2 Methyl­propionohydrazide

organic papers

Acta Cryst.(2007). E63, o1475–o1477 doi:10.1107/S1600536807008896 Engel and Ferrence _C

4H10N2O

o1475

Structure Reports Online

ISSN 1600-5368

2-Methylpropionohydrazide

Sharon E. Engel and Gregory M. Ferrence*

CB 4160, Department of Chemistry, Illinois State University, Normal, IL 61790, USA

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study T= 100 K

Mean(C–C) = 0.003 A˚ Rfactor = 0.073 wRfactor = 0.191

Data-to-parameter ratio = 16.9

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

Received 20 February 2007 Accepted 22 February 2007

#2007 International Union of Crystallography All rights reserved

In the title structure, C4H10N2O, the molecules stack with

intermolecular N—H O hydrogen bonds along the b axis and additional intermolecular N—H N hydrogen bonds form a network orthogonal to thecaxis.

Comment

As part of our investigation into the synthesis of dialkyl- and aryl-substituted triazoles (Jerniganet al., 2007), compound (I) was isolated as a minor by-product in the synthesis of 3,5-diisopropyl-1,2,4-triazole. The title compound, (I), has been known for over 40 years (Rabini & Vita 1965); however, this is the first report of its X-ray crystal structure.

A Mogul (Bruno et al. 2004) geometry check showed all non-H bond angles and distances to be normal. The two most similar molecules identified in the Cambridge Structural Database (Version 5.28; Allen, 2002) are cyclopropane-carboxylic acid hydrazide, (II) (Chesnut & Marsh, 1958), and

n-nonanoic acid hydrazide (Jensen & Lingafelter, 1961). Comparison of these two molecules with the title compound show corresponding bond distances to be nearly indis-tinguishable and corresponding angles to differ by less than two degrees. The obvious exception are the bond angles about C2, where the cyclopropyl-ring-imposed 58.8 _C3—C2—C4

bond angle of (II) is substantially less than the 111.5 (2)_angle

observed in (I). Likewise, the C1—C2—C3 and C1—C2—C4 angles are larger in (II) than in (I).

Figure 1

Compound (I) crystallizes with an extensive network of intermolecular hydrogen bonding (Table 1). The molecules stack with N2—H2N O1ihydrogen bonds along thebaxis (Fig. 2; purple dashes), with moderate 2.831 (2) A˚ D A

separations. N1—H1A N1iii hydrogen bonds across the a -glide planes (Fig. 2; green dashes) pair these stacks together with 3.158 (3) A˚ D Aseparations. These pairs of stacks are further joined to neighboring pairs of stacks through N1— H1B O1iihydrogen bonds (Fig. 2; blue dashes), the pairs of molecules being related by an inversion center. Overall, a two-dimensional network of intermolecularly hydrogen-bonded molecules is formed orthogonal to the c axis (Fig. 3). The hydrophobic isopropyl groups are oriented away from the hydrogen-bonding network, forming layers along the c axis connected only by van der Waals contacts (Fig. 4). This hydrogen-bonding network is essentially the same as that observed in (II) (N1 N10= 3.16, N1 O0= 3.26 and N2 O1 = 2.94 A˚ ). It is worth noting that the 3.078 (3) A˚ N1 O0

D A separations observed for (I) are shorter than those observed for (II) by 0.18 A˚ . This suggests that the modest geometric alterations between isopropyl and cyclopropyl significantly impacted these hydrogen bonds. This is consistent with the conclusion that the N1 O0_{bond must be considered}

a very weak link (Chesnut & Marsh, 1958).

Experimental

The synthesis of 3,5-diisopropyltriazole was carried out in a manner analogous to the literature procedure for the synthesis of 3-tert

-butyl-5-methyltriazole (Jerniganet al., 2007; Pe´rezet al., 1983). During the purification of 3,5-diisopropyltriazole by sublimation under vacuum at 383 K, two separate rings of (I) were deposited on the wall of the sublimation cold-finger. The top band consisted of colorless clear crystals from which one was selected for the single-crystal X-ray diffraction experiment. Once the structure was determined to be that of the title compound, a compound known for over 40 years (Rabini & Vita 1965), no further characterization was carried out.

organic papers

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4H10N2O Acta Cryst.(2007). E63, o1475–o1477

Figure 2

A view of the principal hydrogen bonds (dashed lines) in (I).

Figure 3

A view orthogonal to the ab plane, showing the two-dimensional arrangement of hydrogen bonds (dashed lines).

Figure 4

Crystal data

C4H10N2O

Mr= 102.08

Orthorhombic,Pbca a= 11.0189 (19) A˚

b= 4.8781 (9) A˚

c= 21.677 (4) A˚

V= 1165.2 (4) A˚3

Z= 8

MoKradiation

= 0.09 mm1

T= 100 (2) K 0.590.460.18 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: none 8412 measured reflections

1755 independent reflections 1246 reflections withI> 2(I)

Rint= 0.063

Refinement

R[F2> 2(F2)] = 0.073

wR(F2_{) = 0.191}

S= 1.12 1755 reflections

104 parameters

All H-atom parameters refined

max= 0.44 e A˚

3

min=0.29 e A˚

3

Table 1

Hydrogen-bond geometry (A˚ ,_).

