Ethyl 2-meth­oxy-6-[(triphenyl­phos­pho­ranyl­idene)amino]nicotinate and ethyl 2-methyl­sulfanyl-6-[(tri­phenyl­phospho­ranyl­idene)­amino]­nicotinate

The mol­ecules of ethyl 2-meth­oxy-6-[(triphenyl­phospho­ranyl­idene)amino]nicotinate, C₂₇H₂₅N₂O₃P, (I), and ethyl 2-methylsulfanyl-6-[(triphenyl­phospho­ranyl­idene)amino]nicotinate, C₂₇H₂₅N₂O₂PS, (II), have almost identical bond lengths and mol­ecular conformations, and both show evidence for polarized electronic structures. However, the crystal structures, as illustrated by the weak hydrogen bonds linking the mol­ecules, are significantly different. The significance of this study lies in the observation that two compounds which are almost identical in constitution, configuration and conformation nonetheless adopt different crystal structures.

S1. Comment

2-Aminopyridines are an important class of heterocyclic compounds with applications in the agrochemical and pharmaceutical sectors (Vijn et al., 1993), and an effective route to substituted 2-aminopyridines has been developed (Cobo et al., 1994) based on tandem Diels–Alder/retro Diels–Alder reactions of 6-aminopyrimidin-4(3H)-ones with acetylenic esters. The structures of two such products have been reported (Low et al., 1996). The triphenylphosphoranylidene unit is an effective protecting group for the 6-amino substituent (Wamhoff et al., 1986), and this is readily introduced by reaction of the aminopyrimidine precursor with triphenylphosphine in the presence of hexachloroethane (Wamhoff et al., 1986). The structures of the protected precursors, (III) and (IV) (see scheme), were reported several years ago (Low et al., 1998), and here we report the structures of the title compounds, (I) and (II), derived from (III) and (IV), respectively, using their reactions with ethyl propiolate (ethyl acetylenemonocarboxylate) conducted under microwave irradiation. While the molecular structures of compounds (I) and (II) are almost identical, their crystal structures differ considerably.

Compounds (I) and (II) both crystallize in space group P1 and the repeat vectors of the two unit cells are extremely similar, with the maximum difference, in c, being less than 1%. However, the cell angles in (II) are all close to the supplementary values in (I), i.e. each angle θ (θ = α, β or γ) in (II) corresponds rather closely to (180° - θ) in (I), such that no transformation can interconvert the two unit cells.

The molecular structures of (I) and (II) (Figs. 1 and 2) are very similar. The conformations, as defined by the leading torsion angles (Table 1), are almost identical, with the Ph₃P═N fragments adopting approximate local threefold rotational symmetry, while the chain-extended ester fragment is, in both compounds, directed away from the MeX (X = O, S) substituent at C2. In each compound, there is a reasonably short intramolecular C—H···N hydrogen bond, with almost identical dimensions in the two compounds (Table 2), and these interactions may be of significance in influencing the overall molecular conformations. No such contacts are apparent in the structures of (III) and (IV) (Low et al., 1998).

With the exception of the parameters involving the MeX substituents, the corresponding bond distances in (I) and (II) are also very similar. The distances and angles around the P atoms are similar to the corresponding parameters in the precursor compounds, (III) and (IV) (Low et al., 1998). In particular, all of (I)–(IV) exhibit wide angles at N6 and all exhibit a range of ca 10° in the bond angles at P6. Within each pyridine ring, the N1—C2 bond is significantly shorter than N1—C6, while C4—C5 is significantly shorter than all of the other C—C bonds in this ring. In addition, the C3—C31 bond is somewhat short for its type (mean value 1.487 Å; Allen et al., 1987), while C31—O31 is somewhat long (mean value 1.196 Å). These observations, taken all together, support a degree of quinonoidal bond fixation within the pyridine rings, corresponding to the polarized forms (Ia) and (IIa). The bond distances in the precursor compounds, (III) and (IV), similarly show clear evidence for polarization of the molecular-electronic structures, with the short exocyclic C—N bonds, the long carbonyl C—O bonds and the similarity of the two C—C distances in the polarized fragments all pointing towards the significance of the forms (IIIa) and (IVa) in addition to the classical forms (III) and (IV).

The molecules of (I) are linked, albeit rather weakly, by three C—H···O hydrogen bonds, all involving the polarized carbonyl atom O31 as the acceptor. Atoms C64 and C65 in the molecule at (x, y, z) both act as hydrogen-bond donors to atom O31 in the molecule at (-1 + x, y, 1 + z), so forming a C(12)C(13)[R¹₂(5)] (Bernstein et al., 1995) chain of rings running parallel to the [101] direction. Anti-parallel pairs of such chains are linked by the third C—H···O hydrogen bond to form a more complex chain containing three types of ring, with alternating centrosymmetric R²₂(26) and R²₄(24) rings and pairs of R¹₂(5) rings flanking the R²₄(24) rings (Fig. 3).

By contrast, the molecules of (II) are linked by one C—H···O hydrogen bond and one C—H···π(pyridyl) hydrogen bond (Table 2), with the former generating C(12) chains running parallel to the [001] direction and the latter linking anti-parallel pairs of such chains into a chain of edge-fused centrosymmetric rings (Fig. 4). Hence, despite the almost identical intramolecular geometries of (I) and (II), their patterns of supramolecular aggregation are different. Such a contrast between the similarity in molecular structures and the difference in crystal structures could provide an interesting test for methods for crystal-structure prediction from first principles.

The original report on the structures of the precursor compounds, (III) and (IV), did not discuss the intermolecular interactions (Low et al., 1998). Analysis using the original atom coordinates shows that the molecules of (III) are linked by paired C—H···O hydrogen bonds to form a centrosymmetric R²₂(20) dimer (Fig. 5), while in (IV) a single C—H···O hydrogen bond links molecules related by translation into a C(9) chain (Fig. 6).

Related literature

For related literature, see: Allen et al. (1987); Bernstein et al. (1995); Cobo et al. (1994); Low et al. (1996, 1998); Vijn et al. (1993); Wamhoff et al. (1986).

