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Acta Crystallogr Sect E Struct Rep Online. 2008 April 1; 64(Pt 4): o677.
Published online 2008 March 7. doi:  10.1107/S1600536808002973
PMCID: PMC2961068

N 2′,N 5′-Diisopropylidene­pyrazine-2,5-dicarbohydrazide dihydrate

Abstract

In the title compound, C12H16N6O2·2H2O, the organic mol­ecule, except for the methyl H atoms, is essentially planar, the r.m.s. deviation from planarity being 0.044 Å. The crystal structure is stabilized by inter­molecular O—H(...)O and O—H(...)N hydrogen bonds which form chains.

Related literature

For related literature, see: Wu et al. (2003 [triangle]); Wardell et al. (2006 [triangle]).

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Object name is e-64-0o677-scheme1.jpg

Experimental

Crystal data

  • C12H16N6O2·2H2O
  • M r = 312.34
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o677-efi1.jpg
  • a = 7.1924 (5) Å
  • b = 9.9409 (8) Å
  • c = 11.0903 (9) Å
  • α = 80.261 (6)°
  • β = 84.605 (5)°
  • γ = 89.537 (6)°
  • V = 778.03 (10) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 296 (2) K
  • 0.50 × 0.16 × 0.16 mm

Data collection

  • Bruker P4 diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2000 [triangle]) T min = 0.965, T max = 0.984
  • 12989 measured reflections
  • 3643 independent reflections
  • 1540 reflections with I > 2σ(I)
  • R int = 0.049

Refinement

  • R[F 2 > 2σ(F 2)] = 0.065
  • wR(F 2) = 0.209
  • S = 1.00
  • 3643 reflections
  • 224 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.23 e Å−3
  • Δρmin = −0.25 e Å−3

Data collection: CrystalClear (Rigaku, 2000 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808002973/wn2238sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808002973/wn2238Isup2.hkl

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

Acknowledgments

We are grateful for financial support from the National Science Foundation of Fujian Province of China (No. E0610017, 2003 F 006).

supplementary crystallographic information

Comment

Research into amine and hydrazine derivatives has become a major growth area of biological chemistry, structural chemistry, medicine and catalysis. As part of our work in this area, we here present the crystal structure of the title compound.

The structure of the title compound is illustrated in Fig. 1. Except for the H atoms of the methyl groups, the organic molecule is essentially planar, the r.m.s. deviation being 0.044 Å. In the hydrazino fragment, the N—N bond lengths are normal, while the C—N distances are slightly longer than those in pyrazine-2-carbohydrazide (Wardell et al., 2006). In the crystal structure, molecules are linked to form chains by intermolecular O—H···O and O—H···N hydrogen bonds (Fig. 2 and Table 1).

Experimental

The title compound was prepared by the hydroponics method. 2,5-Pyrazinedihydrazide, as a yellow powder, was synthesized from 2,5-pyrazinedicarboxylic acid dihydrate by esterification and acylation (Wu et al., 2003). 2,5-Pyrazinedihydrazide (20 mg) was dissolved in acetone (20 ml) with stirring for one hour. Transparent orange crystals of the title compound were obtained from the mother liquor by slow evaporation at room temperature after one week.

Refinement

The positions of the O-bound H atoms were located from a difference Fourier map and refined freely; the refined O—H distances lie in the range 0.76 (4) - 0.99 (7) Å. The H atoms of methyl groups C11 and C12 were also located in a difference map. Other H atoms bonded to C or N were placed in calculated positions. All C– and N-bound C atoms were refined as riding, with N—H = 0.86 Å, Csp2—H = 0.93 Å and Csp3—H = 0.96 Å; Uiso(H) = 1.2Ueq(C,N).

Figures

Fig. 1.
The structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen atoms are shown as spheres of arbitrary radius.
Fig. 2.
A packing diagram of the title compound, showing the hydrogen bond interactions as dashed lines.

