Unusual conformations of 1,3-dialk­oxy­thia­calix[4]arenes in the solid state

The structures of three syn-1,3-dialkoxy­thia­calix[4]arenes with unusual conformations in the solid state are reported. The pinched cone conformation of syn-2²,4²-dihydroxy-1²,3²-bis­(prop-2-enyl­oxy)thia­calix[4]arene, C₃₀H₂₄O₄S₄, (3a), is stabilized by two intra­molecular hydrogen bonds, remarkably formed from both OH groups to the same ether O atom. In syn-2²,4²-dihydroxy-1⁵,2⁵,3⁵,4⁵-tetra­nitro-1²,3²-bis­(prop-2-enyl­oxy)thia­calix[4]arene acetone disolvate, C₃₀H₂₀N₄O₁₂S₄·2C₃H₆O, (3b1), the mol­ecule is found in the 1,3-alternate conformation. The crystallographic C2 symmetry is due to a twofold rotation axis running through the centre of the calixarene ring. The hydroxy groups cannot form intra­molecular hydrogen bonds as in (3a) and both are bonded to an acetone solvent mol­ecule. The mol­ecule of the pseudo-polymorph of (3b1) in which the same compound crystallized without any solvent, viz. (3b2), is located on a crystallographic mirror plane. Only one of the two hydroxy groups forms a hydrogen bond, and this is with a nitro group of a neighbouring mol­ecule as acceptor. Mol­ecular mechanics calculations for syn-1,3-diethers suggest a preference of the 1,3-alternate over the usual cone conformation for thia­calix[4]arene versus calix[4]arene and for para-nitro versus para-H derivatives.

S1. Comment

In principle, thiacalix[4]arenes (1) can undergo analogous chemical modifications as calix[4]arenes (2) on their wide rim (e.g. transbutylation and electrophilic substitutions) and on their narrow rim (e.g. O-alkylation) (Böhmer, 1995). Subtle differences are found, however, in both cases. Ether residues introduced to (1) must be larger than propyl (Lang et al., 1999; Lhotak, 2004) [which is sufficient for (2) (Böhmer, 1995)] to prevent a rotation through the annulus, and the introduction of four ether groups leads usually to derivatives in which the 1,3-alternate conformation is fixed (Lhotak et al., 1998; Lhotak, 2004). Derivatives in the cone conformation are only formed with alkylating agents of the type X—CH₂—C(O)—R (Iki et al., 1998; Akdas et al., 1999) or X—CH₂—Ar (Yamato et al., 2002) in the presence of sodium cations. For both calix[4]arenes, 1,3-diethers with a syn-orientation of the ether residues are easily obtained with a variety of alkylating agents. The conformational analysis of thiacalixarenes and their derivatives in solution is complicated by the fact, that the spectroscopic information given by methylene H atoms is not available in the ¹H NMR spectra. The ¹³C chemical shift of the methylene bridges, often useful for the conformational assignment (Jaime et al., 1991) is also lacking. This makes conformational information from the crystalline state more important.

All five X-ray structures reported for syn-1,3-diether derivatives (3) (Dudic et al., 2003, 2004; Clemente, 2003; Bhalla et al. 2004) show the compounds in the cone conformation. 103 structures of syn-1,3-diethers (4) (metal complexes are not included) are found in the Cambridge Structural Database (CSD version 5.27 plus one update; Mogul Version 1.1; Allen, 2002), among which only one example has a 1,3-alternate conformation (Simaan et al., 2003) while the rest assume the (pinched) cone conformation. (From 15 structures of syn-1,3-diesters two partial cone and one 1,3-alternate conformation are found.) The reason for this disparity is usually searched for in the stabilization of the cone conformation by intramolecular hydrogen bonds between the phenol hydroxy groups and the adjacent ether O atoms. From further O-alkylation products it can be deduced, however, that the molecules can assume the partial cone or the 1,3-alternate conformation by passing of the OH groups through the annulus. We recently prepared (Böhmer & Kasyan, 2006) the 1,3-diallylethers (3a) and (3b) and report their crystal structures in the following. For (3b), which was crystallized from different solvents, two pseudo-polymorphs, (3b1) and (3b2), were obtained.

Perspective views of (3a), (3b1) and (3b2) are shown in Figs. 1–3. Bond lengths and angles can be regarded as normal (CSD).

Single crystals of (3a) were obtained from acetonitrile. As expected, the molecule is found in a pinched cone conformation, with the ether units bent towards the cavity and the phenol units bent outwards. In Table 4, the angles between the mean planes through the aromatic rings and the reference/mean plane defined by the four S atoms are listed and used to characterize the conformation. One of these angles is even smaller than 90°, which means that this plane is oriented `into' the cavity, while the opposite one is oriented outwards. Thus, the planes of the ether substituted phenyl rings are almost coplanar [6.53 (8)°], a situation also found for other 1,3-diethers of (1). The packing of the molecules is obviously determined by π–π stacking of aromatic units. Chains of molecules with alternating orientation extend along the c axis (Fig. 4) with aryl–aryl contacts between the phenylether rings [the distance between the centroids of the aromatic rings C21–C26 and C41ⁱⁱⁱ–C46ⁱⁱⁱ is 3.980 Å; symmetry code: (iii) x, 3/2 − y, 1/2 + z], while along the a axis contacts between the phenol units exist [the distance between the centroids of the aromatic rings C11–C16 and C31^iv–C36^iv is 4.204 Å; symmetry operator: (ii) −1 + x, y, z]. It is remarkable that both OH groups form hydrogen bonds to the same ether O atom.

Single crystals of (3b) were obtained from acetone and from ethanol/methylene chloride, resulting in two different crystal structures, (3b1) and (3b2), respectively. The crystals of (3b1) include two molecules of acetone per calixarene molecule. Surprisingly, and in contrast to (3a), here the molecules assume a `perfect' 1,3-alternate conformation with crystallographic twofold symmetry (see Fig. 2).

Although the quality of (3b2) was not as good, the crystal structure clearly shows the molecules, which are located on a crystallographic mirror plane, in the 1,3-alternate conformation again. Small differences in shape are evident from the values collected in Table 1 and the least-squares fit (Fig. 5). However, the overall conformation of (3b1) and (3b2) is very similar.

In contrast to (3a), interactions via π–π stacking are not pronounced in the structures of either (3b1) or (3b2). For (3b1), molecular columns of head-to-tail-oriented molecules along the c axis are found. Subsequent molecules are alternately turned by 72.8° around the column axis. As seen in Fig. 6, adjacent columns have the opposite direction.

Fig. 7 suggests a similar arrangement into columns along the a axis for (3b2). However, subsequent molecules are not directly stacked above one another, but shifted by c/2 with respect to each other.

The structures of (3b1) and (3b2) are the first examples in which a derivative of type 3 is found in the 1,3-alternate conformation (see above). The question arises why the molecule does not assume a cone conformation, which should be stabilized by intramolecular hydrogen bonds. For the 1,3-diether (Simaan et al., 2003) a favourable packing was assumed as the reason for the 1,3-alternate conformation. In the case of (3b1) two intermolecular hydrogen bonds between calixarene molecules and solvent molecules are found in the crystal lattice and in the case of (3b2) one hydrogen bond to an adjacent molecule. However, it seems likely that the reason must be searched for also in the molecule itself.

Therefore, molecular mechanics calculations using the MMFF94 force field (Halgren, 1990) have been performed to assess the energy differences of the cone and 1,3-alternate conformations of the syn-1,3-diethers of `classical' and of thiacalix[4]arenes. The results of these conformational analyses are summarized in Table 5.

The calculations suggest a different conformational behaviour for the two classes of compounds. In agreement with the experimental observations, the calix[4]arene derivatives prefer the cone conformation, which is stabilized over the 1,3-alternate form by hydrogen bonding [(IVa)–(IVc)]. In contrast, the syn-1,3-diethers of thiacalixarenes are predicted to exist predominantly in the 1,3-alternate arrangement [(IIIa)–(IIIc)]. This results mainly from unfavourable bonding contributions to the steric energy of the cone form, which are, however, in part compensated by favourable non-bonding terms due to hydrogen bonding for (IIIb) and (IIIc). For (IIIa), the 1,3-alternate conformer is also favoured by the non-bonding term, which may arise from the compensation of the dipole moments in this form.

Since it may be hypothesized that the distorted pinched cone conformation found in the crystal structure of (3a) is the result of packing forces due to π–π interactions we have optimized this structure with the help of the MMFF94 force field. The resulting energy minimized conformer is very similar to the crystal structure (the r.m.s. deviation of the calixarene C atoms is 0.18 Å), indicating that this pinched cone form is indeed an energy minimum. However, its energy is 5.5 kcal mol⁻¹ above the global minimum (which corresponds to the 1,3-alternate arrangement) suggesting that the packing forces contribute to the stabilization of this conformation in the crystal structure.

