Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
The title compound, C48H60O8·3C3H7NO, is a derivative of calix­[4]­arene in the cone conformation, modified with distal carboxylic acid functional groups at the lower rim. A clathrate di­methyl­form­amide (DMF) mol­ecule is located within the calix­[4]­arene cone, and two DMF solvate mol­ecules participate in hydrogen bonding with the carboxylic acid groups. Intramolecular hydrogen bonds are also formed between the OH groups and the adjacent ether groups in the partially substituted calix­[4]­arene.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010401323X/hj1009sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010401323X/hj1009Isup2.hkl
Contains datablock I

CCDC reference: 245931

Comment top

Calixarenes have macrocyclic structural frameworks that are known to exist in a variety of conformations, and well developed synthetic procedures are available for functionaliztion at the upper or lower rim. Modification of the basic framework has led to applications in catalysis, ionic and molecular separations, sensors, scaffolds for supramolecular arrays, ligands for metal binding, and in host–guest interactions (Gutsche, 1998). Calixarenes functionalized with carboxylic acid groups have been shown to be active towards extraction of heavy metals (Dung & Ludwig, 1999), as well as to display complexation properties toward alkali and alkali earth metal cations (McKervey et al., 1996), and lanthanide cations (Arnaud-Neu et al., 1997).

This report describes the crystal structure of the title compound, (I), initially prepared by Ungaro & Pochini (1984) and subsequently by Collins et al. (1991), but of which the structure has not been reported previously. \sch

Compound (I) is a calix[4]arene in the cone conformation which has been functionalized at the lower rim with distal carboxylic acid groups. Intramolecular hydrogen bonding between the phenols and the O atoms of adjacent ether groups on the lower rim stabilize the cone conformation. Carboxylic acids tend to crystallize as like-like acid pairs that make up a common synthon in crystal engineering (Frankenbach & Etter, 1992). It is rare to obtain unlike acid pairs, although they can occur when the balance of shapes and intermolecular van der Waals forces is suitable, such as with the facial amphiphile Kemp's triacid (Childs & Hagen, 2002). A number of crystallizations from different solvent systems, including ones with potential carboxylic acid co-crystals, resulted in the formation of very fine needles. It was only from DMF/H2O (Ratio?) that we were able to grow sufficiently large needles for this study, which have a DMF clathrate molecule inside the cone of the calix[4]arene. It is common for calixarenes to host solvent molecules inside the cone, although only one other example of a DMF clathrate has been reported (Froidevaux et al., 2000). In both cases, the DMF molecule adopts a `methyl in, carbonyl out' orientation.

The calixarenes in (I) crystallize in a face-to-face pattern with the acid groups directed towards, but not interacting directly with inversion-related pairs. Instead, the other two DMF solvate molecules participate in intermolecular hydrogen bonding with the carboxylic acid groups on the lower rim of the calix[4]arene. However, each of the carboxylic acid groups of the diacid interacts differently with a DMF molecule. In one carboxylic acid group, the OH is hydrogen-bonded to the carbonyl atom O9 of a DMF molecule [D···A 2.582 (2) Å], and atom O5 of the carboxylic acid forms a hydrogen bond to the carbonyl C—H atom of the DMF molecule [D···A 2.690 (2) Å].

There are only a few cases of DMF-carboxylic acid inclusion compounds in which the formyl group of the DMF is involved in (C)H···O-type weak hydrogen-bonding interactions in addition to traditional (O)H···O-type hydrogen bonding, resulting in cyclic hydrogen-bonded pairs (Desiraju & Steiner, 1999). This cyclic group is decidedly non-planar in (I), with an angle of 128° between the planes of the carboxylic acid and amide.

The other carboxylic acid group has only one hydrogen bond between the carboxylic acid OH and the carbonyl atom O11 of the DMF molecule [D···A 2.578 (2) Å]. Instead of being positioned toward the O atom of the carboxylic acid, the carbonyl C—H is oriented towards atom O4 of a neighboring molecule in the lattice [D···A 3.19 Å]. The net balance of all intermolecular forces results in close interactions between acid atom O7 and O8, and C atoms of neighboring calixarenes (O7···C47A 3.07, O7···C48A 2.93 and O8···C45A 3.40 Å).

Experimental top

Compound (I) was prepared as described by Collins et al. (1991) and was recrystallized from DMF/H2O (Ratio?).

Refinement top

H atoms were placed in geometric positions, with O—H distances of 0.84 Å and C—H distances in the range 0.95–0.99 Å, and refined using a riding model, with Uiso(H) = 1.2Ueq(C,O). Please check added text.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1]
[Figure 2]
Fig. 1. A view of the structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and intra- and intermolecular hydrogen bonds are shown as dotted lines. H atoms have been omitted for clarity, except for those involved in hydrogen bonding.
(5,11,17,23-Tetra-tert-butyl-26,28-dihydroxycalix[4]arene-25,27-dioxy)diacetic acid N,N-dimethylformamide trisolvate top
Crystal data top
C48H60O8·3C3H7NOF(000) = 2128
Mr = 984.25Dx = 1.200 Mg m3
Monoclinic, P21/cCu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybcCell parameters from 7352 reflections
a = 11.3624 (3) Åθ = 5.0–131.9°
b = 35.224 (1) ŵ = 0.66 mm1
c = 13.7180 (4) ÅT = 100 K
β = 96.991 (2)°Needle, colorless
V = 5449.6 (3) Å30.30 × 0.11 × 0.07 mm
Z = 4
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer
9142 independent reflections
Radiation source: fine-focus sealed tube6845 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.056
ω scansθmax = 66.2°, θmin = 2.5°
Absorption correction: integration
face-indexing of crystal Reference
h = 1213
Tmin = 0.862, Tmax = 0.961k = 4141
25773 measured reflectionsl = 1516
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.127H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0712P)2]
where P = (Fo2 + 2Fc2)/3
9142 reflections(Δ/σ)max = 0.012
662 parametersΔρmax = 0.25 e Å3
0 restraintsΔρmin = 0.28 e Å3
Crystal data top
C48H60O8·3C3H7NOV = 5449.6 (3) Å3
Mr = 984.25Z = 4
Monoclinic, P21/cCu Kα radiation
a = 11.3624 (3) ŵ = 0.66 mm1
b = 35.224 (1) ÅT = 100 K
c = 13.7180 (4) Å0.30 × 0.11 × 0.07 mm
β = 96.991 (2)°
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer
9142 independent reflections
Absorption correction: integration
face-indexing of crystal Reference
6845 reflections with I > 2σ(I)
Tmin = 0.862, Tmax = 0.961Rint = 0.056
25773 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0440 restraints
wR(F2) = 0.127H-atom parameters constrained
S = 1.07Δρmax = 0.25 e Å3
9142 reflectionsΔρmin = 0.28 e Å3
662 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.