Crystal data

C12H16N6O2·2H2OZ = 2
Mr = 312.34F000 = 332
Triclinic, P1Dx = 1.333 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 7.1924 (5) ÅCell parameters from 1817 reflections
b = 9.9409 (8) Åθ = 2.8–22.6º
c = 11.0903 (9) ŵ = 0.10 mm1
α = 80.261 (6)ºT = 296 (2) K
β = 84.605 (5)ºPrism, orange
γ = 89.537 (6)º0.50 × 0.16 × 0.16 mm
V = 778.03 (10) Å3

Data collection

Bruker P4 diffractometer3643 independent reflections
Radiation source: fine-focus sealed tube1540 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.049
Detector resolution: 14.6306 pixels mm-1θmax = 27.9º
T = 296(2) Kθmin = 1.9º
CCD_Profile_fitting scansh = −9→9
Absorption correction: multi-scan(CrystalClear (Rigaku, 2000)k = −13→13
Tmin = 0.965, Tmax = 0.984l = −14→14
12989 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.065H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.209  w = 1/[σ2(Fo2) + (0.0979P)2 + 0.03P] where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
3643 reflectionsΔρmax = 0.23 e Å3
224 parametersΔρmin = −0.25 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

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.
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)

xyzUiso*/Ueq
N50.4457 (3)0.9409 (2)0.18538 (19)0.0570 (6)
H5A0.32730.95490.18980.068*
N20.2140 (3)0.8126 (2)0.05799 (19)0.0543 (6)
N10.3605 (3)0.6324 (2)−0.09296 (18)0.0538 (6)
N30.1252 (3)0.5072 (2)−0.22285 (19)0.0563 (6)
H3A0.24430.4978−0.23340.068*
N40.0048 (3)0.4399 (2)−0.2847 (2)0.0580 (6)
O1−0.1200 (2)0.6055 (2)−0.12989 (18)0.0732 (6)
C30.3958 (3)0.7863 (2)0.0460 (2)0.0482 (6)
C10.1776 (3)0.6578 (2)−0.0798 (2)0.0463 (6)
N60.5616 (3)1.0070 (2)0.25097 (19)0.0580 (6)
C50.0469 (4)0.5873 (3)−0.1459 (2)0.0515 (6)
C60.5253 (4)0.8541 (3)0.1146 (2)0.0578 (7)
O20.6916 (3)0.8306 (2)0.1056 (2)0.0898 (8)
C20.1058 (3)0.7480 (3)−0.0051 (2)0.0543 (7)
H2A−0.02200.76390.00120.065*
C40.4690 (3)0.6970 (3)−0.0294 (2)0.0551 (7)
H4A0.59700.6818−0.03590.066*
C100.4878 (4)1.0898 (3)0.3168 (2)0.0573 (7)
C120.6179 (5)1.1587 (4)0.3842 (3)0.0696 (9)
H12A0.592 (4)1.136 (3)0.468 (3)0.084*
H12B0.609 (4)1.264 (3)0.364 (2)0.084*
H12C0.742 (5)1.131 (3)0.363 (3)0.084*
C70.0747 (4)0.3704 (3)−0.3630 (2)0.0581 (7)
C9−0.0602 (4)0.2998 (3)−0.4275 (3)0.0764 (9)
