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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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S205698902300587X/wm5685sup1.cif
Contains datablocks 1, 2, 3, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S205698902300587X/wm56851sup5.hkl
Contains datablock 1

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S205698902300587X/wm56852sup6.hkl
Contains datablock 2

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S205698902300587X/wm56853sup7.hkl
Contains datablock 3

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S205698902300587X/wm56851sup5.cml
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S205698902300587X/wm56852sup6.cml
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S205698902300587X/wm56853sup7.cml
Supplementary material

CCDC references: 2279192; 2279191; 2279190

Key indicators

Structure: 1
  • Single-crystal X-ray study
  • T = 213 K
  • Mean [sigma](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 [sigma](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 [sigma](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

Computing details top

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
C13H15NO2F(000) = 464
Mr = 217.26Dx = 1.270 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 11.7356 (14) ÅCell parameters from 7396 reflections
b = 9.2401 (8) Åθ = 2.9–26.0°
c = 11.3970 (14) ŵ = 0.09 mm1
β = 113.148 (14)°T = 213 K
V = 1136.4 (2) Å3Block, clear yellow
Z = 40.33 × 0.15 × 0.12 mm
Data collection top
STOE IPDS 2
diffractometer
Rint = 0.078
rotation scansθmax = 26.0°, θmin = 2.9°
7396 measured reflectionsh = 1313
2159 independent reflectionsk = 1111
1414 reflections with I > 2σ(I)l = 1313
Refinement top
Refinement on F2Primary atom site location: iterative
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H-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 reflectionsΔρmax = 0.18 e Å3
147 parametersΔρmin = 0.17 e Å3
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
xyzUiso*/Ueq
C10.29032 (19)0.4837 (2)1.16212 (15)0.0391 (5)
H10.23340.41361.17240.059*
H20.27180.57901.18580.059*
H30.37470.45741.21650.059*
C20.27629 (16)0.48567 (19)1.02452 (14)0.0284 (4)
C30.34838 (15)0.58355 (17)0.98050 (14)0.0239 (4)
C40.43034 (16)0.69625 (18)1.06114 (14)0.0265 (4)
C50.4992 (2)0.7943 (2)1.00520 (17)0.0404 (5)
H40.44050.84130.92940.061*
H50.55710.73740.98270.061*
H60.54420.86701.06760.061*
C60.34363 (15)0.56658 (17)0.85623 (14)0.0244 (4)
H70.39490.62770.83240.029*
C70.27877 (17)0.45955 (19)0.64354 (14)0.0297 (4)
H90.26770.35730.61860.036*
H100.36100.48900.64920.036*
C80.18161 (16)0.54814 (17)0.53978 (14)0.0235 (4)
C90.15894 (17)0.51739 (19)0.41290 (15)0.0307 (4)
H110.20170.44120.39350.037*
C100.07407 (18)0.5979 (2)0.31512 (15)0.0353 (5)
H120.05880.57540.22980.042*
C110.01179 (18)0.7110 (2)0.34239 (16)0.0363 (5)
H130.04440.76700.27600.044*
C120.03245 (19)0.7418 (2)0.46829 (17)0.0394 (5)
H140.01080.81780.48730.047*
C130.11704 (17)0.66035 (19)0.56594 (16)0.0329 (4)
H150.13070.68160.65110.040*
N0.27486 (14)0.47394 (15)0.76962 (11)0.0290 (4)
