# Electronic Supplementary Material (ESI) for Chemical Communications
# This journal is © The Royal Society of Chemistry 2012


data_global
_journal_name_full               Chem.Commun.
_journal_coden_cambridge         0182
_journal_year                    ?
_journal_volume                  ?
_journal_page_first              ?
_publ_contact_author_name        'Marco Evangelisti'
_publ_contact_author_email       evange@unizar.es
loop_
_publ_author_name
'Giulia Lorusso'
'Maria Palacios'
'Gary Nichol'
'Euan Brechin'
'Olivier Roubeau'
'Marco Evangelisti'

data_eb2081
_database_code_depnum_ccdc_archive 'CCDC 881702'
#TrackingRef '- EB2081.CIF'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C5 H11 Gd O8'
_chemical_formula_sum            'C5 H11 Gd O8'
_chemical_formula_weight         356.39

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'
Gd Gd -0.1653 3.9035 '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/m'

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

_cell_length_a                   7.9966(4)
_cell_length_b                   6.5839(2)
_cell_length_c                   9.9447(4)
_cell_angle_alpha                90.00
_cell_angle_beta                 109.425(5)
_cell_angle_gamma                90.00
_cell_volume                     493.77(4)
_cell_formula_units_Z            2
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    2173
_cell_measurement_theta_min      2.8422
_cell_measurement_theta_max      29.0665

_exptl_crystal_description       plate
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.09
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    2.397
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             338
_exptl_absorpt_coefficient_mu    6.734
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_correction_T_min  0.2608
_exptl_absorpt_correction_T_max  0.5825
_exptl_absorpt_process_details   
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
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)
;

_exptl_special_details           
;
In this structure H atoms have been refined with distance restraints, rather
than fixed X-H distance, to account for imposed space group symmetry, since the
Gd3+ ion and coordinated ligands lie on parallel crystallographic mirror
planes. The displacement ellipsoid of atom C5 was refined to be similar to
O3. The largest residual peak is 2.49 e.3 high located 0.92 from Gd1.
;

_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Agilent Technologies XCalibur'
_diffrn_measurement_method       '\w scans'
_diffrn_detector_area_resol_mean 16.1042
_diffrn_reflns_number            4816
_diffrn_reflns_av_R_equivalents  0.0439
_diffrn_reflns_av_sigmaI/netI    0.0379
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_theta_min         2.85
_diffrn_reflns_theta_max         29.13
_reflns_number_total             1283
_reflns_number_gt                1095
_reflns_threshold_expression     I>2\s(I)

_computing_data_collection       'CrysAlisPro (Agilent Technologies, 2011)'
_computing_cell_refinement       'CrysAlisPro (Agilent Technologies, 2011)'
_computing_data_reduction        'CrysAlisPro (Agilent Technologies, 2011)'
_computing_structure_solution    'SHELXTL (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXTL (Sheldrick, 2008)'
_computing_molecular_graphics    'DIAMOND (Brandenburg & Putz, 1999)'
_computing_publication_material  'SHELXTL (Sheldrick, 2008) and local programs'

_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. All non-hydrogens were
refined anisotropically. In the structure the Gd3+ ion and coordinated
ligands all lie on parallel crystallographic mirror planes. To account
for this imposed symmetry, H atoms have been refined with distance
restraints, rather than fixed X-H distance. In addition, the displacement
ellipsoid of atom C5 was refined to be similar to that of O3. At the
end of the refinement, the largest residual peak was 2.49 e.3 located
0.92 angstrom from Gd1.
;

