Synthesis of bis-phosphonium salts from 6-bromo-1,2-naphthoquinone and α,ω-bis(diphenylphosphino)alkanes

Article abstract of DOI:10.1016/j.mencom.2011.11.019

1,4-Bis(diphenylphosphino)butane and 1,5-bis(diphenylphosphino)pentane add two molecules of 6-bromo-1,2-naphthoquinone to afford bis-ylides which on treatment with protic acids are converted into the corresponding P,P'-bis(7-bromo-3,4-dihydroxy-1-naphthyl)-substituted bis-phosphonium salts.

Full text of DOI:10.1016/j.mencom.2011.11.019

Mendeleev
Communications
Mendeleev Commun., 2011, 21, 346–348
Synthesis of bis-phosphonium salts from 6-bromo-1,2-naphthoquinone
and a,w-bis(diphenylphosphino)alkanes
Nadezhda R. Khasiyatullina, Vladimir F. Mironov,*
Andrei V. Bogdanov, Dmitry B. Krivolapov and Igor A. Litvinov
A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Centre of the Russian Academy
of Sciences, 420088 Kazan, Russian Federation. Fax: +7 843 273 1872; e-mail: mironov@iopc.ru
DOI: 10.1016/j.mencom.2011.11.019
1,4-Bis(diphenylphosphino)butane and 1,5-bis(diphenylphosphino)pentane add two molecules of 6-bromo-1,2-naphthoquinone to afford
bis-ylides which on treatment with protic acids are converted into the corresponding P,P'-bis(7-bromo-3,4-dihydroxy-1-naphthyl)-
substituted bis-phosphonium salts.
O
Development of the efficient synthesis of multifunctional organo-
Ph2P(CH2)nPPh2
O
phosphorus compounds is one of the important trends of organo-
element chemistry. Phosphonium salts are of special interest
2, 3
Br
since they can serve as diagnostic agents for tumor and anti-
1
oxidants for cell mitochondria,1–6 extragents,7 organocatalysts,8,9
phase transfer catalysts,10 reagents for synthesis,11–14 organogel
O
O
gelators of silicates polymerization,15 ionic liquids,16–18 receptors
of the selective anion recognition,19 and additives for electrolytes
in lithium batteries.20 In this respect phosphonium derivatives
bearing 1,2-dihydroxyarene or ortho-quinone fragments as sub-
stituents at phosphorus can be versatile precursors for the diverse
heterocyclic compounds as well as promising ligands for metal
complexes.21–24
5
4a
3
OH
HO
4
1
6
7
+
2
8a
Br
Br
8
PhP
(CH2)n
PPh2
9
10
2, 4 n = 4
3, 7 n = 5
12
11
4, 7
Recently, we have shown that 1,2-bis(diphenylphosphino)-
ethane having two tertiary phosphine fragments easily reacts
with 6-bromo-1,2-naphthoquinone 1 to form a P-(7-bromo-
3,4-dihyroxynaphth-1-yl)-substituted phosphonium salt with the
participation of only one phosphorus atom of this bis-phos-
phine.25 Meanwhile, the access to bridging P,P'-bis(7-bromo-
3,4-dihydroxynaphth-1-yl)-substituted bis-phosphonium salt looks
more challenging for the known useful properties of relative bis-
catecholates.26 We supposed that participation of only one phos-
phorus atom of 1,2-bis(diphenylphosphino)ethane in the reaction
with quinone 1 is connected with steric hindrances caused by
the short length of ethane-1,2-diyl spacer. In this work we used
a,w-bis(diphenylphosphino)alkanes 2 and 3 having longer spacers
