The crystal structures of three Schiff bases synthesized from 3-formylaceylacetone and different primary amines were determined and compared with simulated gas phase structures based on DFT calculations.
Supporting information
CCDC references: 2279192; 2279191; 2279190
Key indicators
Structure: 1
- Single-crystal X-ray study
- T = 213 K
- Mean
(C-C) = 0.003 Å
- R factor = 0.041
- wR factor = 0.097
- Data-to-parameter ratio = 14.7
Structure: 2
- Single-crystal X-ray study
- T = 170 K
- Mean
(C-C) = 0.002 Å
- R factor = 0.036
- wR factor = 0.104
- Data-to-parameter ratio = 22.6
Structure: 3
- Single-crystal X-ray study
- T = 170 K
- Mean
(C-C) = 0.005 Å
- R factor = 0.048
- wR factor = 0.131
- Data-to-parameter ratio = 36.0
checkCIF/PLATON results
No syntax errors found
Datablock: 1
Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for C3 --C6 . 6.2 s.u.
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ...... 2.044 Check
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L= 0.600 28 Report
Alert level G
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms .............. 1 Report
PLAT899_ALERT_4_G SHELXL2018 is Deprecated and Succeeded by SHELXL 2019/3 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min). 1 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 20 Note
PLAT913_ALERT_3_G Missing # of Very Strong Reflections in FCF .... 1 Note
PLAT941_ALERT_3_G Average HKL Measurement Multiplicity ........... 3.4 Low
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density. 2 Info
0 ALERT level A = Most likely a serious problem - resolve or explain
0 ALERT level B = A potentially serious problem, consider carefully
3 ALERT level C = Check. Ensure it is not caused by an omission or oversight
7 ALERT level G = General information/check it is not something unexpected
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
2 ALERT type 2 Indicator that the structure model may be wrong or deficient
5 ALERT type 3 Indicator that the structure quality may be low
2 ALERT type 4 Improvement, methodology, query or suggestion
1 ALERT type 5 Informative message, check
Datablock: 2
Alert level C
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L= 0.600 10 Report
Alert level G
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms .............. 1 Report
PLAT480_ALERT_4_G Long H...A H-Bond Reported H4 ..O1 . 2.69 Ang.
PLAT480_ALERT_4_G Long H...A H-Bond Reported H11 ..O2 . 2.67 Ang.
PLAT899_ALERT_4_G SHELXL2018 is Deprecated and Succeeded by SHELXL 2019/3 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min). 1 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 5 Note
PLAT913_ALERT_3_G Missing # of Very Strong Reflections in FCF .... 1 Note
PLAT941_ALERT_3_G Average HKL Measurement Multiplicity ........... 2.6 Low
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density. 7 Info
PLAT992_ALERT_5_G Repd & Actual _reflns_number_gt Values Differ by 4 Check
0 ALERT level A = Most likely a serious problem - resolve or explain
0 ALERT level B = A potentially serious problem, consider carefully
1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
10 ALERT level G = General information/check it is not something unexpected
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
1 ALERT type 2 Indicator that the structure model may be wrong or deficient
4 ALERT type 3 Indicator that the structure quality may be low
4 ALERT type 4 Improvement, methodology, query or suggestion
2 ALERT type 5 Informative message, check
Datablock: 3
Alert level C
STRVA01_ALERT_2_C Chirality of atom sites is inverted?
From the CIF: _refine_ls_abs_structure_Flack 2.900
From the CIF: _refine_ls_abs_structure_Flack_su 0.700
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds ............... 0.00458 Ang.
PLAT907_ALERT_2_C Flack x > 0.5, Structure Needs to be Inverted? . 2.90 Check
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L= 0.600 50 Report
PLAT918_ALERT_3_C Reflection(s) with I(obs) much Smaller I(calc) . 25 Check
PLAT939_ALERT_3_C Large Value of Not (SHELXL) Weight Optimized S . 14.48 Check
Alert level G
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms .............. 2 Report
PLAT032_ALERT_4_G Std. Uncertainty on Flack Parameter Value High . 0.700 Report
PLAT033_ALERT_4_G Flack x Value Deviates > 3.0 * sigma from Zero . 2.900 Note
PLAT480_ALERT_4_G Long H...A H-Bond Reported H17 ..O4 . 2.66 Ang.
PLAT870_ALERT_4_G ALERTS Related to Twinning Effects Suppressed .. ! Info
PLAT899_ALERT_4_G SHELXL2018 is Deprecated and Succeeded by SHELXL 2019/3 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min). 3 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 41 Note
PLAT913_ALERT_3_G Missing # of Very Strong Reflections in FCF .... 1 Note
PLAT916_ALERT_2_G Hooft y and Flack x Parameter Values Differ by . 2.40 Check
PLAT931_ALERT_5_G CIFcalcFCF Twin Law ( 0 0 1) Est.d BASF 0.30 Check
PLAT933_ALERT_2_G Number of HKL-OMIT Records in Embedded .res File 2 Note
PLAT941_ALERT_3_G Average HKL Measurement Multiplicity ........... 3.2 Low
0 ALERT level A = Most likely a serious problem - resolve or explain
0 ALERT level B = A potentially serious problem, consider carefully
6 ALERT level C = Check. Ensure it is not caused by an omission or oversight
13 ALERT level G = General information/check it is not something unexpected
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
4 ALERT type 2 Indicator that the structure model may be wrong or deficient
7 ALERT type 3 Indicator that the structure quality may be low
6 ALERT type 4 Improvement, methodology, query or suggestion
2 ALERT type 5 Informative message, check
For all structures, data collection: X-AREA WinXpose (Stoe, 2016); cell refinement: X-AREA Recipe (Stoe, 2015); data reduction: X-AREA (Stoe, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 2019); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).
