Rational addition of capping groups to the phosphomolybdate Keggin anion [PMo<sub>12</sub>O<sub>40</sub>]<sup>3-</sup> by mild, non-aqueous reductive aggregation
Ridla Bakri; Andrew Booth; Gavin Harle; Paul S. Middleton; Corinne Wills; William Clegg; Ross W. Harrington; R. John Errington; Chem. Commun. 48 (2012) 2779–; doi:10.1039/c2cc17670j

data_7107450
_publ_section_title
;
 Rational addition of capping groups to the phosphomolybdate Keggin anion
 [PMo<sub>12</sub>O<sub>40</sub>]<sup>3-</sup> by mild, non-aqueous
 reductive aggregation
;
_journal_name_full               'Chem. Commun.'
_journal_page_first              2779
_journal_paper_doi               10.1039/c2cc17670j
_journal_volume                  48
_journal_year                    2012
_chemical_formula_moiety         '3 C16 H36 N +,Mo12 O40 P Sb2 3-'
_chemical_formula_sum            'C48 H108 Mo12 N3 O40 P Sb2'
_chemical_formula_weight         2793.12
_chemical_name_systematic
;
?
;
_space_group_IT_number           5
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  'C 2y'
_symmetry_space_group_name_H-M   'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 96.447(16)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   26.922(10)
_cell_length_b                   14.066(4)
_cell_length_c                   11.8345(11)
_cell_measurement_reflns_used    27116
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      27.5
_cell_measurement_theta_min      2.5
_cell_volume                     4453(2)
_computing_cell_refinement       EvalCCD
_computing_data_collection       'Nonius COLLECT'
_computing_data_reduction        EvalCCD
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL and local programs'
_computing_structure_refinement  'Bruker SHELXTL'
_computing_structure_solution    'Bruker SHELXTL'
_diffrn_ambient_temperature      150(2)
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_device_type  'Nonius KappaCCD diffractometer'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0265
_diffrn_reflns_av_sigmaI/netI    0.0365
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            27110
_diffrn_reflns_theta_full        25.00
_diffrn_reflns_theta_max         27.52
_diffrn_reflns_theta_min         3.91
_exptl_absorpt_coefficient_mu    2.319
_exptl_absorpt_correction_T_max  0.543
_exptl_absorpt_correction_T_min  0.457
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            blue
_exptl_crystal_density_diffrn    2.083
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             2716
_exptl_crystal_size_max          0.40
_exptl_crystal_size_mid          0.35
_exptl_crystal_size_min          0.30
_platon_squeeze_details
;
;
_refine_diff_density_max         1.022
_refine_diff_density_min         -1.387
_refine_diff_density_rms         0.148
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.47(5)
_refine_ls_extinction_coef       0.00015(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     461
_refine_ls_number_reflns         9548
_refine_ls_number_restraints     326
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0585
_refine_ls_R_factor_gt           0.0468
_refine_ls_shift/su_max          0.068
_refine_ls_shift/su_mean         0.002
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0353P)^2^+58.2558P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1042
_refine_ls_wR_factor_ref         0.1102
_reflns_number_gt                8182
_reflns_number_total             9548
_reflns_threshold_expression     I>2\s(I)
_cod_data_source_file            c2cc17670j.txt
_cod_data_source_block           rje419_salt_of_3
_cod_original_sg_symbol_H-M      'C 2'
_cod_database_code               7107450
_computing_special_details
;
TITL rje419 in C2
CELL 0.71073 26.922 14.066 11.8345 90.000 96.447 90.000
ZERR 2.00 0.010 0.004 0.0011 0.000 0.016 0.000
LATT -7
SYMM -X, Y, -Z
SFAC C H N O P MO SB
UNIT 96 216 6 80 2 24 4