between phosphine moieties (Scheme 1). Indeed, reaction of
quinone 1 with 1,4-bis(diphenylphosphino)butane 2 led to the
expected bis-ylide 4 (53% yield). Two other compounds 5 (21%
yield) and 6 (16% yield), whose formation during the process
can be readily rationalized, were also isolated by the fractional
crystallization.†
O
O
5
8
OH
4a
8a
3
OH
6
7
4
1
+
2
Br
Br
O
12
10
Ph2P
PhP
PPh2
PPh
25
9
11
13
6
14
26
15
16
27
28
5
Scheme 1
dC: 164.30 [s (s), C4], 143.89 [dd (d), C3, 3JPCCC 9.5 Hz, 2JHCC 4.0 Hz],
134.32 [dt (br.s), C12, 1JHC 161.8 Hz, 2JHCC 3.3 Hz], 133.39 [ddd (d), C10,
1JHC 165.1 Hz, JPCC 9.5 Hz, JHCCC 7.7 Hz], 131.77 [m (d), C8a, JPCC
7.7 Hz, overlaps with the signal of C2], 130.83 [dd (d), C2, 1JHC 163.2 Hz,
2JPC 9.2 Hz], 130.31 [ddd (d), C11, 3JPCCC 11.7 Hz, 3JHCCC 8.1 Hz, 3JHCCC
7.7 Hz], 129.48 [m (s), C6, overlaps with the C11 signal], 128.90 [m (d),
C8, 3JPCCC 4.0 Hz, overlaps with the components of C4a and C11 signals],
2
3
2
3
1
127.88 [m (d), C4a, JPCCC 11.4 Hz], 127.59 [d (s), C5, JHC 167.6 Hz],
†
(Butane-1,4-diyl)bis[(7-bromo-3-hydroxy-4-oxonaphthalen-1(4H)-
124.63 [m (d), C9, 1JPC 75.9 Hz], 122.36 [dd (br.d), C1, 1JPC 81.2 Hz, 3JHCCC
3
2
ylidene)(diphenyl)phosphorane] 4. To a solution of quinone 1 (0.5 g,
2.10 mmol) in 20 ml of refluxing benzene, 1,4-bis(diphosphino)butane 2
(0.45 g, 1.05 mmol) was added in five portions during 30 min with intense
bubbling of dry argon. The reaction occurred immediately. The reaction
mixture turned black, and green solid of the product 4 was filtered off,
recrystallized from chloroform and dried at 12 Torr, yield 0.50 g (53%),
mp 180–183°C. IR (n/cm–1): 3419 (OH), 1763, 1655, 1579, 1540, 1306,
1271, 1212, 1109, 1074, 1026, 994, 966, 895, 820, 742, 721, 692, 512.
4.0 Hz], 122.36 [dd (s), C7, JHCCC 5.8 Hz, JHCC 2.2 Hz], 22.30–23.58
[br.dt (br.m), C13, C14]. 31P / 31P-{1H} NMR (DMSO-d6) dP: 19.4 [m (s)].
MS, m/z: 900.9 (C48H38Br2O4P2). Found (%): C, 63.95; H, 4.15; Br, 17.74;
P, 6.90. Calc. for C48H38Br2O4P2 (%): C, 64.00; H, 4.22; Br, 17.77; P, 6.88.
P-{4-[(7-Bromo-3-hydroxy-4-oxonaphthalen-1(4H)-ylidene)(diphenyl)-
phosphoranyl]butyl}-P,P-diphenylphosphine oxide 5 precipitated from
the above filtrate after 24 h of standing. The crystals were filtered off and
dried under reduced pressure (14 Torr). Yield 0.21 g (21%, excluding the
solvated benzene molecules), mp 188–192°C. IR (Nujol, n/cm–1): 3441
(OH), 1704, 1678, 1593, 1561, 1536, 1338, 1182, 1269 (P=O), 1119, 983,
964, 845, 747, 694, 555, 510. 1H NMR (CDCl3) d: 8.47 (dd, H6, 3JHCCH
3
3
1H NMR (DMF-d7) d: 8.53 (d, H6, JHCCH 8.6 Hz), 8.37 (d, H5, JHCCH
8.9 Hz), 8.20 (br.s, H8, overlaps with the signal of H12), 8.20 (dt, H12,
3JHCCH 6.9 Hz, overlaps with the signal of H8), 8.03 (m, H10, H11), 7.50 (d,
H2, 3JPCCH 16.2 Hz), 2.74 (m, H13), 2.15 (m, H14). 13C NMR (DMSO-d6)
4
3
4
8.9 Hz, JHCCCH 1.7 Hz), 7.70 (dt, H16, JHCCH 8.6 Hz, JHCCCH 1.4 Hz,
© 2011 Mendeleev Communications. All rights reserved.