In conclusionhe conformation of (thia)calix[4]arenes and their derivatives is determined by various competing factors. The thiacalix[4]arene skeleton obviously prefers the 1,3-alternate conformation. Thus, tetraethers are usually obtained as 1,3-alternate conformers from thiacalixarenes and as cone conformers from methylene-bridged calixarenes. A circular array of intramolecular hydrogen bonds between hydroxy groups explains the preference of the cone conformation of the tetrahydroxy compounds in both cases. The competition between intramolecular hydrogen bonds (stabilizing the cone conformation) and compensation of dipole moments (in the 1,3-alternate conformation) explains why (3a) is found in the cone conformation and (3b) in the 1,3-alternate conformation. 1,3-Diethers of calix[4]arenes, however, are (nearly) always found in the cone conformation.

S2. Experimental

Compounds (3a) and (3b) were obtained under standard conditions, refluxing thiacalix[4]arene [(1), R = H] or tetranitrothiacalix[4]arene [(1), R = NO₂] with an excess of allylbromide and sodium carbonate in acetone or acetonitrile, respectively. Details will be published in a wider context (Böhmer & Kasyan, 2006)

S3. Refinement

For all compounds, H atoms were located in a difference electron density map, and for (3a) and (3b1) the hydroxy H atoms were refined isotropically. All other H atoms were refined with fixed individual displacement parameters [U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C_methyl,O)] using a riding model, with C—H ranging from 0.95 to 0.99 Å and, for (3b2), O—H = 0.84 Å. For (3a), one terminal atom of a propenoxy chain is disordered over two positions with site occupation factors of 0.556 (7) and 0.444 (7). For (3b2), one terminal atom of a propenoxy chain is disordered over two positions with site occupation factors of 0.726 (15) and 0.274 (15); these two atoms were refined isotropically. The two hydroxy H atoms of (3b2) are disordered over two equally occupied positions. The conformational search of (III)/(IV) was performed with the Randomsearch module of the Sybyl program package (TRIPOS Associates, 1996). Starting structures were generated manually from the 1,3-alternate and cone conformers of a previously calculated p-tert-butylcalix[4]arene. All Ar—X bonds and the single bonds of the ether groups were chosen as rotatable. A maximum of 2000 cycles of random perturbation of the dihedral angles was allowed using an energy cutoff of 20 kcal mol⁻¹ above the actual minimum. A constant dielectric with ε = 1 was used. The resulting structures were minimized with the MMFF94 force field, which is included in the Sybyl program, until the r.m.s. energy gradient was less than 10⁻³ kcal mol⁻¹ Å⁻¹. Please check; text rearranged to avoid repetition of similar methods.

Computing details

For all compounds, data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A perspective view of (3a), with the atom numbering. Displacement ellipsoids are shown at the 50% probability level, and atoms of the minor occupied disordered component have been omitted for clarity. Hydrogen bonds are shown as dashed lines.
	Fig. 2. A perspective view of (3b1), with the atom numbering. Displacement ellipsoids are shown at the 50% probability level. Hydrogen bonds are shown as dashed lines. Non-labelled atoms are generated by the symmetry operator (−x + 3/2, −y + 3/2, z).
	Fig. 3. A perspective view of (3b2) with the atom numbering. Displacement ellipsoids are shown at the 30% probability level, and H atoms bonded to C atoms have been omitted for clarity. Only one of the disordered atoms is shown. Non-labelled atoms are generated by the symmetry operator (x, −y + 3/2, z).
	Fig. 4. A packing diagram of (3a), viewed along the a axis; atoms of the minor occupied disordered component have been omitted for clarity.
	Fig. 5. A least-squares fit of (3b1) and (3b2); only the S atoms are fitted (the r.m.s. deviation is 0.170 Å).
	Fig. 6. A packing diagram of (3b1), viewed along the a axis. Hydrogen bonds are indicated as dashed lines.
	Fig. 7. A packing diagram of (3b2), viewed along the c axis; atoms of the minor occupied disordered component have been omitted for clarity. Hydrogen bonds are indicated as dashed lines. R

(3a) syn-2²,4²-dihydroxy-1²,3²-bis(prop-2-enoxy)thiacalix[4]arene

Crystal data

C30H24O4S4	F(000) = 1200
Mr = 576.73	Dx = 1.374 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 33932 reflections
a = 9.2591 (8) Å	θ = 2.7–27.3°
b = 18.5282 (13) Å	µ = 0.38 mm^−1
c = 16.7729 (17) Å	T = 173 K
β = 104.297 (7)°	Rod, colourless
V = 2788.3 (4) Å^3	0.36 × 0.12 × 0.10 mm
Z = 4

Data collection

STOE IPDS-II two-circle- diffractometer	6073 independent reflections
Radiation source: fine-focus sealed tube	4194 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.096
ω scans	θmax = 27.1°, θmin = 2.7°
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995)	h = −11→11
Tmin = 0.877, Tmax = 0.963	k = −21→23
39745 measured reflections	l = −21→21

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) = 0.124	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0693P)^2] where P = (Fo^2 + 2Fc^2)/3
6073 reflections	(Δ/σ)max = 0.001
361 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.33 e Å^−3

Special details

Experimental.

