Aluminylation: a generalizable route towards low-valent aluminum under moderate conditions with controlled product nuclearity through precursor design
Reuel, Paris C.; Shandilya, Yogesh; Wattoo, M. Talha; Altman, Alison B.; Chemical Science  (2026) –; doi:10.1039/D6SC02187E

data_1577086
_publ_section_title
;
 Aluminylation: a generalizable route towards low-valent aluminum under
 moderate conditions with controlled product nuclearity through precursor
 design.
;
_journal_issue                   20
_journal_name_full               'Chemical science'
_journal_page_first              10251
_journal_page_last               10259
_journal_paper_doi               10.1039/d6sc02187e
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety         'C64.989 H93.979 Al2 N4, 1[C7H8]'
_chemical_formula_sum            'C71.99 H101.98 Al2 N4'
_chemical_formula_weight         1077.38
_chemical_properties_physical    Air-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           7
_space_group_name_Hall           'P -2yac'
_space_group_name_H-M_alt        'P 1 n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2qyrs7
_audit_creation_date             2026-02-02
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2026-02-13 deposited with the CCDC.	2026-04-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.104(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.4020(5)
_cell_length_b                   10.7732(4)
_cell_length_c                   24.5107(10)
_cell_measurement_reflns_used    9015
_cell_measurement_temperature    110.00
_cell_measurement_theta_max      71.30
_cell_measurement_theta_min      4.49
_cell_volume                     3233.6(2)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      110.00
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0451
_diffrn_reflns_av_unetI/netI     0.0353
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            52816
_diffrn_reflns_point_group_measured_fraction_full 0.962
_diffrn_reflns_point_group_measured_fraction_max 0.936
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         71.834
_diffrn_reflns_theta_min         3.652
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.722
_exptl_absorpt_correction_T_max  0.7535
_exptl_absorpt_correction_T_min  0.3363
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1673 before and 0.1223 after correction.
The Ratio of minimum to maximum transmission is 0.4463.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.107
_exptl_crystal_description       block
_exptl_crystal_F_000             1176
_exptl_crystal_size_max          0.544
_exptl_crystal_size_mid          0.253
_exptl_crystal_size_min          0.215
_refine_diff_density_max         0.681
_refine_diff_density_min         -0.657
_refine_diff_density_rms         0.077
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.58(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     517
_refine_ls_number_reflns         11872
_refine_ls_number_restraints     559
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.1050
_refine_ls_R_factor_gt           0.0834
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1415P)^2^+2.8005P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2160
_refine_ls_wR_factor_ref         0.2485
_reflns_Friedel_coverage         0.899
_reflns_Friedel_fraction_full    0.929
_reflns_Friedel_fraction_max     0.887
