5,17-Dibromo-26,28-bis­[(meth­oxy­carbon­yl)meth­oxy]-25,27-diprop­oxy-2,8,14,20-tetra­thia­calix[4]arene

Zhang, L.-J.; Liu, L.-L.; Liu, Q.-K.; Guo, D.-S.

doi:10.1107/S1600536812014559

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Pages o1353-o1354

doi:10.1107/S1600536812014559

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5,17-Dibromo-26,28-bis[(methoxycarbonyl)methoxy]-25,27-dipropoxy-2,8,14,20-tetrathiacalix[4]arene

Li-Jing Zhang,^a Ling-Ling Liu,^a Qi-Kui Liu ^a and Dian-Shun Guo ^a ^*

^aDepartment of Chemistry, Shandong Normal University, Jinan 250014, People's Republic of China
^*Correspondence e-mail: chdsguo@sdnu.edu.cn

(Received 14 March 2012; accepted 3 April 2012; online 13 April 2012)

The title thiacalix[4]arene derivative, C₃₆H₃₄Br₂O₈S₄, adopts an unusual pinched cone conformation with the propoxy-substituted benzene rings inclined inward [forming a dihedral angle of 33.4 (1)°] and with the brominated benzene rings bent outward, making a dihedral angle of 66.1 (1)°. In the crystal, the molecules form chains along [001] via C—H⋯S hydrogen bonds and S⋯S contacts [S⋯S = 3.492 (3) Å]. The chains are associated into bilayers through C—H⋯O hydrogen bonds, generating an R₂²(10) motif.

Related literature

For general background to the chemistry of thiacalix[4]arenes, see: Shokova & Kovalev (2003 ); Lhoták (2004 ); Morohashi et al. (2006 ); Kajiwara et al. (2007 ); Guo et al. (2007 ). For related structures, see: Lhoták et al. (2000 , 2003 ); Himl et al. (2005 ); Xu et al. (2008 ); Chen et al. (2010 ); Liu et al. (2011 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ); Hu et al. (2009 ). For atomic van der Waals radii, see: Bondi (1964 ).

Experimental

Crystal data

C₃₆H₃₄Br₂O₈S₄
M_r = 882.69
Monoclinic, P 2₁ /c
a = 16.024 (3) Å
b = 14.808 (3) Å
c = 15.872 (3) Å
β = 100.065 (3)°
V = 3708.3 (12) Å³
Z = 4
Mo Kα radiation
μ = 2.46 mm⁻¹
T = 173 K
0.38 × 0.18 × 0.13 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1999 ) T_min = 0.455, T_max = 0.740
19322 measured reflections
6989 independent reflections
4908 reflections with I > 2σ(I)
R_int = 0.060

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.091
S = 0.93
6989 reflections
455 parameters
H-atom parameters constrained
Δρ_max = 0.62 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯S3ⁱ	0.95	2.91	3.755 (3)	149
C33—H33A⋯O7ⁱⁱ	0.98	2.58	3.551 (5)	169
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+2.

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812014559/ld2052sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812014559/ld2052Isup2.hkl

checkCIF report

Comment top

Thiacalix[4]arenes have attracted much interest because of their specific affinity, selectivity in molecular recognition, and supramolecular assembly (Shokova & Kovalev, 2003; Lhoták, 2004; Morohashi et al., 2006; Kajiwara et al., 2007; Guo et al., 2007). Numerous crystal structures of thiacalix[4]arenes uniformly substituted at the lower rim or at the upper rim are known (Lhoták et al., 2000, 2003; Himl et al., 2005). Recently, we have presented structures of several dibromo and tetrabromothiacalix[4]arene derivatives that possess four identical or four different substituents at the lower rim (Xu et al., 2008; Chen et al., 2010; Liu et al., 2011). Here we report the crystal structure of another dibromothiacalix[4]arene compound with different substituents at the lower rim – 5,17-dibromo-26,28-bis[(methoxycarbonyl)methoxy]-25,27-dipropoxy-2,8,14,20-tetrathiacalix[4]arene.

In the crystal structure of the title compound, C₃₆H₃₄Br₂O₈S₄, (Fig. 1), the thiacalix[4]arene unit adopts an unusual pinched cone conformation. Two opposite bromosubstituted phenolic rings are strongly bent outwards the thiacalix cavity with a Br···Br distance of 13.819 (3) Å [larger than that reported previously - 13.165 (2) Å (Liu et al., 2011)]. The other two opposing phenolic rings are bent inwards. The phenolic rings form dihedral angles of 26.09 (7), 65.57 (7), 40.29 (6) and 81.18 (7)° with the virtual plane defined by the four bridging S atoms.