S2. Experimental

For the synthesis of compounds (I) and (II), mixtures of the precursors, (III) or (IV), respectively (0.5 mmol), and ethyl propiolate (2.5 mmol) in dry acetonitrile (0.9 ml) were subjected to microwave irradiation (100 W for 0.5 h) in sealed tubes under magnetic stirring. The resulting mixtures were evaporated to dryness under reduced pressure, and the products were purified by chromatography on silica using dichloromethane–acetone (98:2, v/v) as eluent. After removal of the solvent, crystallization from ethanol gave samples of (I) and (II) suitable for single-crystal X-ray diffraction. Compound (I), yellow blocks, m. p. 483–484 K, yield 54%. Compound (II), yellow blocks, m. p. 492 K, yield 18%.

S3. Refinement

Crystals of (I) and (II) are triclinic. For each, the space group P1 was selected, and confirmed by the structure analysis. All H atoms were located in difference maps and then treated as riding atoms in geometrically idealized positions with C—H = 0.95 (aromatic and heteroaromatic), 0.98 (CH₃) or 0.99 Å (CH₂), and with U_iso(H) = kU_eq(C), where k = 1.5 for the methyl groups and 1.2 for all other H atoms.

Computing details

For both compounds, data collection: COLLECT (Nonius, 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 compound (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The molecular structure of compound (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 3. A stereoview of part of the crystal structure of compound (I), showing the formation of a chain of rings along [101], built from C—H···O hydrogen bonds only. For the sake of clarity, the H atoms not involved in the motifs shown have been omitted.
	Fig. 4. A stereoview of part of the crystal structure of compound (II), showing the formation of a chain of rings along [001], built from C—H···O and C—H···π(pyridyl) hydrogen bonds. For the sake of clarity, H atoms bonded to those C atoms which are not involved in the motifs shown have been omitted.
	Fig. 5. A stereoview of part of the crystal structure of compound (III), showing the formation of a hydrogen-bonded R^22(20) dimer. The original atom coordinates (Low et al., 1998) have been used and, for the sake of clarity, H atoms not involved in the motif shown have been omitted.
	Fig. 6. A stereoview of part of the crystal structure of compound (IV), showing the formation of a hydrogen-bonded C(9) chain along [010]. The original atom coordinates (Low et al., 1998) have been used and, for the sake of clarity, H atoms not involved in the motif shown have been omitted.

(I) ethyl 2-methoxy-6-[(triphenylphosphoranylidene)amino]nicotinate

Crystal data

C27H25N2O3P	Z = 2
Mr = 456.46	F(000) = 480
Triclinic, P1	Dx = 1.307 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.5336 (18) Å	Cell parameters from 5321 reflections
b = 11.063 (3) Å	θ = 2.2–27.5°
c = 13.426 (3) Å	µ = 0.15 mm^−1
α = 73.722 (18)°	T = 120 K
β = 72.389 (16)°	Block, yellow
γ = 85.93 (2)°	0.22 × 0.20 × 0.15 mm
V = 1159.5 (5) Å^3

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	5321 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	3750 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.080
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 2.2°
ϕ and ω scans	h = −10→11
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −14→14
Tmin = 0.972, Tmax = 0.978	l = −17→17
30925 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) = 0.121	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0304P)^2 + 1.1007P] where P = (Fo^2 + 2Fc^2)/3
5321 reflections	(Δ/σ)max < 0.001
300 parameters	Δρmax = 0.32 e Å^−3
0 restraints	Δρmin = −0.40 e Å^−3

