Synthesis and crystal structure of chiral substituted (S)-2-[(4- methoxyphenoxy) methyl]-15-crown-5 ether with sodium perchlorate complex

Article abstract of DOI:10.1007/s10870-008-9417-8

The crystal and molecular structure of chiral crown ether, (S)-2-[(4-methoxyphenoxy)methyl]-15-crown-5...NaClO₄, has been determined by single-crystal X-ray diffraction. The complex crystallizes in the orthorombic space group Pbca with Z = 8. Lattice parameters are a = 11.451(2), b = 12.842(3), c = 31.330(7) A. The structure was refined to R factor of 0.0547. The Na ion is heptacoordinated. The Na-O_ether distances range from 2.363(4) to 2.433(4) A and average 2.404(5) A. Perchlorate anion is bounded to sodium ion asymmetrically; the Na-O8 and Na-O9 distances are 2.444(5) A and 2.607(5) A. The C-O and C-C distances of the 15-membered ring average 1.419(9) and 1.478(12) A while the O-C-C and C-O-C angles average 108.2(6°) and 115.4(6°).

Full text of DOI:10.1007/s10870-008-9417-8

J Chem Crystallogr (2008) 38:943–947
DOI 10.1007/s10870-008-9417-8
ORIGINAL PAPER
Synthesis and Crystal Structure of Chiral Substituted
(S)-2-[(4-Methoxyphenoxy) Methyl]-15-Crown-5 Ether
with Sodium Perchlorate Complex
¨
˘
Nermin Dogan Æ Su¨heyla Ozbey Æ Mehmet Karakaplan Æ
Tarık Aral
Received: 11 October 2006 / Accepted: 7 May 2008 / Published online: 30 May 2008
ꢀ Springer Science+Business Media, LLC 2008
Abstract Thecrystalandmolecular structureofchiral crown
ether, (S)-2-[(4-methoxyphenoxy)methyl]-15-crown-5 ꢀ
NaClO4, has been determined by single-crystal X-ray dif-
fraction. The complex crystallizes in the orthorombic space
group Pbca with Z = 8. Lattice parameters are a =
and S toward alkali metal cations [2]. Assessing the ability
of p-donors to interact with alkali metal has proved elusive.
The importance of alkali metal cation–p interactions is
potentially great, especially in biological systems where
nearly 10 % of amino acid chains are terminated by aro-
matic residues benzene (in phenyl alanine), phenol (in
tyrosine) and indole (in tryptophane).
˚
11.451(2), b = 12.842(3), c = 31.330(7) A. The structure
was refined to R factor of 0.0547. The Na ion is heptacoor-
dinated. The Na–Oether distances range from 2.363(4) to
Hoffman and Weiss [3] have reported a solid state
structure of KBPh4 in which K+ was cradled between two
benzene rings. Atwood and co-workers [4] reported a
structure in which an apical interaction a molecules of
benzene and a crown-complexed K+ cation appeared to
stabilize the complex. Meadows and co-workers [5]
reported six solid state structures of 18-crown-6 ethers in
which the cation is p-coordinated by phenyl, phenol or
indoles with K+ but less data was reported for Na+ arene
interaction.
˚
2.433(4) A and average 2.404(5) A. Perchlorate anion is
˚
bounded to sodium ion asymmetrically; the Na–O8 and Na–
˚
˚
O9 distances are 2.444(5) A and 2.607(5) A. The C–O and
C–C distances of the 15-membered ring average 1.419(9)
˚
and 1.478(12) A while the O–C–C and C–O–C angles
˚
average 108.2(6) and 115.4(6).
˚
Keywords Chiral crown ether ꢀ Sodium complex ꢀ
15-Crown-5 ꢀ Crystal structure
Although various racemic lariat ethers containing
4-methoxyphenoxy methyl moiety have been synthesized
and their binding properties [6], influence cardiac behavior
[7], and solvent extraction behavior [8] were investigated,
there are no reports about their metal complexation.
Therefore, our aim was to investigate the complexation of
Na+ cation with the synthesized chiral lariat ether which
also bearing electron-donating 4-methoxyphenoxy methyl
flexible side arm. Thus, we have selected a precursor of
b-blockers (S)-3-(p-methoxyphenoxy) methyl-1,2-propane-
diol (1) as a chiral building block for synthesize of chiral
15-crown-5 (2) lariat ether (see Scheme 1). In this paper,
we have described the characterization of complex of
ligand (2) with sodium perchlorate. The solid state struc-
ture of the complex was determined by X-ray diffraction in
order to obtain the conformation of the macrocycle and
further to investigate the steric and/or electronic effects of
the 4-methoxyphenoxy methyl side arm.
