# Supplementary Material (ESI) for Chemical Communications

# This journal is © The Royal Society of Chemistry 2002





data_global



_journal_coden_Cambridge         182



loop_

_publ_author_name

'Robert E. Mulvey'

'William Clegg'

'Glenn C. Forbes'

'Alan R. Kennedy'

'Stephen L. Liddle'



_publ_contact_author_name        'Prof Robert E Mulvey'

_publ_contact_author_address     

;

Pure and Applied Chemistry

University of Strathclyde

295 Cathedral Street

Glasgow

G1 1XL

UNITED KINGDOM

;



_publ_contact_author_email       R.E.MULVEY@STRATH.AC.UK



_publ_requested_journal          'Chemical Communications'



_publ_section_title              

;

Potassium-zinc induced synergic enhancement of the

basicity of hexamethyldisilazide (HMDS) towards arene molecules

;



data_rem285

_database_code_CSD               198623



_audit_creation_method           SHELXL-97

_chemical_name_systematic        

;

?

;

_chemical_name_common            ?

_chemical_melting_point          ?

_chemical_formula_moiety         ?

_chemical_formula_sum            'C19 H43 K N2 Si4 Zn'

_chemical_formula_weight         516.38



loop_

_atom_type_symbol

_atom_type_description

_atom_type_scat_dispersion_real

_atom_type_scat_dispersion_imag

_atom_type_scat_source

C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

Si Si 0.0817 0.0704 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

K K 0.2009 0.2494 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

Zn Zn 0.2839 1.4301 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'



_symmetry_cell_setting           monoclinic

_symmetry_space_group_name_H-M   'P 21/n'



loop_

_symmetry_equiv_pos_as_xyz

'x, y, z'

'-x+1/2, y+1/2, -z+1/2'

'-x, -y, -z'

'x-1/2, -y-1/2, z-1/2'



_cell_length_a                   9.2390(18)

_cell_length_b                   20.764(4)

_cell_length_c                   15.064(3)

_cell_angle_alpha                90.00

_cell_angle_beta                 91.90(3)

_cell_angle_gamma                90.00

_cell_volume                     2888.3(10)

_cell_formula_units_Z            4

_cell_measurement_temperature    160(2)

_cell_measurement_reflns_used    77

_cell_measurement_theta_min      19.95

_cell_measurement_theta_max      24.70



_exptl_crystal_description       block

_exptl_crystal_colour            colourless

_exptl_crystal_size_max          0.69

_exptl_crystal_size_mid          0.46

_exptl_crystal_size_min          0.27

_exptl_crystal_density_meas      ?

_exptl_crystal_density_diffrn    1.188

_exptl_crystal_density_method    'not measured'

_exptl_crystal_F_000             1104

_exptl_absorpt_coefficient_mu    1.168

_exptl_absorpt_correction_type   psi-scan

_exptl_absorpt_correction_T_min  0.132

_exptl_absorpt_correction_T_max  0.779

_exptl_absorpt_process_details   XPREP



_exptl_special_details           

;

Data were relatively weak, leading to high R(int) and R(sigma) values.

;



_diffrn_ambient_temperature      160(2)

_diffrn_radiation_wavelength     0.71073

_diffrn_radiation_type           MoK\a

_diffrn_radiation_source         'fine-focus sealed tube'

_diffrn_radiation_monochromator  graphite

_diffrn_measurement_device_type  'Stoe-Siemens diffractometer'

_diffrn_measurement_method       'ω/θ scans with on-line profile fitting'

_diffrn_detector_area_resol_mean .

_diffrn_standards_number         5

_diffrn_standards_interval_count .

_diffrn_standards_interval_time  60

_diffrn_standards_decay_%        7.5

_diffrn_reflns_number            14016

_diffrn_reflns_av_R_equivalents  0.2082

_diffrn_reflns_av_sigmaI/netI    0.1549

_diffrn_reflns_limit_h_min       -11

_diffrn_reflns_limit_h_max       11

_diffrn_reflns_limit_k_min       -24

_diffrn_reflns_limit_k_max       24

_diffrn_reflns_limit_l_min       -17

_diffrn_reflns_limit_l_max       16

_diffrn_reflns_theta_min         1.67

_diffrn_reflns_theta_max         25.21

_reflns_number_total             4975

_reflns_number_gt                4438

_reflns_threshold_expression     I>2σ(I)



_computing_data_collection       'Stoe DIF4'

_computing_cell_refinement       'Stoe DIF4'

_computing_data_reduction        'local programs'

_computing_structure_solution    'Siemens SHELXTL'

_computing_structure_refinement  'Siemens SHELXTL'

_computing_molecular_graphics    'Siemens SHELXTL'

_computing_publication_material  'SHELXTL and local programs'



_refine_special_details          

;

Refinement of F² against ALL reflections.  The weighted R-factor wR and

goodness of fit S are based on F², conventional R-factors R are based

on F, with F set to zero for negative F². The threshold expression of

F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is

not relevant to the choice of reflections for refinement.  R-factors based

on F² are statistically about twice as large as those based on F, and R-

factors based on ALL data will be even larger.

