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Acta Crystallogr Sect E Struct Rep Online. 2009 April 1; 65(Pt 4): o751.
Published online 2009 March 14. doi:  10.1107/S1600536809008496
PMCID: PMC2969086

(5E)-Dimethyl 2-bromo­methyl-5-cyclo­hexyl­imino-2-phenyl-2,5-dihydro­furan-3,4-dicarboxyl­ate

Abstract

The mol­ecule of the title compound, C21H24BrNO5, has a planar furan ring [maximum deviation = 0.025 (3) Å]. The carboxy­methyl group in the 3-position is nearly coplanar with this ring [dihedral angle = 7.9 (1)°], whereas that in the 4-position is nearly perpendicular to it [dihedral angle = 78.9 (1) Å].

Related literature

The imino­lactone was synthesized by the one-pot, solvent-free reaction of dimethyl acetyl­enedicarboxyl­ate, cyclo­hexyl isocyanide and α-bromo­acetophenone under microwave irradiation; for other synthetic methods, see: Ma & Xie (2002 [triangle], 2005 [triangle]); Nair et al. (2000 [triangle]); Villemin & Liao (2003 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0o751-scheme1.jpg

Experimental

Crystal data

  • C21H24BrNO5
  • M r = 450.32
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o751-efi1.jpg
  • a = 16.8599 (3) Å
  • b = 7.2871 (1) Å
  • c = 17.4145 (3) Å
  • β = 97.330 (1)°
  • V = 2122.06 (6) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.97 mm−1
  • T = 123 K
  • 0.30 × 0.15 × 0.10 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.590, T max = 0.828
  • 19142 measured reflections
  • 4873 independent reflections
  • 4034 reflections with I > 2σ(I)
  • R int = 0.046

Refinement

  • R[F 2 > 2σ(F 2)] = 0.053
  • wR(F 2) = 0.156
  • S = 1.08
  • 4873 reflections
  • 255 parameters
  • H-atom parameters constrained
  • Δρmax = 2.31 e Å−3
  • Δρmin = −0.67 e Å−3

Data collection: APEX2 (Bruker, 2008 [triangle]); cell refinement: SAINT (Bruker, 2008 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2009 [triangle]).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809008496/tk2389sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809008496/tk2389Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We thank the Research Council of Tehran University and the University of Malaya for supporting this study.

supplementary crystallographic information

Experimental

To a mixture of 2-bromo-1-phenyl ethanone (α-bromo acetophenone, 0.398 g, 2 mmol) and dimethyl acetylenedicarboxylate (0.25 ml, 2 mmol), cyclohexyl isocyanide (0.25 ml, 2 mmol) was added. Irradiation of the mixture with microwave radiation (180 W) for 5 min produced the title iminolactone. The reaction was monitored by TLC (ethyl acetate n-hexane 4:1) until no α-bromoacetophenone was detectable. The product was recrystalized from methanol; yield 90%, m.p. 351 K.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C–H 0.95 to 0.99 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2 to 1.5Ueq(C).

The final difference Fourier map had a large peak/deep hole in the vicinity of the bromide atom. Attempts to model the bromide atom as being disordered over two positions did not lead to any improvement in the refinement.

Figures

Fig. 1.
Thermal ellisoid plot (Barbour, 2001) of C21H24BrNO5; probability levels are set at 70% and H-atoms are drawn as spheres of arbitrary radius.

Crystal data

C21H24BrNO5F(000) = 928
Mr = 450.32Dx = 1.410 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3661 reflections
a = 16.8599 (3) Åθ = 2.7–28.3°
b = 7.2871 (1) ŵ = 1.97 mm1
c = 17.4145 (3) ÅT = 123 K
β = 97.330 (1)°Prism, colorless
V = 2122.06 (6) Å30.30 × 0.15 × 0.10 mm
Z = 4

