.
It was recrystallized with a methanol:chloroform (9:1)
mixture. Yield 85%, M.P. 170 (d), Calc: %C (22.30), %H
(2.50) %N (2.89), Found: %C (22.82) %H (2.90) %N
(2.91). IR spectrum: m N–H 3198–3122, d N–H 1577, m C–
N 1208, m Se–C 464 cm-1; 1H-NMR: Ar–H 7.27–7.48 (m,
5H), N–CH2 3.38 (s, 2H), Se–CH2 2.96 (t, 2H, JH–H
6.9 Hz), NH2 ? CH2 1.89–1.92 ppm (2H, s). 13C-NMR:
Se–Cipso 129.86, o to Se 131.27, m to Se 129.23, p to Se
126.53, N–CH2 42.33, CH2 30.37, Se–CH2 23.41 ppm.
Further reactions of L1 with Hg(ClO4)2, [Hg(PPh3)2]
(ClO4)2, HgCl2 and Ph2SnCl2 are illustrated in Scheme 2
producing compounds whose elemental analysis provides
supporting evidence of their stoichiometry. Compounds
2–4 are soluble in methanol, ethanol and chloroform and
very stable under ambient conditions as they may be stored
for 3–4 months without change. Compounds 1 and 2
exhibits conductance in methanol corresponding to a 1:1
and 1:2 dissociation whereas compound 3 and 4 behave as
non-electrolytes.
Spectroscopic Studies
Reaction of Ph2SnCl2 with L1 (4)
L1 and compounds 1–4 were characterized by elemental
analysis, ESI mass, IR, 1H, 13C-NMR. L1 and Compound 1
were characterized by single crystal structure determination.
In the ESI mass spectrum of L1, the molecular ion peak at m/
z = 274 was not observed, however a peak at m/z = 292
assigned to a water molecule associated with ligand is
observed. The base peak at m/z = 216 is assigned to
3-(phenylseleno) propylamine. In the IR spectrum of L1 a
strong absorption band in the region 3,370–3,280 cm-1
To a solution L1 solution (0.274 g, 1 mmol) and diphe-
nyltin dichloride (0.343 g, 1 mmol) in acetone {5 mL} and
the mixture was stirred for 24 h at 30–40 °C. The resultant
brown colored solution was filtered and clear solution was
then concentrated under reduced pressure, and the oil
obtained was purified through TLC (pet.ether: chloroform)
(9:1) mixture. Yield 72%, Color: brown oil, Calc: %C
(45.25), %H (4.15) %N (2.51), Found: %C (45.82) %H
(4.80) %N (2.81). IR spectrum: m N–H 3236–3160, d N–H
?
arises due to stretching vibration in the NH3 group [23].
The band at 1634 cm-1 originates from the NH3? bending
1
1578, m C–N 1208, m Se–C 476 cm-1; H-NMR: Ar–H
7.23–7.48 (m, 5H), N–CH2 4.38 (s, 2H), Se–CH2 2.93 (s,
vibration. The acetate ion group shows the m
and
asC O
2H), NH2 ? CH2 1.90–1.98 ppm (s, 2H).
m
at 1,371 and 1,566 cm-1, respectively. The med-
ium intensity band at 468 cm-1 in L1 is the characteristic m
sC O
X-ray Crystallographic Studies
1
Se–Calkyl vibration. The H and 13C-NMR spectra of L1
display the expected resonances and peak multiplicities.
X-ray data for both L1 and compound 1 were collected
with an Oxford Diffraction Gemini R CCD area detector
using CrysAlisPro software. Graphite-monochromated
In the IR spectrum of compound 1 absence of m
asC O
and appearance of two new bands are due to
and m
sC O
1
˚
Cu-Ka (k = 1.54178 A) radiation was used for L and
an ionic perchlorate group at 1089 and 628 cm-1, which
clearly establishes the displacement of a acetate group from
L1 on reaction with Hg(ClO4)2. In the proton NMR spec-
trum, the absence of signal, due to CH3 in compound 1,
indicates the displacement of the acetate ion from L1.
Similarly the absence of C=O and CH3 signals in the
13C-NMR spectrum of compound 1 are in agreement with
˚
Mo-Ka (k = 0.71073 A) radiation was used for Com-
pound 1. Structure solution was accomplished by
SHELXS97 [21] and structure refinement by SHELXL97
[21] with all of the non-hydrogen atoms refined aniso-
tropically by full-matrix least-squares on F2. Hydrogen
atoms were placed in their calculated positions and
included in the refinement using the riding model.
