Dicerium letterbox-shaped tetraphenolates: f-block complexes designed for two-electron chemistry.
Arnold, Polly L.; Wang, Kai; Gray, Steven J.; Moreau, Liane M.; Booth, Corwin H.; Curcio, Massimiliano; Wells, Jordann A. L.; Slawin, Alexandra M. Z.; Dalton transactions (Cambridge, England : 2003) 49 (2020) 877–884; doi:10.1039/c9dt03291f

data_7703028
_publ_section_title
;
 Dicerium letterbox-shaped tetraphenolates: f-block complexes designed for
 two-electron chemistry.
;
_journal_issue                   3
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              877
_journal_page_last               884
_journal_paper_doi               10.1039/c9dt03291f
_journal_volume                  49
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         '2(C144 H204 Ce2 O12), 2(C6 H6)'
_chemical_formula_sum            'C300 H420 Ce4 O24'
_chemical_formula_weight         4970.81
_space_group_crystal_system      monoclinic
_space_group_IT_number           7
_space_group_name_Hall           'P -2yac'
_space_group_name_H-M_alt        'P 1 n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-07-15
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-07-18 deposited with the CCDC.	2019-12-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.828(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   16.5331(2)
_cell_length_b                   31.1551(4)
_cell_length_c                   36.0837(6)
_cell_measurement_reflns_used    86415
_cell_measurement_temperature    93
_cell_measurement_theta_max      28.24
_cell_measurement_theta_min      1.79
_cell_volume                     18313.6(5)
_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    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      93.15
_diffrn_detector_area_resol_mean 5.811
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.881
_diffrn_measurement_device_type  'Rigaku XtaLAB P200'
_diffrn_measurement_method
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Spherical absorption correction
 using equivalent radius and absorption coefficient.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71075
_diffrn_reflns_av_R_equivalents  0.1330
_diffrn_reflns_av_unetI/netI     0.1104
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.881
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       41
_diffrn_reflns_limit_k_min       -41
_diffrn_reflns_limit_l_max       46
_diffrn_reflns_limit_l_min       -47
_diffrn_reflns_number            253908
_diffrn_reflns_point_group_measured_fraction_full 0.976
_diffrn_reflns_point_group_measured_fraction_max 0.816
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.38
_diffrn_reflns_theta_min         1.60
_exptl_absorpt_coefficient_mu    0.534
_exptl_absorpt_correction_T_max  0.958
_exptl_absorpt_correction_T_min  0.562
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Spherical absorption correction
 using equivalent radius and absorption coefficient.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dull bluish blue'
_exptl_crystal_colour_lustre     dull
_exptl_crystal_colour_modifier   bluish
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    0.901
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             5288
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.08
_refine_diff_density_max         3.913
_refine_diff_density_min         -2.639
_refine_diff_density_rms         0.165
_refine_ls_abs_structure_details
;
 Flack x determined using 19216 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.004(5)
_refine_ls_extinction_coef       0.00029(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2883
_refine_ls_number_reflns         74873
_refine_ls_number_restraints     3048
_refine_ls_restrained_S_all      1.108
_refine_ls_R_factor_all          0.1239
_refine_ls_R_factor_gt           0.1112
_refine_ls_shift/su_max          8.074
_refine_ls_shift/su_mean         0.181
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2768
_refine_ls_wR_factor_ref         0.2878
_reflns_Friedel_coverage         0.851
_reflns_Friedel_fraction_full    0.953
_reflns_Friedel_fraction_max     0.751
_reflns_number_gt                58411
_reflns_number_total             74873
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9dt03291f2.cif
_cod_data_source_block           shelxl
_cod_depositor_comments
'Adding full bibliography for 7703018--7703028.cif.'
