Layered poly[μ₂-aqua-μ₃-dimethyl­formamide-di-μ₃-phenyl­phosphon­ato-dipotassium]

The first structurally characterized alkali metal phospho­nate, the title compound, [K₂(C₆H₆O₃P)₂(C₃H₇NO)(H₂O)]_n, has a complex structure, with layers parallel to the crystallographic bc plane consisting of two crystallographically independent K atoms sandwiched between the three types of ligands present in the structure, viz. water molecules, dimethyl­formamide molecules and two crystallographically independent phenyl­phospho­nate ligands. Six O atoms coordinate to one K atom and seven to the other. The interlayer distance is 15.327 (4) Å. The K—O distances are in the range 2.739 (2)–2.932 (2) Å for the seven-coordinate K atom and 2.650 (2)–2.821 (2) Å for the six-coordinate K atom.

S1. Comment

Metal phosphonates have been much used as inorganic–organic hybrid materials because of their potential applications (Clearfield, 1996, 2002). Complexes with metal ions frequently form laminar structures in the solid state that consist of PO₃···M···O₃P layers separated by the organic groups (Vioux et al., 2004). The phosphonate group permits flexibility in the construction of solids, with the possibility of forming strong hydrogen bonds between the hydroxy groups and terminal O atoms (Mahmoudkhani & Langer, 2002). Complexes with a variety of metal centres (alkaline earth, transition, main group or lanthanide, usually in the +2 to +4 oxidation state) have been studied (Cao et al., 1988, 1990; Poojary et al., 1996; Mahmoudkhani & Langer, 2001; Mahmoudkhani et al., 2002). However, until now, no structure of a phosphonate complex with a monovalent metal has been reported. The only similar complex whose structure has been reported is aquapyrazole-4-sulfonatepotassium (Mezei & Raptis, 2003). The sulfonate group, SO₃⁻, has a structure similar to that of the phosphonate but forms much weaker bonds to metal atoms (Côté & Shimizu, 2003).

Alkali and alkaline earth metals have a rich coordination chemistry with O-atom donor ligands (Poonia & Bajaj, 1979), which prompted us to study their phosphinate complexes. In the case of potassium phenylphosphinate, accidental aerial oxidation of the anion during the preparation led to the formation of potassium phenylphosphonate, (I). Repetition of the synthesis with hydrogen peroxide as the oxidation agent led to the pure product. A DSC analysis of (I) showed no peaks from 323–623 K, demonstrating the thermal robustness of the compound. A sample of (I) prepared in methanol showed good crystallinity [T_m = 585.5 K, ΔH_m = 66.8 J^.g⁻¹ and T_c = 512.6 K, ΔH_c = −24.3 J^.g⁻¹. Crystallization of (1), by the slow evaporation of an aqueous dimethylformamide solution of potassium phenylphosphonate in a desiccator produced good quality plate-like crystals of the title compound, (II).

We report the here the structure of (II). A view of the asymmetric unit is given in Fig. 1. Table 1 lists selected distances and angles. The extended structure of (II) consists of complex layers parallel to the crystallographic bc plane. The interlayer distance is 15.327 (4) Å. Layers consisting of two crystallographically independent K atoms lie between double layers of the ligands (water, dimethylformamide and two crystallographically independent phenylphosphonate ligands), which form bonds to the K atoms via their O atoms. An extensive network of hydrogen bonds (Table 2) is observed. An approximately square two-dimensional net is formed, with chains of phosphonate ligands parallel to the y axis linked by hydrogen bonding between their hydroxy H atoms and anionic O atoms, and interconnected in the crystallographic z direction by hydrogen bonds between the doubly bonded O atoms and water H atoms (Fig. 2). The packing is shown in Fig. 3.