3-[(Benzylamino)methylidene]pentane-2,4-dione (1)
top
Crystal data top
C13H15NO2 | F(000) = 464 |
Mr = 217.26 | Dx = 1.270 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.7356 (14) Å | Cell parameters from 7396 reflections |
b = 9.2401 (8) Å | θ = 2.9–26.0° |
c = 11.3970 (14) Å | µ = 0.09 mm−1 |
β = 113.148 (14)° | T = 213 K |
V = 1136.4 (2) Å3 | Block, clear yellow |
Z = 4 | 0.33 × 0.15 × 0.12 mm |
Data collection top
STOE IPDS 2 diffractometer | Rint = 0.078 |
rotation scans | θmax = 26.0°, θmin = 2.9° |
7396 measured reflections | h = −13→13 |
2159 independent reflections | k = −11→11 |
1414 reflections with I > 2σ(I) | l = −13→13 |
Refinement top
Refinement on F2 | Primary atom site location: iterative |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.041 | H-atom parameters constrained |
wR(F2) = 0.097 | w = 1/[σ2(Fo2) + (0.0469P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.94 | (Δ/σ)max < 0.001 |
2159 reflections | Δρmax = 0.18 e Å−3 |
147 parameters | Δρmin = −0.17 e Å−3 |
0 restraints | |
Special details top
Geometry. 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.29032 (19) | 0.4837 (2) | 1.16212 (15) | 0.0391 (5) | |
H1 | 0.2334 | 0.4136 | 1.1724 | 0.059* | |
H2 | 0.2718 | 0.5790 | 1.1858 | 0.059* | |
H3 | 0.3747 | 0.4574 | 1.2165 | 0.059* | |
C2 | 0.27629 (16) | 0.48567 (19) | 1.02452 (14) | 0.0284 (4) | |
C3 | 0.34838 (15) | 0.58355 (17) | 0.98050 (14) | 0.0239 (4) | |
C4 | 0.43034 (16) | 0.69625 (18) | 1.06114 (14) | 0.0265 (4) | |
C5 | 0.4992 (2) | 0.7943 (2) | 1.00520 (17) | 0.0404 (5) | |
H4 | 0.4405 | 0.8413 | 0.9294 | 0.061* | |
H5 | 0.5571 | 0.7374 | 0.9827 | 0.061* | |
H6 | 0.5442 | 0.8670 | 1.0676 | 0.061* | |
C6 | 0.34363 (15) | 0.56658 (17) | 0.85623 (14) | 0.0244 (4) | |
H7 | 0.3949 | 0.6277 | 0.8324 | 0.029* | |
C7 | 0.27877 (17) | 0.45955 (19) | 0.64354 (14) | 0.0297 (4) | |
H9 | 0.2677 | 0.3573 | 0.6186 | 0.036* | |
H10 | 0.3610 | 0.4890 | 0.6492 | 0.036* | |
C8 | 0.18161 (16) | 0.54814 (17) | 0.53978 (14) | 0.0235 (4) | |
C9 | 0.15894 (17) | 0.51739 (19) | 0.41290 (15) | 0.0307 (4) | |
H11 | 0.2017 | 0.4412 | 0.3935 | 0.037* | |
C10 | 0.07407 (18) | 0.5979 (2) | 0.31512 (15) | 0.0353 (5) | |
H12 | 0.0588 | 0.5754 | 0.2298 | 0.042* | |
C11 | 0.01179 (18) | 0.7110 (2) | 0.34239 (16) | 0.0363 (5) | |
H13 | −0.0444 | 0.7670 | 0.2760 | 0.044* | |
C12 | 0.03245 (19) | 0.7418 (2) | 0.46829 (17) | 0.0394 (5) | |
H14 | −0.0108 | 0.8178 | 0.4873 | 0.047* | |
C13 | 0.11704 (17) | 0.66035 (19) | 0.56594 (16) | 0.0329 (4) | |
H15 | 0.1307 | 0.6816 | 0.6511 | 0.040* | |
N | 0.27486 (14) | 0.47394 (15) | 0.76962 (11) | 0.0290 (4) | |
H8 | 0.2245 | 0.4184 | 0.7884 | 0.035* | |
O1 | 0.20370 (13) | 0.39610 (15) | 0.95112 (11) | 0.0439 (4) | |
O2 | 0.44589 (13) | 0.71536 (15) | 1.17367 (10) | 0.0418 (4) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0467 (13) | 0.0475 (12) | 0.0277 (9) | −0.0032 (10) | 0.0196 (9) | 0.0032 (8) |
C2 | 0.0266 (10) | 0.0345 (10) | 0.0231 (8) | 0.0034 (8) | 0.0087 (7) | 0.0020 (7) |
C3 | 0.0247 (10) | 0.0277 (9) | 0.0173 (7) | 0.0044 (7) | 0.0063 (7) | 0.0020 (6) |
C4 | 0.0271 (10) | 0.0277 (9) | 0.0220 (8) | 0.0066 (7) | 0.0068 (7) | −0.0002 (7) |
C5 | 0.0527 (14) | 0.0324 (10) | 0.0329 (9) | −0.0132 (9) | 0.0135 (9) | −0.0055 (8) |
C6 | 0.0246 (10) | 0.0226 (8) | 0.0234 (8) | 0.0020 (7) | 0.0066 (7) | 0.0039 (7) |
C7 | 0.0372 (11) | 0.0319 (9) | 0.0194 (8) | 0.0020 (8) | 0.0104 (7) | −0.0029 (7) |
C8 | 0.0253 (10) | 0.0253 (8) | 0.0197 (8) | −0.0045 (7) | 0.0087 (7) | −0.0024 (6) |
C9 | 0.0364 (11) | 0.0335 (10) | 0.0230 (8) | 0.0026 (8) | 0.0125 (7) | −0.0022 (7) |
C10 | 0.0423 (12) | 0.0435 (11) | 0.0186 (8) | −0.0020 (9) | 0.0105 (8) | 0.0006 (8) |
C11 | 0.0345 (12) | 0.0358 (11) | 0.0311 (9) | 0.0005 (8) | 0.0049 (8) | 0.0089 (8) |
C12 | 0.0378 (12) | 0.0376 (11) | 0.0389 (10) | 0.0106 (9) | 0.0107 (9) | −0.0035 (8) |
