Two phosphate-imidazole complexes with and without a hydrogen-bonded guest mol­ecule

The mol­ecular structures of the complexes imidazolium 6,6'-di-tert-butyl-4,4'-dimethyl-2,2'-thio­diphenyl phosphate, C₃H₅N₂⁺·C₂₂H₂₈O₄PS^-, (I), and imidazolium 6,6'-di-tert-butyl-4,4'-dimethyl-2,2'-thio­diphenyl phosphate diisopropyl hydrazo­dicarboxyl­ate hemisolvate, C₃H₅N₂⁺·C₂₂H₂₈O₄PS^-·0.5C₈H₁₆N₂O₄, (II), have been determined. While (I) forms the expected hydrogen-bonded chain utilizing the two imidazole N-bound H atoms, in (II), the substituted hydrazine solvent mol­ecule inserts itself between the chains. Compound (I) exhibits a strong N-H...O hydrogen bond, with an N...O distance of 2.603 (2) Å. The hydrazine solvent molecule in (II) lies about a twofold axis and the N-bound H atoms are involved in bifurcated hydrogen bonds with phosphate O atoms. A C-bound H atom of the imidazolium cation is involved in a C-H...O inter­action with a carbonyl O atom of the hydrazine solvent mol­ecule.

S1. Comment

The imidazolium moiety of the hystidine residue plays an important role in the hydrolysis and cyclization of RNA-related biomolecules (Perreault & Anslyn, 1997). In previous reports of the imidazolium salts of diorganophosphates (Holmes et al., 1992; Clark et al., 1984; Blessing & McGandy, 1972), there were no additional guest molecules except in the salt reported by Kumara Swamy et al. (2001). In the latter salt, a hydrogen-bonded methanol molecule exhibiting C—H···O interactions with the imidazolyl CH located in between the two N atoms was included as a guest. We report here the X-ray structures of two imidazolyl compounds, imidazolium 6,6'-di-tert-butyl-4,4'-dimethyl-2,2'-thiodiphenylphosphate, [{S(6 - ^tBu-4-Me—C₆H₂O)₂}P(O)(O)][C₃N₂H₅], (I), and imidazolium 6,6'-di-tert-butyl-4,4'-dimethyl-2,2'-thiodiphenylphosphate diisopropyl hydrazodicarboxylate hemisolvate, [{S(6 - ^tBu-4-Me—C₆H₂O)₂}P(O)(O)] [C₃N₂H₅][(CH₃)₂CHO(O)CN(H)—N(H)(C(O)O(CH(CH₃)₂)], (II), the latter containing the carboxylate-substituted hydrazine as a hydrogen-bonded guest. Compounds (I) and (II) were obtained in the reaction of [{S(6 - ^tBu-4-Me—C₆H₂O)₂}PCl[N(C(O)O(CH(CH₃)₂)N—C(OCH(CH₃)₂O–] with imidazole in the presence of adventitious moisture. Compound (I) was also obtained by the direct route by treating the in situ prepared phosphate with imidazole.

The structures of (I) and (II) are shown in Figs. 1 and 2, respectively. The P—O bond distances in both compounds are in the expected range (Kumara Swamy et al., 2001, Kumaraswamy & Kumara Swamy, 2002). The eight-membered phosphocin ring has a boat–chair conformation. This situation is similar to that in the salts and methanol/ethanol solvates of [{CH₂(6 - ^tBu-4-Me—C₆H₂O)₂}P(O)(OH)] (Kumara Swamy et al., 2001), but unlike the tub conformation observed by Holmes et al. (1992) for the phosphate salt [{S(6- ^tBu-4-Me—C₆H₂O)₂}P(O)(O)][{HOC₆H₂-2,4-(CH₃)₂-6- CH₂}₂N(CH₃)H], (III) (Chandrasekaran et al., 1999). Perhaps as a consequence, the P···S distance of 3.58 Å in (I) and (II) is close to the sum of van der Waals radii (3.65 Å), with essentially no sulfur-to-phosphorus interaction. In (III), by contrast, the P···S distance was 3.281 (2) Å. This feature shows that the sulfur donor action in these phosphate salts is case sensitive and could depend on the nature of hydrogen-bonding interactions involving the cation.

In (I), hydrogen bonding (Fig. 1b) leads to the formation of a chain utilizing the H atoms on the two imidazolyl N atoms and the two phosphate O atoms. This type of chain appears to be common for the imidazolyl salts of diorganophosphates (Holmes et al., 1992, Clark et al., 1984, Blessing & McGandy, 1972, Kumara Swamy et al., 2001). The same type of chain is also present in (II), but in addition, one of the phosphoryl O atoms is involved in `bifurcated' hydrogen bonding, with additional interaction from the N-bound H atoms of the substituted hydrazine residue. These interactions lead to a `ladder' type of structure, as shown in Fig. 2(b). The hydrogen-bond angles involving the phosphoryl O atom in the bifurcated hydrogen bonds in (II) are less linear than that at the corresponding O atom (O3) in (I), as expected. Accordingly, the O···N(imidazolyl) distance in (II) is also lower than that in (I). We made an attempt to incorporate dimethyl maleate (MeO₂CCH═CHCO₂Me) in place of the substituted hydrazine, but no insertion took place.

Among the imidazolium salts of diorganophosphates, the N(—H)···O distances in (I) are the shortest; the N2···O3 distance of 2.603 (2) Å is at the lower end for such hydrogen bonds (Kumara Swamy et al., 2001) and hence comes under the category of very stong N—H···O hydrogen bonds. Since such strong hydrogen bonds were also observed by us in the salts of the analogous organophosphate, [{CH₂(6 - ^tBu-4-Me—C₆H₂O)₂}P(O)(OH)] (Kumara Swamy et al., 2001), we think that this feature is the result of the 1,3,2-dioxaphosphocin ring present in these compounds.

Although there is no significant interaction of the NCHN H atom with acceptor sites in I, there is one such interaction in (II), involving the carbonyl O atom of the substituted hydrazine and the NCHN H atom in (II). The C···O distance is short [2.980 (3) Å] and is comparable to that known for strong C—H···O hydrogen bonds (Kumara Swamy et al., 2001; Kariuki et al., 1997); the angle at the H atom, however, is quite far from linearity and the H···O distance is 2.30 Å. This `non-innocent' behaviour of the imidazolyl NCHN H atom has been reported previously (Steiner, 1997; Kumara Swamy et al., 2001). Such a feature may have some implications as regards the hydrolysis of RNA where the hystidine residue comes close to the active phosphorus site, perhaps with the NCHN H atom interacting with the ribosolyl O atom as pointed out previously by us (Kumara Swamy et al., 2001). This could `lock' the imidazolyl residue until the hydrolysis is complete. Substantiation of this hypothesis would require more structural studies, preferably containing hystidine itself.

