O-Phenyl (triphenyl-phospho-niometh-yl)-phospho-nate phenol solvate: Supra-molecular structure generated by O - H...O, C - H...arene) hydr...πogen bonds

Article abstract of DOI:10.1107/S0108270107032453

The title compound, C25H22O3P2·C6H6O, has a zwitterionic betaine-like structure and crystallizes as a phenol solvate. The two mol-ecular components are held together by an almost linear inter-molecular O - H...O hydrogen bond. The structure also contains

Full text of DOI:10.1107/S0108270107032453

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
tentatively assigned by MS, NMR and elemental analysis;
however, an unequivocal con®rmation was obtained from
crystallographic analysis.
ISSN 0108-2701
O-Phenyl (triphenylphosphonio-
methyl)phosphonate phenol solvate:
supramolecular structure generated
by OÐHÁ Á ÁO, CÐHÁ Á ÁO and
CÐHÁ Á Áp(arene) hydrogen bonds
The molecular structure of (I), with the atom-numbering
scheme, is shown in Fig. 1. The phosphonate molecule exists as
a zwitterion. The positive charge is located on atom P1, while
the negative charge is attributed formally to atom O2. Taking
into account the P2ÐO2 and P2ÐO3 bond lengths (Table 1),
partial delocalization of the charge between the two O atoms
within the O2 P2 O3 fragment can be proposed. The P2Ð
O3 bond is slightly shorter than the P2ÐO2 bond; however,
both distances are longer than the P O linkage within
a
a
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Lilianna CheÎcinska, * Agnieszka J. Rybarczyk-Pirek,
Zbigniew H. Kudzinb and Andrzej Okruszekc
a
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Department of Crystallography and Crystal Chemistry, University of èodz, Pomorska
149/153, 90 236 èodz, Poland, bDepartment of Organic Chemistry, University of
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èodz, Narutowicza 68, 90 136 èodz, Poland, and cDepartment of Bioorganic
Â
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. . . . . .
Chemistry, Centre of Molecular and Macromolecular Studies, Polish Academy of
Â
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Sciences, Sienkiewicza 112, 90 363 èodz, Poland, and Institute of Technical
Â
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Biochemistry, Technical University of èodz, Stefanowskiego 4/10, 90 924 èodz,
Poland
Ê
(C,N)(O)2ÐP O systems [1.457 (9) A; Allen et al., 1987] and
Correspondence e-mail: lilach@uni.lodz.pl
. . .
Ê
close to the mean value of 1.483 (8) A for (CÐO)2P( O)2
systems, indicating bond delocalization (Allen et al., 1987).
In the molecule of (I), two P atoms are joined through a
Csp3 atom. The P1ÐC1 and P2ÐC1 distances differ from each
other signi®cantly (Table 1). The coordination around P1 is
nearly tetrahedral, with angles ranging from 106.98 (7) to
114.31 (7)ꢀ, whereas within the phosphonate group, the
geometry around atom P2 indicates a considerable distortion
of the tetrahedron, especially in the O2ÐP2ÐO3 and O1Ð
P2ÐC1 bond angles (Table 1). The P+ÐC(phenyl) bond
Received 27 June 2007
Accepted 3 July 2007
Online 9 August 2007
The title compound, C25H22O3P2ÁC6H6O, has a zwitterionic
betaine-like structure and crystallizes as a phenol solvate. The
two molecular components are held together by an almost
linear intermolecular OÐHÁ Á ÁO hydrogen bond. The struc-
ture also contains three weak CÐHÁ Á ÁO and two CÐ
HÁ Á Áꢀ(arene) interactions.
