Regioselective alkylation of a methylene group via meta-bridging of calix[4]arenes
Petr Slavik; Hana Dvorakova; Vaclav Eigner; Pavel Lhotak; Chem.Commun. 50 (2014) 10112–; doi:10.1039/C4cc04356A

data_7115536
_publ_section_title
;
 Regioselective alkylation of a methylene group via meta-bridging of
 calix[4]arenes
;
_journal_name_full               Chem.Commun.
_journal_page_first              10112
_journal_paper_doi               10.1039/C4cc04356A
_journal_volume                  50
_journal_year                    2014
_chemical_formula_moiety         '2(C80 H90 O8), C H2 Cl2 '
_chemical_formula_sum            'C161 H182 Cl2 O16'
_chemical_formula_weight         2444.11
_space_group_IT_number           14
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_cell_angle_alpha                90
_cell_angle_beta                 99.7860(7)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.22632(10)
_cell_length_b                   25.83704(17)
_cell_length_c                   20.88126(15)
_cell_measurement_reflns_used    73292
_cell_measurement_temperature    190
_cell_measurement_theta_max      76
_cell_measurement_theta_min      4
_cell_volume                     7031.90(9)
_computing_cell_refinement       'CrysAlis, (Oxford Diffraction, 2002)'
_computing_data_collection       'Xcalibur, (Oxford Diffraction, 2002)'
_computing_data_reduction        'CrysAlis, (Oxford Diffraction, 2002)'
_computing_molecular_graphics    'CAMERON (Watkin et al., 1996)'
_computing_publication_material  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_refinement  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_solution    'SIR92 (Altomare et al., 1994)'
_diffrn_ambient_pressure         101
_diffrn_ambient_temperature      190
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.980
_diffrn_measurement_device       Area
_diffrn_measurement_device_type  'Oxford Diffraction XCALIBUR'
_diffrn_measurement_method       \w
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54180
_diffrn_reflns_av_R_equivalents  0.036
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            160835
_diffrn_reflns_theta_full        70.666
_diffrn_reflns_theta_max         75.985
_diffrn_reflns_theta_min         4.626
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.908
_exptl_absorpt_correction_T_max  0.90
_exptl_absorpt_correction_T_min  0.71
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrysAlis, (Oxford Diffraction, 2002)'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.154
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             2620
_exptl_crystal_size_max          0.320