The potassium centres in (II) exhibit very different coordination geometries. Most of the K—O distances are slightly longer than the sum of the covalent radii (2.69 Å; Allen et al., 1987) but may be considered weak ionic bonds because of their directionality; other K—O interactions are considerably longer. Atom K1 is seven-coordinate, with an approximately pentagonal-bipyramidal coordination geometry. Atoms O2, from a dimethylformamide molecule, and O21, from a phenylphosphonate ligand, occupy the apical positions. Atoms O12 and O13 from a chelating phenylphosphonate ligand, O2(1 − x, y − 1/2, 1/2 − z) from a symmetry-related dimethylformamide molecule, O1 from a bridging water molecule, and O22(1 − x, 1 − y, 1 − z), a bridging O atom from a symmetry-related phenylphosphonate ligand, complete the equatorial positions. The K1—O distances range from 2.739 (2)– 2.932 (2) Å, in agreement with the average K—O distance for KO₇ moieties in the Cambridge Structural Database [CSD; 2.80 (11) Å for 446 observations; Allen, 2002]. The next longest (non-bonded) interaction is 3.544 (4) Å for K1···O1ⁱⁱ [symmetry code: (ii) 1 − x, 1 − y, 1 − z].

Atom K2 is six-coordinate, with atoms O12 and O11^iv from two different phenylphosphinate ligands, O22ⁱⁱⁱ and O23ⁱⁱⁱ from a chelating phenylphosphinate ligand, and O1ⁱⁱⁱ and O2^iv from bridging water and dimethylformamide molecules, respectively, making up the primary coordination environment [symmetry codes: (iii) 1 − x, 1/2 + y, 1/2-zi; (iv) 1 − x, y − 1/2, 1/2 − z]. The geometry is far from regular octahedral, because of the small bite angle of the chelating phenylphosphonate; the O22ⁱⁱⁱ—K2—O23ⁱⁱⁱ angle is 52.46 (6)\%. The K2—O distances range from 2.650 (2)–2.821 (2) Å, similar to the average for KO₆ groups found in the CSD [2.80 (9) Å for 1506 observations]. The next longest K2···O non-bonded interaction is to atom O11, at 3.491 (4) Å. The closest distance between the K atoms is 3.9769 (15) Å [K1—K2^v; symmetry code: (v) x, 1/2 − y, 1/2 + z].

The geometries of the phenylphosphonate ligands are very similar, both forming similar bonds via their O atoms to the K atoms, creating a system of bridges between the metal atoms that extends in the crystal in two dimensions. Each of the two phenylphosphinate ligands exhibits three different P—O distances, with one long distance – associated with bond to the hydroxy group – and two much shorter distances, the slightly longer of which can be attributed to the bond to the anionic O atom and the other to the doubly bonded O atom. The small differences [0.022 (3) and 0.020 (3) Å for atoms P1 and P2, respectively] between the bonds to the anionic (P—O1) and doubly bonded O atoms (P—O2) is common for phosphonate ligands bound to metal centres. The median difference for similar phosphonates in the CSD is 0.016 Å (86 observations). The two ligands bind in the same fashion to the potassium centres, chelating one metal centre via the hydroxy and anion O atoms (the latter also forms a bifurcated bond to another metal centre), and forming a bond between the doubly bound O atom and another metal centre.

The water molecules form symmetric bridges between atoms K1 and K2, with additional hydrogen-bond interactions to atoms O21 and O11. The O atom of the dimethylformamide molecule exhibits interactions to three K atoms, with a closer interaction to K2 and two longer distances to K1. A hydrogen bond from the C1/H1 group to atom O22(1 − x, 2 − y, 1 − z) of a neighbouring phosphonate group is also observed.

S2. Experimental

Compound (1) was synthesized by dissolving K₂CO₃ (0.200 g, 1.447 mmol) in distilled water (30 ml) and then adding phenylphosphinic acid (0.411 g, 2.892 mmol). To the clear and colourless solution, hydrogen peroxide (10%, 10 ml) was added and the solution was refluxed for 2 h. The water was removed under vacuum to give a white powder (yield 0.447 g, 78.9%). Caution: concentrated hydrogen peroxide is explosive in the presence of bases. Crystals of (II) were formed by the slow evaporation of a solution of (I) in a mixture of dimethylformamide and water (1:1, v/v) in a desiccator. Analysis found: C 36.73, H 4.80, N 2.68%; calculated: C 37.26, H 4.38, N 2.90%.

S3. Refinement

All H atoms were located in a difference Fourier map. Phenyl H atoms were placed at idealized positions, with C—H distances of 0.95 Å, and refined using a riding model, with U_iso(H) values of 1.2U_eq(C). Methyl H atoms were positioned by a best fit to the Fourier peaks, with C—H distances of 0.98 Å, and refined as idealized rigid groups allowed to rotate but not tip [U_iso(H) = 1.5U_eq(C)]. Aldehyde atom H1 was refined freely with U_iso(H) values of 1.2U_eq(C), and the hydroxy and water H atoms were refined freely with U_iso(H) values of 1.5U_eq(O).

