Supramolecular structures of 5-[3-(4-methyl­phenyl)- and 5-[3-(4-chloro­phenyl)-2-propenyl­idene]-2,2-di­methyl-1,3-dioxane-4,6-dione

2,2-Di­methyl-5-[3-(4-methyl­phenyl)-2-propenyl­idene]-1,3-di­ox­ane-4,6-dione, C₁₆H₁₆O₄, crystallizes in the triclinic space group , with two mol­ecules in the asymmetric unit. These mol­ecules and a centrosymmetrically related pair, linked together by weak C-H...O hydrogen bonds, form a tetramer. 5-[3-(4-Chloro­phenyl)-2-propenyl­idene]-2,2-di­methyl-1,3-dioxane-4,6-dione, C₁₅H₁₃ClO₄, also crystallizes in the triclinic space group , with one mol­ecule in the asymmetric unit. Centrosymmetrically related mol­ecules are linked together by weak C-H...O hydrogen bonds to form dimers which are further linked by yet another pair of centrosymmetrically related C-H...O hydrogen bonds to form a tube which runs parallel to the a axis.

S1. Comment

Meldrum's acid and its derivatives serve as good synthetic equivalents, most often in preparation of arylidene condensation products, which have received little attention as intermediates in heterocyclic synthesis. The condensation of Meldrum's acid arylidene derivatives with heterocyclic monoamines to afford pyridines has been reported(Morales et al., 1996, Quiroga et al., 1997, Quiroga et al., 1998, Quiroga et al., 1999, Rodríguez et al., 1996 and Rodríguez et al., 1997) or with α,β-unsaturated or dicarbonyl compounds to coumarins (Margaretha, 1972)

Here, we report an attempt to prepare triazolopyrimidines or triazolopyridazine using such condensation reaction with Meldrum's acid, 1,2-diaminotriazole and benzaldehyde. The final product was surprisingly the 3-(phenyl)-2-propenylidene derivative of Meldrum's acid, which comes from condensation of two molecules of Meldrum's acid with one of benzaldehyde. A further reaction using only the Meldrum's acid and benzaldehydes also produced that compound.

Both the title compounds crystallize in spacegroup P-1, in the case of compound (3a) with two molecules in the asymmetric unit which was chosen such that it formed a centrosymmetric dimer, see below. A view of the molecules of (3a) are shown in Figures 1a and 1 b. A view of molecule (3 b) is shown in Figure 2. The numbering system is chosen so that it is consistent for all three molecules.

The bonds and angles for the three molecules discussed in this study show no major differences except for the torsion angles involving the junction of the phenyl group and the propylidene chain. These difference are probably related to the differences in supramolecular structures found for the compounds. Selected torsion angles are given in Tables 1 for (3a) and 3 for (3 b).

The supramolecular structures of each compound are different. In compound (3a) the two molecules in the asymmetric unit are linked together head-to-tail via the C193–H193···O21 and C293–H293···O11 weak hydrogen bonds to form a dimer comprising an R²₂(20) ring, (Bernstein et al., 1995). These dimers are further linked together by two centrosymmetrically related pairs of weak C–H···O hydrogen bonds in which O24 at (-x, 1 - y, 2 - z) is an acceptor for H29 and H296 thus forming an R¹₂(6) ring, (Bernstein et al., 1995). Hence a discrete tetramer is formed by the molecules in the asymmetric unit dimer and the dimer related to it by the centre of symmetry at (0, 1/2, 1), Figure 3.

In compound (3 b) in which there is only one molecule in the centrosymmetric unit, the C95–H95···O4(1 - x,2 - y,2 - z) weak hydrogen bond links the molecules into a centrosymmetric dimer centred on (1/2, 1.0, 1.0) giving an R²₂(20) ring, (Bernstein et al., 1995). In addition the molecules are linked by the C9–H9···O6(-1 + x,y,z) weak hydrogen bond to form C(7) chain running parallel to the a axis. Operation of the centre of symmetry at (0,1,1) produces an R⁴₄(28) ring, (Bernstein et al., 1995), resulting from a combination of centrosymmetrically related pairs of the C95–H95···O4 and C9–H9···O6 hydrogen bonds, Figure 4. The result is a tube like three-dimensional ribbon which runs parallel to the a axis.

Details of the hydrogen bonding is given in Tables 2 for (3a) and and (3 b).

There is also a short Cl97···Cl97(1 - x,1 - y,3 - z) contact of 3.4927 (8) Å in (3 b). A preliminary search of the CSD (Allen & Kennard, 1993) gave 1544 hits for short Cl–Cl contacts less than the van der Waals contact of 3.6 Å, for Cl atoms attached to C.

S2. Experimental

Preparation of 5-(3-(4-methylphenyl)-2-propenylidene]-2,2-dimethyl-[1,3] dioxane-4,6-dione (3a). A solution of 4-methylbenzaldehyde, (1a), (2.0 mmoles) and Meldrum's acid, (2), (4.0 mmoles) in ethoxyethanol (5 ml) with catalytic amounts of triethylamine was refluxed during 30 minutes (TLC control), the resulting precipitate was filtered, washed with ethanol, dried and purified by silica gel chromatography with chloroform. Orange crystals suitable of (3a) for X-ray diffraction were prepared by diffusion using ethyl acetate and hexane. Mp 401 K, yield 65%.

Preparation of 5-(3-(4-chlorophenyl)-2-propenylidene]-2,2-dimethyl-[1,3] dioxane-4,6-dione (3 b). A solution of 4-chlorobenzaldehyde, (1 b), (2.0 mmoles) and Meldrum's acid, (2), (4.0 mmoles) in ethoxyethanol (5 ml) with catalytic amounts of triethylamine was refluxed during 30 minutes (TLC control), the resulting precipitate was filtered, washed with ethanol, dried and purified by silica gel chromatography with chloroform. Orange crystals suitable of (3 b) for X-ray diffraction were prepared by diffusion using ethyl acetate and hexane. Mp 455 K, yield 70%.