– 346 –

Mendeleev Commun., 2011, 21, 346–348
OH
OH
OH
HO
HX
2X–
(CH2)n
8 n = 4, X = Br
4, 7
Br
Br
C(19)
Ph2P
PPh2
C(13)
Br(1)
C(7)
C(25)
P(1)
C(8)
C(9)
C(12)
9 n = 4, X = CF3SO3
10 n = 5, X = CF3SO3
C(6)
P(2)
C(11)
C(8a)
C(4a)
C(10)
C(1)
O(3)
C(5)
C(31)
Scheme 2
C(2)
C(4)
O(1)
C(3)
O(2)
overlaps with H15 signal), 7.67 (dd, H15, 3JHCCH 9.9 Hz, overlaps with H16
signal), 7.58 (ddd, H14, 3JPCCH 12.9 Hz, 3JHCCH 4.8 Hz, 4JHCCCH 1.4 Hz),
7.51 (dt, H28, 3JHCCH 7.2 Hz, 4JHCCCH 1.4 Hz), 7.45 (m, H26, overlaps with
H27 signal), 7.23 (dd, H5, JHCCH 8.9 Hz, JPCCCCH 2.0 Hz), 7.12 (br.s,
H8), 6.94 (d, H2, 3JPCCH 15.0 Hz), 2.93 (m, H9), 1.77 (m, H10, H11), 2.20
(m, H12). 31P / 31P-{1H} NMR (DMSO-d6) dP: 31.8 [m (s), 1P, P=O], 20.6
[m (s), 1P, P+). MS, m/z: 677.0 [M]+• (C38H33BrO3P2). Found (%): C, 73.49;
H, 5.48; Br, 8.30; P, 6.70. Calc. for C56H51BrO3P2 (%): C, 73.60; H, 5.58;
Br, 8.76; P, 6.79.
P-(7-Bromo-3-hydroxy-4-oxonaphthalen-1(4H)-ylidene)-P-(4-diphenyl-
phosphinobut-1-yl)-P,P-(diphenyl)phosphorane 6 was obtained after slow
evaporation of the solvent from the abovementioned filtrate (after isolation
of compound 5 ) as colourless crystals, yield 0.11 g (16%), mp 186–190°C.
IR (n/cm–1): 3612, 3545 (OH), 1573, 1538, 1460 (P–Ph), 1377, 1165,
1108, 1072, 994, 965, 819, 740, 721, 690, 516, 438. 31P / 31P-{1H} NMR
(DMSO-d6) dP: 18.6 [m (s), 1P, Piv], –15.6 [m (s), 1P, Piii].
(Pentane-1,5-diyl)bis[(7-bromo-3-hydroxy-4-oxonaphthalen-1(4H)-
ylidene)(diphenyl)phosphorane] 7. Yield 81%, mp 185–188°C. For syn-
thesis and characterization of compound 7, see Online Supplementary
Materials.
Figure 1 Molecular structure and atom-labeling scheme for compound 5
(solvate with three benzene molecules, one benzene molecule is omitted for
clarity). Selected bond lengths (Å), bond and torsion angles (°): Br(1)–C(7)
1.912(4), P(1)–C(1) 1.760(4), P(1)–C(9) 1.814(3), P(1)–C(13) 1.813(4),
P(2)–O(3) 1.482(2), C(2)–C(1) 1.424(5), C(2)–C(3) 1.359(5), O(2)–C(3)
1.402(5), C(4)–O(1) 1.286(5), C(4)–C(3) 1.412(5), C(1)–P(1)–C(9) 110.2(2),
C(1)–C(2)–C(3) 123.2(4), C(4a)–C(8a)–C(1) 118.7(3), C(4)–C(4a)–C(8a)
122.1(4), O(1)–C(4)–C(3) 120.8(4), O(1)–C(4)–C(4a) 123.1(4), C(3)–C(4)–
C(4a) 116.1(4), C(2)–C(1)–P(1) 118.3(3), C(8a)–C(1)–P(1) 125(2), O(2)–
C(3)–C(4) 118.2(4), C(1)–P(1)–C(9) 110.18(18), O(3)–P(2)–C(16) 114.3(2),
O(3)–P(2)–C(17) 112.2(2). For more data, see Online Supplementary
Materials.
3
5
For compound 4, the signal with dP 19.4 ppm in 31P-{1H} NMR
spectrum is related to the ylide phosphorus atom. The electron
impact mass spectrum (EI-MS) contains a peak of molecular ion
with m/z 900.9. According to the 13C-{1H} NMR spectra the signal
of C1 atom is manifested in relatively high field (dC 122.36 ppm)
that may indicate the here C-centred negative charge. The 31P -{1H}
NMR spectrum of compound 5 contains two signals with dP 20.6
and 31.8 ppm with equal integral intensity corresponding to phos-
phonium and phosphine oxide functions.27 In addition, its IR
spectrum contains an intense absorption band of P=O bond.
