25,26,27,28-Tetra-kis(3-bromo-benzyl-oxy)calix[4]arene.

In the title compound, C(56)H(44)Br(4)O(4), the calix[4]arene unit displays the 1,2-alternate conformation with crystallograpically imposed inversion symmetry. The four phen-oxy rings of the calix[4]arene unit are twisted about the mean plane defined by the four methyl-ene C atoms bridging the benzene rings, with dihedral angles of 46.73 (6) and 66.11 (5)°. The dihedral angle between adjacent phen-oxy rings is 74.75 (7)°. The two pendant bromo-phenyl rings on the same side of the calix[4]arene unit are nearly perpendicular to each other, with a dihedral angle of 72.85 (10)° due to an intra-molecular C-H⋯π inter-action. In the crystal, a Br⋯Br contact of 3.6350 (5) Å, an inter-molecular C-H⋯Br hydrogen bond and an inter-molecular C-H⋯π inter-action are observed.

Related literature

For calix[4]arene chemistry and its applications, see: Gutsche (2008 ▶); Ikeda & Shinkai (1997 ▶). For the use of calixarenes in crystal engineering, see: Dalgrano et al. (2007 ▶). For the modification of calix[4]arenes, see: Asfari et al. (2001 ▶); Mandolini & Ungaro (2000 ▶).

Experimental

Crystal data

C56H44Br4O4

M = 1100.55

Monoclinic,

a = 13.4377 (8) Å

b = 10.4789 (7) Å

c = 17.1666 (12) Å

β = 103.822 (2)°

V = 2347.3 (3) Å3

Z = 2

Mo Kα radiation

μ = 3.48 mm−1

T = 173 K

0.21 × 0.20 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996) ▶ T min = 0.529, T max = 0.624

22506 measured reflections

5813 independent reflections

3929 reflections with I > 2σ(I)

R int = 0.037

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.106

S = 1.02

5813 reflections

289 parameters

H-atom parameters constrained

Δρmax = 0.63 e Å−3

Δρmin = −0.91 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811022975/wn2436sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811022975/wn2436Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C56H44Br4O4	F(000) = 1104
Mr = 1100.55	Dx = 1.557 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5179 reflections
a = 13.4377 (8) Å	θ = 2.3–27.1°
b = 10.4789 (7) Å	µ = 3.48 mm−1
c = 17.1666 (12) Å	T = 173 K
β = 103.822 (2)°	Block, colourless
V = 2347.3 (3) Å3	0.21 × 0.20 × 0.15 mm
Z = 2

Bruker APEXII CCD diffractometer	5813 independent reflections
Radiation source: fine-focus sealed tube	3929 reflections with I > 2σ(I)
graphite	Rint = 0.037
φ and ω scans	θmax = 28.3°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→17
Tmin = 0.529, Tmax = 0.624	k = −13→10
22506 measured reflections	l = −22→22

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.106	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0447P)2 + 1.723P] where P = (Fo2 + 2Fc2)/3
5813 reflections	(Δ/σ)max = 0.001
289 parameters	Δρmax = 0.63 e Å−3
0 restraints	Δρmin = −0.91 e Å−3

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.