Introduction
Prior to the late 1960’s the experimental study of alkali
metal cation chemistry was difficult at best. The advent of
crown ethers [1] provided a vehicle for such studies and the
field has since burgeoned. Numerous studies have defined
the p-donor abilities of a variety of elements such as O, N,
¨
˘
N. Dogan ꢀ S. Ozbey (&)
Department of Engineering Physics, Faculty of Engineering,
Hacettepe University, 06800 Beytepe, Ankara, Turkey
e-mail: sozbey@hacettepe.edu.tr
M. Karakaplan ꢀ T. Aral
Department of Chemistry, Faculty of Arts and Sciences,
University of Dicle, 21280 Diyarbakır, Turkey
123

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J Chem Crystallogr (2008) 38:943–947
(S)-2-(4-Methoxyphenoxy) Propane-1,2-Diol (1)
Experimental Section
Apparatus and Chemicals
This compound prepared as the method described [9] from
(S)-glycidol (3.7 g, 0.05 mol), 4-methoxyphenol (6.2 g,
0.05 mol) and piperidine hydrochloride (0.3 g, 2.5 mmol)
as a catalyst to give 8.51 g (86%), m.p. 80–82 ꢁC,
Melting points were determined with GALLENKAMP
Model apparatus with open capillaries. Infrared spectra
_
were recorded on a MIDAC-FTIR Model 1700 spectro-
[a]D20: + 7.5ꢁ (c = 7,CHCl3). H NMR d: 3.65–3.77(m,
1
7H), 3.93–3.94(m, 2H), 4.01(m, 1H), 6.76–6.83(m, 4H).
13C NMR d: 63.15, 64.16, 69.49, 71.50, 114.98, 121.62,
129.62, 158.54. Anal. Calcd. for C10H14O4: C, 60.60; H,
7.07, found: C, 60.45; H, 7.10%.
photometer. The Elemental analyses were obtained with
CARLO-ERBA Model 1108 apparatus. 1H NMR
(400 MHz) and 13C NMR (100 MHz) spectra were
recorded on BRUKER DPX-400 high performance digital
FT-NMR spectrometer, with tetramethysilane as the
internal standard solutions in deuteriochloroform. Optical
rotations were recorded using PERKIN ELMER Model
341 polarimeter. All chemicals were reagent grade unless
otherwise specified. THF dried over NaH and distilled
prior to use.
(S)-2-[(4-Methoxyphenoxy) Methyl]-15-Crown-5 (2)
This compound prepared as the method described [10]. To
a suspension of 0.984 g (32.8 mmol, 80% in mineral oil) of
NaH in 200 mL of the dry THF at 0 ꢁC was added a
solution of 1.30 g (6.56 mmol) of (S)-3-(4-methoxyphen-
oxy)-1,2-propanediol, in 250 mL of THF. The reaction
mixture was refluxed for 2 h. After cooling to 0 ꢁC a
solution of 3.29 g (6.56 mmol) of tetra (ethylene glycol)
di(4-toluenesulfonate) in 250 mL of THF was added
slowly. The suspension was refluxed for 48 h. The solvent
was evaporated and 100 mL of water was added to the
residue. The mixture was extracted with CH2Cl2
(4 9 20 mL) and the combined organic layers were
washed with 50 mL of water, dried on MgSO4 and solvent
was evaporated. The crude product was purified column
chromatography (eluent: EtOAc/hexane/triethylamine: 5/5/
1) to yield as a viscous oil 0.91 g. (39 %) of pure product.
Synthesis
Scheme 1: Reagent and conditions, i: Piperidine hydro-
chloride, 70–80 ꢁC, 4 h; ii: NaH, THF.
