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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108016429/sk3237sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108016429/sk3237Isup2.hkl
Contains datablock I

CCDC reference: 697581

Comment top

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 ππ 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 ππ 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 top

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

Experimental top

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).

Refinement top

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 Uiso(H) = kUiso(C), where k = 1.5 for the methyl groups and k = 1.2 for the other H atoms.

Computing details top

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 top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] 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.
[Figure 3] 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 top
Crystal data top
C34H31N2O8PSF(000) = 1376
Mr = 658.64Dx = 1.376 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 7297 reflections
a = 14.8046 (12) Åθ = 3.1–27.5°
b = 12.0095 (12) ŵ = 0.21 mm1
c = 18.9720 (16) ÅT = 120 K
β = 109.499 (8)°Block, colourless
V = 3179.7 (5) Å30.32 × 0.21 × 0.10 mm
Z = 4
Data collection top
Bruker–Nonius KappaCCD
diffractometer
7297 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode4859 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.075
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.1°
ϕ and ω scansh = 1919
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1515
Tmin = 0.942, Tmax = 0.979l = 2424
68029 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.104H-atom parameters constrained
S = 1.10 w = 1/[σ2(Fo2) + (0.0198P)2 + 3.9308P]
where P = (Fo2 + 2Fc2)/3
7297 reflections(Δ/σ)max < 0.001
420 parametersΔρmax = 0.38 e Å3
0 restraintsΔρmin = 0.36 e Å3
Crystal data top
C34H31N2O8PSV = 3179.7 (5) Å3
Mr = 658.64Z = 4
Monoclinic, P21/nMo Kα radiation
a = 14.8046 (12) ŵ = 0.21 mm1
b = 12.0095 (12) ÅT = 120 K
c = 18.9720 (16) Å0.32 × 0.21 × 0.10 mm
β = 109.499 (8)°
Data collection top
Bruker–Nonius KappaCCD
diffractometer
7297 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
4859 reflections with I > 2σ(I)
Tmin = 0.942, Tmax = 0.979Rint = 0.075
68029 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0550 restraints
wR(F2) = 0.104H-atom parameters constrained
S = 1.10Δρmax = 0.38 e Å3
7297 reflectionsΔρmin = 0.36 e Å3
420 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S20.74173 (5)0.56098 (6)0.37156 (4)0.02837 (16)
P90.47168 (4)0.05220 (5)0.25395 (3)0.01546 (13)
O310.66366 (16)0.74853 (18)0.43157 (13)0.0486 (6)
O320.58270 (13)0.68317 (14)0.50383 (9)0.0267 (4)
O410.39904 (13)0.71695 (14)0.39923 (10)0.0278 (4)
