Acidic and anionic forms of 1,3-cyclic dihy­droxy­acetone phosphate (cDHAP) dimethyl acetal

The six-membered cyclic phosphate diester, 5,5-dimeth­oxy-2-hydroxy-1,3,2-dioxaphospho­rinan-2-one, C₅H₁₁O₆P or (MeO)₂cDHAP, which is the dimethyl acetal of cyclic dihy­droxy­acetone phosphate (cDHAP), has been obtained in the form of two new cyclo­hexyl­ammonium (cha) salts, cyclohexylammonium 5,5-dimeth­oxy-2-oxo-1,3,2-dioxaphospho­rinan-2-ol­ate monohydrate, (cha)[(MeO)₂cDHAP]·H₂O or C₆H₁₄N⁺·C₅H₁₀O₆P^-·H₂O, and cyclohexylammonium 5,5-dimeth­oxy-2-oxo-1,3,2-dioxaphospho­rinan-2-olate, (cha)[(MeO)₂cDHAP] or C₆H₁₄N⁺·C₅H₁₀O₆P^-, as well as in the form of the anhydrous free acid, (MeO)₂cDHAP. It is shown that protonation of the cyclic phosphate group influences the chair conformation of the P/O/C/C/C/O 1,3,2-dioxaphosphorinane ring, and that differences in the ring conformation correlate with different deformations observed in the ionized and protonated phosphate groups. The ring is more evenly puckered in the anions, in contrast with the flattening observed in the structure of the free acid.

S1. Comment

Six-membered cyclic phosphate esters are constituents of a number of biologically important molecules such as 3':5'-cyclic nucleotides, e.g. cAMP. Dihydroxyacetone phosphate (DHAP), the linear form of cDHAP, is one of the most important biochemical intermediates and of high importance for all living cells [for a review, see Ślepokura & Lis (2010)]. The cyclic form, cDHAP, became interesting recently as a new molecule of biological importance (Goswami & Adak, 2002). Occurring in living organisms, small cyclic phosphates of cDHAP-like structure began to attract attention when their biological activity as signalling molecules had been suggested (Shinitzky et al., 2000). Cyclic glycerophosphates can be formed by enzymatic degradation of phospholipids, e.g. 1,3-cyclic glycerophosphate is naturally formed by the action of phospholipase C on phosphatidyl glycerol.

Only five of over 160 hits for cyclic phosphates with six-membered rings deposited with the Cambridge Structural Database (CSD, Version 5.32; Allen, 2002) bear the H atom at the exocyclic O atom. We will discuss just three of the reported protonated cyclic phosphates [CSD refcodes ETPHOS (Gerlt et al., 1980), KADPUA (Johnson et al., 1989) and SEZRUL (Samas et al., 2007)], because the remaining two have high R factors and low bond precision, and the positions of the H atoms were not determined. The present paper concerns the synthesis and crystal structure of 5,5-dimethoxy-2-oxo-1,3,2-dioxaphosphorinane-2-ol, the dimethyl acetal of cyclic dihydroxyacetone phosphate, (MeO)₂cDHAP, in the form of two crystalline cyclohexylammonium (cha) salts, (cha)[(MeO)₂cDHAP].H₂O, (5i) [polymorphous form of (5b)], and anhydrous (cha)[(MeO)₂cDHAP], (5j), as well as in the form of the acid, (MeO)₂cDHAP, (5k).

Previously, we have reported the synthesis and structural investigations of nine different salts of (MeO)₂cDHAP with both organic and inorganic cations [(5a)–(5e) and (5e')–(5h); Ślepokura, 2008], along with its phenyl derivative, (MeO)₂cDHAP(Ph) [(4); Ślepokura & Lis, 2004b]. Among these, the structures of two cha salts and the acid in the form of an oxonium salt were presented: (cha)[(MeO)₂cDHAP].3H₂O, (5a), (cha)[(MeO)₂cDHAP].H₂O, (5b), and (H₅O₂)[(MeO)₂cDHAP], (5c). Here, the conformation of the P/O/C/C/C/O 1,3,2-dioxaphosphorinane ring in (5i)–(5k) will be compared with that in the previously reported (MeO)₂cDHAP salts (5a)–(5h), as well as with that of the phenyl derivative, (4). In addition, the arrangements in the crystal structures will be presented, with an emphasis on the comparison of the crystal packing diagrams of two polymorphous forms of (cha)[(MeO)₂cDHAP].H₂O, monoclinic (5b) (Ślepokura, 2008) and triclinic (5i) (this work).

The overall structures of the (MeO)₂cDHAP anions in compounds (5i) and (5j) bear great similarities with each other and with the previously reported anions in (5a)–(5h) (Ślepokura, 2008). The six-membered 1,3,2-dioxaphosphorinane ring adopts a chair (C) conformation only slightly distorted towards an envelope (E), which is reflected in the values of the dihedral angles between the least-squares plane through the four central atoms of the ring (O1/O3/C1/C3) and the O1/P/O3 and C1/C2/C3 planes (ϕ₁ and ϕ₂), as well as in the Cremer–Pople puckering parameters (Cremer & Pople, 1975; see Table 1). The values of |ϕ₂ - ϕ₁| for (5a)–(5j) clearly show that the flattening of the dioxaphosphorinane ring at the P atom is negligible in the (MeO)₂cDHAP anions and that the conformation of the rings is close to an ideal chair.

Selected geometric parameters for (5i)–(5k) are given in Table 2. The deformation of the phosphate group from the ideal tetrahedral shape, which was been observed previously in (5a)–(5h), is also observed in (5i) and (5j). The deformation of the ionized cyclic phosphate is especially seen in the endocyclic O1—P1—O3 and exocyclic O4—P1—O5 bond angles, which are, respectively, the smallest (about 102° on average [Vague. Please give either arithmetic mean, with s.u., or actual smallest value]) and the largest [119.97 (5)°]. The values of the endo- and exocyclic O—P—O angles correlate with the respective P—O bond lengths. In all the known (MeO)₂cDHAP anions, the P—O_endo bonds are about 1.6 Å, more than 0.1 Å longer than the P—O_exo bonds.