D—H A D—H H A D A D—H A

N2—H2N O1i

0.85 (3) 1.98 (3) 2.831 (2) 175 (3) N1—H1B O1ii 0.92 (3) 2.17 (3) 3.078 (3) 169 (2) N1—H1A N1iii

0.90 (3) 2.26 (3) 3.158 (3) 172 (2)

Symmetry codes: (i)x;yþ1;z; (ii)xþ1;yþ1;zþ1; (iii)xþ1 2;y

1 2;z.

All H atoms were identified in difference Fourier maps and refined with isotropic displacement parameters.

Data collection:SMART(Bruker, 2002); cell refinement: SAINT-Plus(Bruker, 2003); data reduction:SAINT-Plus; program(s) used to solve structure:SIR2004(Burlaet al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics:

ORTEP-3 for Windows(Farrugia, 1997) andMERCURY(Macraeet

al., 2006); software used to prepare material for publication:WinGX

(Farrugia, 1997) andpublCIF(Westrip, 2007).

GMF gratefully acknowledges the Research Corporation (Grant CC6205) and the National Science Foundation (NSF; Grant CHE-0348158) for support. SEE thanks the NSF for a GK-12 Graduate Fellowship. GMF thanks Matthias Zeller of Youngstown State University Structure & Chemical Instru-mentation Facility for the data collection and useful discus-sions. The diffractometer was funded by NSF grant 0087210, Ohio Board of Regents grant CAP-491, and YSU.

References

Allen, F. H. (2002).Acta Cryst.B58, 380–388.

Bruker (2002). SMART for WNT/2000. Version 5.630. Bruker AXS Inc, Madison, Wisconsin, USA.

Bruker (2003). SAINT-Plus. Version 6.45. Bruker AXS Inc, Madison, Wisconsin, USA.

Bruno, I. J., Cole, J. C., Kessler, M., Luo, J., Motherwell, W. D. S., Purkis, L. H., Smith, B. R., Taylor, R., Cooper, R. I., Harris, S. E. & Orpen, A. G. (2004).J. Chem. Inf. Comput. Sci.44, 2133–2144.

Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005).J. Appl. Cryst.38, 381–388.

Chesnut, D. B. & Marsh, R. E. (1958).Acta Cryst.11, 413–419. Farrugia, L. J. (1997).J. Appl. Cryst.30, 565.

Jensen, L. H. & Lingafelter, E. C. (1961).Acta Cryst.14, 507–520.

Jernigan, F. E. III, Sieracki, N. A., Taylor, M. T., Jenkins, A. S., Engel, S. E., Rowe, B. W., Jove´, F. A., Yap, G. P. A., Papish, E. T. & Ferrence, G. F. (2007).

Inorg. Chem.46, 360–362.

Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006).J. Appl. Cryst.39, 453–457. Pe´rez, M. A., Dorado, C. A. & Soto, J. L. (1983).Synthesis,6, 483–486. Rabini, T. & Vita, G. (1965).J. Org. Chem.30, 2486–2488.

Sheldrick, G. M. (1997).SHELXL97. University of Go¨ttingen, Germany. Westrip, S. P. (2007).publCIF. In preparation.

organic papers

Acta Cryst.(2007). E63, o1475–o1477 Engel and Ferrence _C

supporting information

sup-1 Acta Cryst. (2007). E63, o1475–o1477

supporting information

Acta Cryst. (2007). E63, o1475–o1477 [https://doi.org/10.1107/S1600536807008896]

2-Methylpropionohydrazide

Sharon E. Engel and Gregory M. Ferrence

2-Methylpropionohydrazide

Crystal data

C4H10N2O

Mr = 102.08

Orthorhombic, Pbca

Hall symbol: -P 2ac 2ab

a = 11.0189 (19) Å

b = 4.8781 (9) Å

c = 21.677 (4) Å

V = 1165.2 (4) Å3

Z = 8

F(000) = 448

Dx = 1.165 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 9311 reflections

θ = 5.3–61.0°

µ = 0.09 mm−1

T = 100 K Plate, colourless 0.59 × 0.46 × 0.18 mm

Data collection

Bruker SMART APEX CCD diffractometer

Radiation source: sealed tube Graphite monochromator

ω scans

8412 measured reflections 1755 independent reflections

1246 reflections with I > 2σ(I)

Rint = 0.063

θmax = 30.5°, θmin = 1.9°

h = −15→14

k = −6→6

l = −30→30

Refinement

Refinement on F2 Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.073}

wR(F2_{) = 0.191}

S = 1.12 1755 reflections 104 parameters

0 restraints

All H-atom parameters refined

w = 1/[σ2_(F

o2) + (0.0748P)2 + 0.9877P] where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001 Δρmax = 0.44 e Å−3 Δρmin = −0.29 e Å−3