S3. Refinement

Molecules (3a & 3 b) crystallized in the triclinic system; space group P-1 assumed and confirmed by the analysis. H atoms were treated as riding atoms with C—H 0.95 to 0.98 Å. Methyl hydrogen were calculated a six half H atoms at the corners of a regular hexagon. Examination of the structure with PLATON (Spek, 2001) showed that there were no solvent accessible voids in the crystal lattice.

Computing details

For both compounds, data collection: Kappa-CCD server software (Nonius, 1997). Cell refinement: DENZO-SMN (Otwinowski & Minor, 1997) for (3a); Kappa-CCD server software (Nonius, 1997) for (3b). Data reduction: DENZO-SMN (Otwinowski & Minor, 1997) for (3a); Kappa-CCD server software (Nonius, 1997) for (3b). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: ORTEP (Johnson, 1976), PLATON (Spek, 2001) for (3a); NRCVAX96, ORTEP (Johnson, 1976), PLATON (Spek, 2001) for (3b). For both compounds, software used to prepare material for publication: SHELXL97 and WORDPERFECT macro PRPKAPPA (Ferguson, 2000).

Figures

	Fig. 1. A view of the molecules of (3a). Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A view of (3 b) with our numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 3. A view of the discrete tetramer formed by the molecules of (3a). The atoms labelled * are at (-x,1 - y, 2 - z). The unit cell is omitted for the sake of clarity.
	Fig. 4. A view of (3 b) showing the R^22(20) dimers and C(7)chains and the R^44(28) ring. The unit cell is omitted for the sake of clarity. The atoms labelled, * are at (-1 + x,y,z), # at (-x,2 - y,2 - z), $ at (1 - x,2 - y,2 - z), ? at (-2 + x,y,z) and & at (2 - x,2 - y,2 - z).

(3a) 5-(3-(4-methylphenyl)-2-propenylidene]-2,2-dimethyl-[1,3] dioxane-4,6-dione

Crystal data

C16H16O4	Z = 4
Mr = 272.29	F(000) = 576
Triclinic, P1	Dx = 1.288 Mg m^−3
Hall symbol: -P 1	Melting point: 401 K
a = 11.2891 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.4128 (4) Å	Cell parameters from 6331 reflections
c = 13.4504 (5) Å	θ = 2.9–27.5°
α = 91.217 (2)°	µ = 0.09 mm^−1
β = 114.640 (3)°	T = 120 K
γ = 113.7590 (15)°	Lath, colourless
V = 1403.88 (8) Å^3	0.15 × 0.15 × 0.1 mm

Data collection

Kappa-CCD diffractometer	6331 independent reflections
Radiation source: fine-focus sealed X-ray tube	3359 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.080
ϕ scans and ω scans with κ offsets	θmax = 27.5°, θmin = 2.9°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = −14→14
Tmin = 0.991, Tmax = 0.999	k = −14→14
21945 measured reflections	l = −17→17

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.165	H-atom parameters constrained
S = 0.96	w = 1/[σ^2(Fo^2) + (0.0809P)^2] where P = (Fo^2 + 2Fc^2)/3
6331 reflections	(Δ/σ)max < 0.001
367 parameters	Δρmax = 0.25 e Å^−3
0 restraints	Δρmin = −0.50 e Å^−3

Special details

Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm (Fox & Holmes, 1966) which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL97 input file.

