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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o205.
Published online 2007 December 6. doi:  10.1107/S160053680706391X
PMCID: PMC2915266

Di-tert-butyl 2-benzoyl­hydrazine-1,1-dicarboxyl­ate

Abstract

The crystal structure of the title compound, C17H24N2O5, was determined in the course of our studies on the preparation of two families of pseudopeptides, viz. hydrazino- and N-amino- peptides. The most significant inter­action in the crystal structure is a bifurcated inter­molecular N—H(...)O hydrogen bond.

Related literature

For the synthesis, see: Brosse et al. (2003 [triangle]). For geometry, see: Allen (2002 [triangle]); Kauffmann et al. (2004 [triangle]); Fong et al. (1996 [triangle]).

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Object name is e-64-0o205-scheme1.jpg

Experimental

Crystal data

  • C17H24N2O5
  • M r = 336.38
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o205-efi1.jpg
  • a = 9.9794 (2) Å
  • b = 11.5763 (3) Å
  • c = 16.0720 (4) Å
  • V = 1856.71 (8) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 293 (2) K
  • 0.3 × 0.05 × 0.05 mm

Data collection

  • Nonius KappaCCD area-detector diffractometer
  • Absorption correction: none
  • 9649 measured reflections
  • 1944 independent reflections
  • 1559 reflections with I > 2σ(I)
  • R int = 0.032

Refinement

  • R[F 2 > 2σ(F 2)] = 0.038
  • wR(F 2) = 0.109
  • S = 1.03
  • 1944 reflections
  • 226 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.16 e Å−3
  • Δρmin = −0.15 e Å−3

Data collection: COLLECT (Nonius, 1998 [triangle]); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 [triangle]); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997 [triangle]); program(s) used to solve structure: SIR92 (Altomare et al., 1999 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]) and WebLab ViewerPro 3.5 (MSI, 1999 [triangle]); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680706391X/hj2004sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680706391X/hj2004Isup2.hkl

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

Acknowledgments

The authors thank the National Research Agency (ANR) for financial support (No. NT05_4_42848) and the Service Commun de Diffraction X (Nancy Université) for providing access to experimental crystallographic facilities.

supplementary crystallographic information

Comment

As part of our continuing studies on the synthesis and structure of hydrazino- and N-amino-peptides, we have described the crystal structure of N-(tert-Butyloxycarbonylamino)phthalimide (Kauffmann et al., 2004). Here we report the crystal structure of the title compound, N-benzoyl-Nβ, Nα- bis (tert-butoxycarbonyl) hydrazine (Fig. 1).

Although the title compound is not chiral, it crystallizes in the non-centrosymmetric space group P212121. The angle between the amide plane and the mean plane of the imidodicarbonate group is 78.43 (18)°, showing that these two groups are nearly perpendicular. The angle between the best-fit phenyl plane and the amide plane of 27.34 (7)° is similar to that reported for the benzamide group (Fong et al., 1996).

In the crystal structure of the title compound, molecules are linked into infinite chains parallel to a via bifurcated N—H···O hydrogen bonds involving both carbonate of the aminoimidodicarbonate group (Fig. 2). All other intermolecular interactions are due to van der Waals forces.

Experimental

The title compound was prepared from N-(tert-Butyloxycarbonylamino)phthalimide (Brosse et al., 2003), and was crystallized by slow evaporation of an ethanol solution.

Refinement

All H atoms were located in difference maps. The C-bonded H atoms were placed at calculated positions and refined using a riding model, with C—H distances of 0.93–0.96 Å. The N-bonded H atom was refined with free positional parameters. The H-atom Uiso parameters were fixed at 1.3Ueq(C) for aromatic C—H groups, at 1.3Ueq(N) for the N—H group and at 1.5Ueq(C) for methyl C—H.

Figures

Fig. 1.
The molecular structure of title compound showing the atom-numbering scheme. All non-H atoms are represented by 25% probability displacement ellipsoids.
Fig. 2.
Part of the crystal structure of the title compound showing the chains along [100]. The intermolecular hydrogen bonds are shown as dashed lines.

Crystal data

C17H24N2O5F000 = 720
Mr = 336.38Dx = 1.203 Mg m3
Orthorhombic, P212121Mo Kα radiation λ = 0.7107 Å
Hall symbol: P 2ac 2abCell parameters from 9649 reflections
a = 9.9794 (2) Åθ = 2.5–25.5º
b = 11.5763 (3) ŵ = 0.09 mm1
c = 16.0720 (4) ÅT = 293 (2) K
V = 1856.71 (8) Å3Prism, colorless
Z = 40.3 × 0.05 × 0.05 mm

Data collection

Nonius KappaCCD area-detector diffractometer1559 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.032
Monochromator: graphiteθmax = 25.5º
ω and [var phi] scansθmin = 2.5º
Absorption correction: noneh = −11→11
9649 measured reflectionsk = −14→14
1944 independent reflectionsl = −19→19

Refinement

Refinement on F2H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full  w = 1/[σ2(Fo2) + (0.0717P)2 + 0.077P] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.038(Δ/σ)max = 0.044
wR(F2) = 0.109Δρmax = 0.16 e Å3
S = 1.03Δρmin = −0.15 e Å3
1944 reflectionsExtinction correction: none
226 parameters

Special details

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.

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

xyzUiso*/Ueq
C10.5100 (2)−0.0209 (2)−0.17416 (18)0.0659 (7)
C20.6320 (3)0.0439 (4)−0.2024 (2)0.0978 (11)
H2A0.65660.0997−0.16090.147*
H2B0.61280.0829−0.25380.147*
H2C0.7046−0.0092−0.21060.147*
C30.3937 (3)0.0597 (3)−0.1641 (3)0.1131 (13)
H3A0.31370.0158−0.1540.17*
H3B0.38290.1045−0.21390.17*
H3C0.40990.1104−0.11790.17*
C40.4826 (5)−0.1216 (4)−0.2302 (2)0.1084 (12)
H4A0.5609−0.1695−0.23340.163*
H4B0.4602−0.094−0.28480.163*
H4C0.4092−0.1657−0.20840.163*
O10.55435 (15)−0.06767 (16)−0.09296 (11)0.0615 (5)
C50.4705 (2)−0.1231 (2)−0.04390 (17)0.0556 (6)
O20.35449 (18)−0.14394 (19)−0.05764 (15)0.0834 (6)
N10.53802 (19)−0.15842 (17)0.02859 (13)0.0533 (5)
N20.67171 (18)−0.12688 (16)0.03912 (13)0.0493 (5)
H20.723 (3)−0.177 (2)0.0211 (18)0.064*
C60.7009 (2)−0.0142 (2)0.05343 (15)0.0501 (6)
O30.61438 (18)0.05698 (16)0.06796 (13)0.0722 (5)
C70.8465 (2)0.0151 (2)0.04796 (15)0.0530 (6)
C80.9465 (2)−0.0644 (2)0.06302 (17)0.0629 (7)
H80.9244−0.1390.07950.082*
C91.0804 (3)−0.0334 (3)0.0536 (2)0.0855 (10)
H91.1477−0.08720.06370.111*
C101.1127 (3)0.0761 (4)0.0296 (2)0.0952 (11)
H101.20220.09650.02320.124*
C111.0149 (4)0.1561 (3)0.0149 (2)0.0937 (11)
H111.03780.2304−0.00190.122*
C120.8811 (3)0.1263 (3)0.02503 (19)0.0735 (8)
