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_7128229
_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         'C174 H174 B2 F40 Mg4 N8'
_chemical_formula_sum            'C174 H174 B2 F40 Mg4 N8'
_chemical_formula_weight         3256.06
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-09-25
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-03-29 deposited with the CCDC.	2021-04-26 downloaded from the CCDC.
;
_cell_angle_alpha                111.8037(19)
_cell_angle_beta                 101.0099(17)
_cell_angle_gamma                100.4072(16)
_cell_formula_units_Z            2
_cell_length_a                   14.1185(3)
_cell_length_b                   25.0351(5)
_cell_length_c                   25.6684(5)
_cell_measurement_reflns_used    20049
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      73.6790
_cell_measurement_theta_min      3.2800
_cell_volume                     7947.3(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (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 0.991
_diffrn_measured_fraction_theta_max 0.956
_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    -81.00  11.00   1.00    1.50    --  -40.61  19.00-120.00   92
  2  \w    -64.00  34.00   1.00    1.50    --  -40.61  38.00 -60.00   98
  3  \w    -57.00  33.00   1.00    1.50    --  -40.61  57.00  60.00   90
  4  \w     26.00  85.00   1.00    1.50    --   40.61-125.00-180.00   59
  5  \w     13.00  64.00   1.00    1.50    --   40.61 -99.00 -30.00   51
  6  \w     60.00 110.00   1.00    6.00    --  107.07 -94.00  90.00   50
  7  \w     94.00 141.00   1.00    6.00    --  107.07 125.00   0.00   47
  8  \w     34.00  75.00   1.00    6.00    --  107.07 -45.00  90.00   41
  9  \w     53.00 140.00   1.00    6.00    --  107.07 -77.00 150.00   87
 10  \w     42.00 118.00   1.00    6.00    --  107.07-125.00   0.00   76
 11  \w     35.00 133.00   1.00    6.00    --  107.07 -61.00 -30.00   98
 12  \w     90.00 178.00   1.00    6.00    --  107.07  45.00 120.00   88
 13  \w     93.00 178.00   1.00    6.00    --  107.07  45.00-180.00   85
 14  \w     93.00 130.00   1.00    6.00    --  107.07 -45.00  90.00   37
 15  \w     85.00 175.00   1.00    6.00    --  107.07  77.00  60.00   90
;
_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      0.0471009000
_diffrn_orient_matrix_UB_12      -0.0491421000
_diffrn_orient_matrix_UB_13      -0.0315721000
_diffrn_orient_matrix_UB_21      0.0974203000
_diffrn_orient_matrix_UB_22      0.0306827000
_diffrn_orient_matrix_UB_23      0.0508514000
_diffrn_orient_matrix_UB_31      -0.0408314000
_diffrn_orient_matrix_UB_32      -0.0373985000
_diffrn_orient_matrix_UB_33      0.0309624000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0297
_diffrn_reflns_av_unetI/netI     0.0413
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.956
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            51180
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.956
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.735
_diffrn_reflns_theta_min         3.296
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.097
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75834
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.361
_exptl_crystal_description       block
_exptl_crystal_F_000             3384
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.33
_exptl_crystal_size_min          0.193
_refine_diff_density_max         0.393
_refine_diff_density_min         -0.344
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2430
_refine_ls_number_reflns         30713
_refine_ls_number_restraints     739
_refine_ls_restrained_S_all      1.010
_refine_ls_R_factor_all          0.0676
_refine_ls_R_factor_gt           0.0485
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0581P)^2^+4.8698P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1300
_refine_ls_wR_factor_ref         0.1433
_reflns_Friedel_coverage         0.000
_reflns_number_gt                23496
_reflns_number_total             30713
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc01691a2.cif
_cod_data_source_block           hasj180918a
_cod_depositor_comments
'Adding full bibliography for 7128228--7128235.cif.'