In the packing, there are several intermolecular short contacts (Table 1). The molecules are linked into an infinite zigzag one-dimensional chain along [001] (Hu et al., 2009) by intermolecular C4—H4···S3(x, -y + 1/2, z - 1/2) hydrogen bonds, locally forming a C(8) motif (Bernstein et al., 1995) (Fig. 2). Interestingly, in such a chain all 'tails' of the molecules extend to the same orientation and a significant S···S interaction between the adjacent thiacalix[4]arenes stabilizes the motif, with a S1···S3 distance of 3.492 (3) Å (S = 1.80 Å; Bondi, 1964). Finally, these chains are packed into a complex tail-to-tail-oriented bilayer system by a combination of interchain C—H···O hydrogen bonds, giving an R₂²(10) motif.

Related literature top

For general background to the chemistry of thiacalix[4]arenes, see: Shokova & Kovalev (2003); Lhoták (2004); Morohashi et al. (2006); Kajiwara et al. (2007); Guo et al. (2007). For related structures, see: Lhoták et al. (2000, 2003); Himl et al. (2005); Xu et al. (2008); Chen et al. (2010); Liu et al. (2011). For hydrogen-bond motifs, see: Bernstein et al. (1995); Hu et al. (2009). For atomic van der Waals radii, see: Bondi (1964).

Experimental top

BrCH₂CO₂Me (0.08 ml, 0.84 mmol) was added to a suspension of 5,17-dibromo-26,28-dihydroxy-25,27-dipropoxy-2,8,14,20-tetrathiacalix[4]arene (0.080 g, 0.14 mmol) and anhydrous K₂CO₃ (0.022 g, 0.17 mmol) in dry acetone (15 ml). The resulting mixture was stirred for 3 h at 343 K and cooled to room temperature. The solvent was removed under reduced pressure. The residue was neutralized with 5% aqueous HCl and extracted with CH₂Cl₂. The organic layer was separated and washed with saturated sodium hydrogen carbonate and brine, and dried over anhydrous MgSO₄. The solvent was evaporated in vacuo and the residue was chromatographed on a silica gel column (CH₂Cl₂/petroleum ether = 1:1) to give the title compound as a white solid (yield 63%, R_f = 0.3) and another product (yield 28%, R_f = 0.45). ¹H NMR (300 MHz, CDCl₃) for the title product: δ 7.67 (s, 4H), 6.55 (d, 4H, J = 7.26 Hz), 6.46 (t, 2H, J = 7.57 Hz), 5.10 (s, 4H), 3.88 (t, 4H, J = 7.47 Hz), 3.74 (s, 6H), 1.89~1.77 (m, 4H), 1.05 (t, 6H, J = 7.39 Hz). IR (KBr pellets, cm^-1): 1763 (C=O). Single crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of a solution in CH₃OH and CHCl₃ at 298 K.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level for non-H atoms. The hydrogen atoms have been omitted for clarity.
	Fig. 2. The hydrogen-bonded one-dimensional chain of the title compound, viewed along the crystallographic a axis, showing the C(8) motif. For the sake of clarity, H atoms not involved in the motifs have been omitted. [Symmetry codes: (i) x, -y + 1/2, z - 1/2; (iii) x, -y + 1/2, z + 1/2.]

5,17-Dibromo-26,28-bis[(methoxycarbonyl)methoxy]-25,27-dipropoxy-2,8,14,20- tetrathiacalix[4]arene top

Crystal data top

C₃₆H₃₄Br₂O₈S₄	F(000) = 1792
M_r = 882.69	D_x = 1.581 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.024 (3) Å	Cell parameters from 4762 reflections
b = 14.808 (3) Å	θ = 2.4–24.5°
c = 15.872 (3) Å	µ = 2.46 mm⁻¹
β = 100.065 (3)°	T = 173 K
V = 3708.3 (12) Å³	Block, colourless
Z = 4	0.38 × 0.18 × 0.13 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	6989 independent reflections
Radiation source: fine-focus sealed tube	4908 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.060
phi and ω scans	θ_max = 25.6°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −19→10
T_min = 0.455, T_max = 0.740	k = −18→17
19322 measured reflections	l = −17→19

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.091	H-atom parameters constrained
S = 0.93	w = 1/[σ²(F_o²) + (0.0393P)²] where P = (F_o² + 2F_c²)/3
6989 reflections	(Δ/σ)_max = 0.001
455 parameters	Δρ_max = 0.62 e Å⁻³
0 restraints	Δρ_min = −0.55 e Å⁻³