H80.22450.41840.78840.035*
O10.20370 (13)0.39610 (15)0.95112 (11)0.0439 (4)
O20.44589 (13)0.71536 (15)1.17367 (10)0.0418 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0467 (13)0.0475 (12)0.0277 (9)0.0032 (10)0.0196 (9)0.0032 (8)
C20.0266 (10)0.0345 (10)0.0231 (8)0.0034 (8)0.0087 (7)0.0020 (7)
C30.0247 (10)0.0277 (9)0.0173 (7)0.0044 (7)0.0063 (7)0.0020 (6)
C40.0271 (10)0.0277 (9)0.0220 (8)0.0066 (7)0.0068 (7)0.0002 (7)
C50.0527 (14)0.0324 (10)0.0329 (9)0.0132 (9)0.0135 (9)0.0055 (8)
C60.0246 (10)0.0226 (8)0.0234 (8)0.0020 (7)0.0066 (7)0.0039 (7)
C70.0372 (11)0.0319 (9)0.0194 (8)0.0020 (8)0.0104 (7)0.0029 (7)
C80.0253 (10)0.0253 (8)0.0197 (8)0.0045 (7)0.0087 (7)0.0024 (6)
C90.0364 (11)0.0335 (10)0.0230 (8)0.0026 (8)0.0125 (7)0.0022 (7)
C100.0423 (12)0.0435 (11)0.0186 (8)0.0020 (9)0.0105 (8)0.0006 (8)
C110.0345 (12)0.0358 (11)0.0311 (9)0.0005 (8)0.0049 (8)0.0089 (8)
C120.0378 (12)0.0376 (11)0.0389 (10)0.0106 (9)0.0107 (9)0.0035 (8)
C130.0345 (11)0.0383 (10)0.0239 (8)0.0019 (8)0.0092 (8)0.0076 (7)
N0.0351 (9)0.0317 (8)0.0184 (7)0.0059 (7)0.0087 (6)0.0007 (6)
O10.0468 (9)0.0559 (9)0.0285 (7)0.0222 (7)0.0145 (6)0.0036 (6)
O20.0464 (9)0.0535 (8)0.0232 (6)0.0082 (7)0.0111 (6)0.0115 (6)
Geometric parameters (Å, º) top
C1—C21.511 (2)C7—C81.519 (2)
C1—H10.9700C7—H90.9800
C1—H20.9700C7—H100.9800
C1—H30.9700C8—C131.384 (2)
C2—O11.245 (2)C8—C91.393 (2)
C2—C31.456 (2)C9—C101.384 (2)
C3—C61.404 (2)C9—H110.9400
C3—C41.469 (2)C10—C111.379 (3)
C4—O21.2350 (19)C10—H120.9400
C4—C51.512 (3)C11—C121.388 (3)
C5—H40.9700C11—H130.9400
C5—H50.9700C12—C131.386 (2)
C5—H60.9700C12—H140.9400
C6—N1.316 (2)C13—H150.9400
C6—H70.9400N—H80.8700
C7—N1.462 (2)
C2—C1—H1109.5C8—C7—H9108.7
C2—C1—H2109.5N—C7—H10108.7
H1—C1—H2109.5C8—C7—H10108.7
C2—C1—H3109.5H9—C7—H10107.6
H1—C1—H3109.5C13—C8—C9118.63 (16)
H2—C1—H3109.5C13—C8—C7122.88 (14)
O1—C2—C3121.22 (14)C9—C8—C7118.47 (15)
O1—C2—C1117.12 (16)C10—C9—C8120.64 (17)
C3—C2—C1121.60 (15)C10—C9—H11119.7
C6—C3—C2118.70 (15)C8—C9—H11119.7
C6—C3—C4117.82 (15)C11—C10—C9120.23 (16)
C2—C3—C4123.44 (14)C11—C10—H12119.9
O2—C4—C3122.95 (16)C9—C10—H12119.9
O2—C4—C5117.85 (16)C10—C11—C12119.73 (17)
C3—C4—C5119.20 (14)C10—C11—H13120.1
C4—C5—H4109.5C12—C11—H13120.1
C4—C5—H5109.5C13—C12—C11119.84 (18)
H4—C5—H5109.5C13—C12—H14120.1
C4—C5—H6109.5C11—C12—H14120.1
H4—C5—H6109.5C8—C13—C12120.91 (16)
H5—C5—H6109.5C8—C13—H15119.5
N—C6—C3126.77 (16)C12—C13—H15119.5
N—C6—H7116.6C6—N—C7123.33 (16)
C3—C6—H7116.6C6—N—H8118.3
N—C7—C8114.34 (15)C7—N—H8118.3
N—C7—H9108.7
O1—C2—C3—C65.9 (2)N—C7—C8—C9165.58 (16)
C1—C2—C3—C6171.41 (17)C13—C8—C9—C100.3 (3)
O1—C2—C3—C4176.69 (17)C7—C8—C9—C10178.03 (17)
C1—C2—C3—C46.0 (3)C8—C9—C10—C110.8 (3)
C6—C3—C4—O2176.37 (17)C9—C10—C11—C121.5 (3)
C2—C3—C4—O21.1 (3)C10—C11—C12—C131.1 (3)
C6—C3—C4—C53.8 (2)C9—C8—C13—C120.7 (3)
C2—C3—C4—C5178.77 (16)C7—C8—C13—C12177.57 (18)
C2—C3—C6—N3.6 (3)C11—C12—C13—C80.0 (3)
C4—C3—C6—N178.82 (15)C3—C6—N—C7177.67 (16)
N—C7—C8—C1316.1 (2)C8—C7—N—C694.4 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N—H8···O10.871.972.6177 (18)130
C6—H7···O2i0.942.573.434 (2)154
Symmetry code: (i) x, y+3/2, z1/2.