_cod_database_code               7128229
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C H N Mg B F '
_reflns_odcompleteness_completeness 99.49
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
2. Restrained distances
 C194-C195 \\sim C88-C87 \\sim C89-C87 \\sim C194-C196
 with sigma of 0.02
 C86-C194 \\sim C87-C86
 with sigma of 0.02
 C206-C208 \\sim C171-C169 \\sim C170-C169 \\sim C206-C207
 with sigma of 0.02
 C169-C168 \\sim C168-C206
 with sigma of 0.02
 C183-C182 \\sim C21-C20 \\sim C22-C20 \\sim C184-C182
 with sigma of 0.02
 C12-C182 \\sim C20-C12
 with sigma of 0.02
 C109-C107 \\sim C203-C205 \\sim C108-C107 \\sim C203-C204
 with sigma of 0.02
 C92-C90 \\sim C197-C199 \\sim C91-C90 \\sim C198-C197
 with sigma of 0.02
 C202-C200 \\sim C106-C104 \\sim C105-C104 \\sim C201-C200
 with sigma of 0.02
 C103-C200 \\sim C104-C103
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C175 \\sim C176 \\sim C177 \\sim
C178 \\sim C179: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
C59 \\sim C60 \\sim C61 \\sim C62 \\sim C63 \\sim C185 \\sim C186 \\sim C187
\\sim C188 \\sim C189: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C172 \\sim C174 \\sim C210: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
C82 \\sim C83 \\sim C84 \\sim C85 \\sim C90 \\sim C91 \\sim C92 \\sim C190
\\sim C191 \\sim C192 \\sim C193 \\sim C197 \\sim C198 \\sim C199: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08
C109 \\sim C205: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
C107 \\sim C108 \\sim C109 \\sim C203 \\sim C204 \\sim C205: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
C104 \\sim C105 \\sim C106 \\sim C200 \\sim C201 \\sim C202: within 4A with
sigma of 0.02 and sigma for terminal atoms of 0.4
C181 \\sim C18: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
4. Rigid body (RIGU) restrains
 C168, C169, C206
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C175, C176, C177, C178, C179
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C172, C210
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C200, C201
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C17, C181
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C192)=Sof(H192)=Sof(C191)=Sof(H191)=Sof(C190)=Sof(C193)=Sof(H193)=
 Sof(C194)=Sof(H194)=Sof(C195)=Sof(H19d)=Sof(H19e)=Sof(H19f)=Sof(C196)=
 Sof(H19g)=Sof(H19h)=Sof(H19i)=Sof(C197)=Sof(H197)=Sof(C198)=Sof(H19j)=
 Sof(H19k)=Sof(H19l)=Sof(C199)=Sof(H19m)=Sof(H19n)=Sof(H19o)=1-FVAR(1)
 Sof(C82)=Sof(C83)=Sof(H83)=Sof(C84)=Sof(H84)=Sof(C85)=Sof(H85)=Sof(C87)=
 Sof(H87)=Sof(C88)=Sof(H88a)=Sof(H88b)=Sof(H88c)=Sof(C89)=Sof(H89a)=Sof(H89b)=
 Sof(H89c)=Sof(C90)=Sof(H90)=Sof(C91)=Sof(H91a)=Sof(H91b)=Sof(H91c)=Sof(C92)=
 Sof(H92a)=Sof(H92b)=Sof(H92c)=FVAR(1)
 Sof(H17a)=Sof(C180)=Sof(H18d)=Sof(H18e)=Sof(H18f)=Sof(C181)=Sof(H18g)=
 Sof(H18h)=Sof(H18i)=1-FVAR(2)
 Sof(H17)=Sof(C18)=Sof(H18a)=Sof(H18b)=Sof(H18c)=Sof(C19)=Sof(H19a)=Sof(H19b)=
 Sof(H19c)=FVAR(2)
 Sof(H15d)=Sof(H15e)=Sof(H15f)=Sof(H17b)=Sof(C209)=Sof(H20s)=Sof(H20t)=
 Sof(H20u)=Sof(C210)=Sof(H21d)=Sof(H21e)=Sof(H21f)=1-FVAR(3)
 Sof(H15a)=Sof(H15b)=Sof(H15c)=Sof(H172)=Sof(C173)=Sof(H17i)=Sof(H17j)=
 Sof(H17k)=Sof(C174)=Sof(H17l)=Sof(H17m)=Sof(H17n)=FVAR(3)
 Sof(C206)=Sof(H206)=Sof(C207)=Sof(H20m)=Sof(H20n)=Sof(H20o)=Sof(C208)=
 Sof(H20p)=Sof(H20q)=Sof(H20r)=1-FVAR(4)
 Sof(C169)=Sof(H169)=Sof(C170)=Sof(H17c)=Sof(H17d)=Sof(H17e)=Sof(C171)=
 Sof(H17f)=Sof(H17g)=Sof(H17h)=FVAR(4)
 Sof(C175)=Sof(H175)=Sof(C176)=Sof(H176)=Sof(C177)=Sof(H177)=Sof(C178)=