S2. Experimental

For the preparation of (I), the phosphate S{(6 - ^tBu-4-Me—C₆H₂O)₂}P(O)OH (m.p. > 523 K; Chandrasekaran et al., 1999) was prepared by a procedure similar to that used to prepare CH₂{(6 - ^tBu-4-Me—C₆H₂O)₂}P(O)OH (Kumara Swamy et al., 2001). The phosphate (0.2 g, 0.4 mmol) was dissolved in chloroform (5 ml), and imidazole (0.032 g, 0.4 mmol) in chloroform (2 ml) was added slowly to obtain a clear solution followed by (immediate) crystallization of (I). A small amount (ca 5%) of the same compound also crystallized along with (II). M.p. > 543 K. IR (Nujol mull, cm⁻¹): 3158 (sharp), 1460, 1253. ¹H NMR (400 MHz, DMSO-d₆, p.p.m.): 1.35 (s, 18H, ^tBu—H), 2.19 (s, 6H, Ar—CH₃), 7.08, 7.29, 7.46 (s each, 6H, Ar—H + imidazolyl-H), 8.71 (s, 1H, imidazolyl-H). The signals for imidazolyl N-bound H atoms were very broad. The solubility was too low for recording a satisfactory ¹³C NMR spectrum. ³¹P NMR (160 MHz, DMSO-d₆, p.p.m.): −10.6. For the preparation of (II), to a stirred solution S{(6 - ^tBu-4-Me—C₆H₂O)₂}PCl (0.92 g, 2.2 mmol) in toluene, diisopropyl azodicarboxylate (0.45 g, 2.2 mmol) was added dropwise at 195 K and the contents were stirred overnight. Imidazole (0.15 g, 2.2 mmol) and triethylamine (0.22 g, 2.2 mmol) in toluene (5 ml) were then added. The mixture was stirred for a further 12 h and then filtered, and the solvent was evaporated in vacuo. The residue upon crystallization from dichloromethane–hexane mixture in air yielded compound (II) [0.3 g, 21.4%; a small quantity of (I) also crystallized, which could be separated by hand-picking]. M.p. 464–466 K (charring). IR (Nujol mull, cm⁻¹): 3223 (br), 3152, 1732, 1711, 1464, 1256. ¹H NMR (400 MHz, DMSO-d₆, p.p.m.): 1.15 {d, ³J(HH) = 5.2 Hz, 12H, [CH(CH₃)₂]}, 1.34 (s, 18H, ^tBu—H), 2.18 (s, 6H, Ar—CH₃), 2.48 (s, 2H, N—H), 4.74 [m, 2H, CH(CH₃)₂], 7.07 and 7.45 (s each, 5H, Ar—H + imidazolyl-H), 8.65 and 8.84 (s each, 2H, imidazolyl-H). The signals for imidazolyl N-bound H atoms were very broad. The solubility was too low for recording a satisfactory ¹³C NMR spectrum. ³¹P NMR (160 MHz, DMSO-d₆, p.p.m.): −10.5.

S3. Refinement

The N-bound H atom of the hydrazine residue in (II) was located in a difference Fourier map and refined isotropically. All other H atoms were placed geometrically and refined using a riding model, with C—H distances constrained to 0.98 Å (methine), 0.96 Å (CH₃) and 0.93 Å (aromatic), N—H distances constrained to 0.86 Å (imidazolyl), and U_iso(H) values of 1.5U_eq(C) for methyl groups and 1.2U_eq(C,N) otherwise. Compound (I) is not chiral but crystallized in a non-centrosymmetric space group and hence the absolute configuration for this structure is not relevant.

Computing details

For both compounds, data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-NT (Sheldrick, 1999); software used to prepare material for publication: SHELXTL-NT.

Figures

	Fig. 1. (a) The molecular structure of (I), showing the atom-numbering scheme and displacement ellipsoids at the 35% probability level. (b) The hydrogen-bonding scheme.
	Fig. 2. (a) The molecular structure of (II), showing the atom-numbering scheme and displacement ellipsoids at the 35% probability level. (b) The hydrogen-bonding scheme.

(I) 6,6'-di-tert-butyl-4,4'-dimethyl-2,2'-thiodiphenylphosphate

Crystal data

C3H5N2^+·C22H28O4PS^−	F(000) = 1040
Mr = 488.56	Dx = 1.271 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C-2yc	Cell parameters from 3061 reflections
a = 7.6466 (6) Å	θ = 2.5–24.6°
b = 17.0714 (12) Å	µ = 0.22 mm^−1
c = 19.7596 (14) Å	T = 295 K
β = 98.060 (1)°	Needle, colorless
V = 2553.9 (3) Å^3	0.44 × 0.30 × 0.22 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	5940 independent reflections
Radiation source: fine-focus sealed tube	4683 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
ϕ and ω scans	θmax = 28.3°, θmin = 2.1°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.762, Tmax = 0.953	k = −21→21
14692 measured reflections	l = −26→25

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.039	H-atom parameters constrained
wR(F^2) = 0.087	w = 1/[σ^2(Fo^2) + (0.0459P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.93	(Δ/σ)max = 0.032
5940 reflections	Δρmax = 0.29 e Å^−3
306 parameters	Δρmin = −0.22 e Å^−3
2 restraints	Absolute structure: Flack (1983), 2760 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (5)