Computing details

Data collection: Collect (Nonius, 2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. An ORTEP-3 (Farrugia, 1997) representation (50% probability displacement ellipsoids) of the asymmetric unit of (II), showing the coordination geometry around the K atoms. Further residues are included to complete the coordination spheres but are simplified for clarity. [Symmetry codes: (i) 1 − x, 2 − y, 1 − z; (ii) 1 − x, 1 − y, 1 − z; (iii) 1 − x, 1/2 + y, 1/2 − z; (iv) 1 − x, y − 1/2, 1/2 − z.
	Fig. 2. A view of the two-dimensional net in (II), showing hydrogen bonding between the phenylphosphonate ligands and dimethylformamide and water molecules. The vertical direction is parallel to the b axis and the horizontal is parallel to the c axis. Phenyl C atoms are shown as lines.
	Fig. 3. A view (a) perpendicular and (b) parallel to the bc plane of the polymeric structure of (II). Phenyl C atoms are shown as lines.

poly[µ₂-aqua-m₃-dimethylformide-bis(µ₃-phenylphosphonato)dipotassium]

Crystal data

[K2(C3H7NO)(C6H6O3P)2(H2O)]	F(000) = 1000
Mr = 483.47	Dx = 1.52 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 16207 reflections
a = 16.988 (5) Å	θ = 0.4–26.0°
b = 8.264 (5) Å	µ = 0.64 mm^−1
c = 16.684 (5) Å	T = 153 K
β = 115.545 (5)°	Plate, colorless
V = 2113.3 (16) Å^3	0.14 × 0.12 × 0.08 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	4152 independent reflections
Radiation source: Enraf–Nonius FR590	2927 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.082
ϕ or ω scans?	θmax = 26.0°, θmin = 2.5°
Absorption correction: multi-scan (Blessing, 1995)	h = −20→20
Tmin = 0.901, Tmax = 0.951	k = −10→10
25724 measured reflections	l = −20→18

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0612P)^2] where P = (Fo^2 + 2Fc^2)/3
4152 reflections	(Δ/σ)max = 0.001
270 parameters	Δρmax = 0.33 e Å^−3
0 restraints	Δρmin = −0.45 e Å^−3

Special details

Experimental. Differential scanning calorimetry was performed with samples encapsulated in aluminium pans on a Perkin-Elmer Pyris Diamond with two successive and identical heat/cool cycles under N₂ atmosphere from 10 °C to 350 °C at heating/cooling rates of 20 °C/min and 1 min ute isotherms 10 °C or 350 °C.

