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

Ślepokura, K.; Mitaszewska, I.

doi:10.1107/S0108270111011723

organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 67| Part 5| May 2011| Pages o161-o165

doi:10.1107/S0108270111011723

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

Katarzyna Ślepokura ^a ^* and Irmina Mitaszewska ^a

^aFaculty of Chemistry, University of Wrocław, 14 F. Joliot-Curie Street, 50-383 Wrocław, Poland
^*Correspondence e-mail: slep@eto.wchuwr.pl

(Received 3 February 2011; accepted 29 March 2011; online 13 April 2011)

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.

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 great importance for all living cells [for a review, see Ślepokura & Lis (2010 )]. The cyclic form, cDHAP, has aroused interest 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 was 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 more than 160 hits for cyclic phosphates with six-membered rings deposited in 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.

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 cyclohexylammonium (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).

The present paper concerns the synthesis and crystal structure of 5,5-dimethoxy-2-hydroxy-1,3,2-dioxaphosphorinan-2-one, the dimethyl acetal of cyclic dihydroxyacetone phosphate, (MeO)₂cDHAP, in the form of two crystalline 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 free acid, (MeO)₂cDHAP, (5k).

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), (5b), (5i) and (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 observed previously in (5a)–(5h), is also observed in (5i) and (5j). The deformation of the ionized cyclic phosphate is seen particularly in the endocyclic O1—P1—O3 and exocyclic O4—P1—O5 bond angles, which are, respectively, the smallest [101.73 (11)° on average for (5a)–(5j)] and the largest [119.24 (12)° on average]. 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 all approximately 1.60 Å and more than 0.1 Å longer than the P—O_exo bonds.

A completely different deformation is present in the protonated phosphate group of the (MeO)₂cDHAP molecule in (5k). The hydroxy 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 (Table 2), 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 acidic cyclic phosphates ETPHOS and SEZRUL.

It has been shown that the acetal group in the analogous linear compounds, different salts of (MeO)₂DHAP and (MeO)₂DHAP(Ph) [(6a)–(6e); 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) (see scheme above): 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 the N⁺—H⋯OW and OW—H⋯O⁻ type (OW 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 OW—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 structure 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 [10 $[\overline{1}]$ ].

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).

Figure 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.

Figure 2
The 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.]

Figure 3
A comparison of the layer constructions observed in two polymorphous forms of (cha)[(MeO)₂cDHAP]·H₂O, viz. 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 paper).

Figure 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 − $[{1\over 2}]$ , −y + $[{1\over 2}]$ , −z + 1.]

Figure 5
The ribbons in (5k)

resulting from centrosymmetric molecular dimers [with R₂²(8) rings formed by the (MeO)₂cDHAP molecules joined via strong O—H⋯O hydrogen bonds; dashed lines (red in the electronic version of the paper)] 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.]

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, viz. 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 minimum 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).

Compound (5i)

Crystal data

C₆H₁₄N⁺·C₅H₁₀O₆P⁻·H₂O
M_r = 315.30
Triclinic, $[P \overline 1]$
a = 7.064 (2) Å
b = 8.475 (4) Å
c = 13.966 (6) Å
α = 102.48 (3)°
β = 92.58 (3)°
γ = 99.96 (3)°
V = 801.1 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 100 K
0.37 × 0.23 × 0.04 mm

Data collection

Kuma KM-4 CCD κ-geometry diffractometer with a Sapphire CCD camera
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED, in Xcalibur PX and Kuma KM-4 CCD software. Versions 1.171.33.42. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ) T_min = 0.913, T_max = 1.000
13552 measured reflections
4519 independent reflections
3579 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.094
S = 1.03
4519 reflections
190 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Compound (5j)

Crystal data

C₆H₁₄N⁺·C₅H₁₀O₆P⁻
M_r = 297.28
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.678 (2) Å
b = 8.877 (2) Å
c = 24.930 (6) Å
V = 1477.9 (7) Å³
Z = 4
Cu Kα radiation
μ = 1.86 mm⁻¹
T = 120 K
0.13 × 0.08 × 0.01 mm

