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The title compound, C44H52N4·C2H5OH, is a calix­[4]­pyrrole-type macrocycle acting as a receptor, by means of hydrogen-bond interactions to an ethanol solvent. The pyrrole groups are arranged in a 1,3-alternate conformation which gives rise to disorder in the ethanol guest, due to its ability to coordinate both above and below the plane of the macrocycle.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801002719/tk6005sup1.cif
Contains datablocks global, s92

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801002719/tk6005Isup2.hkl
Contains datablock I

CCDC reference: 159864

Key indicators

  • Single-crystal X-ray study
  • T = 150 K
  • Mean [sigma](C-C) = 0.027 Å
  • H-atom completeness 97%
  • Disorder in main residue
  • R factor = 0.088
  • wR factor = 0.267
  • Data-to-parameter ratio = 12.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry
Amber Alert Alert Level B:
SHFSU_01 Alert B The absolute value of parameter shift to su ratio > 0.10 Absolute value of the parameter shift to su ratio given 0.189 Additional refinement cycles may be required.
Yellow Alert Alert Level C:
RFACR_01 Alert C The value of the weighted R factor is > 0.25 Weighted R factor given 0.267 PLAT_301 Alert C Main Residue Disorder ........................ 4.00 Perc. PLAT_302 Alert C Anion/Solvent Disorder ....................... 38.00 Perc. PLAT_360 Alert C Short C(sp3)-C(sp3) Bond C5 - C7 = 1.40 Ang. General Notes
FORMU_01 There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:C46 H58 N4 O1 Atom count from the _atom_site data: C46 H56 N4 O1 CELLZ_01 From the CIF: _cell_formula_units_Z 4 From the CIF: _chemical_formula_sum C46 H58 N4 O TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff C 184.00 184.00 0.00 H 232.00 224.00 8.00 N 16.00 16.00 0.00 O 4.00 4.00 0.00 Difference between formula and atom_site contents detected. WARNING: H atoms missing from atom site list. Is this intentional?
0 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
4 Alert Level C = Please check

Comment top

There has been considerable interest over the past decade in the application of calix[4]pyrroles as anion and neutral substrate receptors (Sessler & Gale, 2000). A large number of pyrrolic macrocycles with a wide range of substituents have been shown to coordinate a variety of anions and neutral molecules via a combination of hydrogen-bonding and electrostatic interactions.

The structure of the title compound, (I) (Fig. 1), is the meso-octacyclopropyl derivative of calix[4]pyrrole, coordinated through hydrogen-bonding interactions (see Table 1) to an ethanol guest molecule. The symmetry of the macrocycle is approximately fourfold; however, due to the orientational flexibility of the cyclopropyl groups, it possesses crystallographic twofold symmetry. The geometry of the macrocyclic ring is in reasonable accordance with expected values and related structures (Sessler & Gale, 2000) in the Cambridge Structural Database (Allen et al., 1983). The macrocycle adopts a 1,3-alternate conformation such that adjacent pyrrole rings are orientated in opposite directions. This orientation is observed in the methyl analogue (Gale et al., 1996) and is presumably due to steric interactions within the macrocycle.

In these systems, the geometry of the macrocyclic backbone is of particular importance in determining receptor properties. The nitrogen–nitrogen cross-ring distances are 4.61 (3) and 4.57 (3) Å for N1···N1i and N2···N2i, respectively [symmetry code: (i) -x, y, 0.5 - z]. The meso-C atoms deviate from coplanarity, with an average r.m.s. deviation of 0.2541 (5) Å from their plane, with the dihedral angles between this plane and the pyrrole rings being 57.26 (5) and 56.63 (6)° for the N1 and N2 rings, respectively. The average angles about these meso-C atoms are 109.41 (2) and 109.45 (2)° for C1 and C12, respectively, indicating a strain-free macrocycle. The cavity formed by the meso-C atoms is 5.07 (5) Å in length and has a diagonal distance of 7.15 (4) Å. A comparison with the same geometric parameters of the methyl analogue (Gale et al., 1996), which has no guest molecule present, shows (I) to have a similar macrocyclic geometry, thus demonstrating that the interaction with the ethanol solvent has little effect on the backbone geometry. However, the pyrrole rings are significantly more angled into the cavity than in the methyl substituted case [average N···N = 4.83 (4) Å and average dihedral between pyrrole and meso-C atom plane = 71.5 (2)°], which is presumably due to the interactions with the ethanol guest molecule.