Absorption corrections were performed using CrysAlis
RED and all calculations were performed using SHEL-
XTL [22]. Thermal ellipsoid drawings of the ionic
structures were generated with SHELXTL [22].
1
IR and H-NMR spectra.
The ESI mass of compound 3 shows a dimer peak at m/
z = 974 with low intensity. Another peak at m/z = 216
with high intensity corresponds to the 3-(phenylseleno)
propylamine group, which is obtained due to the loss of
HgCl. This shows that during reaction with HgCl2, acetic
acid is removed and 3-(phenylseleno) propylamine is
coordinated with HgCl2 in the form of a dimer. Whereas, in
Results and Discussion
the IR spectra of 2–4, the absence of m
and
The reactions given in Scheme 1 produce L1, which
remains stable under ambient conditions for 2–3 months.
L1 and compound 1–4 are very soluble in ethanol, meth-
anol, chloroform and dichloromethane but exhibit poor
solubility in benzene.
asC O
m
and appearance of a new band at 1,027 cm-1 is
sC O
assigned to the mC-N stretching mode, this is indicative of
displacement of an acetic acid moiety from L1 leaving
behind 3-(phenylseleno) propylamine. Thus, the remaining
123

J Chem Crystallogr (2011) 41:391–400
395
Fig. 1 Proposed structures
of Compounds 2–4
Se
N
Cl
Ph
Se
N
Se
Cl
Cl
Cl
P'
P'
Sn
Hg
Hg
Hg
Ph
N
Cl
N
Cl
Se
P'= PPh3
2
3
4
compound forms a compound with a metal salt, which is
coordinated through the NH2 group and is evident by a
lowering of mN–H in the IR spectra of compounds 2–4. The
peak in which there is contribution from the mSe–C
vibration is found unaffected, indicating that Se does not
participate in coordination to the metal salts. The stretching
frequency of ionic perchlorate appears at 630 and
1,180 cm-1, respectively, in compound 2. The 1H and
13C-NMR spectra of 2–4 are normal. In a d10 system,
coordination shifts in the NMR spectra are found to be
occurring between 70 and 80 °C with a peak value at 78 °C
(Fig. 2a). It appears that two peaks are merging together
suggesting the possibility of reaction otherwise to a single
peak, which should have been observed. In order to con-
firm the kind of peak, the DSC thermogram of the sample
was re-recorded under similar conditions and is shown in
Fig. 2b. This thermogram shows that the peak observed
between 70 and 80 °C disappears. It can thus be concluded
that the thermogram peak at 70–80 °C is not due to any
transition but due to some kind of side reaction or an
irreversible change brought out during the reaction. Simi-
larly, Fig. 2a shows another endothermic peak at 180 °C
which is very broad and has an irregular baseline. Fig-
ure 2b does not show any peak at 180 °C, which can also
be assigned to a reaction or transition change and occurs in
succession to the first reaction. Figure 2b also shows an
exothermic decomposition peak at 330 °C in the compound
formed due to the reaction carried out 70–80 °C or 180 °C
or reactant left out. It is proposed, therefore, that the fol-
lowing reaction can occur in succession at 70–80 °C and
180 °C. The heat absorbed during the reaction was deter-
mined with the help of DSC software provided by the
instrument manufacturer. The heat absorbed during the first
proposed reaction is found to be -0.043 J/g. Similarly the
heat absorbed during the second reaction is found to be
-0.013 J/g. This study shows the reaction of the reactant
and how it occurs at two temperatures in succession at 78
and 180 °C. The compound formed during the reaction
shows a decomposition temperature of 330 °C.
1
insignificant, and this is true for 2 and 3. In the H-NMR
spectra of compound 2 and 3, a NH2 group merges with the
CH2 protons which shows a multiplet. However, in com-
pound 4, the NH2 signal appears at 4.38 ppm. In com-
?
pounds 2–4, the absence of NH3 and CH3 and the
presence of NH2 indicates that on reaction with metal salts
the acetic acid group is displaced from L1 leaving behind
3-(phenylseleno) propylamine. The downfield shift of
the NH2 signal clearly establishes the coordination of
3-(phenylseleno) propylamine through nitrogen to the
metal atom. In the 13C{1H}-NMR spectra of compound
2–4, the deshielding of the N–CH2 signal (*3 ppm) with
respect to those of a free ligand, L1, again indicates that
there is coordination of a nitrogen atom to the metal salt.