C13 | 0.0345 (11) | 0.0383 (10) | 0.0239 (8) | 0.0019 (8) | 0.0092 (8) | −0.0076 (7) |
N | 0.0351 (9) | 0.0317 (8) | 0.0184 (7) | −0.0059 (7) | 0.0087 (6) | −0.0007 (6) |
O1 | 0.0468 (9) | 0.0559 (9) | 0.0285 (7) | −0.0222 (7) | 0.0145 (6) | −0.0036 (6) |
O2 | 0.0464 (9) | 0.0535 (8) | 0.0232 (6) | −0.0082 (7) | 0.0111 (6) | −0.0115 (6) |
Geometric parameters (Å, º) top
C1—C2 | 1.511 (2) | C7—C8 | 1.519 (2) |
C1—H1 | 0.9700 | C7—H9 | 0.9800 |
C1—H2 | 0.9700 | C7—H10 | 0.9800 |
C1—H3 | 0.9700 | C8—C13 | 1.384 (2) |
C2—O1 | 1.245 (2) | C8—C9 | 1.393 (2) |
C2—C3 | 1.456 (2) | C9—C10 | 1.384 (2) |
C3—C6 | 1.404 (2) | C9—H11 | 0.9400 |
C3—C4 | 1.469 (2) | C10—C11 | 1.379 (3) |
C4—O2 | 1.2350 (19) | C10—H12 | 0.9400 |
C4—C5 | 1.512 (3) | C11—C12 | 1.388 (3) |
C5—H4 | 0.9700 | C11—H13 | 0.9400 |
C5—H5 | 0.9700 | C12—C13 | 1.386 (2) |
C5—H6 | 0.9700 | C12—H14 | 0.9400 |
C6—N | 1.316 (2) | C13—H15 | 0.9400 |
C6—H7 | 0.9400 | N—H8 | 0.8700 |
C7—N | 1.462 (2) | | |
| | | |
C2—C1—H1 | 109.5 | C8—C7—H9 | 108.7 |
C2—C1—H2 | 109.5 | N—C7—H10 | 108.7 |
H1—C1—H2 | 109.5 | C8—C7—H10 | 108.7 |
C2—C1—H3 | 109.5 | H9—C7—H10 | 107.6 |
H1—C1—H3 | 109.5 | C13—C8—C9 | 118.63 (16) |
H2—C1—H3 | 109.5 | C13—C8—C7 | 122.88 (14) |
O1—C2—C3 | 121.22 (14) | C9—C8—C7 | 118.47 (15) |
O1—C2—C1 | 117.12 (16) | C10—C9—C8 | 120.64 (17) |
C3—C2—C1 | 121.60 (15) | C10—C9—H11 | 119.7 |
C6—C3—C2 | 118.70 (15) | C8—C9—H11 | 119.7 |
C6—C3—C4 | 117.82 (15) | C11—C10—C9 | 120.23 (16) |
C2—C3—C4 | 123.44 (14) | C11—C10—H12 | 119.9 |
O2—C4—C3 | 122.95 (16) | C9—C10—H12 | 119.9 |
O2—C4—C5 | 117.85 (16) | C10—C11—C12 | 119.73 (17) |
C3—C4—C5 | 119.20 (14) | C10—C11—H13 | 120.1 |
C4—C5—H4 | 109.5 | C12—C11—H13 | 120.1 |
C4—C5—H5 | 109.5 | C13—C12—C11 | 119.84 (18) |
H4—C5—H5 | 109.5 | C13—C12—H14 | 120.1 |
C4—C5—H6 | 109.5 | C11—C12—H14 | 120.1 |
H4—C5—H6 | 109.5 | C8—C13—C12 | 120.91 (16) |
H5—C5—H6 | 109.5 | C8—C13—H15 | 119.5 |
N—C6—C3 | 126.77 (16) | C12—C13—H15 | 119.5 |
N—C6—H7 | 116.6 | C6—N—C7 | 123.33 (16) |
C3—C6—H7 | 116.6 | C6—N—H8 | 118.3 |
N—C7—C8 | 114.34 (15) | C7—N—H8 | 118.3 |
N—C7—H9 | 108.7 | | |
| | | |
O1—C2—C3—C6 | −5.9 (2) | N—C7—C8—C9 | −165.58 (16) |
C1—C2—C3—C6 | 171.41 (17) | C13—C8—C9—C10 | 0.3 (3) |
O1—C2—C3—C4 | 176.69 (17) | C7—C8—C9—C10 | −178.03 (17) |
C1—C2—C3—C4 | −6.0 (3) | C8—C9—C10—C11 | 0.8 (3) |
C6—C3—C4—O2 | −176.37 (17) | C9—C10—C11—C12 | −1.5 (3) |
C2—C3—C4—O2 | 1.1 (3) | C10—C11—C12—C13 | 1.1 (3) |
C6—C3—C4—C5 | 3.8 (2) | C9—C8—C13—C12 | −0.7 (3) |
C2—C3—C4—C5 | −178.77 (16) | C7—C8—C13—C12 | 177.57 (18) |
C2—C3—C6—N | 3.6 (3) | C11—C12—C13—C8 | 0.0 (3) |
C4—C3—C6—N | −178.82 (15) | C3—C6—N—C7 | −177.67 (16) |
N—C7—C8—C13 | 16.1 (2) | C8—C7—N—C6 | −94.4 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N—H8···O1 | 0.87 | 1.97 | 2.6177 (18) | 130 |
C6—H7···O2i | 0.94 | 2.57 | 3.434 (2) | 154 |
Symmetry code: (i) x, −y+3/2, z−1/2. |
3-[(
tert-Butylamino)methylidene]pentan-2,4-dione (2)
top
Crystal data top
C10H17NO2 | F(000) = 400 |
Mr = 183.24 | Dx = 1.177 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.8226 (7) Å | Cell parameters from 2011 reflections |
b = 9.8323 (6) Å | θ = 3.7–29.5° |
c = 11.2700 (8) Å | µ = 0.08 mm−1 |
β = 108.171 (5)° | T = 170 K |
V = 1034.16 (12) Å3 | Block, colourless |
Z = 4 | 0.32 × 0.28 × 0.21 mm |
Data collection top
STOE IPDS 2 diffractometer | Rint = 0.033 |
rotation scans | θmax = 29.1°, θmin = 2.8° |
7337 measured reflections | h = −13→13 |
2774 independent reflections | k = −13→13 |
2126 reflections with I > 2σ(I) | l = −11→15 |
Refinement top
Refinement on F2 | Primary atom site location: iterative |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.036 | H-atom parameters constrained |
wR(F2) = 0.104 | w = 1/[σ2(Fo2) + (0.0562P)2 + 0.1178P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
2774 reflections | Δρmax = 0.30 e Å−3 |
123 parameters | Δρmin = −0.14 e Å−3 |
0 restraints | |
Special details top