Data collection

Bruker SMART APEX diffractometer4873 independent reflections
Radiation source: fine-focus sealed tube4034 reflections with I > 2σ(I)
graphiteRint = 0.046
ω scansθmax = 27.5°, θmin = 1.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −21→21
Tmin = 0.590, Tmax = 0.828k = −9→9
19142 measured reflectionsl = −22→22

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.053Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.156H-atom parameters constrained
S = 1.08w = 1/[σ2(Fo2) + (0.0837P)2 + 3.6326P] where P = (Fo2 + 2Fc2)/3
4873 reflections(Δ/σ)max = 0.001
255 parametersΔρmax = 2.31 e Å3
0 restraintsΔρmin = −0.67 e Å3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Br10.25611 (3)1.02341 (5)0.45239 (2)0.03930 (16)
O10.29800 (12)0.6088 (3)0.49013 (12)0.0216 (4)
O20.09230 (13)0.3244 (3)0.36320 (12)0.0240 (5)
O30.11434 (15)0.5554 (4)0.28251 (13)0.0297 (5)
O40.06942 (14)0.8094 (3)0.54175 (13)0.0289 (5)
O50.02390 (13)0.6629 (3)0.43103 (13)0.0259 (5)
N10.30562 (15)0.4537 (4)0.37308 (15)0.0207 (5)
C10.23476 (17)0.6816 (4)0.53027 (16)0.0186 (6)
C20.16009 (17)0.6470 (4)0.47364 (16)0.0185 (6)
C30.17954 (17)0.5531 (4)0.41267 (16)0.0183 (6)
C40.26637 (18)0.5307 (4)0.42102 (16)0.0185 (6)
C50.25368 (19)0.8840 (4)0.54633 (17)0.0240 (6)
H5A0.30620.89430.57870.029*
H5B0.21280.93690.57590.029*
C60.23270 (17)0.5743 (4)0.60559 (16)0.0190 (6)
C70.25969 (18)0.3940 (4)0.61047 (17)0.0219 (6)
H70.27900.33820.56720.026*
C80.25852 (19)0.2952 (4)0.67858 (19)0.0251 (6)
H80.27710.17200.68150.030*
C90.2307 (2)0.3741 (5)0.74210 (19)0.0281 (7)
H90.23050.30600.78860.034*
C100.2030 (2)0.5530 (5)0.73749 (19)0.0308 (7)
H100.18360.60800.78090.037*
C110.20363 (19)0.6531 (5)0.66923 (18)0.0252 (6)
H110.18410.77550.66620.030*
C120.08049 (18)0.7155 (4)0.48724 (17)0.0212 (6)
C13−0.05632 (18)0.7330 (5)0.4356 (2)0.0291 (7)
H13A−0.09420.67410.39570.044*
H13B−0.05710.86600.42730.044*
H13C−0.07170.70590.48680.044*
C140.12496 (18)0.4812 (4)0.34460 (17)0.0194 (6)
C150.0330 (2)0.2459 (5)0.3044 (2)0.0329 (8)
H15A0.01360.12940.32320.049*
H15B0.05720.22400.25700.049*
H15C−0.01200.33120.29340.049*
C160.39323 (18)0.4490 (5)0.38899 (18)0.0236 (6)
H160.40970.45440.44620.028*
C170.4273 (2)0.6150 (5)0.3507 (2)0.0330 (8)
H17A0.40510.61890.29530.040*
H17B0.41090.72880.37550.040*
C180.5186 (2)0.6070 (6)0.3579 (2)0.0382 (9)
H18A0.53850.71190.32970.046*