Full matrix refinement of F2 against all reflections until complete convergence was attained.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.31598 (10)0.12410 (3)0.94587 (9)0.0178 (3)
O20.34102 (11)0.06257 (4)0.82534 (9)0.0245 (3)
H20.31830.08050.85870.029*
O30.59093 (11)0.03554 (3)0.89186 (9)0.0233 (3)
O40.56290 (11)0.10848 (3)0.96288 (10)0.0229 (3)
H40.58480.08710.94490.027*
O50.10168 (12)0.09340 (4)0.98019 (10)0.0289 (3)
O60.10918 (12)0.12491 (4)1.12268 (10)0.0284 (3)
H60.04800.11231.12930.034*
O70.70029 (14)0.05300 (4)0.86587 (12)0.0405 (4)
O80.50933 (13)0.04164 (4)0.88456 (11)0.0357 (4)
H80.49730.06200.85300.043*
C10.24570 (15)0.15702 (5)0.79782 (13)0.0172 (4)
C20.16915 (15)0.12320 (5)0.76170 (13)0.0189 (4)
H2A0.09300.13250.72720.023*
H2B0.15150.10800.81880.023*
C30.22973 (15)0.09805 (5)0.69245 (13)0.0189 (4)
C40.20678 (16)0.10365 (5)0.59103 (13)0.0214 (4)
H4A0.15260.12300.56730.026*
C50.25977 (16)0.08206 (6)0.52325 (14)0.0241 (4)
C60.33886 (16)0.05401 (6)0.56190 (14)0.0246 (4)
H6A0.37480.03830.51760.030*
C70.36754 (16)0.04798 (5)0.66177 (14)0.0210 (4)
C80.46173 (16)0.01909 (5)0.69972 (15)0.0241 (4)
H8A0.46200.00200.65210.029*
H8B0.44290.00840.76280.029*
C90.58372 (16)0.03755 (5)0.71473 (15)0.0226 (4)
C100.63838 (16)0.04808 (5)0.63327 (15)0.0249 (4)
H100.60110.04140.56980.030*
C110.74489 (17)0.06790 (6)0.64050 (15)0.0256 (4)
C120.79476 (16)0.07819 (5)0.73512 (15)0.0238 (4)
H120.86620.09250.74230.029*
C130.74451 (16)0.06844 (5)0.81873 (14)0.0211 (4)
C140.79754 (16)0.08400 (5)0.91776 (14)0.0214 (4)
H14A0.88500.08200.92330.026*
H14B0.77020.06840.97060.026*
C150.76307 (15)0.12517 (5)0.93182 (13)0.0189 (4)
C160.84545 (16)0.15416 (5)0.92653 (13)0.0198 (4)
H160.92250.14770.91180.024*
C170.81946 (15)0.19216 (5)0.94192 (13)0.0182 (4)
C180.70517 (15)0.20050 (5)0.96389 (13)0.0178 (4)
H180.68490.22620.97470.021*
C190.62031 (15)0.17253 (5)0.97038 (13)0.0169 (4)
C200.49912 (15)0.18234 (5)0.99909 (13)0.0169 (4)
H20A0.50400.20711.03360.020*
H20B0.47640.16291.04550.020*
C210.40318 (15)0.18457 (5)0.91173 (13)0.0159 (4)
C220.39801 (15)0.21723 (5)0.85309 (13)0.0182 (4)
H220.45180.23740.87110.022*
C230.31639 (15)0.22103 (5)0.76922 (13)0.0185 (4)
C240.24388 (15)0.18981 (5)0.74201 (13)0.0187 (4)
H240.19120.19110.68280.022*
C250.32193 (15)0.15580 (5)0.88565 (13)0.0165 (4)
C260.64955 (15)0.13468 (5)0.95281 (13)0.0179 (4)
C270.64114 (16)0.04650 (5)0.80746 (14)0.0210 (4)
C280.31214 (15)0.07023 (5)0.72758 (14)0.0203 (4)
C290.30050 (16)0.25810 (5)0.71075 (14)0.0226 (4)
C300.29568 (17)0.24998 (6)0.59996 (14)0.0274 (5)
H30A0.28460.27390.56330.041*
H30B0.22930.23290.57930.041*
H30C0.37010.23800.58680.041*
C310.40149 (19)0.28580 (6)0.74001 (16)0.0325 (5)
H31A0.40520.29160.81020.049*
H31B0.38770.30930.70190.049*
H31C0.47660.27440.72670.049*
C320.18311 (19)0.27648 (6)0.73175 (16)0.0350 (5)
H32A0.18620.28150.80230.053*
H32B0.11720.25920.71100.053*
H32C0.17130.30040.69530.053*
C330.91014 (16)0.22424 (5)0.93626 (14)0.0224 (4)
C340.8755 (2)0.24774 (7)0.84402 (19)0.0500 (7)
H34A0.93320.26820.84060.075*
H34B0.79650.25870.84620.075*
H34C0.87440.23150.78600.075*
C350.9123 (2)0.25015 (7)1.0259 (2)0.0532 (7)
H35A0.93140.23511.08590.080*