Geometry. 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.83575 (10) | 0.46662 (12) | 0.88153 (11) | 0.0344 (2) | |
H1 | 0.8632 | 0.4892 | 0.9706 | 0.052* | |
H2 | 0.8823 | 0.5299 | 0.8392 | 0.052* | |
H3 | 0.8660 | 0.3735 | 0.8715 | 0.052* | |
C2 | 0.67575 (9) | 0.47771 (10) | 0.82522 (10) | 0.0268 (2) | |
C3 | 0.60104 (9) | 0.41294 (10) | 0.70726 (9) | 0.0247 (2) | |
C4 | 0.67422 (10) | 0.36658 (10) | 0.62027 (10) | 0.0274 (2) | |
C5 | 0.59161 (12) | 0.28835 (12) | 0.50456 (10) | 0.0351 (2) | |
H4 | 0.5154 | 0.3460 | 0.4516 | 0.053* | |
H5 | 0.5493 | 0.2070 | 0.5290 | 0.053* | |
H6 | 0.6567 | 0.2614 | 0.4582 | 0.053* | |
C6 | 0.45217 (10) | 0.39420 (10) | 0.67456 (9) | 0.0245 (2) | |
H7 | 0.4075 | 0.3445 | 0.6003 | 0.029* | |
C7 | 0.21415 (9) | 0.41512 (10) | 0.71095 (9) | 0.0242 (2) | |
C8 | 0.14674 (10) | 0.35776 (12) | 0.58053 (9) | 0.0305 (2) | |
H9 | 0.1901 | 0.2694 | 0.5740 | 0.046* | |
H10 | 0.1632 | 0.4206 | 0.5189 | 0.046* | |
H11 | 0.0435 | 0.3463 | 0.5647 | 0.046* | |
C9 | 0.14777 (11) | 0.55234 (11) | 0.72323 (12) | 0.0355 (2) | |
H12 | 0.0449 | 0.5409 | 0.7097 | 0.053* | |
H13 | 0.1622 | 0.6154 | 0.6609 | 0.053* | |
H14 | 0.1935 | 0.5891 | 0.8071 | 0.053* | |
C10 | 0.19622 (11) | 0.31624 (12) | 0.80911 (10) | 0.0324 (2) | |
H15 | 0.0940 | 0.3027 | 0.7973 | 0.049* | |
H16 | 0.2428 | 0.3535 | 0.8926 | 0.049* | |
H17 | 0.2403 | 0.2289 | 0.8006 | 0.049* | |
N | 0.36968 (8) | 0.43920 (9) | 0.73734 (8) | 0.02652 (19) | |
H8 | 0.4115 | 0.4898 | 0.8030 | 0.032* | |
O1 | 0.60963 (7) | 0.53863 (9) | 0.88675 (8) | 0.0377 (2) | |
O2 | 0.80125 (8) | 0.39082 (10) | 0.63547 (8) | 0.0414 (2) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0207 (4) | 0.0420 (6) | 0.0379 (6) | −0.0005 (4) | 0.0056 (4) | −0.0040 (5) |
C2 | 0.0207 (4) | 0.0270 (5) | 0.0328 (5) | −0.0015 (3) | 0.0084 (4) | −0.0005 (4) |
C3 | 0.0202 (4) | 0.0253 (4) | 0.0296 (5) | −0.0003 (3) | 0.0092 (3) | 0.0014 (4) |
C4 | 0.0250 (4) | 0.0272 (5) | 0.0326 (5) | 0.0005 (4) | 0.0126 (4) | 0.0039 (4) |
C5 | 0.0353 (5) | 0.0404 (6) | 0.0342 (6) | −0.0024 (4) | 0.0174 (4) | −0.0044 (4) |
C6 | 0.0217 (4) | 0.0265 (4) | 0.0255 (4) | −0.0005 (3) | 0.0078 (3) | 0.0008 (4) |
C7 | 0.0172 (4) | 0.0296 (4) | 0.0259 (5) | −0.0008 (3) | 0.0068 (3) | −0.0009 (4) |
C8 | 0.0230 (4) | 0.0421 (6) | 0.0250 (5) | −0.0027 (4) | 0.0056 (4) | −0.0015 (4) |
C9 | 0.0263 (5) | 0.0335 (5) | 0.0477 (7) | 0.0026 (4) | 0.0131 (4) | −0.0034 (5) |
C10 | 0.0310 (5) | 0.0387 (6) | 0.0288 (5) | −0.0018 (4) | 0.0109 (4) | 0.0020 (4) |
N | 0.0177 (3) | 0.0336 (4) | 0.0279 (4) | −0.0015 (3) | 0.0065 (3) | −0.0055 (3) |
O1 | 0.0239 (3) | 0.0462 (5) | 0.0420 (5) | −0.0017 (3) | 0.0089 (3) | −0.0172 (4) |
O2 | 0.0270 (4) | 0.0555 (5) | 0.0479 (5) | −0.0069 (3) | 0.0207 (3) | −0.0060 (4) |
Geometric parameters (Å, º) top
C1—C2 | 1.5042 (13) | C7—N | 1.4815 (11) |
C1—H1 | 0.9800 | C7—C8 | 1.5197 (14) |
C1—H2 | 0.9800 | C7—C9 | 1.5235 (14) |
C1—H3 | 0.9800 | C7—C10 | 1.5237 (14) |
C2—O1 | 1.2419 (12) | C8—H9 | 0.9800 |
C2—C3 | 1.4502 (14) | C8—H10 | 0.9800 |
C3—C6 | 1.4043 (12) | C8—H11 | 0.9800 |
C3—C4 | 1.4578 (13) | C9—H12 | 0.9800 |
C4—O2 | 1.2287 (12) | C9—H13 | 0.9800 |
C4—C5 | 1.5135 (15) | C9—H14 | 0.9800 |
C5—H4 | 0.9800 | C10—H15 | 0.9800 |
C5—H5 | 0.9800 | C10—H16 | 0.9800 |
C5—H6 | 0.9800 | C10—H17 | 0.9800 |
C6—N | 1.3079 (12) | N—H8 | 0.8800 |
C6—H7 | 0.9500 | | |
| | | |
C2—C1—H1 | 109.5 | C8—C7—C9 | 110.29 (8) |
C2—C1—H2 | 109.5 | N—C7—C10 | 107.56 (8) |
H1—C1—H2 | 109.5 | C8—C7—C10 | 110.56 (8) |
C2—C1—H3 | 109.5 | C9—C7—C10 | 110.45 (8) |
H1—C1—H3 | 109.5 | C7—C8—H9 | 109.5 |
H2—C1—H3 | 109.5 | C7—C8—H10 | 109.5 |
O1—C2—C3 | 121.36 (8) | H9—C8—H10 | 109.5 |
O1—C2—C1 | 117.32 (9) | C7—C8—H11 | 109.5 |
C3—C2—C1 | 121.22 (8) | H9—C8—H11 | 109.5 |
C6—C3—C2 | 119.08 (8) | H10—C8—H11 | 109.5 |
C6—C3—C4 | 118.29 (9) | C7—C9—H12 | 109.5 |
C2—C3—C4 | 122.63 (8) | C7—C9—H13 | 109.5 |