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

	x	y	z	Uiso*/Ueq
P6	0.42082 (7)	0.76380 (5)	0.41097 (5)	0.01679 (14)
O21	0.7713 (2)	0.73146 (15)	0.04432 (13)	0.0259 (4)
O31	0.8155 (2)	0.56356 (16)	−0.07349 (14)	0.0351 (4)
O32	0.6941 (2)	0.37623 (14)	0.01935 (12)	0.0239 (4)
N1	0.5680 (2)	0.69210 (17)	0.20646 (15)	0.0189 (4)
N6	0.3660 (2)	0.64965 (17)	0.37722 (15)	0.0195 (4)
C2	0.6495 (3)	0.6544 (2)	0.12023 (17)	0.0197 (5)
C3	0.6204 (3)	0.5403 (2)	0.10165 (18)	0.0200 (5)
C4	0.4932 (3)	0.4646 (2)	0.18253 (18)	0.0216 (5)
C5	0.4064 (3)	0.5009 (2)	0.27276 (18)	0.0217 (5)
C6	0.4478 (3)	0.6161 (2)	0.28530 (18)	0.0194 (5)
C21	0.8079 (3)	0.8419 (2)	0.0698 (2)	0.0340 (6)
C31	0.7198 (3)	0.4995 (2)	0.00711 (18)	0.0219 (5)
C32	0.7958 (3)	0.3266 (2)	−0.06761 (19)	0.0277 (5)
C33	0.7453 (3)	0.1914 (2)	−0.0417 (2)	0.0360 (6)
C61	0.3189 (3)	0.7353 (2)	0.55353 (17)	0.0184 (4)
C62	0.3765 (3)	0.7890 (2)	0.61844 (19)	0.0236 (5)
C63	0.2907 (3)	0.7701 (2)	0.72700 (19)	0.0253 (5)
C64	0.1479 (3)	0.6973 (2)	0.77224 (19)	0.0260 (5)
C65	0.0922 (3)	0.6420 (2)	0.70846 (19)	0.0253 (5)
C66	0.1762 (3)	0.6613 (2)	0.59944 (19)	0.0231 (5)
C71	0.3557 (3)	0.9185 (2)	0.34794 (18)	0.0188 (4)
C72	0.2649 (3)	0.9969 (2)	0.4092 (2)	0.0260 (5)
C73	0.2129 (3)	1.1131 (2)	0.3582 (2)	0.0314 (6)
C74	0.2494 (3)	1.1524 (2)	0.2464 (2)	0.0303 (6)
C75	0.3381 (3)	1.0743 (2)	0.1858 (2)	0.0335 (6)
C76	0.3909 (3)	0.9588 (2)	0.2350 (2)	0.0285 (5)
C81	0.6387 (3)	0.7744 (2)	0.39215 (17)	0.0187 (5)
C82	0.7251 (3)	0.8878 (2)	0.34761 (19)	0.0233 (5)
C83	0.8943 (3)	0.8902 (2)	0.3303 (2)	0.0279 (5)
C84	0.9758 (3)	0.7795 (2)	0.3571 (2)	0.0316 (6)
C85	0.8895 (3)	0.6666 (2)	0.4026 (2)	0.0330 (6)
C86	0.7211 (3)	0.6633 (2)	0.4206 (2)	0.0265 (5)
H4	0.4669	0.3866	0.1744	0.026*
H5	0.3193	0.4493	0.3264	0.026*
H21A	0.8340	0.8172	0.1389	0.051*
H21B	0.7123	0.8970	0.0757	0.051*
H21C	0.9023	0.8869	0.0121	0.051*
H32A	0.9133	0.3326	−0.0728	0.033*
H32B	0.7795	0.3749	−0.1378	0.033*
H33A	0.6290	0.1868	−0.0371	0.054*
H33B	0.7618	0.1447	0.0280	0.054*
H33C	0.8121	0.1546	−0.0990	0.054*
H62	0.4747	0.8386	0.5880	0.028*
H63	0.3299	0.8073	0.7709	0.030*
H64	0.0886	0.6854	0.8467	0.031*
H65	−0.0043	0.5905	0.7397	0.030*
H66	0.1365	0.6240	0.5559	0.028*
H72	0.2385	0.9707	0.4862	0.031*
H73	0.1516	1.1660	0.4005	0.038*
H74	0.2140	1.2320	0.2117	0.036*
H75	0.3630	1.1007	0.1089	0.040*
H76	0.4517	0.9064	0.1920	0.034*
H82	0.6688	0.9641	0.3288	0.028*
H83	0.9534	0.9680	0.3002	0.034*
H84	1.0915	0.7808	0.3443	0.038*
H85	0.9460	0.5905	0.4216	0.040*