H35B0.83440.26201.02630.080*
H35C0.97250.26991.02290.080*
C361.03490 (17)0.20917 (6)0.93302 (17)0.0336 (5)
H36A1.03650.19340.87440.050*
H36B1.05880.19390.99180.050*
H36C1.08990.23050.93080.050*
C370.80728 (18)0.07844 (6)0.55114 (15)0.0307 (5)
C380.84109 (19)0.12065 (6)0.55457 (16)0.0343 (5)
H38A0.88060.12700.49700.051*
H38B0.89490.12580.61450.051*
H38C0.76940.13610.55440.051*
C390.7291 (2)0.07112 (8)0.45466 (16)0.0495 (7)
H39A0.65310.08420.45530.074*
H39B0.71510.04380.44660.074*
H39C0.76870.08060.40000.074*
C400.9205 (2)0.05453 (7)0.55418 (19)0.0445 (6)
H40A0.89950.02760.54980.067*
H40B0.97140.05930.61590.067*
H40C0.96300.06150.49880.067*
C410.23573 (18)0.08807 (6)0.41193 (14)0.0297 (5)
C420.18277 (19)0.05193 (6)0.36245 (15)0.0357 (5)
H42A0.10640.04650.38590.054*
H42B0.23710.03060.37870.054*
H42C0.17090.05560.29110.054*
C430.1498 (2)0.12097 (7)0.38517 (16)0.0458 (6)
H43A0.13760.12410.31370.069*
H43B0.18320.14440.41560.069*
H43C0.07380.11550.40910.069*
C440.3528 (2)0.09693 (8)0.37082 (16)0.0441 (6)
H44A0.33750.10020.29940.066*
H44B0.40860.07590.38610.066*
H44C0.38700.12030.40070.066*
C450.65036 (18)0.00402 (5)0.94496 (15)0.0288 (5)
H45A0.62510.00281.01150.035*
H45B0.73700.00850.95250.035*
C460.62358 (18)0.03334 (6)0.89346 (15)0.0282 (5)
C470.27178 (16)0.13161 (5)1.03710 (13)0.0201 (4)
H47A0.26670.15941.04640.024*
H47B0.32810.12131.09150.024*
C480.15161 (16)0.11430 (5)1.04161 (14)0.0211 (4)
O90.06440 (13)0.08202 (4)1.15967 (11)0.0348 (4)
O100.57827 (13)0.21186 (4)0.49546 (10)0.0376 (4)
O110.44046 (14)0.10180 (4)0.78636 (11)0.0404 (4)
N10.08627 (15)0.01792 (5)1.17031 (13)0.0294 (4)
N20.56878 (13)0.17466 (4)0.63073 (12)0.0240 (4)
N30.29204 (15)0.14556 (5)0.76332 (12)0.0294 (4)
C490.03327 (18)0.04883 (6)1.14392 (16)0.0309 (5)
H490.03420.04561.11010.037*
C500.1865 (2)0.02034 (7)1.2258 (2)0.0554 (7)
H50A0.20000.04691.24240.083*
H50B0.17020.00551.28630.083*
H50C0.25730.01031.18630.083*
C510.0476 (3)0.01966 (7)1.1479 (2)0.0660 (9)
H51A0.01790.01791.10770.099*
H51B0.11360.03361.11160.099*
H51C0.02060.03311.20910.099*
C520.53787 (18)0.18500 (6)0.53816 (16)0.0296 (5)
H520.47860.17020.50110.036*
C530.51504 (18)0.14287 (6)0.67597 (16)0.0313 (5)
H53A0.45730.13050.62730.047*
H53B0.47490.15200.73070.047*
H53C0.57670.12460.70050.047*
C540.65705 (19)0.19631 (7)0.69364 (16)0.0397 (6)
H54A0.68780.21680.65550.060*
H54B0.72230.17950.71930.060*
H54C0.62050.20720.74840.060*
C550.34690 (19)0.11609 (6)0.80825 (15)0.0308 (5)
H550.31230.10500.86110.037*
C560.3373 (2)0.16370 (7)0.68058 (16)0.0390 (6)
H56A0.40700.14980.66420.058*
H56B0.27580.16360.62390.058*
H56C0.35950.19000.69780.058*
C570.18544 (19)0.16116 (7)0.79615 (16)0.0365 (5)
H57A0.16530.14670.85280.055*
H57B0.19910.18780.81500.055*
H57C0.11990.15960.74280.055*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0180 (7)0.0161 (6)0.0200 (7)0.0006 (5)0.0053 (5)0.0024 (5)
O20.0273 (7)0.0230 (7)0.0228 (7)0.0045 (6)0.0014 (6)0.0013 (6)
O30.0223 (7)0.0185 (7)0.0298 (8)0.0011 (6)0.0059 (5)0.0007 (6)
O40.0183 (7)0.0152 (6)0.0356 (8)0.0017 (5)0.0055 (5)0.0029 (6)
O50.0250 (8)0.0349 (8)0.0275 (8)0.0104 (6)0.0057 (6)0.0041 (7)
O60.0268 (8)0.0313 (8)0.0296 (8)0.0086 (6)0.0134 (6)0.0038 (7)
