# Electronic Supplementary Material (ESI) for Green Chemistry
# This journal is © The Royal Society of Chemistry 2011


data_global

_journal_coden_Cambridge         1048

loop_
_publ_author_name
'Schroder, M.'
'Ibarra, Ilich'
'Bayliss, Peter'
'Perez Velilla, Eduardo'
'Yang, Sihai'
'Blake, Alexander'
'Nowell, Harriott'
'Allan, David'
'Poliakoff, Martyn'

_publ_contact_author_name        'Schroder, M.'
_publ_contact_author_email       m.schroder@nottingham.ac.uk

_publ_section_title              
;
Near-Critical Water, a Cleaner Solvent for
the Synthesis of a Metal-Organic Framework
;

# Attachment 'ZNIILB.CIF'

data_2
#TrackingRef 'ZNIILB.CIF'

_database_code_depnum_ccdc_archive 'CCDC 831133'
#ZNIILB #8927

_refine_special_details          
;
Approximately 32% of the unit cell volume comprises a large region of
disordered solvent which could not be modelled as discrete atomic sites.
We employed PLATON SQUEEZE to calculate the contribution to the diffraction
from the solvent region and thereby produced a set of solvent-free diffraction
intensities. SQUEEZE estimated a total count of 204 electrons per unit cell,
which were assigned to be 1.5 water molecules per zinc. The final formula was
calculated from the TGA combined with elemental analysis data.
;

loop_
_platon_squeeze_void_nr
_platon_squeeze_void_average_x
_platon_squeeze_void_average_y
_platon_squeeze_void_average_z
_platon_squeeze_void_volume
_platon_squeeze_void_count_electrons
1 0.000 -0.053 0.250 120 16
2 0.000 0.010 0.750 120 16
3 0.250 -0.041 0.250 170 35
4 0.250 -0.041 0.750 170 35
5 0.500 -0.004 0.250 120 16
6 0.500 -0.057 0.750 120 16
7 0.750 -0.030 0.250 170 35
8 0.750 -0.052 0.750 170 35

_platon_squeeze_details          
;
;

_audit_creation_method           'enCIFer editing of SHELXL97 CIF output'
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'Zn (C17 O4 H9), 1.5(H2 O)'
_chemical_formula_sum            'C17 H12 O5.5 Zn'
_chemical_formula_weight         369.64

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'
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   'C 2/c'

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

_cell_length_a                   31.97(4)
_cell_length_b                   6.334(9)
_cell_length_c                   20.49(3)
_cell_angle_alpha                90.00
_cell_angle_beta                 120.078(13)
_cell_angle_gamma                90.00
_cell_volume                     3590(9)
_cell_formula_units_Z            8
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    3575
_cell_measurement_theta_min      2.23
_cell_measurement_theta_max      31.55

_exptl_crystal_description       prism
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.04
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.368
_exptl_crystal_density_method    ?
_exptl_crystal_F_000             1504
_exptl_absorpt_coefficient_mu    1.391
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.633
_exptl_absorpt_correction_T_max  1.00
_exptl_absorpt_process_details   'Jacobson, R. (1998) Private communication'

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     0.6889
_diffrn_radiation_type           synchrotron
_diffrn_radiation_source         'Diamond Light Source Beamline I19'
_diffrn_radiation_monochromator  'silicon double crystal'
_diffrn_measurement_device_type  'Rigaku Saturn724+'
_diffrn_measurement_method       '\w scans'
_diffrn_detector_area_resol_mean 28.5714
_diffrn_standards_decay_%        0
_diffrn_reflns_number            5442
_diffrn_reflns_av_R_equivalents  0.102
_diffrn_reflns_av_sigmaI/netI    0.124
_diffrn_reflns_limit_h_min       -36
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_theta_min         2.60
_diffrn_reflns_theta_max         23.32
_reflns_number_total             2801
_reflns_number_gt                1302
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Rigaku CrystalClear (Rigaku, 2009)'
#Rigaku(2009). CrystalClear. Rigaku Corporation, Tokyo, Japan.
_computing_cell_refinement       'Rigaku CrystalClear'
_computing_data_reduction        'Rigaku CrystalClear'
_computing_structure_solution    'SHELXS97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL97 (Sheldrick, 2008)'
_computing_publication_material  
'enCIFer (Allen et al., 2004); PLATON (Spek, 2009)'