_reflns_number_gt                9334
_reflns_number_total             11872
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6sc02187e2.cif
_cod_data_source_block           pcr_2025_179_b
_cod_depositor_comments
'Adding full bibliography for 1577082--1577086.cif.'
_cod_database_code               1577086
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.860
_shelx_estimated_absorpt_t_min   0.695
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.41878
 0.58122
2. Restrained distances
 C213-C214 \\sim C213-C216
 with sigma of 0.02
 C214-C215 \\sim C216-C217
 with sigma of 0.02
 C213-C215 \\sim C213-C217
 with sigma of 0.04
 C113-C114 \\sim C113-C116
 with sigma of 0.02
 C114-C115 \\sim C116-C117
 with sigma of 0.02
 C113-C115 \\sim C113-C117
 with sigma of 0.04
 C361-C362 \\sim C361-C364
 with sigma of 0.02
 C361-C363 \\sim C361-C365
 with sigma of 0.02
 C36-C362 \\sim C36-C364
 with sigma of 0.04
 C36-C363 \\sim C36-C365
 with sigma of 0.04
 C362-C363 \\sim C364-C365
 with sigma of 0.04
3. Rigid bond restraints
 Al1, Al2
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C362, C364, C363, C365
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
Uanis(C362) = Uanis(C364) = Uanis(C363) = Uanis(C365)
Uanis(C3A) = Uanis(C2A) = Uanis(C6A) = Uanis(C5A)
5. Others
 1*[Sof(H018)+Sof(C3A)+Sof(H1H)+Sof(H1B)+Sof(H1A)]+1*[Sof(H01Q)+Sof(C5A)+
 Sof(H26A)+Sof(H26B)+Sof(H26C)]+1*[Sof(H00X)+Sof(C6A)+Sof(H25A)+Sof(H25B)+
 Sof(H25C)]+1*[Sof(H00Q)+Sof(C2A)+Sof(H12A)+Sof(H12B)+Sof(H12C)]=1 with esd of
 0.01
 Sof(H00P)=Sof(H00T)=Sof(C216)=Sof(H3A)=Sof(H3B)=Sof(C217)=Sof(H40D)=Sof(H40E)=
 Sof(H215)=1-FVAR(1)
 Sof(H00U)=Sof(H00V)=Sof(C214)=Sof(H1)=Sof(HB)=Sof(C215)=Sof(H40A)=Sof(H40B)=
 Sof(H40C)=FVAR(1)
 Sof(H00M)=Sof(H00N)=Sof(C116)=Sof(H5A)=Sof(H5B)=Sof(C117)=Sof(H8A)=Sof(H8B)=
 Sof(H8C)=1-FVAR(2)
 Sof(H00K)=Sof(H00L)=Sof(C114)=Sof(H01Z)=Sof(HA)=Sof(C115)=Sof(H2)=Sof(HC)=
 Sof(HD)=FVAR(2)
 Sof(H01D)=Sof(C364)=Sof(H6AA)=Sof(H6AB)=Sof(H6AC)=Sof(C365)=Sof(H21D)=
 Sof(H21E)=Sof(H21F)=1-FVAR(3)
 Sof(H015)=Sof(C362)=Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C363)=Sof(H21A)=Sof(H21B)=
 Sof(H21C)=FVAR(3)
 Sof(H018)=1-FVAR(4)
 Sof(C3A)=Sof(H1H)=Sof(H1B)=Sof(H1A)=FVAR(4)
 Sof(H01Q)=1-FVAR(5)
 Sof(C5A)=Sof(H26A)=Sof(H26B)=Sof(H26C)=FVAR(5)
 Sof(H00X)=1-FVAR(6)
 Sof(C6A)=Sof(H25A)=Sof(H25B)=Sof(H25C)=FVAR(6)
 Sof(H00Q)=1-FVAR(7)
 Sof(C2A)=Sof(H12A)=Sof(H12B)=Sof(H12C)=FVAR(7)
 Fixed U11: Al1(0.04972) N2(0.038566) C11(0.058467) C13(0.042183)
 C111(0.046592) C21(0.046746) C22(0.053977) C1(0.073724) N4(0.04637)
 C32(0.062115) C34(0.055773) C221(0.050311) C213(0.057594) C4(0.082876)
 C112(0.054004) C43(0.066696) C14(0.049904) C262(0.08603) C25(0.066902)
 C321(0.065269) C42(0.046287) C23(0.053439) C461(0.056183) C46(0.050678)
 C215(0.050777) C217(0.085794) C421(0.056765) C422(0.075415)
 Fixed U12: Al1(0) N2(0) C11(0.004051) C13(0.005064) C111(0) C21(-0.000269)
 C22(-0.00032) C1(0) N4(0.003891) C32(0.005064) C34(0) C221(0) C213(0.009115)
 C4(0.009006) C112(-0.001442) C43(-0.002884) C14(0.002026) C262(0.001545)
 C25(0.018012) C321(0) C42(0.002288) C23(-0.002243) C461(-0.002564)
 C46(0.001064) C215(0.021268) C217(0.012679) C421(0.007557) C422(-0.008974)
 Fixed U13: Al1(-0.003045) N2(-0.003846) C11(0.003666) C13(-0.007211) C111(-
 0.002724) C21(-0.003686) C22(-0.004006) C1(0.007826) N4(-0.002352) C32(-