A completely different deformation reveals the protonated phosphate group of the (MeO)₂cDHAP molecule in (5k). The hydroxyl group in (5k) adopts an axial position similar to the previously reported structures ETPHOS, KADPUA and SEZRUL. As can be seen by the P—O_endo, P—O(H) and P═O distances, the protonation of the phosphate group affects to a larger extent the length of the P—O_endo bonds (becoming on average 0.03 Å shorter than in the anion) than that of the exocyclic equatorially oriented P1═O5 bond [becoming formally double, but only slightly shortened compared with the P—O_exo bonds in the (MeO)₂cDHAP anions]. Within the O—P—O angles in (5k), the exocyclic O4—P1—O5 angle is the largest [115.13 (6)°], although none of them is distinctly smaller than the others. Instead, in the protonated phosphate group, three lower values for the angles involving endocyclic O atoms and three higher values for the angles involving P═O bonds are observed. It may be noted that the geometry of the phosphate group in (5k) is similar to that observed in the phenyl derivative, (4). These differences in the deformations observed in the ionized and protonated phosphate groups are accompanied by different distortions of the P/O/C/C/C/O rings. In contrast with the almost ideal chair conformation in the (MeO)₂cDHAP anions of (5a)–(5j), the ring in acidic (5k) is significantly flattened at the P atom (see Table 1), which is comparable with the conformations observed in phenyl derivative (4) and the two acidic cyclic phosphates, ETPHOS and SEZRUL.

It has been shown that the acetal group in the analogous linear compounds, (MeO)₂DHAP and (MeO)₂DHAP(Ph) [(6a)–(6e) [Two structures given but five compounds implied - please clarify]; Ślepokura & Lis, 2006], and in the unphosphorylated species (MeO)₂DHA [(3); Ślepokura & Lis, 2004a], seems to be very rigid, and its conformation is independent of phosphorylation, the ionization state of the inserted phosphate group, or additional substitution. It is likely that such a conformation is determined and stabilized by the generalized anomeric effect. The acetal group in the cyclic compounds (5i)–(5k), as in (4) and (5a)–(5h), reveals some common features with linear (3) and (6a)–(6e): the relevant C4—O21—C2—O22 and C5—O22—C2—O21 torsion angles show a synclinal orientation of the methyl groups (C4 and C5) in relation to the acetal atoms O22 and O21. Similarly, as was observed in the structures of (3), (4), (5a)–(5h) and (6a)–(6e), two of the angles with their vertex on acetal atom C2 are much smaller than the others (Table 2).

The cations and anions in (5i) and (5j) are arranged in a way that leads to the aggregation of their hydrophilic and hydrophobic groups into distinct regions in the crystals. The packing schemes of (5i) and (5j) are dominated by N⁺—H···O^- hydrogen bonds, but in the hydrated salt (5i), as in (5a) and (5b) (Ślepokura, 2008), an additional important role is played by contacts of N⁺—H···O_w and O_w—H···O^- type (O_w is the water O atom). Geometric parameters of hydrogen bonds and close contacts are given in Table 3.

The crystal structure of the monohydrated salt (5i) has a layered architecture (Fig. 2), similar to that observed in the other hydrated cha salts, (5a) and (5b). Each cha cation is directly linked by two charge–assisted N—H···O hydrogen bonds to two adjacent (MeO)₂cDHAP anions, resulting in centrosymmetric R₄²(8) motifs (Fig. 3) [see Bernstein et al. (1995) for graph-set notation]. The same cation is linked to two additional anions via water-mediated hydrogen bonds. Thus, another type of ring is formed, R₆⁶(16), this time also involving water molecules in addition to cha cations and (MeO)₂cDHAP anions. Another R₄²(8) ring results from the centrosymmetric O_w—H···O^- bonds between two water molecules and two anions. The sequence of these three rings generates double layers parallel to the (001) plane, as shown in Figs. 2 and 3. The same types of interaction, namely cation···anion, cation···H₂O···anion and anion···H₂O···anion, were also observed in the polymorphous salt (5b). However, as shown in Fig. 3, the construction of the layers observed in (5b) is different: three unique rings generate the layer, R₄⁴(12) involving two cations and two anions, R₅⁴(12) involving one cation, two anions and two water molecules, and R₆⁴(12) involving two cations, two anions and two water molecules.

The arrangement of organic ions in the crystal structuree of the anhydrous salt (5j) is different. Each cha cation is linked directly by three N⁺—H···O^- hydrogen bonds to three adjacent (MeO)₂cDHAP anions. These interactions generate R₄³(10) rings forming ribbons with ladder-type hydrogen bonding along the a axis, as shown in Fig. 4.

The crystal packing of (5k) is determined by the strong centrosymmetric almost linear O—H···O hydrogen bonds formed by the phosphate groups of two adjacent (MeO)₂cDHAP molecules. In this way, centrosymmetric molecular dimers are formed (Fig. 5), giving rise to R₂²(8) rings. Adjacent dimers interact with each other via weak C—H···O contacts, as shown in Fig. 5, resulting in ribbons along [101].

In conclusion, we have shown that protonation of the cyclic phosphate group influences the conformation of the 1,3,2-dioxaphosphorinane ring, causing its flattening, i.e. deformation from the ideal chair towards an envelope. In other words, the ring is more evenly puckered in compounds with an ionized phosphate group than in the acid molecule. We have also demonstrated that differences in the ring conformation correlate with different deformations observed in the ionized and protonated phosphate groups. Some common features for analogous protonated and esterified compounds have been revealed. In addition, we have shown that the arrangement of the ions in the crystal structures of four different (cha)[(MeO)₂cDHAP] salts results in different crystal architectures, depending on water content, and gives rise to layers in hydrated (5a), (5b) and (5i) and to ribbons in anhydrous (5j). Furthermore, a comparison of the layer constructions observed in monoclinic and triclinic (cha)[(MeO)₂cDHAP].H₂O has been reported.

[As so many compounds are cited for comparison, it would be helpful for the reader if a second scheme were provided illustrating these. Please consider providing such an additional scheme]

Related literature

For related literature, see: Allen (2002); Bernstein et al. (1995); Cremer & Pople (1975); Gerlt et al. (1980); Goswami & Adak (2002); Johnson et al. (1989); Samas et al. (2007); Shinitzky et al. (2000); Ślepokura (2008); Ślepokura & Lis (2004a, 2004b, 2006, 2010).

S2. Experimental

The cyclohexylammonium salt of (MeO)₂cDHAP was obtained by isolation of an intermediate in the basic hydrolysis of the cyclic triester derivative, using a method described previously (Ślepokura, 2008). Excess cyclohexylamine was removed by washing the crude product with diethyl ether. Concentration of the resulting mixture under vacuum and then under a nitrogen stream at room temperature gave two kinds of crystals: small plates of (5j) and needles of the monohydrated monoclinic form described previously, (5b). Recrystallization of (5b) from water at room temperature resulted in large plates of its triclinic form, (5i).