O420.35397 (12)0.55774 (14)0.44002 (10)0.0251 (4)
O710.49018 (13)0.43501 (14)0.14740 (10)0.0249 (4)
O720.61009 (12)0.31050 (13)0.16831 (9)0.0208 (4)
O810.50517 (13)0.03683 (14)0.09866 (9)0.0256 (4)
O820.44688 (12)0.20833 (14)0.06575 (9)0.0202 (4)
N10.58947 (14)0.42991 (16)0.32063 (11)0.0177 (4)
N60.46794 (14)0.29495 (15)0.27623 (11)0.0154 (4)
C20.62252 (17)0.5220 (2)0.36065 (13)0.0191 (5)
C30.56855 (17)0.58407 (19)0.39514 (13)0.0188 (5)
C40.47571 (17)0.54667 (19)0.38571 (12)0.0166 (5)
C50.44245 (17)0.44979 (19)0.34681 (12)0.0164 (5)
C60.50129 (17)0.39372 (19)0.31402 (12)0.0157 (5)
C70.48687 (16)0.26589 (19)0.21604 (12)0.0149 (5)
C80.47266 (16)0.15495 (18)0.18875 (13)0.0151 (5)
C210.77980 (19)0.4421 (3)0.33141 (17)0.0367 (7)
C310.61049 (19)0.6809 (2)0.44344 (14)0.0250 (6)
C320.6070 (2)0.7815 (2)0.54975 (17)0.0420 (8)
C410.40768 (18)0.6180 (2)0.40989 (13)0.0196 (5)
C420.2858 (2)0.6214 (2)0.46393 (16)0.0316 (7)
C710.52783 (17)0.34875 (19)0.17355 (13)0.0178 (5)
C720.6510 (2)0.3769 (2)0.12290 (16)0.0334 (7)
C810.47788 (16)0.12416 (19)0.11601 (13)0.0165 (5)
C820.4688 (2)0.1922 (2)0.00229 (14)0.0343 (7)
C9110.57495 (17)0.0724 (2)0.33703 (13)0.0204 (5)
C9120.5754 (2)0.0405 (2)0.40736 (14)0.0312 (6)
C9130.6573 (2)0.0550 (3)0.46885 (16)0.0400 (7)
C9140.7388 (2)0.1008 (2)0.46113 (16)0.0337 (7)
C9150.73912 (19)0.1322 (2)0.39129 (16)0.0304 (6)
C9160.65755 (18)0.1185 (2)0.32905 (15)0.0259 (6)
C9210.36350 (16)0.0474 (2)0.27783 (12)0.0159 (5)
C9220.34509 (17)0.0475 (2)0.31377 (13)0.0196 (5)
C9230.26194 (17)0.0535 (2)0.33151 (13)0.0220 (5)
C9240.19690 (18)0.0335 (2)0.31356 (13)0.0221 (6)
C9250.21404 (17)0.1267 (2)0.27668 (13)0.0202 (5)
C9260.29722 (17)0.13390 (19)0.25848 (13)0.0173 (5)
C9310.47811 (19)0.08571 (19)0.21800 (14)0.0220 (6)
C9320.5556 (2)0.1549 (2)0.25078 (16)0.0324 (7)
C9330.5577 (3)0.2602 (2)0.2195 (2)0.0468 (9)
C9340.4845 (3)0.2932 (2)0.1572 (2)0.0493 (10)
C9350.4065 (3)0.2253 (2)0.12509 (19)0.0418 (8)
C9360.4025 (2)0.1219 (2)0.15592 (15)0.0299 (6)
H50.38080.42160.34230.020*
H21A0.77120.37450.35740.055*
H21B0.84760.45030.33660.055*
H21C0.74140.43650.27830.055*
H32A0.67670.79120.56800.063*
H32B0.58410.77350.59240.063*
H32C0.57670.84660.52010.063*
H42A0.32030.67560.50200.047*
H42B0.24960.57080.48500.047*
H42C0.24150.66060.42090.047*
H72A0.60280.38890.07350.050*
H72B0.70630.33790.11720.050*
H72C0.67170.44900.14720.050*
H82A0.53790.18100.01000.051*
H82B0.44880.25810.03420.051*
H82C0.43440.12670.02880.051*
H9120.51970.00870.41340.037*
H9130.65730.03320.51700.048*
H9140.79460.11060.50370.040*
H9150.79530.16340.38570.036*
H9160.65800.14050.28110.031*
H9220.38950.10750.32590.024*
H9230.24940.11760.35610.026*
H9240.14030.02940.32650.026*
H9250.16870.18570.26390.024*
H9260.30880.19750.23300.021*
H9320.60650.13140.29380.039*
H9330.61020.30880.24160.056*
