# Supplementary Material (ESI) for Chemical Communications
# This journal is © The Royal Society of Chemistry 2008

data_global

_journal_name_full               Chem.Commun.

_journal_coden_Cambridge         0182
_journal_volume                  ?
_journal_page_first              ?
_journal_year                    ?

_publ_contact_author_name        'Simon Humphrey'
_publ_contact_author_email       SMH49@CAM.AC.UK

_publ_section_title              
;
Hysteretic Sorption of Light Gases by a Porous
Metal-Organic Framework Containing Tris(p-Carboxylated)
Triphenylphosphine Oxide
;

# Attachment 'pcm4a_SQUEEZE.cif'

_publ_contact_author             'Dr Simon M. Humphrey'
loop_
_publ_author_name
'Simon Humphrey'
'Jong-San Chang.'
'Young Kyu Hwang.'
'Shaunt E Oungoulian'
;
E.R.Wise
;
'Ji Woong Yoon.'

data_pcm4a_SQUEEZE
_database_code_depnum_ccdc_archive 'CCDC 682285'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C42 H31 O18 P2 Zn3'
_chemical_formula_sum            'C42 H31 O18 P2 Zn3'
_chemical_formula_weight         1081.72

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'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
P P 0.1023 0.0942 '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           cubic
_symmetry_space_group_name_H-M   Pa-3

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

_cell_length_a                   22.9079(9)
_cell_length_b                   22.9079(9)
_cell_length_c                   22.9079(9)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     12021.4(8)
_cell_formula_units_Z            8
_cell_measurement_temperature    180(2)
_cell_measurement_reflns_used    22240
_cell_measurement_theta_min      1.02
_cell_measurement_theta_max      24.11

_exptl_crystal_description       prism
_exptl_crystal_colour            colorless
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.16
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.195
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             4376
_exptl_absorpt_coefficient_mu    1.297
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.841
_exptl_absorpt_correction_T_max  0.943
_exptl_absorpt_process_details   
;
multi-scan from symmetry-related measurements
Sortav (Blessing 1995)
;

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      180(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_measurement_device_type  'Nonius Kappa CCD'
_diffrn_measurement_method       'Thin slice \w and \f scans'
_diffrn_reflns_number            10121
_diffrn_reflns_av_R_equivalents  0.0943
_diffrn_reflns_av_sigmaI/netI    0.0811
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_limit_l_max       6
_diffrn_reflns_theta_min         3.56
_diffrn_reflns_theta_max         22.49
_diffrn_measured_fraction_theta_max 0.991
_diffrn_reflns_theta_full        22.49
_diffrn_measured_fraction_theta_full 0.991
_reflns_number_total             2602
_reflns_number_gt                1600
_reflns_threshold_expression     >2sigma(I)

_computing_cell_refinement       'HKL Scalepack (Otwinowski & Minor 1997)'
_computing_data_reduction        
;
HKL Denzo and Scalepack (Otwinowski & Minor 1997)
;
_computing_structure_solution    'SIR-92 (Altomare et al. 1994)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick 1997)'
_computing_publication_material  'SHELXL-97 (Sheldrick 1997)'

_refine_special_details          
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and R-
factors based on ALL data will be even larger.

Geometric constraints were applied to fix the O-H distances for O5-H5A,
O6-H6A and O6-H6B, in order to improve the stability of the refinement.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[\s^2^(Fo^2^)+(0.1972P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         2602
_refine_ls_number_parameters     203
_refine_ls_number_restraints     4
_refine_ls_R_factor_all          0.1462
_refine_ls_R_factor_gt           0.1040
_refine_ls_wR_factor_ref         0.2915
_refine_ls_wR_factor_gt          0.2589
_refine_ls_goodness_of_fit_ref   1.013
_refine_ls_restrained_S_all      1.023
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_diff_density_max         1.297
_refine_diff_density_min         -0.541
_refine_diff_density_rms         0.172