H86	0.6622	0.5854	0.4523	0.032*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P6	0.0148 (3)	0.0156 (3)	0.0199 (3)	−0.0025 (2)	−0.0041 (2)	−0.0051 (2)
O21	0.0269 (9)	0.0213 (8)	0.0252 (9)	−0.0071 (7)	−0.0003 (7)	−0.0055 (7)
O31	0.0433 (11)	0.0269 (10)	0.0257 (9)	−0.0085 (8)	0.0061 (8)	−0.0077 (8)
O32	0.0281 (9)	0.0210 (8)	0.0222 (8)	−0.0008 (7)	−0.0045 (7)	−0.0081 (7)
N1	0.0171 (9)	0.0184 (9)	0.0214 (10)	−0.0015 (7)	−0.0054 (8)	−0.0057 (8)
N6	0.0179 (9)	0.0185 (9)	0.0231 (10)	−0.0044 (7)	−0.0044 (8)	−0.0081 (8)
C2	0.0187 (11)	0.0187 (11)	0.0188 (11)	−0.0023 (9)	−0.0050 (9)	−0.0003 (9)
C3	0.0200 (11)	0.0182 (11)	0.0215 (11)	0.0022 (9)	−0.0066 (9)	−0.0052 (9)
C4	0.0239 (12)	0.0159 (11)	0.0259 (12)	−0.0017 (9)	−0.0088 (9)	−0.0054 (9)
C5	0.0197 (11)	0.0202 (11)	0.0233 (12)	−0.0042 (9)	−0.0022 (9)	−0.0068 (9)
C6	0.0166 (11)	0.0194 (11)	0.0227 (11)	0.0004 (8)	−0.0071 (9)	−0.0047 (9)
C21	0.0301 (14)	0.0268 (13)	0.0386 (15)	−0.0139 (11)	0.0042 (11)	−0.0108 (12)
C31	0.0243 (12)	0.0197 (11)	0.0212 (12)	0.0011 (9)	−0.0065 (10)	−0.0052 (10)
C32	0.0335 (14)	0.0264 (13)	0.0223 (12)	0.0038 (10)	−0.0049 (10)	−0.0093 (10)
C33	0.0400 (15)	0.0289 (14)	0.0416 (16)	−0.0011 (11)	−0.0062 (12)	−0.0196 (12)
C61	0.0191 (11)	0.0161 (11)	0.0195 (11)	0.0007 (8)	−0.0057 (9)	−0.0042 (9)
C62	0.0254 (12)	0.0203 (12)	0.0253 (12)	−0.0037 (9)	−0.0077 (10)	−0.0055 (10)
C63	0.0320 (13)	0.0229 (12)	0.0241 (12)	0.0023 (10)	−0.0126 (10)	−0.0070 (10)
C64	0.0268 (13)	0.0288 (13)	0.0190 (12)	0.0053 (10)	−0.0036 (10)	−0.0055 (10)
C65	0.0205 (12)	0.0277 (13)	0.0239 (12)	−0.0030 (9)	−0.0003 (9)	−0.0072 (10)
C66	0.0192 (11)	0.0237 (12)	0.0272 (12)	−0.0031 (9)	−0.0064 (9)	−0.0079 (10)
C71	0.0138 (10)	0.0155 (10)	0.0268 (12)	−0.0028 (8)	−0.0060 (9)	−0.0044 (9)
C72	0.0270 (13)	0.0242 (12)	0.0299 (13)	0.0015 (10)	−0.0120 (10)	−0.0085 (10)
C73	0.0331 (14)	0.0231 (13)	0.0433 (16)	0.0061 (10)	−0.0151 (12)	−0.0144 (12)
C74	0.0223 (12)	0.0227 (13)	0.0433 (16)	−0.0007 (10)	−0.0136 (11)	−0.0001 (11)
C75	0.0297 (14)	0.0334 (14)	0.0292 (14)	0.0016 (11)	−0.0061 (11)	0.0014 (11)
C76	0.0248 (13)	0.0287 (13)	0.0262 (13)	0.0041 (10)	−0.0036 (10)	−0.0037 (10)
C81	0.0154 (10)	0.0228 (11)	0.0193 (11)	−0.0037 (8)	−0.0052 (8)	−0.0068 (9)
C82	0.0227 (12)	0.0211 (12)	0.0263 (12)	−0.0047 (9)	−0.0065 (10)	−0.0064 (10)
C83	0.0213 (12)	0.0292 (13)	0.0332 (14)	−0.0114 (10)	−0.0056 (10)	−0.0081 (11)
C84	0.0180 (12)	0.0384 (15)	0.0423 (15)	−0.0048 (10)	−0.0095 (11)	−0.0154 (12)
C85	0.0238 (13)	0.0315 (14)	0.0483 (16)	0.0035 (10)	−0.0181 (12)	−0.0107 (12)
C86	0.0227 (12)	0.0211 (12)	0.0357 (14)	−0.0025 (9)	−0.0102 (10)	−0.0055 (10)