H9340.48740.36400.13580.059*
H9350.35580.24930.08210.050*
H9360.34820.07540.13490.036*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S20.0219 (3)0.0317 (4)0.0328 (4)0.0092 (3)0.0109 (3)0.0070 (3)
P90.0197 (3)0.0121 (3)0.0165 (3)0.0012 (3)0.0087 (2)0.0004 (3)
O310.0614 (15)0.0396 (13)0.0565 (15)0.0296 (12)0.0351 (12)0.0253 (11)
O320.0438 (11)0.0166 (9)0.0182 (9)0.0034 (8)0.0086 (8)0.0056 (7)
O410.0377 (11)0.0145 (9)0.0341 (11)0.0054 (8)0.0158 (9)0.0005 (8)
O420.0298 (10)0.0213 (9)0.0295 (10)0.0049 (8)0.0170 (8)0.0013 (8)
O710.0355 (10)0.0159 (9)0.0281 (10)0.0049 (8)0.0170 (8)0.0038 (8)
O720.0210 (9)0.0205 (9)0.0253 (10)0.0012 (7)0.0139 (8)0.0009 (7)
O810.0409 (11)0.0186 (9)0.0229 (10)0.0057 (8)0.0180 (8)0.0021 (7)
O820.0251 (9)0.0225 (9)0.0143 (9)0.0043 (7)0.0084 (7)0.0011 (7)
N10.0187 (10)0.0164 (10)0.0185 (10)0.0016 (8)0.0070 (8)0.0014 (8)
N60.0180 (10)0.0132 (10)0.0161 (10)0.0012 (8)0.0071 (8)0.0008 (8)
C20.0200 (13)0.0187 (13)0.0172 (12)0.0023 (10)0.0044 (10)0.0021 (10)
C30.0259 (13)0.0142 (12)0.0156 (12)0.0000 (10)0.0061 (10)0.0005 (9)
C40.0235 (13)0.0139 (11)0.0138 (11)0.0039 (10)0.0080 (10)0.0029 (10)
C50.0194 (12)0.0147 (11)0.0156 (12)0.0006 (10)0.0065 (9)0.0024 (10)
C60.0210 (13)0.0132 (11)0.0129 (12)0.0029 (10)0.0056 (10)0.0023 (9)
C70.0142 (12)0.0147 (12)0.0150 (12)0.0020 (9)0.0037 (10)0.0007 (9)
C80.0180 (12)0.0132 (11)0.0155 (12)0.0011 (9)0.0076 (10)0.0001 (9)
C210.0186 (14)0.0467 (18)0.0454 (18)0.0005 (13)0.0116 (13)0.0107 (15)
C310.0280 (15)0.0199 (13)0.0254 (15)0.0024 (11)0.0066 (12)0.0042 (11)
C320.063 (2)0.0308 (17)0.0301 (17)0.0116 (15)0.0123 (15)0.0166 (13)
C410.0252 (14)0.0196 (13)0.0121 (12)0.0008 (11)0.0036 (10)0.0019 (10)
C420.0334 (16)0.0342 (16)0.0342 (16)0.0088 (13)0.0207 (13)0.0004 (13)
C710.0228 (13)0.0143 (12)0.0174 (12)0.0003 (10)0.0083 (10)0.0028 (10)
C720.0350 (16)0.0355 (16)0.0372 (17)0.0090 (13)0.0220 (14)0.0022 (13)
C810.0158 (12)0.0162 (12)0.0182 (12)0.0011 (10)0.0064 (10)0.0004 (10)
C820.0474 (19)0.0420 (18)0.0161 (14)0.0094 (14)0.0141 (13)0.0060 (12)
C9110.0228 (13)0.0175 (13)0.0197 (13)0.0042 (10)0.0053 (10)0.0002 (10)
C9120.0366 (16)0.0319 (16)0.0225 (14)0.0065 (13)0.0065 (12)0.0009 (12)
C9130.0506 (19)0.0416 (18)0.0213 (15)0.0123 (16)0.0032 (13)0.0001 (14)
C9140.0331 (16)0.0258 (15)0.0301 (16)0.0010 (13)0.0058 (13)0.0041 (12)
C9150.0194 (14)0.0252 (15)0.0419 (17)0.0035 (11)0.0042 (12)0.0003 (13)
C9160.0231 (14)0.0257 (14)0.0291 (15)0.0068 (11)0.0090 (12)0.0030 (11)
C9210.0180 (12)0.0174 (12)0.0125 (11)0.0026 (10)0.0054 (9)0.0035 (10)
C9220.0242 (13)0.0164 (12)0.0188 (12)0.0007 (10)0.0081 (10)0.0022 (10)
C9230.0304 (14)0.0220 (13)0.0161 (12)0.0068 (12)0.0110 (11)0.0031 (11)
C9240.0195 (13)0.0294 (15)0.0203 (13)0.0081 (11)0.0105 (10)0.0076 (11)