3-[(tert-Butylamino)methylidene]pentan-2,4-dione (2) top
Crystal data top
C10H17NO2F(000) = 400
Mr = 183.24Dx = 1.177 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 9.8226 (7) ÅCell parameters from 2011 reflections
b = 9.8323 (6) Åθ = 3.7–29.5°
c = 11.2700 (8) ŵ = 0.08 mm1
β = 108.171 (5)°T = 170 K
V = 1034.16 (12) Å3Block, colourless
Z = 40.32 × 0.28 × 0.21 mm
Data collection top
STOE IPDS 2
diffractometer
Rint = 0.033
rotation scansθmax = 29.1°, θmin = 2.8°
7337 measured reflectionsh = 1313
2774 independent reflectionsk = 1313
2126 reflections with I > 2σ(I)l = 1115
Refinement top
Refinement on F2Primary atom site location: iterative
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036H-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 reflectionsΔρmax = 0.30 e Å3
123 parametersΔρmin = 0.14 e Å3
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
xyzUiso*/Ueq
C10.83575 (10)0.46662 (12)0.88153 (11)0.0344 (2)
H10.86320.48920.97060.052*
H20.88230.52990.83920.052*
H30.86600.37350.87150.052*
C20.67575 (9)0.47771 (10)0.82522 (10)0.0268 (2)
C30.60104 (9)0.41294 (10)0.70726 (9)0.0247 (2)
C40.67422 (10)0.36658 (10)0.62027 (10)0.0274 (2)
C50.59161 (12)0.28835 (12)0.50456 (10)0.0351 (2)
H40.51540.34600.45160.053*
H50.54930.20700.52900.053*
H60.65670.26140.45820.053*
C60.45217 (10)0.39420 (10)0.67456 (9)0.0245 (2)
H70.40750.34450.60030.029*
C70.21415 (9)0.41512 (10)0.71095 (9)0.0242 (2)
C80.14674 (10)0.35776 (12)0.58053 (9)0.0305 (2)
H90.19010.26940.57400.046*
H100.16320.42060.51890.046*
H110.04350.34630.56470.046*
C90.14777 (11)0.55234 (11)0.72323 (12)0.0355 (2)
H120.04490.54090.70970.053*
H130.16220.61540.66090.053*
H140.19350.58910.80710.053*
C100.19622 (11)0.31624 (12)0.80911 (10)0.0324 (2)
H150.09400.30270.79730.049*
H160.24280.35350.89260.049*
H170.24030.22890.80060.049*
N0.36968 (8)0.43920 (9)0.73734 (8)0.02652 (19)
H80.41150.48980.80300.032*
O10.60963 (7)0.53863 (9)0.88675 (8)0.0377 (2)
O20.80125 (8)0.39082 (10)0.63547 (8)0.0414 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0207 (4)0.0420 (6)0.0379 (6)0.0005 (4)0.0056 (4)0.0040 (5)
C20.0207 (4)0.0270 (5)0.0328 (5)0.0015 (3)0.0084 (4)0.0005 (4)
C30.0202 (4)0.0253 (4)0.0296 (5)0.0003 (3)0.0092 (3)0.0014 (4)
C40.0250 (4)0.0272 (5)0.0326 (5)0.0005 (4)0.0126 (4)0.0039 (4)
C50.0353 (5)0.0404 (6)0.0342 (6)0.0024 (4)0.0174 (4)0.0044 (4)
C60.0217 (4)0.0265 (4)0.0255 (4)0.0005 (3)0.0078 (3)0.0008 (4)
C70.0172 (4)0.0296 (4)0.0259 (5)0.0008 (3)0.0068 (3)0.0009 (4)
C80.0230 (4)0.0421 (6)0.0250 (5)0.0027 (4)0.0056 (4)0.0015 (4)
C90.0263 (5)0.0335 (5)0.0477 (7)0.0026 (4)0.0131 (4)0.0034 (5)
C100.0310 (5)0.0387 (6)0.0288 (5)0.0018 (4)0.0109 (4)0.0020 (4)
N0.0177 (3)0.0336 (4)0.0279 (4)0.0015 (3)0.0065 (3)0.0055 (3)
O10.0239 (3)0.0462 (5)0.0420 (5)0.0017 (3)0.0089 (3)0.0172 (4)