The absence of signals due to C=O and CH3 in compounds
2–4 authenticate the findings of the IR and 1H-NMR
spectra. The Se-CH2 signal exhibits an insignificant shift in
the spectra of compounds 2–4. Thus, the IR and NMR data
shows that the 3-(phenylseleno) propylamine group
behaves as a monofunctional ligand coordinated through N
to the metal salts and support from the previous work, the
following most possible structures have been proposed on
presumption that geometry of compound 2, 3 and 4 are
trigonal [24, 25], tetrahedral [26–28] and trigonal bipyra-
midal [29] (Fig. 1). Attempts to grow good quality single
crystals of compounds 2–4 were unsuccessful.
Crystal Structure Determination of the
3-(Phenylseleno) Propylammonium Acetate Salt (L1)
3-(Phenylseleno) propylammonium acetate, C9H14NSe?
C2H3O2-, L1, represents the first example of a selenium
bearing acetate salt characterized by single crystal X-ray
crystallographic techniques. L1 crystallizes in the mono-
clinic space group P 21/c with unit cell parameters
Thermal Analysis
˚
a = 13.3910(3), b = 5.9621(2), c = 15.5419(4), A, b =
A differential scanning calorimeter (DSC) thermogram of
the compound L1 shows an endothermic reaction/transition
90.507(2)°, Z = 4. It crystallizes with one cation–anion
[C9H14NSe?]. [C2H3O2-] pair in the asymmetric unit
123

396
J Chem Crystallogr (2011) 41:391–400
Fig. 2 a DSC thermogram for ((C6H5)SeCH2CH2CH2NH3)?CH3COO- (L1). b Exothermic decomposition peak for ((C6H5)SeCH2CH2CH2
NH3)?CH3COO-(L1)
(Fig. 3). Crystal and experimental data for L1 are listed in
Table 1. Bond lengths and bond angles are all within
expected ranges, Table 2 [30]
group are nearly equal and lie midway between the single
and double C–O bond lengths in the carboxylic acid frag-
ment implying virtually complete electron delocalization
´
´
˚
The C–Se bond lengths of 1.916(2) and 1.953(3)A are
˚
[33]. The carboxylic bond (O(2)–C(11) = 1.276 (2) A) is
consistent with earlier reports [31]. The Se–C(Ar) bond
distance is somewhat shorter than the Se–C(alkyl) distance,
as expected [32]. C–O bond distances in the carboxylate
slightly shorter than an average carboxylic bond length
´
´
˚
˚
(1.29 A). The carbonyl bond (O(1)–C(11) = 1.243 (3) A)
is similar to that of an average carbonyl bond length (1.24
123

J Chem Crystallogr (2011) 41:391–400
397
Fig. 3 ORTEP drawing of
C9H14NSe? C2H3O2-, L1,
showing the cation–anion pair
and the atom numbering scheme
of the asymmetric unit with
40% probability displacement
ellipsoids of the non-H atoms.
The dashed line indicates a
N–HꢀꢀꢀO hydrogen bond
interaction
Table 1 Crystal data and structure refinement for L1 and Compound 1
Empirical formula
Formula weight
CCDC Deposit No.
