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Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296

Two polymorphs of (2-carb­­oxy­eth­yl)(phen­yl)phosphinic acid

aCollege of Chemistry and Life Science, Gannan Normal University, Ganzhou, Jiangxi 341000, People's Republic of China
*Correspondence e-mail: ziyidu@gmail.com

(Received 29 January 2011; accepted 8 April 2011; online 5 May 2011)

Two polymorphs of (2-carb­oxy­eth­yl)(phen­yl)­phosphinic acid, C9H11O4P, crystallize in the chiral P212121 space group with similar unit-cell parameters. They feature an essentially similar hydrogen-bonding motif but differ slightly in their detailed geometric parameters. For both polymorphs, the unequivocal location of the hydroxy H atoms together with the expected differences in the P—O bond lengths establish unequivocally that both forms contain the S isomer; the protonated phosphinic acid and carboxy O atoms serve as hydrogen-bond donors, while the second phosphinic acid O atom acts as a double hydrogen-bond acceptor and the remaining carboxy O atom is not involved in hydrogen bonding. Thus, an undulating two-dimensional supra­molecular layer aggregate is formed based on an R43(20) ring unit. Such polymorphism derives from the rotation of the C—C single bonds between the two hydrogen-bond-involved carboxy and phosphi­nic acid moieties.

Comment

(2-Carb­oxy­eth­yl)(phen­yl)phosphinic acid (H2L) is a flame-retardant additive for polymers such as polyesters (Levchik & Weil, 2005[Levchik, S. V. & Weil, E. D. (2005). Polym. Int. 54, 11-35.]). Its related homologue, (carb­oxy­meth­yl)(phen­yl)­phosphinic acid, has also been investigated for the construction of metal–organic frameworks (Midollini et al., 2005[Midollini, S., Orlandini, A., Rosa, P. & Sorace, L. (2005). Inorg. Chem. 44, 2060-2066.]). Such organic mol­ecules feature two polar phosphinic acid and carboxy moieties at both ends of a flexible –(CH2)n– spacer (n = 1 or 2). Recently, on searching for an efficient asymmetric ligand to induce the formation of noncentrosymmetric structures for metal complexes, we have undertaken research work on the coordination and supra­molecular chemistry of (2-carb­oxy­eth­yl)(phen­yl)phosphinic acid. During our initial studies on its crystallization behaviour, we obtained two polymorphs, (I)[link] and (II)[link].

[Scheme 1]

Single-crystal structural determination reveals that both polymorphs crystallize in the chiral space group P212121. Although a racemic mixture of both R and S forms might have been expected, the unequivocal location of the hydroxy H atoms together with the expected differences in the P—O bond lengths establish unequivocally that both forms contain the S isomer. The Flack values from the refinements [−0.09 (10) for (I)[link] and 0.11 (11) for (II)[link]] are consistent with this. The displacement-ellipsoid drawing of S-configuration polymorph (I) is given in Fig. 1[link].

In the H2L molecules of (I)[link] and (II)[link], the clear location of the hydroxy H atoms at O1 and O4 in difference maps are entirely consistent with the long P1—O1 bond and the long C9—O4 bond (Tables 1[link] and 3[link]). The protonated phosphinic acid and carboxy O atoms (O1 and O4) both serve as hydrogen-bond donors, while the second phosphinic acid O atom (O2) acts as a double hydrogen-bond acceptor and the remaining carboxy O atom (O3) is not involved in hydrogen-bond inter­action (Table 2[link]). The hydrogen-bond inter­actions among these H2L mol­ecules lead to the formation of an undulating two-dimensional supra­molecular layer aggregate (Fig. 2[link]). The supra­molecular layer features a 20-membered ring composed of two H2L mol­ecules and two phosphinic acid fragments from another two H2L mol­ecules (Fig. 3[link]), which can be specified as having an R43(20) pattern according to graph-set analysis nomenclature (Bernstein et al., 1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]). Adjacent mol­ecules hydrogen bonded via O4—H4B⋯O2(x, y − 1, z) are associated by translational symmetry; thus, their phenyl rings are parallel to each other. In contrast, adjacent mol­ecules hydrogen bonded via O1—H1A⋯O2(x + [{1\over 2}], −y + [{3\over 2}], −z + 1) are related by 21 symmetry, and their phenyl rings are nonparallel with a dihedral angle of 66.31 (7)°. Overall, the undulating supra­molecular layers stack along the c axis to form a three-dimensional supra­molecular architecture (Fig. 4[link]).