Crystal data top

C₃₆H₃₄Br₂O₈S₄	V = 3708.3 (12) Å³
M_r = 882.69	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 16.024 (3) Å	µ = 2.46 mm⁻¹
b = 14.808 (3) Å	T = 173 K
c = 15.872 (3) Å	0.38 × 0.18 × 0.13 mm
β = 100.065 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	6989 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1999)	4908 reflections with I > 2σ(I)
T_min = 0.455, T_max = 0.740	R_int = 0.060
19322 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.091	H-atom parameters constrained
S = 0.93	Δρ_max = 0.62 e Å⁻³
6989 reflections	Δρ_min = −0.55 e Å⁻³
455 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.11682 (2)	0.60398 (2)	0.21293 (2)	0.04232 (12)
Br2	0.03760 (2)	0.38070 (3)	1.04064 (3)	0.04869 (13)
C1	0.20213 (19)	0.6405 (2)	0.4739 (2)	0.0258 (7)
C2	0.16788 (18)	0.6550 (2)	0.38842 (19)	0.0271 (7)
H2	0.1460	0.7128	0.3702	0.033*
C3	0.16546 (19)	0.5857 (2)	0.32980 (19)	0.0274 (7)
C4	0.19244 (19)	0.5003 (2)	0.35546 (19)	0.0285 (7)
H4	0.1884	0.4527	0.3148	0.034*
C5	0.22583 (19)	0.48368 (19)	0.44142 (19)	0.0255 (7)
C6	0.23380 (18)	0.5547 (2)	0.49994 (19)	0.0256 (7)
C7	0.17985 (19)	0.3580 (2)	0.54785 (18)	0.0235 (7)
C8	0.1014 (2)	0.4000 (2)	0.5355 (2)	0.0301 (8)
H8	0.0837	0.4348	0.4852	0.036*
C9	0.0489 (2)	0.3920 (2)	0.5948 (2)	0.0324 (8)
H9	−0.0048	0.4209	0.5852	0.039*
C10	0.0742 (2)	0.3419 (2)	0.6690 (2)	0.0310 (8)
H10	0.0381	0.3367	0.7104	0.037*
C11	0.1524 (2)	0.2996 (2)	0.68202 (19)	0.0271 (7)
C12	0.20550 (19)	0.30606 (19)	0.62144 (19)	0.0242 (7)
C13	0.1789 (2)	0.3319 (2)	0.85101 (19)	0.0272 (7)
C14	0.12273 (19)	0.3240 (2)	0.90827 (19)	0.0298 (8)
H14	0.0927	0.2692	0.9118	0.036*
C15	0.1109 (2)	0.3961 (2)	0.9597 (2)	0.0295 (8)
C16	0.1492 (2)	0.4789 (2)	0.95107 (19)	0.0306 (8)
H16	0.1377	0.5292	0.9844	0.037*
C17	0.20401 (19)	0.4872 (2)	0.89340 (19)	0.0267 (7)
C18	0.22386 (19)	0.4120 (2)	0.84720 (19)	0.0246 (7)
C19	0.1805 (2)	0.62323 (19)	0.77646 (19)	0.0270 (7)
C20	0.0935 (2)	0.6079 (2)	0.7646 (2)	0.0320 (8)
H20	0.0688	0.5829	0.8096	0.038*
C21	0.0431 (2)	0.6290 (2)	0.6875 (2)	0.0347 (8)
H21	−0.0162	0.6181	0.6795	0.042*
C22	0.0782 (2)	0.6657 (2)	0.6223 (2)	0.0315 (8)
H22	0.0430	0.6797	0.5693	0.038*
C23	0.1646 (2)	0.68234 (19)	0.63296 (19)	0.0264 (7)
C24	0.21621 (19)	0.6616 (2)	0.7109 (2)	0.0249 (7)
C25	0.3470 (2)	0.5133 (2)	0.6152 (2)	0.0320 (8)
H25A	0.3524	0.4502	0.5965	0.038*
H25B	0.3578	0.5140	0.6786	0.038*
C26	0.4131 (2)	0.5699 (2)	0.5838 (2)	0.0358 (8)
C27	0.5595 (2)	0.5920 (3)	0.5987 (3)	0.0608 (12)
H27A	0.5548	0.5831	0.5369	0.091*
H27B	0.6126	0.5655	0.6283	0.091*
H27C	0.5588	0.6568	0.6113	0.091*
C28	0.2829 (2)	0.1705 (2)	0.6167 (2)	0.0519 (11)
H28A	0.2342	0.1425	0.6375	0.062*