Geometric parameters (Å, º)

P6—N6	1.5975 (18)	C62—H62	0.95
P6—C61	1.792 (2)	C63—C64	1.386 (3)
P6—C81	1.807 (2)	C63—H63	0.95
P6—C71	1.814 (2)	C64—C65	1.384 (3)
O21—C2	1.358 (3)	C64—H64	0.95
O21—C21	1.435 (3)	C65—C66	1.383 (3)
O31—C31	1.207 (3)	C65—H65	0.95
O32—C31	1.352 (3)	C66—H66	0.95
O32—C32	1.448 (3)	C71—C72	1.396 (3)
N1—C2	1.319 (3)	C71—C76	1.397 (3)
N1—C6	1.359 (3)	C72—C73	1.388 (3)
N6—C6	1.359 (3)	C72—H72	0.95
C2—C3	1.406 (3)	C73—C74	1.381 (4)
C3—C4	1.401 (3)	C73—H73	0.95
C3—C31	1.466 (3)	C74—C75	1.382 (4)
C4—C5	1.365 (3)	C74—H74	0.95
C4—H4	0.95	C75—C76	1.377 (3)
C5—C6	1.413 (3)	C75—H75	0.95
C5—H5	0.95	C76—H76	0.95
C21—H21A	0.98	C81—C82	1.385 (3)
C21—H21B	0.98	C81—C86	1.389 (3)
C21—H21C	0.98	C82—C83	1.392 (3)
C32—C33	1.500 (3)	C82—H82	0.95
C32—H32A	0.99	C83—C84	1.377 (4)
C32—H32B	0.99	C83—H83	0.95
C33—H33A	0.98	C84—C85	1.381 (4)
C33—H33B	0.98	C84—H84	0.95
C33—H33C	0.98	C85—C86	1.384 (3)
C61—C66	1.392 (3)	C85—H85	0.95
C61—C62	1.394 (3)	C86—H86	0.95
C62—C63	1.382 (3)
N6—P6—C61	105.47 (10)	C63—C62—H62	120.0
N6—P6—C81	114.99 (10)	C61—C62—H62	120.0
C61—P6—C81	107.20 (10)	C62—C63—C64	120.4 (2)
N6—P6—C71	115.46 (10)	C62—C63—H63	119.8
C61—P6—C71	105.61 (10)	C64—C63—H63	119.8
C81—P6—C71	107.39 (10)	C63—C64—C65	119.7 (2)
C2—O21—C21	116.54 (18)	C63—C64—H64	120.2
C31—O32—C32	115.16 (18)	C65—C64—H64	120.2
C2—N1—C6	118.93 (19)	C66—C65—C64	120.4 (2)
C6—N6—P6	124.02 (15)	C66—C65—H65	119.8
N1—C2—O21	117.30 (19)	C64—C65—H65	119.8
N1—C2—C3	124.9 (2)	C65—C66—C61	120.0 (2)
O21—C2—C3	117.8 (2)	C65—C66—H66	120.0
C4—C3—C2	115.3 (2)	C61—C66—H66	120.0
C4—C3—C31	121.7 (2)	C72—C71—C76	118.6 (2)
C2—C3—C31	122.9 (2)	C72—C71—P6	121.92 (18)
C5—C4—C3	121.3 (2)	C76—C71—P6	119.38 (17)
C5—C4—H4	119.4	C73—C72—C71	120.2 (2)
C3—C4—H4	119.4	C73—C72—H72	119.9
C4—C5—C6	119.2 (2)	C71—C72—H72	119.9
C4—C5—H5	120.4	C74—C73—C72	120.6 (2)
C6—C5—H5	120.4	C74—C73—H73	119.7
N6—C6—N1	120.49 (19)	C72—C73—H73	119.7
N6—C6—C5	119.1 (2)	C73—C74—C75	119.1 (2)
N1—C6—C5	120.4 (2)	C73—C74—H74	120.4
O21—C21—H21A	109.5	C75—C74—H74	120.4
O21—C21—H21B	109.5	C76—C75—C74	121.1 (2)
H21A—C21—H21B	109.5	C76—C75—H75	119.5
O21—C21—H21C	109.5	C74—C75—H75	119.5
H21A—C21—H21C	109.5	C75—C76—C71	120.3 (2)
H21B—C21—H21C	109.5	C75—C76—H76	119.9
O31—C31—O32	121.6 (2)	C71—C76—H76	119.9
O31—C31—C3	126.6 (2)	C82—C81—C86	119.8 (2)
O32—C31—C3	111.79 (19)	C82—C81—P6	122.38 (18)
O32—C32—C33	107.3 (2)	C86—C81—P6	117.81 (17)
O32—C32—H32A	110.3	C81—C82—C83	120.1 (2)
C33—C32—H32A	110.3	C81—C82—H82	119.9
O32—C32—H32B	110.3	C83—C82—H82	119.9
C33—C32—H32B	110.3	C84—C83—C82	119.9 (2)
H32A—C32—H32B	108.5	C84—C83—H83	120.1
C32—C33—H33A	109.5	C82—C83—H83	120.1
C32—C33—H33B	109.5	C83—C84—C85	120.0 (2)
H33A—C33—H33B	109.5	C83—C84—H84	120.0
C32—C33—H33C	109.5	C85—C84—H84	120.0
H33A—C33—H33C	109.5	C84—C85—C86	120.5 (2)
H33B—C33—H33C	109.5	C84—C85—H85	119.7
C66—C61—C62	119.4 (2)	C86—C85—H85	119.7
C66—C61—P6	119.08 (17)	C85—C86—C81	119.7 (2)
C62—C61—P6	121.44 (17)	C85—C86—H86	120.2
C63—C62—C61	120.0 (2)	C81—C86—H86	120.2
C61—P6—N6—C6	−161.23 (18)	C61—C62—C63—C64	0.4 (3)
C81—P6—N6—C6	−43.4 (2)	C62—C63—C64—C65	0.8 (4)
C71—P6—N6—C6	82.6 (2)	C63—C64—C65—C66	−1.4 (4)
C6—N1—C2—O21	−178.51 (19)	C64—C65—C66—C61	0.8 (4)
C6—N1—C2—C3	1.0 (3)	C62—C61—C66—C65	0.4 (3)
C21—O21—C2—N1	4.8 (3)	P6—C61—C66—C65	−177.57 (18)
C21—O21—C2—C3	−174.7 (2)	N6—P6—C71—C72	124.57 (19)
N1—C2—C3—C4	0.6 (3)	C61—P6—C71—C72	8.5 (2)
O21—C2—C3—C4	−179.9 (2)	C81—P6—C71—C72	−105.68 (19)
N1—C2—C3—C31	−176.8 (2)	N6—P6—C71—C76	−52.7 (2)
O21—C2—C3—C31	2.7 (3)	C61—P6—C71—C76	−168.77 (18)
C2—C3—C4—C5	−0.5 (3)	C81—P6—C71—C76	77.1 (2)
C31—C3—C4—C5	176.9 (2)	C76—C71—C72—C73	−0.7 (3)
C3—C4—C5—C6	−1.0 (3)	P6—C71—C72—C73	−178.01 (18)
P6—N6—C6—N1	−11.1 (3)	C71—C72—C73—C74	0.3 (4)
P6—N6—C6—C5	168.82 (17)	C72—C73—C74—C75	0.2 (4)
C2—N1—C6—N6	177.3 (2)	C73—C74—C75—C76	−0.3 (4)
C2—N1—C6—C5	−2.6 (3)	C74—C75—C76—C71	−0.1 (4)
C4—C5—C6—N6	−177.3 (2)	C72—C71—C76—C75	0.6 (4)
C4—C5—C6—N1	2.6 (3)	P6—C71—C76—C75	177.96 (19)
C32—O32—C31—O31	3.4 (3)	N6—P6—C81—C82	136.53 (19)
C32—O32—C31—C3	−176.17 (19)	C61—P6—C81—C82	−106.6 (2)
C4—C3—C31—O31	169.0 (2)	C71—P6—C81—C82	6.5 (2)
C2—C3—C31—O31	−13.8 (4)	N6—P6—C81—C86	−41.3 (2)
C4—C3—C31—O32	−11.5 (3)	C61—P6—C81—C86	75.6 (2)
C2—C3—C31—O32	165.7 (2)	C71—P6—C81—C86	−171.33 (18)
C31—O32—C32—C33	−177.9 (2)	C86—C81—C82—C83	0.7 (3)
N6—P6—C61—C66	−23.7 (2)	P6—C81—C82—C83	−177.12 (18)
C81—P6—C61—C66	−146.68 (18)	C81—C82—C83—C84	0.3 (4)
C71—P6—C61—C66	99.03 (19)	C82—C83—C84—C85	−1.0 (4)
N6—P6—C61—C62	158.42 (18)	C83—C84—C85—C86	0.7 (4)
C81—P6—C61—C62	35.4 (2)	C84—C85—C86—C81	0.3 (4)
C71—P6—C61—C62	−78.9 (2)	C82—C81—C86—C85	−1.0 (4)
C66—C61—C62—C63	−1.0 (3)	P6—C81—C86—C85	176.87 (19)
P6—C61—C62—C63	176.91 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C76—H76···N1	0.95	2.48	3.284 (3)	142
C64—H64···O31^i	0.95	2.55	3.138 (3)	120
C65—H65···O31^i	0.95	2.46	3.096 (3)	124
C74—H74···O31^ii	0.95	2.54	3.466 (3)	164

