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The title compound, C25H32N2O3, was synthesized as part of a series of related compounds using a modified Eschenmoser-Claisen rearrangement reaction. The compound is racemic and the structure features a centrosymmetric hydrogen-bonded dimerization along with some aromatic stacking stabilization.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536806032041/bt2166sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536806032041/bt2166Isup2.hkl
Contains datablock I

CCDC reference: 620695

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.049
  • wR factor = 0.143
  • Data-to-parameter ratio = 15.8

checkCIF/PLATON results

No syntax errors found



Alert level A PLAT410_ALERT_2_A Short Intra H...H Contact H9 .. H11 .. 1.77 Ang.
Author Response: This unusally short H...H contact distance is discussed in the text of the paper, with reference made to Fourier maps to help determine the likely hydrogen atom location and show that this would appear to be a genuine observation, even though the hydrogen atom positions are constrained.

Alert level B PLAT230_ALERT_2_B Hirshfeld Test Diff for C17 - C18 .. 9.19 su
Alert level C PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ? PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 3.15 Ratio PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.83 Ratio PLAT230_ALERT_2_C Hirshfeld Test Diff for C18 - C19 .. 5.26 su PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C6 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C11 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C12 PLAT368_ALERT_2_C Short C(sp2)-C(sp2) Bond C18 - C19 ... 1.22 Ang.
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
1 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 8 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 8 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Computing details top

Data collection: APEXII (Bruker, 2003); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Version 1.4; Macrae et al., 2006); software used to prepare material for publication: SHELXTL, publCIF (Westrip, 2006) and local programs.

(1R,2S)-Benzyl N-[3-(diisopropylaminocarbonyl)-2-phenylprop-3-enyl]carbamate top
Crystal data top
C25H32N2O3Z = 2
Mr = 408.53F(000) = 440
Triclinic, P1Dx = 1.147 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 10.3807 (12) ÅCell parameters from 8655 reflections
b = 11.2172 (14) Åθ = 2.1–24.4°
c = 11.7700 (14) ŵ = 0.08 mm1
α = 112.085 (7)°T = 293 K
β = 108.206 (7)°Block, colourless
γ = 93.159 (7)°0.40 × 0.30 × 0.20 mm
V = 1183.0 (2) Å3
Data collection top
Bruker APEXII CCD
diffractometer
4406 independent reflections
Radiation source: sealed tube3298 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.032
ω and φ scansθmax = 25.5°, θmin = 2.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
h = 1211
Tmin = 0.891, Tmax = 0.985k = 1312
32705 measured reflectionsl = 014
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049Hydrogen site location: difference Fourier map
wR(F2) = 0.143H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0645P)2 + 0.2666P]
where P = (Fo2 + 2Fc2)/3
4406 reflections(Δ/σ)max < 0.001
279 parametersΔρmax = 0.29 e Å3
0 restraintsΔρmin = 0.21 e Å3
Special details top

Experimental. Data for this structure were collected at room temperature and so the anisotropic displacement ellipsoids are somewhat larger than is usually the case with low temperature data sets (C14 in particular). We believe that that their size results from high thermal vibration, not disorder, and that they would be appreciably reduced in size if data were collected at low temperature.

