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_7703027
_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_formula_moiety         '2(C104 H134 B2 Ce2 N8 O4), 5(C5 H5 N)'
_chemical_formula_sum            'C233 H293 B4 Ce4 N21 O8'
_chemical_formula_weight         4119.59
_chemical_name_systematic        WK-LPT-BH4
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-07-01
_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                82.210(2)
_cell_angle_beta                 74.578(2)
_cell_angle_gamma                82.7970(10)
_cell_formula_units_Z            2
_cell_length_a                   19.7117(3)
_cell_length_b                   23.3826(4)
_cell_length_c                   25.9038(6)
_cell_measurement_reflns_used    14980
_cell_measurement_temperature    100
_cell_measurement_theta_max      24.0310
_cell_measurement_theta_min      3.2210
_cell_volume                     11353.2(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_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_temperature      100
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1042
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -91.00 -34.00   1.00   15.00    --  -16.47-179.00 -60.00   57
  2  \w    -25.00  24.00   1.00   15.00    --  -16.47 -99.00-120.00   49
  3  \w    -45.00  53.00   1.00   15.00    --  -16.47  77.00   0.00   98
  4  \w    -35.00  52.00   1.00   15.00    --  -16.47  57.00  60.00   87
  5  \w    -91.00 -34.00   1.00   15.00    --  -16.47-179.00  60.00   57
  6  \w    -50.00  37.00   1.00   15.00    --   18.03 -57.00-150.00   87
  7  \w    -25.00  59.00   1.00   15.00    --   18.03 -99.00 120.00   84
  8  \w     -5.00  89.00   1.00   15.00    --   18.03  37.00  90.00   94
  9  \w    -15.00  37.00   1.00   15.00    --   18.03 -57.00   0.00   52
 10  \w    -20.00  90.00   1.00   15.00    --   18.03  19.00  30.00  110
 11  \w    -28.00  -2.00   1.00   15.00    --   18.03 -57.00-120.00   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0073025000
_diffrn_orient_matrix_UB_12      -0.0089924000
_diffrn_orient_matrix_UB_13      0.0253996000
_diffrn_orient_matrix_UB_21      -0.0197540000
_diffrn_orient_matrix_UB_22      0.0254018000
_diffrn_orient_matrix_UB_23      0.0101241000
_diffrn_orient_matrix_UB_31      -0.0310179000
_diffrn_orient_matrix_UB_32      -0.0148178000
_diffrn_orient_matrix_UB_33      0.0082774000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1102
_diffrn_reflns_av_unetI/netI     0.1338
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            177897
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.682
_diffrn_reflns_theta_min         2.851
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.845
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89044
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.205
_exptl_crystal_description       plate
_exptl_crystal_F_000             4308
_exptl_crystal_recrystallization_method 'from pyridine at -30 degree Celsius'
_exptl_crystal_size_max          0.462
_exptl_crystal_size_mid          0.176
_exptl_crystal_size_min          0.055
_refine_diff_density_max         0.915
_refine_diff_density_min         -0.857
_refine_diff_density_rms         0.103
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.010
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2616
_refine_ls_number_reflns         43075
_refine_ls_number_restraints     468
_refine_ls_restrained_S_all      1.120
_refine_ls_R_factor_all          0.1345
_refine_ls_R_factor_gt           0.0655
_refine_ls_shift/su_max          0.007
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0429P)^2^+4.2502P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1120
_refine_ls_wR_factor_ref         0.1340
_reflns_Friedel_coverage         0.000
_reflns_number_gt                24837
_reflns_number_total             43075
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9dt03291f2.cif
_cod_data_source_block           p17023
_cod_depositor_comments
'Adding full bibliography for 7703018--7703028.cif.'
_cod_database_code               7703027
_shelx_shelxl_version_number     2018/3
_audit_contact_letter
;
chemkai.wang@gmail.com;
polly.arnold@ed.ac.uk;
;
_publ_section_exptl
;
Any special experimental details
;
_chemical_oxdiff_formula         'C70 H70 O4 Pr2 B2'
_reflns_odcompleteness_completeness 99.84
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.63
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H,H,H,H,H,H,H,H,H,H,H,H,H,H) groups
2. Restrained distances
 B2-H2D = B2-H2B = B2-H2A = B2-H2C
 1.2 with sigma of 0.02
 B3-H3C = B3-H3E = B3-H3D = B3-H3B
 1.2 with sigma of 0.02
 B4-H4E = B4-H4C = B4-H4B = B4-H4D
 1.2 with sigma of 0.02
 B1-H1B = B1-H1C = B1-H1E = B1-H1D
 1.2 with sigma of 0.02
 H1D-H89A
 1.85 with sigma of 0.02
 B4-H4E \\sim B4-H4C \\sim B4-H4B \\sim B4-H4D
 with sigma of 0.02
 B3-H3D \\sim B3-H3C \\sim B3-H3B \\sim B3-H3E
 with sigma of 0.02
 B2-H2A \\sim B2-H2C \\sim B2-H2B \\sim B2-H2D
 with sigma of 0.02
 H3B-H3C \\sim H3C-H3D
 with sigma of 0.02
 H3C-H3D \\sim H3D-H3E
 with sigma of 0.02
 H3D-H3E \\sim H3E-H3C
 with sigma of 0.02
 H3E-H3B \\sim H3B-H3C
 with sigma of 0.02
 H3B-H3C \\sim H3C-H3E
 with sigma of 0.02
 B4-H4D \\sim B4-H4E \\sim B4-H4C \\sim B4-H4B
 with sigma of 0.02
 B2-H2A \\sim B2-H2C \\sim B2-H2D \\sim B2-H2B
 with sigma of 0.02
 O2-O1 \\sim O2-N1 \\sim O2-N3 \\sim O1-N1 \\sim O1-N21 \\sim O1-B1 \\sim N1-N2
\\sim N2-N3 \\sim N2-B1 \\sim N21-
 N3 \\sim N21-B1
 with sigma of 0.04
 Ce1-O2 \\sim Ce1-O1 \\sim Ce1-N1 \\sim Ce1-N2 \\sim Ce1-N21 \\sim Ce1-N3 \\sim
Ce1-B1
 with sigma of 0.02
 H1B-H1C \\sim H1B-H1E \\sim H1C-H1E \\sim H1B-H1D \\sim H1C-H1D \\sim H1E-H1D
 with sigma of 0.02
 H2B-Ce2 \\sim Ce2-H2C
 with sigma of 0.02
 H2A-Ce2 \\sim Ce2-H2C
 with sigma of 0.02
 H2A-Ce2 \\sim Ce2-H2B
 with sigma of 0.02
 H4C-Ce4 \\sim Ce4-H4D
 with sigma of 0.02
 H4C-Ce4 \\sim Ce4-H4B
 with sigma of 0.02
 H4B-Ce4 \\sim Ce4-H4D
 with sigma of 0.02
 Ce1-H1C \\sim Ce1-H1B \\sim Ce1-H1D
 with sigma of 0.02
 Ce4-H4C \\sim Ce4-H4D \\sim Ce4-H4B
 with sigma of 0.02
 C84-C840 \\sim C84-C90A
 with sigma of 0.02
 C840-C841 \\sim C90A-C91A
 with sigma of 0.02
 C840-C842 \\sim C90A-C93A
 with sigma of 0.02
 C840-C843 \\sim C90A-C92A
 with sigma of 0.02
 C84-C841 \\sim C84-C91A
 with sigma of 0.04
 C84-C842 \\sim C84-C93A
 with sigma of 0.04
 C84-C843 \\sim C84-C92A
 with sigma of 0.04
 C841-C842 \\sim C91A-C93A
 with sigma of 0.04
 C841-C843 \\sim C91A-C92A
 with sigma of 0.04
 C842-C843 \\sim C93A-C92A
 with sigma of 0.04
 Ce1-N21 \\sim Ce1-N21A
 with sigma of 0.02
 C85A-C86A \\sim C850-C851
 with sigma of 0.02
 C85A-N21 \\sim C850-N21A
 with sigma of 0.02
 C86A-C87A \\sim C851-C852
 with sigma of 0.02
 C87A-C88A \\sim C852-C853
 with sigma of 0.02
 C88A-C89A \\sim C853-C854
 with sigma of 0.02
 C89A-N21 \\sim C854-N21A
 with sigma of 0.02
 Ce1-C85A \\sim Ce1-C850
 with sigma of 0.04
 Ce1-C89A \\sim Ce1-C854
 with sigma of 0.04
 C85A-C87A \\sim C850-C852
 with sigma of 0.04
 C85A-C89A \\sim C850-C854
 with sigma of 0.04
 C86A-C88A \\sim C851-C853
 with sigma of 0.04
 C86A-N21 \\sim C851-N21A
 with sigma of 0.04
 C87A-C89A \\sim C852-C854
 with sigma of 0.04
 C88A-N21 \\sim C853-N21A
 with sigma of 0.04
 C441-C442 \\sim C442-C443
 with sigma of 0.02
 C442-C443 \\sim C443-C441
 with sigma of 0.02
 C443-C441 \\sim C441-C442
 with sigma of 0.02
 H1B-Ce1 \\sim Ce1-H1D
 with sigma of 0.02
 H1B-Ce1 \\sim Ce1-H1C
 with sigma of 0.02
 H1C-Ce1 \\sim Ce1-H1D
 with sigma of 0.02
 H1C-H905 \\sim H89A-H1D
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 N12, C959, C960, C961, C962, C963
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N16, C979, C980, C981, C982, C983
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N3, C910, C911, C912, C913, C914
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N21
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C840, C841, C842, C843
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C841, C842, C843