_exptl_crystal_size_mid          0.210
_exptl_crystal_size_min          0.120
_refine_diff_density_max         0.57
_refine_diff_density_min         -0.61
_refine_ls_extinction_method     None
_refine_ls_goodness_of_fit_ref   1.0443
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     961
_refine_ls_number_reflns         14412
_refine_ls_number_restraints     278
_refine_ls_R_factor_all          0.0802
_refine_ls_R_factor_gt           0.0722
_refine_ls_shift/su_max          0.0031676
_refine_ls_shift/su_mean         0.0001817
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) 
 [weight] = 1.0/[A~0~*T~0~(x)+A~1~*T~1~(x) ... +A~n-1~]*T~n-1~(x)] 
 where A~i~ are the Chebychev coefficients listed below and x= Fcalc/Fmax 
 Method = Robust Weighting (Prince, 1982) 
 W = [weight] * [1-(deltaF/6*sigmaF)^2^]^2^ 
 A~i~ are: 
 0.115E+04 0.180E+04 890. 214. 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.1379
_refine_ls_wR_factor_gt          0.1299
_refine_ls_wR_factor_ref         0.1379
_reflns_limit_h_max              15
_reflns_limit_h_min              -16
_reflns_limit_k_max              32
_reflns_limit_k_min              0
_reflns_limit_l_max              26
_reflns_limit_l_min              0
_reflns_number_gt                12059
_reflns_number_total             14412
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   4.62
_oxford_diffrn_Wilson_scale      0.12
_oxford_refine_ls_r_factor_ref   0.0802
_oxford_refine_ls_scale          3.271(19)
_oxford_reflns_number_all        14412
_oxford_reflns_threshold_expression_ref I>-3.0\s(I)
_cod_data_source_file            c4cc04356a2.cif
_cod_data_source_block           1a
_cod_original_sg_symbol_H-M      'P 1 21/c 1 '
_cod_database_code               7115536
_iucr_refine_instruction_details_constraints
;
BLOCK SCALE X'S, U'S 
EQUIVALENCE PART(1001, OCC) PART(1002, OCC) 
WEIGHT -1 PART(1002, OCC) 
EQUIVALENCE PART(2001, OCC) PART(2002, OCC) 
WEIGHT -1 PART(2002, OCC) 
EQUIVALENCE PART(3001, OCC) PART(3002, OCC) 
WEIGHT -1 PART(3002, OCC) 
EQUIVALENCE PART(4001, OCC) PART(4002, OCC) 
WEIGHT -1 PART(4002, OCC) 
EQUIVALENCE PART(5001, OCC) PART(5002, OCC) 
WEIGHT -1 PART(5002, OCC) 
EQUIVALENCE PART(6001, OCC) PART(6002, OCC) 
WEIGHT -1 PART(6002, OCC) 
RIDE C   (   2,X'S) H   (  21,X'S) H   (  22,X'S) 
RIDE C   (   4,X'S) H   (  41,X'S) 
RIDE C   (   5,X'S) H   (  51,X'S) 
RIDE C   (   8,X'S) H   (  81,X'S) 
RIDE C   (  11,X'S) H   ( 111,X'S) 
RIDE C   (  12,X'S) H   ( 121,X'S) 
RIDE C   (  14,X'S) H   ( 141,X'S) H   ( 142,X'S) 
RIDE C   (  16,X'S) H   ( 161,X'S) 
RIDE C   (  17,X'S) H   ( 171,X'S) 
RIDE C   (  18,X'S) H   ( 181,X'S) 