Data collection

Oxford Diffraction Xcalibur PX κ-geometry diffractometer with an Onyx CCD camera
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED, in Xcalibur PX and Kuma KM-4 CCD software. Versions 1.171.33.42. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ) T_min = 0.832, T_max = 0.978
11210 measured reflections
2803 independent reflections
1876 reflections with I > 2σ(I)
R_int = 0.062

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.060
S = 1.02
2803 reflections
175 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.21 e Å⁻³
Absolute structure: Flack (1983 ), with 988 Friedel pairs
Flack parameter: −0.03 (3)

Compound (5k)

Crystal data

C₅H₁₁O₆P
M_r = 198.11
Triclinic, $[P \overline 1]$
a = 6.859 (2) Å
b = 7.114 (3) Å
c = 8.939 (3) Å
α = 89.13 (3)°
β = 76.00 (3)°
γ = 81.18 (3)°
V = 418.1 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 100 K
0.41 × 0.22 × 0.06 mm

Data collection

Kuma KM-4 CCD κ-geometry diffractometer with a Sapphire CCD camera
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED, in Xcalibur PX and Kuma KM-4 CCD software. Versions 1.171.33.42. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ) T_min = 0.970, T_max = 1.000
5919 measured reflections
2274 independent reflections
1985 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.086
S = 1.08
2274 reflections
112 parameters
H-atom parameters constrained
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Values of φ₁ and φ₂, and the Cremer–Pople puckering parameters Q, θ and φ for the P/O1/C1/C2/C3/O3 rings in the (MeO)₂cDHAP anions in (5i) and (5j) and in the molecule of (5k), along with the relevant values for the previously reported compounds (4), (5a) and (5b)

Compound	φ₁ (°)	φ₂ (°)	\|φ₂ − φ₁\| (°)	Q (Å)	θ (°)	φ (°)
(5i)	46.9 (1)	52.4 (1)	5.5	0.580 (1)	176.4 (1)	280 (2)
(5j)	47.4 (2)	48.0 (3)	0.6	0.558 (2)	176.0 (2)	189 (4)
(5k)	40.4 (1)	53.0 (1)	12.6	0.541 (1)	171.1 (1)	342 (1)
(5a)^a	47.3 (1)	50.8 (1)	3.6	0.573 (1)	178.4 (1)	234 (4)
(5b)^a	48.2 (1)	50.3 (1)	2.1	0.577 (1)	177.5 (1)	199 (2)
(4)^b	35.9 (1)	51.8 (2)	15.9	0.514 (2)	167.5 (2)	349 (1)
References: (a) Ślepokura (2008) {(5a) is (cha)[(MeO)₂cDHAP]·3H₂O and (5b) is monoclinic (cha)[(MeO)₂cDHAP]·H₂O}; (b) Ślepokura & Lis (2004b) [(4) is (MeO)₂cDHAP(Ph)].

Table 2
Selected geometric parameters (Å, °) for (5i)–(5k)

	(5i)	(5j)	(5k)
P1—O1	1.6061 (10)	1.5929 (18)	1.5721 (10)
P1—O3	1.6004 (10)	1.6013 (18)	1.5614 (11)
P1—O4	1.4866 (10)	1.4846 (18)	1.5453 (11)
P1—O5	1.4784 (11)	1.4753 (18)	1.4727 (10)
O1—C1	1.4343 (14)	1.445 (3)	1.4488 (14)
O21—C2	1.4118 (13)	1.415 (3)	1.4071 (14)
O21—C4	1.4328 (15)	1.436 (4)	1.4304 (16)
O22—C2	1.4080 (13)	1.417 (3)	1.3999 (13)
O22—C5	1.4229 (15)	1.431 (3)	1.4319 (14)
O3—C3	1.4304 (14)	1.425 (3)	1.4543 (15)
C1—C2	1.5270 (15)	1.510 (4)	1.5253 (16)
C2—C3	1.5297 (16)	1.515 (4)	1.5267 (16)