Ê
lengths are very close to the mean distance of 1.793 (10) A
Comment
Betaine (N,N,N-trimethylglycine) acts as an important bio-
chemical donor of the methyl group for tetrahydrofolic acid
(N5,N10-methylenetetrahydrofolate synthesis) and homo-
cysteinic acid (methionine synthesis) (Stryer, 1995). The
phosphonic analogue of betaine ± trimethylammonium-
methanophosphonic acid ± was ®rst synthesized over ®ve
decades ago (Medved & Kabachnik, 1951; Kabachnik &
Medved, 1953; Myers & Jibril, 1957); more than a decade ago,
its biological activity became recognized (Abdel-Ghany et al.,
1993). However, to our knowledge, no example of a betaine
analogue containing two P atoms (phosphoniummethylene-
phosphonic acid or its ester) has been described in the
literature. We present here the synthesis and crystal and
molecular structures of the ®rst phosphoniophosphonic
analogue of betaine, namely O-phenyl (triphenylphospho-
niomethyl)phosphonate as a phenol solvate, (I).
The ®rst example of phosphoniummethylenephosphonic
acid was synthesized in the form of the O-phenyl ester by
controlled hydrolysis of [(diphenoxyphosphinyl)methyl-
idene]triphenylphosphorane, (II), and obtained in the crys-
talline form as the phenol solvate, (I). Its structure was
Figure 1
The structure of (I), showing the atom-numbering scheme. Displacement
ellipsoids are drawn at the 30% probability level and H atoms are shown
as small spheres of arbitrary radii.
o504 # 2007 International Union of Crystallography
DOI: 10.1107/S0108270107032453
Acta Cryst. (2007). C63, o504±o506

organic compounds
found for 118 Ph3P+ÐCsp3H2 fragments (3 Â 118 = 354
values) in the Cambridge Structural Database (Version 5.27;
Allen, 2002); the minimum and maximum distances are
Ê
1.752 (3) and 1.854 (3) A, respectively.
All benzene rings, including the phenol ring, are planar; a
Ê
maximum deviation of 0.010 (2) A was observed for atom
C12 from the least-squares plane of ring A. (The labelling
scheme, A±E, applied for phenyl rings, is introduced in Fig. 1.)
The CÐC bond lengths and angles within these rings are
Ê
typical for aromatic systems [1.384 (13) A; Allen et al., 1987],
hence no detailed discussion is needed. The dihedral angles
between the mean planes of the rings are summarized in
Table 3. This spatial arrangement enables the formation of
CÐHÁ Á ÁO and CÐHÁ Á Áꢀ(arene) interactions; however,
aromatic ꢀ±ꢀ stacking interactions are absent in the structure.
Two molecular components are linked within the selected
asymmetric unit by an almost linear O4ÐH4Á Á ÁO2 inter-
molecular hydrogen bond (Fig. 1 and Table 2).
There are also three short intermolecular CÐHÁ Á ÁO
contacts (Table 2), which on the basis of observed HÁ Á ÁO and
CÁ Á ÁO distances can be regarded as weak hydrogen-bonding
interactions (Taylor & Kennard, 1982). Atoms C1 and C12 act
as hydrogen-bond donors to atom O3i [symmetry code: (i)
Figure 4
Part of the crystal structure of (I), showing (010) sheets generated by CÐ
HÁ Á Áꢀ interactions between chains of dimers. For the sake of clarity, C-
bound H atoms that are not involved in the motif shown have been
omitted. [Symmetry code: (iii) x + 1, y + 1, z + 1.]
x + 1, y + 1, z + 2], forming a centrosymmetric dimer. The
former of these hydrogen bonds generates a graph-set motif of
R22(8), while the second generates an R22(14) ring (Bernstein et
al., 1995) (Fig. 2). Such a dimer is additionally stabilized by
C1ÐH1AÁ Á Áꢀ(ring D) hydrogen bonds.
Fig. 3 shows another hydrogen-bonded motif that plays an
important role in the supramolecular structure of (I). Atom
C35, via atom H35, acts as a hydrogen-bond donor towards
atom O3ii [symmetry code: (ii) x + 1, y, z], thereby producing
an in®nite C(8) chain running parallel to the [100] direction.
In summary, the combination of all three weak CÐHÁ Á ÁO
interactions produces in®nite chains of centrosymmetric
dimers along the a axis. The aforementioned chains are linked
into (010) sheets by C25ÐH25Á Á Áꢀiii interactions [ring E;
symmetry code: (iii) x + 1, y + 1, z + 1; Fig. 4]. Every
sheet passes through the unit cell in the domain 0.07 < y <
1.07. There are no direction-speci®c interactions between
adjacent sheets.