 Sof(H178)=Sof(C179)=Sof(H179)=1-FVAR(5)
 Sof(C1)=Sof(H1)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(H4)=Sof(C5)=
 Sof(H5)=FVAR(5)
 Sof(C185)=Sof(H185)=Sof(C186)=Sof(H186)=Sof(C187)=Sof(H187)=Sof(C188)=
 Sof(H188)=Sof(C189)=Sof(H189)=1-FVAR(6)
 Sof(C59)=Sof(H59)=Sof(C60)=Sof(H60)=Sof(C61)=Sof(H61)=Sof(C62)=Sof(H62)=
 Sof(C63)=Sof(H63)=FVAR(6)
 Sof(C182)=Sof(H182)=Sof(C183)=Sof(H18j)=Sof(H18k)=Sof(H18l)=Sof(C184)=
 Sof(H18m)=Sof(H18n)=Sof(H18o)=1-FVAR(7)
 Sof(C20)=Sof(H20)=Sof(C21)=Sof(H21a)=Sof(H21b)=Sof(H21c)=Sof(C22)=Sof(H22a)=
 Sof(H22b)=Sof(H22c)=FVAR(7)
 Sof(C203)=Sof(H203)=Sof(C204)=Sof(H20g)=Sof(H20h)=Sof(H20i)=Sof(C205)=
 Sof(H20j)=Sof(H20k)=Sof(H20l)=1-FVAR(8)
 Sof(C107)=Sof(H107)=Sof(C108)=Sof(H10j)=Sof(H10k)=Sof(H10l)=Sof(C109)=
 Sof(H10m)=Sof(H10n)=Sof(H10o)=FVAR(8)
 Sof(C200)=Sof(H200)=Sof(C201)=Sof(H20a)=Sof(H20b)=Sof(H20c)=Sof(C202)=
 Sof(H20d)=Sof(H20e)=Sof(H20f)=1-FVAR(9)
 Sof(C104)=Sof(H104)=Sof(C105)=Sof(H10d)=Sof(H10e)=Sof(H10f)=Sof(C106)=
 Sof(H10g)=Sof(H10h)=Sof(H10i)=FVAR(9)
6.a Ternary CH refined with riding coordinates:
 C17(H17), C17(H17a), C29(H29), C32(H32), C75(H75), C78(H78), C116(H116),
 C119(H119), C157(H157), C160(H160), C172(H172), C172(H17b), C20(H20), C87(H87),
  C90(H90), C104(H104), C107(H107), C169(H169), C182(H182), C194(H194),
 C197(H197), C200(H200), C203(H203), C206(H206)
6.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C13(H13), C14(H14), C15(H15), C25(H25), C26(H26), C27(H27), C66(H66),
 C71(H71), C72(H72), C73(H73), C95(H95), C100(H100), C101(H101), C102(H102),
 C112(H112), C113(H113), C114(H114), C148(H148), C153(H153), C154(H154),
 C155(H155), C165(H165), C166(H166), C167(H167), C1(H1), C2(H2), C3(H3), C4(H4),
  C5(H5), C59(H59), C60(H60), C61(H61), C62(H62), C63(H63), C83(H83), C84(H84),
 C85(H85), C175(H175), C176(H176), C177(H177), C178(H178), C179(H179),
 C185(H185), C186(H186), C187(H187), C188(H188), C189(H189), C192(H192),
 C191(H191), C193(H193)
6.c Fitted hexagon refined as free rotating group:
 C192(C191,C190,C81,C86,C193)
6.d Idealised Me refined as rotating group:
 C6(H6a,H6b,H6c), C10(H10a,H10b,H10c), C30(H30a,H30b,H30c), C31(H31a,H31b,
 H31c), C33(H33a,H33b,H33c), C34(H34a,H34b,H34c), C64(H64a,H64b,H64c), C68(H68a,
 H68b,H68c), C76(H76a,H76b,H76c), C77(H77a,H77b,H77c), C79(H79a,H79b,H79c),
 C80(H80a,H80b,H80c), C93(H93a,H93b,H93c), C97(H97a,H97b,H97c), C117(H11a,H11b,
 H11c), C118(H11d,H11e,H11f), C120(H12a,H12b,H12c), C121(H12d,H12e,H12f),
 C146(H14a,H14b,H14c), C150(H15d,H15e,H15f), C150(H15a,H15b,H15c), C158(H15g,
 H15h,H15i), C159(H15j,H15k,H15l), C161(H16a,H16b,H16c), C162(H16d,H16e,H16f),
 C18(H18a,H18b,H18c), C19(H19a,H19b,H19c), C21(H21a,H21b,H21c), C22(H22a,H22b,
 H22c), C88(H88a,H88b,H88c), C89(H89a,H89b,H89c), C91(H91a,H91b,H91c), C92(H92a,
 H92b,H92c), C105(H10d,H10e,H10f), C106(H10g,H10h,H10i), C108(H10j,H10k,H10l),
 C109(H10m,H10n,H10o), C170(H17c,H17d,H17e), C171(H17f,H17g,H17h), C173(H17i,
 H17j,H17k), C174(H17l,H17m,H17n), C180(H18d,H18e,H18f), C181(H18g,H18h,H18i),
 C183(H18j,H18k,H18l), C184(H18m,H18n,H18o), C195(H19d,H19e,H19f), C196(H19g,
 H19h,H19i), C198(H19j,H19k,H19l), C199(H19m,H19n,H19o), C201(H20a,H20b,H20c),
 C202(H20d,H20e,H20f), C204(H20g,H20h,H20i), C205(H20j,H20k,H20l), C207(H20m,
 H20n,H20o), C208(H20p,H20q,H20r), C209(H20s,H20t,H20u), C210(H21d,H21e,H21f)
;
_olex2_date_sample_data_collection 2018-09-18
_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 1.323
_oxdiff_exptl_absorpt_empirical_full_min 0.526