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

	x	y	z	Uiso*/Ueq
O11	0.25428 (17)	0.07135 (15)	0.57136 (13)	0.0359 (4)
C12	0.3651 (2)	0.0548 (2)	0.55603 (18)	0.0327 (6)
C121	0.4221 (3)	0.1634 (2)	0.5019 (2)	0.0412 (6)
C122	0.4809 (3)	0.0560 (2)	0.66668 (18)	0.0426 (6)
O13	0.30146 (16)	−0.06671 (14)	0.47684 (11)	0.0320 (4)
C14	0.2119 (2)	−0.1784 (2)	0.49390 (17)	0.0288 (5)
O14	0.19023 (17)	−0.28312 (16)	0.44886 (12)	0.0378 (4)
C15	0.1453 (2)	−0.1604 (2)	0.56262 (16)	0.0275 (5)
C16	0.1585 (2)	−0.0295 (2)	0.59303 (17)	0.0304 (5)
O16	0.08966 (18)	−0.00424 (16)	0.63185 (13)	0.0412 (4)
C17	0.0672 (2)	−0.2682 (2)	0.59001 (16)	0.0297 (5)
C18	−0.0094 (2)	−0.2771 (2)	0.65323 (17)	0.0302 (5)
C19	−0.0818 (2)	−0.3936 (2)	0.67307 (16)	0.0294 (5)
C191	−0.1641 (2)	−0.4159 (2)	0.73519 (16)	0.0261 (5)
C192	−0.1893 (2)	−0.3190 (2)	0.77604 (17)	0.0289 (5)
C193	−0.2664 (2)	−0.3448 (2)	0.83681 (16)	0.0301 (5)
C194	−0.3221 (2)	−0.4687 (2)	0.85977 (16)	0.0275 (5)
C91	−0.4076 (3)	−0.4976 (2)	0.92450 (18)	0.0358 (6)
C195	−0.2986 (2)	−0.5650 (2)	0.81877 (17)	0.0307 (5)
C196	−0.2230 (2)	−0.5409 (2)	0.75661 (17)	0.0298 (5)
O21	−0.31404 (16)	−0.06950 (14)	0.89824 (12)	0.0312 (4)
C22	−0.2865 (3)	−0.0430 (2)	1.01284 (18)	0.0325 (6)
C221	−0.4148 (3)	−0.1473 (2)	1.0201 (2)	0.0500 (7)
C222	−0.1419 (3)	−0.0383 (2)	1.09044 (18)	0.0384 (6)
O23	−0.28717 (17)	0.08017 (14)	1.03894 (12)	0.0344 (4)
C24	−0.2123 (2)	0.1856 (2)	1.00726 (17)	0.0282 (5)
O24	−0.19663 (17)	0.29170 (15)	1.04345 (12)	0.0363 (4)
C25	−0.1633 (2)	0.1603 (2)	0.92736 (16)	0.0262 (5)
C26	−0.2246 (2)	0.0246 (2)	0.86595 (17)	0.0282 (5)
O26	−0.20926 (17)	−0.00941 (15)	0.78898 (12)	0.0383 (4)
C27	−0.0675 (2)	0.2672 (2)	0.91029 (16)	0.0279 (5)
C28	−0.0046 (2)	0.2744 (2)	0.83730 (17)	0.0278 (5)
C29	0.0899 (2)	0.3936 (2)	0.83520 (17)	0.0289 (5)
C291	0.1671 (2)	0.4208 (2)	0.76888 (16)	0.0272 (5)
C292	0.1696 (2)	0.3235 (2)	0.70598 (17)	0.0304 (5)
C293	0.2447 (2)	0.3554 (2)	0.64403 (17)	0.0326 (5)
C294	0.3214 (2)	0.4858 (2)	0.64154 (17)	0.0330 (6)
C92	0.4030 (3)	0.5200 (3)	0.57376 (19)	0.0442 (7)
C295	0.3203 (2)	0.5827 (2)	0.70421 (18)	0.0349 (6)
C296	0.2457 (2)	0.5523 (2)	0.76738 (17)	0.0305 (5)
H12A	0.4569	0.2485	0.5492	0.062*
H12B	0.3436	0.1520	0.4279	0.062*
H12C	0.5031	0.1604	0.4935	0.062*
H12D	0.4368	−0.0182	0.6960	0.064*
H12E	0.5230	0.1385	0.7205	0.064*
H12F	0.5581	0.0486	0.6552	0.064*
H17	0.0632	−0.3482	0.5635	0.036*
H18	−0.0096	−0.2004	0.6818	0.036*
H19	−0.0783	−0.4678	0.6434	0.035*
H192	−0.1526	−0.2339	0.7617	0.035*
H193	−0.2818	−0.2772	0.8635	0.036*
H91A	−0.3994	−0.5691	0.9614	0.054*
H91B	−0.5106	−0.5238	0.8730	0.054*
H91C	−0.3687	−0.4187	0.9814	0.054*
H195	−0.3353	−0.6498	0.8336	0.037*
H196	−0.2108	−0.6098	0.7281	0.036*
H22A	−0.4230	−0.2340	0.9991	0.075*
H22B	−0.5045	−0.1431	0.9687	0.075*
H22C	−0.4007	−0.1327	1.0971	0.075*
H22D	−0.0633	0.0341	1.0835	0.058*
H22E	−0.1423	−0.1216	1.0703	0.058*
H22F	−0.1259	−0.0244	1.1681	0.058*
H27	−0.0385	0.3495	0.9540	0.033*
H28	−0.0283	0.1966	0.7904	0.033*
H29	0.1072	0.4677	0.8828	0.035*
H292	0.1186	0.2339	0.7059	0.037*
H293	0.2444	0.2872	0.6021	0.039*
H92D	0.5075	0.5509	0.6235	0.066*
H92E	0.3882	0.5895	0.5367	0.066*