O20.0270 (4)0.0555 (5)0.0479 (5)0.0069 (3)0.0207 (3)0.0060 (4)
Geometric parameters (Å, º) top
C1—C21.5042 (13)C7—N1.4815 (11)
C1—H10.9800C7—C81.5197 (14)
C1—H20.9800C7—C91.5235 (14)
C1—H30.9800C7—C101.5237 (14)
C2—O11.2419 (12)C8—H90.9800
C2—C31.4502 (14)C8—H100.9800
C3—C61.4043 (12)C8—H110.9800
C3—C41.4578 (13)C9—H120.9800
C4—O21.2287 (12)C9—H130.9800
C4—C51.5135 (15)C9—H140.9800
C5—H40.9800C10—H150.9800
C5—H50.9800C10—H160.9800
C5—H60.9800C10—H170.9800
C6—N1.3079 (12)N—H80.8800
C6—H70.9500
C2—C1—H1109.5C8—C7—C9110.29 (8)
C2—C1—H2109.5N—C7—C10107.56 (8)
H1—C1—H2109.5C8—C7—C10110.56 (8)
C2—C1—H3109.5C9—C7—C10110.45 (8)
H1—C1—H3109.5C7—C8—H9109.5
H2—C1—H3109.5C7—C8—H10109.5
O1—C2—C3121.36 (8)H9—C8—H10109.5
O1—C2—C1117.32 (9)C7—C8—H11109.5
C3—C2—C1121.22 (8)H9—C8—H11109.5
C6—C3—C2119.08 (8)H10—C8—H11109.5
C6—C3—C4118.29 (9)C7—C9—H12109.5
C2—C3—C4122.63 (8)C7—C9—H13109.5
O2—C4—C3122.54 (10)H12—C9—H13109.5
O2—C4—C5117.84 (9)C7—C9—H14109.5
C3—C4—C5119.61 (8)H12—C9—H14109.5
C4—C5—H4109.5H13—C9—H14109.5
C4—C5—H5109.5C7—C10—H15109.5
H4—C5—H5109.5C7—C10—H16109.5
C4—C5—H6109.5H15—C10—H16109.5
H4—C5—H6109.5C7—C10—H17109.5
H5—C5—H6109.5H15—C10—H17109.5
N—C6—C3125.72 (9)H16—C10—H17109.5
N—C6—H7117.1C6—N—C7127.69 (8)
C3—C6—H7117.1C6—N—H8116.2
N—C7—C8111.38 (8)C7—N—H8116.2
N—C7—C9106.50 (8)
O1—C2—C3—C613.30 (15)C2—C3—C4—C5174.41 (9)
C1—C2—C3—C6163.02 (9)C2—C3—C6—N5.34 (15)
O1—C2—C3—C4166.44 (10)C4—C3—C6—N174.40 (9)
C1—C2—C3—C417.25 (15)C3—C6—N—C7175.98 (9)
C6—C3—C4—O2172.63 (10)C8—C7—N—C614.03 (14)
C2—C3—C4—O27.11 (15)C9—C7—N—C6134.31 (11)
C6—C3—C4—C55.85 (14)C10—C7—N—C6107.27 (11)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N—H8···O10.90 (2)1.90 (2)2.6322 (16)136 (2)
C5—H4···O1i0.97 (2)2.69 (2)3.630 (2)163 (2)
C8—H11···O2ii0.98 (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
C14H17NO2F(000) = 496
Mr = 231.28Dx = 1.235 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
a = 10.0459 (9) ÅCell parameters from 17500 reflections
b = 8.1011 (5) Åθ = 2.5–29.7°
c = 15.7052 (13) ŵ = 0.08 mm1
β = 103.372 (7)°T = 170 K
V = 1243.48 (17) Å3Block, colourless
Z = 40.44 × 0.21 × 0.14 mm
Data collection top
STOE IPDS 2T
diffractometer
Rint = 0.042
rotation scansθmax = 29.3°, θmin = 2.7°
11343 measured reflectionsh = 1313
11343 independent reflectionsk = 1111
9181 reflections with I > 2σ(I)l = 2121
Refinement top
Refinement on F2H-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) = 0.131Δρmax = 0.27 e Å3
S = 1.05Δρmin = 0.28 e Å3
11343 reflectionsExtinction correction: SHELXL-2018/3 (Sheldrick 2014, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
315 parametersExtinction coefficient: 0.044 (6)
1 restraintAbsolute structure: Classical Flack method preferred over Parsons because s.u. lower.