H28B	0.2753	0.1611	0.5541	0.062*
C29	0.3602 (3)	0.1274 (3)	0.6572 (3)	0.0784 (16)
H29A	0.3724	0.1453	0.7182	0.094*
H29B	0.4075	0.1491	0.6300	0.094*
C30	0.3564 (3)	0.0260 (3)	0.6516 (3)	0.0887 (17)
H30A	0.3166	0.0032	0.6869	0.133*
H30B	0.4129	0.0009	0.6722	0.133*
H30C	0.3373	0.0079	0.5919	0.133*
C31	0.3558 (2)	0.3663 (2)	0.8103 (2)	0.0387 (9)
H31A	0.3885	0.3744	0.7634	0.046*
H31B	0.3375	0.3024	0.8097	0.046*
C32	0.4124 (2)	0.3854 (2)	0.8935 (2)	0.0351 (8)
C33	0.5475 (2)	0.3478 (3)	0.9742 (2)	0.0577 (11)
H33A	0.5603	0.4115	0.9871	0.087*
H33B	0.5993	0.3163	0.9663	0.087*
H33C	0.5250	0.3202	1.0217	0.087*
C34	0.3351 (2)	0.7543 (2)	0.7622 (2)	0.0371 (9)
H34A	0.3119	0.7636	0.8155	0.045*
H34B	0.3190	0.8067	0.7241	0.045*
C35	0.4294 (2)	0.7450 (2)	0.7823 (2)	0.0397 (9)
H35A	0.4516	0.7370	0.7284	0.048*
H35B	0.4443	0.6906	0.8179	0.048*
C36	0.4710 (2)	0.8276 (3)	0.8296 (2)	0.0508 (10)
H36A	0.4612	0.8806	0.7922	0.076*
H36B	0.5321	0.8171	0.8459	0.076*
H36C	0.4465	0.8381	0.8812	0.076*
O1	0.26345 (13)	0.54324 (13)	0.58541 (13)	0.0284 (5)
O2	0.28416 (13)	0.26639 (13)	0.63464 (13)	0.0300 (5)
O3	0.28207 (13)	0.42264 (14)	0.79386 (13)	0.0307 (5)
O4	0.30214 (13)	0.67228 (13)	0.72072 (13)	0.0302 (5)
O5	0.40072 (16)	0.62414 (17)	0.52780 (17)	0.0546 (7)
O6	0.48904 (15)	0.54881 (17)	0.62764 (17)	0.0510 (7)
O7	0.39604 (17)	0.4311 (2)	0.94997 (18)	0.0649 (8)
O8	0.48456 (15)	0.34097 (18)	0.89600 (15)	0.0484 (7)
S1	0.25109 (5)	0.37085 (5)	0.47437 (5)	0.0301 (2)
S2	0.20796 (5)	0.73180 (5)	0.54737 (5)	0.0321 (2)
S3	0.18647 (6)	0.24030 (5)	0.77987 (5)	0.0335 (2)
S4	0.24789 (5)	0.59458 (6)	0.87516 (5)	0.0325 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0565 (3)	0.0436 (2)	0.02588 (19)	0.00021 (18)	0.00459 (16)	0.00639 (16)
Br2	0.0532 (3)	0.0523 (3)	0.0492 (2)	0.01553 (19)	0.03265 (19)	0.0158 (2)
C1	0.0273 (19)	0.0213 (16)	0.0312 (18)	−0.0038 (14)	0.0115 (14)	0.0021 (15)
C2	0.0270 (19)	0.0239 (17)	0.0325 (18)	−0.0030 (14)	0.0110 (14)	0.0077 (15)
C3	0.0261 (19)	0.0338 (19)	0.0229 (17)	−0.0051 (15)	0.0063 (13)	0.0046 (15)
C4	0.039 (2)	0.0250 (17)	0.0244 (17)	−0.0048 (15)	0.0142 (14)	−0.0011 (15)
C5	0.0321 (19)	0.0210 (16)	0.0260 (17)	−0.0008 (14)	0.0121 (14)	0.0032 (14)
C6	0.0243 (18)	0.0281 (18)	0.0257 (17)	−0.0035 (14)	0.0082 (13)	0.0027 (15)
C7	0.0315 (19)	0.0198 (16)	0.0197 (16)	−0.0062 (14)	0.0055 (13)	−0.0032 (13)
C8	0.035 (2)	0.0293 (18)	0.0250 (17)	−0.0039 (16)	0.0022 (14)	0.0053 (15)
C9	0.029 (2)	0.0337 (19)	0.0345 (19)	0.0021 (15)	0.0055 (15)	−0.0005 (16)
C10	0.034 (2)	0.0300 (18)	0.0306 (19)	−0.0040 (16)	0.0103 (15)	−0.0032 (16)
C11	0.039 (2)	0.0210 (16)	0.0211 (17)	−0.0035 (15)	0.0035 (14)	0.0017 (14)