_cod_database_code               7703028
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.959
_shelx_estimated_absorpt_t_min   0.901
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.430(6)
 0.570(6)
2. 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
3. Restrained distances
 C3C-C2C
 1.45 with sigma of 0.02
 C3C-C4C
 1.45 with sigma of 0.02
 C4C-C5C
 1.45 with sigma of 0.02
 C905-C904
 1.5 with sigma of 0.02
 C628-C625
 1.56 with sigma of 0.02
 C626-C625
 1.56 with sigma of 0.02
 C447-C445
 1.56 with sigma of 0.02
 C446-C445
 1.56 with sigma of 0.02
 C448-C445
 1.56 with sigma of 0.02
 C900-C901
 1.56 with sigma of 0.02
 C902-C901
 1.56 with sigma of 0.02
 C903-C902
 1.56 with sigma of 0.02
 C906-C907 = C905-C906 = C905-C904
 1.56 with sigma of 0.02
 C930-C929 = C930-C931 = C932-C931
 1.56 with sigma of 0.02
 C342-C340 = C340-C341 = C340-C343
 1.55 with sigma of 0.02
 C443-C440 = C441-C440 = C442-C440
 1.55 with sigma of 0.02
 C841-C840 = C842-C840 = C840-C843
 1.55 with sigma of 0.02
 C914-C913
 1.45 with sigma of 0.02
 O18-C907 = O18-C904
 1.45 with sigma of 0.02
 C905-C904 = C905-C906 = C906-C907
 1.46 with sigma of 0.02
 C902-C901 = C900-C901 = C903-C902
 1.45 with sigma of 0.02
 C918-C919
 1.45 with sigma of 0.02
 Ce3-O15
 2.146 with sigma of 0.02
 C918-C917
 1.5 with sigma of 0.02
 C247-C245
 1.55 with sigma of 0.02
 C248-C245
 1.55 with sigma of 0.02
 C246-C245
 1.55 with sigma of 0.02
 C241-C240
 1.55 with sigma of 0.02
 C146-C145
 1.55 with sigma of 0.02
 C145-C147
 1.55 with sigma of 0.02
 C145-C148
 1.55 with sigma of 0.02
 C248-C247 = C247-C246 = C248-C246
 2.55 with sigma of 0.02
 C247-C24A = C24A-C248
 2.65 with sigma of 0.02
 C24A-C246
 2.65 with sigma of 0.02
 C24A-C245
 1.5 with sigma of 0.02
 O14-C21A
 1.45 with sigma of 0.02
 C44A-C445
 1.55 with sigma of 0.02
 C645-C646
 1.55 with sigma of 0.02
 C142-C140
 1.55 with sigma of 0.02
 C547-C545 = C548-C545
 1.55 with sigma of 0.02
 C227-C225
 1.5 with sigma of 0.02
 C225-C228
 1.5 with sigma of 0.02
 C225-C227
 1.5 with sigma of 0.02
 C225-C226
 1.5 with sigma of 0.02
 C243-C240
 1.5 with sigma of 0.02
 C243-C23
 2.8 with sigma of 0.02
 C228-C226
 1.5 with sigma of 0.02
 C23-C243
 2.9 with sigma of 0.02
 C243-C242 = C243-C241
 2.5 with sigma of 0.02
 C241-C242
 2.5 with sigma of 0.02
 C228-C225
 1.5 with sigma of 0.02
 C228-C227
 1.5 with sigma of 0.02
 C227-C225 = C227-C226 = C226-C225
 2.5 with sigma of 0.02
 C22A-C225
 1.5 with sigma of 0.02
 C22A-C228
 2.5 with sigma of 0.02
 C22A-C227
 2.5 with sigma of 0.02
 C22A-C226
 2.5 with sigma of 0.02
 C225-C21A
 2.5 with sigma of 0.02
 C21A-C225 = C225-C23A
 2.5 with sigma of 0.02
 C228-C227 = C227-C226
 2.5 with sigma of 0.02
 C227-C226 = C226-C228
 2.5 with sigma of 0.02
 C226-C228 = C228-C227
 2.5 with sigma of 0.02
