# Electronic Supplementary Material (ESI) for New Journal of Chemistry.
# This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2017

####################################################################### 
# 
# 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_added_by_encifer
_database_code_depnum_ccdc_archive 'CCDC 1444757'
#Added by publCIF



_audit_update_record             
;
2016-01-12 deposited with the CCDC.
2017-04-19 downloaded from the CCDC.
;
#Added by publCIF


_publcif_datablock.id            {fee072c9-e0a0-49bf-b1bf-6afde7aa1c33}
# start Validation Reply Form
_vrf_PUBL006_GLOBAL              
;
PROBLEM: _publ_requested_journal is missing
RESPONSE: Acta Crystallographica Section E
;
# end Validation Reply Form

#Added by publCIF (\"O\"U\"E\"A 5\^O\^A 8 08:53:38 2014)


# start Validation Reply Form
_vrf_PUBL007_GLOBAL              
;
PROBLEM: _publ_requested_journal is missing
RESPONSE: ...
;
# publcif _publ_body_element loop end

_audit_creation_method           SHELXL-97
_chemical_name_systematic        (5R)-5-cyano-3-carbmenthoxy-2-pyrazoline
_chemical_name_common            ?
_chemical_melting_point          309.15
_chemical_formula_moiety         'C15 H23 N3 O2'
_chemical_formula_sum            'C15 H23 N3 O2'
_chemical_formula_weight         277.36
_chemical_absolute_configuration rmad

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'

_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_H-M   P2(1)2(1)2(1)
_symmetry_space_group_name_Hall  P2ac2ab


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'

_cell_length_a                   7.2202(2)
_cell_length_b                   10.6578(3)
_cell_length_c                   20.9068(5)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     1608.81(7)
_cell_formula_units_Z            4
_cell_measurement_temperature    297(2)
_cell_measurement_reflns_used    9981
_cell_measurement_theta_min      4.66
_cell_measurement_theta_max      63.14

_exptl_crystal_description       block
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.20
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.20
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.145
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             600
_exptl_absorpt_coefficient_mu    0.619
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.8862
_exptl_absorpt_correction_T_max  0.8862
_exptl_absorpt_process_details   'SADABS, Sheldrick,1997'

_exptl_special_details           ?