;



_refine_ls_structure_factor_coef Fsqd

_refine_ls_matrix_type           full

_refine_ls_weighting_scheme      calc

_refine_ls_weighting_details     

'calc w=1/[σ²(Fo²)+(0.0126P)²+4.7772P] where P=(Fo²+2Fc²)/3'

_atom_sites_solution_primary     direct

_atom_sites_solution_secondary   difmap

_atom_sites_solution_hydrogens   geom

_refine_ls_hydrogen_treatment    constr

_refine_ls_extinction_method     SHELXL

_refine_ls_extinction_coef       0.0072(8)

_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^

_refine_ls_number_reflns         4975

_refine_ls_number_parameters     257

_refine_ls_number_restraints     0

_refine_ls_R_factor_all          0.0619

_refine_ls_R_factor_gt           0.0571

_refine_ls_wR_factor_ref         0.1770

_refine_ls_wR_factor_gt          0.1688

_refine_ls_goodness_of_fit_ref   1.043

_refine_ls_restrained_S_all      1.043

_refine_ls_shift/su_max          0.000

_refine_ls_shift/su_mean         0.000



loop_

_atom_site_label

_atom_site_type_symbol

_atom_site_fract_x

_atom_site_fract_y

_atom_site_fract_z

_atom_site_U_iso_or_equiv

_atom_site_adp_type

_atom_site_occupancy

_atom_site_symmetry_multiplicity

_atom_site_calc_flag

_atom_site_refinement_flags

_atom_site_disorder_assembly

_atom_site_disorder_group

K1 K 0.61941(13) 0.18738(5) 0.84993(6) 0.0457(3) Uani 1 1 d . . .

Zn1 Zn 0.43798(6) 0.23605(2) 0.66515(3) 0.0343(2) Uani 1 1 d . . .

N1 N 0.4438(4) 0.14447(14) 0.7084(2) 0.0307(7) Uani 1 1 d . . .

Si1 Si 0.56315(14) 0.09434(5) 0.65932(8) 0.0359(3) Uani 1 1 d . . .

C1 C 0.7527(6) 0.1157(3) 0.6932(4) 0.0588(14) Uani 1 1 d . . .

H1A H 0.7652 0.1615 0.6891 0.088 Uiso 1 1 calc R . .

H1B H 0.8184 0.0946 0.6546 0.088 Uiso 1 1 calc R . .

H1C H 0.7722 0.1021 0.7533 0.088 Uiso 1 1 calc R . .

C2 C 0.5481(7) 0.0086(2) 0.6937(4) 0.0652(16) Uani 1 1 d . . .

H2A H 0.4556 -0.0081 0.6740 0.098 Uiso 1 1 calc R . .

H2B H 0.5572 0.0056 0.7573 0.098 Uiso 1 1 calc R . .

H2C H 0.6237 -0.0161 0.6677 0.098 Uiso 1 1 calc R . .

C3 C 0.5544(7) 0.0970(3) 0.5363(3) 0.0631(15) Uani 1 1 d . . .

H3A H 0.4572 0.0879 0.5153 0.095 Uiso 1 1 calc R . .

H3B H 0.6190 0.0653 0.5134 0.095 Uiso 1 1 calc R . .

H3C H 0.5823 0.1390 0.5166 0.095 Uiso 1 1 calc R . .

Si2 Si 0.27267(14) 0.11931(5) 0.73486(9) 0.0398(3) Uani 1 1 d . . .

C4 C 0.2721(7) 0.0758(3) 0.8426(4) 0.0697(17) Uani 1 1 d . . .

H4A H 0.3313 0.0379 0.8391 0.105 Uiso 1 1 calc R . .

H4B H 0.1748 0.0635 0.8553 0.105 Uiso 1 1 calc R . .

