On the existence of low-valent magnesium-calcium complexes.
Mai, Jonathan; Rösch, Bastian; Patel, Neha; Langer, Jens; Harder, Sjoerd; Chemical science 14 (2023) 4724–4734; doi:10.1039/d3sc00909b

data_1568863
_publ_section_title
;
 On the existence of low-valent magnesium-calcium complexes.
;
_journal_issue                   18
_journal_name_full               'Chemical science'
_journal_page_first              4724
_journal_page_last               4734
_journal_paper_doi               10.1039/d3sc00909b
_journal_volume                  14
_journal_year                    2023
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C94 H136 Ca Mg N4'
_chemical_formula_sum            'C94 H136 Ca Mg N4'
_chemical_formula_weight         1386.45
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-11-11
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-02-08 deposited with the CCDC.	2023-04-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.5514(3)
_cell_length_b                   13.0869(2)
_cell_length_c                   29.0951(4)
_cell_measurement_reflns_used    13240
_cell_measurement_temperature    100.0(3)
_cell_measurement_theta_max      72.0300
_cell_measurement_theta_min      3.9440
_cell_volume                     8206.0(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2903
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.987
_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    -99.00  45.00   1.00   17.50    --  -40.86   0.00  90.00  144
  2  \w    103.00 161.00   1.00   70.00    --  104.57  77.00   0.00   58
  3  \w    121.00 158.00   1.00   70.00    --  104.57 111.00 150.00   37
  4  \w     80.00 178.00   1.00   70.00    --  104.57  45.00-120.00   98
  5  \w    105.00 177.00   1.00   70.00    --  104.57 111.00 -90.00   72
  6  \w    134.00 177.00   1.00   70.00    --  104.57 111.00   0.00   43
  7  \w    108.00 176.00   1.00   70.00    --  104.57 111.00 120.00   68
  8  \w    117.00 143.00   1.00   70.00    --  104.57  77.00 120.00   26
  9  \w     64.00 113.00   1.00   17.50    --   40.86  55.00  96.00   49
 10  \w     14.00  40.00   1.00   17.50    --   40.86  55.00  96.00   26
 11  \w     19.00  45.00   1.00   17.50    --   40.86 -99.00-120.00   26
 12  \w     90.00 141.00   1.00   70.00    --  104.57  61.00-180.00   51
 13  \w    104.00 140.00   1.00   70.00    --  104.57 111.00  60.00   36
 14  \w     94.00 120.00   1.00   70.00    --  104.57 -45.00 150.00   26
 15  \w    149.00 175.00   1.00   70.00    --  104.57  61.00-180.00   26
 16  \w     46.00  73.00   1.00   70.00    --  104.57 -45.00 150.00   27
;
_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      -0.0478713000
_diffrn_orient_matrix_UB_12      0.0515968000
_diffrn_orient_matrix_UB_13      -0.0317443000
_diffrn_orient_matrix_UB_21      -0.0240147000
_diffrn_orient_matrix_UB_22      -0.1057880000
_diffrn_orient_matrix_UB_23      -0.0149259000
_diffrn_orient_matrix_UB_31      -0.0473198000
_diffrn_orient_matrix_UB_32      0.0015245000
_diffrn_orient_matrix_UB_33      0.0396776000
_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  0.0532
_diffrn_reflns_av_unetI/netI     0.0550
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            38240
_diffrn_reflns_point_group_measured_fraction_full 0.924
_diffrn_reflns_point_group_measured_fraction_max 0.900
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.327
_diffrn_reflns_theta_min         3.038
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.079
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.724
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
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 brownish orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   brownish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.122
_exptl_crystal_description       block
_exptl_crystal_F_000             3040
_exptl_crystal_size_max          0.186
_exptl_crystal_size_mid          0.135
_exptl_crystal_size_min          0.086
_refine_diff_density_max         0.354
_refine_diff_density_min         -0.167
_refine_diff_density_rms         0.041
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   -0.003(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1201
_refine_ls_number_reflns         14603
_refine_ls_number_restraints     2124
_refine_ls_restrained_S_all      0.962
_refine_ls_R_factor_all          0.0591
_refine_ls_R_factor_gt           0.0523
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0945P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1356
_refine_ls_wR_factor_ref         0.1425
_reflns_Friedel_coverage         0.785
_reflns_Friedel_fraction_full    0.844
_reflns_Friedel_fraction_max     0.808
_reflns_number_gt                13121
_reflns_number_total             14603
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc00909b2.cif
_cod_data_source_block           hasj210728b
_cod_depositor_comments
'Adding full bibliography for 1568860--1568864.cif.'
