Rare Earth pcu MOF Platform Based on RE4(μ3-OH)4(COO)62+ Clusters: Rational Design, Directed Synthesis, and Deliberate Tuning of Excitation Wavelengths.
Luo, Tian-Yi; Liu, Chong; Eliseeva, Svetlana V.; Muldoon, Patrick Flynn; Petoud, Stephane; Rosi, Nathaniel L.; Journal of the American Chemical Society  (2017) –; doi:10.1021/jacs.7b04532

data_4126254
_publ_section_title
;
 Rare Earth pcu MOF Platform Based on RE4(\m3-OH)4(COO)62+ Clusters:
 Rational Design, Directed Synthesis, and Deliberate Tuning of Excitation
 Wavelengths.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.7b04532
_journal_year                    2017
_chemical_formula_moiety         'C81.67 H53.9 N8.56 O24 Yb4'
_chemical_formula_sum            'C81.68 H53.92 N8.56 O24 Yb4'
_chemical_formula_weight         2231.41
_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'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-04-13
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5335)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.222(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   23.6058(7)
_cell_length_b                   22.2824(7)
_cell_length_c                   37.1223(10)
_cell_measurement_reflns_used    9997
_cell_measurement_temperature    240.0
_cell_measurement_theta_max      51.10
_cell_measurement_theta_min      2.38
_cell_volume                     19526.0(10)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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      240.0
_diffrn_detector                 'CCD area detector'
_diffrn_detector_type            'APEX II CCD'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker X8 Prospector Ultra'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1863
_diffrn_reflns_av_unetI/netI     0.1751
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            76479
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        51.227
_diffrn_reflns_theta_max         51.227
_diffrn_reflns_theta_min         2.214
_diffrn_source                   'IMuS micro-focus source'
_diffrn_source_target            Cu
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.691
_exptl_absorpt_correction_T_max  0.7501
_exptl_absorpt_correction_T_min  0.6028
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.1139 before and 0.0737 after correction.
The Ratio of minimum to maximum transmission is 0.8036.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    0.759
_exptl_crystal_description       block
_exptl_crystal_F_000             4304
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.763
_refine_diff_density_min         -3.175
_refine_diff_density_rms         0.237
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.112
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1000
_refine_ls_number_reflns         21099
_refine_ls_number_restraints     1375
_refine_ls_restrained_S_all      1.080
_refine_ls_R_factor_all          0.2280
_refine_ls_R_factor_gt           0.1394
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1116P)^2^+720.4960P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3169
_refine_ls_wR_factor_ref         0.3604
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11269
_reflns_number_total             21099
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b04532_si_005.cif
_cod_data_source_block           lty3_130_1_0m_a
_cod_database_code               4126254
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.897
_shelx_estimated_absorpt_t_min   0.709
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C20-C18
 1.55 with sigma of 0.02
 C4-C13 \\sim C6-C13
 with sigma of 0.02
 C35-C31 \\sim C39-C31
 with sigma of 0.02
 C24-C28 \\sim C26-C28
 with sigma of 0.02
 C1-O1 \\sim C1-O2
 with sigma of 0.02
 C20-O3 \\sim C20-O4
 with sigma of 0.02
 C41-O5 \\sim C41-O6
 with sigma of 0.02
 C21-O9 \\sim C21-O10
 with sigma of 0.02
 C40-O11 \\sim C40-O12
 with sigma of 0.02
 C61-O13 \\sim C61-O14
 with sigma of 0.02
 C80-C15 \\sim C80-C16
 with sigma of 0.02
 C10-C14 \\sim C10-C16
 with sigma of 0.02
 C15-C9 \\sim C15-C11
 with sigma of 0.02
 C17-C20 \\sim C19-C20
 with sigma of 0.02
 C3-N1A \\sim C7-N1B
 with sigma of 0.02
 N4B-C47 \\sim N4A-C43
 with sigma of 0.02
 N6A-C76 \\sim N6B-C78
 with sigma of 0.02
 N7B-C67 \\sim N7A-C63
 with sigma of 0.02
3. Restrained planarity
 C31, C34, C39, C35
 with sigma of 0.1
 C25, C24, C26, C28, C31
 with sigma of 0.1
 C35, C34, C39, C31, C28
 with sigma of 0.1
 C5, C13, C10, C14
 with sigma of 0.1
 C45, C48, C49, C50, C51, C52, C53, C54
 with sigma of 0.1
 C34, C31, C30, C29, C28, C33, C32, C25
 with sigma of 0.1
 C68, C69, C70, C71, C72, C73, C74, C65
 with sigma of 0.1
 C2, C5, C13, C12, C11, C10, C9, C8, C15, C18
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
O16 \\sim C80 \\sim O15 \\sim C77 \\sim C76 \\sim C75 \\sim C74 \\sim C79 \\sim
C78 \\sim N6A \\sim N6B: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08
O13 \\sim O14 \\sim C61 \\sim C62 \\sim C63 \\sim C64 \\sim C65 \\sim C66 \\sim
C67 \\sim N7B \\sim N7A: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08
O22S \\sim C100 \\sim N9S \\sim C101 \\sim C102: within 1.7A with sigma of 0.04
and sigma for terminal atoms of 0.08
C68 \\sim C73 \\sim C72 \\sim C71 \\sim C70 \\sim C69: within 1.7A with sigma
of 0.04 and sigma for terminal atoms of 0.08
C40 \\sim C37 \\sim C38 \\sim C39 \\sim C34 \\sim C35 \\sim C36 \\sim N8:
within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
C34 \\sim C31 \\sim C32 \\sim C33 \\sim C28 \\sim C29 \\sim C30: within 1.7A
with sigma of 0.04 and sigma for terminal atoms of 0.08
O10 \\sim C21 \\sim O9 \\sim C23 \\sim C22 \\sim C27 \\sim C26 \\sim C25 \\sim
C24 \\sim N5A \\sim N5B: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim N1B \\sim N1A: within
1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
C13 \\sim C8 \\sim C9 \\sim C10 \\sim C11 \\sim C12: within 1.7A with sigma of
0.04 and sigma for terminal atoms of 0.08
C20 \\sim C18 \\sim C19 \\sim C14 \\sim C15 \\sim C16 \\sim C17: within 1.7A
with sigma of 0.04 and sigma for terminal atoms of 0.08
N4A \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C42 \\sim N4B:
within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
C48 \\sim C49 \\sim C50 \\sim C51 \\sim C52 \\sim C53: within 1.7A with sigma
of 0.04 and sigma for terminal atoms of 0.08
C54 \\sim C55 \\sim C56 \\sim C57 \\sim C58 \\sim C59 \\sim N3A \\sim N3B:
within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
Yb3 \\sim O17 \\sim Yb4 \\sim O23S \\sim O24S: within 1.7A with sigma of 0.04
and sigma for terminal atoms of 0.08
Yb1 \\sim O20: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
Uanis(O17) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(N4B) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C13) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
5. Rigid body (RIGU) restrains
 O13, O14, C61, C62, C63, C64, C65, C66, C67, N7B, N7A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O16, C80, O15, C77, C76, C75, C74, C79, C78, N6A, N6B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O22S, C100, N9S, C101, C102
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C68, C73, C72, C71, C70, C69
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C40, C37, C38, C39, C34, C35, C36, N8
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C34, C31, C32, C33, C28, C29, C30
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O10, C21, O9, C23, C22, C27, C26, C25, C24, N5A, N5B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C3, C4, C5, C6, C7, C2, N1B, N1A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C13, C8, C9, C10, C11, C12
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C20, C18, C19, C14, C15, C16, C17
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N4A, C43, C44, C45, C46, C47, C42, N4B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C48, C49, C50, C51, C52, C53
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C54, C55, C56, C57, C58, C59, N3A, N3B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Yb3, O17, Yb4, O23S, O24S
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Yb1, O20
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(N1B)=Sof(H1BA)=Sof(H1BB)=1-FVAR(1)
 Sof(N1A)=Sof(H1AA)=Sof(H1AB)=FVAR(1)
 Sof(N4B)=Sof(H4BA)=Sof(H4BB)=1-FVAR(2)
 Sof(N4A)=Sof(H4AA)=Sof(H4AB)=FVAR(2)
 Sof(N6B)=Sof(H6BA)=Sof(H6BB)=1-FVAR(3)
 Sof(N6A)=Sof(H6AA)=Sof(H6AB)=FVAR(3)
 Sof(N7B)=Sof(H7BA)=Sof(H7BB)=1-FVAR(4)
 Sof(N7A)=Sof(H7AA)=Sof(H7AB)=FVAR(4)
 Sof(N9S)=Sof(C100)=Sof(H100)=Sof(C101)=Sof(H10A)=Sof(H10B)=Sof(H10C)=
 Sof(C102)=Sof(H10D)=Sof(H10E)=Sof(H10F)=FVAR(5)
 Sof(N5B)=Sof(H5BA)=Sof(H5BB)=1-FVAR(6)
 Sof(N5A)=Sof(H5AA)=Sof(H5AB)=FVAR(6)
 Sof(N3B)=Sof(H3BA)=Sof(H3BB)=1-FVAR(7)
 Sof(N3A)=Sof(H3AA)=Sof(H3AB)=FVAR(7)
7.a Aromatic/amide H refined with riding coordinates:
 C4(H4), C6(H6), C8(H8), C9(H9), C11(H11), C12(H12), C14(H14), C16(H16),
 C19(H19), C24(H24), C26(H26), C29(H29), C30(H30), C32(H32), C33(H33), C35(H35),
  C38(H38), C39(H39), C44(H44), C46(H46), C49(H49), C50(H50), C52(H52),
 C53(H53), C55(H55), C59(H59), C64(H64), C66(H66), C69(H69), C70(H70), C72(H72),
  C73(H73), C75(H75), C79(H79), C100(H100)
7.b Fitted hexagon refined as free rotating group:
 C2(C3,C4,C5,C6,C7), C8(C9,C10,C11,C12,C13), C14(C15,C16,C17,C18,C19), C22(C23,
 C24,C25,C26,C27), C28(C29,C30,C31,C32,C33), C34(C35,C36,C37,C38,C39), C42(C43,
 C44,C45,C46,C47), C48(C49,C50,C51,C52,C53), C54(C55,C56,C57,C58,C59), C62(C63,
 C64,C65,C66,C67), C68(C69,C70,C71,C72,C73), C74(C75,C76,C77,C78,C79)
7.c X=CH2 refined with riding coordinates:
 N1A(H1AA,H1AB), N1B(H1BA,H1BB), N2(H2A,H2B), N3A(H3AA,H3AB), N3B(H3BA,H3BB),
 N4A(H4AA,H4AB), N4B(H4BA,H4BB), N5A(H5AA,H5AB), N5B(H5BA,H5BB), N6A(H6AA,H6AB),
  N6B(H6BA,H6BB), N7A(H7AA,H7AB), N7B(H7BA,H7BB), N8(H8A,H8B)
7.d Idealised Me refined as rotating group:
 C101(H10A,H10B,H10C), C102(H10D,H10E,H10F)
;
_shelx_res_checksum              26528
_shelx_hkl_checksum              39934
_olex2_submission_special_instructions 'No special instructions were received'