EI-MS of this compound contains peak of a molecular ion with
m/z 677.0. The structure of compound 5 (as a solvate with three
benzene molecules) was ultimately confirmed by XRD‡ (Figure 1).
Both phosphorus atoms have a distorted tetrahedral configuration
and tetramethylene spacer is in a gauche-conformation along
C(10)–C(11) bond.
(Butane-1,4-diyl)bis[(7-bromo-3,4-dihydroxy-1-naphthyl)(diphenyl)-
phosphonium] dibromide 8. Dry hydrogen bromide (5-fold excess) was
passed through a solution of bis-ylide 4 (0.50 g, 0.55 mmol) in 10 ml of
benzene. The reaction mixture gradually produced dark-green precipitate,
which was filtered off and dried at reduced pressure (12 Torr). The yield of
compound 8 was 0.43 g (74%), mp 203–206°C.
For characteristics of compound 8, see Online Supplementary Materials.
(Butane-1,4-diyl)bis[(7-bromo-3,4-dihydroxy-1-naphthyl)(diphenyl)-
phosphonium] ditriflate 9. To a solution of compound 4 (0.47 g, 0.52 mmol)
in 5 ml of dichloromethane, a solution of 0.09 ml (1.04 mmol) of triflic
acid was added dropwise under intense argon bubbling. After 3 days of
standing colorless crystals of compound 9 were formed, which were
filtered off and dried under reduced pressure (12 Torr), yield 0.49 g (61%,
excluding two solvated hydroxonium triflate molecules), mp 128–131°C.
IR (n/cm–1): 3302 (OH), 1722, 1625, 1597 (C=Carom), 1566, 1502, 1343
(C–F), 1224, 1168 (nas SO2), 1115, 1078, 1028 (nas SO2), 981, 960, 856,
818, 743, 690, 639, 601, 540, 479. 1H NMR (DMSO-d6) d: 8.20 (dd, H6,
The 31P-{1H} NMR spectrum of phosphino ylide 6 contains two
signals of phosphonium and phosphine groupings (Piv, dP 18.6 ppm
and Piii, dP –15.6 ppm).
Further lengthening of the spacer by one methylene unit on
moving to 1,5-bis(diphenylphosphino)pentane 3 allowed us to
obtain the next bis-ylide 7, whose content in the reaction mixture
was about 100%.
4
3JHCCH 9.1 Hz, JHCCCH 1.9 Hz), 8.02–7.72 (m, H10, H11), 7.89 (m, H12,
5
3JHCCH 7.2 Hz, JPCCCCH 1.6 Hz), 7.60 (dd, H5, 3JHCCH 9.1 Hz, 5JPCCCCH
3
4
1.7 Hz), 7.42 (d, H2, JPCCH 16.7 Hz), 7.37 (br.d, H8, JPCCCH 1.2 Hz),
3.64 (m, H13), 1.76 (m, H14). 13C NMR (DMSO-d6) dC: 146.76 [m (d),
C4, 3JHCCC 5.6–5.8 Hz, 4JPCCCC 2.6 Hz], 140.58 [dd (d), C3, 3JPCCC 17.6 Hz,
2JHCC 3.6 Hz], 135.17 [dt (br.s), C12, 1JHC 170.0 Hz, 3JHCCC 5.6–6.5 Hz],
Treatment of bis-ylides 4 and 7 with dry hydrogen bromide
or triflic acid gave stable P,P'-bis(7-bromo-3,4-dihydroxy-1-
naphthyl)-substituted phosphonium salts 8–10† (Scheme 2). Com-
pound 8 is characterized by a singlet at dP 22.2 ppm in the 31P-{1H}
NMR spectrum. The broad absorption band at 3560–3564 cm–1
in the IR spectrum of salt 8 is related to the stretching vibrations of
hydroxy groups. The signals of C3 and C4 atoms in the 13C-{1H}
NMR spectrum of 8 manifest itself in the higher field (dC 140.31
and 146.71 ppm) than corresponding ones of ylide 4. Upfield shift
of the C1 signal in compound 8 (from dC 122.36 to 97.97 ppm)
points out the change of electronic situation at carbon atom (dis-
appearing of the negative charge) and formation of phosphonium
salt from ylide.