C9250.0181 (13)0.0227 (13)0.0188 (13)0.0004 (10)0.0049 (10)0.0065 (10)
C9260.0225 (13)0.0153 (12)0.0142 (12)0.0021 (10)0.0062 (10)0.0035 (10)
C9310.0351 (15)0.0132 (12)0.0266 (14)0.0002 (11)0.0222 (12)0.0003 (10)
C9320.0492 (18)0.0237 (14)0.0359 (16)0.0123 (13)0.0297 (15)0.0108 (12)
C9330.077 (3)0.0235 (16)0.065 (2)0.0212 (17)0.058 (2)0.0194 (16)
C9340.095 (3)0.0156 (15)0.068 (3)0.0122 (17)0.068 (2)0.0086 (15)
C9350.063 (2)0.0273 (16)0.055 (2)0.0234 (16)0.0456 (18)0.0202 (15)
C9360.0386 (16)0.0221 (14)0.0371 (17)0.0099 (12)0.0235 (14)0.0072 (12)
Geometric parameters (Å, º) top
S2—C21.770 (2)C42—H42C0.98
S2—C211.795 (3)C72—H72A0.98
P9—C81.751 (2)C72—H72B0.98
P9—C9211.805 (2)C72—H72C0.98
P9—C9311.806 (2)C82—H82A0.98
P9—C9111.809 (2)C82—H82B0.98
O31—C311.203 (3)C82—H82C0.98
O32—C311.341 (3)C911—C9121.386 (3)
O32—C321.440 (3)C911—C9161.396 (3)
O41—C411.205 (3)C912—C9131.385 (4)
O42—C411.336 (3)C912—H9120.95
O42—C421.454 (3)C913—C9141.378 (4)
O71—C711.202 (3)C913—H9130.95
O72—C711.336 (3)C914—C9151.379 (4)
O72—C721.447 (3)C914—H9140.95
O81—C811.208 (3)C915—C9161.389 (4)
O82—C811.360 (3)C915—H9150.95
O82—C821.445 (3)C916—H9160.95
N1—C21.338 (3)C921—C9261.391 (3)
N1—C61.342 (3)C921—C9221.401 (3)
N6—C71.311 (3)C922—C9231.382 (3)
N6—C61.389 (3)C922—H9220.95
C2—C31.404 (3)C923—C9241.385 (4)
C3—C41.400 (3)C923—H9230.95
C3—C311.483 (3)C924—C9251.387 (3)
C4—C51.378 (3)C924—H9240.95
C4—C411.505 (3)C925—C9261.388 (3)
C5—C61.400 (3)C925—H9250.95
C5—H50.95C926—H9260.95
C7—C81.419 (3)C931—C9321.385 (4)
C7—C711.528 (3)C931—C9361.396 (4)
C8—C811.455 (3)C932—C9331.401 (4)
C21—H21A0.98C932—H9320.95
C21—H21B0.98C933—C9341.369 (5)
C21—H21C0.98C933—H9330.95
C32—H32A0.98C934—C9351.379 (5)
C32—H32B0.98C934—H9340.95
C32—H32C0.98C935—C9361.382 (4)
C42—H42A0.98C935—H9350.95
C42—H42B0.98C936—H9360.95
C2—S2—C21100.49 (12)H72A—C72—H72C109.5
C8—P9—C921114.65 (11)H72B—C72—H72C109.5
C8—P9—C931111.45 (11)O81—C81—O82121.3 (2)
C921—P9—C931103.21 (11)O81—C81—C8127.4 (2)
C8—P9—C911108.49 (11)O82—C81—C8111.33 (19)
C921—P9—C911110.38 (11)O82—C82—H82A109.5
C931—P9—C911108.44 (12)O82—C82—H82B109.5
C31—O32—C32116.6 (2)H82A—C82—H82B109.5
C41—O42—C42115.0 (2)O82—C82—H82C109.5
C71—O72—C72115.3 (2)H82A—C82—H82C109.5
C81—O82—C82113.78 (19)H82B—C82—H82C109.5
C2—N1—C6118.7 (2)C912—C911—C916119.4 (2)
C7—N6—C6122.3 (2)C912—C911—P9122.2 (2)
N1—C2—C3123.1 (2)C916—C911—P9118.36 (19)
N1—C2—S2116.50 (18)C913—C912—C911119.8 (3)
C3—C2—S2120.37 (18)C913—C912—H912120.1
C4—C3—C2117.2 (2)C911—C912—H912120.1
C4—C3—C31121.4 (2)C914—C913—C912120.8 (3)
C2—C3—C31121.2 (2)C914—C913—H913119.6
C5—C4—C3120.0 (2)C912—C913—H913119.6
C5—C4—C41119.2 (2)C913—C914—C915119.7 (3)
C3—C4—C41120.5 (2)C913—C914—H914120.2
C4—C5—C6118.7 (2)C915—C914—H914120.2
C4—C5—H5120.7C914—C915—C916120.3 (3)
C6—C5—H5120.7C914—C915—H915119.9
N1—C6—N6119.5 (2)C916—C915—H915119.9