H4C H 0.3100 0.1033 0.8889 0.105 Uiso 1 1 calc R . .

C5 C 0.1818(7) 0.0663(3) 0.6491(4) 0.0683(17) Uani 1 1 d . . .

H5A H 0.2393 0.0284 0.6409 0.102 Uiso 1 1 calc R . .

H5B H 0.1718 0.0892 0.5939 0.102 Uiso 1 1 calc R . .

H5C H 0.0878 0.0541 0.6686 0.102 Uiso 1 1 calc R . .

C6 C 0.1466(6) 0.1896(2) 0.7483(5) 0.0678(17) Uani 1 1 d . . .

H6A H 0.1988 0.2248 0.7754 0.102 Uiso 1 1 calc R . .

H6B H 0.0688 0.1772 0.7853 0.102 Uiso 1 1 calc R . .

H6C H 0.1081 0.2025 0.6911 0.102 Uiso 1 1 calc R . .

N2 N 0.5413(4) 0.29789(14) 0.74523(19) 0.0276(7) Uani 1 1 d . . .

Si3 Si 0.68514(13) 0.33298(5) 0.69537(7) 0.0318(3) Uani 1 1 d . . .

C7 C 0.7295(6) 0.2888(3) 0.5902(3) 0.0521(12) Uani 1 1 d . . .

H7A H 0.6489 0.2917 0.5485 0.078 Uiso 1 1 calc R . .

H7B H 0.7486 0.2443 0.6036 0.078 Uiso 1 1 calc R . .

H7C H 0.8134 0.3078 0.5649 0.078 Uiso 1 1 calc R . .

C8 C 0.6508(6) 0.4175(2) 0.6588(3) 0.0536(13) Uani 1 1 d . . .

H8A H 0.6219 0.4428 0.7086 0.080 Uiso 1 1 calc R . .

H8B H 0.5752 0.4181 0.6136 0.080 Uiso 1 1 calc R . .

H8C H 0.7377 0.4353 0.6355 0.080 Uiso 1 1 calc R . .

C9 C 0.8519(6) 0.3298(2) 0.7682(4) 0.0526(12) Uani 1 1 d . . .

H9A H 0.8339 0.3507 0.8236 0.079 Uiso 1 1 calc R . .

H9B H 0.9293 0.3515 0.7395 0.079 Uiso 1 1 calc R . .

H9C H 0.8783 0.2858 0.7789 0.079 Uiso 1 1 calc R . .

Si4 Si 0.44689(14) 0.33865(5) 0.82259(7) 0.0335(3) Uani 1 1 d . . .

C10 C 0.3936(9) 0.2847(3) 0.9155(4) 0.079(2) Uani 1 1 d . . .

H10A H 0.3442 0.2476 0.8916 0.118 Uiso 1 1 calc R . .

H10B H 0.3306 0.3076 0.9539 0.118 Uiso 1 1 calc R . .

H10C H 0.4788 0.2712 0.9487 0.118 Uiso 1 1 calc R . .

C11 C 0.2789(5) 0.3768(2) 0.7754(3) 0.0482(11) Uani 1 1 d . . .

H11A H 0.2166 0.3441 0.7500 0.072 Uiso 1 1 calc R . .

H11B H 0.3037 0.4070 0.7301 0.072 Uiso 1 1 calc R . .

H11C H 0.2297 0.3988 0.8216 0.072 Uiso 1 1 calc R . .

C12 C 0.5544(8) 0.4029(3) 0.8831(4) 0.075(2) Uani 1 1 d . . .

H12A H 0.5681 0.4388 0.8441 0.113 Uiso 1 1 calc R . .

H12B H 0.6470 0.3859 0.9020 0.113 Uiso 1 1 calc R . .

H12C H 0.5030 0.4168 0.9340 0.113 Uiso 1 1 calc R . .

C13 C 0.2856(5) 0.31621(18) 0.5259(3) 0.0345(9) Uani 1 1 d . . .

C14 C 0.1527(5) 0.3379(2) 0.5538(3) 0.0407(10) Uani 1 1 d . . .

H14A H 0.0951 0.3104 0.5861 0.049 Uiso 1 1 calc R . .

C15 C 0.1033(7) 0.3996(2) 0.5349(3) 0.0523(13) Uani 1 1 d . . .

H15A H 0.0134 0.4128 0.5541 0.063 Uiso 1 1 calc R . .

C16 C 0.1880(7) 0.4414(2) 0.4874(3) 0.0576(15) Uani 1 1 d . . .