O2—C4—C3 | 122.54 (10) | H12—C9—H13 | 109.5 |
O2—C4—C5 | 117.84 (9) | C7—C9—H14 | 109.5 |
C3—C4—C5 | 119.61 (8) | H12—C9—H14 | 109.5 |
C4—C5—H4 | 109.5 | H13—C9—H14 | 109.5 |
C4—C5—H5 | 109.5 | C7—C10—H15 | 109.5 |
H4—C5—H5 | 109.5 | C7—C10—H16 | 109.5 |
C4—C5—H6 | 109.5 | H15—C10—H16 | 109.5 |
H4—C5—H6 | 109.5 | C7—C10—H17 | 109.5 |
H5—C5—H6 | 109.5 | H15—C10—H17 | 109.5 |
N—C6—C3 | 125.72 (9) | H16—C10—H17 | 109.5 |
N—C6—H7 | 117.1 | C6—N—C7 | 127.69 (8) |
C3—C6—H7 | 117.1 | C6—N—H8 | 116.2 |
N—C7—C8 | 111.38 (8) | C7—N—H8 | 116.2 |
N—C7—C9 | 106.50 (8) | | |
| | | |
O1—C2—C3—C6 | −13.30 (15) | C2—C3—C4—C5 | 174.41 (9) |
C1—C2—C3—C6 | 163.02 (9) | C2—C3—C6—N | 5.34 (15) |
O1—C2—C3—C4 | 166.44 (10) | C4—C3—C6—N | −174.40 (9) |
C1—C2—C3—C4 | −17.25 (15) | C3—C6—N—C7 | −175.98 (9) |
C6—C3—C4—O2 | 172.63 (10) | C8—C7—N—C6 | −14.03 (14) |
C2—C3—C4—O2 | −7.11 (15) | C9—C7—N—C6 | −134.31 (11) |
C6—C3—C4—C5 | −5.85 (14) | C10—C7—N—C6 | 107.27 (11) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N—H8···O1 | 0.90 (2) | 1.90 (2) | 2.6322 (16) | 136 (2) |
C5—H4···O1i | 0.97 (2) | 2.69 (2) | 3.630 (2) | 163 (2) |
C8—H11···O2ii | 0.98 (2) | 2.67 (2) | 3.642 (2) | 174 (1) |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) −x+1, −y, −z+1. |
3-{[(
S)-Benzyl(methyl)amino]methylidene}pentane-2,4-dione (3)
top
Crystal data top
C14H17NO2 | F(000) = 496 |
Mr = 231.28 | Dx = 1.235 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.0459 (9) Å | Cell parameters from 17500 reflections |
b = 8.1011 (5) Å | θ = 2.5–29.7° |
c = 15.7052 (13) Å | µ = 0.08 mm−1 |
β = 103.372 (7)° | T = 170 K |
V = 1243.48 (17) Å3 | Block, colourless |
Z = 4 | 0.44 × 0.21 × 0.14 mm |
Data collection top
STOE IPDS 2T diffractometer | Rint = 0.042 |
rotation scans | θmax = 29.3°, θmin = 2.7° |
11343 measured reflections | h = −13→13 |
11343 independent reflections | k = −11→11 |
9181 reflections with I > 2σ(I) | l = −21→21 |
Refinement top
Refinement on F2 | H-atom parameters constrained |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.059P)2 + 0.3675P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.048 | (Δ/σ)max < 0.001 |
wR(F2) = 0.131 | Δρmax = 0.27 e Å−3 |
S = 1.05 | Δρmin = −0.28 e Å−3 |
11343 reflections | Extinction correction: SHELXL-2018/3 (Sheldrick 2014, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
315 parameters | Extinction coefficient: 0.044 (6) |
1 restraint | Absolute structure: Classical Flack method preferred over Parsons because s.u. lower. |
Primary atom site location: iterative | Absolute structure parameter: 2.9 (7) |
Hydrogen site location: inferred from neighbouring sites | |
Special details top
Geometry. 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. |
Refinement. Refined as a 2-component twin. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 1.1723 (4) | 0.7494 (5) | 0.1031 (3) | 0.0494 (10) | |
H1 | 1.2297 | 0.7243 | 0.1610 | 0.074* | |
H2 | 1.1712 | 0.8689 | 0.0932 | 0.074* | |
H3 | 1.2093 | 0.6937 | 0.0581 | 0.074* | |
C2 | 1.0289 (3) | 0.6899 (4) | 0.0981 (2) | 0.0307 (6) | |
C3 | 0.9990 (3) | 0.5183 (4) | 0.1133 (2) | 0.0300 (6) | |
C4 | 1.1060 (4) | 0.3913 (4) | 0.1369 (2) | 0.0364 (7) | |
C5 | 1.0664 (4) | 0.2163 (5) | 0.1548 (3) | 0.0455 (9) | |
H4 | 1.1492 | 0.1519 | 0.1788 | 0.068* | |
H5 | 1.0161 | 0.1655 | 0.1002 | 0.068* | |
H6 | 1.0083 | 0.2183 | 0.1971 | 0.068* | |
C6 | 0.8627 (3) | 0.4704 (4) | 0.1047 (2) | 0.0309 (6) | |
H7 | 0.8465 | 0.3569 | 0.1137 | 0.037* | |
C7 | 0.6134 (3) | 0.5100 (4) | 0.0761 (2) | 0.0315 (6) | |
H9 | 0.6158 | 0.3879 | 0.0856 | 0.038* | |
C8 | 0.5280 (3) | 0.5433 (4) | −0.0157 (2) | 0.0289 (6) | |
C9 | 0.5840 (3) | 0.6073 (4) | −0.0821 (2) | 0.0335 (7) | |
H10 | 0.6787 | 0.6336 | −0.0698 | 0.040* | |
C10 | 0.5044 (4) | 0.6331 (5) | −0.1654 (2) | 0.0373 (7) | |
H11 | 0.5446 | 0.6774 | −0.2096 | 0.045* | |
C11 | 0.3657 (4) | 0.5946 (5) | −0.1849 (2) | 0.0379 (7) | |
