Dimethyl 6-[1,2-bis­(methoxy­carbon­yl)-2-(triphenyl-[lambda]⁵-phosphanyl­idene)­ethyl­ideneamino]-2-methyl­sulfanyl-3,4-pyridine­dicarboxyl­ate forms a chain of hydrogen-bonded rings

In the title compound, C₃₄H₃₁N₂O₈PS, the intra­molecular distances provide evidence for polarization of the mol­ecular-electronic structure. The mol­ecules are linked into complex chains of rings by three independent C-H...O hydrogen bonds. The significance of this study lies in its finding that two of the four carbonyl O atoms play no role in the hydrogen bonding, despite the large excess of potential hydrogen-bond donors present.

S1. Comment

The triphenylphosphoranylidene unit has proven to be an effective protecting group for the amino subsitutent in aminopyrimidines and aminopyrimidinones, which are themselves useful precursors for the synthesis of substituted 2-aminopyridines (Cobo et al., 1994). We report here the synthesis and structure of the title compound, (I) (Fig. 1), prepared by reaction of dimethyl acetylenedicarboxylate with the protected 6-aminopyrimidin-4(3H)-one (II), presumably via the intermediate (III) (see the first scheme below). The first step, conversion of (II) to (III) via a Diels–Alder addition followed by a retro Diels–Alder elimination, finds a precedent in the conversion of (II) to the pyridine (IV) (Cobo et al., 2008), while the second step, also involving cycloaddition followed by cycloreversion, is closely analogous to the conversion of (V) to (VI) (Cobo et al., 1999).

The Ph₃P=N fragment of the molecule of (I) has very approximate C₃ local symmetry, as indicated by the relevant torsion angles (Table 1), while the methylsulfanyl substitutent is nearly coplanar with the pyridine ring; the displacement of atom C21 from this plane is only 0.347 (3) Å. The two carboxylate substituents on the pyridine ring are significantly rotated out of the plane of the ring, with dihedral angles between the pyridine ring and the Cx/Cx1/Ox1/Ox2 planes (x = 3 or 4, see Fig. 1) of 37.8 (2) and 44.6 (2)° when x = 3 and 4, respectively. Such similarity of conformation is not mimicked by the other pair of carboxylate substituents; the N6—C7—C8—P9 fragment is markedly non-planar and the torsional angles C8—C7—C71—O71 and C7—C8—C81—O81 differ by well over 20° (Table 1). Associated with this difference in conformation is a significant difference between the C7—C71 and C8—C81 bond lengths of 0.73 (3) Å, whereas C3—C31 and C4—C41 differ by only 0.022 (3) Å. These observations taken together indicate a modest contribution to the overall molecular–electronic structure of the polarized form (Ia) (see scheme below) involving short-range charge separation, but the long-range polarized form (Ib) is effectively ruled out by the molecular geometry. A similar conformational arrangement of the two ester groups was observed in the structure of (VI) (Cobo et al., 1999). Although the intramolecular distances in (VI) were not discussed in the original report, scrutiny of the geometry of (VI) in fact indicates electronic delocalization precisely analogous to that in (Ia).

The molecules of (I) are linked by three independent C—H···O hydrogen bonds (Table 2). The aryl atoms C922 and C934 in the molecule at (x, y, z) act as hydrogen-bond donors, respectively, to carbonyl atoms O41 and O71, both in the molecule at (x, y - 1, z), so forming C(12) and C(10) (Bernstein et al., 1995) chains respectively, generated by translation. In addition, the aryl atom C924 at (x, y, z) acts as hydrogen-bond donor to the carbonyl atom O71 in the molecule at (-x + 1/2, y - 1/2, -z + 1/2), so linking molecules related by the 2₁ screw axis along (1/4, y, 1/4) to form another C(10) chain. The combination of these three hydrogen bonds then forms a complex chain of rings running parallel to the [010] direction and containing rings of R²₂(18), R²₃(22) and R³₃(24) types (Fig. 2). Two chains of this type pass through each unit cell, but there are no direction specific interactions between the chains. In particular, despite the number of aromatic rings within the molecule, there are no C—H···π hydrogen bonds and no π–π stacking interactions.

It is notable that, although there are four independent carbonyl O atoms present in the molecule of (I) (atoms O31, O41, O71 and O81), two of them play no part in the hydrogen bonding, despite the large excess of potential hydrogen-bond donors present, while O71 acts as a double acceptor. By contrast, in the structure of the related compound (VI), there is only one C—H···O hydrogen bond, utilizing the carbonyl O atom closest to the P atom to form a C(9) chain (Cobo et al., 1999). Further analysis of the crystal structure of (VI) now shows that, in addition, pairs of these chains are linked by a single aromatic π–π stacking interaction between the aryl groups of the benzyl substituents in centrosymmetrically related molecules to form a molecular ladder running parallel to the [100] direction (Fig. 3).

Related literature

For related literature, see: Bernstein et al. (1995); Cobo et al. (1994, 1999, 2008).

S2. Experimental

A mixture of 2-methylthio-3-methyl-6-[(triphenyl -λ⁵-phosphanylidene)amino]-4(3H)-pyrimidinone, (II) (0.5 mmol), and dimethyl acetylenedicarboxylate (1.1 mmol) with dry acetonitrile (0.9 ml) was subjected to microwave radiation in a CEM monomode microwave reactor in a sealed tube under magnetic stirring for 12 min, at 323 K and 100 W maximun power; the progress of the reaction was monitored by thin-layer chromatography. After the mixture had been cooled to ambient temperature, the solvent was removed under reduced pressure. The crude product was purified by chromatography on silica gel using a mixture of dichloromethane and acetone (96:4 v/v) as eluant to give the title compound, which was then crystallized from dry ethanol to give crystals suitable for single-crystal X-ray diffraction (yellow [colourless according to CIF] blocks, 67% yield, m.p. 444 K). MS m/z (abundance %): 658 (M⁺, 59), 599 (100), 472 (15), 383 (11), 313 (11), 299 (10), 262 (46), 216 (19), 183 (54), 108 (24), 59 (16), 44 (11).

S3. Refinement

The space group P2₁/n was uniquely assigned from the systematic absences. All H atoms were located in difference maps and then treated as riding atoms, with C—H distances of 0.95 Å (arene and pyridine) or 0.98 Å (methyl), and with U_iso(H) = kU_iso(C), where k = 1.5 for the methyl groups and k = 1.2 for the other H atoms.

Computing details

Data collection: COLLECT (Hooft, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A stereoview of part of the crystal structure of (I), showing the formation of a hydrogen-bonded chain of rings parallel to [010]. For the sake of clarity, H atoms not involved in the interactions shown have been omitted.
	Fig. 3. A stereoview of part of the crystal structure of (VI), showing the formation of a molecular ladder parallel to the [100] direction in the form of a π-stacked pair of hydrogen-bonded chains. The original atom coordinates (Cobo et al., 1999) have been used and, for the sake of clarity, H atoms not involved in the motif shown have been omitted.

Dimethyl 6-[1,2-bis(methoxycarbonyl)-2-(triphenyl-λ⁵- phosphanylidene)ethylideneamino]-2-methylsulfanyl-3,4-pyridinedicarboxylate

Crystal data

C34H31N2O8PS	F(000) = 1376
Mr = 658.64	Dx = 1.376 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7297 reflections
a = 14.8046 (12) Å	θ = 3.1–27.5°
b = 12.0095 (12) Å	µ = 0.21 mm^−1
c = 18.9720 (16) Å	T = 120 K
β = 109.499 (8)°	Block, colourless
V = 3179.7 (5) Å^3	0.32 × 0.21 × 0.10 mm
Z = 4

Data collection

Bruker–Nonius KappaCCD diffractometer	7297 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	4859 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.075
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.1°
ϕ and ω scans	h = −19→19
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −15→15
Tmin = 0.942, Tmax = 0.979	l = −24→24
68029 measured reflections

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.104	H-atom parameters constrained
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0198P)^2 + 3.9308P] where P = (Fo^2 + 2Fc^2)/3
7297 reflections	(Δ/σ)max < 0.001
420 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.36 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S2	0.74173 (5)	0.56098 (6)	0.37156 (4)	0.02837 (16)
P9	0.47168 (4)	0.05220 (5)	0.25395 (3)	0.01546 (13)
O31	0.66366 (16)	0.74853 (18)	0.43157 (13)	0.0486 (6)
O32	0.58270 (13)	0.68317 (14)	0.50383 (9)	0.0267 (4)
O41	0.39904 (13)	0.71695 (14)	0.39923 (10)	0.0278 (4)
O42	0.35397 (12)	0.55774 (14)	0.44002 (10)	0.0251 (4)
O71	0.49018 (13)	0.43501 (14)	0.14740 (10)	0.0249 (4)
O72	0.61009 (12)	0.31050 (13)	0.16831 (9)	0.0208 (4)
O81	0.50517 (13)	0.03683 (14)	0.09866 (9)	0.0256 (4)
O82	0.44688 (12)	0.20833 (14)	0.06575 (9)	0.0202 (4)
N1	0.58947 (14)	0.42991 (16)	0.32063 (11)	0.0177 (4)
N6	0.46794 (14)	0.29495 (15)	0.27623 (11)	0.0154 (4)
C2	0.62252 (17)	0.5220 (2)	0.36065 (13)	0.0191 (5)
C3	0.56855 (17)	0.58407 (19)	0.39514 (13)	0.0188 (5)
C4	0.47571 (17)	0.54667 (19)	0.38571 (12)	0.0166 (5)
C5	0.44245 (17)	0.44979 (19)	0.34681 (12)	0.0164 (5)
C6	0.50129 (17)	0.39372 (19)	0.31402 (12)	0.0157 (5)
C7	0.48687 (16)	0.26589 (19)	0.21604 (12)	0.0149 (5)
C8	0.47266 (16)	0.15495 (18)	0.18875 (13)	0.0151 (5)
C21	0.77980 (19)	0.4421 (3)	0.33141 (17)	0.0367 (7)
C31	0.61049 (19)	0.6809 (2)	0.44344 (14)	0.0250 (6)
C32	0.6070 (2)	0.7815 (2)	0.54975 (17)	0.0420 (8)
C41	0.40768 (18)	0.6180 (2)	0.40989 (13)	0.0196 (5)
C42	0.2858 (2)	0.6214 (2)	0.46393 (16)	0.0316 (7)
C71	0.52783 (17)	0.34875 (19)	0.17355 (13)	0.0178 (5)
C72	0.6510 (2)	0.3769 (2)	0.12290 (16)	0.0334 (7)
C81	0.47788 (16)	0.12416 (19)	0.11601 (13)	0.0165 (5)
C82	0.4688 (2)	0.1922 (2)	−0.00229 (14)	0.0343 (7)
C911	0.57495 (17)	0.0724 (2)	0.33703 (13)	0.0204 (5)
C912	0.5754 (2)	0.0405 (2)	0.40736 (14)	0.0312 (6)
C913	0.6573 (2)	0.0550 (3)	0.46885 (16)	0.0400 (7)
C914	0.7388 (2)	0.1008 (2)	0.46113 (16)	0.0337 (7)
C915	0.73912 (19)	0.1322 (2)	0.39129 (16)	0.0304 (6)
C916	0.65755 (18)	0.1185 (2)	0.32905 (15)	0.0259 (6)
C921	0.36350 (16)	0.0474 (2)	0.27783 (12)	0.0159 (5)
C922	0.34509 (17)	−0.0475 (2)	0.31377 (13)	0.0196 (5)
C923	0.26194 (17)	−0.0535 (2)	0.33151 (13)	0.0220 (5)
C924	0.19690 (18)	0.0335 (2)	0.31356 (13)	0.0221 (6)
C925	0.21404 (17)	0.1267 (2)	0.27668 (13)	0.0202 (5)
C926	0.29722 (17)	0.13390 (19)	0.25848 (13)	0.0173 (5)
C931	0.47811 (19)	−0.08571 (19)	0.21800 (14)	0.0220 (6)
C932	0.5556 (2)	−0.1549 (2)	0.25078 (16)	0.0324 (7)
C933	0.5577 (3)	−0.2602 (2)	0.2195 (2)	0.0468 (9)
C934	0.4845 (3)	−0.2932 (2)	0.1572 (2)	0.0493 (10)
C935	0.4065 (3)	−0.2253 (2)	0.12509 (19)	0.0418 (8)
C936	0.4025 (2)	−0.1219 (2)	0.15592 (15)	0.0299 (6)
H5	0.3808	0.4216	0.3423	0.020*
H21A	0.7712	0.3745	0.3574	0.055*
H21B	0.8476	0.4503	0.3366	0.055*
H21C	0.7414	0.4365	0.2783	0.055*
H32A	0.6767	0.7912	0.5680	0.063*
H32B	0.5841	0.7735	0.5924	0.063*
H32C	0.5767	0.8466	0.5201	0.063*
H42A	0.3203	0.6756	0.5020	0.047*
H42B	0.2496	0.5708	0.4850	0.047*
H42C	0.2415	0.6606	0.4209	0.047*
H72A	0.6028	0.3889	0.0735	0.050*
H72B	0.7063	0.3379	0.1172	0.050*
H72C	0.6717	0.4490	0.1472	0.050*
H82A	0.5379	0.1810	0.0100	0.051*
H82B	0.4488	0.2581	−0.0342	0.051*
H82C	0.4344	0.1267	−0.0288	0.051*
H912	0.5197	0.0087	0.4134	0.037*
H913	0.6573	0.0332	0.5170	0.048*
H914	0.7946	0.1106	0.5037	0.040*
H915	0.7953	0.1634	0.3857	0.036*
H916	0.6580	0.1405	0.2811	0.031*
H922	0.3895	−0.1075	0.3259	0.024*
H923	0.2494	−0.1176	0.3561	0.026*
H924	0.1403	0.0294	0.3265	0.026*
H925	0.1687	0.1857	0.2639	0.024*
H926	0.3088	0.1975	0.2330	0.021*
H932	0.6065	−0.1314	0.2938	0.039*
H933	0.6102	−0.3088	0.2416	0.056*
H934	0.4874	−0.3640	0.1358	0.059*
H935	0.3558	−0.2493	0.0821	0.050*
H936	0.3482	−0.0754	0.1349	0.036*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S2	0.0219 (3)	0.0317 (4)	0.0328 (4)	−0.0092 (3)	0.0109 (3)	−0.0070 (3)
P9	0.0197 (3)	0.0121 (3)	0.0165 (3)	0.0012 (3)	0.0087 (2)	−0.0004 (3)
O31	0.0614 (15)	0.0396 (13)	0.0565 (15)	−0.0296 (12)	0.0351 (12)	−0.0253 (11)
O32	0.0438 (11)	0.0166 (9)	0.0182 (9)	−0.0034 (8)	0.0086 (8)	−0.0056 (7)
O41	0.0377 (11)	0.0145 (9)	0.0341 (11)	0.0054 (8)	0.0158 (9)	0.0005 (8)
O42	0.0298 (10)	0.0213 (9)	0.0295 (10)	0.0049 (8)	0.0170 (8)	0.0013 (8)
O71	0.0355 (10)	0.0159 (9)	0.0281 (10)	0.0049 (8)	0.0170 (8)	0.0038 (8)
O72	0.0210 (9)	0.0205 (9)	0.0253 (10)	−0.0012 (7)	0.0139 (8)	0.0009 (7)
O81	0.0409 (11)	0.0186 (9)	0.0229 (10)	0.0057 (8)	0.0180 (8)	−0.0021 (7)
O82	0.0251 (9)	0.0225 (9)	0.0143 (9)	0.0043 (7)	0.0084 (7)	0.0011 (7)
N1	0.0187 (10)	0.0164 (10)	0.0185 (10)	−0.0016 (8)	0.0070 (8)	−0.0014 (8)
N6	0.0180 (10)	0.0132 (10)	0.0161 (10)	0.0012 (8)	0.0071 (8)	−0.0008 (8)
C2	0.0200 (13)	0.0187 (13)	0.0172 (12)	−0.0023 (10)	0.0044 (10)	0.0021 (10)
C3	0.0259 (13)	0.0142 (12)	0.0156 (12)	0.0000 (10)	0.0061 (10)	0.0005 (9)
C4	0.0235 (13)	0.0139 (11)	0.0138 (11)	0.0039 (10)	0.0080 (10)	0.0029 (10)
C5	0.0194 (12)	0.0147 (11)	0.0156 (12)	0.0006 (10)	0.0065 (9)	0.0024 (10)
C6	0.0210 (13)	0.0132 (11)	0.0129 (12)	0.0029 (10)	0.0056 (10)	0.0023 (9)
C7	0.0142 (12)	0.0147 (12)	0.0150 (12)	0.0020 (9)	0.0037 (10)	0.0007 (9)
C8	0.0180 (12)	0.0132 (11)	0.0155 (12)	0.0011 (9)	0.0076 (10)	0.0001 (9)
C21	0.0186 (14)	0.0467 (18)	0.0454 (18)	0.0005 (13)	0.0116 (13)	−0.0107 (15)
C31	0.0280 (15)	0.0199 (13)	0.0254 (15)	−0.0024 (11)	0.0066 (12)	−0.0042 (11)
C32	0.063 (2)	0.0308 (17)	0.0301 (17)	−0.0116 (15)	0.0123 (15)	−0.0166 (13)
C41	0.0252 (14)	0.0196 (13)	0.0121 (12)	0.0008 (11)	0.0036 (10)	−0.0019 (10)
C42	0.0334 (16)	0.0342 (16)	0.0342 (16)	0.0088 (13)	0.0207 (13)	−0.0004 (13)
C71	0.0228 (13)	0.0143 (12)	0.0174 (12)	0.0003 (10)	0.0083 (10)	−0.0028 (10)
C72	0.0350 (16)	0.0355 (16)	0.0372 (17)	−0.0090 (13)	0.0220 (14)	0.0022 (13)
C81	0.0158 (12)	0.0162 (12)	0.0182 (12)	−0.0011 (10)	0.0064 (10)	−0.0004 (10)
C82	0.0474 (19)	0.0420 (18)	0.0161 (14)	0.0094 (14)	0.0141 (13)	0.0060 (12)
C911	0.0228 (13)	0.0175 (13)	0.0197 (13)	0.0042 (10)	0.0053 (10)	−0.0002 (10)
C912	0.0366 (16)	0.0319 (16)	0.0225 (14)	−0.0065 (13)	0.0065 (12)	0.0009 (12)
C913	0.0506 (19)	0.0416 (18)	0.0213 (15)	−0.0123 (16)	0.0032 (13)	0.0001 (14)
C914	0.0331 (16)	0.0258 (15)	0.0301 (16)	−0.0010 (13)	−0.0058 (13)	−0.0041 (12)
C915	0.0194 (14)	0.0252 (15)	0.0419 (17)	0.0035 (11)	0.0042 (12)	0.0003 (13)
C916	0.0231 (14)	0.0257 (14)	0.0291 (15)	0.0068 (11)	0.0090 (12)	0.0030 (11)
C921	0.0180 (12)	0.0174 (12)	0.0125 (11)	−0.0026 (10)	0.0054 (9)	−0.0035 (10)
C922	0.0242 (13)	0.0164 (12)	0.0188 (12)	−0.0007 (10)	0.0081 (10)	−0.0022 (10)
C923	0.0304 (14)	0.0220 (13)	0.0161 (12)	−0.0068 (12)	0.0110 (11)	−0.0031 (11)
C924	0.0195 (13)	0.0294 (15)	0.0203 (13)	−0.0081 (11)	0.0105 (10)	−0.0076 (11)
C925	0.0181 (13)	0.0227 (13)	0.0188 (13)	−0.0004 (10)	0.0049 (10)	−0.0065 (10)
C926	0.0225 (13)	0.0153 (12)	0.0142 (12)	−0.0021 (10)	0.0062 (10)	−0.0035 (10)
C931	0.0351 (15)	0.0132 (12)	0.0266 (14)	0.0002 (11)	0.0222 (12)	0.0003 (10)
C932	0.0492 (18)	0.0237 (14)	0.0359 (16)	0.0123 (13)	0.0297 (15)	0.0108 (12)
C933	0.077 (3)	0.0235 (16)	0.065 (2)	0.0212 (17)	0.058 (2)	0.0194 (16)
C934	0.095 (3)	0.0156 (15)	0.068 (3)	−0.0122 (17)	0.068 (2)	−0.0086 (15)
C935	0.063 (2)	0.0273 (16)	0.055 (2)	−0.0234 (16)	0.0456 (18)	−0.0202 (15)
C936	0.0386 (16)	0.0221 (14)	0.0371 (17)	−0.0099 (12)	0.0235 (14)	−0.0072 (12)

Geometric parameters (Å, º)

S2—C2	1.770 (2)	C42—H42C	0.98
S2—C21	1.795 (3)	C72—H72A	0.98
P9—C8	1.751 (2)	C72—H72B	0.98
P9—C921	1.805 (2)	C72—H72C	0.98
P9—C931	1.806 (2)	C82—H82A	0.98
P9—C911	1.809 (2)	C82—H82B	0.98
O31—C31	1.203 (3)	C82—H82C	0.98
O32—C31	1.341 (3)	C911—C912	1.386 (3)
O32—C32	1.440 (3)	C911—C916	1.396 (3)
O41—C41	1.205 (3)	C912—C913	1.385 (4)
O42—C41	1.336 (3)	C912—H912	0.95
O42—C42	1.454 (3)	C913—C914	1.378 (4)
O71—C71	1.202 (3)	C913—H913	0.95
O72—C71	1.336 (3)	C914—C915	1.379 (4)
O72—C72	1.447 (3)	C914—H914	0.95
O81—C81	1.208 (3)	C915—C916	1.389 (4)
O82—C81	1.360 (3)	C915—H915	0.95
O82—C82	1.445 (3)	C916—H916	0.95
N1—C2	1.338 (3)	C921—C926	1.391 (3)
N1—C6	1.342 (3)	C921—C922	1.401 (3)
N6—C7	1.311 (3)	C922—C923	1.382 (3)
N6—C6	1.389 (3)	C922—H922	0.95
C2—C3	1.404 (3)	C923—C924	1.385 (4)
C3—C4	1.400 (3)	C923—H923	0.95
C3—C31	1.483 (3)	C924—C925	1.387 (3)
C4—C5	1.378 (3)	C924—H924	0.95
C4—C41	1.505 (3)	C925—C926	1.388 (3)
C5—C6	1.400 (3)	C925—H925	0.95
C5—H5	0.95	C926—H926	0.95
C7—C8	1.419 (3)	C931—C932	1.385 (4)
C7—C71	1.528 (3)	C931—C936	1.396 (4)
C8—C81	1.455 (3)	C932—C933	1.401 (4)
C21—H21A	0.98	C932—H932	0.95
C21—H21B	0.98	C933—C934	1.369 (5)
C21—H21C	0.98	C933—H933	0.95
C32—H32A	0.98	C934—C935	1.379 (5)
C32—H32B	0.98	C934—H934	0.95
C32—H32C	0.98	C935—C936	1.382 (4)
C42—H42A	0.98	C935—H935	0.95
C42—H42B	0.98	C936—H936	0.95
C2—S2—C21	100.49 (12)	H72A—C72—H72C	109.5
C8—P9—C921	114.65 (11)	H72B—C72—H72C	109.5
C8—P9—C931	111.45 (11)	O81—C81—O82	121.3 (2)
C921—P9—C931	103.21 (11)	O81—C81—C8	127.4 (2)
C8—P9—C911	108.49 (11)	O82—C81—C8	111.33 (19)
C921—P9—C911	110.38 (11)	O82—C82—H82A	109.5
C931—P9—C911	108.44 (12)	O82—C82—H82B	109.5
C31—O32—C32	116.6 (2)	H82A—C82—H82B	109.5
C41—O42—C42	115.0 (2)	O82—C82—H82C	109.5
C71—O72—C72	115.3 (2)	H82A—C82—H82C	109.5
C81—O82—C82	113.78 (19)	H82B—C82—H82C	109.5
C2—N1—C6	118.7 (2)	C912—C911—C916	119.4 (2)
C7—N6—C6	122.3 (2)	C912—C911—P9	122.2 (2)
N1—C2—C3	123.1 (2)	C916—C911—P9	118.36 (19)
N1—C2—S2	116.50 (18)	C913—C912—C911	119.8 (3)
C3—C2—S2	120.37 (18)	C913—C912—H912	120.1
C4—C3—C2	117.2 (2)	C911—C912—H912	120.1
C4—C3—C31	121.4 (2)	C914—C913—C912	120.8 (3)
C2—C3—C31	121.2 (2)	C914—C913—H913	119.6
C5—C4—C3	120.0 (2)	C912—C913—H913	119.6
C5—C4—C41	119.2 (2)	C913—C914—C915	119.7 (3)
C3—C4—C41	120.5 (2)	C913—C914—H914	120.2
C4—C5—C6	118.7 (2)	C915—C914—H914	120.2
C4—C5—H5	120.7	C914—C915—C916	120.3 (3)
C6—C5—H5	120.7	C914—C915—H915	119.9
N1—C6—N6	119.5 (2)	C916—C915—H915	119.9
N1—C6—C5	122.2 (2)	C915—C916—C911	120.0 (3)
N6—C6—C5	118.3 (2)	C915—C916—H916	120.0
N6—C7—C8	121.3 (2)	C911—C916—H916	120.0
N6—C7—C71	121.6 (2)	C926—C921—C922	120.1 (2)
C8—C7—C71	117.1 (2)	C926—C921—P9	121.11 (18)
C7—C8—C81	122.4 (2)	C922—C921—P9	118.76 (18)
C7—C8—P9	116.04 (17)	C923—C922—C921	119.6 (2)
C81—C8—P9	120.42 (17)	C923—C922—H922	120.2
S2—C21—H21A	109.5	C921—C922—H922	120.2
S2—C21—H21B	109.5	C922—C923—C924	120.2 (2)
H21A—C21—H21B	109.5	C922—C923—H923	119.9
S2—C21—H21C	109.5	C924—C923—H923	119.9
H21A—C21—H21C	109.5	C923—C924—C925	120.3 (2)
H21B—C21—H21C	109.5	C923—C924—H924	119.9
O31—C31—O32	123.6 (2)	C925—C924—H924	119.9
O31—C31—C3	125.4 (2)	C924—C925—C926	120.2 (2)
O32—C31—C3	111.1 (2)	C924—C925—H925	119.9
O32—C32—H32A	109.5	C926—C925—H925	119.9
O32—C32—H32B	109.5	C925—C926—C921	119.6 (2)
H32A—C32—H32B	109.5	C925—C926—H926	120.2
O32—C32—H32C	109.5	C921—C926—H926	120.2
H32A—C32—H32C	109.5	C932—C931—C936	120.2 (2)
H32B—C32—H32C	109.5	C932—C931—P9	121.4 (2)
O41—C41—O42	124.1 (2)	C936—C931—P9	118.4 (2)
O41—C41—C4	123.7 (2)	C931—C932—C933	118.9 (3)
O42—C41—C4	112.1 (2)	C931—C932—H932	120.5
O42—C42—H42A	109.5	C933—C932—H932	120.5
O42—C42—H42B	109.5	C934—C933—C932	120.2 (3)
H42A—C42—H42B	109.5	C934—C933—H933	119.9
O42—C42—H42C	109.5	C932—C933—H933	119.9
H42A—C42—H42C	109.5	C933—C934—C935	121.0 (3)
H42B—C42—H42C	109.5	C933—C934—H934	119.5
O71—C71—O72	125.0 (2)	C935—C934—H934	119.5
O71—C71—C7	124.6 (2)	C934—C935—C936	119.5 (3)
O72—C71—C7	110.34 (19)	C934—C935—H935	120.2
O72—C72—H72A	109.5	C936—C935—H935	120.2
O72—C72—H72B	109.5	C935—C936—C931	120.1 (3)
H72A—C72—H72B	109.5	C935—C936—H936	120.0
O72—C72—H72C	109.5	C931—C936—H936	120.0
C6—N1—C2—C3	−1.2 (3)	C82—O82—C81—O81	−12.4 (3)
C6—N1—C2—S2	176.59 (17)	C82—O82—C81—C8	167.8 (2)
C21—S2—C2—N1	−7.6 (2)	C7—C8—C81—O81	147.6 (2)
C21—S2—C2—C3	170.2 (2)	P9—C8—C81—O81	−19.9 (3)
N1—C2—C3—C4	−0.7 (4)	C7—C8—C81—O82	−32.6 (3)
S2—C2—C3—C4	−178.34 (17)	P9—C8—C81—O82	159.98 (16)
N1—C2—C3—C31	175.6 (2)	N6—C7—C8—P9	−22.3 (3)
S2—C2—C3—C31	−2.1 (3)	C8—P9—C911—C912	151.8 (2)
C2—C3—C4—C5	2.9 (3)	C921—P9—C911—C912	25.4 (2)
C31—C3—C4—C5	−173.3 (2)	C931—P9—C911—C912	−87.0 (2)
C2—C3—C4—C41	−170.0 (2)	C8—P9—C911—C916	−30.2 (2)
C31—C3—C4—C41	13.8 (3)	C921—P9—C911—C916	−156.65 (19)
C3—C4—C5—C6	−3.3 (3)	C931—P9—C911—C916	91.0 (2)
C41—C4—C5—C6	169.6 (2)	C916—C911—C912—C913	0.3 (4)
C2—N1—C6—N6	−176.4 (2)	P9—C911—C912—C913	178.2 (2)
C2—N1—C6—C5	0.8 (3)	C911—C912—C913—C914	−0.1 (5)
C7—N6—C6—N1	−38.0 (3)	C912—C913—C914—C915	−0.2 (5)
C7—N6—C6—C5	144.7 (2)	C913—C914—C915—C916	0.3 (4)
C4—C5—C6—N1	1.5 (3)	C914—C915—C916—C911	−0.2 (4)
C4—C5—C6—N6	178.7 (2)	C912—C911—C916—C915	−0.1 (4)
C6—N6—C7—C8	164.6 (2)	P9—C911—C916—C915	−178.11 (19)
C6—N6—C7—C71	−13.6 (3)	C8—P9—C921—C926	−13.5 (2)
N6—C7—C8—C81	169.7 (2)	C931—P9—C921—C926	−134.90 (19)
C71—C7—C8—C81	−12.0 (3)	C911—P9—C921—C926	109.4 (2)
C71—C7—C8—P9	155.93 (17)	C8—P9—C921—C922	163.91 (17)
C921—P9—C8—C7	75.2 (2)	C931—P9—C921—C922	42.5 (2)
C931—P9—C8—C7	−168.04 (18)	C911—P9—C921—C922	−73.2 (2)
C911—P9—C8—C7	−48.7 (2)	C926—C921—C922—C923	−1.6 (3)
C921—P9—C8—C81	−116.60 (19)	P9—C921—C922—C923	−179.03 (18)
C931—P9—C8—C81	0.2 (2)	C921—C922—C923—C924	0.3 (3)
C911—P9—C8—C81	119.50 (19)	C922—C923—C924—C925	0.9 (4)
C32—O32—C31—O31	9.7 (4)	C923—C924—C925—C926	−0.9 (4)
C32—O32—C31—C3	−171.3 (2)	C924—C925—C926—C921	−0.4 (3)
C4—C3—C31—O31	−144.5 (3)	C922—C921—C926—C925	1.6 (3)
C2—C3—C31—O31	39.4 (4)	P9—C921—C926—C925	178.99 (17)
C4—C3—C31—O32	36.5 (3)	C8—P9—C931—C932	116.1 (2)
C2—C3—C31—O32	−139.6 (2)	C921—P9—C931—C932	−120.4 (2)
C42—O42—C41—O41	−3.4 (3)	C911—P9—C931—C932	−3.3 (2)
C42—O42—C41—C4	−179.4 (2)	C8—P9—C931—C936	−64.1 (2)
C5—C4—C41—O41	−130.7 (3)	C921—P9—C931—C936	59.4 (2)
C3—C4—C41—O41	42.2 (3)	C911—P9—C931—C936	176.50 (19)
C5—C4—C41—O42	45.3 (3)	C936—C931—C932—C933	1.6 (4)
C3—C4—C41—O42	−141.8 (2)	P9—C931—C932—C933	−178.6 (2)
C72—O72—C71—O71	−4.4 (3)	C931—C932—C933—C934	0.5 (4)
C72—O72—C71—C7	174.28 (19)	C932—C933—C934—C935	−1.5 (4)
N6—C7—C71—O71	−57.9 (3)	C933—C934—C935—C936	0.5 (4)
C8—C7—C71—O71	123.8 (3)	C934—C935—C936—C931	1.6 (4)
N6—C7—C71—O72	123.4 (2)	C932—C931—C936—C935	−2.6 (4)
C8—C7—C71—O72	−54.9 (3)	P9—C931—C936—C935	177.6 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C922—H922···O41^i	0.95	2.50	3.225 (3)	133
C924—H924···O71^ii	0.95	2.43	3.315 (3)	155
C934—H934···O71^i	0.95	2.42	3.272 (3)	149

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