H92F	0.3664	0.4419	0.5169	0.066*
H295	0.3717	0.6721	0.7040	0.042*
H296	0.2477	0.6210	0.8101	0.037*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O11	0.0376 (10)	0.0269 (9)	0.0520 (10)	0.0126 (8)	0.0304 (8)	0.0116 (7)
C12	0.0330 (13)	0.0243 (13)	0.0447 (14)	0.0095 (11)	0.0249 (11)	0.0057 (10)
C121	0.0392 (15)	0.0342 (15)	0.0573 (15)	0.0132 (12)	0.0317 (13)	0.0153 (12)
C122	0.0333 (14)	0.0381 (16)	0.0424 (14)	0.0096 (12)	0.0120 (12)	0.0035 (11)
O13	0.0333 (9)	0.0273 (9)	0.0366 (9)	0.0089 (8)	0.0220 (7)	0.0071 (7)
C14	0.0237 (12)	0.0302 (14)	0.0302 (12)	0.0094 (11)	0.0132 (10)	0.0066 (10)
O14	0.0405 (10)	0.0286 (10)	0.0467 (10)	0.0109 (8)	0.0272 (8)	0.0024 (7)
C15	0.0243 (12)	0.0275 (13)	0.0292 (11)	0.0090 (10)	0.0139 (10)	0.0042 (9)
C16	0.0309 (13)	0.0308 (14)	0.0306 (12)	0.0118 (11)	0.0174 (10)	0.0091 (10)
O16	0.0507 (11)	0.0340 (10)	0.0567 (10)	0.0206 (9)	0.0386 (9)	0.0139 (8)
C17	0.0256 (12)	0.0277 (13)	0.0309 (12)	0.0084 (11)	0.0128 (10)	0.0022 (9)
C18	0.0276 (13)	0.0284 (14)	0.0328 (12)	0.0094 (11)	0.0158 (10)	0.0031 (10)
C19	0.0260 (12)	0.0274 (14)	0.0312 (12)	0.0086 (11)	0.0138 (10)	0.0033 (9)
C191	0.0208 (11)	0.0254 (13)	0.0258 (11)	0.0064 (10)	0.0095 (9)	0.0044 (9)
C192	0.0280 (12)	0.0201 (13)	0.0327 (12)	0.0061 (10)	0.0137 (10)	0.0037 (9)
C193	0.0314 (13)	0.0256 (13)	0.0315 (12)	0.0103 (11)	0.0158 (10)	0.0006 (9)
C194	0.0247 (12)	0.0270 (13)	0.0256 (11)	0.0081 (10)	0.0107 (9)	0.0055 (9)
C91	0.0336 (13)	0.0397 (15)	0.0370 (13)	0.0147 (12)	0.0205 (11)	0.0111 (11)
C195	0.0297 (13)	0.0242 (13)	0.0362 (12)	0.0098 (11)	0.0159 (10)	0.0102 (10)
C196	0.0302 (13)	0.0243 (13)	0.0377 (12)	0.0124 (11)	0.0181 (10)	0.0075 (10)
O21	0.0300 (9)	0.0217 (9)	0.0387 (9)	0.0077 (7)	0.0174 (7)	0.0055 (6)
C22	0.0406 (14)	0.0232 (13)	0.0443 (14)	0.0150 (11)	0.0281 (12)	0.0114 (10)
C221	0.0569 (18)	0.0269 (15)	0.0816 (19)	0.0129 (13)	0.0510 (16)	0.0173 (13)
C222	0.0496 (16)	0.0335 (15)	0.0372 (13)	0.0228 (13)	0.0206 (12)	0.0122 (11)
O23	0.0412 (10)	0.0221 (9)	0.0536 (10)	0.0136 (8)	0.0343 (8)	0.0128 (7)
C24	0.0257 (12)	0.0250 (14)	0.0355 (12)	0.0123 (11)	0.0148 (10)	0.0076 (10)
O24	0.0450 (10)	0.0239 (10)	0.0498 (10)	0.0154 (8)	0.0305 (8)	0.0088 (7)
C25	0.0240 (12)	0.0238 (13)	0.0321 (12)	0.0112 (10)	0.0138 (10)	0.0077 (9)
C26	0.0243 (12)	0.0264 (13)	0.0334 (12)	0.0119 (11)	0.0127 (10)	0.0092 (10)
O26	0.0453 (11)	0.0326 (10)	0.0377 (9)	0.0147 (8)	0.0231 (8)	0.0036 (7)
C27	0.0299 (12)	0.0254 (13)	0.0311 (12)	0.0152 (11)	0.0139 (10)	0.0074 (9)
C28	0.0299 (13)	0.0274 (13)	0.0325 (12)	0.0153 (11)	0.0177 (10)	0.0081 (9)
C29	0.0294 (13)	0.0288 (14)	0.0344 (12)	0.0156 (11)	0.0174 (10)	0.0087 (10)
C291	0.0223 (11)	0.0274 (13)	0.0305 (11)	0.0105 (10)	0.0118 (9)	0.0083 (9)
C292	0.0276 (13)	0.0255 (13)	0.0359 (12)	0.0117 (11)	0.0131 (10)	0.0059 (10)
C293	0.0323 (13)	0.0368 (15)	0.0307 (12)	0.0169 (12)	0.0154 (10)	0.0042 (10)
C294	0.0282 (13)	0.0428 (16)	0.0304 (12)	0.0164 (12)	0.0151 (10)	0.0113 (10)
C92	0.0386 (15)	0.0576 (18)	0.0410 (14)	0.0187 (14)	0.0253 (12)	0.0138 (12)
C295	0.0332 (14)	0.0302 (14)	0.0441 (14)	0.0118 (12)	0.0226 (11)	0.0160 (11)
C296	0.0314 (13)	0.0257 (13)	0.0388 (13)	0.0139 (11)	0.0193 (11)	0.0081 (10)