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
Zn1 Zn 0.22626(6) 0.71180(6) 0.32500(5) 0.0512(6) Uani 1 1 d . . .
P1 P 0.35951(11) 0.35951(11) 0.35951(11) 0.0367(11) Uani 1 3 d S . .
O1P O 0.3219(4) 0.3219(4) 0.3219(4) 0.061(4) Uani 1 3 d S . .
P2 P 0.35183(11) 0.85183(11) 0.64817(11) 0.0329(11) Uani 1 3 d S . .
O2P O 0.3134(4) 0.8134(4) 0.6866(4) 0.054(3) Uani 1 3 d S . .
O1 O 0.2481(4) 0.6304(4) 0.3259(4) 0.075(3) Uani 1 1 d . . .
O2 O 0.3398(4) 0.6534(4) 0.3211(5) 0.088(3) Uani 1 1 d . . .
O3 O 0.2656(4) 0.7471(3) 0.3911(3) 0.064(2) Uani 1 1 d . . .
O4 O 0.3021(3) 0.8341(3) 0.3569(3) 0.054(2) Uani 1 1 d . . .
O5 O 0.2486(2) 0.7514(2) 0.2514(2) 0.025(2) Uani 1 3 d SD . .
H5A H 0.2738 0.7262 0.2262 0.030 Uiso 1 3 calc SRD . .
O6 O 0.3242(2) 0.7298(2) 0.2872(2) 0.0236(13) Uani 1 1 d D . .
H6A H 0.322(3) 0.749(3) 0.3212(18) 0.028 Uiso 1 1 d D . .
H6B H 0.351(3) 0.746(3) 0.263(2) 0.028 Uiso 1 1 d D . .
C1 C 0.3452(4) 0.4362(4) 0.3486(4) 0.041(2) Uani 1 1 d . . .
C2 C 0.3884(4) 0.4764(4) 0.3401(5) 0.052(3) Uani 1 1 d . . .
H2 H 0.4282 0.4646 0.3394 0.062 Uiso 1 1 calc R . .
C3 C 0.3730(5) 0.5360(5) 0.3322(5) 0.055(3) Uani 1 1 d . . .
H3 H 0.4028 0.5640 0.3257 0.066 Uiso 1 1 calc R . .
C4 C 0.3170(5) 0.5536(5) 0.3338(6) 0.060(3) Uani 1 1 d . . .
C5 C 0.2740(5) 0.5127(5) 0.3449(6) 0.063(3) Uani 1 1 d . . .
H5 H 0.2344 0.5247 0.3484 0.076 Uiso 1 1 calc R . .
C6 C 0.2884(5) 0.4538(5) 0.3509(6) 0.060(3) Uani 1 1 d . . .
H6 H 0.2584 0.4258 0.3567 0.071 Uiso 1 1 calc R . .
C7 C 0.3023(6) 0.6172(6) 0.3241(6) 0.074(4) Uani 1 1 d . . .
C8 C 0.3375(4) 0.8379(4) 0.5720(4) 0.036(2) Uani 1 1 d . . .
C9 C 0.3378(5) 0.8816(5) 0.5300(4) 0.051(3) Uani 1 1 d . . .
H9 H 0.3448 0.9210 0.5407 0.062 Uiso 1 1 calc R . .
C10 C 0.3277(5) 0.8666(5) 0.4722(5) 0.050(3) Uani 1 1 d . . .
H10 H 0.3325 0.8953 0.4426 0.060 Uiso 1 1 calc R . .
C11 C 0.3109(5) 0.8119(4) 0.4573(4) 0.045(3) Uani 1 1 d . . .
C12 C 0.3098(7) 0.7709(5) 0.5007(6) 0.089(5) Uani 1 1 d . . .
H12 H 0.2980 0.7323 0.4912 0.106 Uiso 1 1 calc R . .
C13 C 0.3249(6) 0.7830(5) 0.5567(5) 0.072(4) Uani 1 1 d . . .
H13 H 0.3265 0.7527 0.5849 0.086 Uiso 1 1 calc R . .
C14 C 0.2923(5) 0.7961(6) 0.3965(5) 0.061(3) Uani 1 1 d . . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Zn1 0.0507(9) 0.0585(10) 0.0443(9) 0.0037(6) -0.0053(6) -0.0096(6)
P1 0.0367(11) 0.0367(11) 0.0367(11) 0.0054(12) 0.0054(12) 0.0054(12)
O1P 0.061(4) 0.061(4) 0.061(4) 0.022(5) 0.022(5) 0.022(5)
P2 0.0329(11) 0.0329(11) 0.0329(11) -0.0028(11) -0.0028(11) 0.0028(11)
O2P 0.054(3) 0.054(3) 0.054(3) -0.015(4) -0.015(4) 0.015(4)
O1 0.074(6) 0.055(5) 0.094(7) 0.009(5) -0.008(5) 0.002(4)
O2 0.066(6) 0.047(5) 0.152(10) 0.002(5) 0.030(6) -0.011(5)
O3 0.095(6) 0.044(5) 0.054(5) -0.011(4) -0.037(5) 0.007(4)
O4 0.076(5) 0.048(5) 0.039(4) -0.013(4) -0.006(4) 0.004(4)
O5 0.025(2) 0.025(2) 0.025(2) 0.004(3) -0.004(3) -0.004(3)
O6 0.013(3) 0.025(3) 0.032(3) 0.006(3) -0.013(2) -0.008(2)
C1 0.038(6) 0.050(6) 0.036(6) 0.002(5) 0.011(5) 0.009(5)
C2 0.032(6) 0.041(7) 0.083(8) 0.015(6) 0.001(5) 0.001(5)
C3 0.045(7) 0.058(8) 0.061(7) 0.009(6) -0.004(5) -0.007(6)
C4 0.053(8) 0.036(6) 0.092(9) -0.001(6) 0.015(6) 0.012(6)
C5 0.040(7) 0.056(8) 0.094(10) 0.022(7) -0.004(6) 0.005(6)
C6 0.051(8) 0.038(6) 0.090(9) 0.020(6) 0.002(6) -0.003(5)
C7 0.042(8) 0.076(10) 0.104(11) 0.023(8) 0.024(7) 0.013(7)
C8 0.040(6) 0.030(6) 0.038(6) -0.007(4) -0.013(4) 0.010(4)
C9 0.072(8) 0.053(7) 0.030(6) -0.011(5) 0.002(5) -0.006(6)
C10 0.064(7) 0.039(7) 0.048(7) 0.002(5) -0.002(5) -0.004(5)
C11 0.066(7) 0.024(6) 0.046(6) -0.013(5) -0.021(5) 0.024(5)
C12 0.168(15) 0.024(6) 0.074(9) -0.018(6) -0.071(10) 0.020(7)
C13 0.131(12) 0.036(7) 0.049(7) -0.003(5) -0.058(8) 0.017(7)
C14 0.065(8) 0.068(9) 0.050(7) -0.009(7) -0.030(6) 0.022(7)

_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
Zn1 O1 1.930(8) . ?
Zn1 O3 1.938(7) . ?
Zn1 O4 1.944(7) 7_564 ?
Zn1 O5 1.981(4) . ?
Zn1 O6 2.351(6) 7_564 ?
Zn1 O6 2.440(6) . ?
P1 O1P 1.492(16) . ?
P1 C1 1.805(10) 5 ?
P1 C1 1.805(10) . ?
P1 C1 1.805(10) 9 ?
P2 O2P 1.524(15) . ?
P2 C8 1.804(9) . ?
P2 C8 1.804(9) 11_466 ?
P2 C8 1.804(9) 8_656 ?
O1 C7 1.279(14) . ?
O2 C7 1.196(15) . ?
O3 C14 1.283(14) . ?
O4 C14 1.277(14) . ?
O4 Zn1 1.944(7) 10_655 ?
O5 Zn1 1.981(4) 7_564 ?
O5 Zn1 1.981(4) 10_655 ?
O5 H5A 1.0000 . ?
O6 Zn1 2.351(6) 10_655 ?
O6 H6A 0.90(2) . ?
O6 H6B 0.91(2) . ?
C1 C6 1.364(14) . ?
C1 C2 1.365(14) . ?
C2 C3 1.422(15) . ?
C2 H2 0.9500 . ?
C3 C4 1.345(15) . ?
C3 H3 0.9500 . ?
C4 C5 1.383(16) . ?
C4 C7 1.511(17) . ?
C5 C6 1.395(15) . ?
C5 H5 0.9500 . ?
C6 H6 0.9500 . ?
C8 C13 1.336(14) . ?
C8 C9 1.388(14) . ?
C9 C10 1.386(14) . ?
C9 H9 0.9500 . ?
C10 C11 1.354(14) . ?
C10 H10 0.9500 . ?
C11 C12 1.368(17) . ?
C11 C14 1.503(15) . ?
C12 C13 1.359(16) . ?
C12 H12 0.9500 . ?
C13 H13 0.9500 . ?

