# Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.
# This journal is © The Royal Society of Chemistry 2015

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_gugaA
_database_code_depnum_ccdc_archive 'CCDC 1061799'
_audit_update_record             
;
2015-04-27 deposited with the CCDC.
2015-08-13 downloaded from the CCDC.
;
_audit_creation_date             2015-03-31
_audit_creation_method           
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_chemical_name_systematic        
thymin-1-yl-2'-O,4'-C-methylene-β-D-ribofuranosyl-3'-O-(2-thio-4,4-pentamethylene-1,3,2-oxathiaphospholane)
_chemical_name_common            
thymidine-LNA-3'-O-(2-thio-4,4-pentamethylene-1,3,2-oxathiaphospholane)
_chemical_formula_moiety         'C18 H25 N2 O7 P S2'
_chemical_formula_sum            'C18 H25 N2 O7 P S2'
_chemical_compound_source        synthetic
_chemical_properties_physical    Moisture-sensitive
_chemical_formula_weight         476.49
_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_h-m   'P 21 21 21'
_symmetry_int_tables_number      19
_chemical_absolute_configuration ad
_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: acetonitrile'
_chemical_melting_point          403
_exptl_crystal_description       prism
_exptl_crystal_colour            colourless
_diffrn_ambient_temperature      100.15
_diffrn_ambient_pressure         101.30
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 '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 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
P P 0.2955 0.4335 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.3331 0.5567 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_H-M_alt        'P 21 21 21'
_space_group_name_Hall           'P 2ac 2ab'
loop_
_space_group_symop_id
_space_group_symop_operation_xyz
1 'x, y, z'
2 '-x+1/2, -y, z+1/2'
3 'x+1/2, -y+1/2, -z'
4 '-x, y+1/2, -z+1/2'

_cell_length_a                   6.37110(10)
_cell_length_b                   12.1422(3)
_cell_length_c                   27.2294(7)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     2106.44(8)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    ?
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      ?
_cell_measurement_theta_min      ?
_exptl_absorpt_coefficient_mu    3.405
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_type   ?
_exptl_absorpt_process_details   ?
_exptl_crystal_density_diffrn    1.502
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1000
_exptl_crystal_size_max          0.10
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.02
_exptl_special_details           
;
 ? 
;
_diffrn_reflns_av_R_equivalents  0.0344
_diffrn_reflns_av_unetI/netI     0.0491
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            7619
_diffrn_reflns_theta_full        74.97
_diffrn_reflns_theta_max         74.97
_diffrn_reflns_theta_min         3.99
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.979
_diffrn_measured_fraction_theta_max 0.980
_diffrn_measurement_device_type  ?
_diffrn_measurement_method       ?
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_source                   'fine-focus sealed tube'
_diffrn_source_type              'SuperNova Agilent Technologies'
_diffrn_standards_decay_%        ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_number         ?
_reflns_number_gt                3851
_reflns_number_total             4177
_reflns_threshold_expression     >2sigma(I)
_computing_cell_refinement       ?
_computing_data_collection       ?
_computing_data_reduction        ?
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_refine_diff_density_max         0.268
_refine_diff_density_min         -0.323
_refine_diff_density_rms         0.062
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.010(15)
_refine_ls_extinction_coef       ?
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     273
_refine_ls_number_reflns         4177
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0360
_refine_ls_R_factor_gt           0.0310
_refine_ls_restrained_S_all      1.032
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.0387P)²+0.0000P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0726
_refine_ls_wR_factor_ref         0.0750
_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. 
;
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C1'(H1'), C2'(H2'), C3'(H3')
2.b Secondary CH2 refined with riding coordinates:
 C4"(H4"A,H4"B), C5'(H5'A,H5'B), C8(H8A,H8B), C10(H10A,H10B), C11(H11A,H11B),
 C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B)
2.c Aromatic/amide H refined with riding coordinates:
 N3(H3), C6(H6)
2.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C)
2.e Idealised tetrahedral OH refined as rotating group:
 O5'(H5')
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
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_calc_flag
_atom_site_disorder_assembly
_atom_site_disorder_group
_atom_site_refinement_flags_posn
N1 N -1.0041(3) -0.29309(15) -0.10562(6) 0.0123(4) Uani 1 d . . .
C2 C -1.1034(3) -0.27835(19) -0.06100(8) 0.0142(4) Uani 1 d . . .
O2 O -1.0328(3) -0.31600(14) -0.02277(6) 0.0186(3) Uani 1 d . . .
N3 N -1.2878(3) -0.21990(16) -0.06284(7) 0.0145(4) Uani 1 d . . .
H3 H -1.3577 -0.2134 -0.0351 0.017 Uiso 1 calc . . R
C4 C -1.3758(3) -0.16990(18) -0.10404(8) 0.0136(4) Uani 1 d . . .
