A thirty-year old mystery solved: identification of a new heptatungstate from non-aqueous solutions.
Shiels, Dominic; Pascual-Borràs, Magda; Waddell, Paul G.; Wills, Corinne; Poblet, Josep-Maria; Errington, R. John; Chemical communications (Cambridge, England) 59 (2023) 7919–7922; doi:10.1039/d3cc02061d

data_1569249
_publ_section_title
;
 A thirty-year old mystery solved: identification of a new heptatungstate
 from non-aqueous solutions.
;
_journal_issue                   51
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              7919
_journal_page_last               7922
_journal_paper_doi               10.1039/d3cc02061d
_journal_volume                  59
_journal_year                    2023
_chemical_formula_moiety         'O24 W7, 2(O9.5 W3), 7(C16 H36 N), 3(C2 H3 N)'
_chemical_formula_sum            'C118 H261 N10 O43 W13'
_chemical_formula_weight         4898.40
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-12-09
_audit_creation_method
;
Olex2 1.3
(compiled 2020.12.01 svn.r5f60950 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-04-27 deposited with the CCDC.	2023-05-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.691(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   32.1867(8)
_cell_length_b                   17.5143(4)
_cell_length_c                   28.2674(7)
_cell_measurement_reflns_used    29575
_cell_measurement_temperature    150.0(2)
_cell_measurement_theta_max      28.2900
_cell_measurement_theta_min      3.5020
_cell_volume                     15934.0(7)
_computing_cell_refinement       'CrysAlisPro 1.171.41.111a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.111a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.111a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      150.0(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3968
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.867
_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     -4.00  22.00   1.00   40.00    --    9.10  50.00-102.00   26
  2  \w    -38.00 -13.00   1.00   40.00    --    9.10 -50.00 111.00   25
  3  \w    -18.00  71.00   1.00   40.00    --   -8.08  19.00-180.00   89
  4  \w    -19.00  82.00   1.00   40.00    --    9.10  57.00 -60.00  101
  5  \w    -23.00  38.00   1.00   40.00    --    9.10  77.00-180.00   61
  6  \w     12.00  37.00   1.00   40.00    --    9.10 -99.00   0.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0062293000
_diffrn_orient_matrix_UB_12      -0.0246820000
_diffrn_orient_matrix_UB_13      -0.0186807000
_diffrn_orient_matrix_UB_21      0.0208441000
_diffrn_orient_matrix_UB_22      -0.0019684000
_diffrn_orient_matrix_UB_23      -0.0077751000
_diffrn_orient_matrix_UB_31      0.0035237000
_diffrn_orient_matrix_UB_32      -0.0320434000
_diffrn_orient_matrix_UB_33      0.0148411000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0812
_diffrn_reflns_av_unetI/netI     0.0967
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.867
_diffrn_reflns_limit_h_max       43
_diffrn_reflns_limit_h_min       -43
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            139244
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.867
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.930
_diffrn_reflns_theta_min         3.341
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    9.412
_exptl_absorpt_correction_T_max  0.647
_exptl_absorpt_correction_T_min  0.192
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.111a (Rigaku Oxford Diffraction, 2021)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    2.042
_exptl_crystal_description       plate
_exptl_crystal_F_000             9380
_exptl_crystal_size_max          0.39
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.779
_refine_diff_density_min         -2.609
_refine_diff_density_rms         0.259
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.069
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1849
_refine_ls_number_reflns         36504
_refine_ls_number_restraints     2138
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.1213
_refine_ls_R_factor_gt           0.0514
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0223P)^2^+134.1454P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0869
_refine_ls_wR_factor_ref         0.1119
_reflns_Friedel_coverage         0.000
_reflns_number_gt                21681
_reflns_number_total             36504
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc02061d2.cif
_cod_data_source_block           rje210047_fa
_cod_depositor_comments
'Adding full bibliography for 1569248--1569249.cif.'