TEMP -123
SIZE 0.4 0.35 0.3
OMIT -4 0 4

L.S. 8
ACTA 50
BOND
FMAP 2
PLAN 10
FREE MO3 SB

REM DELU $MO SB $O
DELU 0.005 $C $N
SIMU 0.005 $C $N

TWIN
WGHT 0.035300 58.255802
EXTI 0.000145
BASF 0.46571
FVAR 0.40627 0.59608 0.68258 0.68993
MO1 6 0.465005 0.558738 0.194994 11.00000 0.01598 0.11298 =
0.01825 -0.00144 0.00227 -0.00390
MO2 6 0.419028 0.380444 0.358975 11.00000 0.02210 0.04137 =
0.04819 -0.02311 0.00961 -0.01475
MO3 6 0.547842 0.376650 0.338501 11.00000 0.03007 0.03741 =
0.05095 -0.01477 0.01965 0.00311
MO4 6 0.632197 0.567833 0.482286 11.00000 0.01212 0.03231 =
0.02434 0.00391 0.00361 -0.00311
MO5 6 0.550246 0.754041 0.341189 11.00000 0.02995 0.03179 =
0.07019 0.02534 0.01482 -0.00577
MO6 6 0.581975 0.750115 0.637937 11.00000 0.02112 0.04259 =
0.06340 -0.02448 0.00062 -0.00874
SB 7 0.587416 0.562780 0.211793 11.00000 0.01734 0.07449 =
0.02211 0.00207 0.00741 -0.00236
P 5 0.500000 0.567545 0.500000 10.50000 0.00955 0.01567 =
0.01685 0.00000 0.00124 0.00000
O1 4 0.452706 0.557295 0.054025 11.00000 0.02668 0.16864 =
0.02282 -0.00981 0.00068 -0.02450
O2 4 0.424634 0.459066 0.229389 11.00000 0.01791 0.15072 =
0.10258 0.05610 0.01931 0.00528
O3 4 0.380170 0.299400 0.300926 11.00000 0.04791 0.07256 =
0.10621 -0.05917 -0.00862 0.00293
O4 4 0.482651 0.321656 0.314653 11.00000 0.02749 0.06823 =
0.06253 -0.03670 0.01625 -0.00553
O5 4 0.574029 0.290410 0.268621 11.00000 0.06969 0.07548 =
0.12290 -0.05764 0.04566 -0.02951
O6 4 0.560594 0.347038 0.481674 11.00000 0.03511 0.01655 =
0.07654 0.00980 0.00709 0.00883
O7 4 0.527128 0.468888 0.216764 11.00000 0.02120 0.08318 =
0.10508 0.03624 0.01206 0.01002
O8 4 0.526470 0.644939 0.215745 11.00000 0.01878 0.08924 =
0.07055 -0.02804 0.00099 0.00806
O9 4 0.608775 0.656117 0.342993 11.00000 0.05868 0.04226 =
0.02915 0.01148 0.00246 0.01379
O10 4 0.599645 0.482040 0.357881 11.00000 0.05496 0.03843 =
0.02475 0.00048 -0.00292 -0.01306
O11 4 0.486605 0.778753 0.360039 11.00000 0.02907 0.04984 =
0.06025 0.01977 0.00807 0.00166
O12 4 0.574839 0.831093 0.257095 11.00000 0.06511 0.04230 =
0.09831 0.04016 0.04180 -0.00389
O13 4 0.625664 0.475106 0.585597 11.00000 0.08554 0.05770 =
0.03938 0.00861 -0.00205 -0.01729
O14 4 0.693065 0.562041 0.462633 11.00000 0.01788 0.07104 =
0.03360 0.02114 0.00694 0.00748
O15 4 0.578897 0.805508 0.485589 11.00000 0.03906 0.01662 =
0.07666 0.00128 -0.00174 -0.00580
O16 4 0.631123 0.668112 0.583040 11.00000 0.10130 0.04421 =
0.02495 -0.00744 0.00481 0.03998
O17 4 0.571986 0.650467 0.751127 11.00000 0.02293 0.11311 =
0.09371 0.03658 0.01463 0.01532
O18 4 0.616885 0.835949 0.703306 11.00000 0.03357 0.08292 =
0.18048 -0.08188 0.00634 -0.02841
O19 4 0.546363 0.625333 0.488728 11.00000 0.01496 0.02461 =
0.03133 -0.00110 0.00605 -0.00330
O20 4 0.489457 0.497732 0.393226 11.00000 0.01815 0.03311 =
0.01754 -0.00616 0.00578 -0.00426
SAME 0.01 N1 C5 > C16 C1 > C4
SAME 0.01 N1 C13 > C16 C9 > C12 C5 > C8 C1 > C4
SAME 0.01 N1 > C2 C3A C4A C5 C6 C7A C8A C9 > C11 C12A C13 > C15 C16A