Crystals of (MeO)₂cDHAP, (5k), were grown from an acidic solution prepared as follows. The cyclohexylammonium salt of (MeO)₂cDHAP (250 mg dissolved in a minimal quantity of water) was passed through an ion-exchange column (Dowex 50-H⁺). The acidic solution was stirred at 313 K for 3.5 h. Subsequent evaporation of the solvent under a nitrogen stream yielded large blocks of (5k).

S3. Refinement

All H atoms were found in difference Fourier maps. In the final refinement cycles, water H atoms in (5i) were refined with U_iso(H) = 1.5U_eq(O). All remaining H atoms were treated as riding atoms, with C—H = 0.98–1.00 Å, N—H = 0.91 Å and O—H = 0.84 Å, and with U_iso(H) = 1.2U_eq(C) for CH or CH₂, or 1.5U_eq(C,N,O) for CH₃, NH₃ or OH.

Computing details

For all compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Bruker, 1998); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. Views of (5i) (top), (5j) (middle) and (5k) (bottom), showing the atom numbering schemes and the symmetry–independent N^+—H···O^- and O—H···O^- hydrogen bonds (dashed lines). Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A double layer parallel to the (001) plane in (5i), built up from (MeO)2cDHAP anions (solid lines), cha cations (thin lines) and water molecules joined by N—H···O and O—H···O hydrogen bonds and C—H···O contacts (dashed lines). H atoms not involved in hydrogen bonding have been omitted for clarity. [Symmetry codes: (i) -x, -y, -z + 1; (iii) -x + 1, -y + 1, -z + 1.]
	Fig. 3. A comparison of the layer constructions observed in two polymorphous forms of (cha)[(MeO)2cDHAP].H2O, monoclinic (5b) (top; Ślepokura, 2008) and triclinic (5i) (bottom; this work). Phosphate and ammonium groups represent the anions and cations, respectively. N^+—H···O^-/Ow and Ow—H···O^- hydrogen bonds are shown as dashed lines (blue and red, respectively, in the electronic version of the journal).
	Fig. 4. The polymeric ribbons with ladder-type hydrogen bonding formed in (5j) by the (MeO)2cDHAP anions (solid lines) and cha cations (open lines) along the a axis. N^+—H···O^- hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity. [Symmetry codes: (ii) x - 1, y, z; (v) x - 1/2, -y + 1/2, -z + 1.]
	Fig. 5. The ribbons in (5k) resulting from centrosymmetric molecular dimers [with R2^2(8) rings formed by the (MeO)2cDHAP molecules joined via strong O—H···O bonds; dashed lines (red in the electronic version of the journal)] linked through C—H···O contacts; black dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity. [Symmetry codes: (iii) -x + 1, -y + 1, -z + 1; (x) -x + 2, -y + 1, -z.]

(5i) cyclohexylammonium 5,5-dimethoxy-2-oxo-1,3,2-dioxaphosphinane-2-olate monohydrate

Crystal data

C6H14N^+·C5H10O6P^−·H2O	Z = 2
Mr = 315.30	F(000) = 340
Triclinic, P1	Dx = 1.307 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.064 (2) Å	Cell parameters from 8262 reflections
b = 8.475 (4) Å	θ = 2.9–36.9°
c = 13.966 (6) Å	µ = 0.20 mm^−1
α = 102.48 (3)°	T = 100 K
β = 92.58 (3)°	Plate, colourless
γ = 99.96 (3)°	0.37 × 0.23 × 0.04 mm
V = 801.1 (6) Å^3

Data collection

Kuma KM4CCD κ-geometry diffractometer with a Sapphire CCD camera	4519 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3579 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
ω scans	θmax = 30.0°, θmin = 2.9°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −9→8
Tmin = 0.913, Tmax = 1.000	k = −11→11
13552 measured reflections	l = −19→19