O
O
i
OH + MeO
OH
(1)
OMe
OH
HO
+
O
O
O
1
aD30: -14.5ꢁ (c = 7, CHCl3). H NMR (CDCl3) d: 3.64–
OH
HO
4.03 (m, 24 H); 6.81–6.88 (M, 4H). IR (m, cm-1): 3,043,
2,940, 2,874, 1,602, 1,509, 1,463, 1,233, 1,133, 1,041, 941,
829, 743. Anal. Calcd. for C18H28O7: C, 60.66; H, 7.92;
found: C, 60.45; H, 8.05%.
ii
O
O
O
O
O
O
NaClO4 Complexes of (2)
(2)
OMe
A solution of 156 mg (0.5 mmol) of host (2) in 5 mL of
ethyl acetate was added to 70 mg (0.5 mmol) of NaClO4.
H2O dissolved in 2.5 mL ethyl acetate. Slowly evaporation
of the solvent over several days at room temperature yielded
light white crystals of complex. M.p. 114–115 ꢁC. IR (KBr)
(cm-1): 3,015, 2,928, 2,884, 2,363, 2,338, 1,522, 1,471,
1,445, 1,355, 1,240, 1,111, 1,047, 964, 944, 841, 746.
Tetra (Ethylene Glycol) Di(4-Toluenesulfonate)
4-Toluenesulfonyl chloride (10.47 g, 55.00 mmol) in
small portions was added to tetra (ethylene glycol)
(4.45 g, 25.0 mmol) in 30 mL of distilled pyridine at
-10 ꢁC. The mixture was kept overnight at 4 ꢁC. Then,
the mixture was extracted with CH2Cl2 (3 9 50 mL). The
organic layer was extracted with 6 N HCl at 0 ꢁC. The
combined organic layers were washed with water
(2 9 25 mL) and saturated NaHCO3 solution and dried
with CaCl2 and the solvent was evaporated. Purification
by flash column chromatography (eluent: ethanol/CH2Cl2
(98/2) yielded 10.59 g (84%) of tetra (ethylene glycol)
di(4-toluenesulfonate).
X-Ray Diffraction Measurement
The intensities of Bragg reflections which are used for
structure solutions were collected by Enraf-Nonius CAD4
diffractometer in the x/2h scan mode using graphite mono-
˚
chromated CuKa radiation (k = 1.54184 A) at 298 K. The
cell constants were obtained by the least-squares analysis of
123

J Chem Crystallogr (2008) 38:943–947
945
˚
Table 1 Crystal data and details of the structure determination for
(2)
Table 2 Selected interatomic distances (A) and bond angles (ꢁ) of (2)
Cl1–O8
1.412(5)
1.401(5)
1.377(6)
1.392(7)
2.363(4)
2.433(4)
2.419(5)
2.382(5)
2.424(5)
2.444(5)
2.607(5)
1.452(9)
1.390(9)
1.433(10)
1.409(9)
1.424(10)
1.410(8)
1.429(8)
1.418(9)
106.7(3)
110.8(3)
107.6(3)
111.3(3)
110.7(4)
109.8(4)
69.6(2)
O5–C9
1.422(9)
1.398(8)
1.406(8)
1.369(7)
1.377(7)
1.422(8)
1.444(11)
1.512(10)
1.491(11)
1.488(13)
1.488(12)
1.479(13)
1.384(8)
1.393(8)
1.368(8)
1.380(8)
1.380(8)
1.368(9)
Formula
C18H28O11ClNa
478.84
Cl1–O9
O5–C10
O6–C11
O6–C12
O7–C15
O7–C18
C1–C10
C1–C11
C2–C3
Formula weight
Crystal system
Color/shape
Space group
Cl1–O10
Orthorombic
colorless/prismatic
Pbca (No:61)
11.451(2)
12.842(3)
31.330(7)
4607.5(2)
8
Cl1–O11
Na1–O1
Na1–O2
˚
a, A
Na1–O3
˚
b, A
Na1–O4
˚
c, A
Na1–O5
3
˚
V, A
Na1–O8
C4–C5
Z
Na1–O9
C6–C7
Dc, Mg m-3
l, mm-1
1.381
O1–C1
C8–C9
2.146
O1–C2
C12–C13
C12–C17
C13–C14
C14–C15
C15– C16
C16–C17
Crystal size, mm
0.48 9 0.18 9 0.12
CuKa, k = 1.54184
2503
O2–C3
Radiation, k
O2–C4
Reflections measured
Range of relative transm. factors, %
Range of h, deg
O3–C5
59.96–77.14
2.82–59.67
0: 12; 0: 14; –35: 0
1446
O3–C6
O4–C7
Range of hkl
O4–C8
No. of reflections with I [ 2.0r(I)
No. of reflections used in refinement
No. of refined parameters
O8–Cl1–O9
O8–Cl1–O10
O8–Cl1–O11
O9–Cl1–O10
O9–Cl1–O11
O10–Cl1–O11
O1–Na1–O2
O1–Na1–O3
O1–Na1–O4
O1–Na1–O5
O1–Na1–O8
O1–Na1–O9
O2–Na1–O3
O2–Na1–O4
O2–Na1–O5
O2–Na1–O8
O2–Na1–O9
