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Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): o2988.
Published online 2009 November 4. doi:  10.1107/S1600536809045590
PMCID: PMC2971896

3,3,6,6-Tetrakis­(hydroxy­meth­yl)-1,2,4,5-tetra­zinane tetra­hydrate

Abstract

In the title compound, C6H16N4O4·4H2O, the tetra­zinane mol­ecule lies across an inversion centre. The tetra­zinane ring adopts a chair conformation, and all imino H atoms occupy axial positions. In the crystal, adjacent mol­ecules are linked through O—H(...)O, O—H(...)N and N—H(...)O hydrogen bonds with water mol­ecules generating a three-dimensional network.

Related literature

For the synthesis of hexa­hydro-1,2,4,5-tetra­zine derivatives by condensing aldehydes with hydrazine, see: Skorianetz & Kovats (1970 [triangle]). For the synthesis of the 3,6-dimethyl homolog, see: Sun et al. (2003 [triangle]); Zhou et al. (1999 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o2988-scheme1.jpg

Experimental

Crystal data

  • C6H16N4O4·4H2O
  • M r = 280.29
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2988-efi1.jpg
  • a = 6.3067 (1) Å
  • b = 7.0317 (2) Å
  • c = 8.4015 (2) Å
  • α = 71.010 (1)°
  • β = 74.424 (1)°
  • γ = 85.055 (1)°
  • V = 339.36 (1) Å3
  • Z = 1
  • Mo Kα radiation
  • μ = 0.12 mm−1
  • T = 296 K
  • 0.40 × 0.40 × 0.40 mm

Data collection

  • Bruker SMART APEXII diffractometer
  • Absorption correction: none
  • 10198 measured reflections
  • 4231 independent reflections
  • 3630 reflections with I > 2σ(I)
  • R int = 0.018

Refinement

  • R[F 2 > 2σ(F 2)] = 0.042
  • wR(F 2) = 0.137
  • S = 1.01
  • 4231 reflections
  • 114 parameters
  • 8 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.93 e Å−3
  • Δρmin = −0.63 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2005 [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]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809045590/ci2961sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809045590/ci2961Isup2.hkl

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

Acknowledgments

The authors acknowledge support from Chulalongkorn University and the Center of Excellence for Petroleum, Petrochemicals and Advanced Materials of Thailand.

supplementary crystallographic information

Experimental

Dihydroxyacetone (0.90 g, 10 mmol) and hydrazine hydrate (0.49 ml, 10 mmol) in ethanol (50 ml) were heated for 12 h. Slow evaporation of the solvent gave colourless crystals in 80% yield. The formulation of the organic molecule was established by 1H and 13C NMR as well as by mass spectroscopies.

Refinement

The amino and water H-atoms were located in a difference Fourier map, and were refined with a distance restraint of N-H = O-H = 0.85 (1) Å; their Uiso parameters were freely refined. Carbon-bound H-atoms were placed in calculated positions (C-H = 0.97 Å) and were included in the refinement in the riding model approximation, with Uiso(H) set to 1.2Ueq(C). The highest peak and the deepest hole are located 0.73 and 0.58 Å from O1W. Although the displacement parameters of atom O1W are relatively large, no disorder is expected as its H-atoms could be located and refined.

Figures

Fig. 1.
Displacement ellipsoid plot (Barbour, 2001) of C6H16N4O4.4H2O at the 50% probability level. H atoms are drawn as spheres of arbitrary radius. Unlabelled atoms in the tetrazinane derivative are related to labelled atoms by the symmetry operation (1-x, ...

Crystal data

C6H16N4O4·4H2OZ = 1
Mr = 280.29F(000) = 152
Triclinic, P1Dx = 1.371 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.3067 (1) ÅCell parameters from 6318 reflections
b = 7.0317 (2) Åθ = 3.1–40.2°
c = 8.4015 (2) ŵ = 0.12 mm1
α = 71.010 (1)°T = 296 K
β = 74.424 (1)°Cube, colourless
γ = 85.055 (1)°0.40 × 0.40 × 0.40 mm
V = 339.36 (1) Å3

Data collection

Bruker SMART APEXII diffractometer3630 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.018
graphiteθmax = 40.2°, θmin = 3.1°
[var phi] and ω scansh = −11→11
10198 measured reflectionsk = −12→12
4231 independent reflectionsl = −15→15

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)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.137H atoms treated by a mixture of independent and constrained refinement
S = 1.01w = 1/[σ2(Fo2) + (0.0853P)2 + 0.0377P] where P = (Fo2 + 2Fc2)/3
4231 reflections(Δ/σ)max = 0.001
114 parametersΔρmax = 0.93 e Å3
8 restraintsΔρmin = −0.63 e Å3

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

xyzUiso*/Ueq
O10.62982 (10)0.32676 (8)0.59353 (6)0.03101 (11)
O20.12442 (8)−0.12559 (9)0.85708 (8)0.03186 (11)
O1W0.74166 (12)0.53141 (12)0.78141 (13)0.0496 (2)
O2W0.81111 (10)0.46492 (8)0.23874 (7)0.03194 (11)
N10.35398 (7)0.15628 (7)0.93656 (6)0.01863 (8)
N20.53643 (7)−0.16882 (6)0.93673 (6)0.01882 (8)
C30.30946 (11)−0.01190 (10)0.73791 (8)0.02651 (11)
H3A0.25990.11540.66970.032*
H3B0.3856−0.08440.65860.032*
C10.67667 (9)0.13379 (9)0.69956 (7)0.02297 (10)
H1A0.78190.14720.76090.028*
H1B0.74350.05170.62620.028*
C20.46871 (8)0.02767 (7)0.83271 (6)0.01806 (9)
H1O0.661 (3)0.409 (2)0.640 (2)0.051 (4)*
H2O0.140 (3)−0.2396 (16)0.839 (2)0.052 (4)*
H1W10.8827 (15)0.535 (3)0.765 (2)0.057 (4)*
H1W20.688 (3)0.6353 (19)0.810 (2)0.055 (4)*
H2W10.753 (2)0.430 (2)0.3464 (12)0.053 (4)*
H2W20.754 (3)0.5766 (18)0.198 (3)0.069 (5)*
H1N0.2237 (14)0.1097 (17)0.9941 (14)0.026 (2)*
H2N0.4192 (16)−0.2420 (16)0.9932 (15)0.027 (2)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0395 (3)0.0239 (2)0.02234 (19)−0.00194 (17)−0.00506 (17)0.00069 (15)
O20.02304 (19)0.0353 (2)0.0423 (3)−0.00251 (16)−0.00474 (17)−0.0211 (2)
O1W0.0348 (3)0.0488 (4)0.0794 (6)0.0026 (3)−0.0098 (3)−0.0437 (4)
O2W0.0353 (2)0.0254 (2)0.0306 (2)0.00639 (17)−0.00462 (18)−0.00747 (17)
N10.01946 (16)0.01761 (16)0.01842 (16)0.00258 (12)−0.00506 (12)−0.00561 (12)
N20.02248 (17)0.01557 (15)0.01876 (16)0.00090 (12)−0.00525 (12)−0.00611 (12)
C30.0297 (2)0.0293 (3)0.0242 (2)−0.00180 (19)−0.01135 (18)−0.00917 (19)
C10.0244 (2)0.0221 (2)0.01861 (18)−0.00032 (16)−0.00180 (15)−0.00427 (15)
C20.02086 (18)0.01704 (17)0.01609 (16)0.00065 (13)−0.00472 (13)−0.00510 (13)

Geometric parameters (Å, °)

O1—C11.4169 (7)N1—H1N0.86 (1)
O1—H1O0.851 (9)N2—N1i1.4441 (6)
O2—C31.4198 (9)N2—C21.4724 (6)
O2—H2O0.86 (1)N2—H2N0.87 (1)
O1W—H1W10.86 (1)C3—C21.5305 (8)
O1W—H1W20.86 (1)C3—H3A0.97
O2W—H2W10.84 (1)C3—H3B0.97
O2W—H2W20.84 (1)C1—C21.5382 (7)
N1—N2i1.4441 (6)C1—H1A0.97
N1—C21.4712 (7)C1—H1B0.97
C1—O1—H1O105.1 (11)C2—C3—H3B109.4
C3—O2—H2O104.1 (11)H3A—C3—H3B108.0
H1W1—O1W—H1W2107.6 (16)O1—C1—C2112.12 (5)
H2W1—O2W—H2W2105.0 (18)O1—C1—H1A109.2
N2i—N1—C2113.59 (4)C2—C1—H1A109.2
N2i—N1—H1N106.4 (8)O1—C1—H1B109.2
C2—N1—H1N110.2 (8)C2—C1—H1B109.2
N1i—N2—C2113.72 (4)H1A—C1—H1B107.9
N1i—N2—H2N107.4 (8)N1—C2—N2114.01 (4)
C2—N2—H2N108.2 (8)N1—C2—C3107.44 (4)
O2—C3—C2111.33 (5)N2—C2—C3107.54 (4)
O2—C3—H3A109.4N1—C2—C1110.36 (4)
C2—C3—H3A109.4N2—C2—C1107.54 (4)
O2—C3—H3B109.4C3—C2—C1109.89 (4)
N2i—N1—C2—N247.54 (6)O2—C3—C2—N1−65.11 (6)
N2i—N1—C2—C3166.60 (4)O2—C3—C2—N258.02 (6)
N2i—N1—C2—C1−73.60 (5)O2—C3—C2—C1174.80 (5)
N1i—N2—C2—N1−47.60 (6)O1—C1—C2—N1−54.32 (6)
N1i—N2—C2—C3−166.60 (4)O1—C1—C2—N2−179.24 (4)
N1i—N2—C2—C175.09 (5)O1—C1—C2—C363.98 (6)

Symmetry codes: (i) −x+1, −y, −z+2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1O···O1W0.85 (1)1.87 (1)2.704 (1)166 (2)
O2—H2O···O2Wii0.86 (1)1.87 (1)2.723 (1)171 (2)
N1—H1N···O2iii0.86 (1)2.23 (1)3.036 (1)155 (1)
N2—H2N···O1Wi0.87 (1)2.36 (1)3.130 (1)148 (1)
O1W—H1W1···O2Wiv0.86 (1)1.92 (1)2.782 (1)172 (2)
O1W—H1W2···N2v0.86 (1)2.03 (1)2.869 (1)166 (2)
O2W—H2W1···O10.84 (1)1.92 (1)2.759 (1)175 (2)
O2W—H2W2···N1vi0.84 (1)2.02 (1)2.853 (1)171 (2)

Symmetry codes: (ii) −x+1, −y, −z+1; (iii) −x, −y, −z+2; (i) −x+1, −y, −z+2; (iv) −x+2, −y+1, −z+1; (v) x, y+1, z; (vi) −x+1, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI2961).

References

  • Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.
  • Bruker (2005). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Skorianetz, W. & Kovats, E. Sz. (1970). Helv. Chim. Acta, 53, 251–262.
  • Sun, Y.-Q., Hu, W.-X. & Yuan, Q. (2003). Synth. Commun. 33, 2769–2775.
  • Westrip, S. P. (2009). publCIF. In preparation.
  • Zhou, M., Cai, Z.-B., Yang, Z.-Y. & Hu, W.-X. (1999). Jingxi Huagong, 16, 1–4.

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