Special details

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
P1	0.54345 (7)	0.37182 (3)	0.37566 (3)	0.03995 (14)
S1	0.74489 (7)	0.54321 (4)	0.45742 (3)	0.05102 (16)
O1	0.5406 (2)	0.39253 (9)	0.45487 (7)	0.0433 (4)
O2	0.71946 (19)	0.41194 (8)	0.35522 (8)	0.0446 (4)
O3	0.3879 (2)	0.40643 (8)	0.33437 (8)	0.0458 (4)
O4	0.5756 (2)	0.28704 (8)	0.37459 (9)	0.0558 (4)
C1	0.4506 (3)	0.45625 (12)	0.47710 (10)	0.0390 (5)
C2	0.2920 (3)	0.44438 (13)	0.50417 (11)	0.0400 (5)
C3	0.2108 (3)	0.51174 (13)	0.52571 (11)	0.0440 (5)
H3	0.1045	0.5060	0.5430	0.053*
C4	0.2800 (3)	0.58665 (13)	0.52265 (12)	0.0473 (6)
C5	0.4402 (3)	0.59468 (13)	0.49905 (12)	0.0448 (5)
H5	0.4918	0.6440	0.4984	0.054*
C6	0.5254 (3)	0.53035 (13)	0.47624 (10)	0.0406 (5)
C7	0.2108 (4)	0.36348 (14)	0.51318 (13)	0.0513 (6)
C8	0.0495 (4)	0.36733 (15)	0.55093 (16)	0.0656 (8)
H8A	−0.0414	0.3978	0.5248	0.098*
H8B	0.0823	0.3913	0.5948	0.098*
H8C	0.0065	0.3153	0.5569	0.098*
C9	0.3492 (4)	0.31146 (19)	0.55626 (19)	0.0916 (12)
H9A	0.2973	0.2617	0.5644	0.137*
H9B	0.3882	0.3367	0.5992	0.137*
H9C	0.4482	0.3036	0.5321	0.137*
C10	0.1470 (5)	0.32512 (19)	0.44296 (16)	0.0885 (11)
H10A	0.0846	0.2776	0.4497	0.133*
H10B	0.2472	0.3134	0.4204	0.133*
H10C	0.0699	0.3606	0.4154	0.133*
C11	0.1837 (4)	0.65727 (15)	0.54510 (17)	0.0682 (8)
H11A	0.2392	0.7042	0.5319	0.102*
H11B	0.1877	0.6564	0.5939	0.102*
H11C	0.0629	0.6561	0.5238	0.102*
C12	0.7244 (3)	0.55170 (13)	0.36694 (11)	0.0418 (5)
C13	0.7307 (3)	0.62591 (14)	0.33836 (14)	0.0494 (6)
H13	0.7293	0.6698	0.3662	0.059*
C14	0.7390 (3)	0.63567 (14)	0.27041 (13)	0.0501 (6)
C15	0.7475 (3)	0.56845 (14)	0.23111 (13)	0.0489 (6)
H15	0.7576	0.5748	0.1851	0.059*
C16	0.7419 (3)	0.49255 (13)	0.25613 (11)	0.0423 (5)
C17	0.7243 (3)	0.48561 (12)	0.32548 (11)	0.0391 (5)
C18	0.7612 (3)	0.42223 (13)	0.20911 (12)	0.0468 (6)
C19	0.5869 (4)	0.37666 (17)	0.19470 (14)	0.0664 (7)
H19A	0.6013	0.3332	0.1651	0.100*
H19B	0.4958	0.4106	0.1730	0.100*
H19C	0.5545	0.3576	0.2369	0.100*
C20	0.9089 (4)	0.36765 (17)	0.24109 (15)	0.0686 (8)
H20A	1.0168	0.3968	0.2512	0.103*
H20B	0.9248	0.3263	0.2096	0.103*
H20C	0.8778	0.3456	0.2825	0.103*
C21	0.8091 (5)	0.44871 (18)	0.13963 (15)	0.0773 (9)
H21A	0.9208	0.4753	0.1464	0.116*
H21B	0.7196	0.4836	0.1181	0.116*
H21C	0.8167	0.4038	0.1110	0.116*
C22	0.7438 (4)	0.71533 (15)	0.23820 (16)	0.0699 (8)
H22A	0.6326	0.7256	0.2106	0.105*
H22B	0.8365	0.7169	0.2101	0.105*
H22C	0.7655	0.7544	0.2734	0.105*
N1	0.6800 (3)	0.16290 (12)	0.31256 (11)	0.0562 (5)
H1N	0.6416	0.2045	0.3301	0.067*
N2	0.7631 (3)	0.04499 (11)	0.30055 (11)	0.0521 (5)
H2N	0.7882	−0.0034	0.3090	0.063*
C23	0.7004 (3)	0.09434 (16)	0.34190 (13)	0.0581 (7)
H23	0.6745	0.0824	0.3853	0.070*
C24	0.7295 (4)	0.15700 (16)	0.25018 (15)	0.0676 (8)
H24	0.7279	0.1969	0.2181	0.081*
C25	0.7813 (4)	0.08324 (16)	0.24281 (15)	0.0623 (7)
H25	0.8224	0.0622	0.2046	0.075*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0516 (3)	0.0315 (3)	0.0386 (3)	0.0089 (3)	0.0128 (2)	−0.0005 (2)
S1	0.0421 (3)	0.0654 (4)	0.0461 (3)	−0.0048 (3)	0.0080 (2)	−0.0148 (3)
O1	0.0521 (9)	0.0392 (8)	0.0405 (9)	0.0136 (7)	0.0129 (7)	0.0015 (6)
O2	0.0494 (9)	0.0400 (9)	0.0467 (9)	0.0102 (7)	0.0143 (7)	0.0009 (7)
O3	0.0539 (10)	0.0391 (8)	0.0451 (9)	0.0034 (7)	0.0090 (7)	0.0027 (7)
O4	0.0789 (12)	0.0356 (8)	0.0577 (10)	0.0134 (8)	0.0261 (9)	0.0029 (8)
C1	0.0448 (12)	0.0416 (12)	0.0308 (11)	0.0113 (10)	0.0058 (9)	−0.0046 (9)
C2	0.0449 (12)	0.0389 (12)	0.0370 (11)	0.0058 (9)	0.0080 (9)	−0.0003 (9)
C3	0.0431 (13)	0.0440 (13)	0.0467 (13)	0.0044 (10)	0.0132 (10)	−0.0052 (10)
C4	0.0500 (14)	0.0418 (13)	0.0511 (14)	0.0046 (10)	0.0098 (11)	−0.0115 (10)
C5	0.0500 (13)	0.0375 (12)	0.0481 (13)	−0.0028 (10)	0.0104 (10)	−0.0094 (10)
C6	0.0382 (11)	0.0472 (13)	0.0370 (12)	−0.0016 (10)	0.0077 (9)	−0.0073 (10)
C7	0.0633 (15)	0.0414 (13)	0.0544 (14)	0.0046 (11)	0.0260 (12)	0.0014 (11)
C8	0.0722 (19)	0.0532 (16)	0.0766 (19)	−0.0003 (13)	0.0286 (15)	0.0053 (14)
C9	0.097 (3)	0.068 (2)	0.120 (3)	0.0305 (18)	0.051 (2)	0.0466 (19)
C10	0.121 (3)	0.073 (2)	0.080 (2)	−0.047 (2)	0.044 (2)	−0.0231 (17)
C11	0.0605 (17)	0.0520 (15)	0.096 (2)	0.0081 (13)	0.0245 (16)	−0.0220 (15)
C12	0.0366 (12)	0.0474 (13)	0.0427 (13)	−0.0007 (10)	0.0106 (9)	−0.0065 (10)
C13	0.0429 (13)	0.0397 (13)	0.0662 (16)	−0.0009 (10)	0.0106 (11)	−0.0116 (11)
C14	0.0444 (13)	0.0423 (13)	0.0627 (16)	−0.0004 (10)	0.0038 (11)	−0.0011 (11)
C15	0.0489 (14)	0.0485 (14)	0.0491 (14)	0.0012 (10)	0.0060 (11)	0.0054 (11)
C16	0.0405 (12)	0.0427 (13)	0.0449 (13)	0.0032 (10)	0.0100 (10)	−0.0028 (10)
C17	0.0346 (11)	0.0385 (11)	0.0453 (13)	0.0041 (9)	0.0095 (9)	−0.0006 (9)
C18	0.0565 (14)	0.0440 (13)	0.0424 (13)	−0.0002 (11)	0.0156 (11)	−0.0048 (10)
C19	0.0734 (18)	0.0698 (18)	0.0586 (17)	−0.0136 (15)	0.0178 (14)	−0.0209 (13)
C20	0.0727 (19)	0.0664 (19)	0.0684 (18)	0.0209 (15)	0.0166 (15)	−0.0147 (14)
C21	0.114 (3)	0.0676 (19)	0.0580 (17)	−0.0056 (17)	0.0398 (17)	−0.0084 (14)
C22	0.079 (2)	0.0424 (15)	0.086 (2)	0.0007 (13)	0.0037 (15)	0.0074 (14)
N1	0.0596 (13)	0.0456 (12)	0.0624 (14)	0.0178 (10)	0.0051 (11)	−0.0119 (10)
N2	0.0560 (13)	0.0370 (11)	0.0603 (13)	0.0115 (9)	−0.0025 (10)	−0.0022 (9)
C23	0.0669 (17)	0.0590 (16)	0.0471 (14)	0.0184 (13)	0.0034 (12)	0.0003 (13)
C24	0.085 (2)	0.0488 (15)	0.0744 (19)	0.0150 (14)	0.0312 (16)	0.0095 (13)
C25	0.0752 (18)	0.0525 (16)	0.0628 (17)	0.0160 (13)	0.0217 (14)	−0.0048 (13)