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	Occ. (<1)
S1	0.24963 (6)	0.68706 (3)	0.38644 (4)	0.04105 (16)
S2	0.26817 (6)	0.69039 (3)	0.71811 (4)	0.04039 (16)
S3	0.88343 (6)	0.68920 (3)	0.79256 (4)	0.04095 (16)
S4	0.86509 (6)	0.69735 (3)	0.45934 (4)	0.03936 (16)
O12	0.18974 (16)	0.74545 (8)	0.54395 (11)	0.0405 (4)
O22	0.56650 (18)	0.72634 (9)	0.69643 (11)	0.0393 (4)
H22	0.651 (4)	0.7411 (17)	0.6948 (19)	0.065 (10)*
O32	0.81214 (15)	0.75264 (8)	0.62101 (10)	0.0372 (4)
O42	0.55494 (18)	0.72633 (9)	0.48142 (11)	0.0398 (4)
H42	0.640 (4)	0.7383 (18)	0.503 (2)	0.068 (10)*
C11	0.2786 (2)	0.64184 (12)	0.48315 (14)	0.0352 (5)
C12	0.2533 (2)	0.67742 (12)	0.55201 (14)	0.0338 (5)
C13	0.2853 (2)	0.64265 (12)	0.62839 (14)	0.0345 (5)
C14	0.3357 (2)	0.57139 (12)	0.63478 (15)	0.0382 (5)
H14	0.3543	0.5472	0.6863	0.046*
C15	0.3587 (3)	0.53584 (13)	0.56632 (15)	0.0404 (5)
H15	0.3935	0.4874	0.5710	0.048*
C16	0.3310 (2)	0.57059 (12)	0.49119 (15)	0.0382 (5)
H16	0.3477	0.5460	0.4446	0.046*
C21	0.4426 (2)	0.66360 (13)	0.78339 (15)	0.0370 (5)
C22	0.5757 (2)	0.68434 (12)	0.76356 (14)	0.0343 (5)
C23	0.7125 (2)	0.65989 (13)	0.81310 (14)	0.0365 (5)
C24	0.7149 (3)	0.61794 (15)	0.88217 (16)	0.0470 (6)
H24	0.8076	0.6019	0.9156	0.056*
C25	0.5837 (3)	0.59919 (16)	0.90281 (16)	0.0508 (6)
H25	0.5863	0.5711	0.9506	0.061*
C26	0.4473 (3)	0.62203 (14)	0.85253 (16)	0.0452 (6)
H26	0.3570	0.6089	0.8660	0.054*
C31	0.8846 (2)	0.64330 (12)	0.69843 (14)	0.0348 (5)
C32	0.8620 (2)	0.68164 (11)	0.62444 (14)	0.0330 (5)
C33	0.8792 (2)	0.64761 (12)	0.55298 (14)	0.0343 (5)
C34	0.9148 (2)	0.57400 (12)	0.55567 (15)	0.0384 (5)
H34	0.9268	0.5504	0.5074	0.046*
C35	0.9325 (3)	0.53554 (13)	0.62801 (15)	0.0423 (6)
H35	0.9539	0.4854	0.6290	0.051*
C36	0.9192 (2)	0.57008 (13)	0.69934 (15)	0.0397 (5)
H36	0.9339	0.5436	0.7492	0.048*
C41	0.6922 (2)	0.66545 (12)	0.39629 (14)	0.0356 (5)
C42	0.5580 (2)	0.68578 (12)	0.41466 (14)	0.0329 (5)
C43	0.4214 (2)	0.66319 (13)	0.36339 (14)	0.0368 (5)
C44	0.4211 (3)	0.62283 (14)	0.29314 (15)	0.0442 (6)
H44	0.3292	0.6072	0.2584	0.053*
C45	0.5550 (3)	0.60521 (15)	0.27333 (16)	0.0475 (6)
H45	0.5536	0.5791	0.2244	0.057*
C46	0.6899 (3)	0.62588 (13)	0.32529 (15)	0.0422 (6)
H46	0.7809	0.6130	0.3124	0.051*
C121	0.2922 (3)	0.80527 (12)	0.55023 (18)	0.0443 (6)
H12A	0.3730	0.7933	0.5233	0.053*
H12B	0.3373	0.8171	0.6086	0.053*
C122	0.2020 (3)	0.86751 (15)	0.50765 (19)	0.0535 (7)
H122	0.1410	0.8594	0.4539	0.064*
C123	0.2007 (4)	0.93075 (18)	0.5380 (3)	0.0797 (10)
H12C	0.2602	0.9410	0.5916	0.096*
H12D	0.1403	0.9675	0.5070	0.096*
C321	0.9307 (3)	0.80636 (13)	0.63865 (19)	0.0478 (6)
H32A	0.9951	0.8008	0.5999	0.057*
H32B	0.9929	0.7998	0.6953	0.057*
C322	0.8621 (4)	0.87949 (15)	0.62979 (19)	0.0574 (7)
H32C	0.9334	0.9172	0.6358	0.069*	0.556 (7)
H32D	0.7830	0.8846	0.5818	0.069*	0.444 (7)
C323	0.7363 (6)	0.9011 (3)	0.6167 (3)	0.0492 (15)	0.556 (7)
H32E	0.7151	0.9448	0.6411	0.059*	0.556 (7)
H32F	0.6578	0.8745	0.5819	0.059*	0.556 (7)
C324	0.8848 (9)	0.9308 (4)	0.6688 (5)	0.074 (3)	0.444 (7)
H32G	0.8048	0.9619	0.6720	0.089*	0.444 (7)
H32H	0.9837	0.9423	0.6981	0.089*	0.444 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0252 (3)	0.0520 (4)	0.0427 (3)	0.0049 (2)	0.0022 (2)	0.0042 (3)
S2	0.0255 (3)	0.0483 (4)	0.0482 (3)	0.0011 (2)	0.0107 (2)	−0.0096 (3)
S3	0.0262 (3)	0.0522 (4)	0.0416 (3)	−0.0031 (2)	0.0028 (2)	−0.0092 (3)
S4	0.0259 (3)	0.0470 (3)	0.0467 (3)	0.0028 (2)	0.0119 (2)	0.0089 (3)
O12	0.0239 (7)	0.0376 (9)	0.0595 (10)	0.0052 (6)	0.0095 (7)	−0.0012 (8)
O22	0.0252 (8)	0.0431 (9)	0.0486 (10)	−0.0005 (7)	0.0071 (7)	0.0067 (7)
O32	0.0245 (7)	0.0332 (8)	0.0549 (10)	0.0036 (6)	0.0119 (7)	−0.0004 (7)
O42	0.0247 (8)	0.0454 (10)	0.0488 (10)	0.0018 (7)	0.0081 (7)	−0.0083 (8)
C11	0.0215 (10)	0.0402 (12)	0.0421 (12)	−0.0042 (8)	0.0045 (9)	−0.0020 (10)
C12	0.0170 (9)	0.0360 (11)	0.0466 (13)	−0.0005 (8)	0.0045 (9)	−0.0020 (10)
C13	0.0222 (10)	0.0364 (12)	0.0447 (13)	−0.0039 (8)	0.0082 (9)	−0.0054 (10)
C14	0.0334 (11)	0.0370 (12)	0.0432 (13)	−0.0038 (9)	0.0075 (10)	−0.0007 (10)
C15	0.0374 (12)	0.0331 (12)	0.0508 (14)	−0.0026 (9)	0.0109 (10)	−0.0028 (10)
C16	0.0332 (11)	0.0368 (12)	0.0446 (13)	−0.0048 (9)	0.0092 (10)	−0.0076 (10)
C21	0.0300 (11)	0.0410 (12)	0.0404 (13)	−0.0023 (9)	0.0095 (9)	−0.0098 (10)
C22	0.0325 (11)	0.0319 (11)	0.0384 (12)	0.0004 (9)	0.0087 (9)	−0.0055 (9)
C23	0.0291 (10)	0.0412 (13)	0.0374 (12)	−0.0010 (9)	0.0053 (9)	−0.0073 (10)
C24	0.0433 (13)	0.0540 (15)	0.0401 (13)	0.0051 (11)	0.0036 (11)	−0.0021 (12)
C25	0.0534 (15)	0.0609 (17)	0.0384 (14)	−0.0005 (13)	0.0120 (12)	0.0034 (12)
C26	0.0417 (13)	0.0528 (15)	0.0449 (14)	−0.0050 (11)	0.0177 (11)	−0.0047 (12)
C31	0.0226 (9)	0.0411 (12)	0.0387 (12)	−0.0021 (9)	0.0038 (8)	−0.0035 (10)
C32	0.0178 (9)	0.0322 (11)	0.0483 (13)	0.0005 (8)	0.0068 (9)	−0.0006 (10)
C33	0.0231 (9)	0.0382 (12)	0.0413 (12)	0.0034 (8)	0.0071 (9)	0.0041 (10)
C34	0.0295 (11)	0.0379 (12)	0.0452 (13)	0.0028 (9)	0.0044 (9)	−0.0048 (10)
C35	0.0375 (12)	0.0345 (12)	0.0496 (14)	0.0039 (9)	0.0011 (10)	−0.0017 (10)
C36	0.0328 (11)	0.0382 (13)	0.0438 (13)	−0.0006 (9)	0.0013 (10)	0.0044 (10)
C41	0.0325 (11)	0.0365 (12)	0.0387 (12)	0.0045 (9)	0.0104 (9)	0.0095 (9)
C42	0.0293 (10)	0.0328 (11)	0.0363 (12)	0.0047 (8)	0.0072 (9)	0.0048 (9)
C43	0.0314 (11)	0.0396 (12)	0.0381 (12)	0.0022 (9)	0.0058 (9)	0.0056 (10)
C44	0.0407 (13)	0.0528 (15)	0.0355 (12)	0.0020 (11)	0.0025 (10)	0.0052 (11)
C45	0.0513 (14)	0.0562 (16)	0.0356 (13)	0.0079 (12)	0.0119 (11)	0.0016 (11)
C46	0.0424 (13)	0.0476 (14)	0.0389 (13)	0.0101 (11)	0.0142 (10)	0.0096 (11)
C121	0.0360 (12)	0.0332 (12)	0.0666 (17)	0.0032 (9)	0.0182 (12)	−0.0011 (11)
C122	0.0511 (15)	0.0497 (16)	0.0650 (18)	0.0026 (12)	0.0243 (13)	0.0076 (13)
C123	0.089 (2)	0.0504 (19)	0.109 (3)	0.0179 (17)	0.042 (2)	0.0162 (19)
C321	0.0370 (12)	0.0350 (13)	0.0776 (19)	−0.0059 (10)	0.0261 (13)	−0.0051 (12)
C322	0.078 (2)	0.0386 (15)	0.0649 (19)	0.0070 (14)	0.0346 (16)	0.0064 (13)
C323	0.060 (3)	0.044 (3)	0.049 (3)	0.016 (2)	0.023 (2)	0.001 (2)
C324	0.073 (5)	0.045 (4)	0.116 (7)	−0.017 (3)	0.044 (5)	−0.039 (4)

Geometric parameters (Å, º)