_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^)+(0.200P)^2^+20.0P] 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    constr
_refine_ls_extinction_method     SHELXL
_refine_ls_extinction_coef       0.00
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_number_reflns         2801
_refine_ls_number_parameters     200
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.194
_refine_ls_R_factor_gt           0.137
_refine_ls_wR_factor_ref         0.409
_refine_ls_wR_factor_gt          0.348
_refine_ls_goodness_of_fit_ref   1.13
_refine_ls_restrained_S_all      1.13
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.001

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 -0.02347(5) 0.2488(3) -0.01248(9) 0.0560(8) Uani 1 1 d . . .
O1 O 0.0220(3) 0.2817(14) 0.0926(5) 0.052(2) Uani 1 1 d . . .
O2 O 0.0183(3) 0.8033(17) 0.4462(5) 0.057(3) Uani 1 1 d . . .
O3 O 0.0667(4) 0.5489(15) 0.0837(6) 0.068(3) Uani 1 1 d . . .
O4 O 0.0703(3) 1.0568(15) 0.5143(5) 0.066(3) Uani 1 1 d . . .
C1 C 0.1316(5) 0.519(2) 0.2385(9) 0.067(4) Uani 1 1 d . . .
H1A H 0.1302 0.6465 0.2130 0.080 Uiso 1 1 calc R . .
C2 C 0.1662(5) 0.499(3) 0.3115(8) 0.080(5) Uani 1 1 d . . .
H2A H 0.1874 0.6137 0.3369 0.096 Uiso 1 1 calc R . .
C3 C 0.1377(6) 0.143(3) 0.3082(10) 0.082(5) Uani 1 1 d . . .
H3A H 0.1395 0.0096 0.3306 0.098 Uiso 1 1 calc R . .
C4 C 0.1010(6) 0.178(3) 0.2320(9) 0.078(5) Uani 1 1 d . . .
H4A H 0.0786 0.0688 0.2047 0.093 Uiso 1 1 calc R . .
C5 C 0.2089(5) 0.272(2) 0.4258(8) 0.053(3) Uani 1 1 d . . .
C6 C 0.0879(6) 0.564(3) 0.4385(9) 0.074(5) Uani 1 1 d . . .
H6A H 0.0563 0.5054 0.4148 0.089 Uiso 1 1 calc R . .
C7 C 0.0595(5) 0.401(2) 0.1195(9) 0.064(4) Uani 1 1 d . . .
C8 C 0.0979(5) 0.363(3) 0.1987(8) 0.067(4) Uani 1 1 d . . .
C12 C 0.0604(5) 0.887(2) 0.4773(7) 0.056(4) Uani 1 1 d . . .
C13 C 0.1708(4) 0.527(3) 0.4778(7) 0.058(4) Uani 1 1 d . . .
C14 C 0.1263(5) 0.460(2) 0.4441(8) 0.063(4) Uani 1 1 d . . .
H14A H 0.1203 0.3241 0.4213 0.075 Uiso 1 1 calc R . .
C16 C 0.0984(5) 0.768(3) 0.4709(9) 0.075(5) Uani 1 1 d . . .
C29 C 0.1711(4) 0.301(3) 0.3513(8) 0.069(5) Uani 1 1 d . . .
C31 C 0.2468(6) 0.139(3) 0.4409(8) 0.075(5) Uani 1 1 d . . .
H31A H 0.2458 0.0636 0.4002 0.089 Uiso 1 1 calc R . .
C32 C 0.2134(5) 0.390(2) 0.4868(7) 0.056(4) Uani 1 1 d . . .
C34 C 0.1450(5) 0.853(3) 0.5063(8) 0.065(4) Uani 1 1 d . . .
H34A H 0.1509 0.9914 0.5272 0.077 Uiso 1 1 calc R . .
C36 C 0.1807(5) 0.738(2) 0.5102(8) 0.059(4) Uani 1 1 d . . .
H36A H 0.2127 0.7921 0.5342 0.071 Uiso 1 1 calc R . .