Primary atom site location: iterativeAbsolute 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
xyzUiso*/Ueq
C11.1723 (4)0.7494 (5)0.1031 (3)0.0494 (10)
H11.22970.72430.16100.074*
H21.17120.86890.09320.074*
H31.20930.69370.05810.074*
C21.0289 (3)0.6899 (4)0.0981 (2)0.0307 (6)
C30.9990 (3)0.5183 (4)0.1133 (2)0.0300 (6)
C41.1060 (4)0.3913 (4)0.1369 (2)0.0364 (7)
C51.0664 (4)0.2163 (5)0.1548 (3)0.0455 (9)
H41.14920.15190.17880.068*
H51.01610.16550.10020.068*
H61.00830.21830.19710.068*
C60.8627 (3)0.4704 (4)0.1047 (2)0.0309 (6)
H70.84650.35690.11370.037*
C70.6134 (3)0.5100 (4)0.0761 (2)0.0315 (6)
H90.61580.38790.08560.038*
C80.5280 (3)0.5433 (4)0.0157 (2)0.0289 (6)
C90.5840 (3)0.6073 (4)0.0821 (2)0.0335 (7)
H100.67870.63360.06980.040*
C100.5044 (4)0.6331 (5)0.1654 (2)0.0373 (7)
H110.54460.67740.20960.045*
C110.3657 (4)0.5946 (5)0.1849 (2)0.0379 (7)
H120.31090.61160.24210.045*
C120.3084 (3)0.5308 (4)0.1193 (2)0.0349 (7)
H130.21380.50400.13190.042*
C130.3882 (3)0.5062 (4)0.0357 (2)0.0310 (6)
H140.34750.46350.00850.037*
C140.5532 (4)0.5888 (5)0.1472 (2)0.0408 (8)
H150.46050.54630.14290.061*
H160.54960.70890.13940.061*
H170.61080.56190.20490.061*
N10.7550 (3)0.5668 (3)0.08533 (19)0.0329 (6)
H80.76840.67240.07730.039*
O10.9351 (3)0.7936 (3)0.07897 (18)0.0389 (6)
O21.2273 (3)0.4204 (4)0.1427 (2)0.0560 (8)
C150.5900 (4)0.2575 (5)0.4013 (3)0.0407 (8)
H180.59560.13690.40630.061*
H190.65390.30750.45130.061*
H200.61380.29210.34690.061*
C160.4461 (3)0.3127 (4)0.4004 (2)0.0326 (7)
C170.4062 (3)0.4854 (4)0.3894 (2)0.0297 (6)
C180.4988 (3)0.6153 (4)0.3729 (2)0.0327 (7)
C190.4459 (4)0.7895 (5)0.3518 (3)0.0454 (9)
H210.43510.84390.40550.068*
H220.35720.78540.30960.068*
H230.51110.85180.32660.068*
C200.2753 (3)0.5311 (4)0.3967 (2)0.0302 (6)
H240.25350.64520.39090.036*
C210.0473 (3)0.4873 (4)0.4252 (2)0.0316 (6)
H260.04240.60970.41680.038*
C220.0360 (3)0.4507 (4)0.5191 (2)0.0280 (6)
C230.1422 (3)0.3812 (4)0.5812 (2)0.0323 (6)
H270.22490.35250.56540.039*
C240.1294 (4)0.3531 (4)0.6661 (2)0.0367 (7)
H280.20270.30400.70760.044*
C250.0096 (4)0.3967 (4)0.6906 (2)0.0364 (7)
H290.00110.37900.74890.044*
C260.0973 (3)0.4662 (4)0.6291 (2)0.0332 (7)
H300.17960.49550.64530.040*
C270.0847 (3)0.4932 (4)0.5438 (2)0.0297 (6)
H310.15860.54080.50210.036*
C280.0694 (4)0.4104 (5)0.3571 (2)0.0371 (7)
H320.15700.45180.36560.056*
H330.06630.29010.36350.056*
H340.05970.44000.29830.056*