O70.0413 (9)0.0309 (8)0.0507 (10)0.0079 (7)0.0118 (8)0.0050 (7)
O80.0347 (9)0.0268 (8)0.0456 (10)0.0047 (7)0.0047 (7)0.0066 (7)
C10.0114 (9)0.0202 (10)0.0210 (10)0.0015 (7)0.0065 (7)0.0014 (8)
C20.0133 (9)0.0221 (10)0.0211 (10)0.0012 (8)0.0019 (7)0.0012 (8)
C30.0136 (9)0.0203 (9)0.0230 (10)0.0063 (8)0.0030 (7)0.0017 (8)
C40.0171 (10)0.0235 (10)0.0234 (10)0.0043 (8)0.0013 (7)0.0009 (9)
C50.0201 (10)0.0299 (11)0.0227 (11)0.0094 (8)0.0038 (8)0.0048 (9)
C60.0184 (10)0.0265 (11)0.0301 (11)0.0056 (8)0.0074 (8)0.0092 (9)
C70.0145 (9)0.0205 (10)0.0281 (11)0.0055 (8)0.0028 (7)0.0024 (9)
C80.0184 (10)0.0205 (10)0.0337 (11)0.0032 (8)0.0050 (8)0.0062 (9)
C90.0171 (10)0.0159 (9)0.0353 (12)0.0002 (8)0.0058 (8)0.0056 (9)
C100.0201 (10)0.0240 (10)0.0301 (11)0.0006 (8)0.0009 (8)0.0074 (9)
C110.0187 (10)0.0252 (10)0.0336 (12)0.0007 (8)0.0069 (8)0.0054 (9)
C120.0149 (9)0.0206 (10)0.0357 (12)0.0007 (8)0.0029 (8)0.0058 (9)
C130.0167 (10)0.0156 (9)0.0310 (11)0.0035 (7)0.0031 (8)0.0016 (8)
C140.0144 (9)0.0184 (9)0.0309 (11)0.0006 (8)0.0013 (8)0.0019 (8)
C150.0169 (9)0.0193 (9)0.0200 (10)0.0027 (8)0.0003 (7)0.0012 (8)
C160.0134 (9)0.0219 (10)0.0243 (10)0.0009 (8)0.0031 (7)0.0006 (8)
C170.0150 (9)0.0196 (9)0.0197 (10)0.0011 (8)0.0010 (7)0.0005 (8)
C180.0165 (9)0.0156 (9)0.0208 (10)0.0016 (7)0.0008 (7)0.0007 (8)
C190.0139 (9)0.0187 (9)0.0178 (10)0.0006 (7)0.0006 (7)0.0003 (8)
C200.0147 (9)0.0168 (9)0.0194 (10)0.0001 (7)0.0033 (7)0.0007 (8)
C210.0120 (9)0.0177 (9)0.0189 (10)0.0024 (7)0.0059 (7)0.0017 (8)
C220.0151 (9)0.0181 (9)0.0222 (10)0.0020 (8)0.0061 (7)0.0012 (8)
C230.0170 (9)0.0192 (9)0.0203 (10)0.0023 (8)0.0063 (7)0.0013 (8)
C240.0151 (9)0.0226 (10)0.0183 (10)0.0012 (8)0.0018 (7)0.0011 (8)
C250.0138 (9)0.0158 (9)0.0210 (10)0.0017 (7)0.0064 (7)0.0014 (8)
C260.0138 (9)0.0193 (9)0.0202 (10)0.0021 (7)0.0005 (7)0.0004 (8)
C270.0173 (10)0.0150 (9)0.0309 (11)0.0036 (7)0.0041 (8)0.0024 (8)
C280.0156 (9)0.0191 (10)0.0261 (11)0.0056 (8)0.0027 (7)0.0010 (8)
C290.0234 (10)0.0195 (10)0.0251 (11)0.0006 (8)0.0037 (8)0.0053 (8)
C300.0278 (11)0.0277 (11)0.0265 (11)0.0014 (9)0.0021 (8)0.0070 (9)
C310.0410 (13)0.0245 (11)0.0307 (12)0.0072 (10)0.0010 (9)0.0079 (10)
C320.0382 (13)0.0273 (11)0.0420 (13)0.0114 (10)0.0149 (10)0.0110 (10)
C330.0158 (9)0.0193 (10)0.0325 (11)0.0028 (8)0.0044 (8)0.0016 (9)
C340.0294 (13)0.0432 (14)0.0735 (18)0.0150 (11)0.0091 (12)0.0303 (13)
C350.0367 (14)0.0505 (16)0.0766 (19)0.0250 (12)0.0247 (13)0.0334 (14)
C360.0184 (11)0.0277 (11)0.0556 (15)0.0039 (9)0.0085 (9)0.0016 (11)
C370.0232 (11)0.0369 (12)0.0334 (12)0.0056 (9)0.0088 (9)0.0054 (10)
C380.0291 (12)0.0412 (13)0.0333 (12)0.0011 (10)0.0065 (9)0.0033 (11)
C390.0484 (15)0.0701 (18)0.0319 (13)0.0218 (13)0.0135 (11)0.0090 (13)
C400.0367 (14)0.0433 (14)0.0591 (16)0.0010 (11)0.0284 (12)0.0028 (12)
C410.0281 (11)0.0396 (12)0.0219 (11)0.0045 (10)0.0053 (8)0.0031 (10)
C420.0295 (12)0.0510 (14)0.0264 (12)0.0066 (10)0.0025 (9)0.0074 (11)
C430.0652 (17)0.0515 (15)0.0203 (12)0.0062 (13)0.0031 (11)0.0033 (11)
C440.0436 (14)0.0641 (17)0.0261 (12)0.0205 (12)0.0108 (10)0.0051 (12)
C450.0281 (11)0.0244 (11)0.0333 (12)0.0013 (9)0.0016 (9)0.0013 (9)
C460.0311 (12)0.0248 (11)0.0289 (11)0.0023 (9)0.0043 (9)0.0039 (9)
C470.0205 (10)0.0199 (10)0.0205 (10)0.0016 (8)0.0048 (7)0.0006 (8)
C480.0215 (10)0.0196 (10)0.0221 (10)0.0004 (8)0.0031 (8)0.0024 (9)
O90.0362 (9)0.0268 (8)0.0437 (9)0.0061 (7)0.0142 (7)0.0023 (7)
O100.0486 (10)0.0306 (8)0.0343 (9)0.0028 (7)0.0078 (7)0.0065 (7)
O110.0421 (10)0.0398 (9)0.0402 (9)0.0127 (8)0.0087 (7)0.0061 (8)
N10.0281 (9)0.0241 (9)0.0374 (10)0.0019 (8)0.0094 (7)0.0004 (8)
N20.0203 (8)0.0245 (9)0.0275 (9)0.0044 (7)0.0037 (7)0.0007 (7)
N30.0320 (10)0.0280 (9)0.0280 (10)0.0033 (8)0.0031 (7)0.0016 (8)
C490.0254 (11)0.0328 (12)0.0353 (13)0.0006 (9)0.0076 (9)0.0007 (10)
C500.0590 (18)0.0344 (14)0.081 (2)0.0094 (12)0.0417 (15)0.0019 (13)
C510.078 (2)0.0292 (14)0.099 (2)0.0151 (14)0.0421 (18)0.0074 (15)
C520.0277 (11)0.0287 (11)0.0320 (12)0.0014 (9)0.0017 (9)0.0029 (10)
C530.0298 (12)0.0287 (11)0.0373 (13)0.0014 (9)0.0111 (9)0.0039 (10)
C540.0359 (13)0.0468 (14)0.0357 (13)0.0159 (11)0.0019 (10)0.0045 (11)
C550.0358 (13)0.0297 (12)0.0264 (11)0.0023 (10)0.0022 (9)0.0012 (10)
C560.0411 (14)0.0369 (13)0.0393 (14)0.0002 (11)0.0063 (10)0.0098 (11)
C570.0340 (13)0.0390 (13)0.0367 (13)0.0042 (10)0.0042 (10)0.0042 (11)
Geometric parameters (Å, º) top
O1—C251.396 (2)C32—H32C0.9800
O1—C471.429 (2)C33—C361.519 (3)
O2—C281.368 (2)C33—C341.523 (3)
O2—H20.8400C33—C351.529 (3)
O3—C271.406 (2)C34—H34A0.9800
O3—C451.449 (2)C34—H34B0.9800
O4—C261.369 (2)C34—H34C0.9800
O4—H40.8400C35—H35A0.9800
O5—C481.207 (2)C35—H35B0.9800
O6—C481.319 (2)C35—H35C0.9800
O6—H60.8400C36—H36A0.9800
O7—C461.210 (2)C36—H36B0.9800
O8—C461.322 (2)C36—H36C0.9800
O8—H80.8400C37—C391.524 (3)
C1—C241.384 (2)C37—C381.535 (3)
C1—C251.396 (2)C37—C401.534 (3)
C1—C21.522 (2)C38—H38A0.9800
C2—C31.523 (2)C38—H38B0.9800
C2—H2A0.9900C38—H38C0.9800
C2—H2B0.9900C39—H39A0.9800
C3—C41.398 (3)C39—H39B0.9800
C3—C281.400 (3)C39—H39C0.9800
C4—C51.393 (3)C40—H40A0.9800
C4—H4A0.9500C40—H40B0.9800
C5—C61.396 (3)C40—H40C0.9800
C5—C411.533 (3)C41—C421.531 (3)
C6—C71.386 (3)C41—C431.531 (3)
C6—H6A0.9500C41—C441.539 (3)
C7—C281.401 (3)C42—H42A0.9800
C7—C81.522 (3)C42—H42B0.9800
C8—C91.522 (2)C42—H42C0.9800
C8—H8A0.9900C43—H43A0.9800
C8—H8B0.9900C43—H43B0.9800
C9—C101.393 (3)C43—H43C0.9800
C9—C271.393 (3)C44—H44A0.9800
C10—C111.390 (3)C44—H44B0.9800
C10—H100.9500C44—H44C0.9800
C11—C121.399 (3)C45—C461.507 (3)
C11—C371.535 (3)C45—H45A0.9900
C12—C131.385 (3)C45—H45B0.9900
C12—H120.9500C47—C481.504 (3)
C13—C271.399 (3)C47—H47A0.9900
C13—C141.520 (3)C47—H47B0.9900
C14—C151.520 (2)O9—C491.248 (2)
C14—H14A0.9900O10—C521.230 (2)
C14—H14B0.9900O11—C551.246 (2)
C15—C161.393 (3)N1—C491.316 (3)
C15—C261.396 (2)N1—C511.440 (3)
C16—C171.392 (2)N1—C501.447 (3)
C16—H160.9500N2—C521.327 (3)
C17—C181.400 (2)N2—C531.451 (2)
C17—C331.538 (2)N2—C541.457 (3)
C18—C191.389 (2)N3—C551.324 (3)
C18—H180.9500N3—C571.451 (3)
C19—C261.402 (2)N3—C561.450 (3)
C19—C201.517 (2)C49—H490.9500
C20—C211.521 (2)C50—H50A0.9800
C20—H20A0.9900C50—H50B0.9800
C20—H20B0.9900C50—H50C0.9800
C21—C251.388 (2)C51—H51A0.9800
C21—C221.401 (2)C51—H51B0.9800
C22—C231.394 (2)C51—H51C0.9800
C22—H220.9500C52—H520.9500
C23—C241.397 (2)C53—H53A0.9800
C23—C291.531 (2)C53—H53B0.9800
C24—H240.9500C53—H53C0.9800
C29—C311.522 (3)C54—H54A0.9800
C29—C301.541 (3)C54—H54B0.9800
C29—C321.541 (3)C54—H54C0.9800
C30—H30A0.9800C55—H550.9500
C30—H30B0.9800C56—H56A0.9800
C30—H30C0.9800C56—H56B0.9800
C31—H31A0.9800C56—H56C0.9800
C31—H31B0.9800C57—H57A0.9800
C31—H31C0.9800C57—H57B0.9800
C32—H32A0.9800C57—H57C0.9800
C32—H32B0.9800
C25—O1—C47114.70 (13)C33—C34—H34C109.5
C28—O2—H2109.5H34A—C34—H34C109.5
C27—O3—C45114.42 (14)H34B—C34—H34C109.5
C26—O4—H4109.5C33—C35—H35A109.5
C48—O6—H6109.5C33—C35—H35B109.5
C46—O8—H8109.5H35A—C35—H35B109.5
C24—C1—C25117.95 (16)C33—C35—H35C109.5
C24—C1—C2120.24 (16)H35A—C35—H35C109.5
C25—C1—C2121.79 (16)H35B—C35—H35C109.5
C1—C2—C3112.00 (14)C33—C36—H36A109.5
C1—C2—H2A109.2C33—C36—H36B109.5
C3—C2—H2A109.2H36A—C36—H36B109.5
C1—C2—H2B109.2C33—C36—H36C109.5
C3—C2—H2B109.2H36A—C36—H36C109.5
H2A—C2—H2B107.9H36B—C36—H36C109.5
C4—C3—C28118.52 (17)C39—C37—C38107.94 (19)
C4—C3—C2119.65 (16)C39—C37—C40109.23 (19)
C28—C3—C2121.77 (16)C38—C37—C40108.96 (17)
C5—C4—C3122.92 (18)C39—C37—C11112.07 (17)
C5—C4—H4A118.5C38—C37—C11110.38 (17)
C3—C4—H4A118.5C40—C37—C11108.23 (18)
C4—C5—C6116.32 (18)C37—C38—H38A109.5
C4—C5—C41123.39 (18)C37—C38—H38B109.5
C6—C5—C41120.29 (17)H38A—C38—H38B109.5
C7—C6—C5123.17 (18)C37—C38—H38C109.5
C7—C6—H6A118.4H38A—C38—H38C109.5
C5—C6—H6A118.4H38B—C38—H38C109.5
C6—C7—C28118.77 (17)C37—C39—H39A109.5
C6—C7—C8120.78 (17)C37—C39—H39B109.5
C28—C7—C8120.39 (17)H39A—C39—H39B109.5
C7—C8—C9110.57 (15)C37—C39—H39C109.5
C7—C8—H8A109.5H39A—C39—H39C109.5
C9—C8—H8A109.5H39B—C39—H39C109.5
C7—C8—H8B109.5C37—C40—H40A109.5
C9—C8—H8B109.5C37—C40—H40B109.5
H8A—C8—H8B108.1H40A—C40—H40B109.5
C10—C9—C27117.85 (17)C37—C40—H40C109.5
C10—C9—C8119.52 (17)H40A—C40—H40C109.5
C27—C9—C8122.52 (17)H40B—C40—H40C109.5
C11—C10—C9123.07 (19)C42—C41—C43108.57 (18)
C11—C10—H10118.5C42—C41—C5109.86 (17)
C9—C10—H10118.5C43—C41—C5111.99 (17)
C10—C11—C12116.55 (18)C42—C41—C44108.48 (17)
C10—C11—C37123.18 (18)C43—C41—C44108.23 (19)
C12—C11—C37120.27 (17)C5—C41—C44109.63 (17)
C13—C12—C11122.86 (18)C41—C42—H42A109.5
C13—C12—H12118.6C41—C42—H42B109.5
C11—C12—H12118.6H42A—C42—H42B109.5
C12—C13—C27118.08 (18)C41—C42—H42C109.5
C12—C13—C14119.48 (17)H42A—C42—H42C109.5
C27—C13—C14122.30 (17)H42B—C42—H42C109.5
C13—C14—C15112.17 (15)C41—C43—H43A109.5
C13—C14—H14A109.2C41—C43—H43B109.5
C15—C14—H14A109.2H43A—C43—H43B109.5
C13—C14—H14B109.2C41—C43—H43C109.5
C15—C14—H14B109.2H43A—C43—H43C109.5
H14A—C14—H14B107.9H43B—C43—H43C109.5
C16—C15—C26118.59 (17)C41—C44—H44A109.5
C16—C15—C14120.49 (16)C41—C44—H44B109.5
C26—C15—C14120.90 (16)H44A—C44—H44B109.5
C17—C16—C15122.71 (17)C41—C44—H44C109.5
C17—C16—H16118.6H44A—C44—H44C109.5
C15—C16—H16118.6H44B—C44—H44C109.5
C16—C17—C18117.00 (16)O3—C45—C46112.23 (16)
C16—C17—C33122.90 (16)O3—C45—H45A109.2
C18—C17—C33120.10 (16)C46—C45—H45A109.2
C19—C18—C17122.30 (17)O3—C45—H45B109.2
C19—C18—H18118.9C46—C45—H45B109.2
C17—C18—H18118.9H45A—C45—H45B107.9
C18—C19—C26118.86 (16)O7—C46—O8125.6 (2)
C18—C19—C20120.93 (16)O7—C46—C45122.31 (19)
C26—C19—C20120.18 (16)O8—C46—C45112.11 (17)
C19—C20—C21113.16 (14)O1—C47—C48112.26 (15)
C19—C20—H20A108.9O1—C47—H47A109.2
C21—C20—H20A108.9C48—C47—H47A109.2
C19—C20—H20B108.9O1—C47—H47B109.2
C21—C20—H20B108.9C48—C47—H47B109.2
H20A—C20—H20B107.8H47A—C47—H47B107.9
C25—C21—C22118.12 (16)O5—C48—O6124.92 (18)
C25—C21—C20123.78 (16)O5—C48—C47124.79 (17)
C22—C21—C20118.08 (15)O6—C48—C47110.28 (16)
C23—C22—C21122.01 (16)C49—N1—C51122.67 (19)
C23—C22—H22119.0C49—N1—C50120.78 (18)
C21—C22—H22119.0C51—N1—C50116.54 (19)
C22—C23—C24117.15 (16)C52—N2—C53123.05 (17)
C22—C23—C29122.58 (16)C52—N2—C54120.43 (17)
C24—C23—C29120.20 (16)C53—N2—C54116.48 (17)
C1—C24—C23122.70 (17)C55—N3—C57121.07 (18)
C1—C24—H24118.6C55—N3—C56121.23 (18)
C23—C24—H24118.6C57—N3—C56117.69 (17)
C21—C25—O1120.67 (15)O9—C49—N1125.35 (19)
C21—C25—C1121.56 (16)O9—C49—H49117.3
O1—C25—C1117.75 (15)N1—C49—H49117.3
O4—C26—C15123.58 (16)N1—C50—H50A109.5
O4—C26—C19115.81 (15)N1—C50—H50B109.5
C15—C26—C19120.51 (16)H50A—C50—H50B109.5
C9—C27—C13121.30 (18)N1—C50—H50C109.5
C9—C27—O3119.87 (16)H50A—C50—H50C109.5
C13—C27—O3118.69 (17)H50B—C50—H50C109.5
O2—C28—C3123.10 (16)N1—C51—H51A109.5
O2—C28—C7116.64 (16)N1—C51—H51B109.5
C3—C28—C7120.25 (17)H51A—C51—H51B109.5
C31—C29—C23111.79 (15)N1—C51—H51C109.5
C31—C29—C30108.31 (16)H51A—C51—H51C109.5
C23—C29—C30110.24 (15)H51B—C51—H51C109.5
C31—C29—C32108.87 (17)O10—C52—N2126.59 (19)
C23—C29—C32108.05 (15)O10—C52—H52116.7
C30—C29—C32109.56 (16)N2—C52—H52116.7
C29—C30—H30A109.5N2—C53—H53A109.5
C29—C30—H30B109.5N2—C53—H53B109.5
H30A—C30—H30B109.5H53A—C53—H53B109.5
C29—C30—H30C109.5N2—C53—H53C109.5
H30A—C30—H30C109.5H53A—C53—H53C109.5
H30B—C30—H30C109.5H53B—C53—H53C109.5
C29—C31—H31A109.5N2—C54—H54A109.5
C29—C31—H31B109.5N2—C54—H54B109.5
H31A—C31—H31B109.5H54A—C54—H54B109.5
C29—C31—H31C109.5N2—C54—H54C109.5
H31A—C31—H31C109.5H54A—C54—H54C109.5
H31B—C31—H31C109.5H54B—C54—H54C109.5
C29—C32—H32A109.5O11—C55—N3124.9 (2)
C29—C32—H32B109.5O11—C55—H55117.6
H32A—C32—H32B109.5N3—C55—H55117.6
C29—C32—H32C109.5N3—C56—H56A109.5
H32A—C32—H32C109.5N3—C56—H56B109.5
H32B—C32—H32C109.5H56A—C56—H56B109.5
C36—C33—C34108.26 (17)N3—C56—H56C109.5
C36—C33—C35107.95 (17)H56A—C56—H56C109.5
C34—C33—C35108.72 (19)H56B—C56—H56C109.5
C36—C33—C17112.21 (15)N3—C57—H57A109.5
C34—C33—C17109.53 (16)N3—C57—H57B109.5
C35—C33—C17110.09 (16)H57A—C57—H57B109.5
C33—C34—H34A109.5N3—C57—H57C109.5
C33—C34—H34B109.5H57A—C57—H57C109.5
H34A—C34—H34B109.5H57B—C57—H57C109.5
C24—C1—C2—C384.9 (2)C16—C15—C26—C191.5 (3)
C25—C1—C2—C393.1 (2)C14—C15—C26—C19176.88 (16)
C1—C2—C3—C494.13 (19)C18—C19—C26—O4178.40 (15)
C1—C2—C3—C2883.2 (2)C20—C19—C26—O40.3 (2)
C28—C3—C4—C51.9 (3)C18—C19—C26—C151.8 (3)
C2—C3—C4—C5179.30 (16)C20—C19—C26—C15176.36 (16)
C3—C4—C5—C60.2 (3)C10—C9—C27—C135.9 (3)
C3—C4—C5—C41179.72 (17)C8—C9—C27—C13170.33 (17)
C4—C5—C6—C71.8 (3)C10—C9—C27—O3178.30 (16)
C41—C5—C6—C7177.75 (17)C8—C9—C27—O35.4 (3)
C5—C6—C7—C282.0 (3)C12—C13—C27—C95.8 (3)
C5—C6—C7—C8175.09 (17)C14—C13—C27—C9169.77 (16)
C6—C7—C8—C989.2 (2)C12—C13—C27—O3178.33 (15)
C28—C7—C8—C987.8 (2)C14—C13—C27—O36.1 (3)
C7—C8—C9—C1071.2 (2)C45—O3—C27—C9105.98 (19)
C7—C8—C9—C27104.9 (2)C45—O3—C27—C1378.1 (2)
C27—C9—C10—C111.9 (3)C4—C3—C28—O2179.88 (16)
C8—C9—C10—C11174.44 (17)C2—C3—C28—O22.5 (3)
C9—C10—C11—C121.9 (3)C4—C3—C28—C71.7 (3)
C9—C10—C11—C37178.02 (18)C2—C3—C28—C7179.02 (16)
C10—C11—C12—C132.0 (3)C6—C7—C28—O2178.37 (16)