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₎

x y z Uiso*/Ueq

N1 0.34101 (18) 0.7903 (4) 0.48473 (8) 0.0254 (4)

supporting information

sup-2 Acta Cryst. (2007). E63, o1475–o1477

C1 0.42395 (19) 0.6629 (4) 0.58377 (10) 0.0238 (4)

O1 0.41985 (15) 0.4143 (3) 0.57242 (7) 0.0290 (4)

C2 0.4730 (2) 0.7685 (4) 0.64454 (10) 0.0266 (5)

C3 0.6052 (2) 0.6864 (6) 0.65061 (12) 0.0348 (6)

C4 0.3968 (2) 0.6531 (5) 0.69710 (11) 0.0339 (5)

H1A 0.292 (3) 0.643 (6) 0.4885 (12) 0.033 (7)*

H1B 0.408 (3) 0.734 (6) 0.4627 (13) 0.037 (7)*

H2N 0.392 (2) 1.021 (7) 0.5539 (12) 0.032 (7)*

H2A 0.469 (2) 0.966 (6) 0.6446 (10) 0.028 (6)*

H3A 0.611 (3) 0.482 (7) 0.6498 (13) 0.037 (7)*

H3B 0.640 (3) 0.748 (6) 0.6876 (13) 0.038 (7)*

H3C 0.649 (3) 0.755 (7) 0.6196 (15) 0.048 (8)*

H4A 0.403 (2) 0.447 (6) 0.6966 (12) 0.038 (7)*

H4B 0.426 (2) 0.708 (5) 0.7355 (12) 0.030 (6)*

H4C 0.309 (3) 0.696 (6) 0.6935 (13) 0.040 (7)*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

N1 0.0269 (9) 0.0188 (8) 0.0306 (9) −0.0019 (7) −0.0010 (7) −0.0016 (7)

N2 0.0290 (9) 0.0126 (8) 0.0315 (9) 0.0000 (7) −0.0022 (7) −0.0021 (6)

C1 0.0244 (10) 0.0152 (9) 0.0317 (10) 0.0002 (7) 0.0015 (8) −0.0005 (7)

O1 0.0377 (9) 0.0113 (7) 0.0380 (8) 0.0000 (6) −0.0036 (6) −0.0019 (6)

C2 0.0317 (11) 0.0166 (9) 0.0314 (10) −0.0011 (8) −0.0020 (8) −0.0005 (7)

C3 0.0327 (13) 0.0374 (14) 0.0343 (12) −0.0053 (10) −0.0013 (10) −0.0035 (10)

C4 0.0362 (13) 0.0321 (12) 0.0333 (11) 0.0007 (10) 0.0036 (9) −0.0024 (9)

Geometric parameters (Å, º)

N1—N2 1.415 (2) N2—H2N 0.85 (3)

N2—C1 1.328 (3) C2—H2A 0.96 (3)

C1—O1 1.238 (2) C3—H3A 1.00 (3)

C1—C2 1.514 (3) C3—H3B 0.94 (3)

C2—C3 1.516 (3) C3—H3C 0.89 (3)

C2—C4 1.523 (3) C4—H4A 1.01 (3)

N1—H1A 0.90 (3) C4—H4B 0.93 (3)

N1—H1B 0.92 (3) C4—H4C 1.00 (3)

N1—N2—C1 123.28 (17) H3A—C3—H3C 109 (3)

N2—C1—O1 122.9 (2) H3B—C3—H3C 108 (3)

O1—C1—C2 121.26 (19) C2—C4—H4A 108.7 (16)

N2—C1—C2 115.86 (18) C2—C4—H4B 112.0 (16)

C1—C2—C3 109.18 (18) H4A—C4—H4B 106 (2)

C1—C2—C4 109.16 (18) C2—C4—H4C 113.7 (16)

C3—C2—C4 111.5 (2) H4A—C4—H4C 106 (2)

C1—C2—H2A 109.0 (14) H4B—C4—H4C 110 (2)

C3—C2—H2A 107.9 (16) N2—N1—H1A 107.7 (17)

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sup-3 Acta Cryst. (2007). E63, o1475–o1477

C2—C3—H3A 108.9 (17) H1A—N1—H1B 107 (2)

C2—C3—H3B 112.4 (18) C1—N2—H2N 119.3 (19)

H3A—C3—H3B 108 (2) N1—N2—H2N 117.4 (19)

C2—C3—H3C 111 (2)

O1—C1—C2—C3 62.2 (3) N2—C1—C2—C4 120.4 (2)

N2—C1—C2—C3 −117.4 (2) O1—C1—N2—N1 −0.9 (3)

O1—C1—C2—C4 −60.0 (3) C2—C1—N2—N1 178.73 (18)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

N2—H2N···O1i _{0.85 (3) 1.98 (3) 2.831 (2) 175 (3)}

N1—H1B···O1ii _{0.92 (3) 2.17 (3) 3.078 (3) 169 (2)}

N1—H1A···N1iii _{0.90 (3) 2.26 (3) 3.158 (3) 172 (2)}