H12 | 0.3109 | 0.6116 | −0.2421 | 0.045* | |
C12 | 0.3084 (3) | 0.5308 (4) | −0.1193 (2) | 0.0349 (7) | |
H13 | 0.2138 | 0.5040 | −0.1319 | 0.042* | |
C13 | 0.3882 (3) | 0.5062 (4) | −0.0357 (2) | 0.0310 (6) | |
H14 | 0.3475 | 0.4635 | 0.0085 | 0.037* | |
C14 | 0.5532 (4) | 0.5888 (5) | 0.1472 (2) | 0.0408 (8) | |
H15 | 0.4605 | 0.5463 | 0.1429 | 0.061* | |
H16 | 0.5496 | 0.7089 | 0.1394 | 0.061* | |
H17 | 0.6108 | 0.5619 | 0.2049 | 0.061* | |
N1 | 0.7550 (3) | 0.5668 (3) | 0.08533 (19) | 0.0329 (6) | |
H8 | 0.7684 | 0.6724 | 0.0773 | 0.039* | |
O1 | 0.9351 (3) | 0.7936 (3) | 0.07897 (18) | 0.0389 (6) | |
O2 | 1.2273 (3) | 0.4204 (4) | 0.1427 (2) | 0.0560 (8) | |
C15 | 0.5900 (4) | 0.2575 (5) | 0.4013 (3) | 0.0407 (8) | |
H18 | 0.5956 | 0.1369 | 0.4063 | 0.061* | |
H19 | 0.6539 | 0.3075 | 0.4513 | 0.061* | |
H20 | 0.6138 | 0.2921 | 0.3469 | 0.061* | |
C16 | 0.4461 (3) | 0.3127 (4) | 0.4004 (2) | 0.0326 (7) | |
C17 | 0.4062 (3) | 0.4854 (4) | 0.3894 (2) | 0.0297 (6) | |
C18 | 0.4988 (3) | 0.6153 (4) | 0.3729 (2) | 0.0327 (7) | |
C19 | 0.4459 (4) | 0.7895 (5) | 0.3518 (3) | 0.0454 (9) | |
H21 | 0.4351 | 0.8439 | 0.4055 | 0.068* | |
H22 | 0.3572 | 0.7854 | 0.3096 | 0.068* | |
H23 | 0.5111 | 0.8518 | 0.3266 | 0.068* | |
C20 | 0.2753 (3) | 0.5311 (4) | 0.3967 (2) | 0.0302 (6) | |
H24 | 0.2535 | 0.6452 | 0.3909 | 0.036* | |
C21 | 0.0473 (3) | 0.4873 (4) | 0.4252 (2) | 0.0316 (6) | |
H26 | 0.0424 | 0.6097 | 0.4168 | 0.038* | |
C22 | 0.0360 (3) | 0.4507 (4) | 0.5191 (2) | 0.0280 (6) | |
C23 | 0.1422 (3) | 0.3812 (4) | 0.5812 (2) | 0.0323 (6) | |
H27 | 0.2249 | 0.3525 | 0.5654 | 0.039* | |
C24 | 0.1294 (4) | 0.3531 (4) | 0.6661 (2) | 0.0367 (7) | |
H28 | 0.2027 | 0.3040 | 0.7076 | 0.044* | |
C25 | 0.0096 (4) | 0.3967 (4) | 0.6906 (2) | 0.0364 (7) | |
H29 | 0.0011 | 0.3790 | 0.7489 | 0.044* | |
C26 | −0.0973 (3) | 0.4662 (4) | 0.6291 (2) | 0.0332 (7) | |
H30 | −0.1796 | 0.4955 | 0.6453 | 0.040* | |
C27 | −0.0847 (3) | 0.4932 (4) | 0.5438 (2) | 0.0297 (6) | |
H31 | −0.1586 | 0.5408 | 0.5021 | 0.036* | |
C28 | −0.0694 (4) | 0.4104 (5) | 0.3571 (2) | 0.0371 (7) | |
H32 | −0.1570 | 0.4518 | 0.3656 | 0.056* | |
H33 | −0.0663 | 0.2901 | 0.3635 | 0.056* | |
H34 | −0.0597 | 0.4400 | 0.2983 | 0.056* | |
N2 | 0.1787 (3) | 0.4311 (3) | 0.4108 (2) | 0.0341 (6) | |
H25 | 0.1944 | 0.3242 | 0.4115 | 0.041* | |
O3 | 0.3635 (3) | 0.2058 (3) | 0.4110 (2) | 0.0472 (7) | |
O4 | 0.6200 (2) | 0.5899 (3) | 0.37485 (18) | 0.0418 (6) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.032 (2) | 0.0401 (19) | 0.080 (3) | −0.0035 (15) | 0.0196 (19) | −0.002 (2) |
C2 | 0.0263 (15) | 0.0337 (16) | 0.0336 (15) | −0.0006 (12) | 0.0100 (12) | −0.0033 (13) |
C3 | 0.0267 (15) | 0.0322 (15) | 0.0324 (14) | 0.0005 (12) | 0.0096 (11) | −0.0028 (13) |
C4 | 0.0285 (16) | 0.0407 (18) | 0.0424 (17) | 0.0043 (14) | 0.0132 (13) | 0.0039 (15) |
C5 | 0.039 (2) | 0.0408 (19) | 0.061 (2) | 0.0109 (16) | 0.0206 (18) | 0.0113 (18) |
C6 | 0.0273 (15) | 0.0323 (15) | 0.0336 (15) | 0.0007 (12) | 0.0077 (12) | 0.0000 (13) |
C7 | 0.0221 (14) | 0.0322 (15) | 0.0404 (16) | −0.0024 (12) | 0.0074 (12) | 0.0036 (14) |
C8 | 0.0240 (14) | 0.0258 (13) | 0.0380 (15) | −0.0005 (11) | 0.0093 (12) | −0.0014 (12) |
C9 | 0.0254 (15) | 0.0369 (16) | 0.0394 (16) | −0.0027 (13) | 0.0103 (12) | 0.0002 (14) |
C10 | 0.0348 (18) | 0.0418 (18) | 0.0366 (16) | −0.0046 (14) | 0.0112 (14) | 0.0006 (15) |
C11 | 0.0349 (17) | 0.0395 (17) | 0.0367 (16) | −0.0039 (15) | 0.0032 (13) | 0.0003 (15) |
C12 | 0.0267 (15) | 0.0312 (15) | 0.0459 (17) | −0.0056 (13) | 0.0064 (13) | −0.0012 (14) |
C13 | 0.0250 (14) | 0.0281 (14) | 0.0417 (16) | −0.0025 (12) | 0.0113 (12) | −0.0009 (13) |
C14 | 0.0330 (17) | 0.053 (2) | 0.0373 (16) | −0.0049 (16) | 0.0109 (14) | −0.0009 (16) |
N1 | 0.0231 (13) | 0.0320 (13) | 0.0425 (14) | −0.0017 (10) | 0.0056 (11) | 0.0029 (11) |
O1 | 0.0307 (13) | 0.0320 (12) | 0.0555 (15) | 0.0020 (10) | 0.0129 (11) | 0.0031 (11) |
O2 | 0.0260 (13) | 0.0546 (16) | 0.089 (2) | 0.0059 (12) | 0.0179 (14) | 0.0152 (16) |
C15 | 0.0285 (17) | 0.0375 (17) | 0.059 (2) | 0.0022 (14) | 0.0153 (16) | −0.0033 (16) |
C16 | 0.0283 (16) | 0.0312 (15) | 0.0410 (17) | −0.0016 (12) | 0.0134 (13) | −0.0043 (14) |
C17 | 0.0245 (14) | 0.0317 (15) | 0.0339 (14) | −0.0030 (12) | 0.0091 (11) | −0.0019 (13) |
C18 | 0.0267 (15) | 0.0382 (16) | 0.0345 (15) | −0.0058 (13) | 0.0098 (12) | −0.0018 (14) |
C19 | 0.0350 (19) | 0.0384 (18) | 0.067 (2) | −0.0026 (15) | 0.0194 (17) | 0.0120 (18) |
C20 | 0.0262 (14) | 0.0303 (14) | 0.0357 (14) | −0.0023 (12) | 0.0107 (12) | 0.0010 (12) |
C21 | 0.0227 (14) | 0.0301 (15) | 0.0442 (16) | 0.0031 (12) | 0.0123 (12) | 0.0020 (14) |
C22 | 0.0217 (13) | 0.0239 (13) | 0.0385 (15) | −0.0015 (10) | 0.0075 (11) | −0.0019 (12) |
C23 | 0.0242 (14) | 0.0308 (15) | 0.0409 (16) | 0.0016 (12) | 0.0055 (12) | −0.0029 (13) |
C24 | 0.0342 (17) | 0.0321 (15) | 0.0389 (16) | 0.0004 (13) | −0.0016 (14) | −0.0023 (14) |
C25 | 0.0420 (19) | 0.0315 (15) | 0.0354 (15) | −0.0029 (14) | 0.0085 (14) | −0.0047 (14) |
C26 | 0.0314 (16) | 0.0313 (15) | 0.0400 (16) | −0.0008 (13) | 0.0147 (13) | −0.0022 (14) |
C27 | 0.0243 (14) | 0.0277 (13) | 0.0379 (15) | 0.0013 (11) | 0.0088 (11) | 0.0005 (13) |
C28 | 0.0285 (16) | 0.0476 (19) | 0.0355 (16) | 0.0029 (14) | 0.0079 (13) | −0.0009 (15) |
N2 | 0.0254 (13) | 0.0303 (13) | 0.0510 (16) | 0.0010 (10) | 0.0175 (12) | 0.0009 (12) |
O3 | 0.0349 (14) | 0.0309 (12) | 0.082 (2) | −0.0018 (10) | 0.0256 (14) | −0.0005 (13) |
O4 | 0.0253 (11) | 0.0447 (13) | 0.0583 (15) | −0.0045 (10) | 0.0152 (11) | 0.0020 (13) |
Geometric parameters (Å, º) top
C1—C2 | 1.504 (5) | C15—C16 | 1.510 (5) |
C1—H1 | 0.9800 | C15—H18 | 0.9800 |
C1—H2 | 0.9800 | C15—H19 | 0.9800 |
C1—H3 | 0.9800 | C15—H20 | 0.9800 |
C2—O1 | 1.246 (4) | C16—O3 | 1.236 (4) |
C2—C3 | 1.453 (4) | C16—C17 | 1.455 (4) |
C3—C6 | 1.399 (4) | C17—C20 | 1.396 (4) |
C3—C4 | 1.472 (5) | C17—C18 | 1.468 (4) |
C4—O2 | 1.224 (4) | C18—O4 | 1.228 (4) |
C4—C5 | 1.517 (5) | C18—C19 | 1.518 (5) |
C5—H4 | 0.9800 | C19—H21 | 0.9800 |
C5—H5 | 0.9800 | C19—H22 | 0.9800 |
C5—H6 | 0.9800 | C19—H23 | 0.9800 |
C6—N1 | 1.311 (4) | C20—N2 | 1.321 (4) |
C6—H7 | 0.9500 | C20—H24 | 0.9500 |
C7—N1 | 1.470 (4) | C21—N2 | 1.463 (4) |
C7—C8 | 1.522 (4) | C21—C28 | 1.524 (5) |
C7—C14 | 1.527 (5) | C21—C22 | 1.534 (4) |
C7—H9 | 1.0000 | C21—H26 | 1.0000 |
C8—C9 | 1.394 (4) | C22—C23 | 1.387 (4) |
C8—C13 | 1.399 (4) | C22—C27 | 1.400 (4) |
C9—C10 | 1.383 (5) | C23—C24 | 1.388 (5) |
C9—H10 | 0.9500 | C23—H27 | 0.9500 |
C10—C11 | 1.392 (5) | C24—C25 | 1.392 (5) |
C10—H11 | 0.9500 | C24—H28 | 0.9500 |
C11—C12 | 1.390 (5) | C25—C26 | 1.387 (5) |
C11—H12 | 0.9500 | C25—H29 | 0.9500 |
C12—C13 | 1.385 (5) | C26—C27 | 1.392 (4) |
C12—H13 | 0.9500 | C26—H30 | 0.9500 |
C13—H14 | 0.9500 | C27—H31 | 0.9500 |
C14—H15 | 0.9800 | C28—H32 | 0.9800 |
C14—H16 | 0.9800 | C28—H33 | 0.9800 |
C14—H17 | 0.9800 | C28—H34 | 0.9800 |
N1—H8 | 0.8800 | N2—H25 | 0.8800 |
| | | |
C2—C1—H1 | 109.5 | C16—C15—H18 | 109.5 |
C2—C1—H2 | 109.5 | C16—C15—H19 | 109.5 |
H1—C1—H2 | 109.5 | H18—C15—H19 | 109.5 |
C2—C1—H3 | 109.5 | C16—C15—H20 | 109.5 |
H1—C1—H3 | 109.5 | H18—C15—H20 | 109.5 |
H2—C1—H3 | 109.5 | H19—C15—H20 | 109.5 |
O1—C2—C3 | 120.7 (3) | O3—C16—C17 | 121.0 (3) |
O1—C2—C1 | 117.3 (3) | O3—C16—C15 | 117.5 (3) |
C3—C2—C1 | 122.0 (3) | C17—C16—C15 | 121.5 (3) |
C6—C3—C2 | 119.0 (3) | C20—C17—C16 | 119.0 (3) |
C6—C3—C4 | 118.1 (3) | C20—C17—C18 | 118.2 (3) |
C2—C3—C4 | 122.9 (3) | C16—C17—C18 | 122.8 (3) |
O2—C4—C3 | 122.7 (3) | O4—C18—C17 | 122.8 (3) |
O2—C4—C5 | 117.7 (3) | O4—C18—C19 | 117.2 (3) |
C3—C4—C5 | 119.5 (3) | C17—C18—C19 | 120.1 (3) |
C4—C5—H4 | 109.5 | C18—C19—H21 | 109.5 |
C4—C5—H5 | 109.5 | C18—C19—H22 | 109.5 |
H4—C5—H5 | 109.5 | H21—C19—H22 | 109.5 |
C4—C5—H6 | 109.5 | C18—C19—H23 | 109.5 |
