Reversible water activation driven by contraction and expansion of a 12-vertex-closo-12-vertex-nido biscarborane cluster.
Wong, Yuen Onn; Smith, Mark D.; Peryshkov, Dmitry V.; Chemical communications (Cambridge, England) 52 (2016) 12710–12713; doi:10.1039/c6cc06955j

data_7125124
_publ_section_title
;
 Reversible water activation driven by contraction and expansion of a
 12-vertex-closo-12-vertex-nido biscarborane cluster.
;
_journal_issue                   86
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              12710
_journal_page_last               12713
_journal_paper_doi               10.1039/c6cc06955j
_journal_volume                  52
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C28 H78 B20 N4 O P2, C2 H3 N'
_chemical_formula_sum            'C30 H81 B20 N5 O P2'
_chemical_formula_weight         806.13
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2016-04-13
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_audit_update_record
;
2016-06-22 deposited with the CCDC.
2016-09-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   44.006(2)
_cell_length_b                   9.8902(6)
_cell_length_c                   22.5051(13)
_cell_measurement_reflns_used    9714
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.29
_cell_measurement_theta_min      2.25
_cell_volume                     9794.9(9)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'Bruker APEXII v2014.9-0 (Bruker, 2014)'
_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  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Bruker PHOTON-100 area detector'
_diffrn_detector_area_resol_mean 10.4
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Quest'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1432
_diffrn_reflns_av_unetI/netI     0.0745
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       55
_diffrn_reflns_limit_h_min       -55
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            286896
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        26.418
_diffrn_reflns_theta_max         26.418
_diffrn_reflns_theta_min         2.060
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.121
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.5522
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.1717 before and 0.0859 after correction.
The Ratio of minimum to maximum transmission is 0.7408.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.093
_exptl_crystal_description       needle
_exptl_crystal_F_000             3472
_exptl_crystal_size_max          0.52
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.281
_refine_diff_density_min         -0.399
_refine_diff_density_rms         0.051
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.22(8)
_refine_ls_extinction_coef       0.00067(11)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1246
_refine_ls_number_reflns         20096
_refine_ls_number_restraints     346
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0842
_refine_ls_R_factor_gt           0.0506
_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^)+(0.0484P)^2^+3.0881P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0984
_refine_ls_wR_factor_ref         0.1096
_reflns_Friedel_coverage         0.948
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                15306
_reflns_number_total             20096
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6cc06955j2.cif
_cod_data_source_block           pna21
_cod_original_cell_volume        9794.9(10)
_cod_database_code               7125124
_shelx_estimated_absorpt_t_max   0.990
_shelx_estimated_absorpt_t_min   0.940
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.78(8) 0.22(8)
2. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 O1A-H1AA = O1B-H1BB
 0.85 with sigma of 0.02
 H19H-H11E
 -2 with sigma of 0.02
 P2A-N3A \\sim P2A-N3C
 with sigma of 0.01
 P1A-N1C \\sim P1A-N1A
 with sigma of 0.01
 P1B-N1D \\sim P1B-N1B
 with sigma of 0.01
 P2B-N4D \\sim P2B-N4B
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(N1A) = Uanis(N1C)
Uanis(N3A) = Uanis(N3C)
Uanis(C31A) = Uanis(C31C)
Uanis(C34A) = Uanis(C34C)
Uanis(C36A) = Uanis(C35C)
Uanis(C35A) = Uanis(C36C)
Uanis(C33A) = Uanis(C33C)
Uanis(C31A) = Uanis(C31C)
Uanis(C32A) = Uanis(C32C)
Uanis(N1B) = Uanis(N1D)
Uanis(C13B) = Uanis(C13D)
Uanis(C14B) = Uanis(C14D)
Uanis(C15B) = Uanis(C15D)
Uanis(C16B) = Uanis(C16D)
Uanis(C12B) = Uanis(C12D)
Uanis(C11B) = Uanis(C11D)
Uanis(N4D) = Uanis(N4B)
Uanis(C14C) = Uanis(C14A)
Uanis(C15C) = Uanis(C15A)
Uanis(C16A) = Uanis(C16C)
Uanis(C11C) = Uanis(C11A)
Uanis(C12C) = Uanis(C12A)
Uanis(C13A) = Uanis(C13C)
Uanis(C40D) = Uanis(C40B)
Uanis(C42D) = Uanis(C42B)
Uanis(C41D) = Uanis(C41B)
Uanis(C37D) = Uanis(C37B)
Uanis(C39D) = Uanis(C39B)
Uanis(C38D) = Uanis(C38B)
Uanis(C40D) = Uanis(C40B)
5. Rigid body (RIGU) restrains
 N4D, N4B, C40D, C40B, C41B, C41D, C38B, C42D, C37B, C42B, C38D, C37D, C39B,
 C39D
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Same fragment restrains
{N2A, C17A, C18A, C19A, C20A, C21A, C22A} sigma for 1-2: 0.02, 1-3: 0.04
as
{N3A, C31A, C32A, C33A, C34A, C35A, C36A}
{N2A, C17A, C18A, C19A, C20A, C21A, C22A} sigma for 1-2: 0.02, 1-3: 0.04
as
{N3C, C31C, C32C, C33C, C34C, C35C, C36C}
{N2A, C17A, C18A, C19A, C20A, C21A, C22A} sigma for 1-2: 0.02, 1-3: 0.04
as
{N1A, C11A, C12A, C13A, C14A, C15A, C16A}
{N2A, C17A, C18A, C19A, C20A, C21A, C22A} sigma for 1-2: 0.02, 1-3: 0.04
as
{N1C, C11C, C12C, C13C, C14C, C15C, C16C}
{N2B, C17B, C18B, C19B, C20B, C21B, C22B} sigma for 1-2: 0.02, 1-3: 0.04
as
{N1B, C11B, C12B, C13B, C14B, C15B, C16B}
{N2B, C17B, C18B, C19B, C20B, C21B, C22B} sigma for 1-2: 0.02, 1-3: 0.04
as
{N1D, C11D, C12D, C13D, C14D, C15D, C16D}
{N2B, C17B, C18B, C19B, C20B, C21B, C22B} sigma for 1-2: 0.02, 1-3: 0.04
as
{N4B, C37B, C38B, C39B, C40B, C41B, C42B}
{N2B, C17B, C18B, C19B, C20B, C21B, C22B} sigma for 1-2: 0.02, 1-3: 0.04
as
{N4D, C37D, C38D, C39D, C40D, C41D, C42D}
7. Others
 Sof(N1C)=Sof(C11C)=Sof(H11D)=Sof(C12C)=Sof(H12F)=Sof(H12G)=Sof(H12H)=
 Sof(C13C)=Sof(H13F)=Sof(H13G)=Sof(H13H)=Sof(C14C)=Sof(H14D)=Sof(C15C)=
 Sof(H15H)=Sof(H15I)=Sof(H15J)=Sof(C16C)=Sof(H16F)=Sof(H16G)=Sof(H16H)=1-FVAR(1)
 Sof(N1A)=Sof(C11A)=Sof(H11C)=Sof(C12A)=Sof(H12C)=Sof(H12D)=Sof(H12E)=
 Sof(C13A)=Sof(H13C)=Sof(H13D)=Sof(H13E)=Sof(C14A)=Sof(H14C)=Sof(C15A)=
 Sof(H15E)=Sof(H15F)=Sof(H15G)=Sof(C16A)=Sof(H16C)=Sof(H16D)=Sof(H16E)=FVAR(1)
 Sof(N3C)=Sof(C31C)=Sof(H31C)=Sof(C32C)=Sof(H32D)=Sof(H32E)=Sof(H32F)=
 Sof(C33C)=Sof(H33D)=Sof(H33E)=Sof(H33F)=Sof(C34C)=Sof(H34C)=Sof(C35C)=
 Sof(H35D)=Sof(H35E)=Sof(H35F)=Sof(C36C)=Sof(H36D)=Sof(H36E)=Sof(H36F)=1-FVAR(2)
 Sof(N3A)=Sof(C31A)=Sof(H31A)=Sof(C32A)=Sof(H32A)=Sof(H32B)=Sof(H32C)=
 Sof(C33A)=Sof(H33A)=Sof(H33B)=Sof(H33C)=Sof(C34A)=Sof(H34A)=Sof(C35A)=
 Sof(H35A)=Sof(H35B)=Sof(H35C)=Sof(C36A)=Sof(H36A)=Sof(H36B)=Sof(H36C)=FVAR(2)
 Sof(N1D)=Sof(C11D)=Sof(H11E)=Sof(C12D)=Sof(H12J)=Sof(H12K)=Sof(H12L)=
 Sof(C13D)=Sof(H13K)=Sof(H13L)=Sof(H13M)=Sof(C14D)=Sof(H14E)=Sof(C15D)=
 Sof(H15L)=Sof(H15M)=Sof(H15N)=Sof(C16D)=Sof(H16K)=Sof(H16L)=Sof(H16M)=1-FVAR(3)
 Sof(N1B)=Sof(C11B)=Sof(H1)=Sof(C12B)=Sof(H2)=Sof(H3)=Sof(H12I)=Sof(C13B)=
 Sof(H4)=Sof(H13I)=Sof(H13J)=Sof(C14B)=Sof(H5)=Sof(C15B)=Sof(H6)=Sof(H7)=
 Sof(H15K)=Sof(C16B)=Sof(H8)=Sof(H16I)=Sof(H16J)=FVAR(3)
 Sof(N4D)=Sof(C37D)=Sof(H37D)=Sof(C38D)=Sof(H38G)=Sof(H38H)=Sof(H38I)=
 Sof(C39D)=Sof(H39G)=Sof(H39H)=Sof(H39I)=Sof(C40D)=Sof(H40D)=Sof(C41D)=
 Sof(H41G)=Sof(H41H)=Sof(H41I)=Sof(C42D)=Sof(H42G)=Sof(H42H)=Sof(H42I)=1-FVAR(4)
 Sof(N4B)=Sof(C37B)=Sof(H37B)=Sof(C38B)=Sof(H38D)=Sof(H38E)=Sof(H38F)=
 Sof(C39B)=Sof(H39D)=Sof(H39E)=Sof(H39F)=Sof(C40B)=Sof(H40B)=Sof(C41B)=
 Sof(H41D)=Sof(H41E)=Sof(H41F)=Sof(C42B)=Sof(H42D)=Sof(H42E)=Sof(H42F)=FVAR(4)
8.a Ternary CH refined with riding coordinates:
 C17A(H17C), C20A(H20C), C37A(H37A), C40A(H40A), C31A(H31A), C34A(H34A),
 C31C(H31C), C34C(H34C), C11A(H11C), C14A(H14C), C11C(H11D), C14C(H14D),
 C17B(H17D), C20B(H20D), C11B(H1), C14B(H5), C11D(H11E), C14D(H14E), C31B(H31B),
  C34B(H34B), C37B(H37B), C40B(H40B), C37D(H37D), C40D(H40D)
8.b Idealised Me refined with riding coordinates:
 C32A(H32A,H32B,H32C), C32C(H32D,H32E,H32F)
8.c Idealised Me refined as rotating group:
 C18A(H18C,H18D,H18E), C19A(H19C,H19D,H19E), C21A(H21A,H21B,H21C), C22A(H22A,
 H22B,H22C), C38A(H38A,H38B,H38C), C39A(H39A,H39B,H39C), C41A(H41A,H41B,H41C),
 C42A(H42A,H42B,H42C), C33A(H33A,H33B,H33C), C35A(H35A,H35B,H35C), C36A(H36A,
 H36B,H36C), C33C(H33D,H33E,H33F), C35C(H35D,H35E,H35F), C36C(H36D,H36E,H36F),
 C12A(H12C,H12D,H12E), C13A(H13C,H13D,H13E), C15A(H15E,H15F,H15G), C16A(H16C,
 H16D,H16E), C12C(H12F,H12G,H12H), C13C(H13F,H13G,H13H), C15C(H15H,H15I,H15J),
 C16C(H16F,H16G,H16H), C18B(H18F,H18G,H18H), C19B(H19F,H19G,H19H), C21B(H21D,
 H21E,H21F), C22B(H22D,H22E,H22F), C12B(H2,H3,H12I), C13B(H4,H13I,H13J),
 C15B(H6,H7,H15K), C16B(H8,H16I,H16J), C12D(H12J,H12K,H12L), C13D(H13K,H13L,
 H13M), C15D(H15L,H15M,H15N), C16D(H16K,H16L,H16M), C32B(H32G,H32H,H32I),
 C33B(H33G,H33H,H33I), C35B(H35G,H35H,H35I), C36B(H36G,H36H,H36I), C38B(H38D,
 H38E,H38F), C39B(H39D,H39E,H39F), C41B(H41D,H41E,H41F), C42B(H42D,H42E,H42F),
 C38D(H38G,H38H,H38I), C39D(H39G,H39H,H39I), C41D(H41G,H41H,H41I), C42D(H42G,
 H42H,H42I), C2S(H2SA,H2SB,H2SC), C4S(H4SA,H4SB,H4SC)
8.d Boron cage BH refined with riding coordinates:
 B1A(H1A), B2A(H2A), B3A(H3A), B4A(H4A), B5A(H5A), B6A(H6A), B7A(H7A),
 B8A(H8A), B9A(H9A), B10A(H10A), B13A(H13A), B17A(H17A), B18A(H18A), B20A(H20A),
  B1B(H1B), B2B(H2B), B3B(H3B), B5B(H5B), B6B(H6B), B7B(H7B), B8B(H8B),
 B10B(H10B), B13B(H13B), B17B(H17B), B18B(H18B), B20B(H20B)
;
_shelx_res_checksum              6658
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'