_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^)+(0.0444P)^2^+0.0602P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         1283
_refine_ls_number_parameters     94
_refine_ls_number_restraints     16
_refine_ls_R_factor_all          0.0364
_refine_ls_R_factor_gt           0.0302
_refine_ls_wR_factor_ref         0.0819
_refine_ls_wR_factor_gt          0.0758
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_restrained_S_all      1.075
_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
Gd1 Gd 0.50526(3) 0.2500 0.25406(3) 0.01609(14) Uani 1 2 d S . .
O1 O 0.7097(4) 0.0841(4) 0.1518(3) 0.0268(7) Uani 1 1 d . . .
O2 O 0.7203(4) 0.0842(4) 0.4609(3) 0.0262(7) Uani 1 1 d . . .
O3 O 0.3913(4) -0.0816(4) 0.2263(3) 0.0235(6) Uani 1 1 d U . .
O4 O 0.3134(6) 0.2500 0.0143(5) 0.0237(10) Uani 1 2 d SD . .
H4O H 0.284(6) 0.149(5) -0.040(4) 0.028 Uiso 1 1 d D . .
O5 O 0.3101(7) 0.2500 0.3890(5) 0.0259(10) Uani 1 2 d SD . .
H5O H 0.307(6) 0.346(5) 0.443(4) 0.031 Uiso 1 1 d D . .
C1 C 0.7749(8) 0.2500 0.1275(7) 0.0216(13) Uani 1 2 d S . .
C2 C 0.9295(9) 0.2500 0.0760(7) 0.0304(15) Uani 1 2 d SD . .
H2A H 0.884(7) 0.2500 -0.0283(9) 0.046 Uiso 1 2 d SD . .
H2B H 1.009(5) 0.366(4) 0.110(3) 0.046 Uiso 1 1 d D . .
C3 C 0.7881(8) 0.2500 0.5186(7) 0.0229(13) Uani 1 2 d S . .
C4 C 0.9469(9) 0.2500 0.6494(8) 0.0327(16) Uani 1 2 d SD . .
H4A H 0.917(7) 0.2500 0.737(4) 0.049 Uiso 1 2 d SD . .
H4B H 1.025(5) 0.136(4) 0.650(4) 0.049 Uiso 1 1 d D . .
C5 C 0.4699(8) -0.2500 0.2455(7) 0.0219(8) Uani 1 2 d SDU . .
H5 H 0.5951(19) -0.2500 0.267(7) 0.026 Uiso 1 2 d SD . .

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
Gd1 0.0259(2) 0.00563(19) 0.0171(2) 0.000 0.00756(14) 0.000
O1 0.0412(18) 0.0105(14) 0.0341(18) 0.0018(13) 0.0199(15) 0.0015(13)
O2 0.0403(18) 0.0111(15) 0.0221(16) 0.0012(12) 0.0033(14) -0.0009(13)
O3 0.0289(15) 0.0096(12) 0.0307(16) 0.0006(8) 0.0083(12) 0.0005(7)
O4 0.036(2) 0.014(2) 0.016(2) 0.000 0.0024(19) 0.000
O5 0.045(3) 0.006(2) 0.032(3) 0.000 0.020(2) 0.000
C1 0.032(3) 0.015(3) 0.016(3) 0.000 0.007(3) 0.000
C2 0.033(4) 0.029(4) 0.031(4) 0.000 0.014(3) 0.000
C3 0.029(3) 0.022(3) 0.019(3) 0.000 0.010(3) 0.000
C4 0.028(3) 0.028(4) 0.036(4) 0.000 0.002(3) 0.000
C5 0.0273(17) 0.0083(14) 0.0296(18) 0.000 0.0088(14) 0.000

_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
Gd1 O1 2.450(3) . ?
Gd1 O1 2.450(3) 4_565 ?
Gd1 O2 2.455(3) . ?
Gd1 O2 2.455(3) 4_565 ?
Gd1 O3 2.347(3) . ?
Gd1 O3 2.347(3) 4_565 ?
Gd1 O4 2.368(4) . ?
Gd1 O5 2.373(5) . ?
Gd1 C1 2.835(7) . ?
Gd1 C3 2.842(6) . ?
O1 C1 1.268(4) . ?
O2 C3 1.268(4) . ?
O3 C5 1.257(4) . ?
O4 H4O 0.839(10) . ?
O5 H5O 0.836(10) . ?
C1 O1 1.268(4) 4_565 ?
C1 C2 1.487(9) . ?
C2 H2A 0.979(5) . ?
C2 H2B 0.978(5) . ?
C3 O2 1.268(4) 4_565 ?
C3 C4 1.485(9) . ?
C4 H4A 0.979(5) . ?
C4 H4B 0.979(5) . ?
C5 O3 1.257(4) 4 ?
C5 H5 0.952(10) . ?

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 Gd1 O1 52.93(13) . 4_565 ?
O1 Gd1 O2 76.79(11) . . ?
O1 Gd1 O2 99.66(11) 4_565 . ?
O1 Gd1 O2 76.79(11) 4_565 4_565 ?
O1 Gd1 O2 99.66(11) . 4_565 ?
O1 Gd1 O3 79.81(9) . . ?
O1 Gd1 O3 79.81(9) 4_565 4_565 ?
O1 Gd1 O3 130.72(10) 4_565 . ?
O1 Gd1 O3 130.72(10) . 4_565 ?
O1 Gd1 O4 83.13(13) . . ?
O1 Gd1 O4 83.13(13) 4_565 . ?
O1 Gd1 O5 152.85(7) . . ?
O1 Gd1 O5 152.85(7) 4_565 . ?
O1 Gd1 C1 26.49(7) . . ?
O1 Gd1 C1 26.49(7) 4_565 . ?
O1 Gd1 C3 87.07(14) . . ?
O1 Gd1 C3 87.07(14) 4_565 . ?
O2 Gd1 O2 52.80(14) . 4_565 ?
O2 Gd1 O3 79.71(10) . . ?
O2 Gd1 O3 130.44(10) . 4_565 ?
O2 Gd1 O3 79.71(10) 4_565 4_565 ?
O2 Gd1 O3 130.44(10) 4_565 . ?
O2 Gd1 O4 151.95(8) . . ?
O2 Gd1 O4 151.95(8) 4_565 . ?
O2 Gd1 O5 86.30(13) . . ?
O2 Gd1 O5 86.30(13) 4_565 . ?
O2 Gd1 C1 87.00(14) . . ?
O2 Gd1 C1 87.00(14) 4_565 . ?
O2 Gd1 C3 26.42(7) . . ?
O2 Gd1 C3 26.42(7) 4_565 . ?
O3 Gd1 O3 137.01(14) . 4_565 ?
O3 Gd1 O4 77.60(8) . . ?
O3 Gd1 O4 77.60(8) 4_565 . ?
O3 Gd1 O5 76.34(8) . . ?
O3 Gd1 O5 76.34(8) 4_565 . ?
O3 Gd1 C1 105.70(8) . . ?
O3 Gd1 C1 105.71(8) 4_565 . ?
O3 Gd1 C3 105.50(8) . . ?
O3 Gd1 C3 105.50(8) 4_565 . ?
O4 Gd1 O5 103.98(17) . . ?
O4 Gd1 C1 83.50(17) . . ?
O4 Gd1 C3 169.05(18) . . ?
O5 Gd1 C1 172.52(17) . . ?
O5 Gd1 C3 86.97(18) . . ?
C1 Gd1 C3 85.55(18) . . ?
Gd1 O1 C1 93.9(3) . . ?
Gd1 O2 C3 94.1(3) . . ?
Gd1 O3 C5 130.4(3) . . ?
Gd1 O4 H4O 127(3) . . ?
Gd1 O5 H5O 122(3) . . ?
Gd1 C1 O1 59.6(3) . . ?
Gd1 C1 O1 59.6(3) . 4_565 ?
Gd1 C1 C2 174.2(4) . . ?
O1 C1 O1 119.0(6) . 4_565 ?
O1 C1 C2 120.5(3) . . ?
O1 C1 C2 120.5(3) 4_565 . ?
C1 C2 H2A 108(4) . . ?
C1 C2 H2B 113(3) . . ?
H2A C2 H2B 109.8(8) . . ?
Gd1 C3 O2 59.5(3) . . ?
Gd1 C3 O2 59.5(3) . 4_565 ?
Gd1 C3 C4 174.9(5) . . ?
O2 C3 O2 118.8(6) . 4_565 ?
O2 C3 C4 120.6(3) . . ?
O2 C3 C4 120.6(3) 4_565 . ?
C3 C4 H4A 113(4) . . ?
C3 C4 H4B 112(3) . . ?
H4A C4 H4B 109.7(8) . . ?