H18B0.54100.61760.41300.046*
C190.5467 (2)0.4285 (7)0.3250 (2)0.0402 (9)
H19A0.52800.42260.26880.048*
H19B0.60590.42490.33210.048*
C200.5149 (2)0.2658 (6)0.3648 (2)0.0405 (9)
H20A0.53700.26630.42020.049*
H20B0.53230.15120.34140.049*
C210.4232 (2)0.2705 (5)0.3573 (2)0.0338 (8)
H21A0.40100.25750.30220.041*
H21B0.40400.16560.38600.041*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0740 (3)0.0243 (2)0.0196 (2)−0.01265 (16)0.00615 (16)0.00297 (13)
O10.0240 (10)0.0273 (12)0.0134 (10)−0.0023 (8)0.0023 (8)−0.0049 (8)
O20.0316 (11)0.0228 (11)0.0167 (10)−0.0060 (9)−0.0010 (8)−0.0029 (8)
O30.0384 (13)0.0344 (13)0.0146 (11)−0.0051 (10)−0.0029 (9)0.0058 (9)
O40.0321 (12)0.0330 (13)0.0214 (11)0.0071 (10)0.0022 (9)−0.0057 (10)
O50.0228 (10)0.0296 (12)0.0245 (11)0.0021 (9)0.0007 (8)−0.0072 (9)
N10.0246 (13)0.0224 (13)0.0157 (12)−0.0007 (10)0.0047 (9)−0.0015 (10)
C10.0241 (14)0.0189 (14)0.0129 (13)−0.0010 (10)0.0033 (10)−0.0019 (10)
C20.0261 (14)0.0156 (13)0.0132 (12)−0.0013 (11)0.0006 (10)0.0021 (10)
C30.0244 (14)0.0189 (14)0.0115 (13)−0.0008 (11)0.0015 (10)0.0005 (10)
C40.0260 (14)0.0190 (14)0.0100 (13)−0.0037 (11)0.0007 (10)−0.0002 (10)
C50.0340 (16)0.0218 (15)0.0161 (14)−0.0043 (12)0.0027 (12)−0.0008 (11)
C60.0209 (13)0.0217 (14)0.0139 (13)−0.0006 (11)0.0004 (10)−0.0009 (11)
C70.0258 (14)0.0210 (15)0.0184 (14)−0.0001 (11)0.0007 (11)−0.0031 (11)
C80.0304 (16)0.0195 (14)0.0241 (15)0.0003 (12)−0.0013 (12)0.0023 (12)
C90.0359 (17)0.0299 (17)0.0178 (14)−0.0010 (13)0.0009 (12)0.0061 (13)
C100.045 (2)0.0323 (18)0.0158 (15)0.0074 (15)0.0073 (13)0.0037 (13)
C110.0366 (17)0.0228 (15)0.0167 (14)0.0068 (13)0.0046 (12)0.0001 (12)
C120.0279 (15)0.0191 (14)0.0164 (13)0.0015 (11)0.0025 (11)0.0027 (11)
C130.0236 (15)0.0311 (17)0.0322 (17)0.0024 (13)0.0016 (12)0.0002 (14)
C140.0225 (14)0.0216 (14)0.0141 (13)0.0012 (11)0.0026 (10)−0.0018 (11)
C150.0348 (18)0.0362 (19)0.0265 (17)−0.0122 (15)−0.0015 (13)−0.0112 (14)
C160.0241 (15)0.0324 (17)0.0141 (14)−0.0019 (12)0.0021 (11)−0.0023 (12)
C170.0313 (17)0.036 (2)0.0314 (18)−0.0065 (14)0.0037 (13)0.0027 (15)
C180.0310 (18)0.048 (2)0.036 (2)−0.0099 (16)0.0038 (14)0.0017 (17)
C190.0253 (16)0.063 (3)0.0332 (19)−0.0053 (17)0.0070 (14)−0.0088 (19)
C200.0305 (18)0.046 (2)0.044 (2)0.0075 (16)0.0026 (15)−0.0067 (18)
C210.0279 (17)0.0329 (19)0.041 (2)0.0002 (14)0.0073 (14)−0.0066 (16)