N1—C6—C5122.2 (2)C915—C916—C911120.0 (3)
N6—C6—C5118.3 (2)C915—C916—H916120.0
N6—C7—C8121.3 (2)C911—C916—H916120.0
N6—C7—C71121.6 (2)C926—C921—C922120.1 (2)
C8—C7—C71117.1 (2)C926—C921—P9121.11 (18)
C7—C8—C81122.4 (2)C922—C921—P9118.76 (18)
C7—C8—P9116.04 (17)C923—C922—C921119.6 (2)
C81—C8—P9120.42 (17)C923—C922—H922120.2
S2—C21—H21A109.5C921—C922—H922120.2
S2—C21—H21B109.5C922—C923—C924120.2 (2)
H21A—C21—H21B109.5C922—C923—H923119.9
S2—C21—H21C109.5C924—C923—H923119.9
H21A—C21—H21C109.5C923—C924—C925120.3 (2)
H21B—C21—H21C109.5C923—C924—H924119.9
O31—C31—O32123.6 (2)C925—C924—H924119.9
O31—C31—C3125.4 (2)C924—C925—C926120.2 (2)
O32—C31—C3111.1 (2)C924—C925—H925119.9
O32—C32—H32A109.5C926—C925—H925119.9
O32—C32—H32B109.5C925—C926—C921119.6 (2)
H32A—C32—H32B109.5C925—C926—H926120.2
O32—C32—H32C109.5C921—C926—H926120.2
H32A—C32—H32C109.5C932—C931—C936120.2 (2)
H32B—C32—H32C109.5C932—C931—P9121.4 (2)
O41—C41—O42124.1 (2)C936—C931—P9118.4 (2)
O41—C41—C4123.7 (2)C931—C932—C933118.9 (3)
O42—C41—C4112.1 (2)C931—C932—H932120.5
O42—C42—H42A109.5C933—C932—H932120.5
O42—C42—H42B109.5C934—C933—C932120.2 (3)
H42A—C42—H42B109.5C934—C933—H933119.9
O42—C42—H42C109.5C932—C933—H933119.9
H42A—C42—H42C109.5C933—C934—C935121.0 (3)
H42B—C42—H42C109.5C933—C934—H934119.5
O71—C71—O72125.0 (2)C935—C934—H934119.5
O71—C71—C7124.6 (2)C934—C935—C936119.5 (3)
O72—C71—C7110.34 (19)C934—C935—H935120.2
O72—C72—H72A109.5C936—C935—H935120.2
O72—C72—H72B109.5C935—C936—C931120.1 (3)
H72A—C72—H72B109.5C935—C936—H936120.0
O72—C72—H72C109.5C931—C936—H936120.0
C6—N1—C2—C31.2 (3)C82—O82—C81—O8112.4 (3)
C6—N1—C2—S2176.59 (17)C82—O82—C81—C8167.8 (2)
C21—S2—C2—N17.6 (2)C7—C8—C81—O81147.6 (2)
C21—S2—C2—C3170.2 (2)P9—C8—C81—O8119.9 (3)
N1—C2—C3—C40.7 (4)C7—C8—C81—O8232.6 (3)
S2—C2—C3—C4178.34 (17)P9—C8—C81—O82159.98 (16)
N1—C2—C3—C31175.6 (2)N6—C7—C8—P922.3 (3)
S2—C2—C3—C312.1 (3)C8—P9—C911—C912151.8 (2)
C2—C3—C4—C52.9 (3)C921—P9—C911—C91225.4 (2)
C31—C3—C4—C5173.3 (2)C931—P9—C911—C91287.0 (2)
C2—C3—C4—C41170.0 (2)C8—P9—C911—C91630.2 (2)
C31—C3—C4—C4113.8 (3)C921—P9—C911—C916156.65 (19)
C3—C4—C5—C63.3 (3)C931—P9—C911—C91691.0 (2)
C41—C4—C5—C6169.6 (2)C916—C911—C912—C9130.3 (4)
C2—N1—C6—N6176.4 (2)P9—C911—C912—C913178.2 (2)
C2—N1—C6—C50.8 (3)C911—C912—C913—C9140.1 (5)
C7—N6—C6—N138.0 (3)C912—C913—C914—C9150.2 (5)
C7—N6—C6—C5144.7 (2)C913—C914—C915—C9160.3 (4)
C4—C5—C6—N11.5 (3)C914—C915—C916—C9110.2 (4)
C4—C5—C6—N6178.7 (2)C912—C911—C916—C9150.1 (4)
C6—N6—C7—C8164.6 (2)P9—C911—C916—C915178.11 (19)
C6—N6—C7—C7113.6 (3)C8—P9—C921—C92613.5 (2)
N6—C7—C8—C81169.7 (2)C931—P9—C921—C926134.90 (19)
C71—C7—C8—C8112.0 (3)C911—P9—C921—C926109.4 (2)
C71—C7—C8—P9155.93 (17)C8—P9—C921—C922163.91 (17)
C921—P9—C8—C775.2 (2)C931—P9—C921—C92242.5 (2)
C931—P9—C8—C7168.04 (18)C911—P9—C921—C92273.2 (2)