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

(II) Ethyl 2-methylsulfanyl-6-[(triphenylphosphoranylidene)amino]nicotinate

Crystal data

C27H25N2O2PS	Z = 2
Mr = 472.52	F(000) = 496
Triclinic, P1	Dx = 1.323 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.5671 (14) Å	Cell parameters from 5400 reflections
b = 11.0617 (6) Å	θ = 3.2–27.5°
c = 13.547 (2) Å	µ = 0.23 mm^−1
α = 102.987 (8)°	T = 120 K
β = 106.417 (12)°	Block, yellow
γ = 94.596 (10)°	0.46 × 0.31 × 0.29 mm
V = 1185.7 (3) Å^3

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	5400 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	4362 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.2°
ϕ and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −14→13
Tmin = 0.901, Tmax = 0.936	l = −17→17
24840 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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.098	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0409P)^2 + 0.7635P] where P = (Fo^2 + 2Fc^2)/3
5400 reflections	(Δ/σ)max = 0.001
300 parameters	Δρmax = 0.29 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
S21	0.66708 (5)	0.74151 (4)	0.96911 (3)	0.02315 (11)
P6	0.66502 (5)	0.75652 (4)	0.58072 (3)	0.01650 (10)
O31	0.77752 (16)	0.55697 (12)	1.06406 (9)	0.0302 (3)
O32	0.80751 (15)	0.36788 (11)	0.97403 (9)	0.0242 (3)
N1	0.71708 (16)	0.67783 (12)	0.78131 (10)	0.0178 (3)
N6	0.74784 (16)	0.63978 (12)	0.60969 (10)	0.0187 (3)
C2	0.72802 (19)	0.64059 (14)	0.86988 (12)	0.0185 (3)
C3	0.78322 (19)	0.52838 (15)	0.88577 (12)	0.0193 (3)
C4	0.8278 (2)	0.45357 (15)	0.80280 (12)	0.0206 (3)
C5	0.8181 (2)	0.49073 (15)	0.71169 (12)	0.0205 (3)
C6	0.76002 (19)	0.60440 (14)	0.70141 (12)	0.0177 (3)
C21	0.5695 (3)	0.84629 (17)	0.89579 (15)	0.0316 (4)
C31	0.7891 (2)	0.48939 (16)	0.98338 (12)	0.0214 (3)
C32	0.8040 (2)	0.32149 (17)	1.06586 (13)	0.0263 (4)
C33	0.8286 (3)	0.18668 (18)	1.04022 (16)	0.0361 (4)
C61	0.6295 (2)	0.73180 (14)	0.44001 (12)	0.0192 (3)
C62	0.5093 (2)	0.78628 (15)	0.37914 (13)	0.0234 (3)
C63	0.4863 (2)	0.76680 (17)	0.27077 (13)	0.0270 (4)
C64	0.5804 (2)	0.69269 (17)	0.22276 (13)	0.0284 (4)
C65	0.6988 (2)	0.63766 (17)	0.28251 (14)	0.0289 (4)
C66	0.7246 (2)	0.65804 (16)	0.39133 (13)	0.0235 (3)
C71	0.79198 (19)	0.90912 (15)	0.64353 (13)	0.0196 (3)
C72	0.8179 (2)	0.99309 (16)	0.58480 (14)	0.0264 (4)
C73	0.9195 (2)	1.10820 (17)	0.63560 (16)	0.0309 (4)
C74	0.9966 (2)	1.13934 (16)	0.74425 (15)	0.0288 (4)
C75	0.9735 (2)	1.05526 (17)	0.80279 (14)	0.0289 (4)
C76	0.8719 (2)	0.94080 (16)	0.75309 (13)	0.0249 (4)
C81	0.46807 (19)	0.76946 (15)	0.60262 (12)	0.0190 (3)
C82	0.4237 (2)	0.88451 (16)	0.64168 (13)	0.0233 (3)
C83	0.2713 (2)	0.88936 (17)	0.65897 (14)	0.0291 (4)
C84	0.1643 (2)	0.77977 (19)	0.63712 (15)	0.0316 (4)
C85	0.2075 (2)	0.66544 (18)	0.59706 (16)	0.0322 (4)
C86	0.3588 (2)	0.65907 (16)	0.57938 (14)	0.0248 (4)
H4	0.8650	0.3764	0.8099	0.025*
H5	0.8500	0.4406	0.6561	0.025*
H21A	0.6518	0.8951	0.8767	0.047*
H21B	0.5192	0.9034	0.9399	0.047*
H21C	0.4841	0.7975	0.8308	0.047*
H32A	0.6970	0.3284	1.0793	0.032*