_diffrn_ambient_temperature      297(2)
_diffrn_radiation_wavelength     1.54178
_diffrn_radiation_type           CuK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         0
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            37839
_diffrn_reflns_av_R_equivalents  0.0383
_diffrn_reflns_av_sigmaI/netI    0.0233
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_theta_min         4.23
_diffrn_reflns_theta_max         63.44
_reflns_number_total             2620
_reflns_number_gt                2610
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_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)+(0.0410P)²+0.1457P] where P=(Fo²+2Fc²)/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     SHELXL
_refine_ls_extinction_coef       0.0068(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.0(2)
_refine_ls_number_reflns         2620
_refine_ls_number_parameters     188
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0335
_refine_ls_R_factor_gt           0.0276
_refine_ls_wR_factor_ref         0.0753
_refine_ls_wR_factor_gt          0.0750
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_restrained_S_all      1.057
_refine_ls_shift/su_max          0.001
_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
C1 C 0.1089(2) 0.78866(12) 0.85718(7) 0.0579(3) Uani 1 1 d . . .
H1 H 0.1847 0.7858 0.8183 0.070 Uiso 1 1 calc R . .
C2 C 0.02457(18) 0.65886(12) 0.86607(6) 0.0501(3) Uani 1 1 d . . .
H2A H -0.0512 0.6587 0.9049 0.060 Uiso 1 1 calc R . .
C3 C -0.0935(2) 0.61892(13) 0.81020(7) 0.0580(3) Uani 1 1 d . . .
H3A H -0.1436 0.5360 0.8183 0.070 Uiso 1 1 calc R . .
H3B H -0.0175 0.6144 0.7720 0.070 Uiso 1 1 calc R . .
C4 C -0.2514(2) 0.71066(15) 0.79929(7) 0.0670(4) Uani 1 1 d . . .
H4 H -0.3266 0.7128 0.8383 0.080 Uiso 1 1 calc R . .
C5 C -0.1713(2) 0.84118(15) 0.78916(8) 0.0740(4) Uani 1 1 d . . .
H5A H -0.2718 0.9009 0.7844 0.089 Uiso 1 1 calc R . .
H5B H -0.0992 0.8421 0.7500 0.089 Uiso 1 1 calc R . .
C6 C -0.0488(2) 0.88089(13) 0.84483(8) 0.0722(4) Uani 1 1 d . . .
H6A H -0.1240 0.8878 0.8831 0.087 Uiso 1 1 calc R . .
H6B H 0.0029 0.9630 0.8359 0.087 Uiso 1 1 calc R . .
C7 C -0.3762(3) 0.6700(2) 0.74446(10) 0.1037(7) Uani 1 1 d . . .
H7A H -0.4816 0.7248 0.7422 0.155 Uiso 1 1 calc R . .
H7B H -0.4174 0.5855 0.7516 0.155 Uiso 1 1 calc R . .
H7C H -0.3086 0.6741 0.7050 0.155 Uiso 1 1 calc R . .
C8 C 0.2376(2) 0.82656(16) 0.91266(8) 0.0743(4) Uani 1 1 d . . .
H8 H 0.3271 0.7581 0.9177 0.089 Uiso 1 1 calc R . .
C9 C 0.3493(4) 0.9433(2) 0.89726(13) 0.1189(8) Uani 1 1 d . . .
H9A H 0.4043 0.9347 0.8557 0.178 Uiso 1 1 calc R . .
H9B H 0.4450 0.9539 0.9287 0.178 Uiso 1 1 calc R . .
H9C H 0.2693 1.0153 0.8977 0.178 Uiso 1 1 calc R . .
C10 C 0.1394(3) 0.8399(2) 0.97659(9) 0.1073(7) Uani 1 1 d . . .
H10A H 0.2270 0.8646 1.0087 0.161 Uiso 1 1 calc R . .
H10B H 0.0847 0.7610 0.9882 0.161 Uiso 1 1 calc R . .
H10C H 0.0443 0.9025 0.9732 0.161 Uiso 1 1 calc R . .
C11 C 0.15715(17) 0.47783(11) 0.91605(6) 0.0468(3) Uani 1 1 d . . .
C12 C 0.32677(16) 0.40270(11) 0.92064(6) 0.0457(3) Uani 1 1 d . . .
C13 C 0.50588(18) 0.42456(12) 0.88633(6) 0.0527(3) Uani 1 1 d . . .
H13A H 0.5493 0.5101 0.8916 0.063 Uiso 1 1 calc R . .
H13B H 0.4960 0.4053 0.8411 0.063 Uiso 1 1 calc R . .
C14 C 0.63051(17) 0.33033(12) 0.92149(7) 0.0528(3) Uani 1 1 d . . .
H14 H 0.7001 0.3731 0.9553 0.063 Uiso 1 1 calc R . .
C15 C 0.7577(2) 0.26237(15) 0.87953(9) 0.0723(4) Uani 1 1 d . . .
N1 N 0.32905(15) 0.30425(11) 0.95587(6) 0.0581(3) Uani 1 1 d . . .
N2 N 0.49461(16) 0.24514(11) 0.94970(6) 0.0637(3) Uani 1 1 d D . .
H2 H 0.525(2) 0.2041(14) 0.9850(7) 0.076 Uiso 1 1 d D . .
N3 N 0.8573(3) 0.21167(18) 0.84675(10) 0.1189(7) Uani 1 1 d . . .
O1 O 0.17801(12) 0.57005(8) 0.87402(4) 0.0544(2) Uani 1 1 d . . .
O2 O 0.01862(12) 0.45946(9) 0.94692(5) 0.0669(3) Uani 1 1 d . . .