N1 3 0.734471 0.849105 0.341638 11.00000 0.04478 0.06888 =
0.07378 -0.00199 0.00600 -0.01082
C1 1 0.684249 0.892094 0.352125 11.00000 0.04133 0.06476 =
0.08277 -0.00418 0.00599 -0.00835
AFIX 23
H1A 2 0.665077 0.847585 0.395406 11.00000 -1.20000
H1B 2 0.666086 0.898187 0.274961 11.00000 -1.20000
AFIX 0
C2 1 0.684934 0.988429 0.409382 11.00000 0.04325 0.06685 =
0.09553 -0.00521 0.00582 -0.00382
PART -1
AFIX 23
H2A 2 0.707878 1.031436 0.374070 41.00000 -1.20000
H2B 2 0.697435 0.981586 0.490890 41.00000 -1.20000
AFIX 23
PART -2
H2C 2 0.703412 1.034295 0.366337 -41.00000 -1.20000
H2D 2 0.702462 0.983481 0.487300 -41.00000 -1.20000
AFIX 0
PART -1
C3 1 0.631763 1.032019 0.397744 41.00000 0.04634 0.06600 =
0.09897 -0.00454 0.00676 -0.00036
AFIX 23
H3A 2 0.620046 1.041005 0.316123 41.00000 -1.20000
H3B 2 0.608653 0.987070 0.429455 41.00000 -1.20000
AFIX 0
C4 1 0.630100 1.124758 0.457274 41.00000 0.05029 0.06400 =
0.10465 -0.00557 0.00076 -0.00039
AFIX 33
H4A 2 0.596022 1.150222 0.445891 41.00000 -1.50000
H4B 2 0.653029 1.169480 0.426451 41.00000 -1.50000
H4C 2 0.640152 1.115749 0.538748 41.00000 -1.50000
AFIX 0
PART 0
C5 1 0.766511 0.909991 0.273962 11.00000 0.05654 0.08151 =
0.08258 0.01215 0.01021 -0.01208
AFIX 23
H5A 2 0.798618 0.876708 0.269302 11.00000 -1.20000
H5B 2 0.774068 0.970093 0.315932 11.00000 -1.20000
AFIX 0
C6 1 0.743865 0.934080 0.154403 11.00000 0.07930 0.10394 =
0.08766 0.01990 0.00533 -0.00773
PART -1
AFIX 23
H6A 2 0.718377 0.984603 0.156413 31.00000 -1.20000
H6B 2 0.727614 0.877260 0.117272 31.00000 -1.20000
AFIX 23
PART -2
H6C 2 0.708185 0.950803 0.155186 -31.00000 -1.20000
H6D 2 0.745759 0.877855 0.104749 -31.00000 -1.20000
AFIX 0
PART -1
C7 1 0.787172 0.968986 0.087175 31.00000 0.08547 0.11146 =
0.09032 0.02510 0.00820 -0.00876
AFIX 23
H7A 2 0.815416 0.923774 0.100228 31.00000 -1.20000
H7B 2 0.775368 0.968354 0.004879 31.00000 -1.20000
AFIX 0
C8 1 0.805470 1.065883 0.119549 31.00000 0.08753 0.12791 =
0.10506 0.02102 -0.00084 -0.02316
AFIX 33
H8A 2 0.833415 1.082196 0.076777 31.00000 -1.50000
H8B 2 0.816728 1.067553 0.201201 31.00000 -1.50000
H8C 2 0.778344 1.111854 0.102036 31.00000 -1.50000
AFIX 0
PART 0
C9 1 0.723859 0.753987 0.287290 11.00000 0.04516 0.07261 =
0.07125 -0.01067 0.01043 -0.01030
AFIX 23
H9A 2 0.704235 0.764103 0.212381 11.00000 -1.20000
H9B 2 0.702573 0.717552 0.334835 11.00000 -1.20000
AFIX 0
C10 1 0.769221 0.693437 0.269607 11.00000 0.04537 0.07752 =
0.07491 -0.00924 0.01704 -0.00962
AFIX 23
H10A 2 0.790086 0.685222 0.343333 11.00000 -1.20000
H10B 2 0.789566 0.726880 0.217331 11.00000 -1.20000
AFIX 0
C11 1 0.754252 0.594771 0.219968 11.00000 0.06073 0.08095 =
0.07817 -0.01253 0.02094 -0.00351
PART -1
AFIX 23
H11A 2 0.739858 0.556849 0.278803 31.00000 -1.20000
H11B 2 0.727921 0.602999 0.155279 31.00000 -1.20000
AFIX 23
PART -2
H11C 2 0.728180 0.567679 0.263186 -31.00000 -1.20000
H11D 2 0.739346 0.602912 0.140207 -31.00000 -1.20000
AFIX 0
PART -1