Temperature, K
C11 H17 N O2 Se
C9 H14 Cl N O4 Se
314.62
274.22
700827
700828
110(2)
200(2)
˚
Wavelength, A
1.54178
0.71073
Crystal system
Space group
Monoclinic
Monoclinic
P 21/c
P 21/c
˚
Unit cell dimensions, A, °
a = 13.3910(3)
b = 5.9621(2)
c = 15.5419(4)
b = 90.507(2)
1240.79(6), 4
1.468
a = 12.2499(6)
b = 5.2724(4)
c = 38.0222(16)
b = 95.142(4)
2445.8(2), 8
1.709
3
Volume, A , Z
˚
Density (calculated), Mg/m3
Absorption coefficient, mm-1
F(000)
3.959
3.287
560
1,264
Crystal size, mm3
0.47 9 0.15 9 0.09
5.69–74.06°
4,553
0.52 9 0.15 9 0.08
4.66–32.58°
19,646
Theta range for data collection
Reflections collected
Independent reflections
Max. and min. transmission
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I [ 2sigma(I)]
R indices (all data)
2,445 [R(int) = 0.0228]
1.00000 and 0.34359
2445/0/138
7,970 [R(int) = 0.0829]
1.00000 and 0.49746
7970/0/291
0.938
1.029
R1 = 0.0301, wR2 = 0.0771
R1 = 0.0383, wR2 = 0.0810
0.430/-0.404
R1 = 0.0528, wR2 = 0.0835
R1 = 0.1745, wR2 = 0.1117
0.610/-0.894
-3
˚
Largest diff. peak/hole, e.A
´
˚
1
A) [34]. The ionic hydrogen bond in L confirms an ionic
interaction between the 3-(phenylseleno) propylamine and
acetic acid [35]. A difference in bond lengths could be
assigned to strong secondary N–H(0B)ꢀꢀꢀO(1) intermolec-
ular hydrogen bond interactions with the carbonyl oxygen,
O(1), and a strong bifurcated hydrogen bond intermolecu-
lar interaction with the carboxyl oxygen, O(2)
[N–H(0B)ꢀꢀꢀO(2) & N–H(0C)ꢀꢀꢀO(2) as described in
Table 3. The 3-(phenylseleno) propylamine anion is,
therefore, protonated, while the carboxyl group of acetic
acid is deprotonated [36]. The collective action of these
ionic and intermolecular interactions help stabilize crystal
packing and result in a pattern of infinite one-dimensional
chains arranged diagonally along the (101) plane in the unit
cell (Fig. 4).
Crystal Structure Determination of Compound 1
[3-(Phenylseleno) Propylammonium Perchlorate]
Compound 1, [C9H14NSe]?2 [ClO4]2-, crystallizes in the
monoclinic space group P 21/c with unit cell parameters
˚
a = 12.2499(6), b = 5.2724(4), c = 38.0222(16), A,
b = 95.142(4)°, Z = 8, and with two independent cation–
anion [C9H14NSe?]–[ClO4-] pairs in the asymmetric unit
123

398
J Chem Crystallogr (2011) 41:391–400
Table 2 Selected bond parameters of L1
˚
Bond lengths [A]
Bond angles [°]
Torsion angles [°]
Se–C(1)
1.916(2)
1.953(3)
1.243(3)
1.243(3)
1.482(3)
1.388(4)
1.390(3)
1.391(4)
1.379(4)
1.376(4)
1.393(3)
1.528(3)
1.517(3)
1.511(3)
C(1)–Se–C(7)
101.65(10)
119.9(2)
C(7)–Se–C(1)–C(2)
C(7)–Se–C(6)
144.35(19)
-41.9(2)
Se–C(7)
C(2)–C1)–C(6)
O(1)–C(11)
O(2)–C(11)
N–C(9)
C(2)–C(1)–Se
117.13(18)
122.68(19)
120.0(2)
C(1)–Se–C(7)–C(8)
Se–C(1)–C(6)–C(5)
C(7)–C(8)–C(9)–N
-70.99(18)
-173.22(19)
179.44(18)
C(6)–C(1)–Se
C(1)–C(2)–C(3)
C(4)–C(3)–C(2)
C(5)–C(4)–C(3)
C(4)–C(5)–C(6)
C(1)–C(6)–C(5)
C(8)–C(7)–Se
C(1)–C(2)
C(1)–C(6)
C(2)–C(3)
C(3)–C(4)
C(4)–C(5)
C(5)–C(6)
C(7)–C(8)
C(8)–C(9)
C(11)–C(12)
120.1(3)
120.0(2)
120.6(2)
119.4(2)
113.72(17)
111.44(19)
111.56(18)
124.31(19)
C(9)–C(8)–C(7)
N–C(9)–C(8)
O(1)–C(11)–O(2)
O(1)–C(11)–C(12) 118.58(19)
O(2)–C(11)–C(12) 117.1(2)
1
˚
Table 3 Hydrogen bonds for L [A and °]
The dihedral angle between the least squares planes of
the benzyl rings in the two independent cation
(C9H14NSe?) units in the asymmetric unit is 69.7(5)°. The
average Cl–O bond distance in the two perchlorate ions is
D–HꢀꢀꢀA
d(D–H)
d(HꢀꢀꢀA)
d(DꢀꢀꢀA)
\(DHA)
N–H(0A)ꢀꢀꢀO(2)#1a
N–H(0B)ꢀꢀꢀO(1)#2b
N–H(0C)ꢀꢀꢀO(2)
a
0.91
0.91
0.91
1.91
1.84
1.82
b
2.820(2)
2.728(2)
2.720(2)
173.9
165.3
171.2
˚
1.426(8) and 1.433(5) A while the average O–Cl–O bond
angle is 109.82(5)° and 109.46(6)°, respectively, which
verifies that the perchlorate anions exhibit essentially tet-
rahedral geometry [37]. All eight of the oxygen atoms in
both of the perchlorate anions in the asymmetric unit take
part in strong to intermediate N–HꢀꢀꢀO intermolecular
hydrogen bonding interactions (Table 5) which therefore
help to stabilize crystal packing in the unit cell (Fig. 6).
(#1) -x ? 1, y ? 1/2, -z ? 3/2 ; (#2) x, y ? 1, z
Conclusion
The first example of selenium containing acetate salt,
3-(phenylseleno) propylammonium acetate (L1) has been
synthesized and characterized by spectroscopic and X-ray
crystallographic techniques. Upon reaction with selected
metal salts, the cleavage of L1 takes place in two different
ways. L1 reacts with Hg(ClO4)2 resulting in compound 1 a
3-(phenylseleno) propylammonium perchlorate salt which
has been fully characterized, structurally by single crystal
X-ray diffraction.
Fig. 4 The molecular packing for C9H14NSe? C2H3O2-, L1, viewed
down the c axis. Dashed line indicate a N–HꢀꢀꢀO hydrogen bond
interactions linking the cation (C9H14NSe?) anion (C2H3O2-) pairs
into chains along the [110] plane of the unit cell
Supplementary Data
For L1 and compound 1, crystal data, structural information
(geometric bond distances, bond and torsion angles;
hydrogen bonding) & refinement data are provided.
(Fig. 5). Crystal and experimental data for compound 1 are
listed in Table 1. Bond lengths and bond angles are all
within expected ranges (Table 4) [30].
123

J Chem Crystallogr (2011) 41:391–400
399
Fig. 5 ORTEP drawing of[C9H14NSe]?2 [ClO4]2-, Compound 1,
showing the two cation (C9H14NSe?)–anion (ClO4-) pairs the asym-
metric unit and the atom numbering scheme with 40% probability
displacement ellipsoids of the non-H atoms. Dashed lines indicate
N–HꢀꢀꢀO hydrogen bond interactions between the cation–anion pairs
Table 4 Selected bond parameters of Compound 1
˚
Bond lengths [A]
Bond angles [°]
Torsion angles [°]
Se(1A)–C(1A)
Se(1A)–C(7A)
Se(1B)–C(1B)
Se(1B)–C(7B)
Cl(1)–O(12)
Cl(1)–O(11)
Cl(1)–O(14)
Cl(1)–O(13)
Cl(2)–O(23)
Cl(2)–O(24)
Cl(2)–O(21)
Cl(2)–O(22)
N(1A)–C(9A)
N(1B)–C(9B)
C(7A)–C(8A)
C(8A)–C(9A)
C(7B)–C(8B)
C(8B)–C(9B)
1.920(4)
1.957(4)
1.916(4)
1.956(4)
1.424(3)
1.425(3)
1.427(3)
1.430(3)
1.414(3)
1.431(3)
1.441(3)
1.447(3)
1.489(5)
1.488(5)
1.519(6)
1.505(6)
1.5122(5)
1.497(5)
C(1A)–Se(1A)–C(7A)
C(1B)–Se(1B)–C(7B)
O(12)–Cl(1)–O(11)
O(12)–C(1)–O(14)
O(11)–Cl(1)–O(14)
O(12)–Cl(1)–O(13)
O(11)–Cl(1)–O(13)
O(14)–Cl(1)–O(13)
O(23)–Cl(2)–O(24)
O(23)–Cl(2)–O(21)
O(24)–Cl(2)–O(21)
O(23)–Cl(2)–O(22)
O(24)–Cl(2)–O(22)
O(21)–Cl(2)–O(22)
C(8A)–C(7A)–Se(1A)
C(9A)–C(8A)–C(7A)
N(1A)–C(9A)–C(8A)
C(8B)–C(7B)–Se(1B)
C(9B)–C(8B)–C(7B)
N(1B)–C(9B)–C(8B)
99.33(17)
101.47(18)
111.2(2)
C(1A)–Se(1A)–C(1A)–C(2A)
C(7A–Se(1A)–C(1A)–C(6A)–102.9(3)
Se(1A)–C(1A)–C(2A)–C(3A)