_cod_database_code               1569249
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C96 H218 N6 W12 O40'
_shelx_estimated_absorpt_t_max   0.650
_shelx_estimated_absorpt_t_min   0.120
_reflns_odcompleteness_completeness 99.69
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.30
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N10A-C117 = N10B-C118
 1.1 with sigma of 0.02
 C119-C118
 1.48 with sigma of 0.02
 C117-C118 = C119-C118
 1.48 with sigma of 0.02
 C70A-C69 \\sim C70B-C69
 with sigma of 0.02
 C95A-C96A \\sim C95B-C96B
 with sigma of 0.02
 W13A-O43 \\sim W13B-O43
 with sigma of 0.02
 C93-C95A \\sim C93-C95B
 with sigma of 0.04
 C72A-C71A \\sim C72B-C71B
 with sigma of 0.02
 C94A-C96A \\sim C94B-C96B
 with sigma of 0.04
 N10A-C117 \\sim N10B-C118
 with sigma of 0.02
 C93-C94A \\sim C93-C94B
 with sigma of 0.02
 C71A-C70A \\sim C71B-C70B
 with sigma of 0.02
 C94A-C95A \\sim C94B-C95B
 with sigma of 0.02
 W13A-O41A \\sim W13B-O41B
 with sigma of 0.02
 W13A-O37A \\sim W13B-O37B
 with sigma of 0.02
 O43-O39A \\sim O43-O39B
 with sigma of 0.04
 O41A-O40A \\sim O41B-O40B
 with sigma of 0.04
 O37A-O40A \\sim O37B-O40B
 with sigma of 0.04
 O37A-O38A \\sim O37B-O38B
 with sigma of 0.04
 W11A-O43 \\sim W11B-O43
 with sigma of 0.02
 O41A-O43 \\sim O41B-O43
 with sigma of 0.04
 W11A-O35A \\sim W11B-O35B
 with sigma of 0.02
 O42A-O44A \\sim O42B-O44B
 with sigma of 0.04
 C60A-C59A \\sim C60B-C59B
 with sigma of 0.02
 W12A-O36A \\sim W12B-O36B
 with sigma of 0.02
 O38A-O43 \\sim O38B-O43
 with sigma of 0.04
 W11A-O36A \\sim W11B-O36B
 with sigma of 0.02
 C58-C59A \\sim C58-C59B
 with sigma of 0.02
 O43-O40A \\sim O43-O40B
 with sigma of 0.04
 W11A-O37A \\sim W11B-O37B
 with sigma of 0.02
 O36A-O44A \\sim O36B-O44B
 with sigma of 0.04
 O36A-O39A \\sim O36B-O39B
 with sigma of 0.04
 W13A-O40A \\sim W13B-O40B
 with sigma of 0.02
 O36A-O35A \\sim O36B-O35B
 with sigma of 0.04
 W12A-O43 \\sim W12B-O43
 with sigma of 0.02
 W12A-O44A \\sim W12B-O44B
 with sigma of 0.02
 O37A-O41A \\sim O37B-O41B
 with sigma of 0.04
 W12A-O39A \\sim W12B-O39B
 with sigma of 0.02
 O37A-O43 \\sim O37B-O43
 with sigma of 0.04
 O37A-O35A \\sim O37B-O35B
 with sigma of 0.04
 O41A-O42A \\sim O41B-O42B
 with sigma of 0.04
 O41A-O44A \\sim O41B-O44B
 with sigma of 0.04
 O41A-O39A \\sim O41B-O39B
 with sigma of 0.04
 W11A-O38A \\sim W11B-O38B
 with sigma of 0.02
 O42A-O43 \\sim O42B-O43
 with sigma of 0.04
 W13A-W11A \\sim W13B-W11B
 with sigma of 0.04
 O42A-O39A \\sim O42B-O39B
 with sigma of 0.04
 W13A-W12A \\sim W13B-W12B
 with sigma of 0.04
 O38A-O35A \\sim O38B-O35B
 with sigma of 0.04