Figure 2
Part of the crystal structure of (I), showing the formation of a
centrosymmetric dimer. For the sake of clarity, C-bound H atoms that
are not involved in the motif shown have been omitted. [Symmetry code:
(i) x + 1, y + 1, z + 2.]
Experimental
The title compound, (I), was synthesized from [(diphenoxyphos-
phinyl)methylidene]triphenylphosphorane, (II), which was prepared
Â
exactly as described in our previous paper (CheÎcinska et al., 2003).
Figure 3
For (II): 31P NMR (CD3CN): ꢁ 20.98 (d, Ph3P ), 28.03 [d,
Part of the crystal structure of (I), showing the formation of an in®nite
CÐHÁ Á ÁO chain running parallel to the [100] direction. For the sake of
clarity, C-bound H atoms that are not involved in the motif shown have
been omitted. [Symmetry codes: (ii) x + 1, y, z; (iv) x 1, y, z.]
2
(PhO)2P(O)±, JPP = 46.4 Hz]. The ylide (II) (1.08 g, 1 mmol) was
dissolved in 20 ml of acetonitrile containing 2% water. The solution
was kept for 48 h at 323 K in a closed ¯ask and evaporated. The
ꢁ
Î
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Acta Cryst. (2007). C63, o504±o506
Checinska et al. C25H22O3P2ÁC6H6O o505

organic compounds
residue was crystallized from ethyl acetate, yielding 0.61 g (58%) of
phenol-solvated betaine (I) in the form of colorless crystals (m.p.
476±479 K). 31P NMR (CDCl3): ꢁ 1.64 [d, (PhO)P(O)O ], 212.36
Table 3
The dihedral angles between the mean planes for the phenyl rings (ꢀ).
Symbols A±E refer to the phenyl rings as de®ned in Fig. 1.
2
1
(d, Ph3P+, JPP = 10.1 Hz). H NMR (CDCl3): ꢁ 3.565 (dd, 2H, PÐ
2
Ring/ring
Dihedral angle
CH2ÐP, JHP = 15.7 and 17.1 Hz), 6.7±7.2 (m, 10H, PhO H atoms),
7.45±7.8 (m, 15H, Ph3P H atoms), 9.44 (br s, 1H, OH). MS FAB (Cs+,
negative ions): m/z 431 (16%), 355 (100%), 278 (8%), 261 (28%).
Elemental analysis found: C 70.49, H 5.25, P 11.58%; calculated for
C31H28O4P2: 70.72, H 5.36, P 11.77%.
A/B
A/C
A/D
A/E
B/C
B/D
B/E
C/D
C/E
D/E
78.1 (1)
77.4 (1)
36.1 (1)
44.1 (1)
72.8 (1)
43.8 (1)
68.5 (1)
83.1 (1)
58.6 (1)
52.8 (1)
Crystal data
C25H22O3P2ÁC6H6O
ꢄ = 78.35 (2)ꢀ
V = 1374.9 (5) A
Z = 2
Mo Kꢂ radiation
ꢅ = 0.19 mm
T = 293 (2) K
3
Ê
Mr = 526.47
Triclinic, P1
Ê
a = 9.793 (2) A
b = 10.170 (2) A
Ê
c = 14.374 (2) A
1
Ê
ꢂ = 82.78 (2)ꢀ
ꢃ = 80.07 (2)ꢀ
0.5 Â 0.2 Â 0.1 mm
Atom H4, involved in the O4ÐH4Á Á ÁO2 hydrogen bond, was
located in a difference map and re®ned isotropically. All C-bound H
atoms of methylene and phenyl groups were positioned geometrically
Data collection
Ê
(CÐH = 0.97 and 0.93 A, respectively) and constrained to ride on
their parent atoms [Uiso(H) = 1.2Ueq(C)].
Rigaku AFC-5S diffractometer
6644 measured re¯ections
6293 independent re¯ections
4137 re¯ections with I > 2ꢆ(I)
Rint = 0.013
3 standard re¯ections
every 150 re¯ections
intensity decay: 1.6%
Data collection: MSC/AFC Diffractometer Control Software
(Molecular Structure Corporation, 1989); cell re®nement: MSC/AFC
Diffractometer Control Software; data reduction: TEXSAN (Mol-
ecular Structure Corporation, 1989); program(s) used to solve
structure: SHELXS97 (Sheldrick, 1997); program(s) used to re®ne
structure: SHELXL97 (Sheldrick, 1997); molecular graphics:
PLATON (Spek, 2003); software used to prepare material for
publication: PLATON.
Re®nement
R[F2 > 2ꢆ(F2)] = 0.033
wR(F2) = 0.082
S = 1.02
6293 re¯ections
338 parameters
H atoms treated by a mixture of
independent and constrained
re®nement
3
Ê
Áꢇmax = 0.27 e A
3
Ê
0.24 e A
Áꢇmin
=
Table 1
Selected geometric parameters (A, ).
ꢀ
Ê
This work was supported ®nancially by the University of
 Â
èodz (grant No. 706/505 2007) for LC and AJRP.
P1ÐC1
P1ÐC21
P1ÐC11
P1ÐC31
P2ÐO3
1.7855 (14)
1.7923 (14)
1.7991 (15)
1.8009 (15)
1.4695 (10)
P2ÐO2
P2ÐO1
P2ÐC1
O1ÐC41
O4ÐC51
1.4815 (11)
1.6189 (12)
1.8202 (15)
1.3809 (18)
1.3523 (19)
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SK3145). Services for accessing these data are
described at the back of the journal.
C1ÐP1ÐC21
C1ÐP1ÐC11
C21ÐP1ÐC11
C1ÐP1ÐC31
C21ÐP1ÐC31
C11ÐP1ÐC31
O3ÐP2ÐO2
110.26 (7)
106.98 (7)
109.54 (7)
114.31 (7)
107.97 (7)
107.68 (7)
121.84 (7)
O3ÐP2ÐO1
O2ÐP2ÐO1
O3ÐP2ÐC1
O2ÐP2ÐC1
O1ÐP2ÐC1
C41ÐO1ÐP2
P1ÐC1ÐP2
111.10 (6)
105.09 (7)
107.50 (7)
107.85 (7)
101.60 (7)
124.97 (9)
120.06 (8)
References
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(1993). J. Med. Chem. 36, 784±789.
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Table 2
Hydrogen-bond geometry (A, ).
ꢀ
Ê
Â
CheÎcinska, L., Kudzin, Z. H., Maøecka, M., Nazarski, R. B. & Okruszek, A.
(2003). Tetrahedron, 59, 7681±7693.
CgD and CgE are the centroids of rings D and E, respectively.
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pp. 1126±1127.
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
Medved, T. Ya. & Kabachnik, M. I. (1951). Izv. Akad. Nauk SSSR Ser. Khim.
pp. 620±623.
O4ÐH4Á Á ÁO2
0.89 (2)
0.97
0.93
0.93
0.93
1.72 (2)
2.30
2.57
2.36
2.79
2.601 (2)
3.142 (2)
3.269 (2)
3.200 (3)
3.727 (2)
3.667 (2)
175 (2)
145
133
150
161
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C1ÐH1BÁ Á ÁO3i
C12ÐH12Á Á ÁO3i
C35ÐH35Á Á ÁO3ii
C1ÐH1AÁ Á ÁCgDi
C25ÐH25Á Á ÁCgEiii
0.93
2.90
141
Symmetry codes: (i) x ‡ 1; y ‡ 1; z ‡ 2; (ii) x ‡ 1; y; z; (iii) x ‡ 1, y ‡ 1,
z ‡ 1.
ꢁ
Î
Â
o506 Checinska et al.
C25H22O3P2ÁC6H6O
Acta Cryst. (2007). C63, o504±o506