RIDE C   (  20,X'S) H   ( 201,X'S) H   ( 202,X'S) 
RIDE C   (  22,X'S) H   ( 221,X'S) 
RIDE C   (  23,X'S) H   ( 231,X'S) 
RIDE C   (  24,X'S) H   ( 241,X'S) 
RIDE C   (  30,X'S) H   ( 301,X'S) H   ( 302,X'S) 
CONTINUE C   ( 230,X'S) H   (2301,X'S) H   (2302,X'S) 
RIDE C   (  31,X'S) H   ( 311,X'S) H   ( 312,X'S) 
CONTINUE C   ( 231,X'S) H   (2311,X'S) H   (2312,X'S) 
RIDE C   (  32,X'S) H   ( 321,X'S) H   ( 322,X'S) H   ( 323,X'S) 
RIDE C   ( 232,X'S) H   (2321,X'S) H   (2322,X'S) H   (2323,X'S) 
RIDE C   (  34,X'S) H   ( 341,X'S) H   ( 342,X'S) 
RIDE C   (  35,X'S) H   ( 351,X'S) H   ( 352,X'S) 
RIDE C   (  36,X'S) H   ( 361,X'S) H   ( 362,X'S) H   ( 363,X'S) 
CONTINUE C   ( 236,X'S) H   (2361,X'S) H   (2362,X'S) H   (2363,X'S) 
RIDE C   ( 234,X'S) H   (2341,X'S) H   (2342,X'S) 
RIDE C   ( 235,X'S) H   (2351,X'S) H   (2352,X'S) 
RIDE C   (  38,X'S) H   ( 381,X'S) H   ( 382,X'S) 
CONTINUE C   ( 238,X'S) H   (2381,X'S) H   (2382,X'S) 
RIDE C   (  39,X'S) H   ( 391,X'S) H   ( 392,X'S) 
RIDE C   (  40,X'S) H   ( 401,X'S) H   ( 402,X'S) H   ( 403,X'S) 
RIDE C   ( 239,X'S) H   (2391,X'S) H   (2392,X'S) 
RIDE C   ( 240,X'S) H   (2401,X'S) H   (2402,X'S) H   (2403,X'S) 
RIDE C   (  42,X'S) H   ( 421,X'S) H   ( 422,X'S) 
CONTINUE C   ( 242,X'S) H   (2421,X'S) H   (2422,X'S) 
RIDE C   (  43,X'S) H   ( 431,X'S) H   ( 432,X'S) 
RIDE C   (  44,X'S) H   ( 441,X'S) H   ( 442,X'S) H   ( 443,X'S) 
RIDE C   ( 243,X'S) H   (2431,X'S) H   (2432,X'S) 
RIDE C   ( 244,X'S) H   (2441,X'S) H   (2442,X'S) H   (2443,X'S) 
RIDE C   ( 102,X'S) H   (1021,X'S) H   (1022,X'S) 
RIDE C   ( 104,X'S) H   (1041,X'S) 
RIDE C   ( 105,X'S) H   (1051,X'S) 
RIDE C   ( 108,X'S) H   (1081,X'S) 
RIDE C   ( 111,X'S) H   (1111,X'S) 
RIDE C   ( 112,X'S) H   (1121,X'S) 
RIDE C   ( 114,X'S) H   (1141,X'S) H   (1142,X'S) 
RIDE C   ( 116,X'S) H   (1161,X'S) 
RIDE C   ( 117,X'S) H   (1171,X'S) 
RIDE C   ( 118,X'S) H   (1181,X'S) 
RIDE C   ( 120,X'S) H   (1201,X'S) H   (1202,X'S) 
RIDE C   ( 122,X'S) H   (1221,X'S) 
RIDE C   ( 123,X'S) H   (1231,X'S) 
RIDE C   ( 124,X'S) H   (1241,X'S) 
RIDE C   ( 130,X'S) H   (1301,X'S) H   (1302,X'S) 
RIDE C   ( 131,X'S) H   (1311,X'S) H   (1312,X'S) 
RIDE C   ( 132,X'S) H   (1321,X'S) H   (1322,X'S) H   (1323,X'S) 
RIDE C   ( 134,X'S) H   (1341,X'S) H   (1342,X'S) 
RIDE C   ( 135,X'S) H   (1351,X'S) H   (1352,X'S) 
RIDE C   ( 136,X'S) H   (1361,X'S) H   (1362,X'S) H   (1363,X'S) 
RIDE C   ( 138,X'S) H   (1381,X'S) H   (1382,X'S) 
RIDE C   ( 139,X'S) H   (1391,X'S) H   (1392,X'S) 
RIDE C   ( 140,X'S) H   (1401,X'S) H   (1402,X'S) H   (1403,X'S) 
RIDE C   ( 142,X'S) H   (1421,X'S) H   (1422,X'S) 
RIDE C   ( 143,X'S) H   (1431,X'S) H   (1432,X'S) 
RIDE C   ( 144,X'S) H   (1441,X'S) H   (1442,X'S) H   (1443,X'S) 
RIDE C   ( 342,X'S) H   (3421,X'S) H   (3422,X'S) 
RIDE C   ( 343,X'S) H   (3431,X'S) H   (3432,X'S) 
RIDE C   ( 344,X'S) H   (3441,X'S) H   (3442,X'S) H   (3443,X'S) 
RIDE C   ( 902,X'S) H   (9021,X'S) H   (9022,X'S) 
CONTINUE C   ( 912,X'S) H   (9121,X'S) H   (9122,X'S) 
RIDE CL  ( 901,X'S,U'S) CL  ( 911,X'S,U'S) 
END                                                                             
;
_iucr_refine_instruction_details_restraints
;
NO 
REM   HREST   START (DO NOT REMOVE THIS LINE) 
REM   HREST   END (DO NOT REMOVE THIS LINE) 
DISTANCE 1.441000 , 0.0050000 = O(29) TO C(30) 
DISTANCE 1.525000 , 0.0050000 = C(30) TO C(31) 
DISTANCE 1.539000 , 0.0050000 = C(31) TO C(32) 
ANGLE 109.000000 , 1.000000 = O(29) TO C(30) TO C(31) 
ANGLE 109.000000 , 1.000000 = C(30) TO C(31) TO C(32) 
DISTANCE 1.441000 , 0.0050000 = O(29) TO C(230) 
DISTANCE 1.525000 , 0.0050000 = C(230) TO C(231) 
DISTANCE 1.539000 , 0.0050000 = C(231) TO C(232) 
ANGLE 109.000000 , 1.000000 = O(29) TO C(230) TO C(231) 
ANGLE 109.000000 , 1.000000 = C(230) TO C(231) TO C(232) 
U(IJ)'S  0.0, 0.010000 = O(29) TO C(30) 
U(IJ)'S  0.0, 0.010000 = O(29) TO C(31) 
U(IJ)'S  0.0, 0.010000 = O(29) TO C(32) 
U(IJ)'S  0.0, 0.010000 = O(29) TO C(230) 
U(IJ)'S  0.0, 0.010000 = O(29) TO C(231) 
U(IJ)'S  0.0, 0.010000 = O(29) TO C(232) 
DISTANCE 1.441000 , 0.0050000 = O(33) TO C(34) 
DISTANCE 1.525000 , 0.0050000 = C(34) TO C(35) 
DISTANCE 1.539000 , 0.0050000 = C(35) TO C(36) 
ANGLE 109.000000 , 1.000000 = O(33) TO C(34) TO C(35) 
ANGLE 109.000000 , 1.000000 = C(34) TO C(35) TO C(36) 
DISTANCE 1.441000 , 0.0050000 = O(33) TO C(234) 
DISTANCE 1.525000 , 0.0050000 = C(234) TO C(235) 
DISTANCE 1.539000 , 0.0050000 = C(235) TO C(236) 
ANGLE 109.000000 , 1.000000 = O(33) TO C(234) TO C(235) 
ANGLE 109.000000 , 1.000000 = C(234) TO C(235) TO C(236) 
U(IJ)'S  0.0, 0.010000 = O(33) TO C(34) 
U(IJ)'S  0.0, 0.010000 = O(33) TO C(35) 
U(IJ)'S  0.0, 0.010000 = O(33) TO C(36) 
U(IJ)'S  0.0, 0.010000 = O(33) TO C(234) 
U(IJ)'S  0.0, 0.010000 = O(33) TO C(235) 
U(IJ)'S  0.0, 0.010000 = O(33) TO C(236) 
U(IJ)'S  0.0, 0.001000 = C(36) TO C(236) 
U(IJ)'S  0.0, 0.001000 = C(34) TO C(234) 
DISTANCE 1.441000 , 0.0050000 = O(37) TO C(38) 
DISTANCE 1.525000 , 0.0050000 = C(38) TO C(39) 
DISTANCE 1.539000 , 0.0050000 = C(39) TO C(40) 
ANGLE 109.000000 , 1.000000 = O(37) TO C(38) TO C(39) 
ANGLE 109.000000 , 1.000000 = C(38) TO C(39) TO C(40) 
DISTANCE 1.441000 , 0.0050000 = O(37) TO C(238) 
DISTANCE 1.525000 , 0.0050000 = C(238) TO C(239) 