N20.1787 (3)0.4311 (3)0.4108 (2)0.0341 (6)
H250.19440.32420.41150.041*
O30.3635 (3)0.2058 (3)0.4110 (2)0.0472 (7)
O40.6200 (2)0.5899 (3)0.37485 (18)0.0418 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.032 (2)0.0401 (19)0.080 (3)0.0035 (15)0.0196 (19)0.002 (2)
C20.0263 (15)0.0337 (16)0.0336 (15)0.0006 (12)0.0100 (12)0.0033 (13)
C30.0267 (15)0.0322 (15)0.0324 (14)0.0005 (12)0.0096 (11)0.0028 (13)
C40.0285 (16)0.0407 (18)0.0424 (17)0.0043 (14)0.0132 (13)0.0039 (15)
C50.039 (2)0.0408 (19)0.061 (2)0.0109 (16)0.0206 (18)0.0113 (18)
C60.0273 (15)0.0323 (15)0.0336 (15)0.0007 (12)0.0077 (12)0.0000 (13)
C70.0221 (14)0.0322 (15)0.0404 (16)0.0024 (12)0.0074 (12)0.0036 (14)
C80.0240 (14)0.0258 (13)0.0380 (15)0.0005 (11)0.0093 (12)0.0014 (12)
C90.0254 (15)0.0369 (16)0.0394 (16)0.0027 (13)0.0103 (12)0.0002 (14)
C100.0348 (18)0.0418 (18)0.0366 (16)0.0046 (14)0.0112 (14)0.0006 (15)
C110.0349 (17)0.0395 (17)0.0367 (16)0.0039 (15)0.0032 (13)0.0003 (15)
C120.0267 (15)0.0312 (15)0.0459 (17)0.0056 (13)0.0064 (13)0.0012 (14)
C130.0250 (14)0.0281 (14)0.0417 (16)0.0025 (12)0.0113 (12)0.0009 (13)
C140.0330 (17)0.053 (2)0.0373 (16)0.0049 (16)0.0109 (14)0.0009 (16)
N10.0231 (13)0.0320 (13)0.0425 (14)0.0017 (10)0.0056 (11)0.0029 (11)
O10.0307 (13)0.0320 (12)0.0555 (15)0.0020 (10)0.0129 (11)0.0031 (11)
O20.0260 (13)0.0546 (16)0.089 (2)0.0059 (12)0.0179 (14)0.0152 (16)
C150.0285 (17)0.0375 (17)0.059 (2)0.0022 (14)0.0153 (16)0.0033 (16)
C160.0283 (16)0.0312 (15)0.0410 (17)0.0016 (12)0.0134 (13)0.0043 (14)
C170.0245 (14)0.0317 (15)0.0339 (14)0.0030 (12)0.0091 (11)0.0019 (13)
C180.0267 (15)0.0382 (16)0.0345 (15)0.0058 (13)0.0098 (12)0.0018 (14)
C190.0350 (19)0.0384 (18)0.067 (2)0.0026 (15)0.0194 (17)0.0120 (18)
C200.0262 (14)0.0303 (14)0.0357 (14)0.0023 (12)0.0107 (12)0.0010 (12)
C210.0227 (14)0.0301 (15)0.0442 (16)0.0031 (12)0.0123 (12)0.0020 (14)
C220.0217 (13)0.0239 (13)0.0385 (15)0.0015 (10)0.0075 (11)0.0019 (12)
C230.0242 (14)0.0308 (15)0.0409 (16)0.0016 (12)0.0055 (12)0.0029 (13)
C240.0342 (17)0.0321 (15)0.0389 (16)0.0004 (13)0.0016 (14)0.0023 (14)
C250.0420 (19)0.0315 (15)0.0354 (15)0.0029 (14)0.0085 (14)0.0047 (14)
C260.0314 (16)0.0313 (15)0.0400 (16)0.0008 (13)0.0147 (13)0.0022 (14)
C270.0243 (14)0.0277 (13)0.0379 (15)0.0013 (11)0.0088 (11)0.0005 (13)
C280.0285 (16)0.0476 (19)0.0355 (16)0.0029 (14)0.0079 (13)0.0009 (15)
N20.0254 (13)0.0303 (13)0.0510 (16)0.0010 (10)0.0175 (12)0.0009 (12)