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 0.0457(11) 0.0624(12) 0.0536(11) 0.0048(7) 0.0200(8) -0.0045(7)
O1 0.034(4) 0.076(6) 0.036(4) 0.009(4) 0.010(4) -0.006(4)
O2 0.023(4) 0.107(7) 0.037(4) -0.026(5) 0.014(4) -0.003(4)
O3 0.066(6) 0.061(6) 0.070(6) 0.006(5) 0.029(5) -0.002(5)
O4 0.061(6) 0.068(6) 0.065(6) -0.018(5) 0.030(5) 0.007(5)
C1 0.056(9) 0.050(8) 0.084(10) 0.023(8) 0.029(8) 0.007(7)
C2 0.048(8) 0.104(13) 0.054(9) 0.012(9) 0.001(7) 0.021(9)
C3 0.086(12) 0.068(10) 0.093(12) -0.001(10) 0.046(11) 0.016(9)
C4 0.090(12) 0.067(9) 0.062(9) 0.026(8) 0.026(9) 0.037(9)
C5 0.051(7) 0.054(8) 0.057(8) -0.011(6) 0.030(7) 0.009(6)
C6 0.067(10) 0.067(10) 0.084(11) -0.022(8) 0.036(9) -0.005(8)
C7 0.065(9) 0.052(8) 0.092(11) 0.001(8) 0.052(9) 0.004(7)
C8 0.047(8) 0.076(10) 0.061(9) -0.005(8) 0.014(7) 0.005(8)
C12 0.054(8) 0.063(9) 0.042(7) -0.018(6) 0.018(6) 0.015(7)
C13 0.037(7) 0.093(11) 0.040(7) -0.018(7) 0.016(6) 0.009(7)
C14 0.045(8) 0.071(10) 0.070(9) -0.001(8) 0.027(7) 0.014(7)
C16 0.035(7) 0.130(16) 0.054(8) 0.009(9) 0.017(7) 0.029(8)
C29 0.030(7) 0.109(13) 0.046(8) -0.010(8) 0.001(6) 0.017(7)
C31 0.076(10) 0.083(11) 0.047(8) 0.001(8) 0.017(8) 0.029(9)
C32 0.052(7) 0.068(9) 0.045(7) -0.017(6) 0.022(6) 0.010(7)
C34 0.050(8) 0.073(10) 0.069(9) -0.003(8) 0.029(7) 0.012(7)
C36 0.039(7) 0.078(10) 0.047(8) -0.017(7) 0.011(6) -0.010(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 1.912(9) . ?
Zn1 O2 1.936(9) 6_565 ?
Zn1 O3 1.913(10) 5_565 ?
Zn1 O4 1.913(9) 2_545 ?
O1 C7 1.281(16) . ?
O3 C7 1.281(17) . ?
O4 C12 1.263(15) . ?
C1 C2 1.35(2) . ?
C1 C8 1.39(2) . ?
C1 H1A 0.9500 . ?
C2 C29 1.46(2) . ?
C2 H2A 0.9500 . ?
C3 C29 1.41(2) . ?
C3 C4 1.42(2) . ?
C3 H3A 0.9500 . ?
C4 C8 1.33(2) . ?
C4 H4A 0.9500 . ?
C5 C31 1.375(19) . ?
C5 C32 1.398(17) . ?
C5 C29 1.406(19) . ?
C6 C14 1.35(2) . ?
C6 C16 1.42(2) . ?
C6 H6A 0.9500 . ?
C7 C8 1.48(2) . ?
C12 C16 1.489(19) . ?
C13 C14 1.305(18) . ?
C13 C36 1.451(19) . ?
C13 C32 1.547(17) . ?
C14 H14A 0.9500 . ?
C16 C34 1.40(2) . ?
C31 C32 1.400(18) 7_556 ?
C31 H31A 0.9500 . ?
C34 C36 1.326(19) . ?
C34 H34A 0.9500 . ?
C36 H36A 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 129.6(4) . 5_565 ?
O1 Zn1 O4 103.7(4) . 2_545 ?
O3 Zn1 O4 98.8(4) 5_565 2_545 ?
O1 Zn1 O2 102.1(4) . 6_565 ?
O3 Zn1 O2 100.0(4) 5_565 6_565 ?
O4 Zn1 O2 126.0(4) 2_545 6_565 ?
C7 O1 Zn1 124.6(10) . . ?
C12 O2 Zn1 129.6(8) . 6_566 ?
C7 O3 Zn1 131.3(10) . 5_565 ?
C12 O4 Zn1 125.0(9) . 2_565 ?
C2 C1 C8 123.3(15) . . ?
C2 C1 H1A 118.3 . . ?
C8 C1 H1A 118.3 . . ?
C1 C2 C29 119.8(16) . . ?
C1 C2 H2A 120.1 . . ?
C29 C2 H2A 120.1 . . ?
C29 C3 C4 121.9(17) . . ?
C29 C3 H3A 119.0 . . ?
C4 C3 H3A 119.0 . . ?
C8 C4 C3 120.4(18) . . ?
C8 C4 H4A 119.8 . . ?
C3 C4 H4A 119.8 . . ?
C31 C5 C32 116.1(13) . . ?
C31 C5 C29 120.2(13) . . ?
C32 C5 C29 123.4(12) . . ?
C14 C6 C16 114.7(15) . . ?
C14 C6 H6A 122.7 . . ?
C16 C6 H6A 122.7 . . ?
O3 C7 O1 125.6(15) . . ?
O3 C7 C8 117.2(14) . . ?
O1 C7 C8 117.2(14) . . ?
C4 C8 C1 119.3(15) . . ?
C4 C8 C7 120.6(15) . . ?
C1 C8 C7 120.1(14) . . ?
O4 C12 O2 122.3(12) . . ?
O4 C12 C16 120.9(13) . . ?
O2 C12 C16 116.7(12) . . ?
C14 C13 C36 118.2(13) . . ?
C14 C13 C32 122.7(14) . . ?
C36 C13 C32 119.1(11) . . ?
C13 C14 C6 126.1(16) . . ?
C13 C14 H14A 116.9 . . ?
C6 C14 H14A 116.9 . . ?
C34 C16 C6 122.5(14) . . ?
C34 C16 C12 117.7(15) . . ?
C6 C16 C12 119.3(14) . . ?
C3 C29 C5 124.1(17) . . ?
C3 C29 C2 115.1(14) . . ?
C5 C29 C2 120.7(14) . . ?
C5 C31 C32 123.4(14) . 7_556 ?
C5 C31 H31A 118.3 . . ?
C32 C31 H31A 118.3 7_556 . ?
C5 C32 C31 120.4(13) . 7_556 ?
C5 C32 C13 120.2(11) . . ?
C31 C32 C13 118.7(11) 7_556 . ?
C36 C34 C16 118.6(15) . . ?
C36 C34 H34A 120.7 . . ?
C16 C34 H34A 120.7 . . ?
C34 C36 C13 119.8(13) . . ?
C34 C36 H36A 120.1 . . ?
C13 C36 H36A 120.1 . . ?

_diffrn_measured_fraction_theta_max 0.979
_diffrn_reflns_theta_full        23.32
_diffrn_measured_fraction_theta_full 0.979

_refine_diff_density_max         1.16
_refine_diff_density_min         -1.27
_refine_diff_density_rms         0.18

#=== END of CIF