C12	0.0273 (19)	0.0165 (15)	0.0277 (18)	−0.0018 (14)	0.0016 (14)	−0.0037 (14)
C13	0.036 (2)	0.0268 (18)	0.0195 (16)	0.0079 (15)	0.0070 (14)	0.0024 (14)
C14	0.034 (2)	0.0289 (18)	0.0265 (18)	0.0023 (15)	0.0046 (14)	0.0085 (15)
C15	0.0284 (19)	0.038 (2)	0.0251 (17)	0.0109 (16)	0.0115 (14)	0.0097 (16)
C16	0.035 (2)	0.0345 (19)	0.0229 (17)	0.0092 (16)	0.0076 (14)	0.0015 (15)
C17	0.0302 (19)	0.0282 (17)	0.0212 (16)	0.0005 (15)	0.0031 (13)	0.0029 (14)
C18	0.0244 (18)	0.0294 (18)	0.0202 (16)	0.0012 (15)	0.0046 (13)	0.0049 (14)
C19	0.034 (2)	0.0234 (17)	0.0234 (17)	0.0015 (14)	0.0048 (14)	−0.0048 (14)
C20	0.032 (2)	0.035 (2)	0.0316 (19)	−0.0015 (15)	0.0131 (15)	−0.0010 (16)
C21	0.024 (2)	0.043 (2)	0.038 (2)	−0.0020 (16)	0.0079 (15)	−0.0034 (17)
C22	0.034 (2)	0.0298 (19)	0.0292 (18)	0.0025 (15)	0.0028 (15)	−0.0009 (15)
C23	0.034 (2)	0.0200 (17)	0.0274 (17)	0.0011 (14)	0.0107 (14)	−0.0061 (14)
C24	0.0236 (19)	0.0209 (17)	0.0316 (18)	−0.0014 (14)	0.0090 (14)	−0.0056 (14)
C25	0.037 (2)	0.0294 (18)	0.0289 (18)	0.0020 (16)	0.0050 (15)	−0.0006 (15)
C26	0.039 (2)	0.037 (2)	0.031 (2)	−0.0001 (17)	0.0063 (16)	−0.0057 (18)
C27	0.036 (3)	0.080 (3)	0.068 (3)	−0.004 (2)	0.014 (2)	−0.002 (3)
C28	0.057 (3)	0.047 (2)	0.047 (2)	0.013 (2)	−0.004 (2)	−0.013 (2)
C29	0.085 (4)	0.065 (3)	0.079 (4)	0.032 (3)	−0.005 (3)	−0.006 (3)
C30	0.120 (4)	0.050 (3)	0.099 (4)	0.039 (3)	0.028 (3)	0.011 (3)
C31	0.030 (2)	0.052 (2)	0.036 (2)	0.0029 (17)	0.0106 (15)	−0.0085 (18)
C32	0.031 (2)	0.037 (2)	0.038 (2)	0.0011 (16)	0.0076 (16)	−0.0040 (17)
C33	0.045 (3)	0.067 (3)	0.057 (3)	0.006 (2)	−0.005 (2)	−0.001 (2)
C34	0.034 (2)	0.0312 (19)	0.048 (2)	−0.0075 (16)	0.0108 (16)	−0.0112 (17)
C35	0.037 (2)	0.046 (2)	0.037 (2)	−0.0095 (17)	0.0083 (16)	−0.0046 (18)
C36	0.046 (3)	0.057 (3)	0.050 (2)	−0.017 (2)	0.0107 (19)	−0.012 (2)
O1	0.0318 (13)	0.0296 (12)	0.0246 (12)	0.0010 (10)	0.0075 (9)	0.0009 (10)
O2	0.0325 (14)	0.0259 (12)	0.0321 (13)	0.0025 (10)	0.0067 (10)	0.0012 (10)
O3	0.0303 (14)	0.0371 (13)	0.0271 (12)	0.0034 (10)	0.0117 (10)	0.0021 (11)
O4	0.0267 (13)	0.0298 (12)	0.0350 (13)	−0.0019 (10)	0.0077 (10)	−0.0067 (10)
O5	0.0452 (17)	0.0675 (19)	0.0517 (17)	−0.0077 (14)	0.0100 (13)	0.0237 (15)
O6	0.0332 (16)	0.0567 (17)	0.0619 (18)	0.0023 (13)	0.0050 (13)	0.0099 (14)
O7	0.0580 (19)	0.086 (2)	0.0473 (17)	0.0177 (16)	0.0002 (14)	−0.0265 (17)
O8	0.0379 (16)	0.0612 (17)	0.0436 (15)	0.0107 (13)	0.0006 (12)	−0.0088 (14)
S1	0.0435 (5)	0.0230 (4)	0.0264 (4)	0.0019 (4)	0.0135 (4)	0.0013 (4)
S2	0.0447 (6)	0.0226 (4)	0.0313 (5)	−0.0038 (4)	0.0131 (4)	−0.0007 (4)
S3	0.0530 (6)	0.0247 (4)	0.0237 (4)	0.0024 (4)	0.0095 (4)	0.0026 (4)
S4	0.0393 (5)	0.0310 (5)	0.0258 (4)	−0.0033 (4)	0.0023 (4)	−0.0023 (4)