O30.0349 (14)0.0309 (12)0.082 (2)0.0018 (10)0.0256 (14)0.0005 (13)
O40.0253 (11)0.0447 (13)0.0583 (15)0.0045 (10)0.0152 (11)0.0020 (13)
Geometric parameters (Å, º) top
C1—C21.504 (5)C15—C161.510 (5)
C1—H10.9800C15—H180.9800
C1—H20.9800C15—H190.9800
C1—H30.9800C15—H200.9800
C2—O11.246 (4)C16—O31.236 (4)
C2—C31.453 (4)C16—C171.455 (4)
C3—C61.399 (4)C17—C201.396 (4)
C3—C41.472 (5)C17—C181.468 (4)
C4—O21.224 (4)C18—O41.228 (4)
C4—C51.517 (5)C18—C191.518 (5)
C5—H40.9800C19—H210.9800
C5—H50.9800C19—H220.9800
C5—H60.9800C19—H230.9800
C6—N11.311 (4)C20—N21.321 (4)
C6—H70.9500C20—H240.9500
C7—N11.470 (4)C21—N21.463 (4)
C7—C81.522 (4)C21—C281.524 (5)
C7—C141.527 (5)C21—C221.534 (4)
C7—H91.0000C21—H261.0000
C8—C91.394 (4)C22—C231.387 (4)
C8—C131.399 (4)C22—C271.400 (4)
C9—C101.383 (5)C23—C241.388 (5)
C9—H100.9500C23—H270.9500
C10—C111.392 (5)C24—C251.392 (5)
C10—H110.9500C24—H280.9500
C11—C121.390 (5)C25—C261.387 (5)
C11—H120.9500C25—H290.9500
C12—C131.385 (5)C26—C271.392 (4)
C12—H130.9500C26—H300.9500
C13—H140.9500C27—H310.9500
C14—H150.9800C28—H320.9800
C14—H160.9800C28—H330.9800
C14—H170.9800C28—H340.9800
N1—H80.8800N2—H250.8800
C2—C1—H1109.5C16—C15—H18109.5
C2—C1—H2109.5C16—C15—H19109.5
H1—C1—H2109.5H18—C15—H19109.5
C2—C1—H3109.5C16—C15—H20109.5
H1—C1—H3109.5H18—C15—H20109.5
H2—C1—H3109.5H19—C15—H20109.5
O1—C2—C3120.7 (3)O3—C16—C17121.0 (3)
O1—C2—C1117.3 (3)O3—C16—C15117.5 (3)
C3—C2—C1122.0 (3)C17—C16—C15121.5 (3)
C6—C3—C2119.0 (3)C20—C17—C16119.0 (3)
C6—C3—C4118.1 (3)C20—C17—C18118.2 (3)
C2—C3—C4122.9 (3)C16—C17—C18122.8 (3)
O2—C4—C3122.7 (3)O4—C18—C17122.8 (3)
O2—C4—C5117.7 (3)O4—C18—C19117.2 (3)
C3—C4—C5119.5 (3)C17—C18—C19120.1 (3)
C4—C5—H4109.5C18—C19—H21109.5
C4—C5—H5109.5C18—C19—H22109.5
H4—C5—H5109.5H21—C19—H22109.5
C4—C5—H6109.5C18—C19—H23109.5
H4—C5—H6109.5H21—C19—H23109.5
H5—C5—H6109.5H22—C19—H23109.5
N1—C6—C3126.4 (3)N2—C20—C17126.4 (3)
N1—C6—H7116.8N2—C20—H24116.8
C3—C6—H7116.8C17—C20—H24116.8
N1—C7—C8111.0 (3)N2—C21—C28109.8 (3)
N1—C7—C14109.6 (3)N2—C21—C22111.0 (3)
C8—C7—C14112.8 (3)C28—C21—C22112.3 (3)
N1—C7—H9107.8N2—C21—H26107.8
C8—C7—H9107.8C28—C21—H26107.8
C14—C7—H9107.8C22—C21—H26107.8
C9—C8—C13118.0 (3)C23—C22—C27118.6 (3)
C9—C8—C7122.6 (3)C23—C22—C21122.6 (3)
C13—C8—C7119.4 (3)C27—C22—C21118.7 (3)
C10—C9—C8121.3 (3)C22—C23—C24121.0 (3)
C10—C9—H10119.4C22—C23—H27119.5
C8—C9—H10119.4C24—C23—H27119.5
C9—C10—C11120.3 (3)C23—C24—C25120.1 (3)