Geometric parameters (Å, º)

O11—C16	1.361 (3)	O21—C26	1.369 (3)
O11—C12	1.431 (3)	O21—C22	1.438 (2)
C12—O13	1.439 (3)	C22—O23	1.445 (3)
C12—C121	1.505 (3)	C22—C221	1.503 (3)
C12—C122	1.512 (3)	C22—C222	1.504 (3)
C121—H12A	0.9800	C221—H22A	0.9800
C121—H12B	0.9800	C221—H22B	0.9800
C121—H12C	0.9800	C221—H22C	0.9800
C122—H12D	0.9800	C222—H22D	0.9800
C122—H12E	0.9800	C222—H22E	0.9800
C122—H12F	0.9800	C222—H22F	0.9800
O13—C14	1.366 (3)	O23—C24	1.359 (3)
C14—O14	1.210 (3)	C24—O24	1.210 (2)
C14—C15	1.469 (3)	C24—C25	1.469 (3)
C15—C17	1.358 (3)	C25—C27	1.367 (3)
C15—C16	1.471 (3)	C25—C26	1.471 (3)
C16—O16	1.213 (2)	C26—O26	1.200 (2)
C17—C18	1.424 (3)	C27—C28	1.418 (3)
C17—H17	0.9500	C27—H27	0.9500
C18—C19	1.352 (3)	C28—C29	1.359 (3)
C18—H18	0.9500	C28—H28	0.9500
C19—C191	1.447 (3)	C29—C291	1.447 (3)
C19—H19	0.9500	C29—H29	0.9500
C191—C192	1.401 (3)	C291—C292	1.398 (3)
C191—C196	1.404 (3)	C291—C296	1.408 (3)
C192—C193	1.382 (3)	C292—C293	1.379 (3)
C192—H192	0.9500	C292—H292	0.9500
C193—C194	1.398 (3)	C293—C294	1.397 (3)
C193—H193	0.9500	C293—H293	0.9500
C194—C195	1.383 (3)	C294—C295	1.384 (3)
C194—C91	1.502 (3)	C294—C92	1.503 (3)
C91—H91A	0.9800	C92—H92D	0.9800
C91—H91B	0.9800	C92—H92E	0.9800
C91—H91C	0.9800	C92—H92F	0.9800
C195—C196	1.386 (3)	C295—C296	1.387 (3)
C195—H195	0.9500	C295—H295	0.9500
C196—H196	0.9500	C296—H296	0.9500
C16—O11—C12	119.10 (17)	C26—O21—C22	117.62 (17)
O11—C12—O13	110.18 (17)	O21—C22—O23	109.68 (16)
O11—C12—C121	105.73 (18)	O21—C22—C221	106.72 (19)
O13—C12—C121	106.45 (17)	O23—C22—C221	105.83 (18)
O11—C12—C122	110.58 (18)	O21—C22—C222	109.83 (18)
O13—C12—C122	109.84 (18)	O23—C22—C222	110.53 (18)
C121—C12—C122	113.9 (2)	C221—C22—C222	114.1 (2)
C12—C121—H12A	109.5	C22—C221—H22A	109.5
C12—C121—H12B	109.5	C22—C221—H22B	109.5
H12A—C121—H12B	109.5	H22A—C221—H22B	109.5
C12—C121—H12C	109.5	C22—C221—H22C	109.5
H12A—C121—H12C	109.5	H22A—C221—H22C	109.5
H12B—C121—H12C	109.5	H22B—C221—H22C	109.5
C12—C122—H12D	109.5	C22—C222—H22D	109.5
C12—C122—H12E	109.5	C22—C222—H22E	109.5
H12D—C122—H12E	109.5	H22D—C222—H22E	109.5
C12—C122—H12F	109.5	C22—C222—H22F	109.5
H12D—C122—H12F	109.5	H22D—C222—H22F	109.5
H12E—C122—H12F	109.5	H22E—C222—H22F	109.5
C14—O13—C12	117.70 (16)	C24—O23—C22	118.58 (16)
O14—C14—O13	118.02 (19)	O24—C24—O23	117.51 (19)
O14—C14—C15	125.5 (2)	O24—C24—C25	125.3 (2)
O13—C14—C15	116.41 (19)	O23—C24—C25	117.10 (19)
C17—C15—C14	117.7 (2)	C27—C25—C24	117.0 (2)
C17—C15—C16	123.0 (2)	C27—C25—C26	123.64 (19)
C14—C15—C16	119.17 (19)	C24—C25—C26	119.31 (19)
O16—C16—O11	117.7 (2)	O26—C26—O21	118.2 (2)
O16—C16—C15	126.4 (2)	O26—C26—C25	126.8 (2)
O11—C16—C15	115.87 (19)	O21—C26—C25	114.88 (18)
C15—C17—C18	128.5 (2)	C25—C27—C28	129.9 (2)
C15—C17—H17	115.7	C25—C27—H27	115.0
C18—C17—H17	115.7	C28—C27—H27	115.0
C19—C18—C17	120.7 (2)	C29—C28—C27	119.3 (2)
C19—C18—H18	119.6	C29—C28—H28	120.3
C17—C18—H18	119.6	C27—C28—H28	120.3
C18—C19—C191	126.1 (2)	C28—C29—C291	127.6 (2)
C18—C19—H19	116.9	C28—C29—H29	116.2
C191—C19—H19	116.9	C291—C29—H29	116.2
C192—C191—C196	117.28 (19)	C292—C291—C296	117.4 (2)
C192—C191—C19	123.6 (2)	C292—C291—C29	123.7 (2)
C196—C191—C19	119.1 (2)	C296—C291—C29	118.90 (19)
C193—C192—C191	121.3 (2)	C293—C292—C291	121.1 (2)
C193—C192—H192	119.4	C293—C292—H292	119.5
C191—C192—H192	119.4	C291—C292—H292	119.5
C192—C193—C194	121.2 (2)	C292—C293—C294	121.5 (2)
C192—C193—H193	119.4	C292—C293—H293	119.2
C194—C193—H193	119.4	C294—C293—H293	119.2
C195—C194—C193	117.8 (2)	C295—C294—C293	117.7 (2)
C195—C194—C91	121.0 (2)	C295—C294—C92	121.0 (2)
C193—C194—C91	121.3 (2)	C293—C294—C92	121.3 (2)
C194—C91—H91A	109.5	C294—C92—H92D	109.5
C194—C91—H91B	109.5	C294—C92—H92E	109.5
H91A—C91—H91B	109.5	H92D—C92—H92E	109.5
C194—C91—H91C	109.5	C294—C92—H92F	109.5
H91A—C91—H91C	109.5	H92D—C92—H92F	109.5
H91B—C91—H91C	109.5	H92E—C92—H92F	109.5
C194—C195—C196	121.7 (2)	C294—C295—C296	121.5 (2)
C194—C195—H195	119.2	C294—C295—H295	119.3
C196—C195—H195	119.2	C296—C295—H295	119.3
C195—C196—C191	120.8 (2)	C295—C296—C291	120.8 (2)
C195—C196—H196	119.6	C295—C296—H296	119.6
C191—C196—H196	119.6	C291—C296—H296	119.6
C16—O11—C12—O13	49.5 (2)	C26—O21—C22—O23	55.0 (2)
C16—O11—C12—C121	164.12 (18)	C26—O21—C22—C221	169.22 (18)
C16—O11—C12—C122	−72.1 (2)	C26—O21—C22—C222	−66.6 (2)
O11—C12—O13—C14	−50.6 (2)	O21—C22—O23—C24	−46.0 (2)
C121—C12—O13—C14	−164.80 (17)	C221—C22—O23—C24	−160.77 (19)
C122—C12—O13—C14	71.4 (2)	C222—C22—O23—C24	75.2 (2)
C12—O13—C14—O14	−160.17 (19)	C22—O23—C24—O24	−169.70 (18)
C12—O13—C14—C15	22.2 (3)	C22—O23—C24—C25	13.2 (3)
O14—C14—C15—C17	8.7 (3)	O24—C24—C25—C27	14.0 (3)
O13—C14—C15—C17	−173.80 (18)	O23—C24—C25—C27	−169.16 (18)
O14—C14—C15—C16	−167.8 (2)	O24—C24—C25—C26	−162.6 (2)
O13—C14—C15—C16	9.6 (3)	O23—C24—C25—C26	14.2 (3)
C12—O11—C16—O16	162.67 (19)	C22—O21—C26—O26	154.03 (19)
C12—O11—C16—C15	−19.5 (3)	C22—O21—C26—C25	−29.3 (2)
C17—C15—C16—O16	−9.9 (3)	C27—C25—C26—O26	−6.2 (3)
C14—C15—C16—O16	166.5 (2)	C24—C25—C26—O26	170.2 (2)
C17—C15—C16—O11	172.47 (19)	C27—C25—C26—O21	177.45 (18)
C14—C15—C16—O11	−11.2 (3)	C24—C25—C26—O21	−6.2 (3)
C14—C15—C17—C18	−178.75 (19)	C24—C25—C27—C28	−178.17 (19)
C16—C15—C17—C18	−2.3 (4)	C26—C25—C27—C28	−1.7 (3)
C15—C17—C18—C19	−179.8 (2)	C25—C27—C28—C29	−179.7 (2)
C17—C18—C19—C191	−179.61 (19)	C27—C28—C29—C291	178.55 (19)
C18—C19—C191—C192	5.4 (3)	C28—C29—C291—C292	−8.7 (3)
C18—C19—C191—C196	−174.6 (2)	C28—C29—C291—C296	171.8 (2)
C196—C191—C192—C193	1.2 (3)	C296—C291—C292—C293	−0.7 (3)
C19—C191—C192—C193	−178.8 (2)	C29—C291—C292—C293	179.75 (19)
C191—C192—C193—C194	0.0 (3)	C291—C292—C293—C294	0.0 (3)
C192—C193—C194—C195	−0.5 (3)	C292—C293—C294—C295	0.4 (3)
C192—C193—C194—C91	−179.19 (19)	C292—C293—C294—C92	−179.9 (2)
C193—C194—C195—C196	−0.2 (3)	C293—C294—C295—C296	−0.1 (3)
C91—C194—C195—C196	178.43 (19)	C92—C294—C295—C296	−179.8 (2)
C194—C195—C196—C191	1.5 (3)	C294—C295—C296—C291	−0.6 (3)
C192—C191—C196—C195	−2.0 (3)	C292—C291—C296—C295	1.0 (3)
C19—C191—C196—C195	178.00 (19)	C29—C291—C296—C295	−179.46 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C29—H29···O24^i	0.95	2.52	3.412 (3)	156
C193—H193···O21	0.95	2.60	3.531 (3)	166
C296—H296···O24^i	0.95	2.56	3.425 (3)	152
C293—H293···O11	0.95	2.54	3.422 (3)	154

Symmetry code: (i) −x, −y+1, −z+2.

(3b) 5-(3-(4-chlorophenyl)-2-propenylidene]-2,2-dimethyl-[1,3] dioxane-4,6-dione

Crystal data

C15H13ClO4	Z = 2
Mr = 292.70	F(000) = 304
Triclinic, P1	Dx = 1.423 Mg m^−3
Hall symbol: -P 1	Melting point: 455K K
a = 7.2648 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.4705 (3) Å	Cell parameters from 3057 reflections
c = 13.5855 (6) Å	θ = 3.0–27.5°
α = 90.1799 (13)°	µ = 0.29 mm^−1
β = 99.8452 (14)°	T = 120 K
γ = 109.576 (3)°	Block, yellow
V = 683.01 (4) Å^3	0.15 × 0.10 × 0.10 mm

Data collection

Kappa-CCD diffractometer	3057 independent reflections
Radiation source: fine-focus sealed X-ray tube	2350 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.077
ϕ scans and ω scans with κ offsets	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = −9→8
Tmin = 0.958, Tmax = 0.972	k = −9→9
9407 measured reflections	l = −17→17

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.153	H-atom parameters constrained
S = 0.98	w = 1/[σ^2(Fo^2) + (0.0932P)^2 + 0.2802P] where P = (Fo^2 + 2Fc^2)/3
3057 reflections	(Δ/σ)max = 0.001
183 parameters	Δρmax = 0.62 e Å^−3
0 restraints	Δρmin = −0.66 e Å^−3

Special details

Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm (Fox & Holmes, 1966) which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL97 input file.