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
K1	0.48393 (4)	0.76680 (8)	0.44990 (4)	0.02563 (18)
K2	0.51287 (4)	0.75630 (8)	0.19922 (4)	0.02463 (18)
O1	0.56423 (15)	0.5064 (3)	0.41519 (15)	0.0301 (5)
H1A	0.593 (2)	0.530 (4)	0.388 (2)	0.045*
H1B	0.600 (2)	0.488 (4)	0.469 (2)	0.045*
P1	0.33805 (5)	0.91344 (9)	0.24331 (5)	0.0218 (2)
O11	0.36536 (13)	1.0483 (2)	0.20149 (12)	0.0266 (5)
O12	0.39210 (13)	0.7605 (2)	0.26240 (12)	0.0237 (5)
O13	0.33949 (13)	0.9678 (3)	0.33459 (12)	0.0256 (5)
H13A	0.345 (2)	1.075 (4)	0.349 (2)	0.038*
P2	0.32654 (5)	0.41668 (9)	0.34859 (5)	0.02073 (19)
O21	0.34161 (13)	0.5556 (2)	0.41123 (12)	0.0245 (5)
O22	0.37650 (12)	0.2624 (2)	0.38732 (12)	0.0223 (4)
O23	0.34709 (13)	0.4659 (3)	0.26816 (12)	0.0227 (5)
H23A	0.354 (2)	0.581 (4)	0.2584 (19)	0.034*
O2	0.58219 (14)	1.0514 (3)	0.44093 (14)	0.0330 (5)
C1	0.6599 (2)	1.0863 (4)	0.4900 (2)	0.0312 (7)
H1	0.678 (2)	1.189 (4)	0.523 (2)	0.037*
N	0.72794 (17)	0.9940 (3)	0.50084 (16)	0.0296 (6)
C2	0.7170 (2)	0.8421 (4)	0.4539 (2)	0.0411 (9)
H2A	0.7163	0.7529	0.4922	0.062*
H2B	0.7655	0.8269	0.4376	0.062*
H2C	0.6619	0.8437	0.3999	0.062*
C5	0.8147 (2)	1.0357 (5)	0.5668 (2)	0.0478 (9)
H5A	0.8128	1.1403	0.5936	0.072*
H5B	0.8544	1.0429	0.5383	0.072*
H5C	0.8355	0.9522	0.613	0.072*
C11	0.22678 (19)	0.8596 (3)	0.17227 (18)	0.0233 (6)
C12	0.1865 (2)	0.9167 (4)	0.08473 (19)	0.0303 (7)
H12	0.217	0.9888	0.0637	0.036*
C13	0.1026 (2)	0.8686 (4)	0.0287 (2)	0.0358 (8)
H13	0.0756	0.9095	−0.0303	0.043*
C14	0.0577 (2)	0.7617 (4)	0.0575 (2)	0.0350 (8)
H14	0.0003	0.7285	0.0185	0.042*
C15	0.0970 (2)	0.7035 (4)	0.1436 (2)	0.0317 (7)
H15	0.0667	0.6289	0.1635	0.038*
C16	0.1801 (2)	0.7528 (3)	0.2009 (2)	0.0257 (7)
H16	0.2058	0.714	0.2603	0.031*
C21	0.21195 (19)	0.3656 (3)	0.29914 (18)	0.0221 (6)
C22	0.1563 (2)	0.4214 (3)	0.33420 (19)	0.0270 (7)
H22	0.1779	0.4936	0.3833	0.032*
C23	0.0697 (2)	0.3732 (4)	0.2985 (2)	0.0324 (7)
H23	0.0322	0.4127	0.323	0.039*
C24	0.0376 (2)	0.2671 (4)	0.2266 (2)	0.0329 (8)
H24	−0.0217	0.2336	0.2022	0.04*
C25	0.0923 (2)	0.2106 (4)	0.1911 (2)	0.0309 (7)
H25	0.0706	0.1382	0.1421	0.037*
C26	0.1786 (2)	0.2594 (3)	0.22680 (19)	0.0252 (7)
