(1R,2S)-N,N′-(1,2-Dihydroxy­ethyl­ene)diformamide

Taheri, A.; Moosavi, S.M.

doi:10.1107/S1600536808036209

organic compounds

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Volume 64| Part 12| December 2008| Page o2316

doi:10.1107/S1600536808036209

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(1R,2S)-N,N′-(1,2-Dihydroxyethylene)diformamide

Amir Taheri ^a ^* and Sayed Mojtaba Moosavi ^a

^aDepartment of Chemistry, Imam Hossein University, Tehran, Iran
^*Correspondence e-mail: amir.tahery1@gmail.com

(Received 7 October 2008; accepted 5 November 2008; online 13 November 2008)

The asymmetric unit of the title compound, C₄H₈N₂O₄, contains one half-molecule which is completed via a crystallographic inversion centre. In the crystal structure, molecules are arranged in undulating layers parallel to (001). Intermolecular N—H⋯O and O—H⋯O hydrogen bonds consolidate this arrangement.

Related literature

The title compound has been synthesized as a by-product of a procedure described by Sidney et al. (1965 ) and Ferguson (1968a ,b ). For related literature regarding the synthesis, see: Mitsch (1965 ). For the application of the intermediates, see: Ramakrishnan et al. (1990 ); Vedachalam et al. (1991 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₄H₈N₂O₄
M_r = 148.12
Orthorhombic, P b c a
a = 6.5065 (11) Å
b = 7.2634 (12) Å
c = 12.772 (2) Å
V = 603.59 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.15 mm⁻¹
T = 120 (2) K
0.20 × 0.20 × 0.15 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: none
5931 measured reflections
796 independent reflections
662 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.107
S = 1.00
796 reflections
46 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1ⁱ	0.88	2.04	2.9093 (16)	170
O1—H1O⋯O2ⁱⁱ	0.86	1.81	2.6740 (14)	175
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808036209/wm2200sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808036209/wm2200Isup2.hkl

checkCIF report

Comment top

1,4-Diformyl-2,3,5,6-tetrahydroxypiperazine is an important intermediate (Mitsch, 1965) for the preparation of high energetic materials (Ramakrishnan et al. 1990; Vedachalam et al. 1991). The title compound, (I), was obtained as an unexpected by-product during synthesis of 1,4-diformyl-2,3,5,6-tetrahydroxypiperazine (Sidney et al., 1965; Ferguson, 1968a,b). In a modified procedure we have synthesized compound (I) in much better yield and present its crystal structure in this communication.

Formally, compound (I) is a derivative of ethane with two hydroxyl and two formyl groups as substitutes of the corresponding H atoms. The asymmetric unit of compound (I) contains one half of the molecule that is completed via an inversion centre, leading to a R,S conformation for the two C atoms (Fig. 1). The bond lengths (Allen et al., 1987) and angles in the molecule are within normal ranges.

In the crystal structure, molecules are arranged in undulated layers parallel to (001). Intermolecular N—H···O and O—H···O hydrogen bonds consolidate this arrangement (Fig. 2 and Table 1).

Related literature top

The title compound has been synthesized as a by-product of a procedure described by Sidney et al. (1965) and Ferguson (1968a,b). For related literature regarding the synthesis, see: Mitsch (1965). For the application of the intermediates, see: Ramakrishnan et al. (1990); Vedachalam et al. (1991). For bond-length data, see: Allen et al. (1987).

Experimental top

76 mass parts of glyoxal monohydrate were stirred with 90 parts of formamide at room temperature. Then 6 mass parts of sodium bicarbonate were added. After 3 days, the crude crystalline product was washed with cold methanol and was dried, yielding 84.2 mass parts of 1,4-diformyl-2,3,5,6-tetrahydroxypiperazine (decomposition temperature 463 K). After filtering off the crystals, the aqueous mother liquor was kept at 273 K for 1 day and 2.2 mass parts of 1,2-dihydroxy-1,2-diformamidoethane were obtained (decomposition temperature 408 - 413 K). Crystals suitable for structure determination were grown by recrystallization from dimethyl sulfoxide (DMSO).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus (Bruker, 1998); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldricr, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, drawn with displacement ellipsoids at the 50% probability level. H atoms are shown as spheres of arbitrary radius.
	Fig. 2. A packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

(1R,2S)-1,2-Dihydroxy-1,2-diformamidoethane top

Crystal data top

C₄H₈N₂O₄	F(000) = 312
M_r = 148.12	D_x = 1.630 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 854 reflections
a = 6.5065 (11) Å	θ = 3–30°
b = 7.2634 (12) Å	µ = 0.15 mm⁻¹
c = 12.772 (2) Å	T = 120 K
V = 603.59 (17) Å³	Prism, colourless
Z = 4	0.20 × 0.20 × 0.15 mm

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	662 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.031
Graphite monochromator	θ_max = 29.0°, θ_min = 3.2°
ϕ and ω scans	h = −8→8
5931 measured reflections	k = −9→9
796 independent reflections	l = −17→17