H16A H 0.1545 0.4826 0.4738 0.069 Uiso 1 1 calc R . .

C17 C 0.3212(6) 0.4220(2) 0.4605(3) 0.0500(13) Uani 1 1 d . . .

H17A H 0.3795 0.4504 0.4299 0.060 Uiso 1 1 calc R . .

C18 C 0.3694(6) 0.3598(2) 0.4789(3) 0.0434(11) Uani 1 1 d . . .

H18A H 0.4595 0.3470 0.4595 0.052 Uiso 1 1 calc R . .

C19 C 0.3368(6) 0.25008(19) 0.5463(3) 0.0419(11) Uani 1 1 d . . .

H19A H 0.4024 0.2372 0.5005 0.050 Uiso 1 1 calc R . .

H19B H 0.2539 0.2214 0.5422 0.050 Uiso 1 1 calc R . .






_geom_special_details            

;

All esds (except the esd in the dihedral angle between two l.s. planes)

are estimated using the full covariance matrix.  The cell esds are taken

into account individually in the estimation of esds in distances, angles

and torsion angles; correlations between esds in cell parameters are only

used when they are defined by crystal symmetry.  An approximate (isotropic)

treatment of cell esds is used for estimating esds involving l.s. planes.

;



loop_

_geom_bond_atom_site_label_1

_geom_bond_atom_site_label_2

_geom_bond_distance

_geom_bond_site_symmetry_2

_geom_bond_publ_flag

K1 N1 2.782(3) . ?

K1 N2 2.863(3) . ?

K1 C13 3.019(4) 4_666 ?

K1 C14 3.120(4) 4_666 ?

K1 C18 3.126(4) 4_666 ?

K1 C15 3.328(5) 4_666 ?

K1 C17 3.347(5) 4_666 ?

K1 C16 3.429(5) 4_666 ?

Zn1 N2 1.985(3) . ?

Zn1 N1 2.010(3) . ?

Zn1 C19 2.014(4) . ?

N1 Si1 1.703(4) . ?

N1 Si2 1.724(4) . ?

Si1 C3 1.853(5) . ?

Si1 C1 1.861(5) . ?

Si1 C2 1.862(5) . ?

Si2 C4 1.857(5) . ?

Si2 C5 1.874(5) . ?

Si2 C6 1.882(6) . ?

N2 Si4 1.704(3) . ?

N2 Si3 1.711(3) . ?

Si3 C9 1.862(5) . ?

Si3 C8 1.864(5) . ?

Si3 C7 1.888(5) . ?

Si4 C11 1.863(5) . ?

Si4 C10 1.872(6) . ?

Si4 C12 1.881(6) . ?

C13 C14 1.387(7) . ?

C13 C18 1.399(6) . ?

C13 C19 1.481(5) . ?

C13 K1 3.019(4) 4_565 ?

C14 C15 1.385(6) . ?

C14 K1 3.120(4) 4_565 ?

C15 C16 1.385(8) . ?

C15 K1 3.328(5) 4_565 ?

C16 C17 1.370(9) . ?

C16 K1 3.429(5) 4_565 ?

C17 C18 1.390(6) . ?

C17 K1 3.347(5) 4_565 ?

C18 K1 3.126(4) 4_565 ?



loop_

_geom_angle_atom_site_label_1

_geom_angle_atom_site_label_2

_geom_angle_atom_site_label_3

_geom_angle

_geom_angle_site_symmetry_1

_geom_angle_site_symmetry_3

_geom_angle_publ_flag

N1 K1 N2 72.82(9) . . ?

N1 K1 C13 158.63(10) . 4_666 ?

N2 K1 C13 127.94(10) . 4_666 ?

N1 K1 C14 137.38(12) . 4_666 ?

N2 K1 C14 133.78(11) . 4_666 ?

C13 K1 C14 26.04(13) 4_666 4_666 ?

N1 K1 C18 140.87(11) . 4_666 ?

N2 K1 C18 139.56(12) . 4_666 ?

C13 K1 C18 26.25(12) 4_666 4_666 ?

C14 K1 C18 44.70(14) 4_666 4_666 ?

N1 K1 C15 115.25(11) . 4_666 ?

N2 K1 C15 151.48(13) . 4_666 ?

C13 K1 C15 44.54(12) 4_666 4_666 ?

C14 K1 C15 24.53(11) 4_666 4_666 ?

C18 K1 C15 50.38(15) 4_666 4_666 ?