H9A−0.18530.3262−0.40410.115*
H9B−0.04840.2028−0.40480.115*
H9C−0.03290.3253−0.51470.115*
C110.2879 (4)1.1256 (3)0.3329 (3)0.0796 (9)
H11A0.23391.07990.41150.095*
H11B0.22371.09850.26880.095*
H11C0.27541.22260.32800.095*
C80.2769 (4)0.3527 (3)−0.4004 (3)0.0831 (10)
H8A0.29880.3727−0.48840.125*
H8B0.31220.2603−0.37200.125*
H8C0.34980.4138−0.36510.125*
O30.5953 (4)0.4902 (3)−0.2671 (2)0.0869 (8)
O4−0.0209 (4)0.9821 (3)0.2080 (3)0.0965 (9)
H3D0.710 (6)0.479 (3)−0.271 (3)0.106 (14)*
H3C0.556 (7)0.526 (5)−0.215 (4)0.15 (2)*
H4C0.032 (9)0.939 (7)0.138 (6)0.28 (3)*
H4D−0.127 (6)0.985 (4)0.219 (3)0.096 (14)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N50.0391 (12)0.0708 (14)0.0701 (14)0.0022 (10)−0.0142 (10)−0.0330 (12)
N20.0372 (12)0.0665 (14)0.0653 (13)0.0044 (10)−0.0077 (10)−0.0272 (11)
N10.0385 (12)0.0677 (14)0.0604 (13)0.0037 (10)−0.0050 (10)−0.0260 (11)
N30.0395 (12)0.0720 (14)0.0655 (13)−0.0035 (11)−0.0071 (10)−0.0333 (11)
N40.0466 (13)0.0693 (14)0.0660 (14)−0.0023 (11)−0.0126 (10)−0.0298 (12)
O10.0349 (11)0.0945 (15)0.1046 (15)0.0051 (10)−0.0114 (9)−0.0553 (12)
C30.0375 (14)0.0582 (15)0.0520 (14)0.0020 (12)−0.0073 (11)−0.0166 (12)
C10.0358 (14)0.0528 (15)0.0528 (15)0.0015 (11)−0.0047 (11)−0.0159 (12)
N60.0449 (13)0.0728 (15)0.0641 (13)−0.0030 (11)−0.0125 (10)−0.0293 (12)
C50.0415 (15)0.0583 (16)0.0574 (15)0.0009 (13)−0.0066 (12)−0.0167 (13)
C60.0413 (16)0.0764 (18)0.0618 (17)0.0017 (14)−0.0084 (13)−0.0274 (14)
O20.0381 (11)0.1373 (19)0.1155 (17)0.0089 (11)−0.0134 (10)−0.0795 (15)
C20.0362 (14)0.0670 (17)0.0659 (16)0.0045 (12)−0.0075 (12)−0.0278 (14)
C40.0363 (14)0.0734 (18)0.0621 (16)0.0030 (13)−0.0061 (11)−0.0297 (14)
C100.0491 (17)0.0667 (17)0.0614 (16)−0.0036 (14)−0.0110 (13)−0.0225 (14)
C120.0596 (19)0.085 (2)0.0721 (19)−0.0070 (18)−0.0121 (16)−0.0323 (18)
C70.0552 (17)0.0645 (17)0.0602 (16)−0.0022 (14)−0.0103 (13)−0.0239 (14)
C90.068 (2)0.086 (2)0.088 (2)−0.0015 (17)−0.0230 (16)−0.0406 (17)
C110.0578 (19)0.091 (2)0.104 (2)0.0091 (16)−0.0141 (16)−0.0544 (19)
C80.061 (2)0.114 (3)0.090 (2)0.0072 (18)−0.0084 (16)−0.059 (2)
O30.0485 (14)0.128 (2)0.1033 (18)0.0056 (13)−0.0192 (12)−0.0660 (16)
O40.0506 (15)0.122 (2)0.137 (2)0.0060 (14)−0.0248 (14)−0.0695 (17)