_cod_database_code               1568863
_shelx_shelxl_version_number     2019/2
_chemical_oxdiff_formula         C94H136CaMgN4
_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
2. Restrained distances
 C92A-C91A \\sim C92-C91 \\sim C94-C93 \\sim C93A-C94A \\sim C43A-C42A \\sim
C43-C42 \\sim C41-C40 ~
 C41A-C40A
 with sigma of 0.02
 C65-C66 \\sim C65A-C66A \\sim C66A-C67A \\sim C67-C66
 with sigma of 0.01
 C39A-C42A \\sim C40A-C39A \\sim C42-C39 \\sim C40-C39 \\sim C69A-C72A \\sim
C72-C69 \\sim C70A-C69A ~
 C69-C70 \\sim C74-C75 \\sim C74A-C75A \\sim C77-C78 \\sim C74A-C77A \\sim
C91-C90 \\sim C91A-C90A ~
 C93-C90 \\sim C93A-C90A
 with sigma of 0.02
 C39-C33 \\sim C39A-C33 \\sim C90-C84 \\sim C84-C90A
 with sigma of 0.02
 C65A-C64A \\sim C64-C65 \\sim C67-C68 \\sim C68A-C67A
 with sigma of 0.02
 C68A-C63 \\sim C68-C63 \\sim C64A-C63 \\sim C64-C63
 with sigma of 0.02
 C40A-C42A \\sim C40-C42
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C90 \\sim C91 \\sim C92 \\sim C93 \\sim C94 \\sim C90A \\sim C91A \\sim C92A
\\sim C93A \\sim C94A: within 4A with sigma of 0.02 and sigma for terminal
atoms of 0.04 within 4A
C39 \\sim C40 \\sim C41 \\sim C42 \\sim C43 \\sim C39A \\sim C40A \\sim C41A
\\sim C42A \\sim C43A: within 4A with sigma of 0.02 and sigma for terminal
atoms of 0.04 within 4A
C63 \\sim C64 \\sim C65 \\sim C66 \\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim
C71 \\sim C72 \\sim C73 \\sim C74 \\sim C75 \\sim C76 \\sim C77 \\sim C78 \\sim
C64A \\sim C65A \\sim C66A \\sim C67A \\sim C68A \\sim C69A \\sim C70A \\sim
C71A \\sim C72A \\sim C73A \\sim C74A \\sim C75A \\sim C76A \\sim C77A \\sim
C78A: within 4A with sigma of 0.02 and sigma for terminal atoms of 0.04 within
4A
C42 \\sim C42A \\sim C39 \\sim C39A \\sim C43A: within 4A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 4A
4. Others
 Sof(C90A)=Sof(H90A)=Sof(C91A)=Sof(H91C)=Sof(H91D)=Sof(C92A)=Sof(H92D)=
 Sof(H92E)=Sof(H92F)=Sof(C93A)=Sof(H93C)=Sof(H93D)=Sof(C94A)=Sof(H94D)=
 Sof(H94E)=Sof(H94F)=1-FVAR(1)
 Sof(C90)=Sof(H90)=Sof(C91)=Sof(H91A)=Sof(H91B)=Sof(C92)=Sof(H92A)=Sof(H92B)=
 Sof(H92C)=Sof(C93)=Sof(H93A)=Sof(H93B)=Sof(C94)=Sof(H94A)=Sof(H94B)=Sof(H94C)=
 FVAR(1)
 Sof(C64A)=Sof(C65A)=Sof(H65A)=Sof(C66A)=Sof(H66A)=Sof(C67A)=Sof(H67A)=
 Sof(C68A)=Sof(C69A)=Sof(H69A)=Sof(C70A)=Sof(H70C)=Sof(H70D)=Sof(C71A)=
 Sof(H71D)=Sof(H71E)=Sof(H71F)=Sof(C72A)=Sof(H72C)=Sof(H72D)=Sof(C73A)=
 Sof(H73D)=Sof(H73E)=Sof(H73F)=Sof(C74A)=Sof(H74A)=Sof(C75A)=Sof(H75C)=
 Sof(H75D)=Sof(C76A)=Sof(H76D)=Sof(H76E)=Sof(H76F)=Sof(C77A)=Sof(H77C)=