O3–Na1–O4
O3–Na1–O5
O3–Na1–O8
O3–Na1–O9
O4–Na1–O5
O4–Na1–O8
O4–Na1–O9
O5–Na1–O8
O5–Na1–O9
O8–Na1–O9
Na1–O1–C1
O5–C9–C8
O5–C10–C1
O6–C11–C1
C13–C14–C15
O7–C15–C14
O7–C15–C16
C14–C15–C16
C15–C16–C17
Na1–O1–C2
C1–O1–C2
120.2(5)
124.7(5)
116.1(5)
119.2(6)
121.0(6)
115.4(3)
118.6(5)
108.1(4)
104.4(4)
115.4(5)
114.1(4)
113.6(4)
113.6(6)
107.0(4)
108.1(4)
114.7(6)
112.4(4)
113.6(4)
114.5(6)
117.9(5)
117.2(4)
103.6(3)
96.5(3)
2503
364
P
P
R ¼ jDFj= jF0j
0.0547
h
i
1=2
P
P
2
2
Rw ¼
Goodness of fit
wjDFj = wjF0j
0.1598
1.028
-3
˚
Final Dqmax, Dqmin, e A
0.241, -0.327
138.5(2)
129.2(2)
68.9(2)
Na1–O2–C3
Na1–O2–C4
C3–O2–C4
the setting angles of 15 reflections in the range
20.978 \ 2h \ 23.608. All data were corrected for Lorentz-
polarisation effects and for absorption using empirical psi-
scans. The structure was solved by direct methods using the
program SHELXS97 and refined with SHELXL97 [11].
Crystal data and a summary of intensity data collection and
structure refinement are presented in Table 1.
84.8(2)
Na1–O3–C5
Na1–O3–C6
C5–O3–C6
124.4(2)
68.9(2)
112.8(2)
123.2(2)
98.7(2)
Na1–O4–C7
Na1–O4–C8
C7–O4–C8
Refinement of non-hydrogen atoms with anisotropic
temperature factors led to the final R value of 0.0547 and
Rw = 0.1598. Selected bond lengths and angles are given in
Table 2, while important torsion angles are listed in
Table 3. Crystallographic data for the structure have been
deposited with the the Cambridge Crystallographic Data
Centre CCDC 614164. Copies of the data can be obtained
free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html
[or from the Cambridge Crystallographic Data Centre
(CCDC), 12 Union Road, Cambridge CB2 1EZ, UK; fax:
+44(0)1223–336033; email: deposit@ccdc.cam.ac.uk].
140.9(2)
69.2(2)
Na1–O5–C9
Na1–O5–C10
C9–O5 –C10
C11–O6–C12
C15–O7–C18
Cl1–O8–Na1
Cl1–O9–Na1
O1–C1–C10
O1–C1–C11
C10–C1–C11
O1–C2–C3
138.2(2)
101.4(2)
89.2(2)
69.5(2)
139.4(2)
86.9(2)
109.2(5)
105.6(6)
112.8(6)
106.7(6)
108.7(6)
107.7(6)
108.9(7)
109.2(6)
114.1(2)
94.9(2)
52.9(2)
114.4(4)
108.4(6)
110.6(6)
109.1(6)
O2–C3–C2
Results and Discussions
O2–C4–C5
O3–C5–C4
Figure 1 shows a perspective view of the molecular
O3–C6–C7
structure of compound (2), including the numbering
123

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J Chem Crystallogr (2008) 38:943–947
Table 2 continued
O6–C12–C13
O6–C12–C17
C13–C12–C17
C12–C13–C14
116.9(5)
124.5(5)
118.6(6)
121.0(5)
O4–C7–C6
106.1(6)
106.7(6)
119.9(5)
O4–C8–C9
C12–C17–C16
scheme of non-hydrogen atoms. In the molecule, the
sodium ion is seven coordinated by the five oxygen atoms
(O1–O5) of the crown ether and two oxygen atoms (O8 and
O9) of the perchlorate anion. The perchlorate anion is
asymmetrically bound with Na–O8, Na–O9 contacts of
Fig. 1 ORTEP [12] drawing of the title compound with 35%
probability displacement ellipsoids
˚
˚
2.444(5) A, 2.607(5) A, respectively. The Na–Oether is
˚
distances are in the range 2.363(4)–2.433(4) A. In the
macrocycle ring, three oxygen atoms O1, O3, and O5 are at
one side of the mean plane defined by the all crown ether
oxygens being at distance of -0.232 (1), -0.447(1) and
˚
-0.057(1) A, respectively, while O2 an O4 are on the other
˚
side with deviations of 0.431(1) and 0.306 (1) A. The
deviation of the sodium atom from the oxygen mean plane
˚
is -0.749 (1) A.
