Retro-Diels-Alder decomposition of norbornadiene mediated by a cationic magnesium complex.
Thum, Katharina; Pahl, Jürgen; Eyselein, Jonathan; Elsen, Holger; Langer, Jens; Harder, Sjoerd; Chemical communications (Cambridge, England) 57 (2021) 5278–5281; doi:10.1039/d1cc01691a

data_7128235
_publ_section_title
;
 Retro-Diels-Alder decomposition of norbornadiene mediated by a cationic
 magnesium complex.
;
_journal_issue                   43
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              5278
_journal_page_last               5281
_journal_paper_doi               10.1039/d1cc01691a
_journal_volume                  57
_journal_year                    2021
_chemical_formula_moiety         'Al C16 F36 O4, C63 H87 Mg2 N4'
_chemical_formula_sum            'C79 H87 Al F36 Mg2 N4 O4'
_chemical_formula_weight         1916.12
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-04-01
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2021-03-29 deposited with the CCDC.	2021-04-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.637(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.6397(3)
_cell_length_b                   21.7453(3)
_cell_length_c                   20.3018(4)
_cell_measurement_reflns_used    37875
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      72.7140
_cell_measurement_theta_min      3.6850
_cell_volume                     8669.8(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2903
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.958
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w   -116.00 -17.00   1.00    2.00    --  -41.48 -38.00-150.00   99
  2  \w    -87.00  -6.00   1.00    2.00    --  -41.48 125.00   0.00   81
  3  \w    103.00 178.00   1.00    8.00    --  104.33  77.00 -30.00   75
  4  \w     22.00 106.00   1.00    8.00    --  104.33 -94.00-120.00   84
  5  \w    103.00 178.00   1.00    8.00    --  104.33  77.00 150.00   75
  6  \w     31.00 130.00   1.00    8.00    --  104.33 -45.00-150.00   99
  7  \w    103.00 178.00   1.00    8.00    --  104.33  77.00-120.00   75
  8  \w     31.00 112.00   1.00    8.00    --  104.33-125.00  30.00   81
  9  \w    103.00 178.00   1.00    8.00    --  104.33  77.00 -60.00   75
 10  \w   -114.00 -13.00   1.00    2.00    --  -41.48 -57.00  60.00  101
 11  \w   -114.00 -13.00   1.00    2.00    --  -41.48 -57.00 -30.00  101
 12  \w     52.00 178.00   1.00    8.00    --  104.33  15.00 120.00  126
 13  \w     22.00  83.00   1.00    8.00    --  104.33 -94.00  90.00   61
 14  \w     75.00 177.00   1.00    8.00    --  104.33  61.00-150.00  102
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0725448000
_diffrn_orient_matrix_UB_12      -0.0223327000
_diffrn_orient_matrix_UB_13      -0.0168151000
_diffrn_orient_matrix_UB_21      -0.0272700000
_diffrn_orient_matrix_UB_22      0.0657826000
_diffrn_orient_matrix_UB_23      0.0096765000
_diffrn_orient_matrix_UB_31      0.0121681000
_diffrn_orient_matrix_UB_32      0.0137965000
_diffrn_orient_matrix_UB_33      -0.0733823000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0331
_diffrn_reflns_av_unetI/netI     0.0243
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.958
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            67462
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.958
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.966
_diffrn_reflns_theta_min         2.978
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.496
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.366
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.468
_exptl_crystal_description       block
_exptl_crystal_F_000             3928
_exptl_crystal_size_max          0.51
_exptl_crystal_size_mid          0.321
_exptl_crystal_size_min          0.155
_refine_diff_density_max         0.630
_refine_diff_density_min         -0.541
_refine_diff_density_rms         0.074
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.149
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1379
_refine_ls_number_reflns         16934
_refine_ls_number_restraints     2929
_refine_ls_restrained_S_all      1.089
_refine_ls_R_factor_all          0.0759
_refine_ls_R_factor_gt           0.0707
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1247P)^2^+13.4413P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2100
_refine_ls_wR_factor_ref         0.2217
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15886
_reflns_number_total             16934
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc01691a2.cif
_cod_data_source_block           hasj200320a
_cod_depositor_comments
'Adding full bibliography for 7128228--7128235.cif.'
_cod_database_code               7128235
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C79H87AlF36Mg2N4O4
_shelx_estimated_absorpt_t_max   0.801
_shelx_estimated_absorpt_t_min   0.516
_reflns_odcompleteness_completeness 99.80
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.8784(9)
 0.1216(9)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C79A-C76 \\sim C79-C76 \\sim C77A-C76 \\sim C77-C76 \\sim C78A-C76 \\sim
C78-C76
 with sigma of 0.02
 F29A-C77A \\sim F28A-C77A \\sim F30A-C77A \\sim F28-C77 \\sim F30-C77 \\sim
F29-C77 \\sim F32A-C78A ~
 F31A-C78A \\sim F33A-C78A \\sim F33-C78 \\sim F31-C78 \\sim F32-C78 \\sim
F35A-C79A \\sim F35-C79 ~
 F36A-C79A \\sim F36-C79 \\sim F34-C79 \\sim F34A-C79A \\sim F26A-C75 \\sim
F26-C75 \\sim F25-C75 ~
 F25A-C75 \\sim F27A-C75 \\sim F27-C75 \\sim F23-C74 \\sim F23A-C74 \\sim
F22-C74 \\sim F22A-C74 \\sim F24-
 C74 \\sim F24A-C74 \\sim F21A-C73 \\sim F21-C73 \\sim F20-C73 \\sim F20A-C73
\\sim F19-C73 \\sim F19A-C73
 with sigma of 0.02
 F30A-F29A \\sim F29A-F28A \\sim F29A-F28A \\sim F31A-F33A \\sim F33A-F32A
\\sim F32A-F31A \\sim F36A-
 F35A \\sim F35A-F34A \\sim F34A-F36A
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
F2 \\sim C76 \\sim F28 \\sim F29 \\sim F30 \\sim F31 \\sim F32 \\sim F33 \\sim
F34 \\sim F35 \\sim F36 \\sim C77 \\sim C78 \\sim C79 \\sim F28A \\sim F29A
\\sim F30A \\sim F31A \\sim F32A \\sim F33A \\sim F34A \\sim F35A \\sim F36A
\\sim C77A \\sim C78A \\sim C79A: within 4A with sigma of 0.02 and sigma for
terminal atoms of 0.04 within 4A
C73 \\sim C74 \\sim C75 \\sim F19 \\sim F20 \\sim F21 \\sim F22 \\sim F23 \\sim
F24 \\sim F25 \\sim F26 \\sim F27 \\sim F19A \\sim F20A \\sim F21A \\sim F22A
\\sim F23A \\sim F24A \\sim F25A \\sim F26A \\sim F27A: within 3A with sigma of
0.02 and sigma for terminal atoms of 0.04 within 3A
C61 \\sim C62 \\sim C63 \\sim C61A \\sim C62A \\sim C63A: within 3A with sigma
of 0.02 and sigma for terminal atoms of 0.04 within 3A
5. Others
 Sof(F25A)=Sof(F26A)=Sof(F27A)=1-FVAR(1)
 Sof(F25)=Sof(F26)=Sof(F27)=FVAR(1)
 Sof(F19A)=Sof(F20A)=Sof(F21A)=1-FVAR(2)
 Sof(F19)=Sof(F20)=Sof(F21)=FVAR(2)
 Sof(F22A)=Sof(F23A)=Sof(F24A)=1-FVAR(3)
 Sof(F22)=Sof(F23)=Sof(F24)=FVAR(3)
 Sof(F28A)=Sof(F29A)=Sof(F30A)=Sof(F31A)=Sof(F32A)=Sof(F33A)=Sof(F34A)=
 Sof(F35A)=Sof(F36A)=Sof(C77A)=Sof(C78A)=Sof(C79A)=1-FVAR(4)
 Sof(F28)=Sof(F29)=Sof(F30)=Sof(F31)=Sof(F32)=Sof(F33)=Sof(F34)=Sof(F35)=
 Sof(F36)=Sof(C77)=Sof(C78)=Sof(C79)=FVAR(4)
 Sof(C61A)=Sof(H61A)=Sof(C62A)=Sof(H62D)=Sof(H62E)=Sof(H62F)=Sof(C63A)=
 Sof(H63D)=Sof(H63E)=Sof(H63F)=1-FVAR(5)
 Sof(C61)=Sof(H61)=Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(H62C)=Sof(C63)=Sof(H63A)=
 Sof(H63B)=Sof(H63C)=FVAR(5)
6.a Ternary CH refined with riding coordinates:
 C17(H17), C20(H20), C29(H29), C32(H32), C46(H46), C49(H49), C58(H58),
 C61(H61), C61A(H61A)
6.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C8(H8), C13(H13), C14(H14), C15(H15),
 C25(H25), C26(H26), C27(H27), C37(H37), C42(H42), C43(H43), C44(H44), C54(H54),
  C55(H55), C56(H56)
6.c Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C10(H10A,H10B,H10C), C18(H18A,H18B,H18C), C19(H19A,H19B,
 H19C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C30(H30A,H30B,H30C), C31(H31A,
 H31B,H31C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C),
 C39(H39A,H39B,H39C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C50(H50A,H50B,
 H50C), C51(H51A,H51B,H51C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C), C62(H62A,
 H62B,H62C), C63(H63A,H63B,H63C), C62A(H62D,H62E,H62F), C63A(H63D,H63E,H63F)
;
_olex2_date_sample_data_collection 2020-03-20
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.134
_oxdiff_exptl_absorpt_empirical_full_min 0.820