 C348-C347
 2.5 with sigma of 0.02
 C226-C228
 2.5 with sigma of 0.02
 C916-C226
 3.3 with sigma of 0.02
 C343-C341 \\sim C341-C342
 with sigma of 0.02
 C341-C342 \\sim C342-C343
 with sigma of 0.02
 C342-C343 \\sim C343-C341
 with sigma of 0.02
 C148-C147 \\sim C147-C146
 with sigma of 0.02
 C147-C146 \\sim C146-C148
 with sigma of 0.02
 C146-C148 \\sim C148-C147
 with sigma of 0.02
 C25A-C245 \\sim C245-C23A
 with sigma of 0.02
 C228-C226 \\sim C226-C227
 with sigma of 0.02
 C227-C228 \\sim C228-C226
 with sigma of 0.02
 C243-C241 \\sim C241-C242
 with sigma of 0.02
 C241-C242 \\sim C242-C243
 with sigma of 0.02
 C242-C241 \\sim C241-C243
 with sigma of 0.02
 C243-C24 \\sim C24-C242
 with sigma of 0.02
 C241-C24 \\sim C24-C242
 with sigma of 0.02
 C241-C24 \\sim C24-C243
 with sigma of 0.02
 C242-C24 \\sim C24-C243
 with sigma of 0.02
 C242-C24 \\sim C24-C241
 with sigma of 0.02
 C25-C240 \\sim C240-C23
 with sigma of 0.02
 C21A-C225 \\sim C225-C23A
 with sigma of 0.02
4. Restrained planarity
 C25A, C20A, C21A, C22A, C23A, C24A, C245
 with sigma of 0.1
 C8BA, C245, C24A, C25A, C20A, C21A, C22A, C23A
 with sigma of 0.1
 C225, C22A, C21A, C23A, C24A
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
Uanis(C81A) \\sim Ueq, Uanis(C328) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C342) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
6. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7.a Ternary CH refined with riding coordinates:
 C1(H1), C1B(H1B), C8(H8), C8B(H8B), C1C(H1C), C1A(H1A), C8C(H8C), C8A(H8A)
7.b Secondary CH2 refined with riding coordinates:
 C900(H90A,H90B), C901(H90C,H90D), C902(H90E,H90F), C903(H90G,H90H), C904(H90I,
 H90J), C905(H90K,H90L), C906(H90M,H90N), C907(H90O,H90P), C908(H90Q,H90R),
 C909(H90S,H90T), C910(H91A,H91B), C911(H91C,H91D), C912(H91E,H91F), C913(H91G,
 H91H), C914(H91I,H91J), C915(H91K,H91L), C916(H91M,H91N), C917(H91O,H91P),
 C918(H91Q,H91R), C919(H91S,H91T), C920(H92A,H92B), C921(H92C,H92D), C922(H92E,
 H92F), C924(H92G,H92H), C925(H92I,H92J), C926(H92K,H92L), C927(H92M,H92N),
 C928(H92O,H92P), C929(H92Q,H92R), C930(H93A,H93B), C931(H93C,H93D), C932(H93E,
 H93F)
7.c Aromatic/amide H refined with riding coordinates:
 C3B(H3B), C4B(H4B), C6(H6), C4(H4), C3(H3), C7(H7), C6B(H6B), C7B(H7B),
 C13(H13), C15(H15), C23(H23), C25(H25), C33(H33), C35(H35), C45(H45), C43(H43),
  C55(H55), C53(H53), C63(H63), C65(H65), C73(H73), C75(H75), C83(H83),
 C85(H85), C3A(H3A), C4A(H4A), C6A(H6A), C7A(H7A), C6C(H6C), C4C(H4C), C3C(H3C),
  C7C(H7C), C13A(H13A), C15A(H15A), C23A(H23A), C25A(H25A), C33A(H33A),
 C35A(H35A), C43A(H43A), C45A(H45A), C53A(H53A), C55A(H55A), C63A(H63A),
 C65A(H65A), C73A(H73A), C75A(H75A), C85A(H85A), C83A(H83A), C937(H937),
 C938(H938), C933(H933), C934(H934), C935(H935), C936(H936), C943(H943),