H26	0.2157	0.2203	0.2018	0.03*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
K1	0.0268 (4)	0.0235 (4)	0.0234 (3)	0.0002 (3)	0.0077 (3)	−0.0020 (3)
K2	0.0245 (4)	0.0237 (4)	0.0269 (3)	0.0020 (3)	0.0121 (3)	0.0034 (3)
O1	0.0280 (13)	0.0362 (14)	0.0256 (11)	−0.0019 (10)	0.0109 (10)	−0.0030 (10)
P1	0.0257 (4)	0.0181 (4)	0.0214 (4)	−0.0020 (3)	0.0099 (3)	−0.0005 (3)
O11	0.0341 (12)	0.0208 (11)	0.0245 (10)	−0.0076 (9)	0.0124 (9)	−0.0004 (8)
O12	0.0237 (11)	0.0207 (11)	0.0267 (11)	0.0011 (9)	0.0109 (9)	0.0003 (8)
O13	0.0358 (13)	0.0209 (11)	0.0210 (10)	−0.0028 (10)	0.0134 (9)	−0.0008 (9)
P2	0.0229 (4)	0.0177 (4)	0.0209 (4)	0.0003 (3)	0.0088 (3)	−0.0002 (3)
O21	0.0291 (12)	0.0208 (11)	0.0247 (10)	−0.0012 (9)	0.0125 (9)	−0.0027 (8)
O22	0.0235 (11)	0.0185 (11)	0.0230 (10)	0.0021 (8)	0.0083 (9)	0.0007 (8)
O23	0.0287 (12)	0.0185 (11)	0.0223 (10)	−0.0014 (9)	0.0122 (9)	0.0000 (8)
O2	0.0291 (14)	0.0327 (13)	0.0329 (12)	0.0016 (10)	0.0094 (10)	0.0047 (10)
C1	0.039 (2)	0.0251 (18)	0.0335 (18)	0.0027 (16)	0.0195 (16)	0.0037 (14)
N	0.0311 (16)	0.0264 (15)	0.0332 (14)	0.0001 (12)	0.0157 (12)	0.0001 (11)
C2	0.050 (2)	0.0309 (19)	0.045 (2)	0.0056 (17)	0.0229 (18)	−0.0052 (16)
C5	0.034 (2)	0.048 (2)	0.056 (2)	−0.0040 (18)	0.0149 (18)	0.0003 (18)
C11	0.0264 (17)	0.0190 (15)	0.0246 (15)	0.0024 (13)	0.0109 (13)	−0.0007 (12)
C12	0.0307 (18)	0.0301 (18)	0.0277 (16)	−0.0020 (14)	0.0101 (14)	0.0022 (13)
C13	0.034 (2)	0.043 (2)	0.0226 (15)	−0.0032 (16)	0.0050 (14)	0.0007 (14)
C14	0.0235 (17)	0.040 (2)	0.0333 (17)	−0.0079 (15)	0.0042 (14)	−0.0048 (15)
C15	0.0255 (18)	0.0311 (18)	0.0385 (18)	−0.0019 (14)	0.0137 (15)	0.0014 (14)
C16	0.0263 (17)	0.0241 (17)	0.0274 (15)	0.0012 (13)	0.0123 (13)	0.0020 (13)
C21	0.0248 (17)	0.0181 (15)	0.0232 (15)	0.0024 (12)	0.0102 (13)	0.0044 (12)
C22	0.0315 (18)	0.0192 (16)	0.0310 (16)	0.0008 (13)	0.0141 (14)	0.0007 (12)
C23	0.0303 (19)	0.0267 (18)	0.0450 (19)	0.0010 (14)	0.0207 (16)	0.0022 (15)
C24	0.0237 (17)	0.0301 (18)	0.0425 (19)	−0.0025 (14)	0.0120 (15)	0.0013 (15)
C25	0.0281 (18)	0.0307 (18)	0.0294 (16)	−0.0002 (14)	0.0081 (14)	0.0014 (13)
C26	0.0254 (17)	0.0259 (17)	0.0234 (15)	0.0024 (13)	0.0097 (13)	0.0018 (12)