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: mixed
wR(F²) = 0.107	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0499P)² + 0.531P] where P = (F_o² + 2F_c²)/3
796 reflections	(Δ/σ)_max < 0.001
46 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₄H₈N₂O₄	V = 603.59 (17) Å³
M_r = 148.12	Z = 4
Orthorhombic, Pbca	Mo Kα radiation
a = 6.5065 (11) Å	µ = 0.15 mm⁻¹
b = 7.2634 (12) Å	T = 120 K
c = 12.772 (2) Å	0.20 × 0.20 × 0.15 mm

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	662 reflections with I > 2σ(I)
5931 measured reflections	R_int = 0.031
796 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.107	H-atom parameters constrained
S = 1.00	Δρ_max = 0.41 e Å⁻³
796 reflections	Δρ_min = −0.24 e Å⁻³
46 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
N1	0.07678 (19)	0.16658 (16)	0.39820 (9)	0.0180 (3)
H1N	0.1170	0.2562	0.4397	0.022*
O1	−0.25095 (15)	0.06643 (13)	0.45643 (7)	0.0193 (3)
H1O	−0.3145	0.0628	0.3970	0.023*
O2	0.07384 (16)	0.05127 (14)	0.23276 (7)	0.0207 (3)
C1	−0.0424 (2)	0.01985 (18)	0.44519 (10)	0.0164 (3)
H1A	−0.0304	−0.0935	0.4012	0.020*
C2	0.1269 (2)	0.16978 (19)	0.29690 (10)	0.0178 (3)
H2A	0.2085	0.2694	0.2725	0.021*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0226 (6)	0.0168 (5)	0.0147 (5)	−0.0028 (4)	−0.0004 (4)	−0.0002 (4)
O1	0.0165 (5)	0.0254 (5)	0.0160 (4)	0.0025 (4)	−0.0025 (4)	−0.0020 (4)
O2	0.0203 (5)	0.0258 (5)	0.0160 (5)	−0.0010 (4)	0.0020 (4)	−0.0012 (4)
C1	0.0164 (6)	0.0182 (6)	0.0146 (6)	−0.0005 (5)	−0.0003 (5)	0.0004 (5)
C2	0.0168 (6)	0.0196 (6)	0.0170 (6)	0.0025 (5)	0.0007 (5)	0.0035 (5)

Geometric parameters (Å, º) top

N1—C2	1.3344 (17)	O2—C2	1.2374 (17)
N1—C1	1.4483 (17)	C1—C1ⁱ	1.532 (3)
N1—H1N	0.88	C1—H1A	1.0000
O1—C1	1.4056 (16)	C2—H2A	0.9500
O1—H1O	0.86

C2—N1—C1	123.06 (11)	O1—C1—H1A	109.3
C2—N1—H1N	119.9	N1—C1—H1A	109.3
C1—N1—H1N	117.0	C1ⁱ—C1—H1A	109.3
C1—O1—H1O	111.4	O2—C2—N1	124.17 (13)
O1—C1—N1	112.47 (11)	O2—C2—H2A	117.9
O1—C1—C1ⁱ	107.45 (13)	N1—C2—H2A	117.9
N1—C1—C1ⁱ	108.91 (13)

C2—N1—C1—O1	−99.08 (15)	C1—N1—C2—O2	1.6 (2)
C2—N1—C1—C1ⁱ	141.93 (15)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱⁱ	0.88	2.04	2.9093 (16)	170
O1—H1O···O2ⁱⁱⁱ	0.86	1.81	2.6740 (14)	175

Symmetry codes: (ii) x+1/2, −y+1/2, −z+1; (iii) x−1/2, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₄H₈N₂O₄
M_r	148.12
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	120
a, b, c (Å)	6.5065 (11), 7.2634 (12), 12.772 (2)
V (Å³)	603.59 (17)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.15
Crystal size (mm)	0.20 × 0.20 × 0.15

Data collection
Diffractometer	Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5931, 796, 662
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.682

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.107, 1.00
No. of reflections	796
No. of parameters	46
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.24

Computer programs: SMART (Bruker, 1998), SAINT-Plus (Bruker, 1998), SHELXTL (Sheldrick, 2008), SHELXTL (Sheldricr, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.88	2.04	2.9093 (16)	170
O1—H1O···O2ⁱⁱ	0.86	1.81	2.6740 (14)	175

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

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bruker (1998). SMART and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Ferguson, A. N. (1968a). US Patent 3 369 020. Google Scholar
Ferguson, A. N. (1968b). US Patent 3 365 454. Google Scholar
Mitsch, R. A. (1965). J. Am. Chem. Soc. 87, 328–333. CrossRef CAS Web of Science Google Scholar
Ramakrishnan, V. T., Vedachalam, M. & Boyer, J. H. (1990). Heterocycles, 31, 479-480. CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sidney, V., Clifford, M. & Barker, R. (1965). J. Org. Chem. 30, 1195-1199. Google Scholar
Vedachalam, M., Ramakrishnan, V. T., Boyer, H., Dagley, I. J., Nelson, K. A. & Adolph, H. G. (1991). J. Org. Chem. 56, 3413–3419. CSD CrossRef CAS Web of Science Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2316

doi:10.1107/S1600536808036209

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