5,11,17,23-Tetra-kis(chloro-meth-yl)-25,26,27,28-tetra-propoxycalix[4]arene.

The title calix[4]arene, C(44)H(52)Cl(4)O(4), displays the 1,3-alternate conformation with crystallographically imposed twofold symmetry. Four phenolic rings of the calixarene backbone are tilted into the calix cavity, making dihedral angles of 77.42 (2) and 77.71 (2)° with the plane of the four bridging methyl-ene C atoms. Pairs of opposite aromatic rings make dihedral angles of 25.16 (3) and 24.58 (4)° with each other. In the crystal, the calixarene mol-ecules pack with the formation of infinite columns along the b axis. The crystal packing shows a network of C-H⋯Cl contacts, which can be considered as non-classical hydrogen bonds.

Related literature

For calixarene derivatives and their applications, see: Gutsche (2008 ▶); Ikeda & Shinkai (1997 ▶). For the use of calixarenes in crystal engineering, see: Dalgrano et al. (2007 ▶). For the previous synthesis of the title compound, see: Ikeda & Shinkai (1994a ▶). For its application in the formation of nanotubes, see: Ikeda & Shinkai (1994b ▶). For reviews on weak non-classical hydrogen bonding, see: Desiraju & Steiner (1999 ▶); Steiner (2002 ▶); Desiraju (2005 ▶).

Experimental

Crystal data

C44H52Cl4O4

M = 786.66

Monoclinic,

a = 23.104 (3) Å

b = 11.5871 (15) Å

c = 17.618 (2) Å

β = 117.655 (2)°

V = 4177.7 (9) Å3

Z = 4

Mo Kα radiation

μ = 0.32 mm−1

T = 100 K

0.49 × 0.31 × 0.15 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.658, T max = 0.746

15796 measured reflections

6176 independent reflections

5280 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.119

S = 0.97

6176 reflections

235 parameters

H-atom parameters constrained

Δρmax = 0.84 e Å−3

Δρmin = −1.05 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: CRYSTALS, enCIFer (Allen et al., 2004 ▶) and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681100660X/rk2266sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681100660X/rk2266Isup2.hkl

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

C44H52Cl4O4	F(000) = 1664
Mr = 786.66	Dx = 1.251 Mg m−3
Monoclinic, C2/c	Melting point = 562–565 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 23.104 (3) Å	Cell parameters from 6719 reflections
b = 11.5871 (15) Å	θ = 2.6–31.2°
c = 17.618 (2) Å	µ = 0.32 mm−1
β = 117.655 (2)°	T = 100 K
V = 4177.7 (9) Å3	Plate, colourless
Z = 4	0.49 × 0.31 × 0.15 mm

Bruker Kappa APEXII CCD diffractometer	6176 independent reflections
Radiation source: fine–focus sealed tube	5280 reflections with I > 2σ(I)
graphite	Rint = 0.019
ω scans	θmax = 31.3°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −32→21
Tmin = 0.658, Tmax = 0.746	k = −16→16
15796 measured reflections	l = −25→24

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.045	H-atom parameters constrained
wR(F2) = 0.119	Method: Modified Sheldrick w = 1/[σ2(F2) + (0.06P)2 + 6.5P], where P = (max(Fo2,0) + 2Fc2)/3
S = 0.97	(Δ/σ)max = 0.001
6176 reflections	Δρmax = 0.84 e Å−3
235 parameters	Δρmin = −1.05 e Å−3
0 restraints