The ethanol guest molecule exhibits disorder, whereby a 50% occupied molecule hydrogen bonds through the alcohol group to a macrocycle above it with the remaining 50% associating via the same mechanism to a macrocycle below it (see Fig. 2). This disorder is assumed to be induced by the alternating orientation of the pyrrole rings in the macrocycle, whereby hydrogen bonding is possible both above and below the calix[4]pyrrole plane. This mode of interaction between guest and host produces a supramolecular assembly of one dimensional `columns'.

Experimental top

Dicyclopropyl ketone and pyrrole (1:1) were stirred in ethanol in the presence of methanesulfonic acid (catalytic quantity) for 24 h. The products were column chromatographed on silica-gel 60 with a chloroform eluent and (I) was then crystallized from ethanol.

Refinement top

The ethanol guest molecule exhibits disorder (see above), which produces unusual geometric parameters. The anisotropic displacement parameters were constrained to their isotropic equivalent through the use of the ISOR command. Attempts to restrain bond lengths resulted in an unstable refinement. Therefore, the geometry of the ethanol molecule was freely refined, which caused difficulty in convergence resulting in a high parameter shift to standard uncertainty ratio. The methyl H atoms of the ethanol molecule were not included as they refined very poorly, due to the nature of the disorder. An attempt was made to solve and refine the structure in the non-centrosymmetric equivalent space group Cc in order to resolve the disordered solvent problem. However, the ethanol molecule occupied two discrete positions and the refinement was problematic to correlation effects. Checks with the ADDSYM and NEWSYM modules of the PLATON package (Spek, 1990), in addition to intensity statistics, confirmed the centrosymmetric nature of the structure.

Computing details top

Cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); data reduction: DENZO, COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: CAMERON (Watkin et al., 1993) and PLATON (Spek, 1990).