H4—C5—H6 | 109.5 | H21—C19—H23 | 109.5 |
H5—C5—H6 | 109.5 | H22—C19—H23 | 109.5 |
N1—C6—C3 | 126.4 (3) | N2—C20—C17 | 126.4 (3) |
N1—C6—H7 | 116.8 | N2—C20—H24 | 116.8 |
C3—C6—H7 | 116.8 | C17—C20—H24 | 116.8 |
N1—C7—C8 | 111.0 (3) | N2—C21—C28 | 109.8 (3) |
N1—C7—C14 | 109.6 (3) | N2—C21—C22 | 111.0 (3) |
C8—C7—C14 | 112.8 (3) | C28—C21—C22 | 112.3 (3) |
N1—C7—H9 | 107.8 | N2—C21—H26 | 107.8 |
C8—C7—H9 | 107.8 | C28—C21—H26 | 107.8 |
C14—C7—H9 | 107.8 | C22—C21—H26 | 107.8 |
C9—C8—C13 | 118.0 (3) | C23—C22—C27 | 118.6 (3) |
C9—C8—C7 | 122.6 (3) | C23—C22—C21 | 122.6 (3) |
C13—C8—C7 | 119.4 (3) | C27—C22—C21 | 118.7 (3) |
C10—C9—C8 | 121.3 (3) | C22—C23—C24 | 121.0 (3) |
C10—C9—H10 | 119.4 | C22—C23—H27 | 119.5 |
C8—C9—H10 | 119.4 | C24—C23—H27 | 119.5 |
C9—C10—C11 | 120.3 (3) | C23—C24—C25 | 120.1 (3) |
C9—C10—H11 | 119.9 | C23—C24—H28 | 119.9 |
C11—C10—H11 | 119.9 | C25—C24—H28 | 119.9 |
C12—C11—C10 | 119.1 (3) | C26—C25—C24 | 119.4 (3) |
C12—C11—H12 | 120.5 | C26—C25—H29 | 120.3 |
C10—C11—H12 | 120.5 | C24—C25—H29 | 120.3 |
C13—C12—C11 | 120.5 (3) | C25—C26—C27 | 120.4 (3) |
C13—C12—H13 | 119.8 | C25—C26—H30 | 119.8 |
C11—C12—H13 | 119.8 | C27—C26—H30 | 119.8 |
C12—C13—C8 | 120.9 (3) | C26—C27—C22 | 120.4 (3) |
C12—C13—H14 | 119.6 | C26—C27—H31 | 119.8 |
C8—C13—H14 | 119.6 | C22—C27—H31 | 119.8 |
C7—C14—H15 | 109.5 | C21—C28—H32 | 109.5 |
C7—C14—H16 | 109.5 | C21—C28—H33 | 109.5 |
H15—C14—H16 | 109.5 | H32—C28—H33 | 109.5 |
C7—C14—H17 | 109.5 | C21—C28—H34 | 109.5 |
H15—C14—H17 | 109.5 | H32—C28—H34 | 109.5 |
H16—C14—H17 | 109.5 | H33—C28—H34 | 109.5 |
C6—N1—C7 | 124.4 (3) | C20—N2—C21 | 124.0 (3) |
C6—N1—H8 | 117.8 | C20—N2—H25 | 118.0 |
C7—N1—H8 | 117.8 | C21—N2—H25 | 118.0 |
| | | |
O1—C2—C3—C6 | 1.2 (5) | O3—C16—C17—C20 | 4.2 (5) |
C1—C2—C3—C6 | −177.8 (3) | C15—C16—C17—C20 | −174.5 (3) |
O1—C2—C3—C4 | −179.4 (3) | O3—C16—C17—C18 | −177.2 (3) |
C1—C2—C3—C4 | 1.6 (5) | C15—C16—C17—C18 | 4.1 (5) |
C6—C3—C4—O2 | 177.2 (4) | C20—C17—C18—O4 | 172.0 (3) |
C2—C3—C4—O2 | −2.2 (5) | C16—C17—C18—O4 | −6.7 (5) |
C6—C3—C4—C5 | −2.7 (5) | C20—C17—C18—C19 | −8.3 (5) |
C2—C3—C4—C5 | 177.8 (3) | C16—C17—C18—C19 | 173.1 (3) |
C2—C3—C6—N1 | −1.5 (5) | C16—C17—C20—N2 | −1.8 (5) |
C4—C3—C6—N1 | 179.0 (3) | C18—C17—C20—N2 | 179.5 (3) |
N1—C7—C8—C9 | 4.7 (4) | N2—C21—C22—C23 | 3.2 (4) |
C14—C7—C8—C9 | 128.1 (3) | C28—C21—C22—C23 | 126.6 (3) |
N1—C7—C8—C13 | −176.5 (3) | N2—C21—C22—C27 | −178.7 (3) |
C14—C7—C8—C13 | −53.1 (4) | C28—C21—C22—C27 | −55.3 (4) |
C13—C8—C9—C10 | −0.2 (5) | C27—C22—C23—C24 | 0.4 (5) |
C7—C8—C9—C10 | 178.7 (3) | C21—C22—C23—C24 | 178.6 (3) |
C8—C9—C10—C11 | −0.3 (6) | C22—C23—C24—C25 | −0.9 (5) |
C9—C10—C11—C12 | 0.4 (6) | C23—C24—C25—C26 | 0.9 (5) |
C10—C11—C12—C13 | 0.1 (5) | C24—C25—C26—C27 | −0.4 (5) |
C11—C12—C13—C8 | −0.6 (5) | C25—C26—C27—C22 | 0.0 (5) |
C9—C8—C13—C12 | 0.6 (5) | C23—C22—C27—C26 | 0.1 (5) |
C7—C8—C13—C12 | −178.3 (3) | C21—C22—C27—C26 | −178.2 (3) |
C3—C6—N1—C7 | 179.4 (3) | C17—C20—N2—C21 | 174.6 (3) |
C8—C7—N1—C6 | −119.2 (3) | C22—C21—N2—C20 | −112.8 (3) |
C14—C7—N1—C6 | 115.5 (4) | C28—C21—N2—C20 | 122.4 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H8···O1 | 0.88 | 1.94 | 2.597 (4) | 131 |
N2—H25···O3 | 0.88 | 1.95 | 2.603 (4) | 130 |
C14—H15···O2i | 0.98 | 2.55 | 3.532 (5) | 175 |
C14—H17···O4 | 0.98 | 2.66 | 3.482 (5) | 142 |
C28—H32···O4i | 0.98 | 2.54 | 3.512 (5) | 173 |
Symmetry code: (i) x−1, y, z. |
Comparison of torsion angles in the crystal
structures of 1–3
and
from
theoretical DFT calculations topCompound | Torsion angle | Crystal structure determination | DFT calculation |
1 | C8—C7—N—C6 | –94.4 (1) | –107.8 |
2 | C8—C7—N—C6 | -14.03 (14) | 0.0 |
| C9—C7—N—C6 | –134.31 (11) | –120.8 |
| C10—C7—N—C6 | 107.27 (11) | 120.8 |
3 | C14—C7—N1—C6 | 115.5 (4); 122.4 (3)* | –167.3 |
| C8—C7—N1—C6 | –119.2 (4); –112.8 (3)* | –43.3 |
*Values for the comparable bond in the second molecule. |