C(1A)–Se(1A)–C(7A)–C(8A)
Se(1A)–C(7A)–C(8A)–C(9A)
C(7A)–C(8A)–C(9A)–N(1A)
C(7B)–Se(1B)–C(1B)–C(6B)
C(7B)–Se(1B)–C(1B)–C(2B)
Se(1B)–C(1B)–C(6B)–C(5B)
C(1B)–Se(1B)–C(7B)–C(8B)
Se(1B)–C(7B)–C(8B)–C(9B)
C(7B)–C(8B)–C(9B)–N(1B)
79.9(3)
176.1(3)
68.9(3)
110.96(19)
107.7(2)
179.2(3)
-66.8(5)
177.5(3)
-0.5(4)
-178.2(3)
82.8(3)
108.01(19)
109.1(2)
109.9(2)
109.47(19)
109.50(19)
109.34(19)
101.4(2)
68.8(4)
-179.8(3)
109.98(19)
107.08(18)
113.3(3)
113.6(4)
112.8(3)
113.4(3)
111.8(3)
112.2(3)
Table 5 Hydrogen bonds for
˚
D–HꢀꢀꢀA
d(D–H)
d(HꢀꢀꢀA)
d(DꢀꢀꢀA)
\(DHA)
Compound 1 [A and °]
N(1A)–H(1AA)ꢀꢀꢀO(13)#1
N(1A)–H(1AA)ꢀꢀꢀO(11)
N(1A)–H(1AA)ꢀꢀꢀO(12)#1a
N(1A)–H(1AB)ꢀꢀꢀO(21)
N(1A)–H(1AC)ꢀꢀꢀO(13)#2b
N(1B)–H(1BA)ꢀꢀꢀO(23)#3c
N(1B)–H(1BA)ꢀꢀꢀO(22)
N(1B)–H(1BA)ꢀꢀꢀO(21)
N(1B)–H(1BB)ꢀꢀꢀO(11)
N(1B)–H(1BB)ꢀꢀꢀO(14)
N(1B)–H(1BC)ꢀꢀꢀO(22)#4d
0.91
0.91
0.91
0.91
0.91
0.91
0.91
0.91
0.91
0.91
0.91
2.26
2.38
2.50
2.22
2.02
2.45
2.47
2.49
2.19
2.44
1.97
3.006(5)
2.867(4)
3.185(4)
3.123(5)
2.863(5)
3.105(5)
3.242(5)
2.932(4)
3.016(5)
3.216(5)
2.882(4)
139.4
113.7
132.8
170.0
153.4
129.3
142.2
110.2
151.2
142.8
175.0
Symmetry transformations used
to generate equivalent atoms
a
(#1) -x ? 1, -y, -z ? 1;
(#2) -x ? 1, -y ? 1, -z ? 1;
(#3) -x ? 2, -y, -z ? 1;
(#4) x, y ? 1, z
b
c
d
123

400
J Chem Crystallogr (2011) 41:391–400
Fig. 6 ORTEP drawing of [C9H14NSe]?2 [ClO4]2-, Compound 1, viewed down the b axis. Dashed lines indicate N–HꢀꢀꢀO hydrogen bond
interactions linking the cation (C9H14NSe?)–anion (ClO4-) pairs into chains along the [101] plane of the unit cell
12. Lipinsky CA, Lombardo FL, Dominy BW, Feeney PJ (1997) Adv
Crystallographic data (CIF) for the structures reported in
Drug Del Rev 23:3
this paper have been deposited with the Cambridge Crys-
13. Prasad H, Frydenvang K, Liljefors T, Sorensen HO, Larsen C
tallographic Data Centre and allocated the deposition
(2004) J Pharm Sci 269:157
14. Fleet C (1997) Nutr Rev 55:277
numbers CCDC 700827 for L1 and CCDC 700828 for
15. Patterson BH, Levander OA (1997) Cancer Epidemiol Biomakers
Prevent 6:63
16. Yu YS, Zhu YS, Li WG (1997) Biol Trace Elem Res 56:117
17. El-Bayoumy K (1991) In: De Vita VTJ, Hellman S, Rosenberg
Compound 1, respectively. These data can be obtained, free
of charge via www.ccdc.cam.ac.uk/data_request/cif, by
sending an e-mail to www.data_request@ccdc.cam.ac.uk.,
from the Cambridge Crystallographic Data Centre, 12,
Union Road, Cambridge CB2 1EZ, UK; fax; ?44 1223
336033.