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N17, C984, C985, C986, C987, C988
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C541, C542, C543
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N20, C890, C891, C892, C893, C894
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N21A, C850, C851, C852, C853, C854
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N21, C85A, C86A, C87A, C88A, C89A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C441, C442, C443
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C440, C441, C442, C443
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C843, C841, C842
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C841, C843, C842
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(C741)=Sof(H74A)=Sof(H74B)=Sof(H74C)=Sof(C742)=Sof(H74D)=Sof(H74E)=
 Sof(H74F)=Sof(C743)=Sof(H74G)=Sof(H74H)=Sof(H74I)=1-FVAR(1)
 Sof(C744)=Sof(H74J)=Sof(H74K)=Sof(H74L)=Sof(C745)=Sof(H74M)=Sof(H74N)=
 Sof(H74O)=Sof(C746)=Sof(H74P)=Sof(H74Q)=Sof(H74R)=FVAR(1)
 Sof(N21A)=Sof(C850)=Sof(H850)=Sof(C851)=Sof(H851)=1-FVAR(2)
 Sof(C85A)=Sof(H85A)=Sof(C86A)=Sof(H86A)=Sof(N21)=FVAR(2)
 Fixed Sof: C852(0.75) H852(0.75) C853(0.75) H853(0.75) C854(0.75) H854(0.75)
 C87A(0.25) H87A(0.25) C88A(0.25) H88A(0.25) C89A(0.25) H89A(0.25) C90A(0.728)
 C91A(0.728) H91A(0.728) H91B(0.728) H91C(0.728) C92A(0.658) H92A(0.658)
 H92B(0.658) H92C(0.658) C93A(0.728) H93A(0.728) H93B(0.728) H93C(0.728)
 C840(0.272) C841(0.272) H84A(0.272) H84B(0.272) H84C(0.272) C842(0.272)
 H84D(0.272) H84E(0.272) H84F(0.272) C843(0.342) H84G(0.342) H84H(0.342)
 H84I(0.342)
5.a Ternary CH refined with riding coordinates:
 C1(H1), C8(H8), C1A(H1A), C8A(H8A)
5.b Aromatic/amide H refined with riding coordinates:
 C850(H850), C851(H851), C852(H852), C853(H853), C854(H854), C3(H3), C4(H4),
 C6(H6), C7(H7), C17(H17), C19(H19), C23(H23), C25(H25), C33(H33), C35(H35),
 C43(H43), C45(H45), C85A(H85A), C86A(H86A), C87A(H87A), C88A(H88A), C89A(H89A),
  C900(H900), C901(H901), C902(H902), C903(H903), C904(H904), C905(H905),
 C906(H906), C907(H907), C908(H908), C909(H909), C910(H910), C911(H911),
 C912(H912), C913(H913), C914(H914), C915(H915), C916(H916), C917(H917),
 C918(H918), C919(H919), C920(H920), C921(H921), C922(H922), C923(H923),
 C924(H924), C925(H925), C926(H926), C927(H927), C928(H928), C929(H929),
 C930(H930), C931(H931), C932(H932), C933(H933), C934(H934), C3A(H3A), C4A(H4A),
  C6A(H6A), C7A(H7A), C53(H53), C55(H55), C63(H63), C65(H65), C73(H73),
 C75(H75), C83(H83), C85(H85), C939(H939), C940(H940), C941(H941), C942(H942),
 C943(H943), C944(H944), C945(H945), C946(H946), C947(H947), C948(H948),
 C949(H949), C950(H950), C951(H951), C952(H952), C953(H953), C954(H954),
 C955(H955), C956(H956), C957(H957), C958(H958), C959(H959), C960(H960),
 C961(H961), C962(H962), C963(H963), C964(H964), C965(H965), C966(H966),
 C967(H967), C968(H968), C969(H969), C970(H970), C971(H971), C972(H972),
 C973(H973), C974(H974), C975(H975), C976(H976), C977(H977), C978(H978),
 C979(H979), C980(H980), C981(H981), C982(H982), C983(H983), C984(H984),
 C985(H985), C986(H986), C987(H987), C988(H988), C989(H989), C990(H990),
 C991(H991), C992(H992), C993(H993), C994(H994), C995(H995), C996(H996),
 C997(H997), C998(H998), C890(H890), C891(H891), C892(H892), C893(H893),
 C894(H894)
5.c Fitted hexagon refined as free rotating group:
 N21A(C850,C851,C852,C853,C854), C85A(C86A,C87A,C88A,C89A,N21), N17(C984,C985,
 C986,C987,C988)
5.d 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), C91A(H91A,
 H91B,H91C), C92A(H92A,H92B,H92C), C93A(H93A,H93B,H93C), 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), C744(H74J,
 H74K,H74L), C745(H74M,H74N,H74O), C746(H74P,H74Q,H74R), C821(H82A,H82B,H82C),
 C822(H82D,H82E,H82F), C823(H82G,H82H,H82I), C841(H84A,H84B,H84C), C842(H84D,
 H84E,H84F), C843(H84G,H84H,H84I)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_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 1.158
_oxdiff_exptl_absorpt_empirical_full_min 0.879