Geometric parameters (Å, º)

K1—O1	2.740 (3)	C2—H2B	0.98
K1—O2	2.925 (3)	C2—H2C	0.98
K1—O2^i	2.932 (2)	C5—H5A	0.98
K1—O12	2.831 (2)	C5—H5B	0.98
K1—O13	2.900 (2)	C5—H5C	0.98
K1—O21	2.822 (2)	C11—C16	1.401 (4)
K1—O22^ii	2.739 (2)	C11—C12	1.401 (4)
K2—O1^iii	2.734 (2)	C12—C13	1.384 (4)
K2—O2^iv	2.772 (2)	C12—H12	0.95
K2—O11^iv	2.650 (2)	C13—C14	1.383 (5)
K2—O12	2.681 (2)	C13—H13	0.95
K2—O22^iii	2.821 (2)	C14—C15	1.383 (4)
K2—O23^iii	2.800 (2)	C14—H14	0.95
O1—H1A	0.82 (4)	C15—C16	1.382 (4)
O1—H1B	0.85 (3)	C15—H15	0.95
P1—O11	1.491 (2)	C16—H16	0.95
P1—O12	1.513 (2)	C21—C22	1.387 (4)
P1—O13	1.578 (2)	C21—C26	1.399 (4)
P1—C11	1.801 (3)	C22—C23	1.388 (4)
O13—H13A	0.92 (3)	C22—H22	0.95
P2—O21	1.499 (2)	C23—C24	1.393 (4)
P2—O22	1.513 (2)	C23—H23	0.95
P2—O23	1.579 (2)	C24—C25	1.381 (4)
P2—C21	1.806 (3)	C24—H24	0.95
O23—H23A	0.98 (3)	C25—C26	1.383 (4)
O2—C1	1.250 (4)	C25—H25	0.95
C1—N	1.331 (4)	C26—H26	0.95
C1—H1	0.99 (3)	K1—K1^i	4.143 (3)
N—C5	1.450 (4)	K1—K2^v	3.9769 (15)
N—C2	1.449 (4)	K2—K2^iv	4.558 (2)
C2—H2A	0.98
O22^ii—K1—O1	80.99 (6)	K1^ii—O22—K2^iv	91.32 (7)
O22^ii—K1—O21	117.53 (6)	P2—O23—K2^iv	98.97 (10)
O1—K1—O21	85.50 (7)	P2—O23—H23A	118.4 (17)
O22^ii—K1—O12	157.37 (6)	K2^iv—O23—H23A	118.9 (18)
O1—K1—O12	80.76 (6)	C1—O2—K2^iii	118.57 (19)
O21—K1—O12	74.12 (6)	C1—O2—K1	128.03 (19)
O22^ii—K1—O13	146.23 (6)	K2^iii—O2—K1	113.36 (8)
O1—K1—O13	131.73 (7)	C1—O2—K1^i	93.12 (19)
O21—K1—O13	78.82 (7)	K2^iii—O2—K1^i	88.35 (7)
O12—K1—O13	51.10 (6)	K1—O2—K1^i	90.02 (7)
O22^ii—K1—O2	81.52 (6)	O2—C1—N	124.6 (3)
O1—K1—O2	105.88 (8)	O2—C1—H1	123.5 (19)
O21—K1—O2	159.58 (6)	N—C1—H1	111.8 (19)
O12—K1—O2	90.73 (6)	C1—N—C5	120.4 (3)
O13—K1—O2	81.00 (7)	C1—N—C2	121.4 (3)
O22^ii—K1—O2^i	80.15 (6)	C5—N—C2	117.9 (3)
O1—K1—O2^i	153.18 (7)	N—C2—H2A	109.5
O21—K1—O2^i	86.50 (7)	N—C2—H2B	109.5
O12—K1—O2^i	121.30 (6)	H2A—C2—H2B	109.5
O13—K1—O2^i	71.18 (6)	N—C2—H2C	109.5
O2—K1—O2^i	89.98 (7)	H2A—C2—H2C	109.5
O11^iv—K2—O12	106.63 (6)	H2B—C2—H2C	109.5
O11^iv—K2—O1^iii	159.49 (7)	N—C5—H5A	109.5
O12—K2—O1^iii	92.70 (7)	N—C5—H5B	109.5
O11^iv—K2—O2^iv	98.34 (7)	H5A—C5—H5B	109.5
O12—K2—O2^iv	94.21 (7)	N—C5—H5C	109.5
O1^iii—K2—O2^iv	86.75 (8)	H5A—C5—H5C	109.5
O11^iv—K2—O23^iii	84.90 (7)	H5B—C5—H5C	109.5
O12—K2—O23^iii	130.21 (6)	C16—C11—C12	118.3 (3)
O1^iii—K2—O23^iii	77.24 (7)	C16—C11—P1	121.2 (2)
O2^iv—K2—O23^iii	132.76 (6)	C12—C11—P1	120.3 (2)
O11^iv—K2—O22^iii	79.56 (6)	C13—C12—C11	120.4 (3)