 O43-O44A \\sim O43-O44B
 with sigma of 0.04
 W11A-W12A \\sim W11B-W12B
 with sigma of 0.04
 O43-O35A \\sim O43-O35B
 with sigma of 0.04
 O44A-O39A \\sim O44B-O39B
 with sigma of 0.04
 O36A-O37A \\sim O36B-O37B
 with sigma of 0.04
 W12A-O41A \\sim W12B-O41B
 with sigma of 0.02
 O36A-O41A \\sim O36B-O41B
 with sigma of 0.04
 O36A-O42A \\sim O36B-O42B
 with sigma of 0.04
 W12A-O42A \\sim W12B-O42B
 with sigma of 0.02
 O36A-O38A \\sim O36B-O38B
 with sigma of 0.04
 O36A-O43 \\sim O36B-O43
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
O43 \\sim W11A \\sim W12A \\sim W13A \\sim O35A \\sim O36A \\sim O37A \\sim
O38A \\sim O39A \\sim O40A \\sim O41A \\sim O42A \\sim O44A \\sim W11B \\sim
W12B \\sim W13B \\sim O35B \\sim O36B \\sim O37B \\sim O38B \\sim O39B \\sim
O40B \\sim O41B \\sim O42B \\sim O44B: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
C70A \\sim C71A \\sim C72A \\sim C70B \\sim C71B \\sim C72B: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C94A \\sim C95A \\sim C96A \\sim C94B \\sim C95B \\sim C96B: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(N10A) = Uanis(C117) = Uanis(N10B) = Uanis(C118) = Uanis(C119)
Uanis(C59A) = Uanis(C59B)
Uanis(C60B) = Uanis(C60A)
4. 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
5. Others
 Fixed Sof: H58A(0.55198) H58B(0.55198) H58C(0.44802) H58D(0.44802)
 H69A(0.56575) H69B(0.56575) H69C(0.43425) H69D(0.43425) H93A(0.5723)
 H93B(0.5723) H93C(0.4277) H93D(0.4277) H11J(0.53587) H11K(0.53587)
 H11L(0.53587) W11A(0.61737) W12A(0.61737) W13A(0.61737) O35A(0.61737)
 O36A(0.61737) O37A(0.61737) O38A(0.61737) O39A(0.61737) O40A(0.61737)
 O41A(0.61737) O42A(0.61737) O44A(0.61737) N10A(0.53587) C59A(0.55198)
 H59A(0.55198) H59B(0.55198) C60A(0.55198) H60A(0.55198) H60B(0.55198)
 H60C(0.55198) C70A(0.56575) H70A(0.56575) H70B(0.56575) C71A(0.56575)
 H71A(0.56575) H71B(0.56575) C72A(0.56575) H72A(0.56575) H72B(0.56575)
 H72C(0.56575) C94A(0.5723) H94A(0.5723) H94B(0.5723) C95A(0.5723) H95A(0.5723)
 H95B(0.5723) C96A(0.5723) H96A(0.5723) H96B(0.5723) H96C(0.5723) C117(0.53587)
 W11B(0.38263) W12B(0.38263) W13B(0.38263) O35B(0.38263) O36B(0.38263)
 O37B(0.38263) O38B(0.38263) O39B(0.38263) O40B(0.38263) O41B(0.38263)
 O42B(0.38263) O44B(0.38263) N10B(0.46413) C59B(0.44802) H59C(0.44802)
 H59D(0.44802) C60B(0.44802) H60D(0.44802) H60E(0.44802) H60F(0.44802)
 C70B(0.43425) H70C(0.43425) H70D(0.43425) C71B(0.43425) H71C(0.43425)
 H71D(0.43425) C72B(0.43425) H72D(0.43425) H72E(0.43425) H72F(0.43425)
 C94B(0.4277) H94C(0.4277) H94D(0.4277) C95B(0.4277) H95C(0.4277) H95D(0.4277)
 C96B(0.4277) H96D(0.4277) H96E(0.4277) H96F(0.4277) C119(0.46413)
 H11M(0.46413) H11N(0.46413) H11O(0.46413)
6.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B),
 C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C13(H13A,H13B), C14(H14A,H14B),
 C15(H15A,H15B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B), C21(H21A,H21B),
  C22(H22A,H22B), C23(H23A,H23B), C25(H25A,H25B), C26(H26A,H26B), C27(H27A,
 H27B), C29(H29A,H29B), C30(H30A,H30B), C31(H31A,H31B), C33(H33A,H33B),
 C34(H34A,H34B), C35(H35A,H35B), C37(H37A,H37B), C38(H38A,H38B), C39(H39A,H39B),
  C41(H41A,H41B), C42(H42A,H42B), C43(H43A,H43B), C45(H45A,H45B), C46(H46A,
 H46B), C47(H47A,H47B), C49(H49A,H49B), C50(H50A,H50B), C51(H51A,H51B),
 C53(H53A,H53B), C54(H54A,H54B), C55(H55A,H55B), C57(H57A,H57B), C58(H58A,H58B),
  C58(H58C,H58D), C61(H61A,H61B), C62(H62A,H62B), C63(H63A,H63B), C65(H65A,
 H65B), C66(H66A,H66B), C67(H67A,H67B), C69(H69A,H69B), C69(H69C,H69D),
 C73(H73A,H73B), C74(H74A,H74B), C75(H75A,H75B), C77(H77A,H77B), C78(H78A,H78B),
  C79(H79A,H79B), C81(H81A,H81B), C82(H82A,H82B), C83(H83A,H83B), C85(H85A,
 H85B), C86(H86A,H86B), C87(H87A,H87B), C89(H89A,H89B), C90(H90A,H90B),
 C91(H91A,H91B), C93(H93A,H93B), C93(H93C,H93D), C97(H97A,H97B), C98(H98A,H98B),
  C99(H99A,H99B), C101(H10F,H10G), C102(H10H,H10I), C103(H10J,H10K), C105(H10O,
 H10P), C106(H10Q,H10R), C107(H10S,H10T), C109(H10X,H10Y), C110(H11C,H11D),
 C111(H11E,H11F), C59A(H59A,H59B), C70A(H70A,H70B), C71A(H71A,H71B), C94A(H94A,
 H94B), C95A(H95A,H95B), C59B(H59C,H59D), C70B(H70C,H70D), C71B(H71C,H71D),
 C94B(H94C,H94D), C95B(H95C,H95D)
6.b Me refined with riding coordinates:
 C118(H11J,H11K,H11L), C60A(H60A,H60B,H60C), C72A(H72A,H72B,H72C), C96A(H96A,
 H96B,H96C), C60B(H60D,H60E,H60F), C72B(H72D,H72E,H72F), C96B(H96D,H96E,H96F),
 C119(H11M,H11N,H11O)
6.c Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C8(H8A,H8B,H8C), C12(H12A,H12B,H12C), C16(H16A,H16B,H16C),
 C20(H20A,H20B,H20C), C24(H24A,H24B,H24C), C28(H28A,H28B,H28C), C32(H32A,H32B,
 H32C), C36(H36A,H36B,H36C), C40(H40A,H40B,H40C), C44(H44A,H44B,H44C), C48(H48A,
 H48B,H48C), C52(H52A,H52B,H52C), C56(H56A,H56B,H56C), C64(H64A,H64B,H64C),
 C68(H68A,H68B,H68C), C76(H76A,H76B,H76C), C80(H80A,H80B,H80C), C84(H84A,H84B,
 H84C), C88(H88A,H88B,H88C), C92(H92A,H92B,H92C), C100(H10C,H10D,H10E),
 C104(H10L,H10M,H10N), C108(H10U,H10V,H10W), C112(H11G,H11H,H11I), C114(H11S,
 H11T,H11U), C116(H11P,H11Q,H11R)
;
_shelx_res_checksum              8938
_shelx_hkl_checksum              49465
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.173
_oxdiff_exptl_absorpt_empirical_full_min 0.888