C12 1 0.796598 0.541086 0.180293 31.00000 0.07516 0.09330 =
0.08240 -0.01482 0.02937 0.00399
AFIX 33
H12A 2 0.784154 0.481597 0.144455 31.00000 -1.50000
H12B 2 0.821308 0.526769 0.245322 31.00000 -1.50000
H12C 2 0.812244 0.579506 0.124951 31.00000 -1.50000
AFIX 0
PART 0
C13 1 0.765044 0.840089 0.455383 11.00000 0.04696 0.06103 =
0.06506 -0.00495 0.00359 -0.01744
AFIX 23
H13A 2 0.772169 0.904495 0.486846 11.00000 -1.20000
H13B 2 0.797410 0.809915 0.444701 11.00000 -1.20000
AFIX 0
C14 1 0.739698 0.782275 0.540604 11.00000 0.05341 0.05969 =
0.05939 -0.01175 -0.00087 -0.02810
AFIX 23
H14A 2 0.737653 0.714885 0.516395 11.00000 -1.20000
H14B 2 0.705249 0.806021 0.543524 11.00000 -1.20000
AFIX 0
C15 1 0.769338 0.789731 0.659678 11.00000 0.06111 0.06473 =
0.05850 -0.00924 0.00312 -0.02734
PART -1
AFIX 23
H15A 2 0.803125 0.762649 0.656953 21.00000 -1.20000
H15B 2 0.773297 0.857616 0.680879 21.00000 -1.20000
AFIX 23
PART -2
H15C 2 0.754093 0.745732 0.711241 -21.00000 -1.20000
H15D 2 0.803865 0.767392 0.654301 -21.00000 -1.20000
AFIX 0
PART -1
C16 1 0.744391 0.738993 0.748555 21.00000 0.06678 0.05685 =
0.06478 0.00543 0.01107 -0.00444
AFIX 33
H16A 2 0.764727 0.745273 0.822221 21.00000 -1.50000
H16B 2 0.740739 0.671557 0.728519 21.00000 -1.50000
H16C 2 0.711318 0.766817 0.753312 21.00000 -1.50000
AFIX 0
PART -2
C3A 1 0.631001 1.024832 0.415004 -41.00000 0.04628 0.06617 =
0.09957 -0.00478 0.00578 -0.00054
AFIX 23
H3C 2 0.612467 0.977497 0.455850 -41.00000 -1.20000
H3D 2 0.632353 1.084728 0.459174 -41.00000 -1.20000
AFIX 0
C4A 1 0.603393 1.042113 0.301092 -41.00000 0.05656 0.06898 =
0.10594 -0.00300 0.00009 0.00832
AFIX 33
H4D 2 0.568673 1.058922 0.309497 -41.00000 -1.50000
H4E 2 0.604036 0.984435 0.254828 -41.00000 -1.50000
H4F 2 0.619244 1.094389 0.263755 -41.00000 -1.50000
AFIX 0
C7A 1 0.771805 1.018422 0.106124 -31.00000 0.08484 0.10847 =
0.09064 0.02439 0.00524 -0.01016
AFIX 23
H7C 2 0.791591 1.051589 0.169861 -31.00000 -1.20000
H7D 2 0.795490 0.993182 0.055326 -31.00000 -1.20000
AFIX 0
C8A 1 0.738277 1.088373 0.041822 -31.00000 0.09758 0.10917 =
0.09952 0.02537 -0.00450 -0.00899
AFIX 33
H8D 2 0.758432 1.137583 0.010086 -31.00000 -1.50000
H8E 2 0.716552 1.117797 0.093039 -31.00000 -1.50000
H8F 2 0.717732 1.055874 -0.020071 -31.00000 -1.50000
AFIX 0
C12A 1 0.796129 0.525855 0.222393 -31.00000 0.07150 0.08728 =
0.08019 -0.01188 0.02354 0.00332
AFIX 33
H12D 2 0.783755 0.465732 0.188113 -31.00000 -1.50000
H12E 2 0.810158 0.514719 0.301318 -31.00000 -1.50000
H12F 2 0.822116 0.551624 0.179347 -31.00000 -1.50000
AFIX 0
C16A 1 0.772056 0.884885 0.712099 -21.00000 0.06029 0.06345 =
0.06062 -0.01135 0.00336 -0.04676
AFIX 33
H16D 2 0.791594 0.881525 0.787023 -21.00000 -1.50000
H16E 2 0.738220 0.907352 0.720601 -21.00000 -1.50000
H16F 2 0.788162 0.929061 0.663534 -21.00000 -1.50000
PART 0

HKLF 4

REM rje419 in C2
REM R1 = 0.0468 for 8182 Fo > 4sig(Fo) and 0.0585 for all 9548 data
REM 461 parameters refined using 326 restraints

END

;