O1—P1—O3	102.13 (5)	101.74 (10)	105.77 (5)
O1—P1—O4	109.24 (5)	109.49 (9)	107.67 (6)
O1—P1—O5	107.69 (5)	109.15 (10)	110.23 (6)
O3—P1—O4	109.74 (5)	109.33 (10)	105.76 (6)
O3—P1—O5	106.58 (6)	108.30 (11)	111.75 (6)
O4—P1—O5	119.97 (5)	117.64 (11)	115.13 (6)
P1—O1—C1	114.57 (7)	115.64 (17)	116.69 (7)
C2—O21—C4	114.41 (9)	114.8 (3)	116.04 (9)
C2—O22—C5	115.66 (9)	115.2 (2)	115.71 (9)
P1—O3—C3	116.69 (7)	115.64 (17)	118.21 (7)
O1—C1—C2	109.64 (9)	111.5 (2)	109.72 (9)
O21—C2—O22	111.81 (9)	111.8 (2)	113.39 (9)
O21—C2—C1	104.21 (9)	111.8 (2)	102.94 (9)
O22—C2—C1	113.65 (9)	105.7 (3)	113.94 (9)
O21—C2—C3	112.14 (9)	103.7 (2)	111.50 (9)
O22—C2—C3	105.01 (9)	112.7 (2)	104.92 (9)
C1—C2—C3	110.21 (9)	111.3 (2)	110.33 (10)
O3—C3—C2	110.72 (9)	112.2 (2)	110.28 (9)

O3—P1—O1—C1	55.31 (8)	54.88 (18)	47.93 (9)
O4—P1—O1—C1	−60.85 (8)	−60.73 (19)	−64.78 (9)
O5—P1—O1—C1	167.33 (7)	169.19 (17)	168.89 (7)
O1—P1—O3—C3	−52.80 (8)	−54.61 (19)	−45.92 (9)
O4—P1—O3—C3	63.00 (9)	61.1 (2)	68.13 (9)
O5—P1—O3—C3	−165.65 (7)	−169.55 (18)	−165.89 (7)
P1—O1—C1—C2	−62.20 (9)	−58.2 (3)	−57.28 (11)
P1—O3—C3—C2	56.68 (10)	57.6 (3)	53.06 (11)
C4—O21—C2—O22	60.27 (12)	−63.4 (3)	50.07 (12)
C4—O21—C2—C1	−176.57 (8)	54.9 (4)	173.64 (9)
C4—O21—C2—C3	−57.38 (12)	174.9 (3)	−68.09 (13)
C5—O22—C2—O21	67.92 (11)	−60.9 (3)	65.74 (12)
C5—O22—C2—C1	−49.72 (12)	177.2 (2)	−51.58 (13)
C5—O22—C2—C3	−170.24 (9)	55.4 (3)	−172.36 (9)
O1—C1—C2—O21	179.58 (7)	168.6 (2)	178.45 (8)
O1—C1—C2—O22	−58.46 (11)	−69.6 (3)	−58.34 (12)
O1—C1—C2—C3	59.08 (11)	53.1 (3)	59.37 (11)
O21—C2—C3—O3	−171.66 (8)	−173.6 (2)	−170.68 (8)
O22—C2—C3—O3	66.71 (11)	65.3 (3)	66.19 (11)
C1—C2—C3—O3	−56.06 (11)	−53.2 (3)	−56.94 (12)

Table 3
Hydrogen-bond geometry (Å, °) for (5i)–(5k)