The structure of polymorph (II)[link] is similar to that of polymorph (I)[link]. As shown in Fig. 3[link], both polymorphs feature an essentially similar hydrogen-bond motif based on the R43(20) pattern, but differ slightly in the detailed geometric parameters (Tables 2[link] and 4[link]). The attachment of two non-hydrogen-bonding O3 atoms on the R43(20) ring is also different for the two polymorphs: in (II)[link] they are on the same side whereas in (I)[link] they are on opposite sides of the ring. On the whole, the three-dimensional supra­molecular architecture of (II)[link] is also similar to that of (I)[link] (Fig. 5[link]). The two polymorphs can be attributed to the two different conformations of the mol­ecule, resulting from the rotation of the C—C single bonds between the two hydrogen-bond-involved carboxy and phos­phin­ic acid groups; the rotation around the C—C single bonds is also regulated by the hydrogen-bonding inter­action.

[Figure 1]
Figure 1
The structure of S-configuration polymorph (I)[link], showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The structure of polymorph (II)[link] is very similar to that of polymorph (I)[link].
[Figure 2]
Figure 2
Hydrogen-bond inter­actions among the (2-carb­oxy­eth­yl)(phen­yl)­phos­phinic acid mol­ecules in S-configuration polymorph (I)[link]. Hydrogen bonds are represented by dashed lines. For clarity, the phenyl rings and H atoms attached to C atoms have been omitted. (P, C, O and H atoms are drawn as purple, black, red and green spheres, respectively, in the electronic version of the paper.)
[Figure 3]
Figure 3
Views of the hydrogen-bond rings of S-configuration polymorphs (I)[link] (top) and (II)[link] (bottom). For clarity, the O atoms as well as the C—O bonds attached behind the rings are displayed as translucent. (In the electronic version of the paper, atom labels are coloured as in Fig. 2[link].) [Symmetry codes: (i) x + [1 \over 2], −y + [3 \over 2], −z + 1; (ii) x + [1 \over 2], −y + [1 \over 2], −z + 1; (iii) x + [1 \over 2], −y + [1 \over 2], −z; (iv) x + [1 \over 2], −y + [3 \over 2], −z.]
[Figure 4]
Figure 4
View of the structure of S-configuration polymorph (I)[link] down the b axis.
[Figure 5]
Figure 5
View of the structure of S-configuration polymorph (II)[link] down the b axis.

Experimental

(2-Carb­oxy­eth­yl)(phen­yl)phosphinic acid was synthesized according to a published procedure (Birum & Jansen, 1978[Birum, G. H. & Jansen, R. F. (1978). US Patent No. 4 081 463.]). A portion (0.08 g) was dissolved in distilled water (12 ml) by heating and stirring, with the addition of two drops of 10% HCl solution. The resulting solution was then left to stand at room temperature. About a week later, plate-shaped crystals formed. The structure of (I)[link] indicated formation of a racemic mixture, so an attempt was made to select a crystal of the opposite enanti­omer. The surprising result was the discovery of the second dimorph, (II)[link]. Since crystals of the two polymorphs have very similar shapes, it is hard to distinguish them by appearance.

Polymorph (I)[link]

Crystal data
  • C9H11O4P

  • Mr = 214.15

  • Orthorhombic, P 21 21 21

  • a = 5.4948 (1) Å

  • b = 8.6830 (1) Å

  • c = 21.3724 (4) Å

  • V = 1019.71 (3) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.26 mm−1

  • T = 296 K

  • 0.30 × 0.20 × 0.10 mm

Data collection
  • Bruker SMART CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2008[Bruker (2008). SMART, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.673, Tmax = 0.746

  • 5497 measured reflections

  • 2326 independent reflections

  • 2089 reflections with I > 2σ(I)

  • Rint = 0.027

Refinement
  • R[F2 > 2σ(F2)] = 0.038

  • wR(F2) = 0.087

  • S = 1.05

  • 2326 reflections

  • 133 parameters

  • 2 restraints

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.24 e Å−3

  • Δρmin = −0.24 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 893 Friedel pairs

  • Flack parameter: −0.09 (10)

Table 1
Selected bond lengths (Å) for polymorph (I)[link]

P1—O2 1.5010 (14)
P1—O1 1.5605 (16)
C9—O3 1.200 (3)
C9—O4 1.321 (3)

Table 2
Hydrogen-bond geometry (Å, °) for polymorph (I)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
O1—H1A⋯O2i 0.81 (1) 1.76 (1) 2.5699 (18) 177 (3)
O4—H4B⋯O2ii 0.82 (1) 1.90 (1) 2.6925 (19) 162 (3)
Symmetry codes: (i) [x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]; (ii) x, y-1, z.