Geometric parameters (Å, °)

Br1—C51.930 (3)C9—H90.9500
O1—C41.376 (3)C10—C111.396 (4)
O1—C11.448 (3)C10—H100.9500
O2—C141.326 (4)C11—H110.9500
O2—C151.454 (4)C13—H13A0.9800
O3—C141.202 (4)C13—H13B0.9800
O4—C121.204 (4)C13—H13C0.9800
O5—C121.333 (4)C15—H15A0.9800
O5—C131.457 (4)C15—H15B0.9800
N1—C41.261 (4)C15—H15C0.9800
N1—C161.468 (4)C16—C211.524 (5)
C1—C21.518 (4)C16—C171.528 (5)
C1—C51.528 (4)C16—H161.0000
C1—C61.531 (4)C17—C181.529 (5)
C2—C31.339 (4)C17—H17A0.9900
C2—C121.479 (4)C17—H17B0.9900
C3—C41.462 (4)C18—C191.521 (6)
C3—C141.499 (4)C18—H18A0.9900
C5—H5A0.9900C18—H18B0.9900
C5—H5B0.9900C19—C201.506 (6)
C6—C111.392 (4)C19—H19A0.9900
C6—C71.389 (4)C19—H19B0.9900
C7—C81.390 (4)C20—C211.535 (5)
C7—H70.9500C20—H20A0.9900
C8—C91.381 (5)C20—H20B0.9900
C8—H80.9500C21—H21A0.9900
C9—C101.384 (5)C21—H21B0.9900
C4—O1—C1110.3 (2)O5—C13—H13C109.5
C14—O2—C15115.9 (3)H13A—C13—H13C109.5
C12—O5—C13116.2 (2)H13B—C13—H13C109.5
C4—N1—C16119.1 (3)O3—C14—O2126.0 (3)
O1—C1—C2103.1 (2)O3—C14—C3124.1 (3)
O1—C1—C5107.0 (2)O2—C14—C3109.9 (2)
C2—C1—C5114.6 (2)O2—C15—H15A109.5
O1—C1—C6109.0 (2)O2—C15—H15B109.5
C2—C1—C6111.4 (2)H15A—C15—H15B109.5
C5—C1—C6111.3 (2)O2—C15—H15C109.5
C3—C2—C12128.2 (3)H15A—C15—H15C109.5
C3—C2—C1109.5 (3)H15B—C15—H15C109.5
C12—C2—C1122.3 (3)N1—C16—C21108.9 (3)
C2—C3—C4108.8 (2)N1—C16—C17108.9 (3)
C2—C3—C14128.2 (3)C21—C16—C17111.0 (3)
C4—C3—C14123.1 (3)N1—C16—H16109.3
N1—C4—O1125.8 (3)C21—C16—H16109.3
N1—C4—C3126.0 (3)C17—C16—H16109.3
O1—C4—C3108.2 (2)C18—C17—C16111.4 (3)
C1—C5—Br1112.3 (2)C18—C17—H17A109.3
C1—C5—H5A109.1C16—C17—H17A109.3
Br1—C5—H5A109.1C18—C17—H17B109.3
C1—C5—H5B109.1C16—C17—H17B109.3
Br1—C5—H5B109.1H17A—C17—H17B108.0
H5A—C5—H5B107.9C19—C18—C17111.2 (3)
C11—C6—C7119.2 (3)C19—C18—H18A109.4
C11—C6—C1121.3 (3)C17—C18—H18A109.4
C7—C6—C1119.5 (3)C19—C18—H18B109.4
C6—C7—C8120.1 (3)C17—C18—H18B109.4
C6—C7—H7119.9H18A—C18—H18B108.0
C8—C7—H7119.9C20—C19—C18110.8 (3)
C9—C8—C7120.7 (3)C20—C19—H19A109.5
C9—C8—H8119.6C18—C19—H19A109.5
C7—C8—H8119.6C20—C19—H19B109.5
C8—C9—C10119.5 (3)C18—C19—H19B109.5
C8—C9—H9120.3H19A—C19—H19B108.1
C10—C9—H9120.3C19—C20—C21110.9 (3)
C9—C10—C11120.2 (3)C19—C20—H20A109.5
C9—C10—H10119.9C21—C20—H20A109.5
C11—C10—H10119.9C19—C20—H20B109.5