Compound	D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
(5i)	N1—H1N⋯O5	0.91	1.87	2.758 (2)	166
	N1—H2N⋯O5ⁱ	0.91	1.96	2.817 (2)	157
	N1—H3N⋯O1Wⁱⁱ	0.91	1.87	2.719 (2)	154
	O1W—H1W⋯O4	0.83 (2)	1.92 (2)	2.749 (2)	176 (2)
	O1W—H2W⋯O4ⁱⁱⁱ	0.83 (2)	1.93 (2)	2.758 (2)	176 (2)
	C4—H4A⋯O1^iv	0.98	2.60	3.534 (2)	159
	C11—H11⋯O1Wⁱⁱⁱ	1.00	2.52	3.416 (2)	149
(5j)	N1—H1N⋯O5	0.91	1.81	2.718 (3)	172
	N1—H2N⋯O4ⁱⁱ	0.91	1.90	2.809 (3)	174
	N1—H3N⋯O4^v	0.91	1.90	2.799 (3)	169
	C3—H3B⋯O22^vi	0.99	2.60	3.495 (3)	150
	C14—H14A⋯O5^vii	0.99	2.50	3.396 (3)	150
(5k)	O4—H4⋯O5ⁱⁱⁱ	0.84	1.70	2.533 (2)	175
	C1—H1A⋯O21^viii	0.99	2.57	3.544 (2)	169
	C3—H3B⋯O22^ix	0.99	2.61	3.560 (2)	161
	C5—H5B⋯O5^x	0.98	2.49	3.423 (2)	159
Symmetry codes: (i) −x, −y, −z + 1; (ii) x − 1, y, z; (iii) −x + 1, −y + 1, −z + 1; (iv) x + 1, y, z; (v) x − $[{1\over 2}]$ , −y + $[{1\over 2}]$ , −z + 1; (vi) −x + 1, y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (vii) x, y + 1, z. (viii) −x + 2, −y + 2, −z + 1; (ix) −x + 2, −y + 2, −z; (x) −x + 2, −y + 1, −z.

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 in geometrically optimized positions, 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 and CH₂, or 1.5U_eq(C,N,O) for CH₃, NH₃ and OH.

For all compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED, in Xcalibur PX and Kuma KM-4 CCD software. Versions 1.171.33.42. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED, in Xcalibur PX and Kuma KM-4 CCD software. Versions 1.171.33.42. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ); data reduction: CrysAlis RED; 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 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, 5i, 5j, 5k. DOI: 10.1107/S0108270111011723/mx3045sup1.cif

Structure factors: contains datablock 5i. DOI: 10.1107/S0108270111011723/mx30455isup2.hkl

Structure factors: contains datablock 5j. DOI: 10.1107/S0108270111011723/mx30455jsup3.hkl

Structure factors: contains datablock 5k. DOI: 10.1107/S0108270111011723/mx30455ksup4.hkl

Comment top

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].

[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 top

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).

Experimental top

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).

Computing details top

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 top

	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^-/O_w and O_w—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 R₂²(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 top

Crystal data top

C₆H₁₄N⁺·C₅H₁₀O₆P⁻·H₂O	Z = 2
M_r = 315.30	F(000) = 340
Triclinic, P1	D_x = 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) Å³

Data collection top

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	R_int = 0.025
ω scans	θ_max = 30.0°, θ_min = 2.9°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −9→8
T_min = 0.913, T_max = 1.000	k = −11→11
13552 measured reflections	l = −19→19

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.034	Hydrogen site location: difference Fourier map
wR(F²) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0606P)²] where P = (F_o² + 2F_c²)/3
4519 reflections	(Δ/σ)_max = 0.001
190 parameters	Δρ_max = 0.49 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₆H₁₄N⁺·C₅H₁₀O₆P⁻·H₂O	γ = 99.96 (3)°
M_r = 315.30	V = 801.1 (6) Å³
Triclinic, P1	Z = 2
a = 7.064 (2) Å	Mo Kα radiation
b = 8.475 (4) Å	µ = 0.20 mm⁻¹
c = 13.966 (6) Å	T = 100 K
α = 102.48 (3)°	0.37 × 0.23 × 0.04 mm
β = 92.58 (3)°