Two of the hydrogen atoms, H9 and H11, have a close approach of only 1.77 Å. Figure 2 shows a three-dimensional Fourier difference electron density map (created using Fourier3D (Tooke & Spek, 2005)) of the residual density surrounding C9 and C11 indicating the likelihood of these two hydrogen atoms facing one another. Here the hydrogen atoms were placed based on the positions of peaks in the Fourier map and then refined with constrained geometry. Hydrogen atom location is always uncertain with X-ray data and so whilst we note the close spacing between these atoms, we can make no further comment as to their behaviour.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. 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 > σ(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.37086 (11)0.10901 (13)0.28031 (11)0.0664 (4)
O20.15650 (13)0.00555 (18)0.14321 (13)0.0907 (5)
O30.40339 (11)0.17134 (12)0.11876 (13)0.0633 (3)
N10.32119 (15)0.03139 (14)0.06589 (13)0.0566 (4)
H1N0.402 (2)0.0651 (19)0.0871 (19)0.067 (6)*
N20.19721 (14)0.28915 (13)0.16464 (14)0.0562 (4)
C10.4781 (2)0.1753 (2)0.6168 (2)0.0856 (7)
H10.43700.09400.60580.103*
C20.5776 (3)0.2573 (3)0.7360 (2)0.1000 (8)
H20.60380.23090.80470.120*
C30.6372 (3)0.3764 (3)0.7530 (2)0.0918 (7)
H30.70350.43240.83360.110*
C40.6000 (2)0.4136 (2)0.6521 (3)0.0923 (7)
H40.64130.49510.66360.111*
C50.5016 (2)0.3316 (2)0.5330 (2)0.0784 (6)
H50.47760.35800.46430.094*
C60.43863 (17)0.21225 (19)0.51382 (17)0.0608 (5)
C70.3253 (2)0.1249 (2)0.38748 (18)0.0781 (6)
H7A0.30220.04010.38780.094*
H7B0.24330.16340.37760.094*
C80.27257 (17)0.04040 (18)0.15967 (17)0.0586 (4)
C90.23741 (16)0.04363 (16)0.07198 (15)0.0503 (4)
H90.14000.05990.08170.060*
C100.28382 (15)0.17476 (16)0.12062 (15)0.0487 (4)
C110.0584 (2)0.3009 (2)0.1557 (3)0.0890 (7)
H110.04290.21180.11490.107*
C120.2412 (2)0.41378 (18)0.2243 (2)0.0708 (5)
H120.16300.48420.25180.085*
C130.0486 (3)0.3696 (3)0.0692 (3)0.1234 (11)
H13A0.06700.45630.10470.185*
H13B0.04260.37530.06580.185*
H13C0.11520.32080.01790.185*
C140.0530 (3)0.3679 (3)0.2929 (4)0.1534 (16)
H14A0.03730.32770.34770.230*
H14B0.14240.35880.28690.230*
H14C0.04950.45930.33040.230*
C150.2669 (4)0.4265 (3)0.3477 (3)0.1110 (9)
H15A0.18960.40780.40430.166*
H15B0.27820.51420.39250.166*
H15C0.34920.36550.32450.166*
C160.3626 (3)0.4370 (3)0.1276 (3)0.1016 (8)
H16A0.44440.37540.10440.152*
H16B0.37690.52470.16750.152*
H16C0.34310.42570.05000.152*
C170.25434 (18)0.03131 (17)0.15411 (17)0.0574 (4)
H170.35320.05390.13680.069*
C180.2006 (3)0.1577 (2)0.1117 (2)0.0841 (6)
H180.11400.15040.10460.101*
C190.2574 (4)0.2681 (3)0.0858 (4)0.1287 (11)
H19A0.34420.28150.09120.154*
H19B0.21390.33870.06060.154*
C210.03861 (19)0.0778 (2)0.35839 (19)0.0702 (5)
H210.01390.04370.30690.084*
C220.0267 (2)0.1527 (2)0.4914 (2)0.0808 (6)
H220.12260.16830.52880.097*
C230.0484 (2)0.2041 (2)0.5687 (2)0.0770 (6)
H230.00420.25450.65840.092*
C240.1900 (2)0.1803 (2)0.5125 (2)0.0776 (6)
H240.24190.21450.56460.093*
C250.2553 (2)0.1065 (2)0.38003 (19)0.0656 (5)
H250.35120.09220.34320.079*
C260.18124 (17)0.05287 (17)0.30049 (16)0.0537 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0459 (6)0.0900 (9)0.0462 (6)0.0046 (6)0.0158 (5)0.0136 (6)
O20.0506 (7)0.1374 (14)0.0588 (8)0.0217 (8)0.0175 (6)0.0215 (8)
O30.0426 (6)0.0640 (8)0.0789 (8)0.0027 (5)0.0227 (6)0.0253 (6)
N10.0437 (8)0.0618 (9)0.0473 (8)0.0100 (7)0.0148 (6)0.0090 (6)
N20.0463 (7)0.0491 (8)0.0611 (8)0.0029 (6)0.0150 (6)0.0155 (6)
C10.0966 (16)0.0888 (15)0.0607 (12)0.0095 (12)0.0246 (11)0.0267 (11)
C20.1067 (19)0.124 (2)0.0510 (12)0.0013 (16)0.0146 (12)0.0310 (13)
C30.0812 (15)0.0967 (18)0.0596 (13)0.0010 (13)0.0160 (11)0.0028 (12)
C40.0805 (15)0.0700 (14)0.1017 (18)0.0014 (11)0.0250 (14)0.0184 (13)
C50.0685 (12)0.0816 (14)0.0813 (14)0.0098 (11)0.0201 (11)0.0361 (12)
C60.0489 (9)0.0767 (12)0.0494 (9)0.0057 (8)0.0209 (8)0.0168 (8)
C70.0572 (11)0.1112 (17)0.0526 (10)0.0058 (11)0.0216 (9)0.0216 (10)
C80.0441 (9)0.0671 (11)0.0514 (9)0.0025 (8)0.0143 (7)0.0151 (8)
C90.0399 (8)0.0522 (9)0.0465 (8)0.0043 (7)0.0123 (7)0.0122 (7)
C100.0410 (8)0.0538 (9)0.0423 (8)0.0026 (7)0.0100 (6)0.0161 (7)
C110.0502 (11)0.0645 (12)0.139 (2)0.0047 (9)0.0318 (12)0.0319 (13)
C120.0793 (13)0.0512 (10)0.0743 (12)0.0031 (9)0.0279 (10)0.0191 (9)
C130.109 (2)0.124 (2)0.154 (3)0.0081 (17)0.078 (2)0.055 (2)
C140.0580 (14)0.134 (3)0.221 (4)0.0304 (16)0.0285 (19)0.095 (3)
C150.166 (3)0.0796 (16)0.0830 (16)0.0247 (16)0.0615 (18)0.0154 (13)
C160.1081 (19)0.0896 (17)0.125 (2)0.0377 (15)0.0423 (17)0.0607 (16)
C170.0551 (10)0.0528 (10)0.0594 (10)0.0012 (8)0.0188 (8)0.0207 (8)
C180.0968 (16)0.0620 (13)0.0820 (14)0.0072 (11)0.0227 (12)0.0267 (11)
C190.126 (2)0.0743 (18)0.170 (3)0.0125 (16)0.046 (2)0.0412 (19)
C210.0545 (10)0.0935 (14)0.0609 (11)0.0153 (10)0.0247 (9)0.0270 (10)
C220.0582 (11)0.1114 (18)0.0616 (12)0.0100 (11)0.0146 (9)0.0305 (12)
C230.0864 (15)0.0849 (14)0.0537 (11)0.0155 (11)0.0211 (10)0.0261 (10)
C240.0846 (15)0.0964 (16)0.0638 (12)0.0344 (12)0.0386 (11)0.0337 (11)
C250.0564 (10)0.0841 (13)0.0680 (12)0.0194 (9)0.0281 (9)0.0384 (10)
C260.0536 (9)0.0565 (10)0.0567 (9)0.0087 (8)0.0219 (8)0.0280 (8)
Geometric parameters (Å, º) top
O1—C71.435 (2)C12—C161.521 (3)
O1—C81.355 (2)C13—H13A0.9600
O2—C81.211 (2)C13—H13B0.9600
O3—C101.2328 (19)C13—H13C0.9600
N1—H1N0.82 (2)C14—H14A0.9600
N1—C81.324 (2)C14—H14B0.9600
N1—C91.452 (2)C14—H14C0.9600
N2—C101.343 (2)C15—H15A0.9600
N2—C111.480 (2)C15—H15B0.9600
N2—C121.479 (2)C15—H15C0.9600
C1—H10.9300C16—H16A0.9600
C1—C21.379 (3)C16—H16B0.9600
C1—C61.376 (3)C16—H16C0.9600
C2—H20.9300C17—H170.9800
C2—C31.357 (4)C17—C181.517 (3)
C3—H30.9300C17—C261.522 (2)
C3—C41.356 (4)C18—H180.9300
C4—H40.9300C18—C191.224 (3)
C4—C51.373 (3)C19—H19A0.9300
C5—H50.9300C19—H19B0.9300
C5—C61.362 (3)C21—H210.9300
C6—C71.496 (3)C21—C221.379 (3)
C7—H7A0.9700C21—C261.384 (2)
C7—H7B0.9700C22—H220.9300
C9—H90.9800C22—C231.366 (3)
C9—C101.530 (2)C23—H230.9300
C9—C171.540 (2)C23—C241.373 (3)
C11—H110.9800C24—H240.9300
C11—C131.512 (4)C24—C251.373 (3)
C11—C141.529 (4)C25—H250.9300
C12—H120.9800C25—C261.381 (2)
C12—C151.514 (3)
C7—O1—C8114.41 (13)C11—C13—H13A109.5
H1N—N1—C8118.7 (14)C11—C13—H13B109.5
H1N—N1—C9119.8 (14)C11—C13—H13C109.5
C8—N1—C9121.37 (14)H13A—C13—H13B109.5