 Sof(H77D)=Sof(C78A)=Sof(H78D)=Sof(H78E)=Sof(H78F)=1-FVAR(2)
 Sof(C64)=Sof(C65)=Sof(H65)=Sof(C66)=Sof(H66)=Sof(C67)=Sof(H67)=Sof(C68)=
 Sof(C69)=Sof(H69)=Sof(C70)=Sof(H70A)=Sof(H70B)=Sof(C71)=Sof(H71A)=Sof(H71B)=
 Sof(H71C)=Sof(C72)=Sof(H72A)=Sof(H72B)=Sof(C73)=Sof(H73A)=Sof(H73B)=Sof(H73C)=
 Sof(C74)=Sof(H74)=Sof(C75)=Sof(H75A)=Sof(H75B)=Sof(C76)=Sof(H76A)=Sof(H76B)=
 Sof(H76C)=Sof(C77)=Sof(H77A)=Sof(H77B)=Sof(C78)=Sof(H78A)=Sof(H78B)=Sof(H78C)=
 FVAR(2)
 Sof(C39A)=Sof(H39A)=Sof(C40A)=Sof(H40C)=Sof(H40D)=Sof(C41A)=Sof(H41D)=
 Sof(H41E)=Sof(H41F)=Sof(C42A)=Sof(H42C)=Sof(H42D)=Sof(C43A)=Sof(H43D)=
 Sof(H43E)=Sof(H43F)=1-FVAR(3)
 Sof(C39)=Sof(H39)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(C41)=Sof(H41A)=Sof(H41B)=
 Sof(H41C)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(H43C)=
 FVAR(3)
5.a Ternary CH refined with riding coordinates:
 C18(H18), C23(H23), C34(H34), C85(H85), C39(H39), C69(H69), C74(H74),
 C90(H90), C39A(H39A), C69A(H69A), C74A(H74A), C90A(H90A)
5.b Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B), C21(H21A,H21B), C24(H24A,H24B), C26(H26A,H26B), C35(H35A,
 H35B), C37(H37A,H37B), C86(H86A,H86B), C88(H88A,H88B), C40(H40A,H40B),
 C42(H42A,H42B), C70(H70A,H70B), C72(H72A,H72B), C75(H75A,H75B), C77(H77A,H77B),
  C91(H91A,H91B), C93(H93A,H93B), C40A(H40C,H40D), C42A(H42C,H42D), C70A(H70C,
 H70D), C72A(H72C,H72D), C75A(H75C,H75D), C77A(H77C,H77D), C91A(H91C,H91D),
 C93A(H93C,H93D)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C14(H14), C15(H15), C16(H16), C30(H30), C31(H31), C32(H32), C60(H60),
 C81(H81), C82(H82), C83(H83), C65(H65), C66(H66), C67(H67), C65A(H65A),
 C66A(H66A), C67A(H67A)
5.d Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C9(H9A,H9B,H9C), C10(H10A,
 H10B,H10C), C11(H11A,H11B,H11C), C20(H20A,H20B,H20C), C22(H22A,H22B,H22C),
 C25(H25A,H25B,H25C), C27(H27A,H27B,H27C), C36(H36A,H36B,H36C), C38(H38A,H38B,
 H38C), C58(H58A,H58B,H58C), C62(H62A,H62B,H62C), C87(H87A,H87B,H87C), C89(H89A,
 H89B,H89C), C41(H41A,H41B,H41C), C43(H43A,H43B,H43C), C71(H71A,H71B,H71C),
 C73(H73A,H73B,H73C), C76(H76A,H76B,H76C), C78(H78A,H78B,H78C), C92(H92A,H92B,
 H92C), C94(H94A,H94B,H94C), C41A(H41D,H41E,H41F), C43A(H43D,H43E,H43F),
 C71A(H71D,H71E,H71F), C73A(H73D,H73E,H73F), C76A(H76D,H76E,H76F), C78A(H78D,
 H78E,H78F), C92A(H92D,H92E,H92F), C94A(H94D,H94E,H94F)
;
_shelx_res_checksum              58452
_shelx_hkl_checksum              51849
_olex2_date_sample_data_collection 2021-07-28
_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 1.339
_oxdiff_exptl_absorpt_empirical_full_min 0.715