Geometric parameters (Å, º) top

Br1—C3	1.902 (3)	C22—H22	0.9500
Br2—C15	1.900 (3)	C23—C24	1.396 (4)
C1—C2	1.389 (4)	C23—S2	1.787 (3)
C1—C6	1.404 (4)	C24—O4	1.368 (3)
C1—S2	1.776 (3)	C25—O1	1.411 (3)
C2—C3	1.381 (4)	C25—C26	1.501 (5)
C2—H2	0.9500	C25—H25A	0.9900
C3—C4	1.375 (4)	C25—H25B	0.9900
C4—C5	1.398 (4)	C26—O5	1.189 (4)
C4—H4	0.9500	C26—O6	1.329 (4)
C5—C6	1.394 (4)	C27—O6	1.440 (4)
C5—S1	1.776 (3)	C27—H27A	0.9800
C6—O1	1.367 (3)	C27—H27B	0.9800
C7—C8	1.385 (4)	C27—H27C	0.9800
C7—C12	1.399 (4)	C28—C29	1.442 (5)
C7—S1	1.779 (3)	C28—O2	1.447 (4)
C8—C9	1.374 (4)	C28—H28A	0.9900
C8—H8	0.9500	C28—H28B	0.9900
C9—C10	1.391 (4)	C29—C30	1.505 (5)
C9—H9	0.9500	C29—H29A	0.9900
C10—C11	1.383 (4)	C29—H29B	0.9900
C10—H10	0.9500	C30—H30A	0.9800
C11—C12	1.394 (4)	C30—H30B	0.9800
C11—S3	1.785 (3)	C30—H30C	0.9800
C12—O2	1.373 (3)	C31—O3	1.432 (4)
C13—C14	1.392 (4)	C31—C32	1.494 (4)
C13—C18	1.395 (4)	C31—H31A	0.9900
C13—S3	1.782 (3)	C31—H31B	0.9900
C14—C15	1.377 (4)	C32—O7	1.188 (4)
C14—H14	0.9500	C32—O8	1.325 (4)
C15—C16	1.389 (4)	C33—O8	1.460 (4)
C16—C17	1.381 (4)	C33—H33A	0.9800
C16—H16	0.9500	C33—H33B	0.9800
C17—C18	1.400 (4)	C33—H33C	0.9800
C17—S4	1.783 (3)	C34—O4	1.437 (3)
C18—O3	1.374 (4)	C34—C35	1.496 (4)
C19—C24	1.393 (4)	C34—H34A	0.9900
C19—C20	1.393 (4)	C34—H34B	0.9900
C19—S4	1.791 (3)	C35—C36	1.526 (4)
C20—C21	1.379 (4)	C35—H35A	0.9900
C20—H20	0.9500	C35—H35B	0.9900
C21—C22	1.373 (4)	C36—H36A	0.9800
C21—H21	0.9500	C36—H36B	0.9800
C22—C23	1.388 (4)	C36—H36C	0.9800