Data collection top

Kuma KM4CCD κ-geometry diffractometer with a Sapphire CCD camera	4519 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	3579 reflections with I > 2σ(I)
T_min = 0.913, T_max = 1.000	R_int = 0.025
13552 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.49 e Å⁻³
4519 reflections	Δρ_min = −0.18 e Å⁻³
190 parameters

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

	x	y	z	U_iso*/U_eq
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 (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
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) top

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) top

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···O5ⁱ	0.91	1.96	2.817 (2)	157
N1—H3N···O1Wⁱⁱ	0.91	1.87	2.719 (2)	154
O1W—H1W···O4	0.83 (2)	1.92 (2)	2.749 (2)	176 (2)
O1W—H2W···O4ⁱⁱⁱ	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···O1Wⁱⁱⁱ	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 top

Crystal data top

C₆H₁₄N⁺·C₅H₁₀O₆P⁻	F(000) = 640
M_r = 297.28	D_x = 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) Å³	Plate, colourless
Z = 4	0.13 × 0.08 × 0.01 mm

Data collection top

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	R_int = 0.062
ω and ϕ scans	θ_max = 76.2°, θ_min = 3.6°
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2009)	h = −7→4
T_min = 0.832, T_max = 0.978	k = −10→9
11210 measured reflections	l = −27→30

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.060	w = 1/[σ²(F_o²) + (0.012P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
2803 reflections	Δρ_max = 0.21 e Å⁻³
175 parameters	Δρ_min = −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)

Crystal data top

C₆H₁₄N⁺·C₅H₁₀O₆P⁻	V = 1477.9 (7) Å³
M_r = 297.28	Z = 4
Orthorhombic, P2₁2₁2₁	Cu Kα radiation
a = 6.678 (2) Å	µ = 1.86 mm⁻¹
b = 8.877 (2) Å	T = 120 K
c = 24.930 (6) Å	0.13 × 0.08 × 0.01 mm

Data collection top

Oxford Diffraction Xcalibur PX κ-geometry diffractometer with an Onyx CCD camera	2803 independent reflections
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2009)	1876 reflections with I > 2σ(I)
T_min = 0.832, T_max = 0.978	R_int = 0.062
11210 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.060	Δρ_max = 0.21 e Å⁻³
S = 1.02	Δρ_min = −0.21 e Å⁻³
2803 reflections	Absolute structure: Flack (1983), with how many Friedel pairs?
175 parameters	Absolute structure parameter: −0.03 (3)
0 restraints

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
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) top

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) top

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···O4ⁱ	0.91	1.90	2.799 (3)	169
N1—H2N···O4ⁱⁱ	0.91	1.90	2.809 (3)	174
C3—H3B···O22ⁱⁱⁱ	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 top

Crystal data top

C₅H₁₁O₆P	Z = 2
M_r = 198.11	F(000) = 208
Triclinic, P1	D_x = 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) Å³

Data collection top

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	R_int = 0.016
ω scans	θ_max = 30.0°, θ_min = 2.9°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −7→9
T_min = 0.970, T_max = 1.000	k = −9→9
5919 measured reflections	l = −12→12

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.030	Hydrogen site location: difference Fourier map
wR(F²) = 0.086	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0517P)² + 0.0903P] where P = (F_o² + 2F_c²)/3
2274 reflections	(Δ/σ)_max = 0.001
112 parameters	Δρ_max = 0.55 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₅H₁₁O₆P	γ = 81.18 (3)°
M_r = 198.11	V = 418.1 (3) Å³
Triclinic, P1	Z = 2
a = 6.859 (2) Å	Mo Kα radiation
b = 7.114 (3) Å	µ = 0.32 mm⁻¹
c = 8.939 (3) Å	T = 100 K
α = 89.13 (3)°	0.41 × 0.22 × 0.06 mm
β = 76.00 (3)°

Data collection top

Kuma MK4CCD κ-geometry diffractometer with a Sapphire CCD camera	2274 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	1985 reflections with I > 2σ(I)
T_min = 0.970, T_max = 1.000	R_int = 0.016
5919 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.086	H-atom parameters constrained
S = 1.08	Δρ_max = 0.55 e Å⁻³
2274 reflections	Δρ_min = −0.25 e Å⁻³
112 parameters

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
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) top

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) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O5ⁱ	0.84	1.70	2.533 (2)	175
C1—H1B···O21ⁱⁱ	0.99	2.57	3.544 (2)	169
C3—H3B···O22ⁱⁱⁱ	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.

Experimental details

	(5i)	(5j)	(5k)
Crystal data
Chemical formula	C₆H₁₄N⁺·C₅H₁₀O₆P⁻·H₂O	C₆H₁₄N⁺·C₅H₁₀O₆P⁻	C₅H₁₁O₆P
M_r	315.30	297.28	198.11
Crystal system, space group	Triclinic, P1	Orthorhombic, P2₁2₁2₁	Triclinic, P1
Temperature (K)	100	120	100
a, b, c (Å)	7.064 (2), 8.475 (4), 13.966 (6)	6.678 (2), 8.877 (2), 24.930 (6)	6.859 (2), 7.114 (3), 8.939 (3)
α, β, γ (°)	102.48 (3), 92.58 (3), 99.96 (3)	90, 90, 90	89.13 (3), 76.00 (3), 81.18 (3)
V (Å³)	801.1 (6)	1477.9 (7)	418.1 (3)
Z	2	4	2
Radiation type	Mo Kα	Cu Kα	Mo Kα
µ (mm⁻¹)	0.20	1.86	0.32
Crystal size (mm)	0.37 × 0.23 × 0.04	0.13 × 0.08 × 0.01	0.41 × 0.22 × 0.06

Data collection
Diffractometer	Kuma KM4CCD κ-geometry diffractometer with a Sapphire CCD camera	Oxford Diffraction Xcalibur PX κ-geometry diffractometer with an Onyx CCD camera	Kuma MK4CCD κ-geometry diffractometer with a Sapphire CCD camera
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	Analytical (CrysAlis RED; Oxford Diffraction, 2009)	Multi-scan (CrysAlis RED; Oxford Diffraction, 2009)
T_min, T_max	0.913, 1.000	0.832, 0.978	0.970, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	13552, 4519, 3579	11210, 2803, 1876	5919, 2274, 1985
R_int	0.025	0.062	0.016
(sin θ/λ)_max (Å⁻¹)	0.703	0.630	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.094, 1.03	0.037, 0.060, 1.02	0.030, 0.086, 1.08
No. of reflections	4519	2803	2274
No. of parameters	190	175	112
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.18	0.21, −0.21	0.55, −0.25
Absolute structure	?	Flack (1983), with how many Friedel pairs?	?
Absolute structure parameter	?	−0.03 (3)	?

Computer programs: CrysAlis CCD (Oxford Diffraction, 2009), CrysAlis RED (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), XP (Bruker, 1998), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Values of ϕ₁, ϕ₂ and the Cremer–Pople puckering parameters Q, θ and ϕ for the P/O1/C1/C2/C3/O3 rings in the (MeO)₂cDHAP anions in (5i) and (5j) and in the molecule of (5k), along with the relevant values for the previously reported compounds (4), (5a) and (5b) top

Compound	ϕ₁ (°)	ϕ₂ (°)	\|ϕ₂ - ϕ₁\| (°)	Q (Å)	θ (°)	ϕ (°)
(5i)	46.9 (1)	52.4 (1)	5.5	0.580 (1)	176.4 (1)	280 (2)
(5j)	47.4 (2)	48.0 (3)	0.6	0.558 (2)	176.0 (2)	189 (4)
(5k)	40.4 (1)	53.0 (1)	12.6	0.541 (1)	171.1 (1)	342 (1)
(5a)^a	47.3 (1)	50.8 (1)	3.6	0.573 (1)	178.4 (1)	234 (4)
(5b)^a	48.2 (1)	50.3 (1)	2.1	0.577 (1)	177.5 (1)	199 (2)
(4)^b	35.9 (1)	51.8 (2)	15.9	0.514 (2)	167.5 (2)	349 (1)

References: (a) Ślepokura (2008) {(5a) is (cha)[(MeO)₂cDHAP].3H₂O and (5b) is monoclinic (cha)[(MeO)₂cDHAP].H₂O}; (b) Ślepokura & Lis (2004b) [(4) is (MeO)₂cDHAP(Ph)].

Selected geometric parameters (Å, °) for (5i)–(5k). top

Bond/angle	(5i)	(5j)	(5k)
P1—O1	1.6061 (10)	1.59329 (18)	1.5721 (10)
P1—O3	1.6004 (10)	1.6013 (18)	1.5614 (11)
P1—O4	1.4866 (10)	1.4846 (18)	1.5453 (11)
P1—O5	1.4784 (11)	1.4753 (18)	1.4727 (10)
O1—C1	1.4343 (14)	1.445 (3)	1.4488 (14)
O21—C2	1.4118 (13)	1.415 (3)	1.4071 (14)
O21—C4	1.4328 (15)	1.436 (4)	1.4304 (16)
O22—C2	1.4080 (13)	1.417 (3)	1.3999 (13)
O22—C5	1.4229 (15)	1.431 (3)	1.4319 (14)
O3—C3	1.4304 (14)	1.425 (3)	1.4543 (15)
C1—C2	1.5270 (15)	1.510 (4)	1.5253 (16)
C2—C3	1.5297 (16)	1.515 (4)	1.5267 (16)
O1—P1—O3	102.13 (5)	101.74 (10)	105.77 (5)
O1—P1—O4	109.24 (5)	109.49 (9)	107.67 (6)
O1—P1—O5	107.69 (5)	109.15 (10)	110.23 (6)
O3—P1—O4	109.74 (5)	109.33 (10)	105.76 (6)
O3—P1—O5	106.58 (6)	108.30 (11)	111.75 (6)
O4—P1—O5	119.97 (5)	117.64 (11)	115.13 (6)
P1—O1—C1	114.57 (7)	115.64 (17)	116.69 (7)
C2—O21—C4	114.41 (9)	114.8 (3)	116.04 (9)
C2—O22—C5	115.66 (9)	115.2 (2)	115.71 (9)
P1—O3—C3	116.69 (7)	115.64 (17)	118.21 (7)
O1—C1—C2	109.64 (9)	111.5 (2)	109.72 (9)
O21—C2—O22	111.81 (9)	111.8 (2)	113.39 (9)
O21—C2—C1	104.21 (9)	111.8 (2)	102.94 (9)
O22—C2—C1	113.65 (9)	105.7 (3)	113.94 (9)
O21—C2—C3	112.14 (9)	103.7 (2)	111.50 (9)
O22—C2—C3	105.01 (9)	112.7 (2)	104.92 (9)
C1—C2—C3	110.21 (9)	111.3 (2)	110.33 (10)
O3—C3—C2	110.72 (9)	112.2 (2)	110.28 (9)
O3—P1—O1—C1	55.31 (8)	54.88 (18)	47.93 (9)
O4—P1—O1—C1	-60.85 (8)	-60.73 (19)	-64.78 (9)
O5—P1—O1—C1	167.33 (7)	169.19 (17)	168.89 (7)
O1—P1—O3—C3	-52.80 (8)	-54.61 (19)	-45.92 (9)
O4—P1—O3—C3	63.00 (9)	61.1 (2)	68.13 (9)
O5—P1—O3—C3	-165.65 (7)	-169.55 (18)	-165.89 (7)
P1—O1—C1—C2	-62.20 (9)	-58.2 (3)	-57.28 (11)
P1—O3—C3—C2	56.68 (10)	57.6 (3)	53.06 (11)
C4—O21—C2—O22	60.27 (12)	-63.4 (3)	50.07 (12)
C4—O21—C2—C1	-176.57 (8)	54.9 (4)	173.64 (9)
C4—O21—C2—C3	-57.38 (12)	174.9 (3)	-68.09 (13)
C5—O22—C2—O21	67.92 (11)	-60.9 (3)	65.74 (12)
C5—O22—C2—C1	-49.72 (12)	177.2 (2)	-51.58 (13)
C5—O22—C2—C3	-170.24 (9)	55.4 (3)	-172.36 (9)
O1—C1—C2—O21	179.58 (7)	168.6 (2)	178.45 (8)
O1—C1—C2—O22	-58.46 (11)	-69.6 (3)	-58.34 (12)
O1—C1—C2—C3	59.08 (11)	53.1 (3)	59.37 (11)
O21—C2—C3—O3	-171.66 (8)	-173.6 (2)	-170.68 (8)
O22—C2—C3—O3	66.71 (11)	65.3 (3)	66.19 (11)
C1—C2—C3—O3	-56.06 (11)	-53.2 (3)	-56.94 (12)