Geometric parameters (Å, º)

P1—O3	1.4687 (16)	C12—C17	1.394 (3)
P1—O4	1.4688 (15)	C13—C14	1.363 (3)
P1—O1	1.6077 (15)	C13—H13	0.9300
P1—O2	1.6112 (16)	C14—C15	1.392 (3)
S1—C12	1.779 (2)	C14—C22	1.504 (3)
S1—C6	1.783 (2)	C15—C16	1.390 (3)
O1—C1	1.391 (2)	C15—H15	0.9300
O2—C17	1.391 (2)	C16—C17	1.401 (3)
C1—C6	1.389 (3)	C16—C18	1.538 (3)
C1—C2	1.407 (3)	C18—C20	1.531 (4)
C2—C3	1.401 (3)	C18—C19	1.535 (4)
C2—C7	1.535 (3)	C18—C21	1.537 (4)
C3—C4	1.389 (3)	C19—H19A	0.9600
C3—H3	0.9300	C19—H19B	0.9600
C4—C5	1.377 (3)	C19—H19C	0.9600
C4—C11	1.512 (3)	C20—H20A	0.9600
C5—C6	1.384 (3)	C20—H20B	0.9600
C5—H5	0.9300	C20—H20C	0.9600
C7—C8	1.529 (4)	C21—H21A	0.9600
C7—C9	1.543 (4)	C21—H21B	0.9600
C7—C10	1.550 (4)	C21—H21C	0.9600
C8—H8A	0.9600	C22—H22A	0.9600
C8—H8B	0.9600	C22—H22B	0.9600
C8—H8C	0.9600	C22—H22C	0.9600
C9—H9A	0.9600	N1—C23	1.306 (3)
C9—H9B	0.9600	N1—C24	1.343 (3)
C9—H9C	0.9600	N1—H1N	0.8600
C10—H10A	0.9600	N2—C23	1.310 (3)
C10—H10B	0.9600	N2—C25	1.339 (3)
C10—H10C	0.9600	N2—H2N	0.8600
C11—H11A	0.9600	C23—H23	0.9300
C11—H11B	0.9600	C24—C25	1.334 (4)
C11—H11C	0.9600	C24—H24	0.9300
C12—C13	1.391 (3)	C25—H25	0.9300
O3—P1—O4	120.85 (10)	C14—C13—C12	121.4 (2)
O3—P1—O1	109.38 (9)	C14—C13—H13	119.3
O4—P1—O1	104.82 (9)	C12—C13—H13	119.3
O3—P1—O2	109.24 (9)	C13—C14—C15	117.5 (2)
O4—P1—O2	105.53 (9)	C13—C14—C22	122.3 (2)
O1—P1—O2	106.03 (9)	C15—C14—C22	120.2 (2)
C12—S1—C6	105.47 (10)	C16—C15—C14	124.3 (2)
C1—O1—P1	123.66 (13)	C16—C15—H15	117.8
C17—O2—P1	124.25 (13)	C14—C15—H15	117.8
C6—C1—O1	119.03 (19)	C15—C16—C17	116.0 (2)
C6—C1—C2	120.93 (19)	C15—C16—C18	120.2 (2)
O1—C1—C2	119.91 (19)	C17—C16—C18	123.8 (2)
C3—C2—C1	116.1 (2)	O2—C17—C12	118.77 (19)
C3—C2—C7	119.96 (19)	O2—C17—C16	120.11 (19)
C1—C2—C7	123.92 (19)	C12—C17—C16	120.9 (2)
C4—C3—C2	123.7 (2)	C20—C18—C19	109.8 (2)
C4—C3—H3	118.2	C20—C18—C21	107.1 (2)
C2—C3—H3	118.2	C19—C18—C21	107.0 (2)
C5—C4—C3	118.0 (2)	C20—C18—C16	110.7 (2)
C5—C4—C11	120.9 (2)	C19—C18—C16	110.68 (19)
C3—C4—C11	121.1 (2)	C21—C18—C16	111.42 (19)
C4—C5—C6	120.8 (2)	C18—C19—H19A	109.5
C4—C5—H5	119.6	C18—C19—H19B	109.5
C6—C5—H5	119.6	H19A—C19—H19B	109.5
C5—C6—C1	120.3 (2)	C18—C19—H19C	109.5
C5—C6—S1	118.03 (17)	H19A—C19—H19C	109.5
C1—C6—S1	121.06 (16)	H19B—C19—H19C	109.5
C8—C7—C2	112.64 (19)	C18—C20—H20A	109.5
C8—C7—C9	107.0 (2)	C18—C20—H20B	109.5
C2—C7—C9	108.9 (2)	H20A—C20—H20B	109.5
C8—C7—C10	106.3 (2)	C18—C20—H20C	109.5
C2—C7—C10	111.0 (2)	H20A—C20—H20C	109.5
C9—C7—C10	110.8 (2)	H20B—C20—H20C	109.5
C7—C8—H8A	109.5	C18—C21—H21A	109.5
C7—C8—H8B	109.5	C18—C21—H21B	109.5
H8A—C8—H8B	109.5	H21A—C21—H21B	109.5
C7—C8—H8C	109.5	C18—C21—H21C	109.5
H8A—C8—H8C	109.5	H21A—C21—H21C	109.5
H8B—C8—H8C	109.5	H21B—C21—H21C	109.5
C7—C9—H9A	109.5	C14—C22—H22A	109.5
C7—C9—H9B	109.5	C14—C22—H22B	109.5
H9A—C9—H9B	109.5	H22A—C22—H22B	109.5
C7—C9—H9C	109.5	C14—C22—H22C	109.5
H9A—C9—H9C	109.5	H22A—C22—H22C	109.5
H9B—C9—H9C	109.5	H22B—C22—H22C	109.5
C7—C10—H10A	109.5	C23—N1—C24	108.0 (2)
C7—C10—H10B	109.5	C23—N1—H1N	126.0
H10A—C10—H10B	109.5	C24—N1—H1N	126.0
C7—C10—H10C	109.5	C23—N2—C25	108.0 (2)
H10A—C10—H10C	109.5	C23—N2—H2N	126.0
H10B—C10—H10C	109.5	C25—N2—H2N	126.0
C4—C11—H11A	109.5	N1—C23—N2	109.3 (2)
C4—C11—H11B	109.5	N1—C23—H23	125.3
H11A—C11—H11B	109.5	N2—C23—H23	125.3
C4—C11—H11C	109.5	C25—C24—N1	107.3 (2)
H11A—C11—H11C	109.5	C25—C24—H24	126.4
H11B—C11—H11C	109.5	N1—C24—H24	126.4
C13—C12—C17	119.7 (2)	C24—C25—N2	107.4 (2)
C13—C12—S1	118.64 (17)	C24—C25—H25	126.3
C17—C12—S1	121.16 (17)	N2—C25—H25	126.3