O12—K2—O22^iii	173.05 (6)	C13—C12—H12	119.8
O1^iii—K2—O22^iii	81.57 (6)	C11—C12—H12	119.8
O2^iv—K2—O22^iii	81.58 (6)	C14—C13—C12	120.7 (3)
O23^iii—K2—O22^iii	52.46 (6)	C14—C13—H13	119.7
K2^iv—O1—K1	127.52 (9)	C12—C13—H13	119.7
K2^iv—O1—H1A	91 (3)	C13—C14—C15	119.4 (3)
K1—O1—H1A	114 (3)	C13—C14—H14	120.3
K2^iv—O1—H1B	121 (2)	C15—C14—H14	120.3
K1—O1—H1B	96 (2)	C16—C15—C14	120.5 (3)
H1A—O1—H1B	108 (3)	C16—C15—H15	119.7
O11—P1—O12	116.09 (12)	C14—C15—H15	119.7
O11—P1—O13	111.11 (12)	C15—C16—C11	120.6 (3)
O12—P1—O13	106.22 (11)	C15—C16—H16	119.7
O11—P1—C11	109.07 (13)	C11—C16—H16	119.7
O12—P1—C11	107.56 (12)	C22—C21—C26	118.4 (3)
O13—P1—C11	106.30 (12)	C22—C21—P2	121.7 (2)
P1—O11—K2^iii	120.58 (10)	C26—C21—P2	119.8 (2)
P1—O12—K2	115.22 (10)	C21—C22—C23	120.9 (3)
P1—O12—K1	102.28 (9)	C21—C22—H22	119.6
K2—O12—K1	106.52 (7)	C23—C22—H22	119.6
P1—O13—K1	97.67 (10)	C22—C23—C24	120.0 (3)
P1—O13—H13A	119.3 (19)	C22—C23—H23	120
K1—O13—H13A	114 (2)	C24—C23—H23	120
O21—P2—O22	116.87 (11)	C25—C24—C23	119.7 (3)
O21—P2—O23	111.18 (11)	C25—C24—H24	120.1
O22—P2—O23	106.94 (11)	C23—C24—H24	120.1
O21—P2—C21	108.90 (12)	C24—C25—C26	120.0 (3)
O22—P2—C21	107.08 (12)	C24—C25—H25	120
O23—P2—C21	105.18 (12)	C26—C25—H25	120
P2—O21—K1	120.35 (10)	C25—C26—C21	121.0 (3)
P2—O22—K1^ii	125.73 (10)	C25—C26—H26	119.5
P2—O22—K2^iv	99.86 (9)	C21—C26—H26	119.5
O22^ii—K1—O1—K2^iv	148.83 (11)	O23—P2—O22—K2^iv	12.39 (11)
O21—K1—O1—K2^iv	30.01 (11)	C21—P2—O22—K2^iv	124.72 (10)
O12—K1—O1—K2^iv	−44.61 (10)	O21—P2—O23—K2^iv	116.22 (11)
O13—K1—O1—K2^iv	−40.67 (15)	O22—P2—O23—K2^iv	−12.45 (11)
O2—K1—O1—K2^iv	−132.73 (10)	C21—P2—O23—K2^iv	−126.07 (11)
O2^i—K1—O1—K2^iv	103.06 (16)	O22^ii—K1—O2—C1	13.9 (2)
O12—P1—O11—K2^iii	−86.07 (14)	O1—K1—O2—C1	−64.1 (3)
O13—P1—O11—K2^iii	35.43 (16)	O21—K1—O2—C1	173.8 (2)
C11—P1—O11—K2^iii	152.28 (12)	O12—K1—O2—C1	−144.7 (2)
O11—P1—O12—K2	−6.79 (15)	O13—K1—O2—C1	164.9 (3)
O13—P1—O12—K2	−130.85 (11)	O2^i—K1—O2—C1	94.0 (3)
C11—P1—O12—K2	115.65 (12)	O22^ii—K1—O2—K2^iii	−168.26 (8)
O11—P1—O12—K1	108.30 (11)	O1—K1—O2—K2^iii	113.69 (8)
O13—P1—O12—K1	−15.76 (12)	O21—K1—O2—K2^iii	−8.3 (2)
C11—P1—O12—K1	−129.25 (11)	O12—K1—O2—K2^iii	33.10 (8)
O11^iv—K2—O12—P1	155.80 (10)	O13—K1—O2—K2^iii	−17.27 (7)
O1^iii—K2—O12—P1	−17.26 (12)	O2^i—K1—O2—K2^iii	−88.21 (8)
O2^iv—K2—O12—P1	−104.19 (12)	O22^ii—K1—O2—K1^i	−80.05 (6)
O23^iii—K2—O12—P1	58.28 (14)	O1—K1—O2—K1^i	−158.09 (6)
O11^iv—K2—O12—K1	43.17 (8)	O21—K1—O2—K1^i	79.88 (17)
O1^iii—K2—O12—K1	−129.89 (7)	O12—K1—O2—K1^i	121.31 (6)
O2^iv—K2—O12—K1	143.18 (7)	O13—K1—O2—K1^i	70.94 (6)
O23^iii—K2—O12—K1	−54.35 (10)	O2^i—K1—O2—K1^i	0
O22^ii—K1—O12—P1	−136.66 (14)	K2^iii—O2—C1—N	−118.9 (3)
O1—K1—O12—P1	−173.27 (10)	K1—O2—C1—N	58.9 (4)
O21—K1—O12—P1	98.82 (10)	K1^i—O2—C1—N	151.3 (3)
O13—K1—O12—P1	10.51 (8)	O2—C1—N—C5	−173.0 (3)
O2—K1—O12—P1	−67.29 (10)	O2—C1—N—C2	1.1 (5)
O2^i—K1—O12—P1	23.14 (12)	O11—P1—C11—C16	−170.6 (2)
O22^ii—K1—O12—K2	−15.37 (18)	O12—P1—C11—C16	62.8 (3)
O1—K1—O12—K2	−51.98 (7)	O13—P1—C11—C16	−50.7 (3)
O21—K1—O12—K2	−139.89 (8)	O11—P1—C11—C12	13.2 (3)
O13—K1—O12—K2	131.79 (9)	O12—P1—C11—C12	−113.4 (2)
O2—K1—O12—K2	53.99 (7)	O13—P1—C11—C12	133.1 (2)
O2^i—K1—O12—K2	144.42 (7)	C16—C11—C12—C13	0.3 (4)
O11—P1—O13—K1	−111.95 (11)	P1—C11—C12—C13	176.6 (3)
O12—P1—O13—K1	15.15 (11)	C11—C12—C13—C14	−1.1 (5)
C11—P1—O13—K1	129.52 (11)	C12—C13—C14—C15	0.5 (5)
O22^ii—K1—O13—P1	148.03 (10)	C13—C14—C15—C16	0.8 (5)
O1—K1—O13—P1	−14.92 (14)	C14—C15—C16—C11	−1.6 (5)
O21—K1—O13—P1	−88.45 (10)	C12—C11—C16—C15	1.0 (4)
O12—K1—O13—P1	−9.93 (8)	P1—C11—C16—C15	−175.3 (2)
O2—K1—O13—P1	88.38 (10)	O21—P2—C21—C22	−15.3 (3)
O2^i—K1—O13—P1	−178.54 (11)	O22—P2—C21—C22	112.0 (2)
O22—P2—O21—K1	84.59 (14)	O23—P2—C21—C22	−134.5 (2)
O23—P2—O21—K1	−38.54 (15)	O21—P2—C21—C26	168.6 (2)
C21—P2—O21—K1	−153.97 (11)	O22—P2—C21—C26	−64.2 (2)
O22^ii—K1—O21—P2	−105.53 (12)	O23—P2—C21—C26	49.4 (3)
O1—K1—O21—P2	−28.13 (12)	C26—C21—C22—C23	0.0 (4)
O12—K1—O21—P2	53.52 (11)	P2—C21—C22—C23	−176.2 (2)
O13—K1—O21—P2	105.98 (12)	C21—C22—C23—C24	0.2 (5)
O2—K1—O21—P2	97.0 (2)	C22—C23—C24—C25	−0.2 (5)
O2^i—K1—O21—P2	177.48 (12)	C23—C24—C25—C26	0.0 (5)
O21—P2—O22—K1^ii	−14.06 (17)	C24—C25—C26—C21	0.2 (4)
O23—P2—O22—K1^ii	111.23 (13)	C22—C21—C26—C25	−0.2 (4)
C21—P2—O22—K1^ii	−136.44 (13)	P2—C21—C26—C25	176.0 (2)
O21—P2—O22—K2^iv	−112.90 (11)

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+1, −y+1, −z+1; (iii) −x+1, y+1/2, −z+1/2; (iv) −x+1, y−1/2, −z+1/2; (v) x, −y+3/2, z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O11^iv	0.82 (4)	1.91 (4)	2.711 (3)	164 (4)
O1—H1B···O21^ii	0.85 (3)	1.85 (4)	2.686 (3)	169 (3)
O13—H13A···O22^vi	0.92 (3)	1.67 (3)	2.573 (3)	169 (3)
O23—H23A···O12	0.98 (3)	1.61 (3)	2.566 (3)	164 (3)
C1—H1···O21^i	0.99 (3)	2.47 (3)	3.393 (4)	156 (3)

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