DISTANCE 1.539000 , 0.0050000 = C(239) TO C(240) 
ANGLE 109.000000 , 1.000000 = O(37) TO C(238) TO C(239) 
ANGLE 109.000000 , 1.000000 = C(238) TO C(239) TO C(240) 
U(IJ)'S  0.0, 0.010000 = O(37) TO C(38) 
U(IJ)'S  0.0, 0.010000 = O(37) TO C(39) 
U(IJ)'S  0.0, 0.010000 = O(37) TO C(40) 
U(IJ)'S  0.0, 0.010000 = O(37) TO C(238) 
U(IJ)'S  0.0, 0.010000 = O(37) TO C(239) 
U(IJ)'S  0.0, 0.010000 = O(37) TO C(240) 
U(IJ)'S  0.0, 0.001000 = C(38) TO C(238) 
DISTANCE 1.441000 , 0.0050000 = O(41) TO C(42) 
DISTANCE 1.525000 , 0.0050000 = C(42) TO C(43) 
DISTANCE 1.539000 , 0.0050000 = C(43) TO C(44) 
ANGLE 109.000000 , 1.000000 = O(41) TO C(42) TO C(43) 
ANGLE 109.000000 , 1.000000 = C(42) TO C(43) TO C(44) 
DISTANCE 1.441000 , 0.0050000 = O(41) TO C(242) 
DISTANCE 1.525000 , 0.0050000 = C(242) TO C(243) 
DISTANCE 1.539000 , 0.0050000 = C(243) TO C(244) 
ANGLE 109.000000 , 1.000000 = O(41) TO C(242) TO C(243) 
ANGLE 109.000000 , 1.000000 = C(242) TO C(243) TO C(244) 
U(IJ)'S  0.0, 0.0100000 = O(41) TO C(42) 
U(IJ)'S  0.0, 0.0100000 = O(41) TO C(43) 
U(IJ)'S  0.0, 0.0100000 = O(41) TO C(44) 
U(IJ)'S  0.0, 0.0100000 = O(41) TO C(242) 
U(IJ)'S  0.0, 0.0100000 = O(41) TO C(243) 
U(IJ)'S  0.0, 0.0100000 = O(41) TO C(244) 
U(IJ)'S  0.0, 0.0010000 = C(42) TO C(242) 
DISTANCE 1.441000 , 0.0050000 = O(141) TO C(142) 
DISTANCE 1.525000 , 0.0050000 = C(142) TO C(143) 
DISTANCE 1.539000 , 0.0050000 = C(143) TO C(144) 
ANGLE 109.000000 , 1.000000 = O(141) TO C(142) TO C(143) 
ANGLE 109.000000 , 1.000000 = C(142) TO C(143) TO C(144) 
DISTANCE 1.441000 , 0.0050000 = O(141) TO C(342) 
DISTANCE 1.525000 , 0.0050000 = C(342) TO C(343) 
DISTANCE 1.539000 , 0.0050000 = C(343) TO C(344) 
ANGLE 109.000000 , 1.000000 = O(141) TO C(342) TO C(343) 
ANGLE 109.000000 , 1.000000 = C(342) TO C(343) TO C(344) 
U(IJ)'S  0.0, 0.0100000 = O(141) TO C(142) 
U(IJ)'S  0.0, 0.0100000 = O(141) TO C(143) 
U(IJ)'S  0.0, 0.0100000 = O(141) TO C(144) 
U(IJ)'S  0.0, 0.0100000 = O(141) TO C(342) 
U(IJ)'S  0.0, 0.0100000 = O(141) TO C(343) 
U(IJ)'S  0.0, 0.0100000 = O(141) TO C(344) 
DISTANCE 1.720000 , 0.0050000 = CL(901) TO C(902) 
DISTANCE 1.720000 , 0.0050000 = C(902) TO CL(903) 
ANGLE 111.000000 , 1.000000 = CL(901) TO C(902) TO CL(903) 
DISTANCE 1.720000 , 0.0050000 = CL(911) TO C(912) 
DISTANCE 1.720000 , 0.0050000 = C(912) TO CL(913) 
ANGLE 111.000000 , 1.000000 = CL(911) TO C(912) TO CL(913) 
U(IJ)'S  0.0, 0.001000 = C(902) TO C(912) 
U(IJ)'S  0.0, 0.001000 = CL(903) TO CL(913) 
U(IJ)'S  0.0, 0.020000 = O(133) TO C(136) 
END                                                                             
;