C10—N2—C11124.39 (15)H13A—C13—H13C109.5
C10—N2—C12119.41 (14)H13B—C13—H13C109.5
C11—N2—C12116.20 (14)C11—C14—H14A109.5
H1—C1—C2119.5C11—C14—H14B109.5
H1—C1—C6119.5C11—C14—H14C109.5
C2—C1—C6120.9 (2)H14A—C14—H14B109.5
C1—C2—H2120.1H14A—C14—H14C109.5
C1—C2—C3119.8 (2)H14B—C14—H14C109.5
H2—C2—C3120.1C12—C15—H15A109.5
C2—C3—H3120.1C12—C15—H15B109.5
C2—C3—C4119.9 (2)C12—C15—H15C109.5
H3—C3—C4120.1H15A—C15—H15B109.5
C3—C4—H4119.8H15A—C15—H15C109.5
C3—C4—C5120.3 (2)H15B—C15—H15C109.5
H4—C4—C5119.8C12—C16—H16A109.5
C4—C5—H5119.5C12—C16—H16B109.5
C4—C5—C6121.0 (2)C12—C16—H16C109.5
H5—C5—C6119.5H16A—C16—H16B109.5
C1—C6—C5118.01 (18)H16A—C16—H16C109.5
C1—C6—C7120.08 (19)H16B—C16—H16C109.5
C5—C6—C7121.86 (19)C9—C17—H17108.3
O1—C7—C6109.04 (14)C9—C17—C18109.63 (16)
O1—C7—H7A109.9C9—C17—C26111.24 (13)
O1—C7—H7B109.9H17—C17—C18108.3
C6—C7—H7A109.9H17—C17—C26108.3
C6—C7—H7B109.9C18—C17—C26111.11 (15)
H7A—C7—H7B108.3C17—C18—H18116.1
O1—C8—O2123.01 (16)C17—C18—C19127.8 (3)
O1—C8—N1111.05 (14)H18—C18—C19116.1
O2—C8—N1125.94 (16)C18—C19—H19A120.0
N1—C9—H9109.4C18—C19—H19B120.0
N1—C9—C10108.63 (13)H19A—C19—H19B120.0
N1—C9—C17110.69 (13)H21—C21—C22119.6
H9—C9—C10109.4H21—C21—C26119.6
H9—C9—C17109.4C22—C21—C26120.84 (18)
C10—C9—C17109.41 (13)C21—C22—H22119.7
O3—C10—N2121.35 (16)C21—C22—C23120.51 (19)
O3—C10—C9117.39 (14)H22—C22—C23119.7
N2—C10—C9121.26 (14)C22—C23—H23120.4
N2—C11—H11107.4C22—C23—C24119.29 (19)
N2—C11—C13111.9 (2)H23—C23—C24120.4
N2—C11—C14110.4 (2)C23—C24—H24119.8
H11—C11—C13107.4C23—C24—C25120.37 (19)
H11—C11—C14107.4H24—C24—C25119.8
C13—C11—C14111.9 (2)C24—C25—H25119.4
N2—C12—H12106.4C24—C25—C26121.18 (18)
N2—C12—C15111.74 (18)H25—C25—C26119.4
N2—C12—C16113.24 (17)C17—C26—C21121.21 (16)
H12—C12—C15106.4C17—C26—C25120.99 (16)
H12—C12—C16106.4C21—C26—C25117.81 (17)
C15—C12—C16112.2 (2)
C6—C1—C2—C30.5 (4)C10—N2—C11—C14118.3 (2)
C1—C2—C3—C40.9 (4)C12—N2—C11—C1362.4 (3)
C2—C3—C4—C50.4 (4)C12—N2—C11—C1463.0 (2)
C3—C4—C5—C60.6 (4)C10—N2—C12—C1562.7 (2)
C4—C5—C6—C11.0 (3)C10—N2—C12—C1665.2 (2)
C4—C5—C6—C7176.3 (2)C11—N2—C12—C15118.5 (2)
C2—C1—C6—C50.5 (3)C11—N2—C12—C16113.6 (2)
C2—C1—C6—C7176.9 (2)N1—C9—C17—C1863.64 (19)
C8—O1—C7—C6174.79 (17)N1—C9—C17—C26173.06 (14)
C1—C6—C7—O1130.9 (2)C10—C9—C17—C18176.67 (14)
C5—C6—C7—O151.9 (3)C10—C9—C17—C2653.38 (17)
C9—N1—C8—O1176.68 (15)C9—C17—C18—C19131.9 (3)
C9—N1—C8—O23.2 (3)C26—C17—C18—C19104.7 (3)
C7—O1—C8—O21.1 (3)C26—C21—C22—C230.2 (4)
C7—O1—C8—N1179.05 (18)C21—C22—C23—C240.0 (4)
C8—N1—C9—C10102.49 (18)C22—C23—C24—C250.4 (3)
C8—N1—C9—C17137.35 (17)C23—C24—C25—C260.9 (3)
C11—N2—C10—O3172.58 (18)C24—C25—C26—C17178.74 (18)
C11—N2—C10—C98.0 (3)C24—C25—C26—C211.0 (3)
C12—N2—C10—O36.1 (2)C22—C21—C26—C17179.10 (19)
C12—N2—C10—C9173.29 (15)C22—C21—C26—C250.7 (3)
N1—C9—C10—O362.93 (18)C9—C17—C26—C2174.2 (2)
N1—C9—C10—N2117.62 (16)C9—C17—C26—C25106.03 (19)
C17—C9—C10—O358.01 (18)C18—C17—C26—C2148.2 (2)
C17—C9—C10—N2121.44 (16)C18—C17—C26—C25131.53 (19)
C10—N2—C11—C13116.3 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O3i0.82 (2)2.14 (2)2.9470 (19)169.1 (19)
Symmetry code: (i) x+1, y, z.
 

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