_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
C1 C2 1.5229(18) . ?
C1 C6 1.526(2) . ?
C1 C8 1.540(2) . ?
C1 H1 0.9800 . ?
C2 O1 1.4666(14) . ?
C2 C3 1.507(2) . ?
C2 H2A 0.9800 . ?
C3 C4 1.519(2) . ?
C3 H3A 0.9700 . ?
C3 H3B 0.9700 . ?
C4 C7 1.521(2) . ?
C4 C5 1.521(2) . ?
C4 H4 0.9800 . ?
C5 C6 1.522(2) . ?
C5 H5A 0.9700 . ?
C5 H5B 0.9700 . ?
C6 H6A 0.9700 . ?
C6 H6B 0.9700 . ?
C7 H7A 0.9600 . ?
C7 H7B 0.9600 . ?
C7 H7C 0.9600 . ?
C8 C9 1.517(3) . ?
C8 C10 1.520(3) . ?
C8 H8 0.9800 . ?
C9 H9A 0.9600 . ?
C9 H9B 0.9600 . ?
C9 H9C 0.9600 . ?
C10 H10A 0.9600 . ?
C10 H10B 0.9600 . ?
C10 H10C 0.9600 . ?
C11 O2 1.2064(14) . ?
C11 O1 1.3269(14) . ?
C11 C12 1.4663(17) . ?
C12 N1 1.2821(16) . ?
C12 C13 1.4971(17) . ?
C13 C14 1.5359(17) . ?
C13 H13A 0.9700 . ?
C13 H13B 0.9700 . ?
C14 N2 1.4611(17) . ?
C14 C15 1.462(2) . ?
C14 H14 0.9800 . ?
C15 N3 1.131(2) . ?
N1 N2 1.3573(16) . ?
N2 H2 0.886(14) . ?

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 C1 C6 107.89(12) . . ?
C2 C1 C8 112.81(11) . . ?
C6 C1 C8 114.13(12) . . ?
C2 C1 H1 107.2 . . ?
C6 C1 H1 107.2 . . ?
C8 C1 H1 107.2 . . ?
O1 C2 C3 109.43(10) . . ?
O1 C2 C1 107.34(10) . . ?
C3 C2 C1 112.84(10) . . ?
O1 C2 H2A 109.1 . . ?
C3 C2 H2A 109.1 . . ?
C1 C2 H2A 109.1 . . ?
C2 C3 C4 111.03(11) . . ?
C2 C3 H3A 109.4 . . ?
C4 C3 H3A 109.4 . . ?
C2 C3 H3B 109.4 . . ?
C4 C3 H3B 109.4 . . ?
H3A C3 H3B 108.0 . . ?
C3 C4 C7 112.00(15) . . ?
C3 C4 C5 108.91(13) . . ?
C7 C4 C5 112.37(14) . . ?
C3 C4 H4 107.8 . . ?
C7 C4 H4 107.8 . . ?
C5 C4 H4 107.8 . . ?
C4 C5 C6 111.64(12) . . ?
C4 C5 H5A 109.3 . . ?
C6 C5 H5A 109.3 . . ?
C4 C5 H5B 109.3 . . ?
C6 C5 H5B 109.3 . . ?
H5A C5 H5B 108.0 . . ?
C5 C6 C1 112.58(12) . . ?
C5 C6 H6A 109.1 . . ?
C1 C6 H6A 109.1 . . ?
C5 C6 H6B 109.1 . . ?
C1 C6 H6B 109.1 . . ?
H6A C6 H6B 107.8 . . ?
C4 C7 H7A 109.5 . . ?
C4 C7 H7B 109.5 . . ?
H7A C7 H7B 109.5 . . ?
C4 C7 H7C 109.5 . . ?
H7A C7 H7C 109.5 . . ?
H7B C7 H7C 109.5 . . ?
C9 C8 C10 110.98(17) . . ?
C9 C8 C1 112.08(15) . . ?
C10 C8 C1 113.89(15) . . ?
C9 C8 H8 106.4 . . ?
C10 C8 H8 106.4 . . ?
C1 C8 H8 106.4 . . ?
C8 C9 H9A 109.5 . . ?
C8 C9 H9B 109.5 . . ?
H9A C9 H9B 109.5 . . ?
C8 C9 H9C 109.5 . . ?
H9A C9 H9C 109.5 . . ?
H9B C9 H9C 109.5 . . ?
C8 C10 H10A 109.5 . . ?
C8 C10 H10B 109.5 . . ?
H10A C10 H10B 109.5 . . ?
C8 C10 H10C 109.5 . . ?
H10A C10 H10C 109.5 . . ?
H10B C10 H10C 109.5 . . ?
O2 C11 O1 124.65(11) . . ?
O2 C11 C12 124.67(10) . . ?
O1 C11 C12 110.68(10) . . ?
N1 C12 C11 119.69(11) . . ?
N1 C12 C13 113.05(11) . . ?
C11 C12 C13 127.24(10) . . ?
C12 C13 C14 100.08(10) . . ?
C12 C13 H13A 111.8 . . ?
C14 C13 H13A 111.8 . . ?
C12 C13 H13B 111.8 . . ?
C14 C13 H13B 111.8 . . ?
H13A C13 H13B 109.5 . . ?
N2 C14 C15 110.87(12) . . ?
N2 C14 C13 101.89(10) . . ?
C15 C14 C13 113.88(12) . . ?
N2 C14 H14 110.0 . . ?
C15 C14 H14 110.0 . . ?
C13 C14 H14 110.0 . . ?
N3 C15 C14 178.85(19) . . ?
C12 N1 N2 109.67(11) . . ?
N1 N2 C14 109.96(10) . . ?
N1 N2 H2 111.6(11) . . ?
C14 N2 H2 118.5(12) . . ?
C11 O1 C2 117.87(9) . . ?