SA (eds) Cancer principles and practice of oncology. J. B.
Lippincott Co., Philadelphia, p 1
18. Sharpless KB, Young MW (1975) J Org Chem 40:947
19. Harada H (1929) Bull Chem Soc Jpn 4:266
20. Khanna A, Bala A, Khandelwal BL (1995) J Organomet Chem
494:199
Acknowledgements Rupali Rastogi is grateful to UGC, New Delhi,
India for financial assistance. The coauthors thank the Director,
Central Drug Research Institute, Lucknow, India and Chairman CISC,
Banaras Hindu University, Varanasi, India for C, H, N analysis, ESI
measurements and 1H, 13C-NMR spectra, respectively. Further, the
coauthors thank the Head, School of Studies in Chemistry, Jiwaji
University, Gwalior, India (FTIR) and Dr. R.K. Soni, Department of
Chemistry, Chaudhary Charan Singh University, Meerut (DSC) for
their support. Crystallographic studies were supported in part by the
Office of Naval Research (ONR) and the Naval Research Laboratory
(NRL), USA. RJB would like to acknowledge the NSF-MRI program
(CHE-0619278) for funds to purchase an X-ray diffractometer.
21. Sheldrick GM (1997) SHELXS97, SHELXL97. University of
}
Gottingen, Germany
22. Bruker (2000) SHELXTL. Version 6.10. Bruker AXS Inc.,
Madison, Wisconsin, USA
23. Silverstein RM, Webster FX (1998) Spectrometric identification
of organic compounds, 6th edn. Wiley, USA
24. Srivastava SK, Rastogi R, Sharma R, Yadav RS (2006) Phos-
phorus Sulfur Silicon 181:1707
25. Srivastava SK, Sihare S, Rastogi R, Gaur A (2007) J Indian Chem
Soc 84:867
26. Srivastava SK, Pandey Y, Saxena SB (2001) J Indian Chem Soc
78:254
27. Srivastava TN, Siddiqui MA, Srivastava SK (1987) Indian J
Chem 26A:1162
References
28. Singh AK, Srivastava V (1990) Phosphorus Sulfur Silicon 47:471
29. Srivastava TN, Singh JD (1983) Indian J Chem 22A:674
30. Allen FH, Kennard O, Watson DG, Brammer L, Orpen AG,
Taylor R (1987) J. Chem Soc Perkin Trans 2:S1–19
31. Umezawa B, Hoshino O, Sawaki S, Sashida H, Mori K, Hamada
Y, Kotera K, Iitaka Y (1984) Tetrahedron 40:1783
32. Kumar A, Agarwal M, Singh AK (2008) Polyhedron 27:485
33. Stibrany RT, Shugar HJ, Potenza JA (2004) Acta Cryst E60:1012
34. Wade LG (2004) Organic chemistry. Pearson Education, Upper
Saddle River
1. Chowhan ZT (1978) J Pharm Sci 67:1257
2. Gould PL (1986) Int J Pharm 33:201
3. Forbes RT, York P, Davidson JR (1995) Int J Pharm 126:199
4. Fini A, Feroci G, Fazio G, Fernandez Hervas MJ, Holgado MA,
Raasco AM (1996) Int J Pharm Adv 1:269
5. O0 Connor KM, Corrigan OI (2001) Int J Pharm 226:163
6. Prasad H, Frydenvang K, Liljefors T, Larsen C (2002) Int J
Pharm 237:193
7. Rubino JT (1989) J Pharm Sci 78:485
35. Kupper H (2008) Acta Cryst B29:318
8. Thomas E, Rubino J (1996) Int J Pharm 130:170
9. Karigiannis G, Papaioannou D (2000) Eur J Org Chem 2000:1841
10. Wallace HM, Fraser AV, Hughes A (2003) J Biochem 376:1
11. Kowalczyk I (2008) Molecules 13:379 (references there in)
36. Vijayalakshmi J, Srinivasan R (1983) Acta Cryst C29:908
37. Sridhar B, Srinivasan N, Dalhus B, Rajaram RK (2003) Acta
Cryst E59:o28
123