C9—C10—H11119.9C23—C24—H28119.9
C11—C10—H11119.9C25—C24—H28119.9
C12—C11—C10119.1 (3)C26—C25—C24119.4 (3)
C12—C11—H12120.5C26—C25—H29120.3
C10—C11—H12120.5C24—C25—H29120.3
C13—C12—C11120.5 (3)C25—C26—C27120.4 (3)
C13—C12—H13119.8C25—C26—H30119.8
C11—C12—H13119.8C27—C26—H30119.8
C12—C13—C8120.9 (3)C26—C27—C22120.4 (3)
C12—C13—H14119.6C26—C27—H31119.8
C8—C13—H14119.6C22—C27—H31119.8
C7—C14—H15109.5C21—C28—H32109.5
C7—C14—H16109.5C21—C28—H33109.5
H15—C14—H16109.5H32—C28—H33109.5
C7—C14—H17109.5C21—C28—H34109.5
H15—C14—H17109.5H32—C28—H34109.5
H16—C14—H17109.5H33—C28—H34109.5
C6—N1—C7124.4 (3)C20—N2—C21124.0 (3)
C6—N1—H8117.8C20—N2—H25118.0
C7—N1—H8117.8C21—N2—H25118.0
O1—C2—C3—C61.2 (5)O3—C16—C17—C204.2 (5)
C1—C2—C3—C6177.8 (3)C15—C16—C17—C20174.5 (3)
O1—C2—C3—C4179.4 (3)O3—C16—C17—C18177.2 (3)
C1—C2—C3—C41.6 (5)C15—C16—C17—C184.1 (5)
C6—C3—C4—O2177.2 (4)C20—C17—C18—O4172.0 (3)
C2—C3—C4—O22.2 (5)C16—C17—C18—O46.7 (5)
C6—C3—C4—C52.7 (5)C20—C17—C18—C198.3 (5)
C2—C3—C4—C5177.8 (3)C16—C17—C18—C19173.1 (3)
C2—C3—C6—N11.5 (5)C16—C17—C20—N21.8 (5)
C4—C3—C6—N1179.0 (3)C18—C17—C20—N2179.5 (3)
N1—C7—C8—C94.7 (4)N2—C21—C22—C233.2 (4)
C14—C7—C8—C9128.1 (3)C28—C21—C22—C23126.6 (3)
N1—C7—C8—C13176.5 (3)N2—C21—C22—C27178.7 (3)
C14—C7—C8—C1353.1 (4)C28—C21—C22—C2755.3 (4)
C13—C8—C9—C100.2 (5)C27—C22—C23—C240.4 (5)
C7—C8—C9—C10178.7 (3)C21—C22—C23—C24178.6 (3)
C8—C9—C10—C110.3 (6)C22—C23—C24—C250.9 (5)
C9—C10—C11—C120.4 (6)C23—C24—C25—C260.9 (5)
C10—C11—C12—C130.1 (5)C24—C25—C26—C270.4 (5)
C11—C12—C13—C80.6 (5)C25—C26—C27—C220.0 (5)
C9—C8—C13—C120.6 (5)C23—C22—C27—C260.1 (5)
C7—C8—C13—C12178.3 (3)C21—C22—C27—C26178.2 (3)
C3—C6—N1—C7179.4 (3)C17—C20—N2—C21174.6 (3)
C8—C7—N1—C6119.2 (3)C22—C21—N2—C20112.8 (3)
C14—C7—N1—C6115.5 (4)C28—C21—N2—C20122.4 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H8···O10.881.942.597 (4)131
N2—H25···O30.881.952.603 (4)130
C14—H15···O2i0.982.553.532 (5)175
C14—H17···O40.982.663.482 (5)142
C28—H32···O4i0.982.543.512 (5)173
Symmetry code: (i) x1, y, z.
Comparison of torsion angles in the crystal structures of 13 and from theoretical DFT calculations top
CompoundTorsion angleCrystal structure determinationDFT calculation
1C8—C7—N—C6–94.4 (1)–107.8
2C8—C7—N—C6-14.03 (14)0.0
C9—C7—N—C6–134.31 (11)–120.8
C10—C7—N—C6107.27 (11)120.8
3C14—C7—N1—C6115.5 (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.
 

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