Geometry. Mean-plane data from the final SHELXL97 refinement run:-

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	1.2361 (2)	0.8733 (2)	0.73887 (10)	0.0205 (3)
C2	1.1593 (3)	0.8931 (3)	0.63540 (15)	0.0193 (5)
C21	1.3360 (3)	0.9621 (3)	0.58476 (17)	0.0241 (5)
C22	1.0071 (3)	0.7068 (3)	0.58938 (17)	0.0250 (5)
O3	1.0719 (2)	1.0403 (2)	0.63026 (11)	0.0203 (4)
C4	0.9434 (3)	1.0391 (3)	0.69179 (15)	0.0195 (5)
O4	0.8406 (2)	1.1372 (2)	0.67387 (11)	0.0259 (4)
C5	0.9478 (3)	0.9239 (3)	0.78005 (15)	0.0184 (4)
C6	1.1172 (3)	0.8565 (3)	0.80810 (15)	0.0192 (4)
O6	1.1626 (2)	0.7951 (2)	0.88697 (11)	0.0270 (4)
C7	0.8004 (3)	0.8958 (3)	0.83404 (16)	0.0195 (4)
C8	0.7819 (3)	0.8043 (3)	0.92632 (16)	0.0205 (5)
C9	0.6261 (3)	0.7897 (3)	0.97112 (16)	0.0194 (4)
C91	0.5980 (3)	0.7101 (3)	1.06755 (15)	0.0184 (4)
C92	0.7295 (3)	0.6295 (3)	1.12205 (16)	0.0218 (5)
C93	0.7025 (3)	0.5620 (3)	1.21510 (17)	0.0227 (5)
C94	0.5441 (3)	0.5750 (3)	1.25471 (16)	0.0207 (5)
Cl97	0.51673 (8)	0.49493 (8)	1.37336 (4)	0.0283 (2)
C95	0.4077 (3)	0.6503 (3)	1.20245 (16)	0.0220 (5)
C96	0.4360 (3)	0.7163 (3)	1.10875 (16)	0.0201 (5)
H21A	1.4067	0.8705	0.5914	0.036*	0.50
H21B	1.4252	1.0861	0.6162	0.036*	0.50
H21C	1.2916	0.9749	0.5137	0.036*	0.50
H21D	1.3423	1.0838	0.5561	0.036*	0.50
H21E	1.3238	0.8682	0.5313	0.036*	0.50
H21F	1.4574	0.9795	0.6338	0.036*	0.50
H22A	1.0659	0.6061	0.5973	0.038*	0.50
H22B	0.9644	0.7188	0.5180	0.038*	0.50
H22C	0.8921	0.6746	0.6230	0.038*	0.50
H22D	0.8824	0.7269	0.5616	0.038*	0.50
H22E	0.9839	0.6143	0.6408	0.038*	0.50
H22F	1.0562	0.6584	0.5359	0.038*	0.50
H7	0.6968	0.9424	0.8074	0.023*
H8	0.8803	0.7535	0.9561	0.025*
H9	0.5265	0.8350	0.9371	0.023*
H92	0.8385	0.6211	1.0947	0.026*
H93	0.7920	0.5073	1.2514	0.027*
H95	0.2982	0.6563	1.2301	0.026*
H96	0.3434	0.7668	1.0718	0.024*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0196 (8)	0.0316 (8)	0.0127 (7)	0.0118 (6)	0.0035 (6)	0.0026 (6)
C2	0.0223 (11)	0.0269 (11)	0.0115 (10)	0.0123 (9)	0.0024 (8)	0.0035 (8)
C21	0.0241 (12)	0.0324 (13)	0.0192 (11)	0.0120 (9)	0.0084 (9)	0.0053 (9)
C22	0.0265 (12)	0.0284 (12)	0.0191 (11)	0.0089 (9)	0.0022 (9)	−0.0003 (9)
O3	0.0223 (8)	0.0278 (8)	0.0143 (7)	0.0115 (6)	0.0065 (6)	0.0047 (6)
C4	0.0182 (11)	0.0247 (11)	0.0149 (10)	0.0071 (8)	0.0016 (8)	0.0003 (8)
O4	0.0275 (9)	0.0386 (10)	0.0188 (8)	0.0197 (7)	0.0058 (6)	0.0071 (7)
C5	0.0190 (11)	0.0220 (11)	0.0139 (10)	0.0073 (8)	0.0016 (8)	0.0001 (8)
C6	0.0194 (11)	0.0254 (11)	0.0128 (10)	0.0080 (8)	0.0024 (8)	0.0010 (8)
O6	0.0284 (9)	0.0424 (10)	0.0159 (8)	0.0192 (7)	0.0043 (6)	0.0088 (7)
C7	0.0197 (11)	0.0221 (11)	0.0158 (10)	0.0065 (8)	0.0021 (8)	−0.0003 (8)
C8	0.0208 (11)	0.0236 (11)	0.0174 (11)	0.0081 (8)	0.0031 (8)	0.0018 (9)
C9	0.0209 (11)	0.0216 (11)	0.0149 (10)	0.0066 (8)	0.0023 (8)	0.0003 (8)
C91	0.0195 (11)	0.0178 (10)	0.0154 (10)	0.0036 (8)	0.0024 (8)	−0.0006 (8)
C92	0.0191 (11)	0.0280 (12)	0.0186 (11)	0.0080 (9)	0.0045 (8)	0.0013 (9)
C93	0.0235 (11)	0.0239 (11)	0.0206 (11)	0.0086 (9)	0.0026 (9)	0.0038 (9)
C94	0.0248 (11)	0.0210 (11)	0.0134 (10)	0.0042 (8)	0.0029 (8)	0.0009 (8)
Cl97	0.0326 (4)	0.0357 (4)	0.0169 (3)	0.0104 (2)	0.0074 (2)	0.0084 (2)
C95	0.0222 (11)	0.0267 (11)	0.0175 (11)	0.0073 (9)	0.0067 (8)	0.0003 (9)
C96	0.0203 (11)	0.0223 (11)	0.0187 (11)	0.0084 (8)	0.0038 (8)	0.0014 (8)

Geometric parameters (Å, º)