	x	y	z	Uiso*/Ueq
Br1	0.41607 (3)	0.68787 (4)	0.35182 (2)	0.06529 (14)
Br2	0.48689 (2)	1.06993 (6)	0.31500 (3)	0.0952 (2)
O1	0.15137 (12)	0.85506 (17)	0.55860 (10)	0.0291 (4)
O2	0.04423 (11)	0.96810 (15)	0.38948 (9)	0.0242 (3)
C1	0.07450 (16)	0.7816 (2)	0.57737 (13)	0.0232 (5)
C2	0.01333 (17)	0.7075 (2)	0.51741 (14)	0.0244 (5)
C3	−0.06427 (18)	0.6351 (2)	0.53749 (15)	0.0288 (5)
H3	−0.1049	0.5805	0.4983	0.035*
C4	−0.08325 (19)	0.6411 (2)	0.61272 (15)	0.0310 (5)
H4	−0.1357	0.5902	0.6254	0.037*
C5	−0.02539 (18)	0.7217 (2)	0.66956 (14)	0.0283 (5)
H5	−0.0405	0.7282	0.7207	0.034*
C6	0.05422 (17)	0.7931 (2)	0.65368 (13)	0.0249 (5)
C7	−0.04927 (16)	0.9096 (2)	0.35766 (12)	0.0222 (5)
C8	−0.12770 (17)	0.9807 (2)	0.30901 (13)	0.0255 (5)
C9	−0.22207 (18)	0.9204 (3)	0.28019 (15)	0.0336 (6)
H9	−0.2775	0.9669	0.2478	0.040*
C10	−0.23581 (19)	0.7942 (3)	0.29812 (16)	0.0388 (7)
H10	−0.3002	0.7542	0.2776	0.047*
C11	−0.15618 (19)	0.7258 (3)	0.34591 (15)	0.0342 (6)
H11	−0.1662	0.6386	0.3573	0.041*
C12	−0.06149 (17)	0.7829 (2)	0.37760 (13)	0.0245 (5)
C13	0.02461 (18)	0.7085 (2)	0.43178 (14)	0.0266 (5)
H13A	0.0241	0.6196	0.4121	0.032*
H13B	0.0912	0.7474	0.4301	0.032*
C14	−0.11303 (18)	1.1161 (2)	0.28319 (14)	0.0284 (5)
H14A	−0.1817	1.1533	0.2609	0.034*
H14B	−0.0774	1.1124	0.2390	0.034*
C15	0.25431 (18)	0.8158 (3)	0.59555 (16)	0.0380 (6)
H15A	0.2573	0.7862	0.6508	0.046*
H15B	0.3007	0.8901	0.5991	0.046*
C16	0.29142 (17)	0.7103 (3)	0.54979 (16)	0.0333 (6)
C17	0.32711 (17)	0.7399 (3)	0.48246 (16)	0.0318 (6)
H17	0.3272	0.8259	0.4650	0.038*
C18	0.36244 (19)	0.6437 (3)	0.44102 (18)	0.0412 (7)
C19	0.3620 (2)	0.5183 (3)	0.4642 (3)	0.0606 (10)
H19	0.3858	0.4530	0.4348	0.073*
C20	0.3264 (3)	0.4894 (3)	0.5308 (3)	0.0694 (11)
H20	0.3254	0.4032	0.5477	0.083*
C21	0.2918 (2)	0.5851 (3)	0.5734 (2)	0.0536 (8)
H21	0.2681	0.5638	0.6196	0.064*
C22	0.11169 (17)	0.9651 (3)	0.33740 (15)	0.0305 (5)
H22A	0.0812	1.0128	0.2877	0.037*
H22B	0.1226	0.8758	0.3226	0.037*
C23	0.21228 (17)	1.0240 (2)	0.37845 (16)	0.0306 (5)
C24	0.28954 (19)	1.0230 (3)	0.33757 (17)	0.0411 (7)
H24	0.2776	0.9876	0.2852	0.049*
C25	0.3838 (2)	1.0737 (3)	0.3736 (2)	0.0532 (9)
C26	0.4038 (2)	1.1250 (3)	0.4500 (2)	0.0551 (9)
H26	0.4693	1.1591	0.4743	0.066*
C27	0.3268 (2)	1.1255 (3)	0.4897 (2)	0.0485 (8)
H27	0.3396	1.1600	0.5423	0.058*
C28	0.23048 (19)	1.0765 (2)	0.45464 (17)	0.0362 (6)
H28	0.1775	1.0789	0.4827	0.043*

	U11	U22	U33	U12	U13	U23
Br1	0.04985 (19)	0.0996 (3)	0.0523 (2)	−0.00434 (18)	0.02381 (15)	−0.02819 (19)
Br2	0.03236 (17)	0.1775 (5)	0.0785 (3)	−0.0192 (2)	0.01840 (17)	0.0392 (3)
O1	0.0268 (8)	0.0341 (10)	0.0280 (9)	−0.0023 (7)	0.0100 (7)	0.0013 (7)
O2	0.0220 (7)	0.0264 (9)	0.0235 (8)	−0.0031 (6)	0.0043 (6)	−0.0022 (7)
C1	0.0246 (10)	0.0223 (13)	0.0237 (11)	0.0041 (9)	0.0081 (9)	0.0044 (9)
C2	0.0309 (11)	0.0191 (13)	0.0247 (12)	0.0048 (9)	0.0097 (9)	0.0025 (9)
C3	0.0345 (12)	0.0226 (13)	0.0292 (12)	−0.0022 (10)	0.0076 (10)	0.0014 (10)
C4	0.0358 (12)	0.0264 (14)	0.0329 (13)	−0.0022 (10)	0.0126 (10)	0.0073 (11)
C5	0.0359 (12)	0.0284 (14)	0.0230 (12)	0.0035 (10)	0.0116 (10)	0.0070 (10)
C6	0.0299 (11)	0.0228 (13)	0.0219 (11)	0.0052 (9)	0.0061 (9)	0.0036 (9)
C7	0.0232 (10)	0.0287 (13)	0.0153 (10)	−0.0039 (9)	0.0058 (8)	−0.0054 (9)
C8	0.0268 (11)	0.0317 (14)	0.0178 (11)	−0.0006 (10)	0.0052 (9)	−0.0031 (10)
C9	0.0273 (11)	0.0467 (18)	0.0246 (12)	−0.0027 (11)	0.0018 (9)	−0.0032 (11)
C10	0.0302 (12)	0.0511 (19)	0.0322 (14)	−0.0151 (12)	0.0019 (10)	−0.0062 (13)
C11	0.0396 (13)	0.0346 (16)	0.0288 (13)	−0.0142 (11)	0.0090 (11)	−0.0038 (11)
C12	0.0310 (11)	0.0281 (14)	0.0157 (10)	−0.0026 (9)	0.0083 (9)	−0.0040 (9)
C13	0.0345 (12)	0.0227 (13)	0.0241 (12)	0.0012 (10)	0.0100 (9)	−0.0025 (10)
C14	0.0321 (11)	0.0333 (15)	0.0190 (11)	0.0037 (10)	0.0043 (9)	0.0037 (10)
C15	0.0241 (11)	0.0573 (19)	0.0321 (14)	−0.0014 (12)	0.0055 (10)	−0.0067 (13)
C16	0.0216 (11)	0.0373 (16)	0.0398 (14)	−0.0032 (10)	0.0048 (10)	0.0015 (12)
C17	0.0255 (11)	0.0316 (15)	0.0383 (14)	0.0007 (10)	0.0074 (10)	−0.0034 (11)
C18	0.0263 (12)	0.0485 (19)	0.0482 (17)	−0.0011 (12)	0.0075 (11)	−0.0144 (14)
C19	0.0419 (16)	0.036 (2)	0.103 (3)	0.0035 (14)	0.0153 (18)	−0.0216 (19)
C20	0.059 (2)	0.034 (2)	0.117 (3)	−0.0004 (16)	0.023 (2)	0.011 (2)
C21	0.0449 (16)	0.050 (2)	0.068 (2)	−0.0045 (14)	0.0173 (15)	0.0152 (17)
C22	0.0261 (11)	0.0352 (15)	0.0313 (13)	−0.0037 (10)	0.0091 (10)	−0.0013 (11)
C23	0.0252 (11)	0.0253 (14)	0.0395 (14)	−0.0013 (10)	0.0041 (10)	0.0096 (11)
C24	0.0294 (12)	0.0518 (18)	0.0410 (15)	−0.0039 (12)	0.0059 (11)	0.0169 (14)
C25	0.0264 (12)	0.072 (2)	0.060 (2)	−0.0057 (14)	0.0089 (13)	0.0288 (18)
C26	0.0299 (14)	0.055 (2)	0.070 (2)	−0.0142 (14)	−0.0072 (14)	0.0151 (18)
C27	0.0420 (15)	0.0365 (18)	0.0589 (19)	−0.0057 (13)	−0.0041 (14)	−0.0049 (15)
C28	0.0309 (12)	0.0285 (15)	0.0465 (16)	−0.0027 (11)	0.0037 (11)	−0.0010 (12)

Br1—C18	1.899 (3)	C14—C6i	1.515 (3)
Br2—C25	1.897 (3)	C14—H14A	0.9900
O1—C1	1.387 (3)	C14—H14B	0.9900
O1—C15	1.437 (3)	C15—C16	1.508 (4)
O2—C7	1.387 (3)	C15—H15A	0.9900
O2—C22	1.417 (3)	C15—H15B	0.9900
C1—C2	1.390 (3)	C16—C21	1.373 (4)
C1—C6	1.406 (3)	C16—C17	1.388 (4)
C2—C3	1.398 (3)	C17—C18	1.382 (4)
C2—C13	1.513 (3)	C17—H17	0.9500
C3—C4	1.376 (3)	C18—C19	1.373 (5)
C3—H3	0.9500	C19—C20	1.374 (6)
C4—C5	1.381 (4)	C19—H19	0.9500
C4—H4	0.9500	C20—C21	1.385 (5)
C5—C6	1.385 (3)	C20—H20	0.9500
C5—H5	0.9500	C21—H21	0.9500
C6—C14i	1.515 (3)	C22—C23	1.500 (3)
C7—C12	1.391 (3)	C22—H22A	0.9900
C7—C8	1.394 (3)	C22—H22B	0.9900
C8—C9	1.397 (3)	C23—C24	1.385 (3)
C8—C14	1.514 (4)	C23—C28	1.386 (4)
C9—C10	1.381 (4)	C24—C25	1.376 (4)
C9—H9	0.9500	C24—H24	0.9500
C10—C11	1.383 (4)	C25—C26	1.383 (5)
C10—H10	0.9500	C26—C27	1.367 (5)
C11—C12	1.394 (3)	C26—H26	0.9500
C11—H11	0.9500	C27—C28	1.389 (4)
C12—C13	1.516 (3)	C27—H27	0.9500
C13—H13A	0.9900	C28—H28	0.9500
C13—H13B	0.9900
C1—O1—C15	115.49 (19)	H14A—C14—H14B	107.2
C7—O2—C22	113.41 (16)	O1—C15—C16	112.5 (2)
O1—C1—C2	118.64 (19)	O1—C15—H15A	109.1
O1—C1—C6	119.3 (2)	C16—C15—H15A	109.1
C2—C1—C6	121.7 (2)	O1—C15—H15B	109.1
C1—C2—C3	117.7 (2)	C16—C15—H15B	109.1
C1—C2—C13	122.5 (2)	H15A—C15—H15B	107.8
C3—C2—C13	119.8 (2)	C21—C16—C17	118.8 (3)
C4—C3—C2	121.5 (2)	C21—C16—C15	121.7 (3)
C4—C3—H3	119.2	C17—C16—C15	119.5 (2)
C2—C3—H3	119.2	C18—C17—C16	119.7 (3)
C3—C4—C5	119.4 (2)	C18—C17—H17	120.2
C3—C4—H4	120.3	C16—C17—H17	120.2
C5—C4—H4	120.3	C19—C18—C17	121.6 (3)
C4—C5—C6	121.5 (2)	C19—C18—Br1	119.7 (2)
C4—C5—H5	119.3	C17—C18—Br1	118.7 (2)
C6—C5—H5	119.3	C18—C19—C20	118.6 (3)
C5—C6—C1	117.9 (2)	C18—C19—H19	120.7
C5—C6—C14i	119.6 (2)	C20—C19—H19	120.7
C1—C6—C14i	122.5 (2)	C19—C20—C21	120.5 (3)
O2—C7—C12	118.30 (19)	C19—C20—H20	119.8
O2—C7—C8	118.9 (2)	C21—C20—H20	119.8
C12—C7—C8	122.7 (2)	C16—C21—C20	121.0 (3)
C7—C8—C9	117.6 (2)	C16—C21—H21	119.5
C7—C8—C14	122.9 (2)	C20—C21—H21	119.5
C9—C8—C14	119.4 (2)	O2—C22—C23	109.6 (2)
C10—C9—C8	120.8 (2)	O2—C22—H22A	109.8
C10—C9—H9	119.6	C23—C22—H22A	109.8
C8—C9—H9	119.6	O2—C22—H22B	109.8
C9—C10—C11	120.2 (2)	C23—C22—H22B	109.8
C9—C10—H10	119.9	H22A—C22—H22B	108.2
C11—C10—H10	119.9	C24—C23—C28	119.8 (2)
C10—C11—C12	120.9 (2)	C24—C23—C22	117.3 (2)
C10—C11—H11	119.5	C28—C23—C22	122.9 (2)
C12—C11—H11	119.5	C25—C24—C23	119.3 (3)
C7—C12—C11	117.7 (2)	C25—C24—H24	120.3
C7—C12—C13	121.6 (2)	C23—C24—H24	120.3
C11—C12—C13	120.7 (2)	C24—C25—C26	121.7 (3)
C2—C13—C12	111.12 (19)	C24—C25—Br2	117.7 (3)
C2—C13—H13A	109.4	C26—C25—Br2	120.7 (2)
C12—C13—H13A	109.4	C27—C26—C25	118.4 (3)
C2—C13—H13B	109.4	C27—C26—H26	120.8
C12—C13—H13B	109.4	C25—C26—H26	120.8
H13A—C13—H13B	108.0	C26—C27—C28	121.4 (3)
C8—C14—C6i	117.47 (19)	C26—C27—H27	119.3
C8—C14—H14A	107.9	C28—C27—H27	119.3
C6i—C14—H14A	107.9	C23—C28—C27	119.4 (3)
C8—C14—H14B	107.9	C23—C28—H28	120.3
C6i—C14—H14B	107.9	C27—C28—H28	120.3
C15—O1—C1—C2	−112.0 (2)	C1—C2—C13—C12	−105.0 (2)
C15—O1—C1—C6	74.0 (3)	C3—C2—C13—C12	71.8 (3)
O1—C1—C2—C3	−179.4 (2)	C7—C12—C13—C2	97.3 (2)
C6—C1—C2—C3	−5.6 (3)	C11—C12—C13—C2	−82.7 (3)
O1—C1—C2—C13	−2.6 (3)	C7—C8—C14—C6i	−44.1 (3)
C6—C1—C2—C13	171.2 (2)	C9—C8—C14—C6i	139.2 (2)
C1—C2—C3—C4	3.1 (4)	C1—O1—C15—C16	83.6 (3)
C13—C2—C3—C4	−173.8 (2)	O1—C15—C16—C21	−100.1 (3)
C2—C3—C4—C5	0.9 (4)	O1—C15—C16—C17	80.5 (3)
C3—C4—C5—C6	−2.6 (4)	C21—C16—C17—C18	−0.3 (4)
C4—C5—C6—C1	0.2 (3)	C15—C16—C17—C18	179.1 (2)
C4—C5—C6—C14i	177.7 (2)	C16—C17—C18—C19	0.8 (4)
O1—C1—C6—C5	177.8 (2)	C16—C17—C18—Br1	−177.41 (18)
C2—C1—C6—C5	4.0 (3)	C17—C18—C19—C20	−0.7 (5)
O1—C1—C6—C14i	0.3 (3)	Br1—C18—C19—C20	177.6 (3)
C2—C1—C6—C14i	−173.5 (2)	C18—C19—C20—C21	−0.1 (5)
C22—O2—C7—C12	95.5 (2)	C17—C16—C21—C20	−0.5 (4)
C22—O2—C7—C8	−86.3 (2)	C15—C16—C21—C20	−179.9 (3)
O2—C7—C8—C9	−177.8 (2)	C19—C20—C21—C16	0.6 (5)
C12—C7—C8—C9	0.4 (3)	C7—O2—C22—C23	−176.98 (19)
O2—C7—C8—C14	5.5 (3)	O2—C22—C23—C24	176.7 (2)
C12—C7—C8—C14	−176.3 (2)	O2—C22—C23—C28	−2.4 (3)
C7—C8—C9—C10	−1.4 (3)	C28—C23—C24—C25	0.3 (4)
C14—C8—C9—C10	175.5 (2)	C22—C23—C24—C25	−178.7 (3)
C8—C9—C10—C11	0.8 (4)	C23—C24—C25—C26	0.5 (5)
C9—C10—C11—C12	0.8 (4)	C23—C24—C25—Br2	−180.0 (2)
O2—C7—C12—C11	179.3 (2)	C24—C25—C26—C27	−0.5 (5)
C8—C7—C12—C11	1.1 (3)	Br2—C25—C26—C27	180.0 (2)
O2—C7—C12—C13	−0.8 (3)	C25—C26—C27—C28	−0.3 (5)
C8—C7—C12—C13	−179.0 (2)	C24—C23—C28—C27	−1.1 (4)
C10—C11—C12—C7	−1.7 (3)	C22—C23—C28—C27	177.9 (3)
C10—C11—C12—C13	178.3 (2)	C26—C27—C28—C23	1.1 (4)

Cg1 and Cg2 are the centroids of the C23–C28 and C7–C12 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15B···Br2ii	0.99	2.91	3.652 (2)	132
C17—H17···Cg1	0.95	2.74	3.69	175
C5—H5···Cg2iii	0.95	2.68	3.54	151

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C23–C28 and C7–C12 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H15B⋯Br2i	0.99	2.91	3.652 (2)	132
C17—H17⋯Cg1	0.95	2.74	3.69	175
C5—H5⋯Cg2ii	0.95	2.68	3.54	151

Symmetry codes: (i) ; (ii) .