S1—C43	1.783 (2)	C31—C36	1.393 (3)
S1—C11	1.786 (2)	C31—C32	1.400 (3)
C11—C12	1.399 (3)	C32—O32	1.391 (3)
C11—C16	1.401 (3)	C32—C33	1.398 (3)
C12—O12	1.384 (3)	C33—C34	1.401 (3)
C12—C13	1.399 (3)	C33—S4	1.798 (2)
C13—C14	1.396 (3)	C34—C35	1.382 (3)
C13—S2	1.786 (2)	C34—H34	0.9500
C14—C15	1.385 (3)	C35—C36	1.389 (3)
C14—H14	0.9500	C35—H35	0.9500
C15—C16	1.382 (3)	C36—H36	0.9500
C15—H15	0.9500	O32—C321	1.457 (3)
C16—H16	0.9500	C321—C322	1.488 (4)
O12—C121	1.446 (3)	C321—H32A	0.9900
C121—C122	1.498 (4)	C321—H32B	0.9900
C121—H12A	0.9900	C322—C324	1.144 (7)
C121—H12B	0.9900	C322—C323	1.200 (5)
C122—C123	1.279 (4)	C322—H32C	0.9500
C122—H122	0.9500	C322—H32D	0.9500
C123—H12C	0.9500	C323—H32E	0.9500
C123—H12D	0.9500	C323—H32F	0.9500
S2—C21	1.783 (2)	C324—H32G	0.9500
C21—C26	1.384 (4)	C324—H32H	0.9500
C21—C22	1.407 (3)	S4—C41	1.787 (2)
C22—O22	1.354 (3)	C41—C46	1.394 (3)
C22—C23	1.407 (3)	C41—C42	1.404 (3)
C23—C24	1.391 (4)	C42—O42	1.355 (3)
C23—S3	1.786 (2)	C42—C43	1.406 (3)
C24—C25	1.387 (4)	C43—C44	1.395 (3)
C24—H24	0.9500	C44—C45	1.398 (4)
C25—C26	1.400 (4)	C44—H44	0.9500
C25—H25	0.9500	C45—C46	1.389 (4)
C26—H26	0.9500	C45—H45	0.9500
O22—H22	0.83 (3)	C46—H46	0.9500
S3—C31	1.796 (2)	O42—H42	0.82 (3)
C43—S1—C11	97.97 (10)	O32—C32—C31	119.5 (2)
C12—C11—C16	119.3 (2)	C33—C32—C31	120.5 (2)
C12—C11—S1	120.70 (17)	C32—C33—C34	119.2 (2)
C16—C11—S1	120.00 (18)	C32—C33—S4	121.25 (17)
O12—C12—C13	119.9 (2)	C34—C33—S4	119.54 (18)
O12—C12—C11	120.2 (2)	C35—C34—C33	120.4 (2)
C13—C12—C11	119.9 (2)	C35—C34—H34	119.8
C14—C13—C12	119.8 (2)	C33—C34—H34	119.8
C14—C13—S2	120.09 (18)	C34—C35—C36	120.2 (2)
C12—C13—S2	120.05 (17)	C34—C35—H35	119.9
C15—C14—C13	120.2 (2)	C36—C35—H35	119.9
C15—C14—H14	119.9	C35—C36—C31	120.6 (2)
C13—C14—H14	119.9	C35—C36—H36	119.7
C16—C15—C14	120.2 (2)	C31—C36—H36	119.7
C16—C15—H15	119.9	C32—O32—C321	114.35 (16)
C14—C15—H15	119.9	O32—C321—C322	108.7 (2)
C15—C16—C11	120.6 (2)	O32—C321—H32A	110.0
C15—C16—H16	119.7	C322—C321—H32A	110.0
C11—C16—H16	119.7	O32—C321—H32B	110.0
C12—O12—C121	115.83 (16)	C322—C321—H32B	110.0
O12—C121—C122	106.1 (2)	H32A—C321—H32B	108.3
O12—C121—H12A	110.5	C324—C322—C323	82.0 (5)
C122—C121—H12A	110.5	C324—C322—C321	133.3 (6)
O12—C121—H12B	110.5	C323—C322—C321	133.9 (4)
C122—C121—H12B	110.5	C324—C322—H32C	45.7
H12A—C121—H12B	108.7	C323—C322—H32C	113.1
C123—C122—C121	125.1 (3)	C321—C322—H32C	113.1
C123—C122—H122	117.5	C324—C322—H32D	113.4
C121—C122—H122	117.5	C323—C322—H32D	45.7
C122—C123—H12C	120.0	C321—C322—H32D	113.4
C122—C123—H12D	120.0	H32C—C322—H32D	112.7
H12C—C123—H12D	120.0	C322—C323—H32E	120.0
C21—S2—C13	97.13 (10)	C322—C323—H32F	120.0
C26—C21—C22	120.1 (2)	H32E—C323—H32F	120.0
C26—C21—S2	120.38 (18)	C322—C324—H32G	120.0
C22—C21—S2	119.49 (18)	C322—C324—H32H	120.0
O22—C22—C23	122.6 (2)	H32G—C324—H32H	120.0
O22—C22—C21	118.3 (2)	C41—S4—C33	102.06 (10)
C23—C22—C21	119.1 (2)	C46—C41—C42	120.1 (2)
C24—C23—C22	119.9 (2)	C46—C41—S4	120.10 (17)
C24—C23—S3	119.87 (17)	C42—C41—S4	119.58 (18)
C22—C23—S3	119.97 (18)	O42—C42—C41	122.03 (19)
C25—C24—C23	120.9 (2)	O42—C42—C43	118.15 (19)
C25—C24—H24	119.6	C41—C42—C43	119.8 (2)
C23—C24—H24	119.6	C44—C43—C42	119.3 (2)
C24—C25—C26	119.3 (2)	C44—C43—S1	120.04 (17)
C24—C25—H25	120.3	C42—C43—S1	120.61 (18)
C26—C25—H25	120.3	C43—C44—C45	120.6 (2)
C21—C26—C25	120.7 (2)	C43—C44—H44	119.7
C21—C26—H26	119.7	C45—C44—H44	119.7
C25—C26—H26	119.7	C46—C45—C44	119.9 (2)
C22—O22—H22	110 (2)	C46—C45—H45	120.0
C23—S3—C31	102.92 (10)	C44—C45—H45	120.0
C36—C31—C32	119.2 (2)	C45—C46—C41	120.1 (2)
C36—C31—S3	120.19 (18)	C45—C46—H46	119.9
C32—C31—S3	120.46 (17)	C41—C46—H46	119.9
O32—C32—C33	119.9 (2)	C42—O42—H42	108 (2)
C43—S1—C11—C12	131.62 (17)	C23—S3—C31—C32	108.48 (18)
C43—S1—C11—C16	−46.67 (19)	C36—C31—C32—O32	173.26 (18)
C16—C11—C12—O12	−174.53 (18)	S3—C31—C32—O32	−11.6 (3)
S1—C11—C12—O12	7.2 (3)	C36—C31—C32—C33	−2.3 (3)
C16—C11—C12—C13	2.2 (3)	S3—C31—C32—C33	172.85 (16)
S1—C11—C12—C13	−176.06 (15)	O32—C32—C33—C34	−173.53 (18)
O12—C12—C13—C14	173.74 (18)	C31—C32—C33—C34	2.0 (3)
C11—C12—C13—C14	−3.0 (3)	O32—C32—C33—S4	9.3 (3)
O12—C12—C13—S2	−8.5 (3)	C31—C32—C33—S4	−175.10 (16)
C11—C12—C13—S2	174.71 (15)	C32—C33—C34—C35	0.0 (3)
C12—C13—C14—C15	2.1 (3)	S4—C33—C34—C35	177.20 (17)
S2—C13—C14—C15	−175.65 (17)	C33—C34—C35—C36	−1.8 (3)
C13—C14—C15—C16	−0.3 (3)	C34—C35—C36—C31	1.5 (3)
C14—C15—C16—C11	−0.4 (3)	C32—C31—C36—C35	0.6 (3)
C12—C11—C16—C15	−0.5 (3)	S3—C31—C36—C35	−174.62 (17)
S1—C11—C16—C15	177.81 (17)	C33—C32—O32—C321	−92.7 (2)
C13—C12—O12—C121	96.1 (2)	C31—C32—O32—C321	91.7 (2)
C11—C12—O12—C121	−87.2 (2)	C32—O32—C321—C322	177.9 (2)
C12—O12—C121—C122	157.9 (2)	O32—C321—C322—C324	135.0 (6)
O12—C121—C122—C123	129.6 (3)	O32—C321—C322—C323	5.1 (6)
C14—C13—S2—C21	44.94 (19)	C32—C33—S4—C41	−109.04 (18)
C12—C13—S2—C21	−132.79 (17)	C34—C33—S4—C41	73.84 (19)
C13—S2—C21—C26	−116.1 (2)	C33—S4—C41—C46	−114.77 (19)
C13—S2—C21—C22	63.1 (2)	C33—S4—C41—C42	70.8 (2)
C26—C21—C22—O22	−178.6 (2)	C46—C41—C42—O42	−177.7 (2)
S2—C21—C22—O22	2.2 (3)	S4—C41—C42—O42	−3.2 (3)
C26—C21—C22—C23	2.4 (3)	C46—C41—C42—C43	3.0 (3)
S2—C21—C22—C23	−176.81 (17)	S4—C41—C42—C43	177.49 (17)
O22—C22—C23—C24	178.8 (2)	O42—C42—C43—C44	178.5 (2)
C21—C22—C23—C24	−2.2 (3)	C41—C42—C43—C44	−2.2 (3)
O22—C22—C23—S3	4.3 (3)	O42—C42—C43—S1	−0.4 (3)
C21—C22—C23—S3	−176.72 (17)	C41—C42—C43—S1	178.94 (17)
C22—C23—C24—C25	0.5 (4)	C11—S1—C43—C44	118.9 (2)
S3—C23—C24—C25	175.0 (2)	C11—S1—C43—C42	−62.2 (2)
C23—C24—C25—C26	1.0 (4)	C42—C43—C44—C45	−0.4 (4)
C22—C21—C26—C25	−1.0 (4)	S1—C43—C44—C45	178.5 (2)
S2—C21—C26—C25	178.3 (2)	C43—C44—C45—C46	2.2 (4)
C24—C25—C26—C21	−0.8 (4)	C44—C45—C46—C41	−1.3 (4)
C24—C23—S3—C31	114.8 (2)	C42—C41—C46—C45	−1.3 (3)
C22—C23—S3—C31	−70.7 (2)	S4—C41—C46—C45	−175.69 (19)
C23—S3—C31—C36	−76.40 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O22—H22···O32	0.83 (3)	2.17 (3)	2.904 (2)	146 (3)
O42—H42···O32	0.82 (3)	2.23 (3)	2.939 (2)	146 (3)

(3b1) syn-2²,4²-dihydroxy-1⁵,2⁵,3⁵,4⁵-tetranitro-1²,3²– bis(prop-2-enoxy)thiacalix[4]arene acetone disolvate

Crystal data

C30H20N4O12S4·2C3H6O	F(000) = 1808
Mr = 872.90	Dx = 1.447 Mg m^−3
Orthorhombic, Pccn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2ac	Cell parameters from 60450 reflections
a = 8.8760 (3) Å	θ = 2.7–27.8°
b = 17.3100 (5) Å	µ = 0.31 mm^−1
c = 26.0798 (10) Å	T = 173 K
V = 4007.0 (2) Å^3	Plate, colourless
Z = 4	0.42 × 0.37 × 0.19 mm

Data collection

STOE IPDS-II two-circle- diffractometer	4617 independent reflections
Radiation source: fine-focus sealed tube	4227 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.067
ω scans	θmax = 27.7°, θmin = 2.8°
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995)	h = −11→11
Tmin = 0.881, Tmax = 0.944	k = −22→22
56923 measured reflections	l = −34→33

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)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.084	w = 1/[σ^2(Fo^2) + (0.0372P)^2 + 2.018P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
4617 reflections	Δρmax = 0.31 e Å^−3
267 parameters	Δρmin = −0.20 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0023 (3)

Special details

Experimental.

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
S1	1.10374 (4)	0.616317 (19)	0.384606 (13)	0.02121 (9)
S2	0.48375 (4)	0.566071 (19)	0.371849 (13)	0.02109 (9)
O3	0.34739 (15)	0.63844 (7)	0.25405 (4)	0.0372 (3)
O12	0.78776 (11)	0.59610 (5)	0.42519 (4)	0.0212 (2)
O22	0.44018 (12)	0.73365 (6)	0.33263 (4)	0.0268 (2)
H22	0.418 (3)	0.6928 (14)	0.3145 (9)	0.050 (6)*
O151	0.71047 (14)	0.55879 (9)	0.18687 (5)	0.0437 (3)
O152	0.95137 (14)	0.58156 (7)	0.19102 (4)	0.0363 (3)
O251	0.43113 (19)	0.64501 (8)	0.56568 (5)	0.0489 (3)
O252	0.4387 (3)	0.76954 (8)	0.57074 (5)	0.0714 (6)
N15	0.82703 (15)	0.57261 (7)	0.21097 (5)	0.0269 (3)
N25	0.43783 (18)	0.70927 (8)	0.54589 (5)	0.0363 (3)
C3	0.38755 (18)	0.66006 (8)	0.21168 (6)	0.0280 (3)
C11	0.93641 (14)	0.60122 (7)	0.34818 (5)	0.0191 (3)
C12	0.79616 (14)	0.59182 (7)	0.37283 (5)	0.0179 (2)
C13	0.66501 (14)	0.57936 (7)	0.34330 (5)	0.0187 (3)
C14	0.67667 (15)	0.57194 (7)	0.29021 (5)	0.0212 (3)
H14	0.5897	0.5623	0.2700	0.025*
C15	0.81750 (16)	0.57880 (7)	0.26735 (5)	0.0213 (3)
C16	0.94793 (15)	0.59462 (7)	0.29504 (5)	0.0212 (3)
H16	1.0421	0.6007	0.2782	0.025*
C21	0.46619 (14)	0.65281 (7)	0.40820 (5)	0.0190 (2)
C22	0.44599 (14)	0.72503 (8)	0.38356 (5)	0.0188 (3)
C23	0.43351 (14)	0.79279 (7)	0.41390 (5)	0.0189 (2)
C24	0.43420 (15)	0.78768 (8)	0.46700 (5)	0.0222 (3)
H24	0.4277	0.8330	0.4874	0.027*
C25	0.44452 (16)	0.71518 (8)	0.48995 (5)	0.0239 (3)
C26	0.46214 (15)	0.64789 (8)	0.46137 (5)	0.0213 (3)
H26	0.4713	0.5993	0.4780	0.026*
C31	0.4947 (3)	0.72639 (11)	0.20481 (8)	0.0468 (5)
H31A	0.5210	0.7478	0.2384	0.070*
H31B	0.4468	0.7665	0.1839	0.070*
H31C	0.5862	0.7082	0.1876	0.070*
C32	0.3341 (2)	0.61978 (10)	0.16417 (6)	0.0393 (4)
H32A	0.2654	0.5778	0.1736	0.059*
H32B	0.4208	0.5985	0.1457	0.059*
H32C	0.2812	0.6567	0.1421	0.059*
C121	0.79998 (19)	0.52058 (9)	0.44916 (6)	0.0308 (3)
H12A	0.8958	0.4958	0.4388	0.037*
H12B	0.7159	0.4873	0.4376	0.037*
C122	0.7952 (2)	0.52887 (12)	0.50611 (7)	0.0405 (4)
H122	0.8014	0.4824	0.5254	0.049*
C123	0.7834 (2)	0.59327 (14)	0.53252 (7)	0.0473 (5)
H12C	0.7769	0.6414	0.5152	0.057*
H12D	0.7815	0.5916	0.5689	0.057*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.01456 (15)	0.02122 (16)	0.02785 (18)	0.00167 (11)	−0.00244 (12)	−0.00119 (12)
S2	0.01566 (15)	0.02088 (16)	0.02673 (17)	−0.00277 (11)	0.00248 (12)	−0.00672 (12)
O3	0.0437 (7)	0.0449 (6)	0.0230 (5)	−0.0051 (5)	−0.0041 (5)	0.0008 (5)
O12	0.0219 (5)	0.0229 (4)	0.0189 (5)	0.0005 (4)	0.0003 (4)	0.0005 (3)
O22	0.0358 (6)	0.0267 (5)	0.0179 (5)	−0.0019 (4)	−0.0026 (4)	−0.0026 (4)
O151	0.0369 (7)	0.0695 (9)	0.0247 (6)	0.0058 (6)	−0.0054 (5)	−0.0089 (5)
O152	0.0418 (7)	0.0395 (6)	0.0275 (6)	−0.0092 (5)	0.0130 (5)	−0.0089 (5)
O251	0.0747 (10)	0.0446 (7)	0.0274 (6)	0.0040 (7)	0.0125 (6)	0.0093 (5)
O252	0.1446 (18)	0.0467 (8)	0.0229 (6)	0.0033 (10)	0.0126 (8)	−0.0103 (6)
N15	0.0327 (7)	0.0255 (6)	0.0223 (6)	0.0032 (5)	0.0020 (5)	−0.0039 (4)
N25	0.0491 (9)	0.0390 (7)	0.0207 (6)	0.0040 (6)	0.0080 (6)	−0.0010 (5)
C3	0.0333 (8)	0.0249 (7)	0.0258 (7)	0.0027 (6)	−0.0060 (6)	−0.0003 (5)
C11	0.0160 (6)	0.0168 (5)	0.0245 (7)	0.0005 (4)	−0.0015 (5)	−0.0009 (5)
C12	0.0179 (6)	0.0157 (5)	0.0200 (6)	0.0013 (4)	0.0001 (5)	−0.0018 (4)
C13	0.0154 (6)	0.0171 (6)	0.0234 (6)	0.0011 (4)	0.0011 (5)	−0.0027 (5)
C14	0.0191 (6)	0.0205 (6)	0.0238 (7)	0.0020 (5)	−0.0025 (5)	−0.0034 (5)
C15	0.0247 (7)	0.0194 (6)	0.0199 (6)	0.0027 (5)	0.0024 (5)	−0.0023 (5)
C16	0.0192 (6)	0.0197 (6)	0.0249 (7)	0.0017 (5)	0.0038 (5)	−0.0007 (5)
C21	0.0128 (5)	0.0211 (6)	0.0230 (6)	−0.0009 (4)	0.0018 (5)	−0.0042 (5)
C22	0.0128 (5)	0.0243 (6)	0.0194 (6)	−0.0017 (5)	0.0002 (4)	−0.0018 (5)
C23	0.0133 (5)	0.0202 (6)	0.0232 (6)	−0.0009 (4)	0.0012 (5)	−0.0010 (5)
C24	0.0191 (6)	0.0244 (6)	0.0232 (7)	−0.0002 (5)	0.0030 (5)	−0.0053 (5)
C25	0.0238 (7)	0.0293 (7)	0.0184 (6)	0.0006 (5)	0.0043 (5)	−0.0013 (5)
C26	0.0176 (6)	0.0232 (6)	0.0232 (7)	0.0000 (5)	0.0026 (5)	0.0006 (5)
C31	0.0644 (13)	0.0389 (9)	0.0372 (9)	−0.0186 (9)	−0.0048 (9)	−0.0014 (7)
C32	0.0550 (11)	0.0372 (8)	0.0257 (8)	−0.0133 (8)	−0.0079 (7)	−0.0006 (6)
C121	0.0354 (8)	0.0277 (7)	0.0293 (8)	−0.0007 (6)	−0.0022 (6)	0.0088 (6)
C122	0.0360 (9)	0.0578 (11)	0.0278 (8)	−0.0014 (8)	−0.0024 (7)	0.0165 (8)
C123	0.0382 (10)	0.0802 (14)	0.0235 (8)	0.0005 (9)	−0.0004 (7)	0.0018 (8)