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
C6 C1 C2 O1 176.65(11) . . . . ?
C8 C1 C2 O1 -56.36(14) . . . . ?
C6 C1 C2 C3 56.00(15) . . . . ?
C8 C1 C2 C3 -177.00(12) . . . . ?
O1 C2 C3 C4 -178.52(10) . . . . ?
C1 C2 C3 C4 -59.08(15) . . . . ?
C2 C3 C4 C7 -178.14(13) . . . . ?
C2 C3 C4 C5 56.96(16) . . . . ?
C3 C4 C5 C6 -56.01(17) . . . . ?
C7 C4 C5 C6 179.30(16) . . . . ?
C4 C5 C6 C1 56.76(19) . . . . ?
C2 C1 C6 C5 -54.53(17) . . . . ?
C8 C1 C6 C5 179.24(13) . . . . ?
C2 C1 C8 C9 168.71(15) . . . . ?
C6 C1 C8 C9 -67.7(2) . . . . ?
C2 C1 C8 C10 -64.25(19) . . . . ?
C6 C1 C8 C10 59.4(2) . . . . ?
O2 C11 C12 N1 5.5(2) . . . . ?
O1 C11 C12 N1 -175.50(11) . . . . ?
O2 C11 C12 C13 -176.56(13) . . . . ?
O1 C11 C12 C13 2.43(18) . . . . ?
N1 C12 C13 C14 -11.99(15) . . . . ?
C11 C12 C13 C14 169.96(12) . . . . ?
C12 C13 C14 N2 19.84(13) . . . . ?
C12 C13 C14 C15 139.27(12) . . . . ?
N2 C14 C15 N3 172(100) . . . . ?
C13 C14 C15 N3 58(11) . . . . ?
C11 C12 N1 N2 175.97(11) . . . . ?
C13 C12 N1 N2 -2.24(16) . . . . ?
C12 N1 N2 C14 16.94(16) . . . . ?
C15 C14 N2 N1 -144.90(13) . . . . ?
C13 C14 N2 N1 -23.37(15) . . . . ?
O2 C11 O1 C2 2.32(19) . . . . ?
C12 C11 O1 C2 -176.67(10) . . . . ?
C3 C2 O1 C11 -95.80(13) . . . . ?
C1 C2 O1 C11 141.42(11) . . . . ?

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
N2 H2 O2 0.886(14) 2.251(15) 3.0752(14) 154.8(15) 4_557
N2 H2 N1 0.886(14) 2.521(16) 3.1633(16) 129.9(14) 4_557

_diffrn_measured_fraction_theta_max 0.997
_diffrn_reflns_theta_full        63.44
_diffrn_measured_fraction_theta_full 0.997
_refine_diff_density_max         0.202
_refine_diff_density_min         -0.205
_refine_diff_density_rms         0.070

_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: Ethanol'
_chemical_compound_source        '(-)-Menthyl diazoacetate and acrylonitrile'
_chemical_properties_physical    'Heat-sensitive, Photo-sensitive'
_exptl_crystal_preparation       Luminescent