Figures top
[Figure 1] Fig. 1. View of (I) (50% probability displacement ellipsoids).
[Figure 2] Fig. 2. The hydrogen-bonded host–guest assembly, with the cyclopropyl substituents omitted for clarity
(s92) top
Crystal data top
C44H52N4·C2H6OF(000) = 1472
Mr = 682.96Dx = 1.180 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 23.908 (5) ÅCell parameters from 26741 reflections
b = 7.6861 (15) Åθ = 3.1–26.4°
c = 22.947 (5) ŵ = 0.07 mm1
β = 114.31 (3)°T = 150 K
V = 3843.0 (13) Å3Plate, colourless
Z = 40.22 × 0.15 × 0.05 mm
Data collection top
Nonius KappaCCD area-detector
diffractometer
1983 reflections with I > 2σ(I)
ϕ and ω scans to fill Ewald sphereRint = 0.084
Absorption correction: multi-scan
(SORTAV; Blessing, 1997)
θmax = 25.3°, θmin = 3.1°
Tmin = 0.984, Tmax = 0.997h = 2828
25105 measured reflectionsk = 99
3463 independent reflectionsl = 2726
Refinement top
Refinement on F236 restraints
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.088 w = 1/[σ2(Fo2) + (0.1P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.267(Δ/σ)max = 0.189
S = 1.58Δρmax = 0.57 e Å3
3463 reflectionsΔρmin = 0.37 e Å3
269 parameters
Crystal data top
C44H52N4·C2H6OV = 3843.0 (13) Å3
Mr = 682.96Z = 4
Monoclinic, C2/cMo Kα radiation
a = 23.908 (5) ŵ = 0.07 mm1
b = 7.6861 (15) ÅT = 150 K
c = 22.947 (5) Å0.22 × 0.15 × 0.05 mm
β = 114.31 (3)°
Data collection top
Nonius KappaCCD area-detector
diffractometer
3463 independent reflections
Absorption correction: multi-scan
(SORTAV; Blessing, 1997)
1983 reflections with I > 2σ(I)
Tmin = 0.984, Tmax = 0.997Rint = 0.084
25105 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.08836 restraints
wR(F2) = 0.267H-atom parameters constrained
S = 1.58(Δ/σ)max = 0.189
3463 reflectionsΔρmax = 0.57 e Å3
269 parametersΔρmin = 0.37 e Å3
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
N10.1041 (5)0.0915 (15)0.2239 (5)0.056 (3)
H10.08210.00460.23280.067*
N20.0200 (5)0.1262 (16)0.3564 (5)0.058 (4)
H20.01960.22070.33460.07*
C10.1348 (6)0.082 (2)0.1034 (7)0.071 (5)
C20.1628 (8)0.217 (3)0.0479 (7)0.094 (7)
H2A0.20590.24970.03920.113*
C30.1274 (9)0.363 (4)0.0347 (9)0.119 (9)
H3A0.14820.47710.02150.142*
H3B0.08260.36950.06090.142*
C40.1511 (10)0.215 (4)0.0096 (9)0.140 (11)
H4A0.18630.23740.0510.168*
H4B0.1210.130.01170.168*
C50.1773 (9)0.069 (3)0.0794 (11)0.106 (7)
H50.18370.10740.03550.127*
C60.2334 (9)0.095 (3)0.0945 (11)0.116 (8)
H6A0.240.01270.12410.139*
H6B0.27120.14350.06050.139*
C70.1791 (10)0.204 (3)0.1193 (11)0.114 (8)
H7A0.15210.19410.16540.137*
H7B0.1830.32410.10220.137*
C80.1336 (6)0.162 (2)0.1630 (6)0.057 (4)
C90.1622 (7)0.308 (2)0.1705 (7)0.074 (5)
H90.18620.38470.13730.089*
C100.1505 (7)0.325 (2)0.2346 (7)0.071 (5)
H100.16570.4160.25220.085*
C110.1139 (6)0.1923 (19)0.2682 (6)0.054 (4)
C120.0917 (7)0.148 (2)0.3378 (6)0.060 (4)
C130.1372 (7)0.032 (2)0.3503 (7)0.073 (5)
H130.12460.00410.39660.088*
C140.2048 (8)0.050 (3)0.3138 (10)0.107 (7)
H14A0.23090.04010.33780.129*
H14B0.21980.13310.27770.129*
C150.1729 (8)0.108 (3)0.3070 (10)0.099 (7)
H15A0.17930.21710.32660.119*
H15B0.16820.12430.26650.119*
C160.0855 (13)0.321 (3)0.3753 (8)0.113 (9)
H160.12870.36130.36280.135*
C170.0571 (11)0.339 (3)0.4431 (8)0.123 (9)
H17A0.02160.2640.46780.148*
H17B0.08270.37610.46560.148*
C180.0528 (16)0.463 (5)0.3901 (15)0.077 (11)0.5
H18A0.07470.57550.38220.093*0.5
H18B0.01390.46390.38440.093*0.5
C18'0.116 (2)0.407 (8)0.400 (2)0.148 (18)0.5
C190.0307 (6)0.059 (2)0.3623 (7)0.064 (5)
C200.0104 (8)0.086 (3)0.3990 (10)0.113 (7)
H200.03490.16120.41160.136*
C210.0520 (9)0.105 (3)0.4151 (10)0.120 (7)
H210.07720.19640.44040.144*
C220.0710 (7)0.028 (2)0.3887 (7)0.076 (5)
O0100.386 (3)0.250.066 (4)0.5
H010.03630.34920.26470.099*0.25
C0100.539 (14)0.250.225 (5)0.5
H01A0.02520.55430.20370.271*0.25
H01B0.04260.55440.25410.271*0.25
C020.007 (7)0.318 (14)0.266 (7)0.177 (5)0.25
H02A0.03310.32290.28940.265*0.25
H02B0.02580.2440.22840.265*0.25
H02C0.03340.26980.29420.265*0.25
O0200.174 (6)0.250.129 (5)0.5
H020.00270.17320.21230.194*0.25
C01'00.535 (17)0.250.220 (5)0.5
H01C0.00880.45360.22210.329*0.25
H01D0.04170.51550.24660.329*0.25
H01E0.02940.51730.29440.329*0.25
C02'0.004 (11)0.320 (18)0.266 (9)0.192 (5)0.25
H02D0.02460.32010.31140.23*0.25
H02E0.04560.32010.2660.23*0.25
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.041 (6)0.062 (7)0.058 (6)0.003 (5)0.014 (5)0.001 (5)
N20.041 (6)0.080 (8)0.048 (6)0.006 (6)0.014 (5)0.018 (5)
C10.035 (8)0.109 (11)0.063 (8)0.006 (8)0.015 (6)0.028 (8)
C20.046 (9)0.184 (18)0.040 (8)0.018 (11)0.005 (7)0.010 (10)
C30.071 (12)0.22 (2)0.065 (10)0.010 (14)0.026 (9)0.042 (13)
C40.084 (13)0.28 (3)0.050 (10)0.038 (18)0.019 (9)0.016 (15)
C50.076 (12)0.128 (16)0.112 (14)0.017 (12)0.036 (10)0.024 (12)
C60.047 (11)0.159 (19)0.133 (17)0.017 (12)0.028 (11)0.028 (14)
C70.105 (15)0.117 (15)0.114 (15)0.003 (13)0.039 (12)0.017 (13)
C80.034 (7)0.091 (10)0.043 (7)0.006 (7)0.011 (5)0.001 (7)
C90.066 (9)0.104 (11)0.051 (8)0.034 (9)0.024 (7)0.018 (8)
C100.072 (9)0.094 (10)0.052 (7)0.037 (8)0.031 (6)0.008 (7)
C110.042 (7)0.073 (9)0.049 (7)0.000 (7)0.021 (6)0.000 (7)
C120.048 (8)0.083 (10)0.048 (7)0.007 (7)0.020 (6)0.006 (7)
C130.044 (8)0.119 (13)0.059 (8)0.011 (8)0.024 (6)0.011 (9)
C140.049 (9)0.18 (2)0.100 (12)0.002 (12)0.039 (8)0.027 (13)
C150.083 (11)0.127 (15)0.097 (11)0.041 (11)0.048 (9)0.001 (11)
C160.16 (2)0.111 (15)0.053 (10)0.001 (14)0.025 (11)0.007 (10)
C170.116 (15)0.20 (2)0.057 (10)0.001 (16)0.043 (10)0.029 (12)
C180.07 (2)0.08 (2)0.08 (2)0.004 (17)0.022 (16)0.019 (17)
C18'0.12 (3)0.24 (5)0.13 (2)0.02 (3)0.09 (2)0.09 (3)
C190.040 (8)0.090 (10)0.059 (8)0.008 (7)0.017 (6)0.027 (7)
C200.056 (10)0.145 (14)0.136 (13)0.005 (11)0.038 (9)0.089 (11)
C210.056 (10)0.158 (14)0.140 (13)0.015 (11)0.035 (9)0.107 (11)
C220.042 (8)0.113 (12)0.065 (8)0.006 (9)0.015 (7)0.037 (9)
O010.081 (6)0.053 (6)0.065 (6)00.031 (4)0
C010.327 (6)0.123 (7)0.300 (7)00.204 (4)0
C020.294 (6)0.093 (7)0.193 (7)0.003 (5)0.149 (4)0.000 (5)
O020.122 (6)0.104 (6)0.147 (7)00.041 (4)0
C01'0.319 (6)0.136 (7)0.296 (7)00.219 (4)0
C02'0.319 (6)0.106 (7)0.190 (7)0.002 (5)0.146 (4)0.000 (5)
Geometric parameters (Å, º) top
N1—C111.374 (19)C12—C161.56 (3)
N1—C81.391 (17)C13—C151.47 (2)
N2—C221.365 (19)C13—C141.49 (2)
N2—C191.374 (19)C14—C151.48 (3)
C1—C51.49 (3)C16—C18'1.28 (5)
C1—C81.49 (2)C16—C181.30 (4)
C1—C22i1.52 (2)C16—C171.42 (3)
C1—C21.56 (2)C17—C18'1.44 (5)
C2—C41.46 (3)C17—C181.58 (4)
C2—C31.51 (3)C19—C201.36 (2)
C3—C41.48 (3)C20—C211.39 (3)
C5—C71.40 (3)C21—C221.36 (3)
C5—C61.53 (3)C22—C1i1.52 (2)
C6—C71.45 (3)O01—C011.18 (11)
C8—C91.36 (2)C01—C02ii1.19 (15)
C9—C101.39 (2)C02—C01iii1.19 (15)
C10—C111.36 (2)O02—C02'1.20 (15)
C11—C121.501 (19)C01'—C02'iv1.19 (18)
C12—C191.49 (2)C02'—C01'iii1.19 (18)
C12—C131.52 (2)
C11—N1—C8110.7 (11)C19—C12—C16109.1 (14)
C22—N2—C19111.4 (13)C11—C12—C16107.8 (13)
C5—C1—C8114.4 (16)C13—C12—C16108.1 (16)
C5—C1—C22i109.4 (15)C15—C13—C1459.8 (13)
C8—C1—C22i111.4 (11)C15—C13—C12124.2 (15)
C5—C1—C2102.5 (14)C14—C13—C12122.1 (15)
C8—C1—C2108.3 (14)C15—C14—C1359.6 (12)
C22i—C1—C2110.5 (15)C13—C15—C1460.6 (13)
C4—C2—C359.6 (16)C18'—C16—C1881 (3)
C4—C2—C1123.8 (19)C18'—C16—C1764 (2)
C3—C2—C1124.8 (14)C18—C16—C1771 (2)
C4—C3—C258.4 (15)C18'—C16—C12138 (3)
C2—C4—C362.0 (15)C18—C16—C12140 (3)
C7—C5—C1122.5 (18)C17—C16—C12125.5 (19)
C7—C5—C659.2 (16)C16—C17—C18'53 (2)
C1—C5—C6123.3 (19)C16—C17—C1851.0 (16)
C7—C6—C555.9 (15)C18'—C17—C1867 (3)
C5—C7—C664.9 (16)C16—C18—C1758.3 (19)
C9—C8—N1105.5 (12)C16—C18'—C1763 (3)
C9—C8—C1129.6 (13)C20—C19—N2105.3 (14)
N1—C8—C1124.8 (13)C20—C19—C12130.7 (15)
C8—C9—C10108.9 (13)N2—C19—C12123.7 (13)
C11—C10—C9109.3 (14)C19—C20—C21108.9 (16)
C10—C11—N1105.6 (12)C22—C21—C20108.6 (16)
C10—C11—C12129.6 (14)C21—C22—N2105.7 (15)
N1—C11—C12124.5 (13)C21—C22—C1i131.0 (15)
C19—C12—C11111.5 (13)N2—C22—C1i122.8 (14)
C19—C12—C13108.8 (13)O01—C01—C02ii157 (9)
C11—C12—C13111.4 (11)C01'iii—C02'—O02139 (10)
Symmetry codes: (i) x, y, z+1/2; (ii) x, y+1, z; (iii) x, y1, z; (iv) x, y+1, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O020.882.253.08 (3)157
N2—H2···O010.882.23.03 (2)158
O01—H01···N1i0.842.53.23 (2)145
Symmetry code: (i) x, y, z+1/2.

Experimental details

Crystal data
Chemical formulaC44H52N4·C2H6O
Mr682.96
Crystal system, space groupMonoclinic, C2/c
Temperature (K)150
a, b, c (Å)23.908 (5), 7.6861 (15), 22.947 (5)
β (°) 114.31 (3)
V3)3843.0 (13)
Z4
Radiation typeMo Kα
µ (mm1)0.07
Crystal size (mm)0.22 × 0.15 × 0.05
Data collection
DiffractometerNonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SORTAV; Blessing, 1997)
Tmin, Tmax0.984, 0.997
No. of measured, independent and
observed [I > 2σ(I)] reflections
25105, 3463, 1983
Rint0.084
(sin θ/λ)max1)0.600
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.088, 0.267, 1.58
No. of reflections3463
No. of parameters269
No. of restraints36
H-atom treatmentH-atom parameters constrained
(Δ/σ)max0.189
Δρmax, Δρmin (e Å3)0.57, 0.37

Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), DENZO, COLLECT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), CAMERON (Watkin et al., 1993) and PLATON (Spek, 1990).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O020.882.253.08 (3)157
N2—H2···O010.882.23.03 (2)158
O01—H01···N1i0.842.53.23 (2)145
Symmetry code: (i) x, y, z+1/2.
 

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