H120.81460.18120.01640.096*
C130.4706 (2)−0.2161 (2)0.09331 (16)0.0542 (6)
O40.35904 (18)−0.25409 (17)0.08502 (12)0.0743 (6)
O50.54681 (15)−0.22196 (15)0.15998 (11)0.0584 (4)
C140.5017 (3)−0.2927 (2)0.23280 (17)0.0595 (6)
C150.3708 (3)−0.2462 (2)0.26688 (19)0.0715 (8)
H15A0.3791−0.16460.27640.107*
H15B0.3502−0.28430.31840.107*
H15C0.3003−0.26010.22750.107*
C160.4944 (3)−0.4176 (3)0.2060 (2)0.0883 (10)
H16A0.423−0.4270.16650.132*
H16B0.4778−0.46550.25360.132*
H16C0.5777−0.43960.18070.132*
C170.6120 (3)−0.2720 (4)0.2951 (2)0.0920 (10)
H17A0.6962−0.29530.27170.138*
H17B0.5947−0.31620.34450.138*
H17C0.6153−0.19140.30890.138*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0554 (13)0.0720 (17)0.0704 (16)−0.0016 (12)−0.0099 (13)0.0087 (14)
C20.077 (2)0.125 (3)0.091 (2)−0.022 (2)−0.0004 (18)0.034 (2)
C30.080 (2)0.096 (2)0.163 (4)0.026 (2)0.012 (3)0.041 (3)
C40.137 (3)0.108 (3)0.080 (2)−0.020 (3)−0.023 (2)−0.010 (2)
O10.0458 (8)0.0760 (11)0.0626 (10)−0.0073 (9)−0.0035 (8)0.0080 (9)
C50.0431 (13)0.0549 (13)0.0689 (16)−0.0016 (11)0.0006 (12)0.0000 (12)
O20.0423 (10)0.1008 (14)0.1071 (16)−0.0138 (9)−0.0132 (10)0.0264 (13)
N10.0362 (10)0.0588 (11)0.0648 (12)−0.0080 (8)0.0018 (9)0.0017 (10)
N20.0359 (10)0.0495 (11)0.0626 (12)−0.0023 (8)0.0041 (9)−0.0032 (9)
C60.0476 (13)0.0537 (13)0.0490 (13)−0.0005 (10)0.0015 (11)−0.0047 (11)
O30.0571 (10)0.0634 (10)0.0960 (13)0.0068 (9)0.0060 (9)−0.0205 (11)
C70.0470 (12)0.0615 (14)0.0503 (13)−0.0099 (11)0.0009 (11)−0.0090 (11)
C80.0499 (13)0.0681 (15)0.0707 (16)−0.0058 (13)−0.0006 (12)−0.0143 (14)
C90.0511 (15)0.106 (3)0.099 (2)−0.0035 (16)0.0008 (16)−0.032 (2)
C100.0616 (18)0.125 (3)0.099 (2)−0.039 (2)0.0132 (18)−0.022 (2)
C110.088 (2)0.096 (2)0.098 (3)−0.042 (2)0.0036 (19)0.0067 (19)
C120.0696 (17)0.0702 (17)0.0806 (19)−0.0189 (14)−0.0040 (15)0.0049 (16)
C130.0439 (13)0.0551 (13)0.0637 (14)−0.0060 (11)0.0075 (12)−0.0056 (12)
O40.0537 (10)0.0951 (14)0.0740 (12)−0.0262 (10)0.0028 (9)−0.0005 (10)
O50.0451 (8)0.0669 (10)0.0632 (10)−0.0113 (8)0.0039 (8)0.0058 (9)
C140.0508 (13)0.0568 (15)0.0711 (17)−0.0038 (11)0.0058 (12)0.0078 (12)
C150.0632 (16)0.0717 (18)0.0796 (18)0.0039 (14)0.0190 (14)0.0056 (14)
C160.092 (2)0.0553 (17)0.118 (3)0.0054 (16)0.023 (2)0.0053 (16)
C170.0674 (17)0.123 (3)0.086 (2)−0.0129 (19)−0.0080 (17)0.027 (2)

Geometric parameters (Å, °)

C1—O11.481 (3)C8—C91.393 (4)
C1—C31.498 (4)C8—H80.93
C1—C41.498 (5)C9—C101.363 (5)
C1—C21.500 (4)C9—H90.93
C2—H2A0.96C10—C111.367 (5)
C2—H2B0.96C10—H100.93
C2—H2C0.96C11—C121.388 (4)
C3—H3A0.96C11—H110.93
C3—H3B0.96C12—H120.93
C3—H3C0.96C13—O41.204 (3)
C4—H4A0.96C13—O51.316 (3)
C4—H4B0.96O5—C141.498 (3)
C4—H4C0.96C14—C171.508 (4)
O1—C51.317 (3)C14—C161.510 (4)
C5—O21.203 (3)C14—C151.515 (4)
C5—N11.407 (3)C15—H15A0.96
N1—N21.393 (3)C15—H15B0.96
N1—C131.407 (3)C15—H15C0.96
N2—C61.356 (3)C16—H16A0.96
N2—H20.82 (3)C16—H16B0.96
C6—O31.216 (3)C16—H16C0.96
C6—C71.495 (3)C17—H17A0.96
C7—C81.378 (4)C17—H17B0.96
C7—C121.383 (4)C17—H17C0.96
O1—C1—C3111.4 (3)C9—C8—H8119.9
O1—C1—C4107.5 (2)C10—C9—C8119.8 (3)
C3—C1—C4114.0 (3)C10—C9—H9120.1
O1—C1—C2102.0 (2)C8—C9—H9120.1
C3—C1—C2110.5 (3)C9—C10—C11120.7 (3)
C4—C1—C2110.8 (3)C9—C10—H10119.6
C1—C2—H2A109.5C11—C10—H10119.6
C1—C2—H2B109.5C10—C11—C12119.8 (3)
H2A—C2—H2B109.5C10—C11—H11120.1
C1—C2—H2C109.5C12—C11—H11120.1
H2A—C2—H2C109.5C7—C12—C11120.2 (3)
H2B—C2—H2C109.5C7—C12—H12119.9
C1—C3—H3A109.5C11—C12—H12119.9
C1—C3—H3B109.5O4—C13—O5127.3 (2)
H3A—C3—H3B109.5O4—C13—N1122.3 (2)
C1—C3—H3C109.5O5—C13—N1110.47 (18)
H3A—C3—H3C109.5C13—O5—C14119.39 (17)
H3B—C3—H3C109.5O5—C14—C17102.3 (2)
C1—C4—H4A109.5O5—C14—C16108.3 (2)
C1—C4—H4B109.5C17—C14—C16112.2 (3)
H4A—C4—H4B109.5O5—C14—C15110.3 (2)
C1—C4—H4C109.5C17—C14—C15109.4 (2)
H4A—C4—H4C109.5C16—C14—C15113.7 (2)
H4B—C4—H4C109.5C14—C15—H15A109.5
C5—O1—C1121.07 (18)C14—C15—H15B109.5
O2—C5—O1126.8 (3)H15A—C15—H15B109.5
O2—C5—N1123.7 (2)C14—C15—H15C109.5
O1—C5—N1109.43 (19)H15A—C15—H15C109.5
N2—N1—C5118.9 (2)H15B—C15—H15C109.5
N2—N1—C13119.5 (2)C14—C16—H16A109.5
C5—N1—C13121.37 (19)C14—C16—H16B109.5
C6—N2—N1118.55 (19)H16A—C16—H16B109.5
C6—N2—H2127.0 (19)C14—C16—H16C109.5
N1—N2—H2111.5 (19)H16A—C16—H16C109.5
O3—C6—N2122.2 (2)H16B—C16—H16C109.5
O3—C6—C7123.2 (2)C14—C17—H17A109.5
N2—C6—C7114.6 (2)C14—C17—H17B109.5
C8—C7—C12119.1 (2)H17A—C17—H17B109.5
C8—C7—C6122.8 (2)C14—C17—H17C109.5
C12—C7—C6118.0 (2)H17A—C17—H17C109.5
C7—C8—C9120.2 (3)H17B—C17—H17C109.5
C7—C8—H8119.9
C3—C1—O1—C556.4 (3)C12—C7—C8—C9−1.3 (4)
C4—C1—O1—C5−69.2 (3)C6—C7—C8—C9177.3 (3)
C2—C1—O1—C5174.2 (3)C7—C8—C9—C100.2 (5)
C1—O1—C5—O21.2 (4)C8—C9—C10—C110.2 (5)
C1—O1—C5—N1179.81 (19)C9—C10—C11—C120.5 (6)
O2—C5—N1—N2−178.3 (2)C8—C7—C12—C112.0 (4)
O1—C5—N1—N23.1 (3)C6—C7—C12—C11−176.7 (3)
O2—C5—N1—C13−3.7 (4)C10—C11—C12—C7−1.6 (5)
O1—C5—N1—C13177.6 (2)N2—N1—C13—O4−173.4 (2)
C5—N1—N2—C669.7 (3)C5—N1—C13—O412.0 (4)
C13—N1—N2—C6−105.0 (3)N2—N1—C13—O55.8 (3)
N1—N2—C6—O39.7 (4)C5—N1—C13—O5−168.72 (19)
N1—N2—C6—C7−169.0 (2)O4—C13—O5—C146.9 (4)
O3—C6—C7—C8154.6 (3)N1—C13—O5—C14−172.37 (19)
N2—C6—C7—C8−26.7 (4)C13—O5—C14—C17−177.6 (2)
O3—C6—C7—C12−26.7 (4)C13—O5—C14—C1663.8 (3)
N2—C6—C7—C12151.9 (2)C13—O5—C14—C15−61.3 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2···O2i0.82 (3)2.53 (3)3.233 (3)145 (3)
N2—H2···O4i0.82 (3)2.32 (3)3.062 (3)150 (3)

Symmetry codes: (i) x+1/2, −y−1/2, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HJ2004).

References

  • Allen, F. H. (2002). Acta Cryst. B58, 380–388. [PubMed]
  • Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst.32, 115–119.
  • Brosse, N., Pinto, M.-F. & Jamart-Grégoire, B. (2003). Eur. J. Org. Chem.24, 4757–4764.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Fong, M. C., Gable, R. W. & Schiesser, C. H. (1996). Acta Cryst. C52, 1886–1889.
  • Kauffmann, B., Didierjean, C., Brosse, N., Jamart-Grégoire, B. & Aubry, A. (2004). Acta Cryst. E60, o934–o935.
  • MSI (1999). WebLab ViewerPro 3.5 Molecular Simulation Inc., San Diego, USA.
  • Nonius (1998). COLLECT Nonius BV, Delft, The Netherlands.
  • Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.
  • Sheldrick, G. M. (1997). SHELXL97 University of Göttingen, Germany. [PubMed]

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