O4 O -1.5350(3) -0.11483(14) -0.10021(6) 0.0196(3) Uani 1 d . . .
C5 C -1.2625(4) -0.18900(19) -0.14986(8) 0.0146(4) Uani 1 d . . .
C6 C -1.0843(3) -0.24774(18) -0.14862(8) 0.0131(4) Uani 1 d . . .
H6 H -1.0095 -0.2588 -0.1784 0.016 Uiso 1 calc . . R
C7 C -1.3517(4) -0.1378(2) -0.19507(9) 0.0193(5) Uani 1 d . . .
H7A H -1.3375 -0.0576 -0.1931 0.029 Uiso 1 calc . . GR
H7B H -1.5005 -0.1573 -0.1979 0.029 Uiso 1 calc . . GR
H7C H -1.2758 -0.1650 -0.2239 0.029 Uiso 1 calc . . GR
O1' O -0.6840(3) -0.32881(12) -0.14716(6) 0.0133(3) Uani 1 d . . .
C1' C -0.7992(3) -0.34910(19) -0.10298(8) 0.0137(4) Uani 1 d . . .
H1' H -0.7183 -0.3208 -0.0742 0.016 Uiso 1 calc . . R
C2' C -0.8095(4) -0.47608(19) -0.10091(8) 0.0143(4) Uani 1 d . . .
H2' H -0.9259 -0.5071 -0.0805 0.017 Uiso 1 calc . . R
O2' O -0.6031(3) -0.51079(15) -0.08732(6) 0.0175(3) Uani 1 d . . .
C3' C -0.8207(4) -0.50256(18) -0.15586(8) 0.0132(4) Uani 1 d . . .
H3' H -0.9490 -0.4728 -0.1723 0.016 Uiso 1 calc . . R
O3' O -0.7806(2) -0.61600(13) -0.16686(6) 0.0156(3) Uani 1 d . . .
C4' C -0.6224(3) -0.43555(18) -0.16622(8) 0.0128(4) Uani 1 d . . .
C4" C -0.4704(4) -0.4870(2) -0.12927(8) 0.0157(4) Uani 1 d . . .
H4"A H -0.4067 -0.5551 -0.1426 0.019 Uiso 1 calc . . R
H4"B H -0.3573 -0.4347 -0.1204 0.019 Uiso 1 calc . . R
C5' C -0.5508(4) -0.42520(19) -0.21883(8) 0.0159(4) Uani 1 d . . .
H5'A H -0.4373 -0.3697 -0.2209 0.019 Uiso 1 calc . . R
H5'B H -0.4932 -0.4966 -0.2300 0.019 Uiso 1 calc . . R
O5' O -0.7186(3) -0.39357(15) -0.25016(6) 0.0212(4) Uani 1 d . . .
H5' H -0.7169 -0.3249 -0.2540 0.032 Uiso 1 calc . . GR
P1 P -0.96417(9) -0.70010(5) -0.17995(2) 0.01308(12) Uani 1 d . . .
S1 S -1.08699(8) -0.76322(5) -0.11600(2) 0.01640(12) Uani 1 d . . .
S2 S -1.16214(9) -0.63864(5) -0.22598(2) 0.01866(12) Uani 1 d . . .
O5 O -0.8286(3) -0.80160(13) -0.19774(6) 0.0174(3) Uani 1 d . . .
C8 C -0.8583(4) -0.90337(19) -0.16997(9) 0.0180(5) Uani 1 d . . .
H8A H -0.7352 -0.9521 -0.1745 0.022 Uiso 1 calc . . R
H8B H -0.9842 -0.9426 -0.1821 0.022 Uiso 1 calc . . R
C9 C -0.8850(3) -0.87615(19) -0.11542(9) 0.0157(4) Uani 1 d . . .
C10 C -0.6789(4) -0.8390(2) -0.09176(9) 0.0184(5) Uani 1 d . . .
H10A H -0.5712 -0.8967 -0.0968 0.022 Uiso 1 calc . . R
H10B H -0.6295 -0.7711 -0.1082 0.022 Uiso 1 calc . . R
C11 C -0.7021(4) -0.8169(2) -0.03686(10) 0.0240(5) Uani 1 d . . .
H11A H -0.5631 -0.7986 -0.0228 0.029 Uiso 1 calc . . R
H11B H -0.7957 -0.7528 -0.0318 0.029 Uiso 1 calc . . R
C12 C -0.7923(5) -0.9166(2) -0.01034(10) 0.0284(6) Uani 1 d . . .
H12A H -0.8129 -0.8986 0.0248 0.034 Uiso 1 calc . . R
H12B H -0.6915 -0.9785 -0.0124 0.034 Uiso 1 calc . . R
C13 C -1.0016(4) -0.9518(2) -0.03272(10) 0.0248(6) Uani 1 d . . .
H13A H -1.1069 -0.8931 -0.0273 0.030 Uiso 1 calc . . R
H13B H -1.0520 -1.0193 -0.0160 0.030 Uiso 1 calc . . R
C14 C -0.9812(4) -0.97412(19) -0.08782(9) 0.0192(5) Uani 1 d . . .
H14A H -1.1217 -0.9902 -0.1016 0.023 Uiso 1 calc . . R
H14B H -0.8920 -1.0399 -0.0929 0.023 Uiso 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
N1 C2 1.382(3) . ?
N1 C6 1.391(3) . ?
N1 C1' 1.473(3) . ?
C2 O2 1.223(3) . ?
C2 N3 1.373(3) . ?
N3 C4 1.393(3) . ?
C4 O4 1.220(3) . ?
C4 C5 1.460(3) . ?
C5 C6 1.341(3) . ?
C5 C7 1.491(3) . ?
O1' C1' 1.430(3) . ?
O1' C4' 1.450(3) . ?
C1' C2' 1.544(3) . ?
C2' O2' 1.429(3) . ?
C2' C3' 1.532(3) . ?
O2' C4" 1.451(3) . ?
C3' O3' 1.433(3) . ?
C3' C4' 1.529(3) . ?
O3' P1 1.5931(17) . ?
C4' C4" 1.530(3) . ?
C4' C5' 1.509(3) . ?
C5' O5' 1.421(3) . ?
P1 S1 2.0572(8) . ?
P1 S2 1.9284(8) . ?
P1 O5 1.5809(17) . ?
S1 C9 1.880(2) . ?
O5 C8 1.461(3) . ?
C8 C9 1.531(3) . ?
C9 C10 1.531(3) . ?
C9 C14 1.535(3) . ?
C10 C11 1.526(4) . ?
C11 C12 1.523(4) . ?
C12 C13 1.527(4) . ?
C13 C14 1.530(4) . ?

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
C2 N1 C6 121.37(19) . . ?
C2 N1 C1' 115.01(18) . . ?
C6 N1 C1' 123.30(17) . . ?
O2 C2 N1 122.1(2) . . ?
O2 C2 N3 122.6(2) . . ?
N3 C2 N1 115.27(19) . . ?
C2 N3 C4 126.76(19) . . ?
N3 C4 C5 114.84(19) . . ?
O4 C4 N3 120.3(2) . . ?
O4 C4 C5 124.9(2) . . ?
C4 C5 C7 116.8(2) . . ?
C6 C5 C4 118.8(2) . . ?
C6 C5 C7 124.4(2) . . ?
C5 C6 N1 122.9(2) . . ?
C1' O1' C4' 106.61(16) . . ?
N1 C1' C2' 115.17(18) . . ?
O1' C1' N1 109.51(17) . . ?
O1' C1' C2' 102.96(17) . . ?
O2' C2' C1' 105.37(18) . . ?
O2' C2' C3' 103.54(18) . . ?
C3' C2' C1' 100.13(17) . . ?
C2' O2' C4" 105.87(16) . . ?
O3' C3' C2' 113.43(18) . . ?
O3' C3' C4' 109.00(17) . . ?
C4' C3' C2' 91.71(17) . . ?
C3' O3' P1 122.14(14) . . ?
O1' C4' C3' 100.71(16) . . ?
O1' C4' C4" 107.50(17) . . ?
O1' C4' C5' 110.32(18) . . ?
C3' C4' C4" 100.65(18) . . ?
C5' C4' C3' 118.00(18) . . ?
C5' C4' C4" 117.82(18) . . ?
O2' C4" C4' 103.31(17) . . ?
O5' C5' C4' 111.41(18) . . ?
O3' P1 S1 109.18(7) . . ?
O3' P1 S2 112.19(7) . . ?
S2 P1 S1 116.46(4) . . ?
O5 P1 O3' 99.62(9) . . ?
O5 P1 S1 100.17(7) . . ?
O5 P1 S2 117.38(7) . . ?
C9 S1 P1 91.07(8) . . ?
C8 O5 P1 115.48(14) . . ?
O5 C8 C9 109.50(19) . . ?
C8 C9 S1 103.02(15) . . ?
C8 C9 C14 110.63(19) . . ?
C10 C9 S1 112.08(16) . . ?
C10 C9 C8 112.10(19) . . ?
C10 C9 C14 111.4(2) . . ?
C14 C9 S1 107.24(15) . . ?
C11 C10 C9 112.4(2) . . ?
C12 C11 C10 111.2(2) . . ?
C11 C12 C13 111.3(2) . . ?
C12 C13 C14 111.5(2) . . ?
C13 C14 C9 112.1(2) . . ?