Bis-phosphonium ditriflate 9 was obtained after crystalliza-
tion from dichloromethane and its structure was confirmed by
XRD (Figure 2).‡ The crystal of 9 represents a solvate with two
hydroxonium triflate molecules. Note that tetramethylene chain
has an almost ideal planar conformation distinct from the molecule
of 5 (see Figure 1).
133.35 [ddd (d), C10, JHC 169.2 Hz, JPCC 10.3 Hz, JHCCC 6.9 Hz],
1
2
3
130.70 [ddd (d), C11, JHC 160.5 Hz, JPCCC 12.5 Hz, JHCCC 6.9 Hz],
1
3
3
130.07 [dd (d), C2, JHC 160.7 Hz, JPCC 12.1 Hz], 129.88 [m (d), C8a,
2JPCC 9.2 Hz, overlaps with C11 signal], 129.21 [dd (s), C8, 1JHC 163.9 Hz,
3JHCCC 6.0 Hz], 126.33 [ddd (d), C8, 1JHC 167.6 Hz, 3JHCCC 4.7–4.8 Hz,
1
2
3JPCCC 5.9 Hz], 125.66 [d (s), C5, JHC 166.7 Hz], 125.41 [m (d), C4a,
1
3JPCCC 12.1 Hz, overlaps with C8 signal], 120.89 [q (q), C23, 1JFC 321.0 Hz],
1
3
2
119.72 [ddt (d), C9, JPC 85.8 Hz, JHCCC 7.1 Hz, JHCC 1.4–1.6 Hz],
119.70 [ddd (s), C7, 3JHCCC 13.0 Hz, 2JHCC 5.9 Hz, 2JHCC 5.7 Hz], 99.28
[ddd (d), C1, 1JPC 91.3 Hz, 3JHCCC 2.7–3.3 Hz, 2JHCC 1.2–1.4 Hz], 23.83
[tdm (d), C22, JHC 132.2–136.5 Hz, JPCC 2.2 Hz], 21.76 [td (d), C21,
1JHC 132.1–134.3 Hz, 1JPC 51.7 Hz]. 31P / 31P-{1H} NMR (CDCl3) dP: 21.2
[m (s)]. Found(%):Br, 10.51;P, 4.07, S8.16. Calc. forC52H46Br2F12O18P2S4
(%): Br, 10.41; P, 4.04; S 8.33. For more details, see Online Supplementary
Materials.
1
2
(Pentane-1,5-diyl)bis[(7-bromo-3,4-dihydroxy-1-naphthyl)(diphenyl)-
phosphonium] ditriflate 10. Yield 85%, mp 98–100°C. For synthesis and
characteristics of compound 10, see Online Supplementary Materials.
– 347 –

Mendeleev Commun., 2011, 21, 346–348
This work was supported by the RF Federal contract
no. 02.740.11.0633.
Br(1)
C(7)
C(15)
C(9)
C(8)
Online Supplementary Materials
Supplementary data associated with this article can be found
in the online version at doi:10.1016/j.mencom.2011.11.019.
C(6)
C(5)
C(22)
C(21)
C(8a)
P(2)
P(1)
C(2)
C(1)
C(4a)
C(4)
C(3)
O(2)
O(1)
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Figure 2 Molecular structure and atom-labeling scheme for compound 9
(two triflate anions and one hydroxonium cation are omitted for clarity).
Selected bond lengths (Å), bond and torsion angles (°): Br(1)–C(7) 1.895(3),
P(1)–C(1) 1.790(3), P(1)–C(9) 1.792(3), C(2)–C(1) 1.378(4), C(2)–C(3)
1.391(4), O(2)–C(3) 1.363(4), C(4)–O(1) 1.356(3), C(4)–C(3) 1.377(4),
C(1)–P(1)–C(9) 109.4(1), C(1)–C(2)–C(3) 121.8(3), C(4a)–C(8a)–C(8) 17.7(3),
C(4)–C(4a)–C(5) 121.7(3), C(3)–C(4)–P(1) 118.2(2), C(8a)–C(1)–P(1)
121.7(2), O(1)–C(4)–C(3) 120.4(3), O(1)–C(4)–C(4a) 18.4(3), O(2)–C(3)–
C(4) 117.6(3), O(2)–C(3)–C(2) 123.1(3). For more data, see Online
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phonium salts with various lengths of methylene spacer on the
basis of the reaction of 6-bromo-1,2-naphthoquinone with tertiary
diphosphines has been developed. Complexation reactions with
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‡ X-ray diffraction analysis of crystals of compounds 5 and 9 was performed
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Crystals of compound 5 are triclinic, C38H33BrO3P2·3(C6H6), the experi-
ment was performed in a glass capillary for the crystal instability. Unit
cell parameters of a single crystal of 5: a = 10.646(5), b = 12.013(5) and
c = 17.478(9) Å, a = 83.918(8)°, b–= 77.227(13)°, g = 77.347(16)°, V =
= 2123.1(18) Å3, Z = 2, space group P1, M = 835.71, dcalc = 1.307(1) g cm–3,
m(MoKa) = 1.085 mm–1, F(000) = 868, 2.00° £ q £ 28.00°, Rint = 0.1451.