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.034	Hydrogen site location: difference Fourier map
wR(F^2) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0606P)^2] where P = (Fo^2 + 2Fc^2)/3
4519 reflections	(Δ/σ)max = 0.001
190 parameters	Δρmax = 0.49 e Å^−3
0 restraints	Δρmin = −0.18 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
P1	0.31711 (4)	0.28342 (3)	0.66395 (2)	0.01842 (8)
O1	0.26362 (10)	0.33074 (9)	0.77583 (5)	0.01893 (16)
O21	0.71792 (11)	0.38258 (10)	0.91694 (6)	0.02296 (17)
O22	0.48544 (11)	0.14207 (9)	0.86906 (6)	0.02146 (17)
O3	0.47730 (11)	0.17337 (9)	0.67189 (6)	0.02163 (17)
O4	0.40440 (11)	0.43564 (9)	0.63354 (6)	0.02284 (17)
O5	0.14713 (12)	0.17229 (10)	0.60536 (6)	0.02596 (18)
C1	0.42506 (14)	0.40898 (13)	0.84599 (8)	0.0189 (2)
H1A	0.3798	0.4392	0.9124	0.023*
H1B	0.4901	0.5109	0.8286	0.023*
C2	0.56685 (14)	0.29200 (12)	0.84642 (8)	0.0178 (2)
C3	0.63690 (15)	0.24372 (14)	0.74398 (8)	0.0217 (2)
H3A	0.7118	0.3423	0.7268	0.026*
H3B	0.7230	0.1632	0.7442	0.026*
C4	0.87607 (16)	0.29994 (16)	0.92631 (9)	0.0291 (3)
H4A	0.8263	0.1847	0.9266	0.044*
H4B	0.9550	0.3536	0.9880	0.044*
H4C	0.9551	0.3050	0.8708	0.044*
C5	0.38159 (17)	0.15534 (15)	0.95452 (9)	0.0275 (2)
H5A	0.4607	0.2337	1.0098	0.041*
H5B	0.3505	0.0474	0.9707	0.041*
H5C	0.2620	0.1941	0.9420	0.041*
N1	−0.10007 (13)	0.17323 (11)	0.44695 (7)	0.02130 (19)
H1N	−0.0066	0.1884	0.4968	0.032*
H2N	−0.1497	0.0640	0.4257	0.032*
H3N	−0.1956	0.2278	0.4689	0.032*
C11	−0.01544 (15)	0.23810 (13)	0.36398 (8)	0.0201 (2)
H11	0.0384	0.3581	0.3883	0.024*
C12	0.14708 (16)	0.15079 (15)	0.32848 (9)	0.0254 (2)
H12A	0.0973	0.0310	0.3071	0.030*
H12B	0.2484	0.1693	0.3831	0.030*
C13	0.23337 (17)	0.21488 (16)	0.24288 (10)	0.0299 (3)
H13A	0.2968	0.3316	0.2666	0.036*
H13B	0.3330	0.1514	0.2176	0.036*
C14	0.08025 (18)	0.20070 (17)	0.15982 (9)	0.0311 (3)
H14A	0.0302	0.0830	0.1296	0.037*
H14B	0.1391	0.2526	0.1085	0.037*
C15	−0.08662 (18)	0.28347 (16)	0.19673 (9)	0.0294 (3)
H15A	−0.0399	0.4036	0.2189	0.035*
H15B	−0.1881	0.2642	0.1421	0.035*
C16	−0.17213 (16)	0.21707 (14)	0.28154 (8)	0.0224 (2)
H16A	−0.2749	0.2770	0.3065	0.027*
H16B	−0.2303	0.0991	0.2581	0.027*
O1W	0.70098 (13)	0.41696 (11)	0.51321 (7)	0.02652 (19)
H1W	0.608 (2)	0.419 (2)	0.5482 (13)	0.040*
H2W	0.674 (2)	0.460 (2)	0.4674 (13)	0.040*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.02331 (14)	0.01617 (14)	0.01635 (14)	0.00346 (10)	0.00116 (10)	0.00522 (9)
O1	0.0186 (3)	0.0210 (4)	0.0179 (4)	0.0041 (3)	0.0022 (3)	0.0057 (3)
O21	0.0208 (4)	0.0236 (4)	0.0225 (4)	0.0017 (3)	−0.0031 (3)	0.0039 (3)
O22	0.0250 (4)	0.0182 (4)	0.0220 (4)	0.0031 (3)	0.0028 (3)	0.0070 (3)
O3	0.0283 (4)	0.0197 (4)	0.0170 (4)	0.0085 (3)	0.0001 (3)	0.0018 (3)
O4	0.0294 (4)	0.0194 (4)	0.0220 (4)	0.0046 (3)	0.0058 (3)	0.0089 (3)
O5	0.0304 (4)	0.0223 (4)	0.0234 (4)	0.0005 (3)	−0.0064 (3)	0.0066 (3)
C1	0.0215 (5)	0.0184 (5)	0.0166 (5)	0.0043 (4)	0.0020 (4)	0.0027 (4)
C2	0.0187 (4)	0.0174 (5)	0.0171 (5)	0.0027 (4)	0.0007 (4)	0.0041 (4)
C3	0.0223 (5)	0.0246 (5)	0.0200 (5)	0.0089 (4)	0.0036 (4)	0.0053 (4)
C4	0.0215 (5)	0.0382 (7)	0.0294 (6)	0.0063 (5)	−0.0018 (5)	0.0117 (5)
C5	0.0295 (6)	0.0298 (6)	0.0259 (6)	0.0036 (5)	0.0060 (5)	0.0132 (5)
N1	0.0241 (4)	0.0205 (4)	0.0200 (4)	0.0058 (3)	−0.0006 (4)	0.0053 (3)
C11	0.0221 (5)	0.0174 (5)	0.0205 (5)	0.0030 (4)	0.0000 (4)	0.0048 (4)
C12	0.0230 (5)	0.0268 (6)	0.0289 (6)	0.0081 (4)	0.0020 (4)	0.0090 (5)
C13	0.0254 (6)	0.0312 (6)	0.0346 (7)	0.0049 (5)	0.0076 (5)	0.0102 (5)
C14	0.0334 (6)	0.0374 (7)	0.0255 (6)	0.0104 (5)	0.0080 (5)	0.0095 (5)
C15	0.0352 (6)	0.0343 (6)	0.0236 (6)	0.0131 (5)	0.0041 (5)	0.0114 (5)
C16	0.0235 (5)	0.0238 (5)	0.0205 (5)	0.0069 (4)	0.0005 (4)	0.0048 (4)
O1W	0.0280 (4)	0.0311 (5)	0.0267 (4)	0.0128 (3)	0.0079 (4)	0.0134 (4)

Geometric parameters (Å, º)