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O4	0.86	1.77	2.628 (2)	174
N2—H2N···O3^i	0.86	1.76	2.603 (2)	167

Symmetry code: (i) x+1/2, y−1/2, z.

(II) imidazolium 6,6'-di-tert-butyl-4,4'-dimethyl-2,2'-thiodiphenylphosphate diisopropyl hydrazodicarboxylate hemisolvate

Crystal data

C3H5N2^+·C22H28O4PS^−·0.5C8H16N2O4	F(000) = 2520
Mr = 590.68	Dx = 1.248 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C2yc	Cell parameters from 7692 reflections
a = 29.333 (2) Å	θ = 2.5–24.6°
b = 9.9415 (7) Å	µ = 0.20 mm^−1
c = 23.3483 (17) Å	T = 295 K
β = 112.542 (1)°	Needle, colorless
V = 6288.5 (8) Å^3	0.44 × 0.30 × 0.22 mm
Z = 8

Data collection

Bruker SMART CCD area-detector diffractometer	7424 independent reflections
Radiation source: fine-focus sealed tube	4746 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.065
ϕ and ω scans	θmax = 28.3°, θmin = 1.5°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −37→37
Tmin = 0.796, Tmax = 0.958	k = −13→13
35617 measured reflections	l = −31→31

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.135	H atoms treated by a mixture of independent and constrained refinement
S = 0.95	w = 1/[σ^2(Fo^2) + (0.0778P)^2] where P = (Fo^2 + 2Fc^2)/3
7424 reflections	(Δ/σ)max < 0.001
375 parameters	Δρmax = 0.39 e Å^−3
0 restraints	Δρmin = −0.24 e Å^−3