C911—P9—C8—C748.7 (2)C926—C921—C922—C9231.6 (3)
C921—P9—C8—C81116.60 (19)P9—C921—C922—C923179.03 (18)
C931—P9—C8—C810.2 (2)C921—C922—C923—C9240.3 (3)
C911—P9—C8—C81119.50 (19)C922—C923—C924—C9250.9 (4)
C32—O32—C31—O319.7 (4)C923—C924—C925—C9260.9 (4)
C32—O32—C31—C3171.3 (2)C924—C925—C926—C9210.4 (3)
C4—C3—C31—O31144.5 (3)C922—C921—C926—C9251.6 (3)
C2—C3—C31—O3139.4 (4)P9—C921—C926—C925178.99 (17)
C4—C3—C31—O3236.5 (3)C8—P9—C931—C932116.1 (2)
C2—C3—C31—O32139.6 (2)C921—P9—C931—C932120.4 (2)
C42—O42—C41—O413.4 (3)C911—P9—C931—C9323.3 (2)
C42—O42—C41—C4179.4 (2)C8—P9—C931—C93664.1 (2)
C5—C4—C41—O41130.7 (3)C921—P9—C931—C93659.4 (2)
C3—C4—C41—O4142.2 (3)C911—P9—C931—C936176.50 (19)
C5—C4—C41—O4245.3 (3)C936—C931—C932—C9331.6 (4)
C3—C4—C41—O42141.8 (2)P9—C931—C932—C933178.6 (2)
C72—O72—C71—O714.4 (3)C931—C932—C933—C9340.5 (4)
C72—O72—C71—C7174.28 (19)C932—C933—C934—C9351.5 (4)
N6—C7—C71—O7157.9 (3)C933—C934—C935—C9360.5 (4)
C8—C7—C71—O71123.8 (3)C934—C935—C936—C9311.6 (4)
N6—C7—C71—O72123.4 (2)C932—C931—C936—C9352.6 (4)
C8—C7—C71—O7254.9 (3)P9—C931—C936—C935177.6 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C922—H922···O41i0.952.503.225 (3)133
C924—H924···O71ii0.952.433.315 (3)155
C934—H934···O71i0.952.423.272 (3)149
Symmetry codes: (i) x, y1, z; (ii) x+1/2, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC34H31N2O8PS
Mr658.64
Crystal system, space groupMonoclinic, P21/n
Temperature (K)120
a, b, c (Å)14.8046 (12), 12.0095 (12), 18.9720 (16)
β (°) 109.499 (8)
V3)3179.7 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.21
Crystal size (mm)0.32 × 0.21 × 0.10
Data collection
DiffractometerBruker–Nonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.942, 0.979
No. of measured, independent and
observed [I > 2σ(I)] reflections
68029, 7297, 4859
Rint0.075
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.104, 1.10
No. of reflections7297
No. of parameters420
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.38, 0.36

Computer programs: COLLECT (Hooft, 1999), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), SIR2004 (Burla et al., 2005), OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003), SHELXL97 (Sheldrick, 2008) and PRPKAPPA (Ferguson, 1999).

Selected geometric parameters (Å, º) top
C3—C311.483 (3)C7—C711.528 (3)
C4—C411.505 (3)C8—C811.455 (3)
C4—C3—C31—O31144.5 (3)N6—C7—C8—P922.3 (3)
C5—C4—C41—O41130.7 (3)C8—P9—C911—C912151.8 (2)
C8—C7—C71—O71123.8 (3)C8—P9—C921—C922163.91 (17)
C7—C8—C81—O81147.6 (2)C8—P9—C931—C932116.1 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C922—H922···O41i0.952.503.225 (3)133
C924—H924···O71ii0.952.433.315 (3)155
C934—H934···O71i0.952.423.272 (3)149
Symmetry codes: (i) x, y1, z; (ii) x+1/2, y1/2, z+1/2.
 

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