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
O1 Zn1 O3 105.9(3) . . ?
O1 Zn1 O4 95.4(4) . 7_564 ?
O3 Zn1 O4 116.1(3) . 7_564 ?
O1 Zn1 O5 112.7(4) . . ?
O3 Zn1 O5 110.7(3) . . ?
O4 Zn1 O5 114.8(3) 7_564 . ?
O1 Zn1 O6 72.8(3) . 7_564 ?
O3 Zn1 O6 158.6(3) . 7_564 ?
O4 Zn1 O6 85.1(3) 7_564 7_564 ?
O5 Zn1 O6 53.55(19) . 7_564 ?
O1 Zn1 O6 86.0(3) . . ?
O3 Zn1 O6 77.3(3) . . ?
O4 Zn1 O6 165.3(3) 7_564 . ?
O5 Zn1 O6 51.92(19) . . ?
O6 Zn1 O6 81.4(3) 7_564 . ?
O1P P1 C1 112.2(3) . 5 ?
O1P P1 C1 112.2(3) . . ?
C1 P1 C1 106.7(4) 5 . ?
O1P P1 C1 112.2(3) . 9 ?
C1 P1 C1 106.7(4) 5 9 ?
C1 P1 C1 106.7(4) . 9 ?
O2P P2 C8 110.5(3) . . ?
O2P P2 C8 110.5(3) . 11_466 ?
C8 P2 C8 108.4(3) . 11_466 ?
O2P P2 C8 110.5(3) . 8_656 ?
C8 P2 C8 108.4(3) . 8_656 ?
C8 P2 C8 108.4(3) 11_466 8_656 ?
C7 O1 Zn1 118.7(9) . . ?
C14 O3 Zn1 131.4(7) . . ?
C14 O4 Zn1 126.4(7) . 10_655 ?
Zn1 O5 Zn1 106.8(3) 7_564 10_655 ?
Zn1 O5 Zn1 106.8(3) 7_564 . ?
Zn1 O5 Zn1 106.8(3) 10_655 . ?
Zn1 O5 H5A 112.0 7_564 . ?
Zn1 O5 H5A 112.0 10_655 . ?
Zn1 O5 H5A 112.0 . . ?
Zn1 O6 Zn1 83.16(19) 10_655 . ?
Zn1 O6 H6A 69(5) 10_655 . ?
Zn1 O6 H6A 74(4) . . ?
Zn1 O6 H6B 77(5) 10_655 . ?
Zn1 O6 H6B 155(5) . . ?
H6A O6 H6B 112(3) . . ?
C6 C1 C2 120.0(10) . . ?
C6 C1 P1 117.1(8) . . ?
C2 C1 P1 122.9(8) . . ?
C1 C2 C3 118.9(10) . . ?
C1 C2 H2 120.5 . . ?
C3 C2 H2 120.5 . . ?
C4 C3 C2 121.5(10) . . ?
C4 C3 H3 119.3 . . ?
C2 C3 H3 119.3 . . ?
C3 C4 C5 118.8(11) . . ?
C3 C4 C7 119.8(11) . . ?
C5 C4 C7 121.5(10) . . ?
C4 C5 C6 120.3(11) . . ?
C4 C5 H5 119.8 . . ?
C6 C5 H5 119.8 . . ?
C1 C6 C5 120.4(10) . . ?
C1 C6 H6 119.8 . . ?
C5 C6 H6 119.8 . . ?
O2 C7 O1 122.3(13) . . ?
O2 C7 C4 121.2(12) . . ?
O1 C7 C4 116.1(12) . . ?
C13 C8 C9 119.8(9) . . ?
C13 C8 P2 117.4(8) . . ?
C9 C8 P2 122.8(7) . . ?
C10 C9 C8 118.9(10) . . ?
C10 C9 H9 120.5 . . ?
C8 C9 H9 120.5 . . ?
C11 C10 C9 121.1(10) . . ?
C11 C10 H10 119.5 . . ?
C9 C10 H10 119.5 . . ?
C10 C11 C12 117.3(10) . . ?
C10 C11 C14 122.6(10) . . ?
C12 C11 C14 120.1(10) . . ?
C13 C12 C11 122.7(11) . . ?
C13 C12 H12 118.7 . . ?
C11 C12 H12 118.7 . . ?
C8 C13 C12 119.7(11) . . ?
C8 C13 H13 120.1 . . ?
C12 C13 H13 120.1 . . ?
O4 C14 O3 127.7(10) . . ?
O4 C14 C11 116.3(11) . . ?
O3 C14 C11 115.8(11) . . ?

loop_
_platon_squeeze_void_nr
1
_platon_squeeze_void_average_x   -0.016
_platon_squeeze_void_average_y   0.005
_platon_squeeze_void_average_z   0.004
_platon_squeeze_void_volume      5340.5
_platon_squeeze_void_count_electrons 158.6