All of the O–C–C–O torsion angles have gauche-con-
formations (angles in the range 54.6(8)ꢁ–64.0(7)ꢁ) and all
of the C–C–O–C torsion angles are close to the anti-con-
formations (157.9(6)ꢁ–178.7(6)ꢁ range), with the exception
of C10–C1–O1–C2 that is also gauche- (-99.8(7)ꢁ). Thus,
the macrocyclic strand of the molecule displays ag-a,
ag+a, ag-a, ag+a, ag-g- set of torsion angles (Table 3).
The given conformation is essentially similar to that found
in the [R-(-)-2-ethyl-N-benzyl (benzo-monoaza-15-
crown-5) ꢀ NaClO4] and [R-(-)-2-ethyl-N-benzyl (benzo-
monoaza-15-crown-5 ꢀ ClO4] [13, 14], with the exception
which is one syn-angle corresponding to the aromatic ring
in the two molecules. A similar type of conformation was
reported in the [15-crown-5) ꢀ NaClO4] [15] where the
crown molecule differs in the signs of the gauche-angles
Fig. 2 The packing of S-2-[(4-methoxyphenoxy)methyl]-15-crown-
5 ꢀ NaClO4 molecules in the unit cell
and the C–C bonds are defined by g-, g+, g-, g-, g+,
sequences, all C–O bonds being in the anti-conformation.
The perchlorate anion is located over the best plane of
the macrocycle ring in an epical position. As shown in
Fig. 1, the methoxyphenoxy methyl group bonded to chiral
carbon atom C1, that is also positioned on the top of the
crown ether ring seems to provide for more systematic
packing. The dihedral angle between the planes of all
crown ether atoms and the phenyl ring is 88.2(4)ꢁ. In the
macrocycle ring, C–O and C–C distances average
˚
1.419(9) A and 1.478(12) A while the O–C–C and C–O–C
˚
Table 3 Torsion angles about
the 15-crown-5 ligand (ꢁ)
C1–O1–C2–C3
O1–C2–C3–O2
C2–C3–O2–C4
C3–O2–C4–C5
O2–C4–C5–O3
C4–C5–O3–C6
C5–O3–C6–C7
O3–C6–C7–O4
C6–C7–O4–C8
C7–O4–C8–C9
O4–C8–C9–O5
C8–C9–O5–C10
C9–O5–C10–C1
O5–C10–C1–O1
C10–C1–O1–C2
-176.0(6)
-63.0(7)
167.3(6)
177.8(6)
61.3(8)
angles average 108.2(6)ꢁ and 115.4(6)ꢁ. The intramolecular
˚
˚
distances, O1…O4 4.286 A, O1…O3 4.472 A, O5…O3
˚
˚
4.524 A, O5…O4 4.272 A, may indicate the hole size of
the macrocycle.
In the packing, the molecules stack tightly with van der
Waals and the C–H…p interactions (C1–H1…CgA (1/2-
-157.9(6)
162.4(6)
-61.4(8)
-178.7(6)
-178.5(6)
64.0(7)
˚
˚
x, -1/2+y, z): H1…CgA 2.77 A, C1…CgA 3.702(6) A,
C1–H1…CgA 159(5)ꢁ, CgA represents the centroid of the
phenyl ring) to form columns parallel to the ac-crystal
plane (Fig. 2).
-167.3(6)
172.3(6)
-54.6(8)
-99.8(7)
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