 C944(H944), C939(H939), C940(H940), C941(H941), C942(H942)
7.d Fitted hexagon refined as free rotating group:
 C6(C5,C4,C3,C2,C7), C23(C24,C25,C20,C21,C22), C42(C41,C40,C45,C44,C43),
 C54(C55,C50,C51,C2AA,C53), C83(C82,C81,C80,C85,C84), C2A(C3A,C4A,C5A,C6A,C7A),
 C6C(C5C,C4C,C3C,C2C,C7C), C8BA(C12A,C13A,C14A,C15A,C10A), C23A(C22A,C21A,C20A,
 C25A,C24A), C51A(C52A,C53A,C54A,C55A,C50A), C63A(C62A,C61A,C60A,C65A,C64A),
 C85A(C80A,C81A,C82A,C83A,C84A), C937(C938,C933,C934,C935,C936), C943(C944,C939,
 C940,C941,C942)
7.e Idealised Me refined as rotating group:
 C121(H12A,H12B,H12C), C122(H12D,H12E,H12F), C123(H12G,H12H,H12I), C141(H14A,
 H14B,H14C), C142(H14D,H14E,H14F), C143(H14G,H14H,H14I), C221(H22A,H22B,H22C),
 C222(H22D,H22E,H22F), C223(H22G,H22H,H22I), C241(H24A,H24B,H24C), C242(H24D,
 H24E,H24F), C243(H24G,H24H,H24I), C321(H32A,H32B,H32C), C322(H32D,H32E,H32F),
 C323(H32G,H32H,H32I), C341(H34A,H34B,H34C), C342(H34D,H34E,H34F), C343(H34G,
 H34H,H34I), C421(H42A,H42B,H42C), C422(H42D,H42E,H42F), C423(H42G,H42H,H42I),
 C441(H44A,H44B,H44C), C442(H44D,H44E,H44F), C443(H44G,H44H,H44I), C521(H52A,
 H52B,H52C), C522(H52D,H52E,H52F), C523(H52G,H52H,H52I), C541(H54A,H54B,H54C),
 C542(H54D,H54E,H54F), C543(H54G,H54H,H54I), C621(H62A,H62B,H62C), C622(H62D,
 H62E,H62F), C623(H62G,H62H,H62I), C641(H64A,H64B,H64C), C642(H64D,H64E,H64F),
 C643(H64G,H64H,H64I), C721(H72A,H72B,H72C), C722(H72D,H72E,H72F), C723(H72G,
 H72H,H72I), C741(H74A,H74B,H74C), C742(H74D,H74E,H74F), C743(H74G,H74H,H74I),
 C821(H82A,H82B,H82C), C822(H82D,H82E,H82F), C823(H82G,H82H,H82I), C841(H84A,
 H84B,H84C), C842(H84D,H84E,H84F), C843(H84G,H84H,H84I), C7AA(H7AA,H7AB,H7AC),
 C126(H12J,H12K,H12L), C127(H12M,H12N,H12O), C146(H14J,H14K,H14L), C147(H14M,
 H14N,H14O), C148(H14P,H14Q,H14R), C226(H22J,H22K,H22L), C227(H22M,H22N,H22O),
 C228(H22P,H22Q,H22R), C246(H24J,H24K,H24L), C326(H32J,H32K,H32L), C327(H32M,
 H32N,H32O), C328(H32P,H32Q,H32R), C346(H34J,H34K,H34L), C347(H34M,H34N,H34O),
 C348(H34P,H34Q,H34R), C426(H42J,H42K,H42L), C427(H42M,H42N,H42O), C428(H42P,
 H42Q,H42R), C446(H44J,H44K,H44L), C447(H44M,H44N,H44O), C448(H44P,H44Q,H44R),
 C526(H52J,H52K,H52L), C527(H52M,H52N,H52O), C528(H52P,H52Q,H52R), C546(H54J,
 H54K,H54L), C547(H54M,H54N,H54O), C548(H54P,H54Q,H54R), C626(H62J,H62K,H62L),
 C627(H62M,H62N,H62O), C628(H62P,H62Q,H62R), C646(H64J,H64K,H64L), C647(H64M,
 H64N,H64O), C648(H64P,H64Q,H64R), C726(H72J,H72K,H72L), C727(H72M,H72N,H72O),
 C728(H72P,H72Q,H72R), C746(H74J,H74K,H74L), C747(H74M,H74N,H74O), C748(H74P,
 H74Q,H74R), C826(H82J,H82K,H82L), C827(H82M,H82N,H82O), C828(H82P,H82Q,H82R),
 C846(H84J,H84K,H84L), C847(H84M,H84N,H84O), C848(H84P,H84Q,H84R), C248(H24M,
 H24N,H24O), C247(H24P,H24Q,H24R)
;
_olex2_submission_special_instructions 'No special instructions were received'