O3 C5 O3 123.7(5) . 4 ?
O3 C5 H5 118.0(3) . . ?
O3 C5 H5 118.0(3) 4 . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
O1 Gd1 O1 C1 2.6(3) 4_565 . . . ?
O2 Gd1 O1 C1 -110.5(3) . . . . ?
O2 Gd1 O1 C1 -62.6(3) 4_565 . . . ?
O3 Gd1 O1 C1 167.8(3) . . . . ?
O3 Gd1 O1 C1 22.1(4) 4_565 . . . ?
O4 Gd1 O1 C1 89.2(3) . . . . ?
O5 Gd1 O1 C1 -163.4(4) . . . . ?
C3 Gd1 O1 C1 -85.9(3) . . . . ?
O1 Gd1 O2 C3 110.8(3) . . . . ?
O1 Gd1 O2 C3 62.7(3) 4_565 . . . ?
O2 Gd1 O2 C3 -2.5(4) 4_565 . . . ?
O3 Gd1 O2 C3 -167.4(4) . . . . ?
O3 Gd1 O2 C3 -22.1(4) 4_565 . . . ?
O4 Gd1 O2 C3 156.2(4) . . . . ?
O5 Gd1 O2 C3 -90.6(3) . . . . ?
C1 Gd1 O2 C3 86.0(3) . . . . ?
O1 Gd1 O3 C5 38.8(4) . . . . ?
O1 Gd1 O3 C5 54.5(5) 4_565 . . . ?
O2 Gd1 O3 C5 -39.4(4) . . . . ?
O2 Gd1 O3 C5 -55.2(5) 4_565 . . . ?
O3 Gd1 O3 C5 -180.0(4) 4_565 . . . ?
O4 Gd1 O3 C5 124.0(4) . . . . ?
O5 Gd1 O3 C5 -128.1(5) . . . . ?
C1 Gd1 O3 C5 44.5(4) . . . . ?
C3 Gd1 O3 C5 -45.2(5) . . . . ?
Gd1 O1 C1 O1 -4.7(6) . . . 4_565 ?
Gd1 O1 C1 C2 173.3(5) . . . . ?
O1 Gd1 C1 O1 -175.3(6) 4_565 . . . ?
O1 Gd1 C1 O1 175.3(6) . . . 4_565 ?
O1 Gd1 C1 C2 -92.4(3) . . . . ?
O1 Gd1 C1 C2 92.4(3) 4_565 . . . ?
O2 Gd1 C1 O1 65.9(3) . . . . ?
O2 Gd1 C1 O1 118.8(3) 4_565 . . . ?
O2 Gd1 C1 O1 -118.8(3) . . . 4_565 ?
O2 Gd1 C1 O1 -65.9(3) 4_565 . . 4_565 ?
O2 Gd1 C1 C2 -26.44(7) . . . . ?
O2 Gd1 C1 C2 26.44(7) 4_565 . . . ?
O3 Gd1 C1 O1 -12.5(3) . . . . ?
O3 Gd1 C1 O1 -162.8(3) 4_565 . . . ?
O3 Gd1 C1 O1 12.5(3) 4_565 . . 4_565 ?
O3 Gd1 C1 O1 162.8(3) . . . 4_565 ?
O3 Gd1 C1 C2 -104.87(8) . . . . ?
O3 Gd1 C1 C2 104.87(8) 4_565 . . . ?
O4 Gd1 C1 O1 -87.6(3) . . . . ?
O4 Gd1 C1 O1 87.6(3) . . . 4_565 ?
O4 Gd1 C1 C2 180.000(3) . . . . ?
O5 Gd1 C1 O1 92.4(3) . . . . ?
O5 Gd1 C1 O1 -92.4(3) . . . 4_565 ?
O5 Gd1 C1 C2 0.000(4) . . . . ?
C3 Gd1 C1 O1 92.4(3) . . . . ?
C3 Gd1 C1 O1 -92.4(3) . . . 4_565 ?
C3 Gd1 C1 C2 0.000(3) . . . . ?
Gd1 O2 C3 O2 4.4(6) . . . 4_565 ?
Gd1 O2 C3 C4 -174.1(6) . . . . ?
O1 Gd1 C3 O2 -65.7(3) . . . . ?
O1 Gd1 C3 O2 65.7(3) 4_565 . . 4_565 ?
O1 Gd1 C3 O2 118.7(3) . . . 4_565 ?
O1 Gd1 C3 O2 -118.7(3) 4_565 . . . ?
O1 Gd1 C3 C4 26.50(7) . . . . ?
O1 Gd1 C3 C4 -26.50(7) 4_565 . . . ?
O2 Gd1 C3 O2 -175.6(6) . . . 4_565 ?
O2 Gd1 C3 O2 175.6(6) 4_565 . . . ?
O2 Gd1 C3 C4 92.2(3) . . . . ?
O2 Gd1 C3 C4 -92.2(3) 4_565 . . . ?
O3 Gd1 C3 O2 12.9(4) . . . . ?
O3 Gd1 C3 O2 -12.9(4) 4_565 . . 4_565 ?
O3 Gd1 C3 O2 -162.7(3) . . . 4_565 ?
O3 Gd1 C3 O2 162.7(3) 4_565 . . . ?
O3 Gd1 C3 C4 105.08(8) . . . . ?
O3 Gd1 C3 C4 -105.08(8) 4_565 . . . ?
O4 Gd1 C3 O2 -92.2(3) . . . . ?
O4 Gd1 C3 O2 92.2(3) . . . 4_565 ?
O4 Gd1 C3 C4 0.000(14) . . . . ?
O5 Gd1 C3 O2 87.8(3) . . . . ?
O5 Gd1 C3 O2 -87.8(3) . . . 4_565 ?
O5 Gd1 C3 C4 180.000(14) . . . . ?
C1 Gd1 C3 O2 -92.2(3) . . . . ?
C1 Gd1 C3 O2 92.2(3) . . . 4_565 ?
C1 Gd1 C3 C4 0.000(14) . . . . ?
Gd1 O3 C5 O3 -180.0(3) . . . 4 ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
O4 H4O O1 0.839(10) 1.905(17) 2.720(4) 164(4) 3_655
O5 H5O O2 0.836(10) 1.886(14) 2.715(4) 171(5) 2_656

_diffrn_measured_fraction_theta_max 0.896
_diffrn_reflns_theta_full        25.00
_diffrn_measured_fraction_theta_full 0.998
_refine_diff_density_max         2.494
_refine_diff_density_min         -1.067
_refine_diff_density_rms         0.208

_vrf_PLAT094_eb2081              
;
PROBLEM: Ratio of Maximum / Minimum Residual Density .... 2.34
RESPONSE: The largest residual peak is 2.49 e.A3 high located 0.92 A from Gd1.
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_vrf_PLAT391_eb2081              
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PROBLEM: Deviating Methyl C4 H-C-H Bond Angle ...... 101 Deg.
RESPONSE: In this structure H atoms have been refined with distance restraints,
rather than fixed X-H distance, to account for imposed space group symmetry.
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