Hydrogen-bond geometry (Å, °) for (5i)–(5k) top

Compound	D—H···A	D—H	H···A	D···A	D—H···A
(5i)	N1—H1N···O5	0.91	1.87	2.758 (2)	166
	N1—H2N···O5ⁱ	0.91	1.96	2.817 (2)	157
	N1—H3N···O1Wⁱⁱ	0.91	1.87	2.719 (2)	154
	O1W—H1W···O4	0.83 (2)	1.92 (2)	2.749 (2)	176 (2)
	O1W—H2W···O4ⁱⁱⁱ	0.83 (2)	1.93 (2)	2.758 (2)	176 (2)
	C4—H4A···O1^iv	0.98	2.60	3.534 (2)	159
	C11—H11···O1Wⁱⁱⁱ	1.00	2.52	3.416 (2)	149
(5j)	N1—H1N···O5	0.91	1.81	2.718 (3)	172
	N1—H2N···O4ⁱⁱ	0.91	1.90	2.809 (3)	174
	N1—H3N···O4^v	0.91	1.90	2.799 (3)	169
	C3—H3B···O22^vi	0.99	2.60	3.495 (3)	150
	C14—H14A···O5^vii	0.99	2.50	3.396 (3)	150
(5k)	O4—H4···O5ⁱⁱⁱ	0.84	1.70	2.533 (2)	175
	C1—H1A···O21^viii	0.99	2.57	3.544 (2)	169
	C3—H3b···O22^ix	0.99	2.61	3.560 (2)	161
	C5—H5B···O5^x	0.98	2.49	3.423 (2)	159

Symmetry codes: (i) -x, -y, -z + 1; (ii) x - 1, y, z; (iii) -x + 1, -y + 1, -z + 1; (iv) x + 1, y, z; (v) x - 1/2, -y + 1/2, -z + 1; (vi) -x + 1, y + 1/2, -z + 1/2; (vii) x, y + 1, z. (viii) -x + 2, -y + 2, -z + 1; (ix) -x + 2, -y + 2, -z; (x) -x + 2, -y + 1, -z.

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ISSN: 2053-2296

Volume 67| Part 5| May 2011| Pages o161-o165

doi:10.1107/S0108270111011723

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

Comment

Experimental

Compound (5i)

Crystal data

Data collection

Refinement

Compound (5j)

Crystal data

Data collection

Refinement

Compound (5k)

Crystal data

Data collection

Refinement

Supporting information

References

organic compounds

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