Polymorph (II)[link]

Crystal data
  • C9H11O4P

  • Mr = 214.15

  • Orthorhombic, P 21 21 21

  • a = 6.1741 (15) Å

  • b = 8.7308 (19) Å

  • c = 19.844 (4) Å

  • V = 1069.7 (4) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.24 mm−1

  • T = 296 K

  • 0.34 × 0.16 × 0.14 mm

Data collection
  • Bruker SMART CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2008[Bruker (2008). SMART, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.679, Tmax = 0.746

  • 5593 measured reflections

  • 2422 independent reflections

  • 1977 reflections with I > 2σ(I)

  • Rint = 0.026

Refinement
  • R[F2 > 2σ(F2)] = 0.037

  • wR(F2) = 0.090

  • S = 1.03

  • 2422 reflections

  • 133 parameters

  • 2 restraints

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.18 e Å−3

  • Δρmin = −0.22 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 989 Friedel pairs

  • Flack parameter: 0.11 (11)

Table 3
Selected bond lengths (Å) for polymorph (II)[link]

P1—O2 1.5087 (15)
P1—O1 1.5527 (17)
C9—O3 1.203 (2)
C9—O4 1.331 (3)

Table 4
Hydrogen-bond geometry (Å, °) for polymorph (II)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
O1—H1A⋯O2i 0.81 (1) 1.77 (1) 2.566 (2) 169 (3)
O4—H4B⋯O2ii 0.82 (1) 1.85 (1) 2.658 (2) 169 (3)
Symmetry codes: (i) [x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]; (ii) x, y+1, z.

C-bound H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.93 or 0.97 Å, and with Uiso(H) = 1.2Ueq(C). O-bound H atoms were located in a difference map and refined with Uiso(H) values set at 1.2Ueq(O). The O—H distances were restrained to be 0.82 (1) Å.

For both compounds, data collection: SMART (Bruker, 2008[Bruker (2008). SMART, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SMART; data reduction: SAINT (Bruker, 2008[Bruker (2008). SMART, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: DIAMOND (Brandenburg, 1999[Brandenburg, K. (1999). DIAMOND. Version 2.1c. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: SHELXTL (Bruker, 2008[Bruker (2008). SMART, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]).

Supporting information


Comment top

2-Carboxyethyl(phenyl)phosphinic acid (H2L) is a flame-retardant additive for polymers such as polyesters (Levchik & Weil, 2005). Its related homologue, carboxymethyl(phenyl)phosphinic acid, has also been investigated for the construction of metal–organic frameworks (Midollini et al., 2005). Such organic molecules feature two polar phosphinate and carboxylate moieties at both ends of a flexible –(CH2)n– spacer (n = 1 or 2). Recently, on searching for an efficient asymmetric ligand to induce the formation of noncentrosymmetric structures for metal complexes, we have undertaken research work on the coordination and supramolecular chemistry of 2-carboxyethyl(phenyl)phosphinic acid. During our initial studies on its crystallization behaviour, we obtained two polymorphs, (I) and (II).

Single-crystal structural determination reveals that both polymorphs crystallize in the chiral space group P212121. As a weak diprotic acid in aqueous solution, the chirality of 2-carboxyethyl(phenyl)phosphinic acid is not apparent. However, when it crystallizes via hydrogen-bonding interactions, the chiral nature becomes prominent. The molecule itself features a chiral P atom which is bonded to four different groups (2-carboxyethyl, phenyl, O and OH). Hence, both S- and R-enantiomers as a conglomerate were observed for the two polymorphs, as was expected. To facilitate comparison of the two different polymorphs, here we present only two S-configuration enantiomers for detailed discussion. The displacement ellipsoid drawing of the two polymorphs (I) and (II) is given in Fig. 1.