Geometric parameters (Å, º)

S1—C23^i	1.7800 (14)	C21—C26	1.3899 (19)
S1—C11	1.7824 (13)	C21—C22	1.4171 (18)
C11—C16	1.3943 (19)	C22—O22	1.3374 (16)
C11—C12	1.4106 (18)	C22—C23	1.4191 (18)
C12—O12	1.3694 (16)	C23—C24	1.3878 (19)
C12—C13	1.4124 (18)	C23—S1^i	1.7800 (14)
C13—C14	1.3942 (19)	C24—C25	1.393 (2)
C13—S2	1.7877 (13)	C24—H24	0.9500
C14—C15	1.3900 (19)	C25—C26	1.3915 (19)
C14—H14	0.9500	C25—N25	1.4638 (19)
C15—C16	1.3915 (19)	C26—H26	0.9500
C15—N15	1.4768 (18)	N25—O251	1.2277 (19)
C16—H16	0.9500	N25—O252	1.2281 (19)
N15—O152	1.2300 (17)	O22—H22	0.87 (2)
N15—O151	1.2340 (18)	O3—C3	1.220 (2)
O12—C121	1.4531 (17)	C3—C32	1.499 (2)
C121—C122	1.493 (2)	C3—C31	1.502 (2)
C121—H12A	0.9900	C31—H31A	0.9800
C121—H12B	0.9900	C31—H31B	0.9800
C122—C123	1.315 (3)	C31—H31C	0.9800
C122—H122	0.9500	C32—H32A	0.9800
C123—H12C	0.9500	C32—H32B	0.9800
C123—H12D	0.9500	C32—H32C	0.9800
S2—C21	1.7824 (13)
C23^i—S1—C11	101.75 (6)	C26—C21—S2	118.78 (10)
C16—C11—C12	120.56 (12)	C22—C21—S2	120.86 (10)
C16—C11—S1	118.74 (10)	O22—C22—C21	123.61 (12)
C12—C11—S1	120.62 (10)	O22—C22—C23	117.29 (12)
O12—C12—C11	119.76 (11)	C21—C22—C23	119.09 (12)
O12—C12—C13	120.48 (11)	C24—C23—C22	120.23 (12)
C11—C12—C13	119.76 (12)	C24—C23—S1^i	119.04 (10)
C14—C13—C12	119.63 (12)	C22—C23—S1^i	120.38 (10)
C14—C13—S2	117.94 (10)	C23—C24—C25	119.09 (12)
C12—C13—S2	122.29 (10)	C23—C24—H24	120.5
C15—C14—C13	119.00 (12)	C25—C24—H24	120.5
C15—C14—H14	120.5	C26—C25—C24	122.09 (13)
C13—C14—H14	120.5	C26—C25—N25	118.68 (13)
C14—C15—C16	122.85 (13)	C24—C25—N25	119.23 (13)
C14—C15—N15	118.19 (12)	C21—C26—C25	119.08 (13)
C16—C15—N15	118.89 (12)	C21—C26—H26	120.5
C15—C16—C11	118.08 (12)	C25—C26—H26	120.5
C15—C16—H16	121.0	O251—N25—O252	123.24 (15)
C11—C16—H16	121.0	O251—N25—C25	118.97 (14)
O152—N15—O151	124.14 (13)	O252—N25—C25	117.79 (14)
O152—N15—C15	117.62 (12)	C22—O22—H22	117.1 (15)
O151—N15—C15	118.24 (12)	O3—C3—C32	120.91 (15)
C12—O12—C121	112.10 (10)	O3—C3—C31	121.85 (15)
O12—C121—C122	109.84 (13)	C32—C3—C31	117.22 (14)
O12—C121—H12A	109.7	C3—C31—H31A	109.5
C122—C121—H12A	109.7	C3—C31—H31B	109.5
O12—C121—H12B	109.7	H31A—C31—H31B	109.5
C122—C121—H12B	109.7	C3—C31—H31C	109.5
H12A—C121—H12B	108.2	H31A—C31—H31C	109.5
C123—C122—C121	127.24 (17)	H31B—C31—H31C	109.5
C123—C122—H122	116.4	C3—C32—H32A	109.5
C121—C122—H122	116.4	C3—C32—H32B	109.5
C122—C123—H12C	120.0	H32A—C32—H32B	109.5
C122—C123—H12D	120.0	C3—C32—H32C	109.5
H12C—C123—H12D	120.0	H32A—C32—H32C	109.5
C21—S2—C13	101.06 (6)	H32B—C32—H32C	109.5
C26—C21—C22	120.21 (12)
C23^i—S1—C11—C16	118.89 (11)	O12—C121—C122—C123	−0.6 (2)
C23^i—S1—C11—C12	−64.61 (11)	C14—C13—S2—C21	−127.05 (10)
C16—C11—C12—O12	177.96 (11)	C12—C13—S2—C21	57.23 (11)
S1—C11—C12—O12	1.53 (16)	C13—S2—C21—C26	−114.33 (11)
C16—C11—C12—C13	−3.12 (18)	C13—S2—C21—C22	70.09 (11)
S1—C11—C12—C13	−179.55 (9)	C26—C21—C22—O22	−176.19 (12)
O12—C12—C13—C14	−177.32 (11)	S2—C21—C22—O22	−0.67 (18)
C11—C12—C13—C14	3.76 (18)	C26—C21—C22—C23	4.90 (18)
O12—C12—C13—S2	−1.67 (16)	S2—C21—C22—C23	−179.58 (9)
C11—C12—C13—S2	179.41 (9)	O22—C22—C23—C24	178.10 (12)
C12—C13—C14—C15	−1.49 (18)	C21—C22—C23—C24	−2.93 (18)
S2—C13—C14—C15	−177.32 (10)	O22—C22—C23—S1^i	4.98 (16)
C13—C14—C15—C16	−1.5 (2)	C21—C22—C23—S1^i	−176.05 (9)
C13—C14—C15—N15	−178.57 (11)	C22—C23—C24—C25	−1.16 (19)
C14—C15—C16—C11	2.2 (2)	S1^i—C23—C24—C25	172.05 (10)
N15—C15—C16—C11	179.21 (11)	C23—C24—C25—C26	3.4 (2)
C12—C11—C16—C15	0.18 (19)	C23—C24—C25—N25	−177.02 (13)
S1—C11—C16—C15	176.68 (10)	C22—C21—C26—C25	−2.74 (19)
C14—C15—N15—O152	177.42 (13)	S2—C21—C26—C25	−178.35 (10)
C16—C15—N15—O152	0.27 (18)	C24—C25—C26—C21	−1.5 (2)
C14—C15—N15—O151	−2.63 (19)	N25—C25—C26—C21	178.98 (13)
C16—C15—N15—O151	−179.79 (13)	C26—C25—N25—O251	−8.0 (2)
C11—C12—O12—C121	−93.38 (14)	C24—C25—N25—O251	172.48 (15)
C13—C12—O12—C121	87.71 (14)	C26—C25—N25—O252	172.26 (17)
C12—O12—C121—C122	178.16 (12)	C24—C25—N25—O252	−7.3 (2)

Symmetry code: (i) −x+3/2, −y+3/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O22—H22···O3	0.87 (2)	1.94 (2)	2.7558 (16)	155 (2)

(3b2) syn-2²,4²-dihydroxy-1⁵,2⁵,3⁵,4⁵-tetranitro-1²,3²– bis(prop-2-enoxy)thiacalix[4]arene

Crystal data

C30H20N4O12S4	F(000) = 1552
Mr = 756.74	Dx = 1.568 Mg m^−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 23347 reflections
a = 17.2475 (17) Å	θ = 3.4–25.8°
b = 20.4150 (19) Å	µ = 0.37 mm^−1
c = 9.102 (1) Å	T = 173 K
V = 3204.9 (6) Å^3	Plate, colourless
Z = 4	0.39 × 0.12 × 0.04 mm

Data collection

STOE IPDS-II two-circle- diffractometer	3127 independent reflections
Radiation source: fine-focus sealed tube	2375 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.098
ω scans	θmax = 25.8°, θmin = 3.4°
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995)	h = −20→21
Tmin = 0.892, Tmax = 0.961	k = −22→24
44126 measured reflections	l = −11→11

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)] = 0.093	H-atom parameters constrained
wR(F^2) = 0.257	w = 1/[σ^2(Fo^2) + (0.1315P)^2 + 3.5315P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max < 0.001
3127 reflections	Δρmax = 0.74 e Å^−3
239 parameters	Δρmin = −0.48 e Å^−3
1 restraint	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0092 (19)

Special details

Experimental.

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	Occ. (<1)
S1	0.61872 (9)	0.61341 (8)	0.82180 (14)	0.0656 (5)
S2	0.69118 (9)	0.61361 (8)	0.22341 (16)	0.0693 (5)
O12	0.72499 (18)	0.62180 (17)	0.5518 (4)	0.0529 (9)
O22	0.6226 (3)	0.7500	0.2025 (6)	0.089 (2)
H22	0.6069	0.7888	0.1948	0.133*	0.50
O25	0.9692 (3)	0.6984 (3)	0.3656 (11)	0.145 (3)
O151	0.3995 (2)	0.5491 (2)	0.2899 (4)	0.0697 (11)
O152	0.3698 (2)	0.5563 (2)	0.5220 (5)	0.0772 (13)
O32	0.5521 (3)	0.7500	0.7811 (7)	0.090 (2)
H32	0.5362	0.7888	0.7741	0.134*	0.50
O35	0.8993 (3)	0.7006 (3)	0.9325 (11)	0.157 (4)
N15	0.4162 (2)	0.5614 (2)	0.4195 (5)	0.0540 (10)
N25	0.9362 (4)	0.7500	0.3509 (11)	0.082 (2)
N35	0.8678 (4)	0.7500	0.9116 (8)	0.0654 (18)
C11	0.5931 (3)	0.6069 (2)	0.6329 (5)	0.0491 (11)
C12	0.6480 (2)	0.6114 (2)	0.5186 (5)	0.0438 (10)
C13	0.6245 (3)	0.6070 (2)	0.3721 (5)	0.0489 (11)
C14	0.5475 (3)	0.5910 (2)	0.3386 (5)	0.0506 (11)
H14	0.5310	0.5868	0.2395	0.061*
C15	0.4963 (2)	0.5814 (2)	0.4531 (5)	0.0470 (11)
C16	0.5166 (3)	0.5907 (3)	0.5992 (5)	0.0508 (11)
H16	0.4791	0.5860	0.6749	0.061*
C21	0.7377 (3)	0.6903 (3)	0.2582 (5)	0.0575 (13)
C22	0.6982 (4)	0.7500	0.2389 (7)	0.0552 (17)
C25	0.8531 (4)	0.7500	0.3108 (9)	0.062 (2)
C26	0.8163 (3)	0.6903 (3)	0.2952 (7)	0.0628 (14)
H26	0.8438	0.6504	0.3091	0.075*
C31	0.6675 (3)	0.6902 (3)	0.8310 (5)	0.0510 (12)
C32	0.6282 (4)	0.7500	0.8138 (7)	0.0545 (18)
C35	0.7837 (4)	0.7500	0.8833 (7)	0.0501 (16)
C36	0.7464 (3)	0.6904 (3)	0.8664 (5)	0.0497 (11)
H36	0.7739	0.6505	0.8786	0.060*
C121	0.7672 (3)	0.5614 (3)	0.5776 (8)	0.0747 (17)
H12A	0.7616	0.5317	0.4922	0.090*
H12B	0.7465	0.5389	0.6656	0.090*
C122	0.8506 (3)	0.5785 (3)	0.6001 (7)	0.0703 (16)
H12G	0.8630	0.6168	0.6543	0.084*	0.726 (15)
H12H	0.8844	0.5426	0.6181	0.084*	0.274 (15)
C123	0.9054 (5)	0.5438 (4)	0.5499 (9)	0.069 (3)*	0.726 (15)
H12C	0.9533	0.5637	0.5239	0.083*	0.726 (15)
H12D	0.8986	0.4979	0.5381	0.083*	0.726 (15)
C124	0.8827 (11)	0.6354 (7)	0.598 (2)	0.058 (6)*	0.274 (15)
H12E	0.9344	0.6402	0.5642	0.070*	0.274 (15)
H12F	0.8546	0.6727	0.6311	0.070*	0.274 (15)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0660 (8)	0.0898 (11)	0.0411 (7)	−0.0310 (7)	−0.0067 (5)	0.0057 (6)
S2	0.0691 (9)	0.0859 (11)	0.0528 (8)	−0.0209 (7)	0.0181 (6)	−0.0188 (7)
O12	0.0364 (16)	0.062 (2)	0.060 (2)	−0.0051 (14)	−0.0038 (14)	−0.0023 (15)
O22	0.045 (3)	0.169 (7)	0.052 (3)	0.000	−0.006 (2)	0.000
O25	0.050 (3)	0.080 (3)	0.305 (10)	0.010 (2)	−0.012 (4)	−0.008 (5)
O32	0.034 (3)	0.160 (7)	0.075 (4)	0.000	−0.007 (2)	0.000
O35	0.059 (3)	0.064 (3)	0.347 (12)	0.010 (2)	−0.065 (5)	−0.014 (5)
O151	0.057 (2)	0.084 (3)	0.068 (2)	−0.010 (2)	−0.0290 (18)	0.007 (2)
O152	0.0428 (19)	0.093 (3)	0.096 (3)	−0.0105 (19)	0.007 (2)	−0.021 (2)
N15	0.041 (2)	0.055 (2)	0.066 (3)	0.0013 (18)	−0.0107 (19)	−0.0011 (19)
N25	0.040 (3)	0.067 (5)	0.139 (7)	0.000	0.010 (4)	0.000
N35	0.049 (3)	0.050 (4)	0.098 (5)	0.000	−0.019 (3)	0.000
C11	0.045 (2)	0.054 (3)	0.049 (2)	−0.004 (2)	−0.005 (2)	0.004 (2)
C12	0.035 (2)	0.046 (2)	0.050 (2)	−0.0041 (17)	−0.0049 (18)	−0.0015 (19)
C13	0.044 (2)	0.054 (3)	0.049 (2)	−0.005 (2)	0.0015 (19)	−0.005 (2)
C14	0.052 (3)	0.054 (3)	0.045 (2)	−0.003 (2)	−0.009 (2)	−0.001 (2)
C15	0.036 (2)	0.053 (3)	0.053 (3)	−0.0039 (19)	−0.0097 (18)	0.000 (2)
C16	0.040 (2)	0.057 (3)	0.055 (3)	−0.002 (2)	0.0004 (19)	−0.002 (2)
C21	0.051 (3)	0.076 (4)	0.046 (3)	−0.009 (2)	0.016 (2)	−0.007 (2)
C22	0.052 (4)	0.077 (5)	0.037 (3)	0.000	0.011 (3)	0.000
C25	0.041 (4)	0.064 (5)	0.081 (5)	0.000	0.018 (3)	0.000
C26	0.048 (3)	0.066 (3)	0.074 (4)	0.002 (2)	0.021 (2)	−0.007 (3)
C31	0.048 (2)	0.076 (3)	0.029 (2)	−0.010 (2)	0.0011 (18)	−0.002 (2)
C32	0.039 (3)	0.088 (5)	0.036 (3)	0.000	−0.001 (3)	0.000
C35	0.039 (3)	0.063 (4)	0.048 (4)	0.000	−0.010 (3)	0.000
C36	0.050 (3)	0.064 (3)	0.035 (2)	0.002 (2)	−0.0040 (18)	−0.002 (2)
C121	0.045 (3)	0.068 (4)	0.110 (5)	0.002 (3)	−0.021 (3)	0.005 (3)
C122	0.047 (3)	0.089 (4)	0.075 (4)	0.007 (3)	−0.015 (3)	−0.013 (3)

