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

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.

Key indicators

• Single-crystal X-ray study
• T = 120 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.042
• wR factor = 0.107
• Data-to-parameter ratio = 17.3

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PLAT793_ALERT_4_G The Model has Chirality at C1      (Verify) ....          R

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S1. Comment

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

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).

S2. Experimental

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).

S3. Refinement

H atoms were positioned geometrically, with N—H = 0.88 Å (for NH), O—H = 0.86 Å (for OH) and C—H = 0.95 Å (for the aldehyde group) and and C—H = 1.00 Å (for the aliphatic C atom), and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(N, O, C).

Computing details

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

	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

Crystal data

C4H8N2O4	F(000) = 312
Mr = 148.12	Dx = 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) Å^3	Prism, colourless
Z = 4	0.20 × 0.20 × 0.15 mm

Data collection

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

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	Hydrogen site location: mixed
wR(F^2) = 0.107	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0499P)^2 + 0.531P] where P = (Fo^2 + 2Fc^2)/3
796 reflections	(Δ/σ)max < 0.001
46 parameters	Δρmax = 0.41 e Å^−3
0 restraints	Δρmin = −0.24 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.

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

N1—C2	1.3344 (17)	O2—C2	1.2374 (17)
N1—C1	1.4483 (17)	C1—C1^i	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	C1^i—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—C1^i	107.45 (13)	N1—C2—H2A	117.9
N1—C1—C1^i	108.91 (13)
C2—N1—C1—O1	−99.08 (15)	C1—N1—C2—O2	1.6 (2)
C2—N1—C1—C1^i	141.93 (15)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1^ii	0.88	2.04	2.9093 (16)	170
O1—H1O···O2^iii	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.