In the H2L molecule of (I), the two OH groups are indicated by a much longer P—O and C—O bond (Table 1) [compared with?]. The protonated phosphinate and carboxylate O atoms (O1, O4) both serve as hydrogen-bond donors, while the second phosphinate O atom (O2) acts as a double hydrogen-bond acceptor and the remaining carboxylate O atom (O3) is not involved in hydrogen-bond interaction (Table 2). The hydrogen-bond interactions among these H2L molecules lead to the formation of an undulating two-dimensional supramolecular layer aggregate (Fig. 2). The supramolecular layer features a 20-membered ring composed of two H2L molecules and two phosphinate fragments from another two H2L molecules (Fig. 3), which can be specified as having an R43(20) pattern according to graph-set analysis nomenclature (Bernstein et al., 1995). The adjacent molecules hydrogen-bonded via O4—H4B···O2 (symmetry code: x, y - 1, z) are associated by translational symmetry; thus, their phenyl rings are parallel to each other. In contrast, the adjacent molecules hydrogen-bonded via O1—H1A···O2 (symmetry code: x + 1/2, -y + 3/2, -z + 1) are related by 21 symmetry, and their phenyl rings are non-parallel with a dihedral angle of ca 66.3°. Overall, the undulating supramolecular layers stack along the c axis to form a three-dimensional supramolecular architecture (Fig. 4).

The structure of polymorph (II) is similar to that of polymorph (I). As shown in Fig. 3, both polymorphs feature an essentially similar hydrogen-bond motif based on the R43(20) pattern, but differ slightly in the detailed geometric parameters (Tables 2 and 4). The attachment of two non-hydrogen-bonding O3 atoms on the R43(20) ring is also different for the two polymorphs: in (II) they are on the same side whereas in (I) they are on opposite sides of the ring [ok as edited?]. On the whole, the three-dimensional supramolecular architecture of (II) is also similar to that of (I) (Fig. 5). The two polymorphs can be attributed to the two different conformations of the molecule, resulting from the rotation of the C—C single bonds between the two hydrogen-bond-involved carboxylate and phosphonate moieties; the rotation around the C—C single bonds is also regulated by the hydrogen-bonding interaction.

Related literature top

For related literature, see: Bernstein et al. (1995); Birum & Jansen (1978); Levchik & Weil (2005); Midollini et al. (2005).

Experimental top

2-Carboxyethyl(phenyl)phosphinic acid was synthesized using a published procedure (Birum & Jansen, 1978). A portion (0.08 g) was dissolved in distilled water (12 ml) by heating and stirring, with the addition of two drops of 10% HCl solution. The resulting solution was then left at room temperature. About a week later, plate-shaped crystals formed. The structure of (I) indicated formation of a conglomerate, so an attempt was made to select a crystal of the opposite enantiomer. The surprise result was the discovery of the second dimorph, (II). Since crystals of the two polymorphs have very similar shapes, it is hard to distinguish them by appearance.

Refinement top

The C-bound H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.93 or 0.97 Å, and with Uiso(H) = 1.2Ueq(C). The O-bound H atoms were located in a difference map and refined with Uiso(H) values set at 1.2Ueq(O). The O—H distances were restrained to be 0.82 (1) Å.

Computing details top

For both compounds, data collection: SMART (Bruker, 2008); cell refinement: SMART (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Bruker, 2008).

Figures top
[Figure 1] Fig. 1. The structures of polymorphs (I) and (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Hydrogen-bond interactions among the 2-carboxyethyl(phenyl)phosphinc acid molecules in polymorph (I). P, C, O and H atoms are drawn as purple, black, red and green spheres, respectively, in the electronic version of the paper. Hydrogen bonds are represented by dashed lines. For clarity, the phenyl rings and the H atoms attached to the C atoms have been omitted.
[Figure 3] Fig. 3. View of the hydrogen-bond rings of polymorphs (I) and (II). See the caption for Fig. 2 for the colour code details. For clarity, the O atoms as well as the C—O bonds attached behind the rings are displayed as translucent.
[Figure 4] Fig. 4. View of the structure of polymorph (I) down the b axis. For display details, see the caption for Fig. 2.
[Figure 5] Fig. 5. View of the structure of polymorph (II) down the b axis. For display details, see the caption for Fig. 2.
(I) top
Crystal data top
C9H11O4PF(000) = 448
Mr = 214.15Dx = 1.395 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 1796 reflections
a = 5.4948 (1) Åθ = 3.8–25.9°
b = 8.6830 (1) ŵ = 0.26 mm1
c = 21.3724 (4) ÅT = 296 K
V = 1019.71 (3) Å3Block, colourless
Z = 40.30 × 0.20 × 0.10 mm
Data collection top
CCD area detector
diffractometer
2326 independent reflections
Radiation source: fine-focus sealed tube2089 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.027
ϕ and ω scansθmax = 27.5°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
h = 57
Tmin = 0.673, Tmax = 0.746k = 1111
5497 measured reflectionsl = 2727
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.087 w = 1/[σ2(Fo2) + (0.0436P)2 + 0.0664P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
2326 reflectionsΔρmax = 0.24 e Å3
133 parametersΔρmin = 0.24 e Å3
2 restraintsAbsolute structure: Flack (1983), 893 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.09 (10)
Crystal data top
C9H11O4PV = 1019.71 (3) Å3
Mr = 214.15Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 5.4948 (1) ŵ = 0.26 mm1
b = 8.6830 (1) ÅT = 296 K
c = 21.3724 (4) Å0.30 × 0.20 × 0.10 mm
Data collection top
CCD area detector
diffractometer
2326 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
2089 reflections with I > 2σ(I)
Tmin = 0.673, Tmax = 0.746Rint = 0.027
5497 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.038H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.087Δρmax = 0.24 e Å3
S = 1.05Δρmin = 0.24 e Å3
2326 reflectionsAbsolute structure: Flack (1983), 893 Friedel pairs
133 parametersAbsolute structure parameter: 0.09 (10)
2 restraints
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
P10.32891 (10)0.68214 (5)0.41950 (2)0.02644 (14)
C10.2968 (4)0.6999 (2)0.33649 (9)0.0316 (5)
C20.4618 (5)0.6304 (3)0.29583 (9)0.0429 (6)
H2A0.59720.57930.31170.051*
C30.4240 (6)0.6374 (3)0.23175 (11)0.0586 (8)
H3A0.53090.58840.20450.070*
C40.2270 (6)0.7173 (4)0.20876 (12)0.0694 (10)
H4A0.20270.72270.16570.083*
C50.0661 (6)0.7893 (4)0.24807 (12)0.0717 (9)
H5A0.06420.84470.23180.086*
C60.0988 (5)0.7790 (3)0.31248 (11)0.0507 (7)
H6A0.01230.82520.33940.061*
C70.2012 (4)0.5020 (2)0.44335 (10)0.0330 (5)
H7A0.21250.49360.48850.040*
H7B0.03010.50020.43220.040*
C80.3268 (5)0.3637 (2)0.41376 (10)0.0361 (5)
H8A0.32630.37590.36860.043*
H8B0.49510.36110.42740.043*
C90.2073 (5)0.2134 (2)0.43020 (9)0.0342 (5)
O10.6099 (3)0.67442 (18)0.42966 (6)0.0382 (4)
H1A0.644 (5)0.679 (3)0.4666 (5)0.046*
O20.2054 (3)0.81281 (14)0.45275 (6)0.0345 (4)
O30.0050 (3)0.20158 (19)0.45074 (8)0.0536 (5)
O40.3510 (4)0.09573 (15)0.41730 (8)0.0520 (5)
H4B0.285 (5)0.020 (2)0.4328 (12)0.062*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.0347 (3)0.0224 (2)0.0222 (2)0.0002 (2)0.0013 (2)0.00030 (19)
C10.0395 (13)0.0297 (9)0.0257 (9)0.0067 (10)0.0002 (9)0.0024 (8)
C20.0515 (16)0.0456 (12)0.0314 (11)0.0014 (12)0.0055 (11)0.0012 (9)
C30.071 (2)0.0767 (18)0.0277 (11)0.0137 (16)0.0124 (13)0.0038 (12)
C40.074 (2)0.106 (2)0.0278 (12)0.031 (2)0.0075 (14)0.0136 (14)
C50.0596 (19)0.111 (3)0.0448 (15)0.005 (2)0.0156 (15)0.0257 (17)
C60.0435 (15)0.0698 (17)0.0388 (13)0.0056 (14)0.0030 (11)0.0086 (12)
C70.0428 (14)0.0245 (8)0.0319 (10)0.0001 (10)0.0068 (10)0.0015 (7)
C80.0511 (14)0.0241 (8)0.0332 (10)0.0007 (10)0.0078 (12)0.0005 (7)
C90.0524 (15)0.0248 (9)0.0256 (9)0.0024 (10)0.0023 (10)0.0008 (7)
O10.0380 (9)0.0475 (8)0.0291 (7)0.0019 (7)0.0034 (7)0.0042 (7)
O20.0486 (10)0.0242 (6)0.0306 (7)0.0031 (8)0.0066 (7)0.0017 (6)
O30.0547 (12)0.0374 (9)0.0685 (12)0.0094 (9)0.0153 (10)0.0013 (8)
O40.0725 (13)0.0230 (7)0.0605 (11)0.0012 (9)0.0217 (11)0.0025 (7)
Geometric parameters (Å, º) top
P1—O21.5010 (14)C5—H5A0.9300
P1—O11.5605 (16)C6—H6A0.9300
P1—C71.788 (2)C7—C81.523 (3)
P1—C11.7896 (19)C7—H7A0.9700
C1—C61.385 (3)C7—H7B0.9700
C1—C21.393 (3)C8—C91.502 (3)
C2—C31.387 (3)C8—H8A0.9700
C2—H2A0.9300C8—H8B0.9700
C3—C41.377 (4)C9—O31.200 (3)
C3—H3A0.9300C9—O41.321 (3)
C4—C51.370 (4)O1—H1A0.814 (10)
C4—H4A0.9300O4—H4B0.818 (10)
C5—C61.391 (3)
O2—P1—O1114.47 (9)C1—C6—C5120.0 (3)
O2—P1—C7110.40 (9)C1—C6—H6A120.0
O1—P1—C7108.12 (10)C5—C6—H6A120.0
O2—P1—C1111.08 (9)C8—C7—P1113.17 (15)
O1—P1—C1103.83 (10)C8—C7—H7A108.9
C7—P1—C1108.61 (10)P1—C7—H7A108.9
C6—C1—C2119.7 (2)C8—C7—H7B108.9
C6—C1—P1119.16 (17)P1—C7—H7B108.9
C2—C1—P1121.12 (17)H7A—C7—H7B107.8
C3—C2—C1120.0 (2)C9—C8—C7112.94 (18)
C3—C2—H2A120.0C9—C8—H8A109.0
C1—C2—H2A120.0C7—C8—H8A109.0
C4—C3—C2119.5 (3)C9—C8—H8B109.0
C4—C3—H3A120.2C7—C8—H8B109.0
C2—C3—H3A120.2H8A—C8—H8B107.8
C5—C4—C3121.2 (2)O3—C9—O4124.3 (2)
C5—C4—H4A119.4O3—C9—C8124.4 (2)
C3—C4—H4A119.4O4—C9—C8111.22 (19)
C4—C5—C6119.6 (3)P1—O1—H1A111.3 (18)
C4—C5—H5A120.2C9—O4—H4B106 (2)
C6—C5—H5A120.2
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O2i0.81 (1)1.76 (1)2.5699 (18)177 (3)
O4—H4B···O2ii0.82 (1)1.90 (1)2.6925 (19)162 (3)
Symmetry codes: (i) x+1/2, y+3/2, z+1; (ii) x, y1, z.
(II) top
Crystal data top
C9H11O4PF(000) = 448
Mr = 214.15Dx = 1.330 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 1679 reflections
a = 6.1741 (15) Åθ = 2.6–25.7°
b = 8.7308 (19) ŵ = 0.24 mm1
c = 19.844 (4) ÅT = 296 K
V = 1069.7 (4) Å3Block, colorless
Z = 40.34 × 0.16 × 0.14 mm
Data collection top
CCD area detector
diffractometer
2422 independent reflections
Radiation source: fine-focus sealed tube1977 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
ϕ and ω scansθmax = 27.5°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
h = 77
Tmin = 0.679, Tmax = 0.746k = 1111
5593 measured reflectionsl = 2525
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.090 w = 1/[σ2(Fo2) + (0.0465P)2 + 0.0144P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
2422 reflectionsΔρmax = 0.18 e Å3
133 parametersΔρmin = 0.22 e Å3
2 restraintsAbsolute structure: Flack (1983), 989 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.11 (11)
Crystal data top
C9H11O4PV = 1069.7 (4) Å3
Mr = 214.15Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 6.1741 (15) ŵ = 0.24 mm1
b = 8.7308 (19) ÅT = 296 K
c = 19.844 (4) Å0.34 × 0.16 × 0.14 mm
Data collection top
CCD area detector
diffractometer
2422 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
1977 reflections with I > 2σ(I)
Tmin = 0.679, Tmax = 0.746Rint = 0.026
5593 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.037H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.090Δρmax = 0.18 e Å3
S = 1.03Δρmin = 0.22 e Å3
2422 reflectionsAbsolute structure: Flack (1983), 989 Friedel pairs
133 parametersAbsolute structure parameter: 0.11 (11)
2 restraints
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
P10.37137 (10)0.30994 (5)0.07762 (2)0.03642 (15)
C10.2943 (4)0.3038 (3)0.16448 (10)0.0424 (5)
C20.4255 (5)0.3675 (3)0.21432 (11)0.0573 (7)
H2A0.55680.41240.20260.069*
C30.3614 (6)0.3644 (4)0.28125 (12)0.0756 (9)
H3A0.44950.40710.31430.091*
C40.1681 (7)0.2984 (5)0.29860 (14)0.0897 (11)
H4A0.12550.29620.34350.108*
C50.0382 (6)0.2362 (5)0.25059 (16)0.1031 (13)
H5A0.09310.19240.26300.124*
C60.0992 (5)0.2372 (4)0.18286 (13)0.0735 (9)
H6A0.00990.19360.15040.088*
C70.2817 (4)0.4866 (2)0.03997 (11)0.0433 (5)
H7A0.34590.49590.00450.052*
H7B0.12570.48270.03430.052*
C80.3389 (4)0.6269 (2)0.08058 (10)0.0439 (5)
H8A0.48840.61850.09520.053*
H8B0.24880.62940.12060.053*
C90.3113 (4)0.7760 (2)0.04301 (11)0.0387 (5)
O10.6226 (3)0.31246 (18)0.08088 (7)0.0472 (4)
H1A0.685 (4)0.323 (3)0.0452 (7)0.057*
O20.2784 (3)0.17650 (16)0.03892 (7)0.0491 (4)
O30.3148 (3)0.79083 (17)0.01724 (7)0.0476 (4)
O40.2882 (4)0.89173 (16)0.08613 (8)0.0615 (5)
H4B0.288 (5)0.9748 (18)0.0667 (13)0.074*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.0497 (3)0.0264 (2)0.0331 (2)0.0026 (3)0.0043 (3)0.0007 (2)
C10.0509 (13)0.0382 (10)0.0381 (10)0.0024 (13)0.0009 (10)0.0032 (9)
C20.0620 (19)0.0698 (16)0.0400 (12)0.0073 (14)0.0060 (11)0.0006 (11)
C30.092 (2)0.097 (2)0.0383 (12)0.004 (2)0.0095 (15)0.0004 (13)
C40.103 (3)0.122 (3)0.0436 (13)0.012 (3)0.0166 (17)0.0046 (17)
C50.081 (3)0.167 (4)0.0619 (18)0.029 (3)0.0227 (18)0.017 (2)
C60.066 (2)0.101 (2)0.0538 (14)0.0212 (19)0.0009 (14)0.0004 (15)
C70.0581 (15)0.0287 (9)0.0431 (11)0.0016 (11)0.0090 (11)0.0033 (9)
C80.0669 (16)0.0269 (8)0.0379 (10)0.0007 (11)0.0022 (12)0.0042 (9)
C90.0426 (13)0.0285 (10)0.0449 (11)0.0003 (10)0.0017 (10)0.0036 (8)
O10.0486 (9)0.0542 (8)0.0388 (7)0.0079 (10)0.0014 (8)0.0004 (8)
O20.0762 (12)0.0268 (7)0.0443 (8)0.0009 (8)0.0132 (8)0.0011 (6)
O30.0595 (11)0.0418 (8)0.0414 (7)0.0004 (8)0.0027 (7)0.0068 (6)
O40.1068 (16)0.0264 (7)0.0514 (9)0.0032 (9)0.0090 (10)0.0003 (7)
Geometric parameters (Å, º) top
P1—O21.5087 (15)C5—H5A0.9300
P1—O11.5527 (17)C6—H6A0.9300
P1—C11.789 (2)C7—C81.508 (3)
P1—C71.801 (2)C7—H7A0.9700
C1—C61.386 (4)C7—H7B0.9700
C1—C21.394 (3)C8—C91.510 (3)
C2—C31.386 (3)C8—H8A0.9700
C2—H2A0.9300C8—H8B0.9700
C3—C41.369 (5)C9—O31.203 (2)
C3—H3A0.9300C9—O41.331 (3)
C4—C51.358 (5)O1—H1A0.810 (10)
C4—H4A0.9300O4—H4B0.821 (10)
C5—C61.396 (4)
O2—P1—O1114.33 (10)C1—C6—C5119.4 (3)
O2—P1—C1111.47 (10)C1—C6—H6A120.3
O1—P1—C1103.07 (10)C5—C6—H6A120.3
O2—P1—C7109.47 (9)C8—C7—P1113.70 (15)
O1—P1—C7108.19 (12)C8—C7—H7A108.8
C1—P1—C7110.09 (11)P1—C7—H7A108.8
C6—C1—C2119.0 (2)C8—C7—H7B108.8
C6—C1—P1119.83 (18)P1—C7—H7B108.8
C2—C1—P1121.12 (19)H7A—C7—H7B107.7
C3—C2—C1120.4 (3)C7—C8—C9114.20 (17)
C3—C2—H2A119.8C7—C8—H8A108.7
C1—C2—H2A119.8C9—C8—H8A108.7
C4—C3—C2119.9 (3)C7—C8—H8B108.7
C4—C3—H3A120.1C9—C8—H8B108.7
C2—C3—H3A120.1H8A—C8—H8B107.6
C5—C4—C3120.4 (3)O3—C9—O4124.01 (19)
C5—C4—H4A119.8O3—C9—C8125.54 (19)
C3—C4—H4A119.8O4—C9—C8110.42 (17)
C4—C5—C6120.9 (3)P1—O1—H1A116.0 (19)
C4—C5—H5A119.6C9—O4—H4B112 (2)
C6—C5—H5A119.6
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O2i0.81 (1)1.77 (1)2.566 (2)169 (3)
O4—H4B···O2ii0.82 (1)1.85 (1)2.658 (2)169 (3)
Symmetry codes: (i) x+1/2, y+1/2, z; (ii) x, y+1, z.

Experimental details

(I)(II)
Crystal data
Chemical formulaC9H11O4PC9H11O4P
Mr214.15214.15
Crystal system, space groupOrthorhombic, P212121Orthorhombic, P212121
Temperature (K)296296
a, b, c (Å)5.4948 (1), 8.6830 (1), 21.3724 (4)6.1741 (15), 8.7308 (19), 19.844 (4)
V3)1019.71 (3)1069.7 (4)
Z44
Radiation typeMo KαMo Kα
µ (mm1)0.260.24
Crystal size (mm)0.30 × 0.20 × 0.100.34 × 0.16 × 0.14
Data collection
DiffractometerCCD area detector
diffractometer
CCD area detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2008)
Multi-scan
(SADABS; Bruker, 2008)
Tmin, Tmax0.673, 0.7460.679, 0.746
No. of measured, independent and
observed [I > 2σ(I)] reflections
5497, 2326, 2089 5593, 2422, 1977
Rint0.0270.026
(sin θ/λ)max1)0.6490.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.087, 1.05 0.037, 0.090, 1.03
No. of reflections23262422
No. of parameters133133
No. of restraints22
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.24, 0.240.18, 0.22
Absolute structureFlack (1983), 893 Friedel pairsFlack (1983), 989 Friedel pairs
Absolute structure parameter0.09 (10)0.11 (11)

Computer programs: SMART (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), SHELXTL (Bruker, 2008).

Selected bond lengths (Å) for (I) top
P1—O21.5010 (14)C9—O31.200 (3)
P1—O11.5605 (16)C9—O41.321 (3)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O2i0.814 (10)1.757 (10)2.5699 (18)177 (3)
O4—H4B···O2ii0.818 (10)1.903 (13)2.6925 (19)162 (3)
Symmetry codes: (i) x+1/2, y+3/2, z+1; (ii) x, y1, z.
Selected bond lengths (Å) for (II) top
P1—O21.5087 (15)C9—O31.203 (2)
P1—O11.5527 (17)C9—O41.331 (3)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O2i0.810 (10)1.767 (11)2.566 (2)169 (3)
O4—H4B···O2ii0.821 (10)1.847 (11)2.658 (2)169 (3)
Symmetry codes: (i) x+1/2, y+1/2, z; (ii) x, y+1, z.
 

Acknowledgements

This work was supported by the NNSF of China (grant No. 21061001), the NSF of Jiangxi Province (grant No. 2008GQH0013) and the NSF of Jiangxi Provincial Education Department (grant No. GJJ10714).

References

First citationBernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.  CrossRef CAS Web of Science
First citationBirum, G. H. & Jansen, R. F. (1978). US Patent No. 4 081 463.
First citationBrandenburg, K. (1999). DIAMOND. Version 2.1c. Crystal Impact GbR, Bonn, Germany.
First citationBruker (2008). SMART, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationFlack, H. D. (1983). Acta Cryst. A39, 876–881.  CrossRef CAS Web of Science IUCr Journals
First citationLevchik, S. V. & Weil, E. D. (2005). Polym. Int. 54, 11–35.  CrossRef CAS
First citationMidollini, S., Orlandini, A., Rosa, P. & Sorace, L. (2005). Inorg. Chem. 44, 2060–2066.  Web of Science CrossRef PubMed CAS
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals

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