Geometric parameters (Å, º)

S1—C31	1.780 (5)	C123—H12D	0.9500
S1—C11	1.780 (5)	C124—H12E	0.9500
C11—C16	1.394 (6)	C124—H12F	0.9500
C11—C12	1.410 (7)	N15—O152	1.233 (6)
C12—O12	1.378 (5)	N15—O151	1.239 (5)
C12—C13	1.397 (7)	S2—C21	1.787 (6)
C13—C14	1.402 (7)	C21—C26	1.397 (8)
C13—S2	1.781 (5)	C21—C22	1.408 (7)
C14—C15	1.380 (7)	C22—O22	1.346 (9)
C14—H14	0.9500	C25—C26	1.381 (7)
C15—C16	1.389 (7)	C25—N25	1.480 (10)
C15—N15	1.473 (6)	C26—H26	0.9500
C16—H16	0.9500	O22—H22	0.8399
O12—C121	1.451 (7)	N25—O25	1.204 (6)
C121—C122	1.494 (8)	C31—C36	1.399 (7)
C121—H12A	0.9900	C31—C32	1.405 (6)
C121—H12B	0.9900	C32—O32	1.347 (8)
C122—C123	1.266 (9)	C35—C36	1.385 (6)
C122—C124	1.288 (12)	C35—N35	1.473 (8)
C122—H12G	0.9500	C36—H36	0.9500
C122—H12H	0.9500	O32—H32	0.8400
C123—H12C	0.9500	N35—O35	1.162 (6)
C31—S1—C11	103.2 (2)	C122—C124—H12F	120.0
C16—C11—C12	119.3 (4)	H12E—C124—H12F	120.0
C16—C11—S1	117.7 (4)	O152—N15—O151	123.6 (4)
C12—C11—S1	122.7 (3)	O152—N15—C15	118.3 (4)
O12—C12—C13	119.9 (4)	O151—N15—C15	118.1 (4)
O12—C12—C11	119.7 (4)	C13—S2—C21	102.8 (2)
C13—C12—C11	120.3 (4)	C26—C21—C22	119.9 (5)
C12—C13—C14	119.8 (4)	C26—C21—S2	118.6 (5)
C12—C13—S2	122.2 (3)	C22—C21—S2	121.3 (4)
C14—C13—S2	117.7 (4)	O22—C22—C21^i	120.0 (3)
C15—C14—C13	118.4 (4)	O22—C22—C21	120.0 (3)
C15—C14—H14	120.8	C21^i—C22—C21	120.0 (7)
C13—C14—H14	120.8	C26^i—C25—C26	123.9 (7)
C14—C15—C16	122.8 (4)	C26^i—C25—N25	118.0 (4)
C14—C15—N15	118.9 (4)	C26—C25—N25	118.0 (4)
C16—C15—N15	118.3 (4)	C25—C26—C21	118.1 (6)
C15—C16—C11	118.8 (4)	C25—C26—H26	121.0
C15—C16—H16	120.6	C21—C26—H26	121.0
C11—C16—H16	120.6	C22—O22—H22	109.5
C12—O12—C121	112.8 (4)	O25—N25—O25^i	122.0 (8)
O12—C121—C122	107.9 (5)	O25—N25—C25	119.0 (4)
O12—C121—H12A	110.1	O25^i—N25—C25	119.0 (4)
C122—C121—H12A	110.1	C36—C31—C32	119.4 (5)
O12—C121—H12B	110.1	C36—C31—S1	118.3 (4)
C122—C121—H12B	110.1	C32—C31—S1	122.2 (4)
H12A—C121—H12B	108.4	O32—C32—C31	119.6 (3)
C123—C122—C124	100.3 (11)	O32—C32—C31^i	119.6 (3)
C123—C122—C121	122.6 (7)	C31—C32—C31^i	120.7 (6)
C124—C122—C121	128.5 (10)	C36^i—C35—C36	122.9 (6)
C123—C122—H12G	118.7	C36^i—C35—N35	118.5 (3)
C121—C122—H12G	118.7	C36—C35—N35	118.5 (3)
C124—C122—H12H	115.8	C35—C36—C31	118.8 (5)
C121—C122—H12H	115.8	C35—C36—H36	120.6
H12G—C122—H12H	114.1	C31—C36—H36	120.6
C122—C123—H12C	120.0	C32—O32—H32	109.5
C122—C123—H12D	120.0	O35—N35—O35^i	120.7 (7)
H12C—C123—H12D	120.0	O35—N35—C35	119.3 (4)
C122—C124—H12E	120.0	O35^i—N35—C35	119.2 (4)
C31—S1—C11—C16	−130.5 (4)	C13—S2—C21—C26	113.3 (4)
C31—S1—C11—C12	55.5 (5)	C13—S2—C21—C22	−71.3 (5)
C16—C11—C12—O12	−174.4 (4)	C26—C21—C22—O22	179.6 (5)
S1—C11—C12—O12	−0.5 (6)	S2—C21—C22—O22	4.3 (8)
C16—C11—C12—C13	7.2 (7)	C26—C21—C22—C21^i	−0.7 (9)
S1—C11—C12—C13	−178.9 (4)	S2—C21—C22—C21^i	−176.0 (3)
O12—C12—C13—C14	174.6 (4)	C26^i—C25—C26—C21	1.4 (12)
C11—C12—C13—C14	−7.0 (7)	N25—C25—C26—C21	179.6 (6)
O12—C12—C13—S2	0.7 (7)	C22—C21—C26—C25	−0.3 (8)
C11—C12—C13—S2	179.1 (4)	S2—C21—C26—C25	175.1 (5)
C12—C13—C14—C15	1.6 (7)	C26^i—C25—N25—O25	179.7 (9)
S2—C13—C14—C15	175.8 (4)	C26—C25—N25—O25	1.4 (13)
C13—C14—C15—C16	3.7 (8)	C26^i—C25—N25—O25^i	−1.4 (13)
C13—C14—C15—N15	−177.0 (4)	C26—C25—N25—O25^i	−179.7 (9)
C14—C15—C16—C11	−3.5 (8)	C11—S1—C31—C36	−114.5 (4)
N15—C15—C16—C11	177.2 (4)	C11—S1—C31—C32	69.9 (5)
C12—C11—C16—C15	−2.0 (7)	C36—C31—C32—O32	−179.4 (5)
S1—C11—C16—C15	−176.2 (4)	S1—C31—C32—O32	−3.8 (8)
C13—C12—O12—C121	−93.8 (6)	C36—C31—C32—C31^i	0.4 (9)
C11—C12—O12—C121	87.9 (6)	S1—C31—C32—C31^i	175.9 (3)
C12—O12—C121—C122	175.4 (5)	C36^i—C35—C36—C31	−0.1 (9)
O12—C121—C122—C123	−141.3 (7)	N35—C35—C36—C31	−176.3 (5)
O12—C121—C122—C124	0.0 (14)	C32—C31—C36—C35	−0.1 (7)
C14—C15—N15—O152	−176.3 (5)	S1—C31—C36—C35	−175.8 (4)
C16—C15—N15—O152	3.0 (7)	C36^i—C35—N35—O35	176.6 (8)
C14—C15—N15—O151	5.2 (7)	C36—C35—N35—O35	−7.1 (12)
C16—C15—N15—O151	−175.5 (5)	C36^i—C35—N35—O35^i	7.1 (12)
C12—C13—S2—C21	−55.0 (5)	C36—C35—N35—O35^i	−176.6 (8)
C14—C13—S2—C21	131.0 (4)

Symmetry code: (i) x, −y+3/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O22—H22···O25^ii	0.84	2.45	2.915 (8)	116
O22—H22···S2^i	0.84	2.48	3.031 (3)	124
O32—H32···S1^i	0.84	2.49	3.039 (3)	124

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