18711 reflections were measured, 9782 of them were independent, the
number of observed reflections with I > 2s(I) were 3188. The final agree-
ment factors are R = 0.0590, Rw = 0.0663, Rall = 0.0953, Rw all = 0.2100,
GOF = 0.735, the number of refined parameters is 491.
Soc., 2010, 157, A1274.
21 E. K. Brechin, L. Calucci, U. Englert, L. Margheriti, G. Pampaloni,
C. Pinzino and A. Prescimone, Inorg. Chim. Acta, 2008, 361, 2375.
22 L. Calucci, G. Pampaloni, C. Pinzino and A. Prescimone, Inorg. Chim.
Acta, 2006, 359, 3911.
23 M. Oh, G. B. Carpenter and D. A. Sweigart, Acc. Chem. Res., 2004, 37, 1.
24 H. Amouri and J. Le Bras, Acc. Chem. Res., 2002, 35, 501.
25 N. R. Khasiyatullina, A. V. Bogdanov and V. F. Mironov, Zh. Org. Khim.,
2010, 46, 307 (Russ. J. Org. Chem., 2010, 46, 304).
Crystals of compound 9 are triclinic, (C48H40Br2O4P2)2+·2(H3O+)·4(CF3SO3–)
,
dication (C48H40Br2O4P2)2+ is in a special position. Unit cell parameters of
a single crystal of 9: a = 9.3242(10), b = 11.4761(12) and c = 15.6236(16) Å,
a = 76.264(1)°, b = 76.359(1)°, g = 83.466(1)°, V = 1575.2(3) Å3, Z = 1,
–
space group P1, M = 1536.91, dcalc = 1.620 g cm–3, m(MoKa) = 1.573 mm–1,
F(000) = 774, 2.37° £ q £ 24.6°, Rint = 0.0299. 17220 reflections were
measured, 6787 of them were independent, the number of observed reflec-
tions with I > 2s(I) were 4493. The final agreement factors are R = 0.0494,
Rw = 0.1227, Rall = 0.0830, Rw all = 0.1409, GOF = 1.014, the number of
refined parameters is 434.
26 M. Albrecht, Chem. Soc. Rev., 1998, 28, 281.
27 L. C. Baldwin and M. J. Fink, J. Organomet. Chem., 2002, 646, 230.
28 APEX2 (Version 2.1), SAINTPlus. Data Reduction and Correction Program
(Version 7.31A), Bruker Advanced X-ray Solutions, BrukerAXS Inc.,
Madison, Wisconsin, USA, 2006.
29 A. Altomare, G. Cascarano, C. Giacovazzo and D. Viterbo, Acta Crystallogr.
Sect. A, 1991, 47, 744.
30 M. Sheldrick, SHELXL-97 Program for Crystal Structure Refinement,
The structures were solved by direct method using SIR program29 and
refined by the full-matrix least-squares using SHELXL-97 program.30 All
non-hydrogen atoms were refined anisotropically. The hydrogen atoms
were placed into the geometrically calculated positions and refined as
riding atoms. The hydrogen atoms on the OH groups and oxonium cations
were located from the difference Fourier synthesis and refined isotropically.
All the figures and analysis of intermolecular interactions were performed
using PLATON program.31
,
University of Göttingen, Germany, 1997.
31 A. L. Spek, Acta Crystallogr., Sect. A, 1990, 46, 34.
CCDC 818580 and 818558 contain the supplementary crystallographic data
for this paper. These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
For details, see ‘Notice to Authors’, Mendeleev Commun., Issue 1, 2011.
Received: 13th May 2011; Com. 11/3727
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