The proton-controlled synthesis of unprecedented diol functionalized Anderson-type POMs.
Zhang, Jiangwei; Li, Qi; Zeng, Mengyan; Huang, Yichao; Zhang, Jin; Hao, Jian; Wei, Yongge; Chemical communications (Cambridge, England) 52 (2016) 2378–2381; doi:10.1039/c5cc10071b

data_7118314
_publ_section_title
;
 The proton-controlled synthesis of unprecedented diol functionalized
 Anderson-type POMs.
;
_journal_issue                   11
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              2378
_journal_page_last               2381
_journal_paper_doi               10.1039/c5cc10071b
_journal_volume                  52
_journal_year                    2016
_chemical_formula_moiety
'C4 H14 Cr Mo6 N O25, 4(C16 H36 N), 3Br, 7.5(H2O), H4 N'
_chemical_formula_sum            'C68 H177 Br3 Cr Mo6 N6 O32.5'
_chemical_formula_weight         2466.50
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2015-08-12
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2015-09-07 deposited with the CCDC.
2015-12-16 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 96.193(2)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   23.7911(5)
_cell_length_b                   15.3677(4)
_cell_length_c                   28.4337(7)
_cell_measurement_reflns_used    40577
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      29.38
_cell_measurement_theta_min      3.09
_cell_volume                     10335.1(4)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XH (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector_area_resol_mean 16.0971
_diffrn_measured_fraction_theta_full 0.955
_diffrn_measured_fraction_theta_max 0.955
_diffrn_measurement_device_type  'Bruker P4'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0327
_diffrn_reflns_av_unetI/netI     0.0661
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            63809
_diffrn_reflns_theta_full        26.38
_diffrn_reflns_theta_max         26.38
_diffrn_reflns_theta_min         3.09
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    2.038
_exptl_absorpt_correction_T_max  0.443
_exptl_absorpt_correction_T_min  0.306
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            pink
_exptl_crystal_density_diffrn    1.581
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             5044
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.5
_exptl_crystal_size_min          0.4
_refine_diff_density_max         1.886
_refine_diff_density_min         -1.596
_refine_diff_density_rms         0.133
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.0(4)
_refine_ls_extinction_coef       2.738
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2190
_refine_ls_number_reflns         40577
_refine_ls_number_restraints     499
_refine_ls_restrained_S_all      1.018
_refine_ls_R_factor_all          0.0814
_refine_ls_R_factor_gt           0.0472
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0407P)^2^+37.4858P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1047
_refine_ls_wR_factor_ref         0.1230
_reflns_number_gt                28967
_reflns_number_total             40577
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c5cc10071b2.cif
_cod_data_source_block           compound1
_cod_depositor_comments
'Adding full bibliography for 7118311--7118316.cif.'
_cod_original_cell_volume        10335.2(4)
_cod_database_code               7118314
_shelxl_version_number           2013-4
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.48(2) 0.52(2)
2. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, H31 of O31, H3 of O3, H71 of O71, H5 of O5, H30 of O30,
  H70 of O70, H6 of O6, H4 of O4, All N(H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, H66 of O66, H64 of O64, H25 of O25, H63 of O63, H52 of
  O52, H60 of O60, H50 of O50, All N(H,H) groups, All O(H,H) groups
3. Restrained distances
 C51-C52
 1.53 with sigma of 0.02
 O21-Br1
 3.6 with sigma of 0.02
 O61-Br1
 3.6 with sigma of 0.02
 O53-Br2
 3.6 with sigma of 0.02
 C132-C131
 1.53 with sigma of 0.01
 H13I-H13O
 4 with sigma of 0.01
 H10X-H98B
 3 with sigma of 0.02
 H13I-H13P
 3 with sigma of 0.02
 H11V-H42B
 3 with sigma of 0.02
 C102-C101 = C103-C102 = C99-C100 = C98-C97 = C94-C93
 1.53 with sigma of 0.01
 C56-C55 = C54-C53 = C44-C43 = C43-C42 = C42-C41 = C48-C47 = C52-C51
 1.53 with sigma of 0.01
 C102-C101
 1.58 with sigma of 0.01
 C98-C97
 1.5 with sigma of 0.01
 C43-C42
 1.6 with sigma of 0.01
 C44-C43 = C46-C45
 1.53 with sigma of 0.01
 C98-C97
 1.53 with sigma of 0.01
 N8-C97
 1.47 with sigma of 0.01
 N5-C45
 1.47 with sigma of 0.01
 N5-C41
 1.47 with sigma of 0.01
 C42-C41
 1.53 with sigma of 0.01
 C131-C130
 1.53 with sigma of 0.01
 C46-C45
 1.55 with sigma of 0.01
 C43-C42
 1.53 with sigma of 0.01
 N5-C45
 1.47 with sigma of 0.01
 C42-C41
 1.51 with sigma of 0.01
 C98-C97
 1.53 with sigma of 0.01
 N8-C97
 1.47 with sigma of 0.01
 C131-C130
 1.5 with sigma of 0.01
 H10Y-H98A
 4 with sigma of 0.02
 H10X-H98A
 3 with sigma of 0.02
 H42B-H45A
 3 with sigma of 0.02
 H12H-H13G
 3 with sigma of 0.02
 H12H-H13F
 3 with sigma of 0.02
 H10Y-H97B
 2.2 with sigma of 0.01
 H12I-H13F
 2.2 with sigma of 0.01
 N10-C129
 1.47 with sigma of 0.01
 N11-HA = N11-H11Y = N11-HF = N11-HD = N12-H = N12-HE = N12-HC = N12-H12Z
 0.8 with sigma of 0.01
 N12-HE
 0.8 with sigma of 0.01
 H11Y-HD \\sim H11Y-HF \\sim H11Y-HA \\sim HD-HF \\sim HD-HA \\sim HF-HA
 with sigma of 0.02
 HC-H \\sim HC-H12Z \\sim HC-HE \\sim H-H12Z \\sim H-HE \\sim H12Z-HE
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(C3) \\sim Ueq, Uanis(C88) \\sim Ueq, Uanis(O49) \\sim Ueq, Uanis(C30)
\\sim Ueq, Uanis(O2) \\sim Ueq, Uanis(C72) \\sim Ueq: with sigma of 0.1 and
sigma for terminal atoms of 0.2
Uanis(O59) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C65) \\sim Ueq, Uanis(O13)
\\sim Ueq, Uanis(C50) \\sim Ueq, Uanis(N8) \\sim Ueq: with sigma of 0.1 and
sigma for terminal atoms of 0.2
Uanis(C1) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C27) \\sim
Ueq, Uanis(C56) \\sim Ueq, Uanis(O71) \\sim Ueq, Uanis(O70) \\sim Ueq,
Uanis(C106) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(N7) \\sim Ueq, Uanis(C115)
\\sim Ueq, Uanis(C86) \\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C37) \\sim Ueq,
Uanis(C103) \\sim Ueq, Uanis(C104) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O50) \\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(N6)
\\sim Ueq, Uanis(C73) \\sim Ueq, Uanis(C82) \\sim Ueq, Uanis(C101) \\sim Ueq,
Uanis(C61) \\sim Ueq, Uanis(C77) \\sim Ueq, Uanis(C72) \\sim Ueq, Uanis(C46)
\\sim Ueq, Uanis(C67) \\sim Ueq, Uanis(O11) \\sim Ueq, Uanis(C75) \\sim Ueq,
Uanis(C114) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C9) \\sim Ueq, Uanis(C116) \\sim Ueq, Uanis(O8) \\sim Ueq, Uanis(C109)
\\sim Ueq, Uanis(C107) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C93) \\sim Ueq,
Uanis(O35) \\sim Ueq, Uanis(C85) \\sim Ueq, Uanis(O40) \\sim Ueq, Uanis(C21)
\\sim Ueq, Uanis(O5) \\sim Ueq, Uanis(C90) \\sim Ueq, Uanis(C98) \\sim Ueq,
Uanis(O24) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O3) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(N2) \\sim Ueq, Uanis(C7) \\sim
Ueq, Uanis(C38) \\sim Ueq, Uanis(O27) \\sim Ueq, Uanis(O17) \\sim Ueq,
Uanis(C5) \\sim Ueq, Uanis(O44) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(C57)
\\sim Ueq, Uanis(N12) \\sim Ueq, Uanis(N4) \\sim Ueq, Uanis(C29) \\sim Ueq,
Uanis(C103) \\sim Ueq, Uanis(C83) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(O70) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C97)
\\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C68) \\sim Ueq,
Uanis(C45) \\sim Ueq, Uanis(C116) \\sim Ueq, Uanis(O7) \\sim Ueq, Uanis(O37)
\\sim Ueq, Uanis(O26) \\sim Ueq, Uanis(C102) \\sim Ueq, Uanis(O42) \\sim Ueq,
Uanis(O5) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(O77) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C129) \\sim Ueq, Uanis(C4)
\\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C112) \\sim Ueq, Uanis(O30) \\sim Ueq,
Uanis(O8) \\sim Ueq, Uanis(O48) \\sim Ueq, Uanis(C101) \\sim Ueq, Uanis(C30)
\\sim Ueq, Uanis(O59) \\sim Ueq, Uanis(C111) \\sim Ueq, Uanis(C131) \\sim Ueq:
with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(O10) \\sim Ueq, Uanis(O11) \\sim Ueq, Uanis(C91) \\sim Ueq, Uanis(C44)
\\sim Ueq, Uanis(C94) \\sim Ueq, Uanis(C127) \\sim Ueq, Uanis(C53) \\sim Ueq:
with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(O36) \\sim Ueq, Uanis(O50) \\sim Ueq, Uanis(C42) \\sim Ueq: with sigma of
0.0001 and sigma for terminal atoms of 0.0002
Uanis(C131) = Uanis(C132)
5.a Free rotating group:
 O67(H67C,H67D), O63(H63), O52(H52), O54(H54C,H54D), O56(H56D,H56E), N12(H12Z,
 H), O66(H66), O64(H64), O57(H57C,H57D), O65(H65C,H65D), O68(H68D,H68E),
 N11(H11Y,HA), O60(H60)
5.b Ternary CH refined with riding coordinates:
 O71(H71), O3(H3), O31(H31), O5(H5), O30(H30), O70(H70), O6(H6), O4(H4)
5.c Secondary CH2 refined with riding coordinates:
 C134(H13A,H13B), C74(H74A,H74B), C95(H95A,H95B), C62(H62A,H62B), C126(H12D,
 H12E), C125(H12F,H12G), C59(H59A,H59B), C50(H50A,H50B), C8(H8A,H8B), C63(H63A,
 H63B), C114(H11D,H11E), C11(H11W,H11X), C69(H69A,H69B), C101(H10N,H10O),
 C103(H10P,H10Q), C46(H46A,H46B), C33(H33A,H33B), C34(H34A,H34B), C22(H22A,
 H22B), C70(H70A,H70B), C75(H75A,H75B), C98(H98A,H98B), C61(H61A,H61B),
 C26(H26A,H26B), C39(H39A,H39B), C78(H78A,H78B), C109(H10A,H10B), C67(H67A,
 H67B), C43(H43A,H43B), C99(H99A,H99B), C31(H31A,H31B), C105(H10C,H10D),
 C111(H11F,H11G), C83(H83A,H83B), C37(H37A,H37B), C129(H12H,H12I), C131(H13F,
 H13G), C119(H11H,H11I), C110(H11J,H11K), C107(H10H,H10I), C97(H97A,H97B),
 C94(H94A,H94B), C25(H25A,H25B), C45(H45A,H45B), C51(H51A,H51B), C57(H57A,H57B),
  C54(H54A,H54B), C90(H90A,H90B), C82(H82A,H82B), C130(H13H,H13I), C115(H11L,
 H11M), C113(H11N,H11O), C55(H55A,H55B), C38(H38A,H38B), C35(H35A,H35B),
 C89(H89A,H89B), C122(H12J,H12K), C49(H49A,H49B), C71(H71A,H71B), C102(H10X,
 H10Y), C93(H93A,H93B), C15(H15A,H15B), C42(H42A,H42B), C2(H2D,H2E), C58(H58A,
 H58B), C27(H27A,H27B), C118(H11P,H11Q), C41(H41A,H41B), C106(H10J,H10K),
 C18(H18A,H18B), C1(H1D,H1E), C10(H10L,H10M), C53(H53A,H53B), C91(H91A,H91B),
 C9(H9A,H9B), C135(H13J,H13K), C65(H65A,H65B), C13(H13Q,H13R), C73(H73A,H73B),
 C121(H12L,H12M), C4(H4A,H4B), C123(H12N,H12O), C5(H5A,H5B), C30(H30A,H30B),
 C14(H14A,H14B), C133(H13L,H13M), C6(H6A,H6B), C79(H79A,H79B), C87(H87A,H87B),
 C17(H17A,H17B), C117(H11R,H11S), C29(H29A,H29B), C127(H12P,H12Q), C85(H85A,
 H85B), C21(H21A,H21B), C47(H47A,H47B), C66(H66A,H66B), C81(H81A,H81B),
 C19(H19A,H19B), C86(H86A,H86B), C23(H23A,H23B), C77(H77A,H77B)
5.d Idealised Me refined as rotating group:
 N2(H2A,H2B,H2C), N1(H1A,H1B,H1C), C124(H12A,H12B,H12C), C112(H11A,H11B,H11C),
 C24(H24A,H24B,H24C), C136(H13C,H13D,H13E), C44(H44A,H44B,H44C), C80(H80A,H80B,
 H80C), C60(H60A,H60B,H60C), C104(H10R,H10S,H10T), C16(H16A,H16B,H16C),
 C72(H72A,H72B,H72C), C48(H48A,H48B,H48C), C108(H10E,H10F,H10G), C96(H96A,H96B,
 H96C), C120(H12U,H12V,H12W), C68(H68A,H68B,H68C), C64(H64A,H64B,H64C),
 C88(H88A,H88B,H88C), C100(H10U,H10V,H10W), C28(H28A,H28B,H28C), C32(H32A,H32B,
 H32C), C76(H76A,H76B,H76C), C56(H56A,H56B,H56C), C84(H84A,H84B,H84C), C40(H40A,
 H40B,H40C), C36(H36A,H36B,H36C), C92(H92A,H92B,H92C), C12(H12X,H12Y,HB),
 C20(H20A,H20B,H20C), C132(H13N,H13O,H13P), C128(H12R,H12S,H12T), C116(H11T,
 H11U,H11V), C52(H52A,H52B,H52C)
5.e Idealised tetrahedral OH refined as rotating group:
 O25(H25), O50(H50)
;