H32B	0.8928	0.3708	1.1301	0.032*
H33A	0.7428	0.1398	0.9747	0.054*
H33B	0.8221	0.1506	1.0990	0.054*
H33C	0.9371	0.1815	1.0303	0.054*
H62	0.4435	0.8365	0.4117	0.028*
H63	0.4053	0.8046	0.2294	0.032*
H64	0.5638	0.6795	0.1485	0.034*
H65	0.7625	0.5859	0.2492	0.035*
H66	0.8074	0.6215	0.4326	0.028*
H72	0.7661	0.9718	0.5099	0.032*
H73	0.9358	1.1655	0.5953	0.037*
H74	1.0651	1.2181	0.7788	0.035*
H75	1.0277	1.0762	0.8774	0.035*
H76	0.8566	0.8838	0.7938	0.030*
H82	0.4974	0.9599	0.6566	0.028*
H83	0.2411	0.9680	0.6858	0.035*
H84	0.0608	0.7829	0.6496	0.038*
H85	0.1328	0.5904	0.5815	0.039*
H86	0.3877	0.5802	0.5517	0.030*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S21	0.0275 (2)	0.0245 (2)	0.0178 (2)	0.00471 (16)	0.00973 (16)	0.00253 (15)
P6	0.0181 (2)	0.0167 (2)	0.01467 (19)	0.00265 (14)	0.00539 (15)	0.00361 (14)
O31	0.0410 (8)	0.0341 (7)	0.0201 (6)	0.0118 (6)	0.0126 (5)	0.0100 (5)
O32	0.0304 (7)	0.0246 (6)	0.0183 (6)	0.0028 (5)	0.0057 (5)	0.0096 (5)
N1	0.0187 (7)	0.0186 (6)	0.0158 (6)	0.0016 (5)	0.0059 (5)	0.0036 (5)
N6	0.0211 (7)	0.0193 (6)	0.0178 (6)	0.0052 (5)	0.0077 (5)	0.0062 (5)
C2	0.0168 (7)	0.0191 (7)	0.0167 (7)	−0.0014 (6)	0.0043 (6)	0.0013 (6)
C3	0.0188 (8)	0.0218 (8)	0.0159 (7)	0.0001 (6)	0.0041 (6)	0.0045 (6)
C4	0.0223 (8)	0.0190 (8)	0.0193 (8)	0.0032 (6)	0.0037 (6)	0.0059 (6)
C5	0.0243 (8)	0.0202 (8)	0.0177 (7)	0.0054 (6)	0.0079 (6)	0.0036 (6)
C6	0.0172 (7)	0.0182 (7)	0.0162 (7)	0.0000 (6)	0.0043 (6)	0.0035 (6)
C21	0.0428 (11)	0.0276 (9)	0.0331 (10)	0.0138 (8)	0.0218 (9)	0.0093 (8)
C31	0.0181 (8)	0.0262 (8)	0.0190 (8)	0.0022 (6)	0.0035 (6)	0.0073 (6)
C32	0.0280 (9)	0.0312 (9)	0.0215 (8)	0.0010 (7)	0.0065 (7)	0.0133 (7)
C33	0.0464 (12)	0.0337 (10)	0.0332 (10)	0.0064 (9)	0.0128 (9)	0.0179 (8)
C61	0.0212 (8)	0.0183 (7)	0.0163 (7)	−0.0009 (6)	0.0047 (6)	0.0038 (6)
C62	0.0250 (8)	0.0227 (8)	0.0208 (8)	0.0025 (6)	0.0048 (7)	0.0057 (6)
C63	0.0278 (9)	0.0294 (9)	0.0206 (8)	−0.0013 (7)	0.0009 (7)	0.0104 (7)
C64	0.0332 (10)	0.0317 (9)	0.0174 (8)	−0.0059 (7)	0.0071 (7)	0.0053 (7)
C65	0.0355 (10)	0.0304 (9)	0.0233 (9)	0.0035 (8)	0.0143 (8)	0.0056 (7)
C66	0.0275 (9)	0.0239 (8)	0.0217 (8)	0.0054 (7)	0.0097 (7)	0.0080 (6)
C71	0.0171 (7)	0.0187 (7)	0.0225 (8)	0.0039 (6)	0.0068 (6)	0.0034 (6)
C72	0.0260 (9)	0.0245 (9)	0.0271 (9)	0.0022 (7)	0.0033 (7)	0.0101 (7)
C73	0.0301 (10)	0.0215 (9)	0.0401 (10)	0.0002 (7)	0.0070 (8)	0.0123 (8)
C74	0.0231 (9)	0.0205 (8)	0.0380 (10)	−0.0005 (7)	0.0095 (8)	−0.0005 (7)
C75	0.0277 (9)	0.0281 (9)	0.0249 (9)	−0.0028 (7)	0.0083 (7)	−0.0026 (7)
C76	0.0268 (9)	0.0253 (9)	0.0204 (8)	−0.0017 (7)	0.0080 (7)	0.0026 (7)
C81	0.0195 (8)	0.0218 (8)	0.0167 (7)	0.0046 (6)	0.0056 (6)	0.0063 (6)
C82	0.0263 (9)	0.0211 (8)	0.0237 (8)	0.0056 (6)	0.0087 (7)	0.0063 (6)
C83	0.0287 (9)	0.0311 (9)	0.0321 (9)	0.0151 (7)	0.0119 (8)	0.0104 (7)
C84	0.0213 (9)	0.0433 (11)	0.0345 (10)	0.0104 (8)	0.0113 (8)	0.0133 (8)
C85	0.0224 (9)	0.0328 (10)	0.0398 (11)	−0.0007 (7)	0.0095 (8)	0.0080 (8)
C86	0.0225 (8)	0.0221 (8)	0.0285 (9)	0.0024 (6)	0.0082 (7)	0.0038 (7)