Special details

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
P1	0.130053 (18)	0.03372 (5)	0.26349 (2)	0.03602 (14)
S1	0.214948 (18)	0.18642 (5)	0.20616 (2)	0.04206 (15)
O1	0.18893 (5)	0.01164 (12)	0.29554 (6)	0.0382 (3)
O2	0.11911 (5)	0.05899 (12)	0.19132 (6)	0.0404 (3)
O3	0.10864 (5)	−0.09917 (12)	0.26609 (7)	0.0476 (4)
O4	0.11579 (5)	0.15417 (13)	0.28965 (6)	0.0443 (3)
C1	0.22317 (7)	0.11147 (18)	0.32462 (9)	0.0361 (4)
C2	0.24602 (7)	0.11358 (18)	0.38934 (9)	0.0391 (4)
C3	0.28189 (7)	0.2126 (2)	0.41460 (9)	0.0436 (5)
H3	0.2975	0.2169	0.4576	0.052*
C4	0.29581 (7)	0.30490 (19)	0.37990 (9)	0.0433 (5)
C5	0.27336 (7)	0.29728 (19)	0.31618 (9)	0.0411 (5)
H5	0.2826	0.3566	0.2917	0.049*
C6	0.23722 (6)	0.20185 (18)	0.28843 (8)	0.0352 (4)
C7	0.23487 (9)	0.0121 (2)	0.43197 (10)	0.0529 (6)
C8	0.26739 (10)	0.0334 (2)	0.50001 (10)	0.0685 (7)
H8A	0.3013	0.0201	0.5060	0.103*
H8B	0.2584	−0.0298	0.5249	0.103*
H8C	0.2630	0.1233	0.5120	0.103*
C9	0.24525 (16)	−0.1304 (2)	0.41559 (13)	0.1141 (14)
H9A	0.2236	−0.1508	0.3738	0.171*
H9B	0.2398	−0.1933	0.4435	0.171*
H9C	0.2789	−0.1364	0.4192	0.171*
C25	0.17028 (13)	0.5969 (3)	0.31586 (18)	0.1003 (12)
H25	0.1963	0.6573	0.3324	0.120*
C10	0.18173 (11)	0.0268 (4)	0.42690 (13)	0.1065 (13)
H10A	0.1751	0.1195	0.4323	0.160*
H10B	0.1769	−0.0265	0.4584	0.160*
H10C	0.1596	−0.0033	0.3868	0.160*
C11	0.33514 (8)	0.4084 (2)	0.41126 (10)	0.0596 (6)
H11A	0.3540	0.4249	0.3863	0.089*
H11B	0.3566	0.3755	0.4512	0.089*
H11C	0.3199	0.4905	0.4163	0.089*
C12	0.15581 (7)	0.26397 (19)	0.17661 (8)	0.0378 (4)
C13	0.15136 (8)	0.3968 (2)	0.15664 (9)	0.0438 (5)
H13	0.1796	0.4477	0.1635	0.053*
C14	0.10550 (8)	0.4536 (2)	0.12676 (10)	0.0490 (5)
C15	0.06428 (8)	0.3725 (2)	0.11450 (10)	0.0513 (5)
H15	0.0334	0.4099	0.0926	0.062*
C16	0.06619 (7)	0.2389 (2)	0.13281 (9)	0.0441 (5)
C17	0.11339 (7)	0.18841 (18)	0.16726 (8)	0.0376 (4)
C18	0.01847 (8)	0.1550 (3)	0.11564 (11)	0.0601 (6)
C19	0.00099 (11)	0.1597 (4)	0.16928 (15)	0.1106 (13)
H19A	0.0256	0.1204	0.2055	0.166*
H19B	−0.0293	0.1102	0.1583	0.166*
H19C	−0.0044	0.2516	0.1778	0.166*
C20	0.02562 (11)	0.0089 (3)	0.09967 (16)	0.0990 (11)
H20A	0.0425	0.0075	0.0716	0.148*
H20B	−0.0060	−0.0337	0.0805	0.148*
H20C	0.0449	−0.0386	0.1369	0.148*
C21	−0.02257 (10)	0.2129 (3)	0.05740 (14)	0.0916 (10)
H21A	−0.0312	0.3015	0.0663	0.137*
H21B	−0.0511	0.1558	0.0455	0.137*
H21C	−0.0110	0.2176	0.0241	0.137*
C22	0.09953 (10)	0.5998 (2)	0.10678 (13)	0.0717 (7)
H22A	0.1237	0.6534	0.1380	0.107*
H22B	0.0670	0.6301	0.1013	0.107*
H22C	0.1041	0.6086	0.0684	0.107*
N1	0.12714 (7)	0.41688 (17)	0.29291 (8)	0.0487 (4)
H1N	0.1187	0.3337	0.2914	0.058*
N2	0.12334 (10)	0.62712 (19)	0.27852 (12)	0.0779 (7)
H2N	0.1121	0.7063	0.2660	0.093*
C23	0.09822 (9)	0.5163 (2)	0.26484 (11)	0.0571 (6)
H23	0.0650	0.5088	0.2392	0.068*
C24	0.17225 (10)	0.4664 (3)	0.32440 (13)	0.0747 (8)
H24	0.2000	0.4171	0.3481	0.090*
O5	−0.01256 (6)	0.66754 (19)	0.32395 (8)	0.0721 (5)
O6	0.06252 (5)	0.76214 (16)	0.37407 (7)	0.0568 (4)
N3	0.02036 (7)	0.8174 (2)	0.27774 (8)	0.0536 (5)
H3N	0.0463 (8)	0.860 (2)	0.2797 (10)	0.050 (6)*
C26	0.02040 (7)	0.7407 (2)	0.32473 (10)	0.0481 (5)
C27	0.06903 (9)	0.6887 (3)	0.43031 (11)	0.0682 (7)
H27	0.0372	0.6799	0.4345	0.082*
C28	0.10329 (11)	0.7710 (4)	0.48272 (13)	0.0967 (10)
H28A	0.1347	0.7780	0.4790	0.145*
H28B	0.1075	0.7285	0.5214	0.145*
H28C	0.0897	0.8592	0.4814	0.145*
C29	0.08856 (16)	0.5530 (4)	0.42555 (18)	0.1249 (14)
H29A	0.0665	0.5089	0.3888	0.187*
H29B	0.0913	0.5007	0.4613	0.187*
H29C	0.1205	0.5616	0.4235	0.187*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0378 (3)	0.0256 (2)	0.0463 (3)	−0.0014 (2)	0.0180 (2)	0.0017 (2)
S1	0.0392 (3)	0.0503 (3)	0.0397 (3)	0.0015 (2)	0.0185 (2)	0.0019 (2)
O1	0.0383 (7)	0.0311 (7)	0.0446 (8)	−0.0012 (5)	0.0151 (6)	0.0004 (6)
O2	0.0435 (8)	0.0329 (7)	0.0435 (8)	−0.0016 (6)	0.0152 (6)	−0.0007 (6)
O3	0.0452 (8)	0.0286 (7)	0.0668 (10)	−0.0049 (6)	0.0191 (7)	0.0049 (6)
O4	0.0539 (8)	0.0322 (7)	0.0535 (8)	0.0028 (6)	0.0280 (7)	0.0014 (6)
C1	0.0344 (10)	0.0321 (10)	0.0428 (11)	0.0007 (8)	0.0161 (8)	−0.0002 (8)
C2	0.0431 (11)	0.0342 (10)	0.0421 (11)	0.0015 (8)	0.0188 (9)	0.0033 (8)
C3	0.0438 (11)	0.0448 (11)	0.0390 (11)	−0.0008 (9)	0.0126 (9)	−0.0005 (9)
C4	0.0395 (11)	0.0393 (11)	0.0490 (12)	−0.0021 (8)	0.0146 (9)	0.0004 (9)
C5	0.0389 (11)	0.0395 (11)	0.0458 (11)	−0.0015 (8)	0.0173 (9)	0.0068 (9)
C6	0.0330 (9)	0.0362 (10)	0.0366 (10)	0.0039 (8)	0.0138 (8)	0.0036 (8)
C7	0.0687 (15)	0.0510 (13)	0.0395 (12)	−0.0117 (11)	0.0213 (11)	0.0034 (10)
C8	0.0873 (19)	0.0688 (16)	0.0442 (13)	−0.0052 (14)	0.0193 (13)	0.0136 (12)
C9	0.239 (4)	0.0401 (14)	0.0689 (19)	−0.013 (2)	0.066 (2)	0.0069 (13)
C25	0.087 (2)	0.066 (2)	0.169 (4)	−0.0321 (17)	0.073 (2)	−0.055 (2)
C10	0.074 (2)	0.190 (4)	0.0601 (18)	−0.034 (2)	0.0309 (15)	0.031 (2)
C11	0.0580 (14)	0.0578 (14)	0.0561 (14)	−0.0191 (11)	0.0144 (11)	−0.0032 (11)
C12	0.0407 (10)	0.0416 (11)	0.0317 (9)	0.0005 (8)	0.0146 (8)	0.0007 (8)
C13	0.0479 (12)	0.0461 (12)	0.0393 (11)	−0.0045 (9)	0.0190 (9)	0.0043 (9)
C14	0.0560 (13)	0.0469 (12)	0.0481 (12)	0.0040 (10)	0.0244 (10)	0.0086 (10)
C15	0.0453 (12)	0.0564 (13)	0.0508 (13)	0.0102 (10)	0.0168 (10)	0.0143 (10)
C16	0.0423 (11)	0.0506 (12)	0.0388 (11)	−0.0015 (9)	0.0148 (9)	0.0033 (9)
C17	0.0437 (11)	0.0341 (10)	0.0356 (10)	0.0009 (8)	0.0159 (8)	−0.0007 (8)
C18	0.0388 (12)	0.0731 (16)	0.0574 (14)	−0.0050 (11)	0.0061 (11)	0.0089 (12)
C19	0.0563 (17)	0.190 (4)	0.091 (2)	−0.031 (2)	0.0345 (16)	0.010 (2)
C20	0.0682 (19)	0.0683 (19)	0.124 (3)	−0.0246 (15)	−0.0042 (18)	−0.0039 (18)
C21	0.0580 (17)	0.093 (2)	0.088 (2)	−0.0046 (15)	−0.0116 (15)	0.0133 (17)
C22	0.0751 (18)	0.0569 (15)	0.0854 (19)	0.0074 (13)	0.0335 (15)	0.0285 (13)
N1	0.0606 (12)	0.0303 (9)	0.0554 (11)	0.0006 (8)	0.0224 (9)	−0.0031 (8)
N2	0.120 (2)	0.0319 (11)	0.1134 (19)	0.0190 (12)	0.0800 (17)	0.0128 (11)
C23	0.0541 (14)	0.0603 (15)	0.0556 (14)	0.0161 (12)	0.0197 (11)	0.0073 (11)
C24	0.0507 (15)	0.0714 (18)	0.0878 (19)	0.0120 (13)	0.0107 (14)	−0.0272 (15)
O5	0.0516 (10)	0.0908 (13)	0.0681 (11)	−0.0296 (9)	0.0167 (8)	0.0014 (9)
O6	0.0419 (8)	0.0712 (11)	0.0484 (9)	−0.0128 (7)	0.0073 (7)	0.0102 (8)
N3	0.0340 (10)	0.0725 (13)	0.0479 (11)	−0.0076 (9)	0.0086 (8)	0.0035 (9)
C26	0.0355 (11)	0.0572 (13)	0.0504 (13)	−0.0049 (10)	0.0150 (10)	−0.0040 (10)
C27	0.0576 (15)	0.0847 (19)	0.0563 (15)	−0.0131 (13)	0.0154 (12)	0.0179 (13)
C28	0.088 (2)	0.121 (3)	0.0585 (18)	−0.026 (2)	0.0042 (15)	0.0140 (17)
C29	0.148 (4)	0.095 (3)	0.109 (3)	0.008 (3)	0.024 (3)	0.039 (2)

Geometric parameters (Å, º)

P1—O3	1.4741 (13)	C15—C16	1.390 (3)
P1—O4	1.4759 (13)	C15—H15	0.9300
P1—O2	1.6095 (14)	C16—C17	1.401 (3)
P1—O1	1.6125 (14)	C16—C18	1.544 (3)
S1—C12	1.7782 (19)	C18—C19	1.525 (4)
S1—C6	1.7827 (19)	C18—C20	1.534 (4)
O1—C1	1.390 (2)	C18—C21	1.541 (3)
O2—C17	1.388 (2)	C19—H19A	0.9600
C1—C2	1.399 (3)	C19—H19B	0.9600
C1—C6	1.399 (3)	C19—H19C	0.9600
C2—C3	1.396 (3)	C20—H20A	0.9600
C2—C7	1.538 (3)	C20—H20B	0.9600
C3—C4	1.385 (3)	C20—H20C	0.9600
C3—H3	0.9300	C21—H21A	0.9600
C4—C5	1.379 (3)	C21—H21B	0.9600
C4—C11	1.509 (3)	C21—H21C	0.9600
C5—C6	1.385 (2)	C22—H22A	0.9600
C5—H5	0.9300	C22—H22B	0.9600
C7—C8	1.522 (3)	C22—H22C	0.9600
C7—C10	1.524 (4)	N1—C23	1.303 (3)
C7—C9	1.528 (3)	N1—C24	1.337 (3)
C8—H8A	0.9600	N1—H1N	0.8600
C8—H8B	0.9600	N2—C23	1.296 (3)
C8—H8C	0.9600	N2—H2N	0.8600
C9—H9A	0.9600	C23—H23	0.9300
C9—H9B	0.9600	C24—H24	0.9300
C9—H9C	0.9600	O5—C26	1.205 (2)
C25—C24	1.311 (4)	O6—C26	1.344 (2)
C25—N2	1.351 (4)	O6—C27	1.449 (3)
C25—H25	0.9300	N3—C26	1.335 (3)
C10—H10A	0.9600	N3—N3^i	1.385 (3)
C10—H10B	0.9600	N3—H3N	0.86 (2)
C10—H10C	0.9600	C27—C29	1.487 (4)
C11—H11A	0.9600	C27—C28	1.495 (4)
C11—H11B	0.9600	C27—H27	0.9800
C11—H11C	0.9600	C28—H28A	0.9600
C12—C13	1.390 (3)	C28—H28B	0.9600
C12—C17	1.397 (3)	C28—H28C	0.9600
C13—C14	1.377 (3)	C29—H29A	0.9600
C13—H13	0.9300	C29—H29B	0.9600
C14—C15	1.389 (3)	C29—H29C	0.9600
C14—C22	1.516 (3)
O3—P1—O4	121.15 (8)	C15—C16—C18	120.71 (19)
O3—P1—O2	105.42 (8)	C17—C16—C18	123.62 (19)
O4—P1—O2	109.41 (7)	O2—C17—C12	118.22 (16)
O3—P1—O1	104.86 (7)	O2—C17—C16	120.26 (17)
O4—P1—O1	109.97 (8)	C12—C17—C16	121.49 (17)
O2—P1—O1	104.79 (7)	C19—C18—C20	110.4 (3)
C12—S1—C6	106.31 (8)	C19—C18—C21	108.5 (2)
C1—O1—P1	125.05 (11)	C20—C18—C21	105.8 (2)
C17—O2—P1	120.87 (11)	C19—C18—C16	109.1 (2)
O1—C1—C2	119.72 (16)	C20—C18—C16	112.3 (2)
O1—C1—C6	119.23 (16)	C21—C18—C16	110.5 (2)
C2—C1—C6	120.84 (17)	C18—C19—H19A	109.5
C3—C2—C1	116.01 (17)	C18—C19—H19B	109.5
C3—C2—C7	120.13 (18)	H19A—C19—H19B	109.5
C1—C2—C7	123.83 (17)	C18—C19—H19C	109.5
C4—C3—C2	124.29 (19)	H19A—C19—H19C	109.5
C4—C3—H3	117.9	H19B—C19—H19C	109.5
C2—C3—H3	117.9	C18—C20—H20A	109.5
C5—C4—C3	117.96 (18)	C18—C20—H20B	109.5
C5—C4—C11	121.40 (18)	H20A—C20—H20B	109.5
C3—C4—C11	120.63 (19)	C18—C20—H20C	109.5
C4—C5—C6	120.38 (18)	H20A—C20—H20C	109.5
C4—C5—H5	119.8	H20B—C20—H20C	109.5
C6—C5—H5	119.8	C18—C21—H21A	109.5
C5—C6—C1	120.49 (17)	C18—C21—H21B	109.5
C5—C6—S1	117.49 (14)	H21A—C21—H21B	109.5
C1—C6—S1	121.62 (14)	C18—C21—H21C	109.5
C8—C7—C10	106.3 (2)	H21A—C21—H21C	109.5
C8—C7—C9	106.6 (2)	H21B—C21—H21C	109.5
C10—C7—C9	111.4 (3)	C14—C22—H22A	109.5
C8—C7—C2	112.37 (18)	C14—C22—H22B	109.5
C10—C7—C2	110.6 (2)	H22A—C22—H22B	109.5
C9—C7—C2	109.49 (19)	C14—C22—H22C	109.5
C7—C8—H8A	109.5	H22A—C22—H22C	109.5
C7—C8—H8B	109.5	H22B—C22—H22C	109.5
H8A—C8—H8B	109.5	C23—N1—C24	108.3 (2)
C7—C8—H8C	109.5	C23—N1—H1N	125.9
H8A—C8—H8C	109.5	C24—N1—H1N	125.9
H8B—C8—H8C	109.5	C23—N2—C25	108.2 (2)
C7—C9—H9A	109.5	C23—N2—H2N	125.9
C7—C9—H9B	109.5	C25—N2—H2N	125.9
H9A—C9—H9B	109.5	N2—C23—N1	108.8 (2)
C7—C9—H9C	109.5	N2—C23—H23	125.6
H9A—C9—H9C	109.5	N1—C23—H23	125.6
H9B—C9—H9C	109.5	C25—C24—N1	107.7 (3)
C24—C25—N2	107.0 (2)	C25—C24—H24	126.1
C24—C25—H25	126.5	N1—C24—H24	126.1
N2—C25—H25	126.5	C26—O6—C27	117.08 (17)
C7—C10—H10A	109.5	C26—N3—N3^i	119.81 (19)
C7—C10—H10B	109.5	C26—N3—H3N	121.2 (14)
H10A—C10—H10B	109.5	N3^i—N3—H3N	118.6 (14)
C7—C10—H10C	109.5	O5—C26—N3	125.8 (2)
H10A—C10—H10C	109.5	O5—C26—O6	125.2 (2)
H10B—C10—H10C	109.5	N3—C26—O6	108.96 (18)
C4—C11—H11A	109.5	O6—C27—C29	108.1 (2)
C4—C11—H11B	109.5	O6—C27—C28	106.3 (2)
H11A—C11—H11B	109.5	C29—C27—C28	113.6 (3)
C4—C11—H11C	109.5	O6—C27—H27	109.6
H11A—C11—H11C	109.5	C29—C27—H27	109.6
H11B—C11—H11C	109.5	C28—C27—H27	109.6
C13—C12—C17	119.67 (17)	C27—C28—H28A	109.5
C13—C12—S1	119.61 (15)	C27—C28—H28B	109.5
C17—C12—S1	120.36 (14)	H28A—C28—H28B	109.5
C14—C13—C12	120.51 (19)	C27—C28—H28C	109.5
C14—C13—H13	119.7	H28A—C28—H28C	109.5
C12—C13—H13	119.7	H28B—C28—H28C	109.5
C13—C14—C15	118.03 (19)	C27—C29—H29A	109.5
C13—C14—C22	121.6 (2)	C27—C29—H29B	109.5
C15—C14—C22	120.3 (2)	H29A—C29—H29B	109.5
C14—C15—C16	124.24 (19)	C27—C29—H29C	109.5
C14—C15—H15	117.9	H29A—C29—H29C	109.5
C16—C15—H15	117.9	H29B—C29—H29C	109.5
C15—C16—C17	115.67 (18)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O4	0.86	1.79	2.630 (2)	166
N2—H2N···O3^ii	0.86	1.94	2.753 (2)	158
N3—H3N···O3^ii	0.86 (2)	2.01 (2)	2.830 (2)	159 (2)
C23—H23···O5^i	0.93	2.30	2.980 (3)	130

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