Geometric parameters (Å, °)

N5—C61.352 (3)C10—C111.480 (4)
N5—N61.393 (3)C10—C121.489 (4)
N5—H5A0.8600C12—H12A0.92 (3)
N2—C21.330 (3)C12—H12B1.03 (3)
N2—C31.330 (3)C12—H12C0.95 (3)
N1—C41.335 (3)C7—C81.492 (4)
N1—C11.337 (3)C7—C91.502 (3)
N3—C51.346 (3)C9—H9A0.9600
N3—N41.394 (3)C9—H9B0.9600
N3—H3A0.8600C9—H9C0.9600
N4—C71.264 (3)C11—H11A0.9600
O1—C51.213 (3)C11—H11B0.9600
C3—C41.388 (3)C11—H11C0.9600
C3—C61.489 (3)C8—H8A0.9600
C1—C21.386 (3)C8—H8B0.9600
C1—C51.492 (3)C8—H8C0.9600
N6—C101.272 (3)O3—H3D0.83 (4)
C6—O21.215 (3)O3—H3C0.76 (5)
C2—H2A0.9300O4—H4C0.99 (7)
C4—H4A0.9300O4—H4D0.76 (4)
C6—N5—N6117.9 (2)C11—C10—C12116.8 (2)
C6—N5—H5A121.1C10—C12—H12A112.0 (18)
N6—N5—H5A121.1C10—C12—H12B112.1 (16)
C2—N2—C3116.6 (2)H12A—C12—H12B106 (2)
C4—N1—C1116.5 (2)C10—C12—H12C108.8 (17)
C5—N3—N4117.1 (2)H12A—C12—H12C108 (3)
C5—N3—H3A121.5H12B—C12—H12C110 (2)
N4—N3—H3A121.5N4—C7—C8127.2 (2)
C7—N4—N3118.5 (2)N4—C7—C9116.7 (3)
N2—C3—C4121.7 (2)C8—C7—C9116.1 (2)
N2—C3—C6119.6 (2)C7—C9—H9A109.5
C4—C3—C6118.7 (2)C7—C9—H9B109.5
N1—C1—C2121.4 (2)H9A—C9—H9B109.5
N1—C1—C5119.6 (2)C7—C9—H9C109.5
C2—C1—C5119.0 (2)H9A—C9—H9C109.5
C10—N6—N5118.2 (2)H9B—C9—H9C109.5
O1—C5—N3123.8 (2)C10—C11—H11A109.4
O1—C5—C1119.8 (2)C10—C11—H11B109.8
N3—C5—C1116.4 (2)H11A—C11—H11B109.8
O2—C6—N5123.5 (2)C10—C11—H11C109.9
O2—C6—C3120.6 (2)H11A—C11—H11C109.8
N5—C6—C3115.9 (2)H11B—C11—H11C108.2
N2—C2—C1122.1 (2)C7—C8—H8A109.5
N2—C2—H2A118.9C7—C8—H8B109.5
C1—C2—H2A118.9H8A—C8—H8B109.5
N1—C4—C3121.8 (2)C7—C8—H8C109.5
N1—C4—H4A119.1H8A—C8—H8C109.5
C3—C4—H4A119.1H8B—C8—H8C109.5
N6—C10—C11127.2 (2)H3D—O3—H3C115 (4)
N6—C10—C12116.0 (3)H4C—O4—H4D117 (4)
C5—N3—N4—C7175.9 (2)N2—C3—C6—O2179.5 (3)
C2—N2—C3—C40.7 (4)C4—C3—C6—O2−0.7 (4)
C2—N2—C3—C6−179.6 (2)N2—C3—C6—N5−0.5 (4)
C4—N1—C1—C20.7 (4)C4—C3—C6—N5179.3 (2)
C4—N1—C1—C5−178.8 (2)C3—N2—C2—C1−0.1 (4)
C6—N5—N6—C10179.3 (2)N1—C1—C2—N2−0.6 (4)
N4—N3—C5—O1−1.4 (4)C5—C1—C2—N2178.9 (2)
N4—N3—C5—C1179.63 (19)C1—N1—C4—C3−0.2 (4)
N1—C1—C5—O1176.7 (2)N2—C3—C4—N1−0.5 (4)
C2—C1—C5—O1−2.8 (4)C6—C3—C4—N1179.7 (2)
N1—C1—C5—N3−4.3 (3)N5—N6—C10—C110.0 (4)
C2—C1—C5—N3176.2 (2)N5—N6—C10—C12−179.5 (2)
N6—N5—C6—O20.2 (4)N3—N4—C7—C8−1.3 (4)
N6—N5—C6—C3−179.8 (2)N3—N4—C7—C9−180.0 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N5—H5A···O40.862.513.369 (4)177
N3—H3A···O30.862.523.377 (4)176
O3—H3D···N4i0.83 (4)2.15 (4)2.977 (3)177 (3)
O3—H3D···O1i0.83 (4)2.57 (3)3.006 (3)115 (3)
O3—H3C···N10.76 (5)2.24 (5)2.974 (3)162 (5)
O4—H4C···N20.99 (7)2.05 (7)2.972 (3)153 (6)
O4—H4D···N6ii0.76 (4)2.25 (4)3.010 (4)177 (4)
O4—H4D···O2ii0.76 (4)2.58 (4)2.984 (3)115 (3)

Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WN2238).

References

  • Rigaku (2000). CrystalClear Version 1.3. Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Wardell, S. M. S. V., de Souza, M. V. N., Wardell, J. L., Low, J. N. & Glidewell, C. (2006). Acta Cryst. E62, o3765–o3767.
  • Wu, W.-S., Liu, S.-X. & Huang, Z.-X. (2003). Chin. J. Appl. Chem.20, 138–143.

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