O1—C6	1.361 (2)	C5—C7	1.359 (3)
O1—C2	1.448 (2)	C5—C6	1.473 (3)
C2—O3	1.439 (2)	C6—O6	1.205 (2)
C2—C21	1.500 (3)	C7—C8	1.435 (3)
C2—C22	1.509 (3)	C7—H7	0.9500
C21—H21A	0.9800	C8—C9	1.348 (3)
C21—H21B	0.9800	C8—H8	0.9500
C21—H21C	0.9800	C9—C91	1.458 (3)
C21—H21D	0.9800	C9—H9	0.9500
C21—H21E	0.9800	C91—C96	1.401 (3)
C21—H21F	0.9800	C91—C92	1.404 (3)
C22—H22A	0.9800	C92—C93	1.383 (3)
C22—H22B	0.9800	C92—H92	0.9500
C22—H22C	0.9800	C93—C94	1.382 (3)
C22—H22D	0.9800	C93—H93	0.9500
C22—H22E	0.9800	C94—C95	1.392 (3)
C22—H22F	0.9800	C94—Cl97	1.741 (2)
O3—C4	1.353 (2)	C95—C96	1.390 (3)
C4—O4	1.208 (3)	C95—H95	0.9500
C4—C5	1.480 (3)	C96—H96	0.9500
C6—O1—C2	119.05 (16)	C2—C22—H22F	109.5
O3—C2—O1	109.57 (16)	H22A—C22—H22F	56.3
O3—C2—C21	106.71 (17)	H22B—C22—H22F	56.3
O1—C2—C21	106.16 (17)	H22C—C22—H22F	141.1
O3—C2—C22	110.29 (17)	H22D—C22—H22F	109.5
O1—C2—C22	110.17 (17)	H22E—C22—H22F	109.5
C21—C2—C22	113.78 (18)	C4—O3—C2	118.97 (16)
C2—C21—H21A	109.5	O4—C4—O3	118.49 (19)
C2—C21—H21B	109.5	O4—C4—C5	124.7 (2)
H21A—C21—H21B	109.5	O3—C4—C5	116.73 (17)
C2—C21—H21C	109.5	C7—C5—C6	123.64 (19)
H21A—C21—H21C	109.5	C7—C5—C4	117.82 (18)
H21B—C21—H21C	109.5	C6—C5—C4	118.42 (18)
C2—C21—H21D	109.5	O6—C6—O1	117.95 (19)
H21A—C21—H21D	141.1	O6—C6—C5	126.09 (19)
H21B—C21—H21D	56.3	O1—C6—C5	115.91 (17)
H21C—C21—H21D	56.3	C5—C7—C8	128.0 (2)
C2—C21—H21E	109.5	C5—C7—H7	116.0
H21A—C21—H21E	56.3	C8—C7—H7	116.0
H21B—C21—H21E	141.1	C9—C8—C7	120.59 (19)
H21C—C21—H21E	56.3	C9—C8—H8	119.7
H21D—C21—H21E	109.5	C7—C8—H8	119.7
C2—C21—H21F	109.5	C8—C9—C91	125.4 (2)
H21A—C21—H21F	56.3	C8—C9—H9	117.3
H21B—C21—H21F	56.3	C91—C9—H9	117.3
H21C—C21—H21F	141.1	C96—C91—C92	118.28 (19)
H21D—C21—H21F	109.5	C96—C91—C9	119.28 (19)
H21E—C21—H21F	109.5	C92—C91—C9	122.4 (2)
C2—C22—H22A	109.5	C93—C92—C91	120.9 (2)
C2—C22—H22B	109.5	C93—C92—H92	119.6
H22A—C22—H22B	109.5	C91—C92—H92	119.6
C2—C22—H22C	109.5	C94—C93—C92	119.3 (2)
H22A—C22—H22C	109.5	C94—C93—H93	120.3
H22B—C22—H22C	109.5	C92—C93—H93	120.3
C2—C22—H22D	109.5	C93—C94—C95	121.8 (2)
H22A—C22—H22D	141.1	C93—C94—Cl97	118.56 (17)
H22B—C22—H22D	56.3	C95—C94—Cl97	119.68 (17)
H22C—C22—H22D	56.3	C96—C95—C94	118.2 (2)
C2—C22—H22E	109.5	C96—C95—H95	120.9
H22A—C22—H22E	56.3	C94—C95—H95	120.9
H22B—C22—H22E	141.1	C95—C96—C91	121.5 (2)
H22C—C22—H22E	56.3	C95—C96—H96	119.3
H22D—C22—H22E	109.5	C91—C96—H96	119.3
C6—O1—C2—O3	49.7 (2)	C4—C5—C6—O1	−12.8 (3)
C6—O1—C2—C21	164.55 (17)	C4—C5—C7—C8	−174.20 (19)
C6—O1—C2—C22	−71.8 (2)	C6—C5—C7—C8	1.9 (4)
O1—C2—O3—C4	−48.4 (2)	C5—C7—C8—C9	179.3 (2)
C21—C2—O3—C4	−162.88 (17)	C7—C8—C9—C91	−176.20 (19)
C22—C2—O3—C4	73.1 (2)	C8—C9—C91—C92	−3.5 (3)
C2—O3—C4—O4	−165.13 (19)	C8—C9—C91—C96	175.4 (2)
C2—O3—C4—C5	18.1 (3)	C96—C91—C92—C93	−1.5 (3)
O4—C4—C5—C7	13.6 (3)	C9—C91—C92—C93	177.4 (2)
O3—C4—C5—C7	−169.81 (18)	C91—C92—C93—C94	−0.2 (3)
O4—C4—C5—C6	−162.7 (2)	C92—C93—C94—C95	1.5 (3)
O3—C4—C5—C6	13.9 (3)	C92—C93—C94—Cl97	−178.33 (17)
C2—O1—C6—O6	162.40 (19)	C93—C94—C95—C96	−1.1 (3)
C2—O1—C6—C5	−20.1 (3)	Cl97—C94—C95—C96	178.77 (16)
C7—C5—C6—O6	−11.5 (4)	C94—C95—C96—C91	−0.7 (3)
C4—C5—C6—O6	164.5 (2)	C92—C91—C96—C95	2.0 (3)
C7—C5—C6—O1	171.21 (19)	C9—C91—C96—C95	−177.03 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O6^i	0.95	2.53	3.380 (3)	149
C95—H95···O4^ii	0.95	2.56	3.396 (3)	146

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