C2—C1—C6	119.2 (3)	C26—C25—H25A	108.9
C2—C1—S2	119.4 (2)	O1—C25—H25B	108.9
C6—C1—S2	121.4 (2)	C26—C25—H25B	108.9
C3—C2—C1	120.2 (3)	H25A—C25—H25B	107.7
C3—C2—H2	119.9	O5—C26—O6	124.6 (3)
C1—C2—H2	119.9	O5—C26—C25	126.1 (3)
C4—C3—C2	120.9 (3)	O6—C26—C25	109.3 (3)
C4—C3—Br1	118.3 (2)	O6—C27—H27A	109.5
C2—C3—Br1	120.7 (2)	O6—C27—H27B	109.5
C3—C4—C5	119.9 (3)	H27A—C27—H27B	109.5
C3—C4—H4	120.1	O6—C27—H27C	109.5
C5—C4—H4	120.1	H27A—C27—H27C	109.5
C6—C5—C4	119.5 (3)	H27B—C27—H27C	109.5
C6—C5—S1	121.6 (2)	C29—C28—O2	111.4 (3)
C4—C5—S1	118.8 (2)	C29—C28—H28A	109.3
O1—C6—C5	122.9 (3)	O2—C28—H28A	109.3
O1—C6—C1	116.7 (3)	C29—C28—H28B	109.3
C5—C6—C1	120.1 (3)	O2—C28—H28B	109.3
C8—C7—C12	119.5 (3)	H28A—C28—H28B	108.0
C8—C7—S1	121.9 (2)	C28—C29—C30	113.1 (4)
C12—C7—S1	118.5 (2)	C28—C29—H29A	108.9
C9—C8—C7	120.9 (3)	C30—C29—H29A	108.9
C9—C8—H8	119.6	C28—C29—H29B	108.9
C7—C8—H8	119.6	C30—C29—H29B	108.9
C8—C9—C10	120.3 (3)	H29A—C29—H29B	107.8
C8—C9—H9	119.9	C29—C30—H30A	109.5
C10—C9—H9	119.9	C29—C30—H30B	109.5
C11—C10—C9	119.3 (3)	H30A—C30—H30B	109.5
C11—C10—H10	120.3	C29—C30—H30C	109.5
C9—C10—H10	120.3	H30A—C30—H30C	109.5
C10—C11—C12	120.8 (3)	H30B—C30—H30C	109.5
C10—C11—S3	118.9 (2)	O3—C31—C32	113.9 (3)
C12—C11—S3	120.2 (2)	O3—C31—H31A	108.8
O2—C12—C11	121.4 (3)	C32—C31—H31A	108.8
O2—C12—C7	119.4 (3)	O3—C31—H31B	108.8
C11—C12—C7	119.2 (3)	C32—C31—H31B	108.8
C14—C13—C18	119.8 (3)	H31A—C31—H31B	107.7
C14—C13—S3	118.3 (2)	O7—C32—O8	124.6 (3)
C18—C13—S3	121.8 (2)	O7—C32—C31	126.5 (3)
C15—C14—C13	119.6 (3)	O8—C32—C31	108.9 (3)
C15—C14—H14	120.2	O8—C33—H33A	109.5
C13—C14—H14	120.2	O8—C33—H33B	109.5
C14—C15—C16	121.1 (3)	H33A—C33—H33B	109.5
C14—C15—Br2	118.3 (2)	O8—C33—H33C	109.5
C16—C15—Br2	120.6 (2)	H33A—C33—H33C	109.5
C17—C16—C15	119.2 (3)	H33B—C33—H33C	109.5
C17—C16—H16	120.4	O4—C34—C35	107.3 (3)
C15—C16—H16	120.4	O4—C34—H34A	110.3
C16—C17—C18	120.4 (3)	C35—C34—H34A	110.3
C16—C17—S4	120.1 (2)	O4—C34—H34B	110.3
C18—C17—S4	119.5 (2)	C35—C34—H34B	110.3
O3—C18—C13	122.4 (3)	H34A—C34—H34B	108.5
O3—C18—C17	118.2 (3)	C34—C35—C36	111.7 (3)
C13—C18—C17	119.2 (3)	C34—C35—H35A	109.3
C24—C19—C20	119.9 (3)	C36—C35—H35A	109.3
C24—C19—S4	119.1 (2)	C34—C35—H35B	109.3
C20—C19—S4	121.0 (3)	C36—C35—H35B	109.3
C21—C20—C19	120.0 (3)	H35A—C35—H35B	107.9
C21—C20—H20	120.0	C35—C36—H36A	109.5
C19—C20—H20	120.0	C35—C36—H36B	109.5
C22—C21—C20	120.4 (3)	H36A—C36—H36B	109.5
C22—C21—H21	119.8	C35—C36—H36C	109.5
C20—C21—H21	119.8	H36A—C36—H36C	109.5
C21—C22—C23	120.6 (3)	H36B—C36—H36C	109.5
C21—C22—H22	119.7	C6—O1—C25	121.1 (2)
C23—C22—H22	119.7	C12—O2—C28	114.1 (2)
C22—C23—C24	119.5 (3)	C18—O3—C31	116.6 (2)
C22—C23—S2	119.5 (2)	C24—O4—C34	115.6 (2)
C24—C23—S2	121.0 (2)	C26—O6—C27	115.2 (3)
O4—C24—C19	119.9 (3)	C32—O8—C33	117.4 (3)
O4—C24—C23	120.2 (3)	C5—S1—C7	98.88 (14)
C19—C24—C23	119.6 (3)	C1—S2—C23	101.78 (14)
O1—C25—C26	113.4 (3)	C13—S3—C11	97.62 (14)
O1—C25—H25A	108.9	C17—S4—C19	99.14 (14)