C6—C11—C10120.3 (3)C21—C20—H20B109.5
C6—C11—H11119.9H20A—C20—H20B108.0
C10—C11—H11119.9C16—C21—C20111.4 (3)
O4—C12—O5125.0 (3)C16—C21—H21A109.3
O4—C12—C2123.6 (3)C20—C21—H21A109.3
O5—C12—C2111.4 (3)C16—C21—H21B109.3
O5—C13—H13A109.5C20—C21—H21B109.3
O5—C13—H13B109.5H21A—C21—H21B108.0
H13A—C13—H13B109.5
C4—O1—C1—C2−3.2 (3)C11—C6—C7—C8−0.8 (4)
C4—O1—C1—C5−124.4 (2)C1—C6—C7—C8179.7 (3)
C4—O1—C1—C6115.1 (2)C6—C7—C8—C90.0 (5)
O1—C1—C2—C34.5 (3)C7—C8—C9—C100.6 (5)
C5—C1—C2—C3120.4 (3)C8—C9—C10—C11−0.3 (5)
C6—C1—C2—C3−112.2 (3)C7—C6—C11—C101.1 (5)
O1—C1—C2—C12−174.1 (2)C1—C6—C11—C10−179.4 (3)
C5—C1—C2—C12−58.2 (4)C9—C10—C11—C6−0.6 (5)
C6—C1—C2—C1269.2 (3)C13—O5—C12—O42.8 (5)
C12—C2—C3—C4174.5 (3)C13—O5—C12—C2−176.0 (3)
C1—C2—C3—C4−4.0 (3)C3—C2—C12—O4−175.0 (3)
C12—C2—C3—C14−4.6 (5)C1—C2—C12—O43.3 (5)
C1—C2—C3—C14176.9 (3)C3—C2—C12—O53.8 (4)
C16—N1—C4—O1−2.1 (5)C1—C2—C12—O5−177.9 (3)
C16—N1—C4—C3177.6 (3)C15—O2—C14—O3−5.8 (4)
C1—O1—C4—N1−179.2 (3)C15—O2—C14—C3175.4 (3)
C1—O1—C4—C31.1 (3)C2—C3—C14—O3100.1 (4)
C2—C3—C4—N1−177.8 (3)C4—C3—C14—O3−78.9 (4)
C14—C3—C4—N11.4 (5)C2—C3—C14—O2−81.1 (4)
C2—C3—C4—O12.0 (3)C4—C3—C14—O299.9 (3)
C14—C3—C4—O1−178.9 (3)C4—N1—C16—C21146.3 (3)
O1—C1—C5—Br161.4 (3)C4—N1—C16—C17−92.6 (3)
C2—C1—C5—Br1−52.2 (3)N1—C16—C17—C18−173.9 (3)
C6—C1—C5—Br1−179.67 (19)C21—C16—C17—C18−54.1 (4)
O1—C1—C6—C11153.4 (3)C16—C17—C18—C1955.4 (4)
C2—C1—C6—C11−93.6 (3)C17—C18—C19—C20−57.0 (4)
C5—C1—C6—C1135.6 (4)C18—C19—C20—C2157.2 (4)
O1—C1—C6—C7−27.2 (3)N1—C16—C21—C20174.2 (3)
C2—C1—C6—C785.9 (3)C17—C16—C21—C2054.4 (4)
C5—C1—C6—C7−145.0 (3)C19—C20—C21—C16−56.3 (4)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: TK2389).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2008). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Ma, S. & Xie, H. (2002). J. Org. Chem.67, 6575–6578. [PubMed]
  • Ma, S. & Xie, H. (2005). Tetrahedron, 61, 251–258.
  • Nair, V., Vinod, A. U., Nair, J. S., Sreekanth, A. R. & Rath, N. P. (2000). Tetrahedron Lett.41, 6675–6679.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Villemin, D. & Liao, L. (2003). Synth. Commun.33, 1575–1585.
  • Westrip, S. P. (2009). publCIF In preparation.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography