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

Kongsutjarit, S.; Thamyongkit, P.; Muangsin, N.; Chaichit, N.; Petsom, A.; Ng, S.W.

doi:10.1107/S1600536809045590

organic compounds

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Volume 65| Part 12| December 2009| Page o2988

doi:10.1107/S1600536809045590

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

S. Kongsutjarit,^a P. Thamyongkit,^a N. Muangsin,^a N. Chaichit,^b Amorn Petsom ^a and Seik Weng Ng ^c ^*

^aDepartment of Chemistry, Faculty of Science, Chulalongkorn University, Bangkok 10330, Thailand, ^bDepartment of Physics, Faculty of Science and Technology, Thammasart University, Pathum Thani 12121, Thailand, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 28 October 2009; accepted 29 October 2009; online 4 November 2009)

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 ). For the synthesis of the 3,6-dimethyl homolog, see: Sun et al. (2003 ); Zhou et al. (1999 ).

Experimental

Crystal data

C₆H₁₆N₄O₄·4H₂O
M_r = 280.29
Triclinic, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.042
wR(F²) = 0.137
S = 1.01
4231 reflections
114 parameters
8 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.93 e Å⁻³
Δρ_min = −0.63 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯O1W	0.85 (1)	1.87 (1)	2.704 (1)	166 (2)
O2—H2O⋯O2Wⁱ	0.86 (1)	1.87 (1)	2.723 (1)	171 (2)
N1—H1N⋯O2ⁱⁱ	0.86 (1)	2.23 (1)	3.036 (1)	155 (1)
N2—H2N⋯O1Wⁱⁱⁱ	0.87 (1)	2.36 (1)	3.130 (1)	148 (1)
O1W—H1W1⋯O2W^iv	0.86 (1)	1.92 (1)	2.782 (1)	172 (2)
O1W—H1W2⋯N2^v	0.86 (1)	2.03 (1)	2.869 (1)	166 (2)
O2W—H2W1⋯O1	0.84 (1)	1.92 (1)	2.759 (1)	175 (2)
O2W—H2W2⋯N1^vi	0.84 (1)	2.02 (1)	2.853 (1)	171 (2)
Symmetry codes: (i) -x+1, -y, -z+1; (ii) -x, -y, -z+2; (iii) -x+1, -y, -z+2; (iv) -x+2, -y+1, -z+1; (v) x, y+1, z; (vi) -x+1, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

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

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

checkCIF report

Related literature top

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

Experimental top

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.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top

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, -y, 2-z). Two symmetry related water molecules are not shown.

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

Crystal data top

C₆H₁₆N₄O₄·4H₂O	Z = 1
M_r = 280.29	F(000) = 152
Triclinic, P1	D_x = 1.371 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.3067 (1) Å	Cell parameters from 6318 reflections
b = 7.0317 (2) Å	θ = 3.1–40.2°
c = 8.4015 (2) Å	µ = 0.12 mm⁻¹
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 top

Bruker SMART APEXII diffractometer	3630 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.018
Graphite monochromator	θ_max = 40.2°, θ_min = 3.1°
ϕ and ω scans	h = −11→11
10198 measured reflections	k = −12→12
4231 independent reflections	l = −15→15

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0853P)² + 0.0377P] where P = (F_o² + 2F_c²)/3
4231 reflections	(Δ/σ)_max = 0.001
114 parameters	Δρ_max = 0.93 e Å⁻³
8 restraints	Δρ_min = −0.63 e Å⁻³

Crystal data top

C₆H₁₆N₄O₄·4H₂O	γ = 85.055 (1)°
M_r = 280.29	V = 339.36 (1) Å³
Triclinic, P1	Z = 1
a = 6.3067 (1) Å	Mo Kα radiation
b = 7.0317 (2) Å	µ = 0.12 mm⁻¹
c = 8.4015 (2) Å	T = 296 K
α = 71.010 (1)°	0.40 × 0.40 × 0.40 mm
β = 74.424 (1)°