 0.004596) C34(-0.008814) C221(-0.00673) C213(-0.007371) C4(-0.005128) C112(-
 0.000808) C43(-0.00657) C14(0.002859) C262(-0.005609) C25(-0.007852) C321(-
 0.005077) C42(0.002865) C23(-0.007051) C461(-0.004968) C46(-0.003634) C215(-
 0.00259) C217(0.029126) C421(-0.000865) C422(-0.009775)
 Fixed U22: Al1(0.031) N2(0.033) C11(0.036) C13(0.061) C111(0.037) C21(0.043)
 C22(0.066) C1(0.041) N4(0.037) C32(0.041) C34(0.082) C221(0.077) C213(0.04)
 C4(0.028) C112(0.059) C43(0.05) C14(0.063) C262(0.062) C25(0.056) C321(0.036)
 C42(0.048) C23(0.075) C461(0.051) C46(0.045) C215(0.06) C217(0.063)
 C421(0.087) C422(0.134)
 Fixed U23: Al1(0) N2(0) C11(0) C13(0) C111(0) C21(0.008) C22(0.002) C1(0)
 N4(0.001) C32(0) C34(0) C221(0) C213(0) C4(0.007) C112(0.009) C43(0.018)
 C14(0) C262(0.003) C25(0.014) C321(0) C42(0.011) C23(0.014) C461(0.016)
 C46(0.006) C215(0) C217(0.022) C421(0.035) C422(0.056)
 Fixed U33: Al1(0.019) N2(0.024) C11(0.034) C13(0.045) C111(0.017) C21(0.023)
 C22(0.025) C1(0.027) N4(0.021) C32(0.035) C34(0.055) C221(0.042) C213(0.046)
 C4(0.032) C112(0.024) C43(0.041) C14(0.058) C262(0.035) C25(0.049) C321(0.038)
 C42(0.039) C23(0.044) C461(0.031) C46(0.029) C215(0.092) C217(0.09)
 C421(0.037) C422(0.061)
 Fixed X: Al1(0.537826) N2(0.463305) C4(0.595722) C43(0.30244) C461(0.267756)
 C463(0.188153) C215(0.344398) C117(0.742249) C1E(0.57941) C422(0.515388)
 C1Q(0.589952)
 Fixed Y: Al1(0.254986) N2(0.374043) C4(0.069272) C43(0.145563) C461(0.378325)
 C463(0.484221) C215(0.760589) C117(0.548545) C1E(0.013227) C422(0.175374)
 C1Q(0.18539)
 Fixed Z: Al1(0.445395) N2(0.392214) C4(0.555266) C43(0.692158) C461(0.547377)
 C463(0.550694) C215(0.660649) C117(0.249372) C1E(0.294518) C422(0.767199)
 C1Q(0.228628)
6.a Riding coordinates:
 C3A(H1H,H1B,H1A)
6.b Ternary CH refined with riding coordinates:
 C121(H00C), C1(H00O), C221(H00S), C361(H015), C361(H01D), C321(H01K),
 C1A(H01), C261(H19), C421(H22)
6.c Secondary CH2 refined with riding coordinates:
 C212(H00E,H00F), C113(H00K,H00L), C113(H00M,H00N), C213(H00U,H00V), C213(H00P,
 H00T), C112(H00Y,H), C114(H01Z,HA), C214(H1,HB), C216(H3A,H3B), C116(H5A,H5B)
6.d Aromatic/amide H refined with riding coordinates:
 C13(H008), C35(H00J), C2(H00Q), C34(H00R), C6(H00X), C44(H00Z), C14(H012),
 C15(H013), C3(H018), C25(H019), C23(H01O), C5(H01Q), C24(H01R), C45(H01V),
 C33(H18)
6.e Idealised Me refined as rotating group:
 C323(H00A,H00B,H00D), C122(H00G,H00H,H00I), C322(H01A,H01B,H01C), C262(H01E,
 H01F,H01G), C123(H01H,H01I,H01J), C462(H01L,H01M,H01N), C263(H01S,H01T,H01U),
 C463(H01W,H01X,H01Y), C115(H2,HC,HD), C215(H40A,H40B,H40C), C217(H40D,H40E,
 H215), C117(H8A,H8B,H8C), C1E(H13A,H13B,H13C), C222(H15A,H15B,H15C), C223(H16A,
 H16B,H16C), C362(H6A,H6B,H6C), C363(H21A,H21B,H21C), C364(H6AA,H6AB,H6AC),
 C365(H21D,H21E,H21F), C422(H24A,H24B,H24C), C423(H23A,H23B,H23C), C1Q(H17A,
 H17B,H17C), C5A(H26A,H26B,H26C), C2A(H12A,H12B,H12C), C6A(H25A,H25B,H25C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 86 electrons were 
found in a volume of 344\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
1[C7H8] per Asymmetric Unit 
which account for 100 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              69980
_shelx_fab_checksum              34957
_olex2_submission_special_instructions 'No special instructions were received'