C6—C1—C2—C3	−0.3 (4)	C20—C21—C22—C23	−0.2 (5)
S2—C1—C2—C3	177.8 (2)	C21—C22—C23—C24	0.0 (5)
C1—C2—C3—C4	3.6 (5)	C21—C22—C23—S2	−179.0 (2)
C1—C2—C3—Br1	178.8 (2)	C20—C19—C24—O4	−176.6 (3)
C2—C3—C4—C5	−2.4 (5)	S4—C19—C24—O4	3.6 (4)
Br1—C3—C4—C5	−177.8 (2)	C20—C19—C24—C23	−1.6 (4)
C3—C4—C5—C6	−1.9 (5)	S4—C19—C24—C23	178.6 (2)
C3—C4—C5—S1	174.3 (2)	C22—C23—C24—O4	175.9 (3)
C4—C5—C6—O1	178.0 (3)	S2—C23—C24—O4	−5.2 (4)
S1—C5—C6—O1	1.8 (4)	C22—C23—C24—C19	0.9 (4)
C4—C5—C6—C1	5.2 (4)	S2—C23—C24—C19	179.9 (2)
S1—C5—C6—C1	−170.9 (2)	O1—C25—C26—O5	−13.4 (5)
C2—C1—C6—O1	−177.3 (3)	O1—C25—C26—O6	167.7 (2)
S2—C1—C6—O1	4.7 (4)	O2—C28—C29—C30	171.2 (4)
C2—C1—C6—C5	−4.1 (4)	O3—C31—C32—O7	12.0 (5)
S2—C1—C6—C5	177.9 (2)	O3—C31—C32—O8	−169.7 (3)
C12—C7—C8—C9	0.7 (4)	O4—C34—C35—C36	−178.0 (3)
S1—C7—C8—C9	−177.3 (2)	C5—C6—O1—C25	63.4 (4)
C7—C8—C9—C10	0.4 (5)	C1—C6—O1—C25	−123.6 (3)
C8—C9—C10—C11	−0.5 (5)	C26—C25—O1—C6	54.1 (4)
C9—C10—C11—C12	−0.6 (5)	C11—C12—O2—C28	80.2 (4)
C9—C10—C11—S3	176.8 (2)	C7—C12—O2—C28	−103.3 (3)
C10—C11—C12—O2	178.3 (3)	C29—C28—O2—C12	−160.9 (3)
S3—C11—C12—O2	0.9 (4)	C13—C18—O3—C31	−64.3 (4)
C10—C11—C12—C7	1.7 (4)	C17—C18—O3—C31	121.5 (3)
S3—C11—C12—C7	−175.7 (2)	C32—C31—O3—C18	−66.1 (4)
C8—C7—C12—O2	−178.3 (3)	C19—C24—O4—C34	−86.5 (3)
S1—C7—C12—O2	−0.3 (4)	C23—C24—O4—C34	98.5 (3)
C8—C7—C12—C11	−1.7 (4)	C35—C34—O4—C24	169.0 (3)
S1—C7—C12—C11	176.3 (2)	O5—C26—O6—C27	−4.5 (5)
C18—C13—C14—C15	1.1 (4)	C25—C26—O6—C27	174.4 (3)
S3—C13—C14—C15	−175.3 (2)	O7—C32—O8—C33	0.9 (5)
C13—C14—C15—C16	5.0 (5)	C31—C32—O8—C33	−177.5 (3)
C13—C14—C15—Br2	−177.2 (2)	C6—C5—S1—C7	58.3 (3)
C14—C15—C16—C17	−4.0 (5)	C4—C5—S1—C7	−117.9 (3)
Br2—C15—C16—C17	178.2 (2)	C8—C7—S1—C5	33.4 (3)
C15—C16—C17—C18	−3.0 (4)	C12—C7—S1—C5	−144.6 (2)
C15—C16—C17—S4	175.4 (2)	C2—C1—S2—C23	131.6 (3)
C14—C13—C18—O3	178.0 (3)	C6—C1—S2—C23	−50.4 (3)
S3—C13—C18—O3	−5.8 (4)	C22—C23—S2—C1	−72.7 (3)
C14—C13—C18—C17	−7.9 (4)	C24—C23—S2—C1	108.3 (3)
S3—C13—C18—C17	168.4 (2)	C14—C13—S3—C11	118.2 (3)
C16—C17—C18—O3	−176.7 (3)	C18—C13—S3—C11	−58.1 (3)
S4—C17—C18—O3	4.9 (4)	C10—C11—S3—C13	−56.9 (3)
C16—C17—C18—C13	8.9 (4)	C12—C11—S3—C13	120.5 (3)
S4—C17—C18—C13	−169.5 (2)	C16—C17—S4—C19	−101.1 (3)
C24—C19—C20—C21	1.3 (5)	C18—C17—S4—C19	77.2 (3)
S4—C19—C20—C21	−178.8 (2)	C24—C19—S4—C17	−137.2 (3)
C19—C20—C21—C22	−0.4 (5)	C20—C19—S4—C17	43.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···S3ⁱ	0.95	2.91	3.755 (3)	149
C33—H33A···O7ⁱⁱ	0.98	2.58	3.551 (5)	169

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

Experimental details

Crystal data
Chemical formula	C₃₆H₃₄Br₂O₈S₄
M_r	882.69
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	16.024 (3), 14.808 (3), 15.872 (3)
β (°)	100.065 (3)
V (Å³)	3708.3 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.46
Crystal size (mm)	0.38 × 0.18 × 0.13

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1999)
T_min, T_max	0.455, 0.740
No. of measured, independent and observed [I > 2σ(I)] reflections	19322, 6989, 4908
R_int	0.060
(sin θ/λ)_max (Å⁻¹)	0.608

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.091, 0.93
No. of reflections	6989
No. of parameters	455
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.62, −0.55

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···S3ⁱ	0.95	2.91	3.755 (3)	148.8
C33—H33A···O7ⁱⁱ	0.98	2.58	3.551 (5)	169.3

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

Acknowledgements

Financial support from the National Natural Science Foundation of China (grant No. 20572064) and the Natural Science Foundation of Shandong Province (grant No. ZR2010BM022) is gratefully acknowledged.

References

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Volume 68| Part 5| May 2012| Pages o1353-o1354

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

5,17-Di­bromo-26,28-bis­­[(meth­­oxy­carbon­yl)meth­­oxy]-25,27-diprop­­oxy-2,8,14,20-tetra­thia­calix[4]arene

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

5,17-Dibromo-26,28-bis[(methoxycarbonyl)methoxy]-25,27-dipropoxy-2,8,14,20-tetrathiacalix[4]arene