C37—C11—C12—C13177.92 (18)C8—C7—C28—O24.5 (2)
C11—C12—C13—C271.7 (3)C6—C7—C28—C30.2 (3)
C11—C12—C13—C14174.00 (17)C8—C7—C28—C3176.91 (16)
C12—C13—C14—C1577.2 (2)C22—C23—C29—C3113.6 (2)
C27—C13—C14—C1598.3 (2)C24—C23—C29—C31169.48 (17)
C13—C14—C15—C16106.17 (19)C22—C23—C29—C30134.12 (17)
C13—C14—C15—C2675.5 (2)C24—C23—C29—C3048.9 (2)
C26—C15—C16—C170.4 (3)C22—C23—C29—C32106.2 (2)
C14—C15—C16—C17177.92 (17)C24—C23—C29—C3270.8 (2)
C15—C16—C17—C180.3 (3)C16—C17—C33—C3611.6 (3)
C15—C16—C17—C33179.93 (17)C18—C17—C33—C36168.02 (17)
C16—C17—C18—C190.0 (3)C16—C17—C33—C34108.6 (2)
C33—C17—C18—C19179.63 (16)C18—C17—C33—C3471.7 (2)
C17—C18—C19—C261.0 (3)C16—C17—C33—C35131.9 (2)
C17—C18—C19—C20177.07 (16)C18—C17—C33—C3547.8 (2)
C18—C19—C20—C21100.76 (19)C10—C11—C37—C3910.3 (3)
C26—C19—C20—C2181.2 (2)C12—C11—C37—C39169.77 (19)
C19—C20—C21—C25100.88 (19)C10—C11—C37—C38130.6 (2)
C19—C20—C21—C2277.8 (2)C12—C11—C37—C3849.4 (2)
C25—C21—C22—C231.6 (3)C10—C11—C37—C40110.2 (2)
C20—C21—C22—C23177.19 (16)C12—C11—C37—C4069.7 (2)
C21—C22—C23—C243.9 (2)C4—C5—C41—C42119.3 (2)
C21—C22—C23—C29173.17 (16)C6—C5—C41—C4261.2 (2)
C25—C1—C24—C231.3 (3)C4—C5—C41—C431.4 (3)
C2—C1—C24—C23176.87 (16)C6—C5—C41—C43178.06 (18)
C22—C23—C24—C14.0 (3)C4—C5—C41—C44121.6 (2)
C29—C23—C24—C1173.07 (16)C6—C5—C41—C4457.9 (2)
C22—C21—C25—O1174.36 (14)C27—O3—C45—C4674.6 (2)
C20—C21—C25—O16.9 (3)O3—C45—C46—O7119.8 (2)
C22—C21—C25—C17.2 (3)O3—C45—C46—O861.3 (2)
C20—C21—C25—C1171.49 (16)C25—O1—C47—C48110.92 (16)
C47—O1—C25—C2169.0 (2)O1—C47—C48—O56.7 (3)
C47—O1—C25—C1112.54 (17)O1—C47—C48—O6173.95 (15)
C24—C1—C25—C217.1 (3)C51—N1—C49—O9178.5 (2)
C2—C1—C25—C21171.04 (16)C50—N1—C49—O92.7 (4)
C24—C1—C25—O1174.46 (15)C53—N2—C52—O10178.92 (19)
C2—C1—C25—O17.4 (2)C54—N2—C52—O101.4 (3)
C16—C15—C26—O4177.84 (16)C57—N3—C55—O11177.8 (2)
C14—C15—C26—O40.5 (3)C56—N3—C55—O111.3 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O10.841.952.762 (2)163
O4—H4···O30.841.962.780 (2)165
O6—H6···O90.841.752.584 (2)170
O8—H8···O110.841.752.581 (2)168

Experimental details

Crystal data
Chemical formulaC48H60O8·3C3H7NO
Mr984.25
Crystal system, space groupMonoclinic, P21/c
Temperature (K)100
a, b, c (Å)11.3624 (3), 35.224 (1), 13.7180 (4)
β (°) 96.991 (2)
V3)5449.6 (3)
Z4
Radiation typeCu Kα
µ (mm1)0.66
Crystal size (mm)0.30 × 0.11 × 0.07
Data collection
DiffractometerBruker SMART 1000 CCD area-detector
diffractometer
Absorption correctionIntegration
face-indexing of crystal Reference
Tmin, Tmax0.862, 0.961
No. of measured, independent and
observed [I > 2σ(I)] reflections
25773, 9142, 6845
Rint0.056
(sin θ/λ)max1)0.593
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.127, 1.07
No. of reflections9142
No. of parameters662
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.25, 0.28

Computer programs: SMART (Bruker, 2000), SMART, SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000), SHELXTL.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O10.841.952.762 (2)163
O4—H4···O30.841.962.780 (2)165
O6—H6···O90.841.752.584 (2)170
O8—H8···O110.841.752.581 (2)168
 

Subscribe to Acta Crystallographica Section C: Structural Chemistry

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds