organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

Ethyl 2,5-di-tert-butyl-5-eth­­oxy-4-oxo-4,5-di­hydro-1H-pyrrole-3-carboxyl­ate

aDepartment of Pharmaceutical Sciences, School of Pharmacy, University of Maryland, Baltimore, MD 21201, USA, bCenter for Biomedical Engineering and Technology, School of Medicine, University of Maryland, Baltimore, MD 21201, USA, cDepartment of Chemistry and Biochemistry, University of Maryland, College Park, MD 20742, USA, and dDepartment of Physiology, School of Medicine, University of Maryland, Baltimore, MD 21201, USA
*Correspondence e-mail: jkao@umaryland.edu

(Received 22 March 2013; accepted 5 May 2013; online 11 May 2013)

The title compound, C17H29NO4, contains a chiral center and crystallizes as a racemate. The asymmetric unit consists of two non-equivalent mol­ecules, in which the carbeth­oxy groups have markedly different orientations [C(=O)CC(OEt)=O torsion angles = 59.3 (2) and 156.0 (2)°]. In the crystal, mol­ecules form chains along [101] through N—H⋯O hydrogen bonds.

Related literature

The title compound resulted from an attempt to devise a more efficient synthesis of diethyl 2,5,-di(tert-but­yl)-1-hy­droxy­pyrrole-3,4-di­carboxyl­ate, a precursor to an aromatic nitroxide (Ramasseul & Rassat, 1970[Ramasseul, R. & Rassat, A. (1970). Bull. Soc. Chim. Fr. 72, 4330-4340.]). For related synthetic procedures, see also: Riplinger et al. (2009[Riplinger, C., Kao, J. P. Y., Rosen, G. M., Kathirvelu, V., Eaton, G. R., Eaton, S. S., Kutateladze, A. & Neese, F. (2009). J. Am. Chem. Soc. 131, 10092-10106.]); Travis et al. (2003[Travis, B. R., Sivakumar, M., Hollist, G. O. & Borhan, B. (2003). Org. Lett. 5, 3089-3092.]).

[Scheme 1]

Experimental

Crystal data
  • C17H29NO4

  • Mr = 311.41

  • Monoclinic, P 21 /n

  • a = 9.9187 (7) Å

  • b = 16.3916 (11) Å

  • c = 22.2115 (15) Å

  • β = 92.5822 (11)°

  • V = 3607.6 (4) Å3

  • Z = 8

  • Mo Kα radiation

  • μ = 0.08 mm−1

  • T = 150 K

  • 0.42 × 0.40 × 0.33 mm

Data collection
  • Bruker SMART APEXII diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.887, Tmax = 0.974

  • 40948 measured reflections

  • 6356 independent reflections

  • 5812 reflections with I > 2σ(I)

  • Rint = 0.018

Refinement
  • R[F2 > 2σ(F2)] = 0.039

  • wR(F2) = 0.077

  • S = 1.00

  • 6356 reflections

  • 441 parameters

  • H-atom parameters constrained

  • Δρmax = 0.31 e Å−3

  • Δρmin = −0.25 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N4A—H4A⋯O1Bi 0.832 (16) 2.175 (16) 3.0009 (15) 171.8 (14)
N4B—H4B⋯O1A 0.862 (16) 2.156 (17) 3.0089 (15) 170.4 (15)
Symmetry code: (i) [x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}].

Data collection: APEX2 (Bruker, 2010[Bruker (2010). APEX2, SAINT and XSHELL. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: APEX2 and SAINT (Bruker, 2010[Bruker (2010). APEX2, SAINT and XSHELL. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: XSHELL (Bruker, 2010[Bruker (2010). APEX2, SAINT and XSHELL. Bruker AXS Inc., Madison, Wisconsin, USA.]) and Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Comment top

The title compound resulted from an attempt to devise a more efficient synthesis of diethyl 2,5,-di(tert-butyl)-1-hydroxypyrrole-3,4-dicarboxylate, a precursor to an aromatic nitroxide (Ramasseul & Rassat, 1970). The molecular structure is shown in Fig. 1. Despite the steric bulk of the substituents, the pyrroline rings are planar (the r.m.s. deviations of the atoms in the rings containing N4A and N4B are 0.020 and 0.036 Å, respectively). In the crystal, N—H···O hydrogen bonds link the molecules into chains (Fig. 2).

Related literature top

The title compound resulted from an attempt to devise a more efficient synthesis of diethyl 2,5,-di(tert-butyl)-1-hydroxypyrrole-3,4-dicarboxylate, a precursor to an aromatic nitroxide (Ramasseul & Rassat, 1970). For related synthetic procedures, see also: Riplinger et al. (2009); Travis et al. (2003).

Experimental top

The title comnpund was prepared in three steps from the known compound, ethyl 2,5-di(tert-butyl)-1-hydroxypyrrole-3-carboxylate (Ramasseul & Rassat, 1970; Riplinger et al., 2009): 1) O-benzylation, 2) Vilsmeier formylation of the 4 position, and 3) oxidation by Oxone in ethanol (Travis et al. 2003). Instead of the expected conversion of the 4-formyl group into the corresponding ethyl ester, Oxone treatment resulted in the title compound. After purification of the product by flash chromatography, single crystals were obtained by recrystallization from ethyl acetate.

Refinement top

Position of all H atoms was calculated from geometric considerations. H atoms were refined as riding on the attached C atoms, except H atoms in N—H groups which were freely refined. Orientation of CH3 groups was optimized. For all H atoms Uiso were refined but constrained to be equal within CH3 groups.

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: APEX2 and SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008); molecular graphics: XSHELL (Bruker, 2010) and Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound showing nonequivalent molecules A and B, with non-hydrogen atoms labeled. Displacement ellipsoids are shown at the 30% probability level. Note that molecule B was inverted in the center of symmetry to facilitate comparison with molecule A.
[Figure 2] Fig. 2. Packing of molecules A and B shown along b axis depicting chains of molecules linked through N—H···O hydrogen bonds (light blue dashed lines) in the 101 direction. Only half of the unit cell is shown along b for visual clarity.
Ethyl 2,5-di-tert-butyl-5-ethoxy-4-oxo-4,5-dihydro-1H-pyrrole-3-carboxylate top
Crystal data top
C17H29NO4F(000) = 1360
Mr = 311.41Dx = 1.147 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 9.9187 (7) ÅCell parameters from 26267 reflections
b = 16.3916 (11) Åθ = 2.2–32.0°
c = 22.2115 (15) ŵ = 0.08 mm1
β = 92.5822 (11)°T = 150 K
V = 3607.6 (4) Å3Prism, colourless
Z = 80.42 × 0.40 × 0.33 mm
Data collection top
Bruker SMART APEXII
diffractometer
6356 independent reflections
Radiation source: sealed tube5812 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.018
Detector resolution: 8.333 pixels mm-1θmax = 25.0°, θmin = 2.2°
ϕ and ω scansh = 1111
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
k = 1919
Tmin = 0.887, Tmax = 0.974l = 2626
40948 measured reflections
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)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.077H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.010P)2 + 2.698P]
where P = (Fo2 + 2Fc2)/3
6356 reflections(Δ/σ)max < 0.001
441 parametersΔρmax = 0.31 e Å3
0 restraintsΔρmin = 0.25 e Å3
Crystal data top
C17H29NO4V = 3607.6 (4) Å3
Mr = 311.41Z = 8
Monoclinic, P21/nMo Kα radiation
a = 9.9187 (7) ŵ = 0.08 mm1
b = 16.3916 (11) ÅT = 150 K
c = 22.2115 (15) Å0.42 × 0.40 × 0.33 mm
β = 92.5822 (11)°
Data collection top
Bruker SMART APEXII
diffractometer
6356 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
5812 reflections with I > 2σ(I)
Tmin = 0.887, Tmax = 0.974Rint = 0.018
40948 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.077H-atom parameters constrained
S = 1.00Δρmax = 0.31 e Å3
6356 reflectionsΔρmin = 0.25 e Å3
441 parameters
Special details top

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
O1A0.17249 (10)0.17307 (6)0.51228 (4)0.0309 (2)
C1A0.17385 (13)0.21856 (8)0.55631 (6)0.0226 (3)
C2A0.07337 (13)0.27417 (8)0.57559 (6)0.0222 (3)
C3A0.11821 (13)0.30765 (8)0.63052 (6)0.0212 (3)
N4A0.24234 (11)0.28082 (7)0.64688 (5)0.0235 (2)
H4A0.2852 (15)0.2948 (9)0.6782 (7)0.026 (4)*
C5A0.29647 (13)0.22476 (8)0.60283 (6)0.0221 (3)
C21A0.05218 (14)0.28839 (9)0.53915 (6)0.0243 (3)
O21A0.13140 (11)0.23672 (7)0.52273 (5)0.0443 (3)
O22A0.06552 (11)0.36716 (6)0.52314 (5)0.0369 (3)
C23A0.18864 (19)0.38801 (12)0.48838 (9)0.0543 (5)
H23A0.26210.35010.49830.077 (5)*
H23B0.17360.38350.44470.077 (5)*
C24A0.2263 (2)0.47213 (13)0.50333 (10)0.0641 (6)
H24A0.24230.47590.54650.094 (5)*
H24B0.30860.48740.48000.094 (5)*
H24C0.15290.50920.49350.094 (5)*
C31A0.04558 (14)0.36525 (9)0.67184 (6)0.0271 (3)
C32A0.0885 (2)0.45196 (11)0.65724 (10)0.0612 (6)
H32A0.18600.45770.66530.066 (4)*
H32B0.04060.49050.68240.066 (4)*
H32C0.06640.46350.61460.066 (4)*
C33A0.10814 (16)0.35611 (13)0.66379 (7)0.0467 (5)
H33A0.13830.37630.62390.070 (4)*
H33B0.15170.38770.69500.070 (4)*
H33C0.13260.29850.66740.070 (4)*
C34A0.08294 (17)0.34531 (12)0.73789 (7)0.0416 (4)
H34A0.06110.28820.74600.054 (3)*
H34B0.03180.38080.76410.054 (3)*
H34C0.17980.35430.74580.054 (3)*
O51A0.33071 (9)0.14932 (6)0.62981 (4)0.0267 (2)
C52A0.21923 (15)0.10469 (10)0.65294 (7)0.0350 (4)
H52A0.16770.07710.61960.050 (4)*
H52B0.15770.14240.67310.050 (4)*
C53A0.27518 (17)0.04306 (10)0.69693 (8)0.0410 (4)
H53A0.33380.00510.67620.059 (3)*
H53B0.20090.01280.71410.059 (3)*
H53C0.32760.07090.72930.059 (3)*
C54A0.42581 (14)0.25865 (9)0.57484 (6)0.0251 (3)
C55A0.53624 (14)0.27112 (10)0.62480 (7)0.0326 (3)
H55A0.62020.28800.60680.041 (3)*
H55B0.55130.21990.64680.041 (3)*
H55C0.50770.31340.65270.041 (3)*
C56A0.47769 (15)0.19853 (10)0.52844 (7)0.0344 (3)
H56A0.41330.19570.49370.045 (3)*
H56B0.48750.14440.54680.045 (3)*
H56C0.56540.21710.51510.045 (3)*
C57A0.39392 (16)0.34066 (9)0.54419 (7)0.0337 (3)
H57A0.47650.36320.52820.043 (3)*
H57B0.35850.37860.57370.043 (3)*
H57C0.32640.33250.51120.043 (3)*
O1B0.08469 (10)0.15836 (6)0.25177 (4)0.0286 (2)
C1B0.00038 (13)0.13501 (8)0.29014 (6)0.0219 (3)
C2B0.08310 (13)0.06294 (8)0.29281 (6)0.0222 (3)
C3B0.14805 (13)0.06053 (8)0.35069 (6)0.0215 (3)
N4B0.12100 (11)0.12751 (7)0.38204 (5)0.0226 (2)
H4B0.1407 (15)0.1351 (10)0.4198 (7)0.030 (4)*
C5B0.03325 (13)0.18511 (8)0.34818 (6)0.0215 (3)
C21B0.09972 (14)0.00705 (8)0.24244 (6)0.0269 (3)
O21B0.19358 (12)0.03802 (8)0.23510 (5)0.0482 (3)
O22B0.00323 (12)0.01369 (7)0.20099 (5)0.0411 (3)
C23B0.0058 (2)0.03658 (11)0.14761 (8)0.0544 (5)
H23C0.10190.04540.13920.069 (5)*
H23D0.03750.00790.11260.069 (5)*
C24B0.0613 (2)0.11702 (13)0.15562 (11)0.0688 (7)
H24D0.01510.14680.18880.083 (4)*
H24E0.05710.14880.11840.083 (4)*
H24F0.15590.10830.16500.083 (4)*
C31B0.23707 (14)0.00578 (8)0.37980 (6)0.0260 (3)
C32B0.37584 (15)0.00186 (10)0.35174 (8)0.0359 (4)
H32D0.36500.01090.30820.050 (3)*
H32E0.43480.04410.36980.050 (3)*
H32F0.41620.05190.35940.050 (3)*
C33B0.25616 (19)0.00727 (11)0.44792 (7)0.0462 (5)
H33D0.30260.05920.45580.056 (3)*
H33E0.31030.03740.46560.056 (3)*
H33F0.16780.00830.46600.056 (3)*
C34B0.17217 (16)0.08995 (9)0.36926 (8)0.0393 (4)
H34D0.08320.09100.38670.056 (3)*
H34E0.22970.13200.38840.056 (3)*
H34F0.16210.10060.32590.056 (3)*
O51B0.08119 (10)0.20552 (6)0.37952 (4)0.0272 (2)
C52B0.15794 (16)0.13701 (10)0.39956 (7)0.0363 (4)
H52C0.12220.11850.43960.045 (3)*
H52D0.15160.09110.37080.045 (3)*
C53B0.30206 (16)0.16360 (11)0.40323 (7)0.0422 (4)
H53D0.30680.21040.43050.056 (3)*
H53E0.35570.11860.41860.056 (3)*
H53F0.33790.17920.36300.056 (3)*
C54B0.10890 (14)0.26597 (8)0.33434 (6)0.0249 (3)
C55B0.16242 (17)0.30456 (9)0.39357 (7)0.0373 (4)
H55D0.23110.26890.41270.047 (3)*
H55E0.08790.31170.42060.047 (3)*
H55F0.20250.35780.38520.047 (3)*
C56B0.22690 (15)0.24875 (9)0.29401 (7)0.0332 (3)
H56D0.27560.29960.28680.044 (3)*
H56E0.19230.22630.25550.044 (3)*
H56F0.28840.20940.31390.044 (3)*
C57B0.01182 (16)0.32582 (9)0.30168 (7)0.0338 (3)
H57D0.06080.37550.29160.043 (3)*
H57E0.06160.33960.32800.043 (3)*
H57F0.02580.30050.26460.043 (3)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1A0.0366 (6)0.0310 (6)0.0247 (5)0.0040 (4)0.0033 (4)0.0092 (4)
C1A0.0264 (7)0.0216 (7)0.0196 (7)0.0003 (5)0.0007 (5)0.0000 (5)
C2A0.0231 (7)0.0216 (7)0.0216 (7)0.0008 (5)0.0017 (5)0.0005 (5)
C3A0.0214 (7)0.0204 (7)0.0218 (7)0.0006 (5)0.0001 (5)0.0003 (5)
N4A0.0216 (6)0.0298 (6)0.0187 (6)0.0029 (5)0.0041 (5)0.0065 (5)
C5A0.0240 (7)0.0217 (7)0.0205 (6)0.0046 (5)0.0007 (5)0.0014 (5)
C21A0.0244 (7)0.0286 (7)0.0196 (6)0.0014 (6)0.0001 (5)0.0009 (6)
O21A0.0400 (6)0.0415 (7)0.0494 (7)0.0116 (5)0.0210 (5)0.0072 (5)
O22A0.0368 (6)0.0275 (6)0.0449 (6)0.0040 (5)0.0167 (5)0.0044 (5)
C23A0.0488 (11)0.0477 (11)0.0635 (12)0.0136 (9)0.0300 (9)0.0058 (9)
C24A0.0592 (13)0.0605 (13)0.0713 (14)0.0276 (11)0.0126 (11)0.0149 (11)
C31A0.0270 (7)0.0279 (8)0.0265 (7)0.0043 (6)0.0015 (6)0.0065 (6)
C32A0.0923 (16)0.0274 (9)0.0665 (13)0.0017 (10)0.0317 (12)0.0142 (9)
C33A0.0293 (8)0.0763 (13)0.0346 (9)0.0138 (8)0.0013 (7)0.0165 (9)
C34A0.0383 (9)0.0604 (11)0.0259 (8)0.0128 (8)0.0003 (7)0.0133 (8)
O51A0.0229 (5)0.0251 (5)0.0322 (5)0.0034 (4)0.0005 (4)0.0062 (4)
C52A0.0272 (8)0.0334 (8)0.0445 (9)0.0021 (6)0.0012 (7)0.0089 (7)
C53A0.0390 (9)0.0373 (9)0.0460 (10)0.0103 (7)0.0058 (7)0.0130 (8)
C54A0.0244 (7)0.0270 (7)0.0241 (7)0.0022 (6)0.0010 (5)0.0000 (6)
C55A0.0230 (7)0.0432 (9)0.0317 (8)0.0012 (6)0.0008 (6)0.0008 (7)
C56A0.0325 (8)0.0402 (9)0.0312 (8)0.0031 (7)0.0086 (6)0.0041 (7)
C57A0.0346 (8)0.0302 (8)0.0360 (8)0.0030 (7)0.0006 (7)0.0056 (7)
O1B0.0281 (5)0.0305 (5)0.0265 (5)0.0038 (4)0.0059 (4)0.0023 (4)
C1B0.0217 (7)0.0224 (7)0.0215 (7)0.0017 (5)0.0015 (5)0.0022 (5)
C2B0.0229 (7)0.0210 (7)0.0226 (7)0.0001 (5)0.0005 (5)0.0004 (5)
C3B0.0212 (6)0.0193 (7)0.0242 (7)0.0010 (5)0.0027 (5)0.0008 (5)
N4B0.0286 (6)0.0206 (6)0.0182 (6)0.0036 (5)0.0028 (5)0.0004 (5)
C5B0.0231 (7)0.0200 (7)0.0215 (7)0.0045 (5)0.0011 (5)0.0013 (5)
C21B0.0316 (8)0.0226 (7)0.0263 (7)0.0011 (6)0.0006 (6)0.0011 (6)
O21B0.0462 (7)0.0523 (8)0.0452 (7)0.0198 (6)0.0059 (5)0.0231 (6)
O22B0.0543 (7)0.0367 (6)0.0309 (6)0.0120 (5)0.0151 (5)0.0131 (5)
C23B0.0871 (15)0.0425 (10)0.0315 (9)0.0176 (10)0.0197 (9)0.0156 (8)
C24B0.0708 (14)0.0510 (12)0.0817 (16)0.0053 (11)0.0278 (12)0.0296 (11)
C31B0.0281 (7)0.0209 (7)0.0286 (7)0.0049 (6)0.0012 (6)0.0022 (6)
C32B0.0263 (8)0.0337 (8)0.0474 (9)0.0042 (6)0.0020 (7)0.0064 (7)
C33B0.0643 (12)0.0417 (10)0.0316 (9)0.0266 (9)0.0074 (8)0.0044 (7)
C34B0.0358 (9)0.0237 (8)0.0582 (11)0.0023 (7)0.0023 (8)0.0095 (7)
O51B0.0286 (5)0.0240 (5)0.0299 (5)0.0040 (4)0.0092 (4)0.0015 (4)
C52B0.0386 (9)0.0318 (8)0.0398 (9)0.0050 (7)0.0150 (7)0.0002 (7)
C53B0.0333 (9)0.0588 (11)0.0349 (9)0.0081 (8)0.0063 (7)0.0108 (8)
C54B0.0296 (7)0.0191 (7)0.0262 (7)0.0005 (6)0.0017 (6)0.0005 (6)
C55B0.0505 (10)0.0262 (8)0.0348 (8)0.0063 (7)0.0029 (7)0.0040 (7)
C56B0.0326 (8)0.0281 (8)0.0394 (9)0.0036 (6)0.0083 (7)0.0023 (7)
C57B0.0418 (9)0.0218 (7)0.0379 (8)0.0049 (6)0.0017 (7)0.0056 (6)
Geometric parameters (Å, º) top
O1A—C1A1.2294 (16)O1B—C1B1.2279 (16)
C1A—C2A1.4304 (19)C1B—C2B1.4424 (18)
C1A—C5A1.5634 (18)C1B—C5B1.5520 (18)
C2A—C3A1.3925 (18)C2B—C3B1.4123 (18)
C2A—C21A1.4728 (18)C2B—C21B1.4612 (19)
C3A—N4A1.3420 (17)C3B—N4B1.3338 (17)
C3A—C31A1.5206 (18)C3B—C31B1.5257 (18)
N4A—C5A1.4619 (17)N4B—C5B1.4682 (16)
N4A—H4A0.832 (16)N4B—H4B0.862 (16)
C5A—O51A1.4089 (16)C5B—O51B1.3986 (16)
C5A—C54A1.5533 (19)C5B—C54B1.5605 (18)
C21A—O21A1.2009 (17)C21B—O21B1.2053 (18)
C21A—O22A1.3442 (17)C21B—O22B1.3481 (17)
O22A—C23A1.4558 (18)O22B—C23B1.4500 (19)
C23A—C24A1.470 (3)C23B—C24B1.492 (3)
C23A—H23A0.9900C23B—H23C0.9900
C23A—H23B0.9900C23B—H23D0.9900
C24A—H24A0.9800C24B—H24D0.9800
C24A—H24B0.9800C24B—H24E0.9800
C24A—H24C0.9800C24B—H24F0.9800
C31A—C32A1.523 (2)C31B—C33B1.531 (2)
C31A—C34A1.532 (2)C31B—C34B1.536 (2)
C31A—C33A1.534 (2)C31B—C32B1.538 (2)
C32A—H32A0.9800C32B—H32D0.9800
C32A—H32B0.9800C32B—H32E0.9800
C32A—H32C0.9800C32B—H32F0.9800
C33A—H33A0.9800C33B—H33D0.9800
C33A—H33B0.9800C33B—H33E0.9800
C33A—H33C0.9800C33B—H33F0.9800
C34A—H34A0.9800C34B—H34D0.9800
C34A—H34B0.9800C34B—H34E0.9800
C34A—H34C0.9800C34B—H34F0.9800
O51A—C52A1.4398 (17)O51B—C52B1.4385 (17)
C52A—C53A1.495 (2)C52B—C53B1.500 (2)
C52A—H52A0.9900C52B—H52C0.9900
C52A—H52B0.9900C52B—H52D0.9900
C53A—H53A0.9800C53B—H53D0.9800
C53A—H53B0.9800C53B—H53E0.9800
C53A—H53C0.9800C53B—H53F0.9800
C54A—C56A1.5317 (19)C54B—C56B1.5316 (19)
C54A—C57A1.533 (2)C54B—C55B1.533 (2)
C54A—C55A1.5374 (19)C54B—C57B1.5340 (19)
C55A—H55A0.9800C55B—H55D0.9800
C55A—H55B0.9800C55B—H55E0.9800
C55A—H55C0.9800C55B—H55F0.9800
C56A—H56A0.9800C56B—H56D0.9800
C56A—H56B0.9800C56B—H56E0.9800
C56A—H56C0.9800C56B—H56F0.9800
C57A—H57A0.9800C57B—H57D0.9800
C57A—H57B0.9800C57B—H57E0.9800
C57A—H57C0.9800C57B—H57F0.9800
O1A—C1A—C2A129.93 (12)O1B—C1B—C2B130.97 (13)
O1A—C1A—C5A123.06 (12)O1B—C1B—C5B121.72 (12)
C2A—C1A—C5A107.01 (11)C2B—C1B—C5B107.32 (11)
C3A—C2A—C1A108.31 (11)C3B—C2B—C1B107.33 (11)
C3A—C2A—C21A130.38 (12)C3B—C2B—C21B128.09 (12)
C1A—C2A—C21A121.31 (12)C1B—C2B—C21B124.50 (12)
N4A—C3A—C2A111.16 (12)N4B—C3B—C2B110.98 (12)
N4A—C3A—C31A119.60 (11)N4B—C3B—C31B119.43 (12)
C2A—C3A—C31A129.21 (12)C2B—C3B—C31B129.58 (12)
C3A—N4A—C5A112.64 (11)C3B—N4B—C5B112.98 (11)
C3A—N4A—H4A124.4 (10)C3B—N4B—H4B125.8 (11)
C5A—N4A—H4A123.0 (11)C5B—N4B—H4B120.6 (11)
O51A—C5A—N4A110.85 (11)O51B—C5B—N4B112.00 (10)
O51A—C5A—C54A107.25 (10)O51B—C5B—C1B113.02 (11)
N4A—C5A—C54A112.20 (11)N4B—C5B—C1B100.69 (10)
O51A—C5A—C1A112.92 (11)O51B—C5B—C54B107.64 (10)
N4A—C5A—C1A100.66 (10)N4B—C5B—C54B111.59 (11)
C54A—C5A—C1A112.99 (11)C1B—C5B—C54B111.90 (11)
O21A—C21A—O22A122.81 (13)O21B—C21B—O22B121.54 (13)
O21A—C21A—C2A125.50 (13)O21B—C21B—C2B127.03 (13)
O22A—C21A—C2A111.60 (12)O22B—C21B—C2B111.36 (12)
C21A—O22A—C23A115.85 (12)C21B—O22B—C23B116.08 (13)
O22A—C23A—C24A108.39 (15)O22B—C23B—C24B111.12 (17)
O22A—C23A—H23A110.0O22B—C23B—H23C109.4
C24A—C23A—H23A110.0C24B—C23B—H23C109.4
O22A—C23A—H23B110.0O22B—C23B—H23D109.4
C24A—C23A—H23B110.0C24B—C23B—H23D109.4
H23A—C23A—H23B108.4H23C—C23B—H23D108.0
C23A—C24A—H24A109.5C23B—C24B—H24D109.5
C23A—C24A—H24B109.5C23B—C24B—H24E109.5
H24A—C24A—H24B109.5H24D—C24B—H24E109.5
C23A—C24A—H24C109.5C23B—C24B—H24F109.5
H24A—C24A—H24C109.5H24D—C24B—H24F109.5
H24B—C24A—H24C109.5H24E—C24B—H24F109.5
C3A—C31A—C32A107.86 (12)C3B—C31B—C33B111.26 (12)
C3A—C31A—C34A110.16 (12)C3B—C31B—C34B110.17 (11)
C32A—C31A—C34A110.20 (14)C33B—C31B—C34B107.97 (13)
C3A—C31A—C33A111.38 (12)C3B—C31B—C32B108.06 (11)
C32A—C31A—C33A110.60 (15)C33B—C31B—C32B108.76 (13)
C34A—C31A—C33A106.67 (13)C34B—C31B—C32B110.63 (12)
C31A—C32A—H32A109.5C31B—C32B—H32D109.5
C31A—C32A—H32B109.5C31B—C32B—H32E109.5
H32A—C32A—H32B109.5H32D—C32B—H32E109.5
C31A—C32A—H32C109.5C31B—C32B—H32F109.5
H32A—C32A—H32C109.5H32D—C32B—H32F109.5
H32B—C32A—H32C109.5H32E—C32B—H32F109.5
C31A—C33A—H33A109.5C31B—C33B—H33D109.5
C31A—C33A—H33B109.5C31B—C33B—H33E109.5
H33A—C33A—H33B109.5H33D—C33B—H33E109.5
C31A—C33A—H33C109.5C31B—C33B—H33F109.5
H33A—C33A—H33C109.5H33D—C33B—H33F109.5
H33B—C33A—H33C109.5H33E—C33B—H33F109.5
C31A—C34A—H34A109.5C31B—C34B—H34D109.5
C31A—C34A—H34B109.5C31B—C34B—H34E109.5
H34A—C34A—H34B109.5H34D—C34B—H34E109.5
C31A—C34A—H34C109.5C31B—C34B—H34F109.5
H34A—C34A—H34C109.5H34D—C34B—H34F109.5
H34B—C34A—H34C109.5H34E—C34B—H34F109.5
C5A—O51A—C52A115.05 (10)C5B—O51B—C52B114.83 (10)
O51A—C52A—C53A107.95 (12)O51B—C52B—C53B107.99 (13)
O51A—C52A—H52A110.1O51B—C52B—H52C110.1
C53A—C52A—H52A110.1C53B—C52B—H52C110.1
O51A—C52A—H52B110.1O51B—C52B—H52D110.1
C53A—C52A—H52B110.1C53B—C52B—H52D110.1
H52A—C52A—H52B108.4H52C—C52B—H52D108.4
C52A—C53A—H53A109.5C52B—C53B—H53D109.5
C52A—C53A—H53B109.5C52B—C53B—H53E109.5
H53A—C53A—H53B109.5H53D—C53B—H53E109.5
C52A—C53A—H53C109.5C52B—C53B—H53F109.5
H53A—C53A—H53C109.5H53D—C53B—H53F109.5
H53B—C53A—H53C109.5H53E—C53B—H53F109.5
C56A—C54A—C57A109.52 (12)C56B—C54B—C55B109.49 (12)
C56A—C54A—C55A108.74 (12)C56B—C54B—C57B108.74 (12)
C57A—C54A—C55A109.26 (12)C55B—C54B—C57B109.12 (12)
C56A—C54A—C5A110.36 (12)C56B—C54B—C5B110.22 (11)
C57A—C54A—C5A109.49 (11)C55B—C54B—C5B109.42 (11)
C55A—C54A—C5A109.45 (11)C57B—C54B—C5B109.83 (11)
C54A—C55A—H55A109.5C54B—C55B—H55D109.5
C54A—C55A—H55B109.5C54B—C55B—H55E109.5
H55A—C55A—H55B109.5H55D—C55B—H55E109.5
C54A—C55A—H55C109.5C54B—C55B—H55F109.5
H55A—C55A—H55C109.5H55D—C55B—H55F109.5
H55B—C55A—H55C109.5H55E—C55B—H55F109.5
C54A—C56A—H56A109.5C54B—C56B—H56D109.5
C54A—C56A—H56B109.5C54B—C56B—H56E109.5
H56A—C56A—H56B109.5H56D—C56B—H56E109.5
C54A—C56A—H56C109.5C54B—C56B—H56F109.5
H56A—C56A—H56C109.5H56D—C56B—H56F109.5
H56B—C56A—H56C109.5H56E—C56B—H56F109.5
C54A—C57A—H57A109.5C54B—C57B—H57D109.5
C54A—C57A—H57B109.5C54B—C57B—H57E109.5
H57A—C57A—H57B109.5H57D—C57B—H57E109.5
C54A—C57A—H57C109.5C54B—C57B—H57F109.5
H57A—C57A—H57C109.5H57D—C57B—H57F109.5
H57B—C57A—H57C109.5H57E—C57B—H57F109.5
O1A—C1A—C2A—C3A175.84 (14)O1B—C1B—C2B—C3B171.89 (14)
C5A—C1A—C2A—C3A4.57 (15)C5B—C1B—C2B—C3B8.17 (14)
O1A—C1A—C2A—C21A4.3 (2)O1B—C1B—C2B—C21B11.2 (2)
C5A—C1A—C2A—C21A175.27 (12)C5B—C1B—C2B—C21B168.79 (12)
C1A—C2A—C3A—N4A2.80 (16)C1B—C2B—C3B—N4B5.04 (15)
C21A—C2A—C3A—N4A177.03 (13)C21B—C2B—C3B—N4B171.77 (13)
C1A—C2A—C3A—C31A175.43 (13)C1B—C2B—C3B—C31B173.79 (13)
C21A—C2A—C3A—C31A4.7 (2)C21B—C2B—C3B—C31B9.4 (2)
C2A—C3A—N4A—C5A0.37 (16)C2B—C3B—N4B—C5B0.50 (16)
C31A—C3A—N4A—C5A178.79 (12)C31B—C3B—N4B—C5B179.46 (11)
C3A—N4A—C5A—O51A122.73 (12)C3B—N4B—C5B—O51B125.64 (12)
C3A—N4A—C5A—C54A117.39 (12)C3B—N4B—C5B—C1B5.27 (14)
C3A—N4A—C5A—C1A3.01 (14)C3B—N4B—C5B—C54B113.61 (12)
O1A—C1A—C5A—O51A57.67 (17)O1B—C1B—C5B—O51B52.43 (17)
C2A—C1A—C5A—O51A122.71 (12)C2B—C1B—C5B—O51B127.62 (11)
O1A—C1A—C5A—N4A175.89 (13)O1B—C1B—C5B—N4B172.06 (12)
C2A—C1A—C5A—N4A4.49 (13)C2B—C1B—C5B—N4B7.99 (13)
O1A—C1A—C5A—C54A64.28 (17)O1B—C1B—C5B—C54B69.29 (16)
C2A—C1A—C5A—C54A115.35 (12)C2B—C1B—C5B—C54B110.66 (12)
C3A—C2A—C21A—O21A123.99 (18)C3B—C2B—C21B—O21B20.3 (2)
C1A—C2A—C21A—O21A56.2 (2)C1B—C2B—C21B—O21B155.96 (15)
C3A—C2A—C21A—O22A59.31 (19)C3B—C2B—C21B—O22B162.64 (13)
C1A—C2A—C21A—O22A120.50 (14)C1B—C2B—C21B—O22B21.06 (19)
O21A—C21A—O22A—C23A4.9 (2)O21B—C21B—O22B—C23B0.2 (2)
C2A—C21A—O22A—C23A178.30 (14)C2B—C21B—O22B—C23B177.41 (14)
C21A—O22A—C23A—C24A148.27 (16)C21B—O22B—C23B—C24B91.19 (19)
N4A—C3A—C31A—C32A86.56 (17)N4B—C3B—C31B—C33B13.22 (18)
C2A—C3A—C31A—C32A95.34 (18)C2B—C3B—C31B—C33B165.52 (14)
N4A—C3A—C31A—C34A33.74 (18)N4B—C3B—C31B—C34B132.93 (14)
C2A—C3A—C31A—C34A144.35 (15)C2B—C3B—C31B—C34B45.82 (19)
N4A—C3A—C31A—C33A151.90 (14)N4B—C3B—C31B—C32B106.10 (14)
C2A—C3A—C31A—C33A26.2 (2)C2B—C3B—C31B—C32B75.15 (18)
N4A—C5A—O51A—C52A63.24 (15)N4B—C5B—O51B—C52B52.86 (15)
C54A—C5A—O51A—C52A173.96 (11)C1B—C5B—O51B—C52B60.04 (15)
C1A—C5A—O51A—C52A48.84 (15)C54B—C5B—O51B—C52B175.88 (11)
C5A—O51A—C52A—C53A161.21 (12)C5B—O51B—C52B—C53B152.20 (12)
O51A—C5A—C54A—C56A58.82 (14)O51B—C5B—C54B—C56B173.80 (11)
N4A—C5A—C54A—C56A179.22 (11)N4B—C5B—C54B—C56B62.93 (14)
C1A—C5A—C54A—C56A66.26 (14)C1B—C5B—C54B—C56B49.04 (15)
O51A—C5A—C54A—C57A179.45 (11)O51B—C5B—C54B—C55B65.74 (14)
N4A—C5A—C54A—C57A58.60 (14)N4B—C5B—C54B—C55B57.52 (15)
C1A—C5A—C54A—C57A54.36 (15)C1B—C5B—C54B—C55B169.49 (11)
O51A—C5A—C54A—C55A60.81 (14)O51B—C5B—C54B—C57B54.01 (14)
N4A—C5A—C54A—C55A61.15 (14)N4B—C5B—C54B—C57B177.28 (11)
C1A—C5A—C54A—C55A174.11 (11)C1B—C5B—C54B—C57B70.75 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4A—H4A···O1Bi0.832 (16)2.175 (16)3.0009 (15)171.8 (14)
N4B—H4B···O1A0.862 (16)2.156 (17)3.0089 (15)170.4 (15)
Symmetry code: (i) x+1/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC17H29NO4
Mr311.41
Crystal system, space groupMonoclinic, P21/n
Temperature (K)150
a, b, c (Å)9.9187 (7), 16.3916 (11), 22.2115 (15)
β (°) 92.5822 (11)
V3)3607.6 (4)
Z8
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.42 × 0.40 × 0.33
Data collection
DiffractometerBruker SMART APEXII
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.887, 0.974
No. of measured, independent and
observed [I > 2σ(I)] reflections
40948, 6356, 5812
Rint0.018
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.077, 1.00
No. of reflections6356
No. of parameters441
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.31, 0.25