Data collection top

Bruker SMART APEXII diffractometer	3630 reflections with I > 2σ(I)
10198 measured reflections	R_int = 0.018
4231 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	8 restraints
wR(F²) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.93 e Å⁻³
4231 reflections	Δρ_min = −0.63 e Å⁻³
114 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.62982 (10)	0.32676 (8)	0.59353 (6)	0.03101 (11)
O2	0.12442 (8)	−0.12559 (9)	0.85708 (8)	0.03186 (11)
O1W	0.74166 (12)	0.53141 (12)	0.78141 (13)	0.0496 (2)
O2W	0.81111 (10)	0.46492 (8)	0.23874 (7)	0.03194 (11)
N1	0.35398 (7)	0.15628 (7)	0.93656 (6)	0.01863 (8)
N2	0.53643 (7)	−0.16882 (6)	0.93673 (6)	0.01882 (8)
C3	0.30946 (11)	−0.01190 (10)	0.73791 (8)	0.02651 (11)
H3A	0.2599	0.1154	0.6697	0.032*
H3B	0.3856	−0.0844	0.6586	0.032*
C1	0.67667 (9)	0.13379 (9)	0.69956 (7)	0.02297 (10)
H1A	0.7819	0.1472	0.7609	0.028*
H1B	0.7435	0.0517	0.6262	0.028*
C2	0.46871 (8)	0.02767 (7)	0.83271 (6)	0.01806 (9)
H1O	0.661 (3)	0.409 (2)	0.640 (2)	0.051 (4)*
H2O	0.140 (3)	−0.2396 (16)	0.839 (2)	0.052 (4)*
H1W1	0.8827 (15)	0.535 (3)	0.765 (2)	0.057 (4)*
H1W2	0.688 (3)	0.6353 (19)	0.810 (2)	0.055 (4)*
H2W1	0.753 (2)	0.430 (2)	0.3464 (12)	0.053 (4)*
H2W2	0.754 (3)	0.5766 (18)	0.198 (3)	0.069 (5)*
H1N	0.2237 (14)	0.1097 (17)	0.9941 (14)	0.026 (2)*
H2N	0.4192 (16)	−0.2420 (16)	0.9932 (15)	0.027 (2)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0395 (3)	0.0239 (2)	0.02234 (19)	−0.00194 (17)	−0.00506 (17)	0.00069 (15)
O2	0.02304 (19)	0.0353 (2)	0.0423 (3)	−0.00251 (16)	−0.00474 (17)	−0.0211 (2)
O1W	0.0348 (3)	0.0488 (4)	0.0794 (6)	0.0026 (3)	−0.0098 (3)	−0.0437 (4)
O2W	0.0353 (2)	0.0254 (2)	0.0306 (2)	0.00639 (17)	−0.00462 (18)	−0.00747 (17)
N1	0.01946 (16)	0.01761 (16)	0.01842 (16)	0.00258 (12)	−0.00506 (12)	−0.00561 (12)
N2	0.02248 (17)	0.01557 (15)	0.01876 (16)	0.00090 (12)	−0.00525 (12)	−0.00611 (12)
C3	0.0297 (2)	0.0293 (3)	0.0242 (2)	−0.00180 (19)	−0.01135 (18)	−0.00917 (19)
C1	0.0244 (2)	0.0221 (2)	0.01861 (18)	−0.00032 (16)	−0.00180 (15)	−0.00427 (15)
C2	0.02086 (18)	0.01704 (17)	0.01609 (16)	0.00065 (13)	−0.00472 (13)	−0.00510 (13)

Geometric parameters (Å, º) top

O1—C1	1.4169 (7)	N1—H1N	0.86 (1)
O1—H1O	0.851 (9)	N2—N1ⁱ	1.4441 (6)
O2—C3	1.4198 (9)	N2—C2	1.4724 (6)
O2—H2O	0.86 (1)	N2—H2N	0.87 (1)
O1W—H1W1	0.86 (1)	C3—C2	1.5305 (8)
O1W—H1W2	0.86 (1)	C3—H3A	0.97
O2W—H2W1	0.84 (1)	C3—H3B	0.97
O2W—H2W2	0.84 (1)	C1—C2	1.5382 (7)
N1—N2ⁱ	1.4441 (6)	C1—H1A	0.97
N1—C2	1.4712 (7)	C1—H1B	0.97

C1—O1—H1O	105.1 (11)	C2—C3—H3B	109.4
C3—O2—H2O	104.1 (11)	H3A—C3—H3B	108.0
H1W1—O1W—H1W2	107.6 (16)	O1—C1—C2	112.12 (5)
H2W1—O2W—H2W2	105.0 (18)	O1—C1—H1A	109.2
N2ⁱ—N1—C2	113.59 (4)	C2—C1—H1A	109.2
N2ⁱ—N1—H1N	106.4 (8)	O1—C1—H1B	109.2
C2—N1—H1N	110.2 (8)	C2—C1—H1B	109.2
N1ⁱ—N2—C2	113.72 (4)	H1A—C1—H1B	107.9
N1ⁱ—N2—H2N	107.4 (8)	N1—C2—N2	114.01 (4)
C2—N2—H2N	108.2 (8)	N1—C2—C3	107.44 (4)
O2—C3—C2	111.33 (5)	N2—C2—C3	107.54 (4)
O2—C3—H3A	109.4	N1—C2—C1	110.36 (4)
C2—C3—H3A	109.4	N2—C2—C1	107.54 (4)
O2—C3—H3B	109.4	C3—C2—C1	109.89 (4)

N2ⁱ—N1—C2—N2	47.54 (6)	O2—C3—C2—N1	−65.11 (6)
N2ⁱ—N1—C2—C3	166.60 (4)	O2—C3—C2—N2	58.02 (6)
N2ⁱ—N1—C2—C1	−73.60 (5)	O2—C3—C2—C1	174.80 (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—C1	75.09 (5)	O1—C1—C2—C3	63.98 (6)

Symmetry code: (i) −x+1, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O1W	0.85 (1)	1.87 (1)	2.704 (1)	166 (2)
O2—H2O···O2Wⁱⁱ	0.86 (1)	1.87 (1)	2.723 (1)	171 (2)
N1—H1N···O2ⁱⁱⁱ	0.86 (1)	2.23 (1)	3.036 (1)	155 (1)
N2—H2N···O1Wⁱ	0.87 (1)	2.36 (1)	3.130 (1)	148 (1)
O1W—H1W1···O2W^iv	0.86 (1)	1.92 (1)	2.782 (1)	172 (2)
O1W—H1W2···N2^v	0.86 (1)	2.03 (1)	2.869 (1)	166 (2)
O2W—H2W1···O1	0.84 (1)	1.92 (1)	2.759 (1)	175 (2)
O2W—H2W2···N1^vi	0.84 (1)	2.02 (1)	2.853 (1)	171 (2)

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

Experimental details

Crystal data
Chemical formula	C₆H₁₆N₄O₄·4H₂O
M_r	280.29
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	6.3067 (1), 7.0317 (2), 8.4015 (2)
α, β, γ (°)	71.010 (1), 74.424 (1), 85.055 (1)
V (Å³)	339.36 (1)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.40 × 0.40 × 0.40

Data collection
Diffractometer	Bruker SMART APEXII diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	10198, 4231, 3630
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.908

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.137, 1.01
No. of reflections	4231
No. of parameters	114
No. of restraints	8
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.93, −0.63

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O1W	0.85 (1)	1.87 (1)	2.704 (1)	166 (2)
O2—H2O···O2Wⁱ	0.86 (1)	1.87 (1)	2.723 (1)	171 (2)
N1—H1N···O2ⁱⁱ	0.86 (1)	2.23 (1)	3.036 (1)	155 (1)
N2—H2N···O1Wⁱⁱⁱ	0.87 (1)	2.36 (1)	3.130 (1)	148 (1)
O1W—H1W1···O2W^iv	0.86 (1)	1.92 (1)	2.782 (1)	172 (2)
O1W—H1W2···N2^v	0.86 (1)	2.03 (1)	2.869 (1)	166 (2)
O2W—H2W1···O1	0.84 (1)	1.92 (1)	2.759 (1)	175 (2)
O2W—H2W2···N1^vi	0.84 (1)	2.02 (1)	2.853 (1)	171 (2)

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

Acknowledgements

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

References

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