N1 K1 C17 117.71(10) . 4_666 ?

N2 K1 C17 160.72(14) . 4_666 ?

C13 K1 C17 44.59(10) 4_666 4_666 ?

C14 K1 C17 50.28(12) 4_666 4_666 ?

C18 K1 C17 24.50(12) 4_666 4_666 ?

C15 K1 C17 41.83(15) 4_666 4_666 ?

N1 K1 C16 107.72(11) . 4_666 ?

N2 K1 C16 174.87(14) . 4_666 ?

C13 K1 C16 51.11(11) 4_666 4_666 ?

C14 K1 C16 42.61(11) 4_666 4_666 ?

C18 K1 C16 42.45(14) 4_666 4_666 ?

C15 K1 C16 23.59(14) 4_666 4_666 ?

C17 K1 C16 23.28(15) 4_666 4_666 ?

N2 Zn1 N1 114.06(13) . . ?

N2 Zn1 C19 130.30(15) . . ?

N1 Zn1 C19 115.59(15) . . ?

Si1 N1 Si2 121.80(18) . . ?

Si1 N1 Zn1 116.62(18) . . ?

Si2 N1 Zn1 110.28(17) . . ?

Si1 N1 K1 99.15(15) . . ?

Si2 N1 K1 115.84(16) . . ?

Zn1 N1 K1 87.38(11) . . ?

N1 Si1 C3 114.1(2) . . ?

N1 Si1 C1 110.6(2) . . ?

C3 Si1 C1 106.1(3) . . ?

N1 Si1 C2 114.1(2) . . ?

C3 Si1 C2 107.8(3) . . ?

C1 Si1 C2 103.3(3) . . ?

N1 Si2 C4 112.2(2) . . ?

N1 Si2 C5 114.3(3) . . ?

C4 Si2 C5 107.6(3) . . ?

N1 Si2 C6 111.4(2) . . ?

C4 Si2 C6 105.3(3) . . ?

C5 Si2 C6 105.4(3) . . ?

Si4 N2 Si3 120.77(18) . . ?

Si4 N2 Zn1 119.34(19) . . ?

Si3 N2 Zn1 111.95(16) . . ?

Si4 N2 K1 98.43(13) . . ?

Si3 N2 K1 113.46(16) . . ?

Zn1 N2 K1 85.62(10) . . ?

N2 Si3 C9 111.5(2) . . ?

N2 Si3 C8 113.8(2) . . ?

C9 Si3 C8 109.6(2) . . ?

N2 Si3 C7 110.8(2) . . ?

C9 Si3 C7 106.2(3) . . ?

C8 Si3 C7 104.4(2) . . ?

N2 Si4 C11 112.90(19) . . ?

N2 Si4 C10 111.6(2) . . ?

C11 Si4 C10 107.7(3) . . ?

N2 Si4 C12 114.2(3) . . ?

C11 Si4 C12 107.7(3) . . ?

C10 Si4 C12 102.1(3) . . ?

C14 C13 C18 117.0(4) . . ?

C14 C13 C19 121.2(4) . . ?

C18 C13 C19 121.8(5) . . ?

C14 C13 K1 81.1(2) . 4_565 ?

C18 C13 K1 81.1(2) . 4_565 ?

C19 C13 K1 108.0(2) . 4_565 ?

C15 C14 C13 121.8(5) . . ?

C15 C14 K1 86.1(3) . 4_565 ?

C13 C14 K1 72.9(2) . 4_565 ?

C16 C15 C14 119.9(6) . . ?

C16 C15 K1 82.3(3) . 4_565 ?

C14 C15 K1 69.3(3) . 4_565 ?

C17 C16 C15 119.8(4) . . ?

C17 C16 K1 75.0(3) . 4_565 ?

C15 C16 K1 74.1(3) . 4_565 ?

C16 C17 C18 120.0(5) . . ?

C16 C17 K1 81.7(3) . 4_565 ?

C18 C17 K1 68.8(2) . 4_565 ?

C17 C18 C13 121.5(5) . . ?

C17 C18 K1 86.7(3) . 4_565 ?

C13 C18 K1 72.6(2) . 4_565 ?

C13 C19 Zn1 117.0(3) . . ?



_diffrn_measured_fraction_theta_max 0.957

_diffrn_reflns_theta_full        25.21

_diffrn_measured_fraction_theta_full 0.957

_refine_diff_density_max         0.602

_refine_diff_density_min         -0.827

_refine_diff_density_rms         0.094