Geometric parameters (Å, º)

S21—C2	1.7724 (16)	C62—H62	0.95
S21—C21	1.7980 (19)	C63—C64	1.382 (3)
P6—N6	1.5944 (13)	C63—H63	0.95
P6—C61	1.7959 (16)	C64—C65	1.382 (3)
P6—C81	1.8050 (16)	C64—H64	0.95
P6—C71	1.8148 (17)	C65—C66	1.390 (2)
O31—C31	1.212 (2)	C65—H65	0.95
O32—C31	1.348 (2)	C66—H66	0.95
O32—C32	1.4551 (19)	C71—C72	1.394 (2)
N1—C2	1.335 (2)	C71—C76	1.396 (2)
N1—C6	1.3581 (19)	C72—C73	1.394 (2)
N6—C6	1.3637 (19)	C72—H72	0.95
C2—C3	1.403 (2)	C73—C74	1.381 (3)
C3—C4	1.403 (2)	C73—H73	0.95
C3—C31	1.470 (2)	C74—C75	1.387 (3)
C4—C5	1.369 (2)	C74—H74	0.95
C4—H4	0.95	C75—C76	1.387 (2)
C5—C6	1.410 (2)	C75—H75	0.95
C5—H5	0.95	C76—H76	0.95
C21—H21A	0.98	C81—C82	1.390 (2)
C21—H21B	0.98	C81—C86	1.394 (2)
C21—H21C	0.98	C82—C83	1.394 (2)
C32—C33	1.499 (3)	C82—H82	0.95
C32—H32A	0.99	C83—C84	1.380 (3)
C32—H32B	0.99	C83—H83	0.95
C33—H33A	0.98	C84—C85	1.382 (3)
C33—H33B	0.98	C84—H84	0.95
C33—H33C	0.98	C85—C86	1.388 (2)
C61—C66	1.390 (2)	C85—H85	0.95
C61—C62	1.395 (2)	C86—H86	0.95
C62—C63	1.389 (2)
C2—S21—C21	100.65 (8)	C63—C62—H62	120.1
N6—P6—C61	104.98 (7)	C61—C62—H62	120.1
N6—P6—C81	115.68 (7)	C64—C63—C62	120.36 (16)
C61—P6—C81	106.65 (7)	C64—C63—H63	119.8
N6—P6—C71	115.61 (7)	C62—C63—H63	119.8
C61—P6—C71	106.30 (7)	C63—C64—C65	120.13 (16)
C81—P6—C71	106.87 (7)	C63—C64—H64	119.9
C31—O32—C32	115.20 (13)	C65—C64—H64	119.9
C2—N1—C6	119.34 (13)	C64—C65—C66	119.99 (17)
C6—N6—P6	124.59 (11)	C64—C65—H65	120.0
N1—C2—C3	123.27 (14)	C66—C65—H65	120.0
N1—C2—S21	116.16 (12)	C65—C66—C61	120.16 (16)
C3—C2—S21	120.57 (12)	C65—C66—H66	119.9
C2—C3—C4	116.84 (14)	C61—C66—H66	119.9
C2—C3—C31	121.43 (14)	C72—C71—C76	119.12 (15)
C4—C3—C31	121.70 (14)	C72—C71—P6	121.89 (13)
C5—C4—C3	120.61 (15)	C76—C71—P6	118.92 (12)
C5—C4—H4	119.7	C73—C72—C71	120.21 (16)
C3—C4—H4	119.7	C73—C72—H72	119.9
C4—C5—C6	119.13 (14)	C71—C72—H72	119.9
C4—C5—H5	120.4	C74—C73—C72	120.25 (17)
C6—C5—H5	120.4	C74—C73—H73	119.9
N1—C6—N6	120.36 (14)	C72—C73—H73	119.9
N1—C6—C5	120.80 (14)	C73—C74—C75	119.79 (16)
N6—C6—C5	118.85 (14)	C73—C74—H74	120.1
S21—C21—H21A	109.5	C75—C74—H74	120.1
S21—C21—H21B	109.5	C74—C75—C76	120.39 (17)
H21A—C21—H21B	109.5	C74—C75—H75	119.8
S21—C21—H21C	109.5	C76—C75—H75	119.8
H21A—C21—H21C	109.5	C75—C76—C71	120.22 (16)
H21B—C21—H21C	109.5	C75—C76—H76	119.9
O31—C31—O32	122.60 (15)	C71—C76—H76	119.9
O31—C31—C3	124.81 (15)	C82—C81—C86	119.88 (15)
O32—C31—C3	112.59 (13)	C82—C81—P6	122.25 (13)
O32—C32—C33	106.83 (14)	C86—C81—P6	117.87 (12)
O32—C32—H32A	110.4	C81—C82—C83	120.06 (16)
C33—C32—H32A	110.4	C81—C82—H82	120.0
O32—C32—H32B	110.4	C83—C82—H82	120.0
C33—C32—H32B	110.4	C84—C83—C82	119.90 (16)
H32A—C32—H32B	108.6	C84—C83—H83	120.1
C32—C33—H33A	109.5	C82—C83—H83	120.1
C32—C33—H33B	109.5	C83—C84—C85	120.07 (17)
H33A—C33—H33B	109.5	C83—C84—H84	120.0
C32—C33—H33C	109.5	C85—C84—H84	120.0
H33A—C33—H33C	109.5	C84—C85—C86	120.70 (17)
H33B—C33—H33C	109.5	C84—C85—H85	119.6
C66—C61—C62	119.58 (15)	C86—C85—H85	119.6
C66—C61—P6	119.31 (12)	C85—C86—C81	119.38 (16)
C62—C61—P6	121.11 (12)	C85—C86—H86	120.3
C63—C62—C61	119.76 (16)	C81—C86—H86	120.3
C61—P6—N6—C6	−163.70 (13)	C61—C62—C63—C64	0.7 (3)
C81—P6—N6—C6	−46.46 (16)	C62—C63—C64—C65	−0.2 (3)
C71—P6—N6—C6	79.53 (15)	C63—C64—C65—C66	−0.8 (3)
C6—N1—C2—C3	0.4 (2)	C64—C65—C66—C61	1.2 (3)
C6—N1—C2—S21	−179.28 (11)	C62—C61—C66—C65	−0.7 (3)
C21—S21—C2—N1	11.65 (14)	P6—C61—C66—C65	179.90 (13)
C21—S21—C2—C3	−168.05 (14)	N6—P6—C71—C72	128.28 (14)
N1—C2—C3—C4	−0.2 (2)	C61—P6—C71—C72	12.25 (16)
S21—C2—C3—C4	179.50 (12)	C81—P6—C71—C72	−101.37 (14)
N1—C2—C3—C31	−178.32 (14)	N6—P6—C71—C76	−48.76 (15)
S21—C2—C3—C31	1.4 (2)	C61—P6—C71—C76	−164.78 (13)
C2—C3—C4—C5	0.5 (2)	C81—P6—C71—C76	81.60 (14)
C31—C3—C4—C5	178.65 (15)	C76—C71—C72—C73	−1.4 (2)
C3—C4—C5—C6	−1.0 (2)	P6—C71—C72—C73	−178.42 (13)
C2—N1—C6—N6	179.16 (14)	C71—C72—C73—C74	0.7 (3)
C2—N1—C6—C5	−1.0 (2)	C72—C73—C74—C75	0.5 (3)
P6—N6—C6—N1	−7.7 (2)	C73—C74—C75—C76	−0.9 (3)
P6—N6—C6—C5	172.42 (12)	C74—C75—C76—C71	0.1 (3)
C4—C5—C6—N1	1.3 (2)	C72—C71—C76—C75	1.0 (2)
C4—C5—C6—N6	−178.83 (15)	P6—C71—C76—C75	178.11 (13)
C32—O32—C31—O31	3.1 (2)	N6—P6—C81—C82	141.77 (13)
C32—O32—C31—C3	−176.39 (13)	C61—P6—C81—C82	−101.93 (14)
C2—C3—C31—O31	−14.1 (3)	C71—P6—C81—C82	11.45 (16)
C4—C3—C31—O31	167.84 (16)	N6—P6—C81—C86	−38.00 (15)
C2—C3—C31—O32	165.35 (14)	C61—P6—C81—C86	78.30 (14)
C4—C3—C31—O32	−12.7 (2)	C71—P6—C81—C86	−168.32 (13)
C31—O32—C32—C33	−179.24 (15)	C86—C81—C82—C83	0.9 (2)
N6—P6—C61—C66	−23.95 (15)	P6—C81—C82—C83	−178.88 (13)
C81—P6—C61—C66	−147.19 (13)	C81—C82—C83—C84	−0.1 (3)
C71—P6—C61—C66	99.03 (14)	C82—C83—C84—C85	−0.7 (3)
N6—P6—C61—C62	156.65 (13)	C83—C84—C85—C86	0.7 (3)
C81—P6—C61—C62	33.41 (15)	C84—C85—C86—C81	0.1 (3)
C71—P6—C61—C62	−80.36 (15)	C82—C81—C86—C85	−0.9 (2)
C66—C61—C62—C63	−0.3 (2)	P6—C81—C86—C85	178.88 (14)
P6—C61—C62—C63	179.14 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C76—H76···N1	0.95	2.43	3.246 (2)	143
C65—H65···O31^i	0.95	2.50	3.170 (2)	128
C33—H33B···Cg^ii	0.99	2.73	3.560 (2)	141

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