Computer programs: APEX2 (Bruker, 2010), APEX2 and SAINT (Bruker, 2010), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), SHELXL2012 (Sheldrick, 2008), XSHELL (Bruker, 2010) and Mercury (Macrae et al., 2008), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4A—H4A···O1Bi0.832 (16)2.175 (16)3.0009 (15)171.8 (14)
N4B—H4B···O1A0.862 (16)2.156 (17)3.0089 (15)170.4 (15)
Symmetry code: (i) x+1/2, y+1/2, z+1/2.
 

Acknowledgements

This work was supported in part by grants GM056481 (JPYK) and EB2034 (GMR) from the US National Institutes of Health.

References

First citationBruker (2010). APEX2, SAINT and XSHELL. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationMacrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470.  Web of Science CrossRef CAS IUCr Journals
First citationRamasseul, R. & Rassat, A. (1970). Bull. Soc. Chim. Fr. 72, 4330–4340.
First citationRiplinger, C., Kao, J. P. Y., Rosen, G. M., Kathirvelu, V., Eaton, G. R., Eaton, S. S., Kutateladze, A. & Neese, F. (2009). J. Am. Chem. Soc. 131, 10092–10106.  Web of Science CSD CrossRef PubMed CAS
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationTravis, B. R., Sivakumar, M., Hollist, G. O. & Borhan, B. (2003). Org. Lett. 5, 3089–3092.  Web of Science CrossRef PubMed
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals

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