	x	y	z	Uiso*/Ueq
C1	0.50019 (6)	0.26912 (11)	0.95475 (8)	0.0164
C2	0.54654 (6)	0.20061 (11)	0.93269 (8)	0.0149
C3	0.53732 (6)	0.08279 (11)	0.91462 (8)	0.0167
C4	0.57355 (6)	0.02376 (11)	0.88215 (8)	0.0170
C5	0.61874 (6)	0.08366 (11)	0.86547 (8)	0.0168
C6	0.62966 (6)	0.20102 (11)	0.88333 (8)	0.0148
C7	0.67218 (6)	0.27004 (11)	0.85493 (8)	0.0163
C8	0.62887 (6)	0.33794 (11)	0.77464 (8)	0.0143
C9	0.61781 (6)	0.45548 (11)	0.77855 (8)	0.0160
C10	0.57288 (6)	0.51528 (11)	0.70662 (8)	0.0164
C11	0.53667 (6)	0.45584 (11)	0.63009 (8)	0.0159
C12	0.54589 (6)	0.33795 (11)	0.62379 (8)	0.0144
C13	0.59403 (6)	0.28149 (10)	0.69587 (8)	0.0137
C14	0.59478 (6)	0.25714 (10)	0.91977 (8)	0.0145
C15	0.55982 (8)	−0.10064 (12)	0.85763 (10)	0.0239
C16	0.56055 (8)	0.64034 (12)	0.71362 (10)	0.0231
O17	0.60538 (4)	0.37378 (8)	0.93772 (6)	0.0152
C18	0.65446 (7)	0.39656 (12)	1.02414 (8)	0.0203
C19	0.66500 (8)	0.52464 (13)	1.03584 (10)	0.0267
C20	0.71259 (8)	0.55535 (15)	1.12794 (11)	0.0327
O21	0.60378 (5)	0.16480 (8)	0.69063 (6)	0.0160
C22	0.65246 (7)	0.13892 (11)	0.66358 (9)	0.0186
C23	0.64766 (7)	0.01154 (13)	0.64361 (10)	0.0246
C24	0.69974 (8)	−0.02954 (15)	0.61997 (11)	0.0314
Cl25	0.61811 (3)	−0.19788 (3)	0.93509 (3)	0.0381
Cl26	0.62004 (3)	0.73262 (3)	0.70485 (3)	0.0407
H11	0.5243	0.3212	1.0025	0.0157*
H12	0.4747	0.2162	0.9728	0.0143*
H31	0.5042	0.0438	0.9235	0.0150*
H51	0.6414	0.0427	0.8393	0.0158*
H72	0.7020	0.3210	0.9014	0.0138*
H71	0.6988	0.2163	0.8411	0.0144*
H91	0.6406	0.4933	0.8305	0.0136*
H111	0.5048	0.4966	0.5830	0.0128*
H151	0.5183	−0.1218	0.8522	0.0232*
H152	0.5596	−0.1137	0.8038	0.0233*
H162	0.5642	0.6536	0.7693	0.0219*
H161	0.5193	0.6646	0.6685	0.0223*
H181	0.6947	0.3556	1.0335	0.0207*
H182	0.6413	0.3680	1.0656	0.0205*
H192	0.6830	0.5531	0.9985	0.0289*
H191	0.6222	0.5628	1.0206	0.0279*
H201	0.7230	0.6366	1.1318	0.0433*
H203	0.7532	0.5123	1.1473	0.0441*
H202	0.6935	0.5370	1.1652	0.0450*
H221	0.6956	0.1595	0.7082	0.0178*
H222	0.6420	0.1815	0.6115	0.0173*
H231	0.6530	−0.0287	0.6945	0.0258*
H232	0.6051	−0.0045	0.5971	0.0253*
H242	0.6953	−0.1109	0.6068	0.0429*
H241	0.7421	−0.0116	0.6648	0.0429*
H243	0.6957	0.0125	0.5702	0.0441*

	U11	U22	U33	U12	U13	U23
C1	0.0182 (6)	0.0177 (5)	0.0144 (5)	0.0010 (4)	0.0086 (5)	0.0009 (4)
C2	0.0162 (6)	0.0154 (5)	0.0129 (5)	0.0013 (4)	0.0066 (5)	0.0018 (4)
C3	0.0173 (6)	0.0153 (5)	0.0169 (6)	−0.0003 (4)	0.0076 (5)	0.0026 (4)
C4	0.0192 (6)	0.0138 (5)	0.0165 (5)	0.0009 (4)	0.0070 (5)	0.0011 (4)
C5	0.0185 (6)	0.0150 (5)	0.0169 (6)	0.0029 (4)	0.0084 (5)	0.0017 (4)
C6	0.0135 (5)	0.0160 (5)	0.0134 (5)	0.0012 (4)	0.0051 (4)	0.0027 (4)
C7	0.0144 (5)	0.0181 (5)	0.0160 (5)	0.0007 (4)	0.0066 (5)	0.0021 (4)
C8	0.0133 (5)	0.0147 (5)	0.0167 (5)	−0.0002 (4)	0.0085 (5)	0.0012 (4)
C9	0.0172 (6)	0.0152 (5)	0.0170 (6)	−0.0020 (4)	0.0092 (5)	−0.0009 (4)
C10	0.0194 (6)	0.0130 (5)	0.0200 (6)	−0.0006 (4)	0.0119 (5)	0.0006 (4)
C11	0.0166 (6)	0.0147 (5)	0.0172 (6)	0.0008 (4)	0.0086 (5)	0.0026 (4)
C12	0.0160 (6)	0.0151 (5)	0.0147 (5)	−0.0010 (4)	0.0092 (5)	0.0003 (4)
C13	0.0148 (5)	0.0125 (5)	0.0167 (5)	−0.0002 (4)	0.0098 (5)	0.0008 (4)
C14	0.0155 (6)	0.0131 (5)	0.0128 (5)	0.0004 (4)	0.0047 (4)	0.0012 (4)
C15	0.0292 (7)	0.0166 (6)	0.0248 (7)	−0.0011 (5)	0.0117 (6)	−0.0009 (5)
C16	0.0308 (7)	0.0146 (6)	0.0267 (7)	0.0017 (5)	0.0156 (6)	0.0007 (5)
O17	0.0169 (4)	0.0129 (4)	0.0131 (4)	−0.0005 (3)	0.0046 (3)	0.0000 (3)
C18	0.0218 (6)	0.0190 (6)	0.0142 (6)	0.0007 (5)	0.0035 (5)	−0.0003 (4)
C19	0.0296 (8)	0.0202 (6)	0.0237 (7)	−0.0023 (5)	0.0068 (6)	−0.0047 (5)
C20	0.0261 (8)	0.0328 (8)	0.0306 (8)	−0.0005 (6)	0.0059 (6)	−0.0149 (6)
O21	0.0188 (4)	0.0126 (4)	0.0208 (4)	0.0013 (3)	0.0127 (4)	−0.0002 (3)
C22	0.0197 (6)	0.0185 (6)	0.0220 (6)	0.0025 (5)	0.0134 (5)	−0.0003 (5)
C23	0.0223 (7)	0.0215 (6)	0.0300 (7)	0.0024 (5)	0.0122 (6)	−0.0073 (5)
C24	0.0253 (7)	0.0352 (8)	0.0327 (8)	0.0104 (6)	0.0126 (6)	−0.0073 (6)
Cl25	0.0615 (3)	0.01859 (16)	0.02742 (19)	0.01114 (16)	0.01501 (19)	0.00475 (13)
Cl26	0.0690 (3)	0.02000 (17)	0.0518 (3)	−0.01600 (18)	0.0438 (3)	−0.00762 (16)

C1—C12i	1.5220 (17)	C14—O17	1.3837 (15)
C1—C2	1.5214 (18)	C15—Cl25	1.7998 (15)
C1—H11	0.973	C15—H151	0.950
C1—H12	0.998	C15—H152	0.958
C2—C3	1.3956 (17)	C16—Cl26	1.8037 (15)
C2—C14	1.3994 (17)	C16—H162	0.958
C3—C4	1.3927 (18)	C16—H161	0.957
C3—H31	0.962	O17—C18	1.4392 (15)
C4—C5	1.3940 (18)	C18—C19	1.503 (2)
C4—C15	1.4959 (19)	C18—H181	0.988
C5—C6	1.3922 (17)	C18—H182	0.970
C5—H51	0.967	C19—C20	1.521 (2)
C6—C7	1.5203 (18)	C19—H192	0.984
C6—C14	1.4018 (18)	C19—H191	1.000
C7—C8	1.5190 (17)	C20—H201	0.967
C7—H72	0.985	C20—H203	0.974
C7—H71	0.982	C20—H202	0.969
C8—C9	1.3933 (17)	O21—C22	1.4420 (16)
C8—C13	1.4016 (17)	C22—C23	1.5094 (19)
C9—C10	1.3938 (18)	C22—H221	0.971
C9—H91	0.927	C22—H222	0.969
C10—C11	1.3946 (18)	C23—C24	1.521 (2)
C10—C16	1.4929 (18)	C23—H231	0.966
C11—C12	1.3950 (17)	C23—H232	0.961
C11—H111	0.941	C24—H242	0.965
C12—C13	1.4024 (17)	C24—H241	0.952
C13—O21	1.3810 (14)	C24—H243	0.968
C12i—C1—C2	108.63 (10)	C4—C15—H151	110.3
C12i—C1—H11	109.8	Cl25—C15—H151	106.3
C2—C1—H11	110.8	C4—C15—H152	109.9
C12i—C1—H12	110.2	Cl25—C15—H152	108.1
C2—C1—H12	110.4	H151—C15—H152	108.5
H11—C1—H12	107.0	C10—C16—Cl26	112.72 (10)
C1—C2—C3	121.19 (11)	C10—C16—H162	108.1
C1—C2—C14	120.36 (11)	Cl26—C16—H162	106.6
C3—C2—C14	118.00 (12)	C10—C16—H161	111.8
C2—C3—C4	121.13 (12)	Cl26—C16—H161	105.1
C2—C3—H31	118.1	H162—C16—H161	112.5
C4—C3—H31	120.7	C14—O17—C18	112.95 (9)
C3—C4—C5	119.59 (12)	O17—C18—C19	108.92 (11)
C3—C4—C15	120.30 (12)	O17—C18—H181	107.9
C5—C4—C15	119.87 (12)	C19—C18—H181	111.8
C4—C5—C6	120.90 (12)	O17—C18—H182	111.4
C4—C5—H51	118.7	C19—C18—H182	108.7
C6—C5—H51	120.3	H181—C18—H182	108.1
C5—C6—C7	121.09 (12)	C18—C19—C20	111.62 (13)
C5—C6—C14	118.31 (12)	C18—C19—H192	109.3
C7—C6—C14	120.23 (11)	C20—C19—H192	108.3
C6—C7—C8	109.38 (10)	C18—C19—H191	108.8
C6—C7—H72	110.6	C20—C19—H191	108.6
C8—C7—H72	111.6	H192—C19—H191	110.1
C6—C7—H71	108.8	C19—C20—H201	109.7
C8—C7—H71	108.4	C19—C20—H203	110.9
H72—C7—H71	108.0	H201—C20—H203	107.8
C7—C8—C9	121.12 (11)	C19—C20—H202	109.9
C7—C8—C13	120.51 (11)	H201—C20—H202	110.0
C9—C8—C13	118.09 (11)	H203—C20—H202	108.5
C8—C9—C10	121.15 (12)	C13—O21—C22	113.71 (10)
C8—C9—H91	118.5	O21—C22—C23	107.23 (11)
C10—C9—H91	120.3	O21—C22—H221	110.3
C9—C10—C11	119.54 (11)	C23—C22—H221	111.5
C9—C10—C16	119.84 (12)	O21—C22—H222	108.5
C11—C10—C16	120.49 (12)	C23—C22—H222	108.5
C10—C11—C12	121.02 (12)	H221—C22—H222	110.7
C10—C11—H111	118.6	C22—C23—C24	112.83 (13)
C12—C11—H111	120.4	C22—C23—H231	106.9
C1i—C12—C11	121.15 (11)	C24—C23—H231	109.0
C1i—C12—C13	120.33 (11)	C22—C23—H232	108.9
C11—C12—C13	118.09 (11)	C24—C23—H232	109.3
C12—C13—C8	121.91 (11)	H231—C23—H232	109.8
C12—C13—O21	118.79 (11)	C23—C24—H242	111.2
C8—C13—O21	119.11 (11)	C23—C24—H241	110.1
C6—C14—C2	121.86 (11)	H242—C24—H241	111.5
C6—C14—O17	118.64 (11)	C23—C24—H243	109.5
C2—C14—O17	119.34 (11)	H242—C24—H243	108.6
C4—C15—Cl25	113.61 (10)	H241—C24—H243	105.7

D—H···A	D—H	H···A	D···A	D—H···A
C22—H222···Cl25ii	0.97	2.90	3.786 (1)	153
C23—H231···Cl26iii	0.97	2.90	3.557 (2)	127

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C22—H222⋯Cl25i	0.97	2.90	3.786 (1)	153
C23—H231⋯Cl26ii	0.97	2.90	3.557 (2)	127

Symmetry codes: (i) ; (ii) .