P1—O5	1.4784 (11)	N1—H1N	0.91
P1—O4	1.4866 (10)	N1—H2N	0.91
P1—O3	1.6004 (10)	N1—H3N	0.91
P1—O1	1.6061 (10)	C11—C12	1.5158 (16)
O1—C1	1.4343 (14)	C11—C16	1.5201 (16)
O21—C2	1.4118 (13)	C11—H11	1.00
O21—C4	1.4328 (15)	C12—C13	1.5255 (18)
O22—C2	1.4080 (13)	C12—H12A	0.99
O22—C5	1.4229 (15)	C12—H12B	0.99
O3—C3	1.4304 (14)	C13—C14	1.5205 (18)
C1—C2	1.5270 (15)	C13—H13A	0.99
C1—H1A	0.99	C13—H13B	0.99
C1—H1B	0.99	C14—C15	1.5270 (18)
C2—C3	1.5297 (16)	C14—H14A	0.99
C3—H3A	0.99	C14—H14B	0.99
C3—H3B	0.99	C15—C16	1.5230 (17)
C4—H4A	0.98	C15—H15A	0.99
C4—H4B	0.98	C15—H15B	0.99
C4—H4C	0.98	C16—H16A	0.99
C5—H5A	0.98	C16—H16B	0.99
C5—H5B	0.98	O1W—H1W	0.83 (2)
C5—H5C	0.98	O1W—H2W	0.83 (2)
N1—C11	1.4921 (15)
O5—P1—O4	119.97 (5)	H1N—N1—H2N	109.5
O5—P1—O3	106.58 (6)	C11—N1—H3N	109.5
O4—P1—O3	109.74 (5)	H1N—N1—H3N	109.5
O5—P1—O1	107.69 (5)	H2N—N1—H3N	109.5
O4—P1—O1	109.24 (5)	N1—C11—C12	109.86 (9)
O3—P1—O1	102.13 (5)	N1—C11—C16	109.67 (9)
C1—O1—P1	114.57 (7)	C12—C11—C16	111.46 (10)
C2—O21—C4	114.41 (9)	N1—C11—H11	108.6
C2—O22—C5	115.66 (9)	C12—C11—H11	108.6
C3—O3—P1	116.69 (7)	C16—C11—H11	108.6
O1—C1—C2	109.64 (9)	C11—C12—C13	110.32 (10)
O1—C1—H1A	109.7	C11—C12—H12A	109.6
C2—C1—H1A	109.7	C13—C12—H12A	109.6
O1—C1—H1B	109.7	C11—C12—H12B	109.6
C2—C1—H1B	109.7	C13—C12—H12B	109.6
H1A—C1—H1B	108.2	H12A—C12—H12B	108.1
O22—C2—O21	111.81 (9)	C14—C13—C12	111.64 (10)
O22—C2—C1	113.65 (9)	C14—C13—H13A	109.3
O21—C2—C1	104.21 (9)	C12—C13—H13A	109.3
O22—C2—C3	105.01 (9)	C14—C13—H13B	109.3
O21—C2—C3	112.14 (9)	C12—C13—H13B	109.3
C1—C2—C3	110.21 (9)	H13A—C13—H13B	108.0
O3—C3—C2	110.72 (9)	C13—C14—C15	111.53 (11)
O3—C3—H3A	109.5	C13—C14—H14A	109.3
C2—C3—H3A	109.5	C15—C14—H14A	109.3
O3—C3—H3B	109.5	C13—C14—H14B	109.3
C2—C3—H3B	109.5	C15—C14—H14B	109.3
H3A—C3—H3B	108.1	H14A—C14—H14B	108.0
O21—C4—H4A	109.5	C16—C15—C14	111.35 (10)
O21—C4—H4B	109.5	C16—C15—H15A	109.4
H4A—C4—H4B	109.5	C14—C15—H15A	109.4
O21—C4—H4C	109.5	C16—C15—H15B	109.4
H4A—C4—H4C	109.5	C14—C15—H15B	109.4
H4B—C4—H4C	109.5	H15A—C15—H15B	108.0
O22—C5—H5A	109.5	C11—C16—C15	109.89 (10)
O22—C5—H5B	109.5	C11—C16—H16A	109.7
H5A—C5—H5B	109.5	C15—C16—H16A	109.7
O22—C5—H5C	109.5	C11—C16—H16B	109.7
H5A—C5—H5C	109.5	C15—C16—H16B	109.7
H5B—C5—H5C	109.5	H16A—C16—H16B	108.2
C11—N1—H1N	109.5	H1W—O1W—H2W	106.0 (15)
C11—N1—H2N	109.5
O5—P1—O1—C1	167.33 (7)	O1—C1—C2—O21	179.58 (7)
O4—P1—O1—C1	−60.85 (8)	O1—C1—C2—C3	59.08 (11)
O3—P1—O1—C1	55.31 (8)	P1—O3—C3—C2	56.68 (10)
O5—P1—O3—C3	−165.65 (7)	O22—C2—C3—O3	66.71 (11)
O4—P1—O3—C3	63.00 (9)	O21—C2—C3—O3	−171.66 (8)
O1—P1—O3—C3	−52.80 (8)	C1—C2—C3—O3	−56.06 (11)
P1—O1—C1—C2	−62.20 (9)	N1—C11—C12—C13	179.41 (9)
C5—O22—C2—O21	67.92 (11)	C16—C11—C12—C13	57.64 (13)
C5—O22—C2—C1	−49.72 (12)	C11—C12—C13—C14	−55.09 (14)
C5—O22—C2—C3	−170.24 (9)	C12—C13—C14—C15	53.82 (15)
C4—O21—C2—O22	60.27 (12)	C13—C14—C15—C16	−54.52 (14)
C4—O21—C2—C1	−176.57 (8)	N1—C11—C16—C15	179.87 (9)
C4—O21—C2—C3	−57.38 (12)	C12—C11—C16—C15	−58.26 (13)
O1—C1—C2—O22	−58.46 (11)	C14—C15—C16—C11	56.21 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O5	0.91	1.87	2.758 (2)	166
N1—H2N···O5^i	0.91	1.96	2.817 (2)	157
N1—H3N···O1W^ii	0.91	1.87	2.719 (2)	154
O1W—H1W···O4	0.83 (2)	1.92 (2)	2.749 (2)	176 (2)
O1W—H2W···O4^iii	0.83 (2)	1.93 (2)	2.758 (2)	176 (2)
C4—H4C···O1^iv	0.98	2.60	3.534 (2)	159
C11—H11···O1W^iii	1.00	2.52	3.416 (2)	149

Symmetry codes: (i) −x, −y, −z+1; (ii) x−1, y, z; (iii) −x+1, −y+1, −z+1; (iv) x+1, y, z.

(5j) cyclohexylammonium 5,5-dimethoxy-2-oxo-1,3,2-dioxaphosphinane-2-olate

Crystal data

C6H14N^+·C5H10O6P^−	F(000) = 640
Mr = 297.28	Dx = 1.336 Mg m^−3
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: P 2ac 2ab	Cell parameters from 5357 reflections
a = 6.678 (2) Å	θ = 3.5–76.4°
b = 8.877 (2) Å	µ = 1.86 mm^−1
c = 24.930 (6) Å	T = 120 K
V = 1477.9 (7) Å^3	Plate, colourless
Z = 4	0.13 × 0.08 × 0.01 mm

Data collection

Oxford Diffraction Xcalibur PX κ-geometry diffractometer with an Onyx CCD camera	2803 independent reflections
Radiation source: Enhance (Cu) X-ray Source	1876 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.062
ω and ϕ scans	θmax = 76.2°, θmin = 3.6°
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2009)	h = −7→4
Tmin = 0.832, Tmax = 0.978	k = −10→9
11210 measured reflections	l = −27→30

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	H-atom parameters constrained
wR(F^2) = 0.060	w = 1/[σ^2(Fo^2) + (0.012P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
2803 reflections	Δρmax = 0.21 e Å^−3
175 parameters	Δρmin = −0.21 e Å^−3
0 restraints	Absolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.03 (3)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
P1	0.42727 (10)	0.14314 (8)	0.39119 (3)	0.03661 (17)
O1	0.5282 (2)	0.00090 (19)	0.36315 (7)	0.0389 (5)
O21	0.9026 (3)	0.1971 (2)	0.28006 (8)	0.0582 (6)
O22	0.5991 (3)	0.0871 (2)	0.25368 (8)	0.0491 (5)
O3	0.4266 (3)	0.26355 (19)	0.34337 (7)	0.0423 (5)
O4	0.5587 (2)	0.19807 (18)	0.43506 (7)	0.0395 (5)
O5	0.2177 (2)	0.1067 (2)	0.40475 (8)	0.0434 (5)
C1	0.7213 (4)	0.0277 (4)	0.33878 (12)	0.0443 (8)
H1A	0.7701	−0.0666	0.3221	0.053*
H1B	0.8183	0.0577	0.3669	0.053*
C2	0.7101 (4)	0.1497 (4)	0.29668 (12)	0.0436 (7)
C3	0.6159 (4)	0.2918 (3)	0.31896 (12)	0.0453 (8)
H3A	0.7072	0.3368	0.3458	0.054*
H3B	0.5984	0.3656	0.2895	0.054*
C4	1.0310 (5)	0.0786 (4)	0.26128 (16)	0.0854 (13)
H4A	1.0823	0.0215	0.2920	0.128*
H4B	1.1433	0.1222	0.2413	0.128*
H4C	0.9549	0.0112	0.2377	0.128*
C5	0.5618 (5)	0.1872 (4)	0.20980 (12)	0.0677 (10)
H5A	0.4483	0.2528	0.2185	0.102*
H5B	0.5305	0.1284	0.1776	0.102*
H5C	0.6810	0.2489	0.2032	0.102*
N1	−0.0464 (3)	0.2891 (2)	0.45634 (8)	0.0373 (6)
H1N	0.0476	0.2265	0.4421	0.056*
H2N	−0.1707	0.2523	0.4491	0.056*
H3N	−0.0290	0.2952	0.4925	0.056*
C11	−0.0251 (3)	0.4432 (3)	0.43204 (11)	0.0375 (7)
H11	−0.0191	0.4319	0.3922	0.045*
C12	0.1692 (4)	0.5161 (3)	0.45073 (12)	0.0446 (8)
H12A	0.1689	0.5252	0.4903	0.054*
H12B	0.2844	0.4525	0.4402	0.054*
C13	0.1893 (4)	0.6714 (3)	0.42545 (13)	0.0556 (9)
H13A	0.3134	0.7200	0.4386	0.067*
H13B	0.2002	0.6608	0.3860	0.067*
C14	0.0112 (4)	0.7704 (3)	0.43882 (14)	0.0564 (9)
H14A	0.0253	0.8688	0.4205	0.068*
H14B	0.0070	0.7890	0.4780	0.068*
C15	−0.1834 (4)	0.6941 (3)	0.42093 (12)	0.0520 (9)
H15A	−0.2989	0.7573	0.4316	0.062*
H15B	−0.1844	0.6850	0.3814	0.062*
C16	−0.2043 (4)	0.5397 (3)	0.44568 (12)	0.0415 (8)
H16A	−0.3277	0.4909	0.4321	0.050*
H16B	−0.2160	0.5493	0.4851	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0279 (4)	0.0353 (4)	0.0466 (4)	−0.0009 (3)	0.0027 (4)	−0.0012 (4)
O1	0.0306 (10)	0.0353 (10)	0.0510 (12)	−0.0012 (9)	0.0049 (9)	−0.0003 (9)
O21	0.0333 (11)	0.0741 (16)	0.0670 (15)	−0.0049 (11)	0.0104 (11)	0.0037 (12)
O22	0.0445 (11)	0.0573 (14)	0.0455 (13)	−0.0017 (11)	−0.0038 (10)	−0.0023 (10)
O3	0.0337 (11)	0.0397 (12)	0.0536 (13)	0.0036 (10)	0.0055 (10)	0.0057 (9)
O4	0.0282 (10)	0.0442 (11)	0.0461 (11)	−0.0005 (10)	0.0043 (10)	−0.0025 (9)
O5	0.0232 (11)	0.0499 (13)	0.0571 (14)	−0.0063 (8)	0.0060 (9)	−0.0037 (10)
C1	0.0330 (18)	0.051 (2)	0.049 (2)	0.0075 (14)	0.0047 (14)	−0.0031 (15)
C2	0.0328 (17)	0.053 (2)	0.0445 (19)	−0.0048 (16)	0.0050 (14)	−0.0006 (17)
C3	0.047 (2)	0.0434 (18)	0.0458 (18)	−0.0053 (15)	−0.0004 (15)	0.0054 (15)
C4	0.047 (2)	0.110 (3)	0.100 (3)	0.014 (2)	0.033 (2)	−0.002 (2)
C5	0.068 (2)	0.088 (3)	0.0474 (19)	−0.008 (2)	−0.010 (2)	0.0130 (18)
N1	0.0227 (12)	0.0419 (13)	0.0474 (14)	0.0011 (11)	0.0004 (11)	−0.0027 (11)
C11	0.0236 (16)	0.0429 (18)	0.0459 (18)	−0.0046 (13)	0.0014 (13)	0.0022 (14)
C12	0.0269 (15)	0.048 (2)	0.059 (2)	−0.0053 (15)	0.0025 (15)	0.0003 (16)
C13	0.0323 (18)	0.064 (2)	0.070 (2)	−0.0168 (17)	0.0000 (16)	0.0104 (19)
C14	0.0440 (19)	0.0425 (19)	0.083 (2)	−0.0116 (15)	−0.0130 (17)	0.0146 (17)
C15	0.0382 (18)	0.0432 (19)	0.074 (3)	−0.0035 (16)	−0.0101 (17)	0.0094 (17)
C16	0.0259 (16)	0.0391 (18)	0.060 (2)	−0.0027 (14)	−0.0004 (15)	−0.0011 (16)

Geometric parameters (Å, º)

P1—O5	1.4753 (18)	N1—C11	1.503 (3)
P1—O4	1.4846 (18)	N1—H1N	0.9100
P1—O1	1.5929 (18)	N1—H2N	0.9100
P1—O3	1.6013 (18)	N1—H3N	0.9100
O1—C1	1.445 (3)	C11—C16	1.510 (3)
O21—C2	1.415 (3)	C11—C12	1.523 (3)
O21—C4	1.436 (4)	C11—H11	1.0000
O22—C2	1.417 (3)	C12—C13	1.522 (4)
O22—C5	1.431 (3)	C12—H12A	0.9900
O3—C3	1.425 (3)	C12—H12B	0.9900
C1—C2	1.510 (4)	C13—C14	1.516 (4)
C1—H1A	0.9900	C13—H13A	0.9900
C1—H1B	0.9900	C13—H13B	0.9900
C2—C3	1.515 (4)	C14—C15	1.532 (4)
C3—H3A	0.9900	C14—H14A	0.9900
C3—H3B	0.9900	C14—H14B	0.9900
C4—H4A	0.9800	C15—C16	1.510 (3)
C4—H4B	0.9800	C15—H15A	0.9900
C4—H4C	0.9800	C15—H15B	0.9900
C5—H5A	0.9800	C16—H16A	0.9900
C5—H5B	0.9800	C16—H16B	0.9900
C5—H5C	0.9800
O5—P1—O4	117.64 (11)	C11—N1—H2N	109.5
O5—P1—O1	109.15 (10)	H1N—N1—H2N	109.5
O4—P1—O1	109.49 (9)	C11—N1—H3N	109.5
O5—P1—O3	108.30 (11)	H1N—N1—H3N	109.5
O4—P1—O3	109.33 (10)	H2N—N1—H3N	109.5
O1—P1—O3	101.74 (10)	N1—C11—C16	110.5 (2)
C1—O1—P1	115.56 (17)	N1—C11—C12	110.1 (2)
C2—O21—C4	114.8 (3)	C16—C11—C12	111.4 (2)
C2—O22—C5	115.2 (2)	N1—C11—H11	108.2
C3—O3—P1	115.64 (17)	C16—C11—H11	108.2
O1—C1—C2	111.5 (2)	C12—C11—H11	108.2
O1—C1—H1A	109.3	C13—C12—C11	109.5 (2)
C2—C1—H1A	109.3	C13—C12—H12A	109.8
O1—C1—H1B	109.3	C11—C12—H12A	109.8
C2—C1—H1B	109.3	C13—C12—H12B	109.8
H1A—C1—H1B	108.0	C11—C12—H12B	109.8
O21—C2—O22	111.8 (2)	H12A—C12—H12B	108.2
O21—C2—C1	111.8 (2)	C14—C13—C12	111.4 (2)
O22—C2—C1	105.7 (3)	C14—C13—H13A	109.3
O21—C2—C3	103.7 (2)	C12—C13—H13A	109.3
O22—C2—C3	112.7 (2)	C14—C13—H13B	109.3
C1—C2—C3	111.3 (2)	C12—C13—H13B	109.3
O3—C3—C2	112.2 (2)	H13A—C13—H13B	108.0
O3—C3—H3A	109.2	C13—C14—C15	110.2 (2)
C2—C3—H3A	109.2	C13—C14—H14A	109.6
O3—C3—H3B	109.2	C15—C14—H14A	109.6
C2—C3—H3B	109.2	C13—C14—H14B	109.6
H3A—C3—H3B	107.9	C15—C14—H14B	109.6
O21—C4—H4A	109.5	H14A—C14—H14B	108.1
O21—C4—H4B	109.5	C16—C15—C14	111.2 (2)
H4A—C4—H4B	109.5	C16—C15—H15A	109.4
O21—C4—H4C	109.5	C14—C15—H15A	109.4
H4A—C4—H4C	109.5	C16—C15—H15B	109.4
H4B—C4—H4C	109.5	C14—C15—H15B	109.4
O22—C5—H5A	109.5	H15A—C15—H15B	108.0
O22—C5—H5B	109.5	C15—C16—C11	110.5 (2)
H5A—C5—H5B	109.5	C15—C16—H16A	109.6
O22—C5—H5C	109.5	C11—C16—H16A	109.6
H5A—C5—H5C	109.5	C15—C16—H16B	109.6
H5B—C5—H5C	109.5	C11—C16—H16B	109.6
C11—N1—H1N	109.5	H16A—C16—H16B	108.1
O5—P1—O1—C1	169.19 (17)	O1—C1—C2—O22	−69.6 (3)
O4—P1—O1—C1	−60.73 (19)	O1—C1—C2—C3	53.1 (3)
O3—P1—O1—C1	54.88 (18)	P1—O3—C3—C2	57.6 (3)
O5—P1—O3—C3	−169.55 (18)	O21—C2—C3—O3	−173.6 (2)
O4—P1—O3—C3	61.1 (2)	O22—C2—C3—O3	65.3 (3)
O1—P1—O3—C3	−54.61 (19)	C1—C2—C3—O3	−53.2 (3)
P1—O1—C1—C2	−58.2 (3)	N1—C11—C12—C13	179.6 (2)
C4—O21—C2—O22	−63.4 (3)	C16—C11—C12—C13	−57.4 (3)
C4—O21—C2—C1	54.9 (4)	C11—C12—C13—C14	57.1 (3)
C4—O21—C2—C3	174.9 (3)	C12—C13—C14—C15	−56.6 (3)
C5—O22—C2—O21	−60.9 (3)	C13—C14—C15—C16	56.1 (3)
C5—O22—C2—C1	177.2 (2)	C14—C15—C16—C11	−56.5 (3)
C5—O22—C2—C3	55.4 (3)	N1—C11—C16—C15	−179.6 (2)
O1—C1—C2—O21	168.6 (2)	C12—C11—C16—C15	57.6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O5	0.91	1.81	2.718 (3)	172
N1—H3N···O4^i	0.91	1.90	2.799 (3)	169
N1—H2N···O4^ii	0.91	1.90	2.809 (3)	174
C3—H3B···O22^iii	0.99	2.60	3.495 (3)	150
C14—H14A···O5^iv	0.99	2.50	3.396 (3)	150

Symmetry codes: (i) x−1/2, −y+1/2, −z+1; (ii) x−1, y, z; (iii) −x+1, y+1/2, −z+1/2; (iv) x, y+1, z.

(5k) 5,5-dimethoxy-2-oxo-1,3,2-dioxaphosphorinane-2-ol

Crystal data

C5H11O6P	Z = 2
Mr = 198.11	F(000) = 208
Triclinic, P1	Dx = 1.574 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.859 (2) Å	Cell parameters from 4920 reflections
b = 7.114 (3) Å	θ = 2.9–36.8°
c = 8.939 (3) Å	µ = 0.32 mm^−1
α = 89.13 (3)°	T = 100 K
β = 76.00 (3)°	Block, colourless
γ = 81.18 (3)°	0.41 × 0.22 × 0.06 mm
V = 418.1 (3) Å^3

Data collection

Kuma MK4CCD κ-geometry diffractometer with a Sapphire CCD camera	2274 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1985 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
ω scans	θmax = 30.0°, θmin = 2.9°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −7→9
Tmin = 0.970, Tmax = 1.000	k = −9→9
5919 measured reflections	l = −12→12

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.030	Hydrogen site location: difference Fourier map
wR(F^2) = 0.086	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0517P)^2 + 0.0903P] where P = (Fo^2 + 2Fc^2)/3
2274 reflections	(Δ/σ)max = 0.001
112 parameters	Δρmax = 0.55 e Å^−3
0 restraints	Δρmin = −0.25 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
P1	0.68955 (4)	0.65217 (4)	0.35648 (3)	0.01657 (10)
O1	0.91860 (12)	0.57824 (11)	0.35335 (9)	0.01739 (17)
O21	1.15704 (13)	0.99762 (12)	0.28521 (9)	0.01941 (18)
O22	1.10726 (12)	0.79471 (11)	0.09794 (9)	0.01591 (17)
O3	0.69174 (13)	0.82447 (12)	0.24609 (10)	0.01971 (18)
O4	0.58453 (14)	0.73620 (12)	0.51957 (10)	0.02240 (19)
H4	0.5262	0.6537	0.5733	0.034*
O5	0.59591 (14)	0.49970 (13)	0.30533 (10)	0.02284 (19)
C1	1.04158 (17)	0.72019 (16)	0.37282 (13)	0.0166 (2)
H1A	1.1834	0.6586	0.3651	0.020*
H1B	0.9881	0.7820	0.4762	0.020*
C2	1.03745 (16)	0.86932 (15)	0.24875 (12)	0.0144 (2)
C3	0.81960 (17)	0.96562 (15)	0.25925 (14)	0.0185 (2)
H3A	0.7654	1.0358	0.3591	0.022*
H3B	0.8182	1.0582	0.1756	0.022*
C4	1.1996 (2)	1.14556 (19)	0.17759 (15)	0.0277 (3)
H4A	1.2676	1.0891	0.0754	0.042*
H4B	1.2883	1.2230	0.2112	0.042*
H4C	1.0720	1.2260	0.1724	0.042*
C5	1.30135 (18)	0.67544 (17)	0.06463 (14)	0.0221 (2)
H5A	1.3985	0.7379	0.1024	0.033*
H5B	1.3500	0.6532	−0.0470	0.033*
H5C	1.2884	0.5535	0.1157	0.033*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.01801 (16)	0.01863 (16)	0.01301 (15)	−0.00527 (11)	−0.00219 (10)	0.00104 (10)
O1	0.0194 (4)	0.0150 (4)	0.0177 (4)	−0.0031 (3)	−0.0040 (3)	0.0027 (3)
O21	0.0243 (4)	0.0206 (4)	0.0151 (4)	−0.0103 (3)	−0.0040 (3)	0.0009 (3)
O22	0.0170 (4)	0.0180 (4)	0.0112 (3)	0.0001 (3)	−0.0023 (3)	−0.0008 (3)
O3	0.0170 (4)	0.0218 (4)	0.0212 (4)	−0.0046 (3)	−0.0055 (3)	0.0064 (3)
O4	0.0255 (4)	0.0221 (4)	0.0176 (4)	−0.0091 (3)	0.0021 (3)	−0.0025 (3)
O5	0.0284 (5)	0.0280 (4)	0.0143 (4)	−0.0135 (4)	−0.0036 (3)	0.0001 (3)
C1	0.0174 (5)	0.0184 (5)	0.0150 (5)	−0.0041 (4)	−0.0048 (4)	0.0025 (4)
C2	0.0160 (5)	0.0147 (5)	0.0118 (4)	−0.0029 (4)	−0.0018 (4)	−0.0003 (4)
C3	0.0180 (5)	0.0150 (5)	0.0204 (5)	−0.0007 (4)	−0.0019 (4)	0.0027 (4)
C4	0.0390 (7)	0.0237 (6)	0.0231 (6)	−0.0167 (5)	−0.0055 (5)	0.0044 (5)
C5	0.0203 (5)	0.0235 (5)	0.0181 (5)	0.0036 (4)	−0.0005 (4)	−0.0016 (4)

Geometric parameters (Å, º)

P1—O5	1.4727 (10)	C1—H1A	0.99
P1—O4	1.5453 (11)	C1—H1B	0.99
P1—O3	1.5614 (11)	C2—C3	1.5267 (16)
P1—O1	1.5721 (10)	C3—H3A	0.99
O1—C1	1.4488 (14)	C3—H3B	0.99
O21—C2	1.4071 (14)	C4—H4A	0.98
O21—C4	1.4304 (16)	C4—H4B	0.98
O22—C2	1.3999 (13)	C4—H4C	0.98
O22—C5	1.4319 (14)	C5—H5A	0.98
O3—C3	1.4543 (15)	C5—H5B	0.98
O4—H4	0.84	C5—H5C	0.98
C1—C2	1.5253 (16)
O5—P1—O4	115.13 (6)	O21—C2—C3	111.50 (9)
O5—P1—O3	111.75 (6)	C1—C2—C3	110.33 (10)
O4—P1—O3	105.76 (6)	O3—C3—C2	110.28 (9)
O5—P1—O1	110.23 (6)	O3—C3—H3A	109.6
O4—P1—O1	107.67 (6)	C2—C3—H3A	109.6
O3—P1—O1	105.77 (5)	O3—C3—H3B	109.6
C1—O1—P1	116.69 (7)	C2—C3—H3B	109.6
C2—O21—C4	116.04 (9)	H3A—C3—H3B	108.1
C2—O22—C5	115.71 (9)	O21—C4—H4A	109.5
C3—O3—P1	118.21 (7)	O21—C4—H4B	109.5
P1—O4—H4	109.5	H4A—C4—H4B	109.5
O1—C1—C2	109.72 (9)	O21—C4—H4C	109.5
O1—C1—H1A	109.7	H4A—C4—H4C	109.5
C2—C1—H1A	109.7	H4B—C4—H4C	109.5
O1—C1—H1B	109.7	O22—C5—H5A	109.5
C2—C1—H1B	109.7	O22—C5—H5B	109.5
H1A—C1—H1B	108.2	H5A—C5—H5B	109.5
O22—C2—O21	113.39 (9)	O22—C5—H5C	109.5
O22—C2—C1	113.94 (9)	H5A—C5—H5C	109.5
O21—C2—C1	102.94 (9)	H5B—C5—H5C	109.5
O22—C2—C3	104.92 (9)
O5—P1—O1—C1	168.89 (7)	C4—O21—C2—O22	50.07 (12)
O4—P1—O1—C1	−64.78 (9)	C4—O21—C2—C1	173.64 (9)
O3—P1—O1—C1	47.93 (9)	C4—O21—C2—C3	−68.09 (13)
O5—P1—O3—C3	−165.89 (7)	O1—C1—C2—O22	−58.34 (12)
O4—P1—O3—C3	68.13 (9)	O1—C1—C2—O21	178.45 (8)
O1—P1—O3—C3	−45.92 (9)	O1—C1—C2—C3	59.37 (11)
P1—O1—C1—C2	−57.28 (11)	P1—O3—C3—C2	53.06 (11)
C5—O22—C2—O21	65.74 (12)	O22—C2—C3—O3	66.19 (11)
C5—O22—C2—C1	−51.58 (13)	O21—C2—C3—O3	−170.68 (8)
C5—O22—C2—C3	−172.36 (9)	C1—C2—C3—O3	−56.94 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O5^i	0.84	1.70	2.533 (2)	175
C1—H1B···O21^ii	0.99	2.57	3.544 (2)	169
C3—H3B···O22^iii	0.99	2.61	3.560 (2)	161
C5—H5B···O5^iv	0.98	2.49	3.423 (2)	159

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+2, −z+1; (iii) −x+2, −y+2, −z; (iv) −x+2, −y+1, −z.