(IUCr) Crystallography Journals Online

Abstract top

In the title compound, C₈H₁₇N₃O₄, the dihedral angle between the hydrazinecarbonyl and carbamate groups is 44.94 (12)°, and the carbonyl groups are anti to each other. In the crystal, the hydroxy group forms an O-HN_a (a = amine) hydrogen bond and each of the four N-H atoms forms an N-HO hydrogen bond; the hydrazinecarbonyl O atom accepts two such bonds. This results in two-dimensional arrays in the ab plane, mediated by the hydrogen bonding, sandwiched by tert-butyl groups.

Comment top

Continuing our interests in serinyl compounds as potential anti-tuberculosis agents (Pinheiro et al., 2007), we have prepared the title compound, tert-butyl N-[1(S)-1-(hydrazinecarbonyl)-2-hydroxyethyl]carbamate (I) from L-serine methyl ester hydrochloride, as a precursor of a series of tert-butyl N-(2-hydroxy-1-(S)-{N'-[(1E)-(2-aryl)methylidene]-hydrazinecarbonyl}ethyl)carbamates. We now report the syntheses and structure of (I).

The molecular structure of (I), Fig. 1, is twisted with the dihedral angle formed between the least-squares planes through the hydrazinecarbonyl (r.m.s. deviation = 0.0045 Å) and carbamate (r.m.s. deviation = 0.021 Å) residues being 44.94 (12) °. The carbonyl-O1 and O3 atoms lie to opposite sides of the molecule as seen in the pseudo O1–C1···C4–O3 torsion angle of -176.7 (3) °. Finally, each of the N–H groups is anti to the adjacent carbonyl so that the N–H groups, too, lie to opposite sides of the molecule. Although the absolute structure could not be determined experimentally, the assignment of the S-configuration at the C2 atom is based on the starting reagents. There are five acidic H atoms in the structure, and each of these forms a significant hydrogen bonding interaction, Table 1. The hydroxyl-O2–H forms an O–H···N bond with the amino-N1 atom. The carbonyl-O1 atom accepts two N–H hydrogen bonds, one from the amino-N1 atom and the other from the hydrazine-N2. The second amino-N1–H atom forms a hydrogen bond with the hydroxyl-O2 atom, and, finally, the carbamate-N3–H interacts with the O3-carbonyl atom. The hydrogen bonds cooperate with each other to form a 2-D array in the ab plane, Fig. 2, and these stack along the c axis being sandwiched by the t-butyl groups, Fig. 3.

tert-Butyl N-[(S)-1-hydrazinecarbonyl-2-hydroxyethyl]carbamate top

Crystal data top

C₈H₁₇N₃O₄	F(000) = 236
M_r = 219.25	D_x = 1.297 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 10838 reflections
a = 6.9274 (5) Å	θ = 2.9–27.5°
b = 5.0074 (4) Å	µ = 0.10 mm⁻¹
c = 16.2388 (15) Å	T = 120 K
β = 94.483 (5)°	Plate, colourless
V = 561.57 (8) Å³	0.26 × 0.14 × 0.03 mm
Z = 2

Data collection top

Nonius KappaCCD diffractometer	1428 independent reflections
Radiation source: Enraf–Nonius FR591 rotating anode	1168 reflections with I > 2σ(I)
10 cm confocal mirrors	R_int = 0.062
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
φ and ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	k = −6→6
T_min = 0.616, T_max = 0.746	l = −21→18
6687 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.149	w = 1/[σ²(F_o²) + (0.0838P)²] where P = (F_o² + 2F_c²)/3
S = 1.23	(Δ/σ)_max = 0.001
1428 reflections	Δρ_max = 0.30 e Å⁻³
154 parameters	Δρ_min = −0.34 e Å⁻³
6 restraints	Absolute structure: nd
Primary atom site location: structure-invariant direct methods

Crystal data top

C₈H₁₇N₃O₄	V = 561.57 (8) Å³
M_r = 219.25	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 6.9274 (5) Å	µ = 0.10 mm⁻¹
b = 5.0074 (4) Å	T = 120 K
c = 16.2388 (15) Å	0.26 × 0.14 × 0.03 mm
β = 94.483 (5)°

Data collection top

Nonius KappaCCD diffractometer	1428 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	1168 reflections with I > 2σ(I)
T_min = 0.616, T_max = 0.746	R_int = 0.062
6687 measured reflections	θ_max = 27.5°

Refinement top

R[F² > 2σ(F²)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.149	Δρ_max = 0.30 e Å⁻³
S = 1.23	Δρ_min = −0.34 e Å⁻³
1428 reflections	Absolute structure: nd
154 parameters	Flack parameter: ?
6 restraints	Rogers parameter: ?

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
O1	0.2906 (3)	0.6236 (5)	0.55336 (15)	0.0226 (6)
O2	−0.0983 (3)	0.3069 (5)	0.64307 (16)	0.0245 (6)
H1O	−0.149 (6)	0.452 (5)	0.627 (3)	0.037*
O3	0.4633 (4)	−0.1207 (6)	0.74118 (17)	0.0298 (7)
O4	0.6317 (3)	0.2100 (5)	0.81155 (14)	0.0223 (6)
N1	0.2779 (4)	0.2663 (6)	0.42051 (18)	0.0223 (7)
H1N	0.205 (5)	0.414 (5)	0.409 (3)	0.027*
H2N	0.4053 (15)	0.288 (9)	0.412 (2)	0.027*
N2	0.2663 (4)	0.1984 (5)	0.50498 (18)	0.0198 (6)
H3N	0.230 (5)	0.033 (3)	0.513 (2)	0.024*
N3	0.4237 (4)	0.3155 (5)	0.70510 (18)	0.0207 (6)
H4N	0.429 (6)	0.485 (2)	0.720 (2)	0.025*
C1	0.2715 (4)	0.3813 (8)	0.5650 (2)	0.0181 (7)
C2	0.2480 (4)	0.2659 (8)	0.65093 (19)	0.0182 (7)
H2	0.2267	0.0688	0.6460	0.022*
C3	0.0743 (2)	0.3924 (5)	0.68777 (11)	0.0213 (7)
H3A	0.0723	0.3398	0.7465	0.026*
H3B	0.0842	0.5894	0.6852	0.026*
C4	0.5023 (2)	0.1141 (5)	0.75191 (11)	0.0193 (7)
C5	0.7406 (2)	0.0190 (5)	0.86737 (11)	0.0218 (7)
C6	0.8669 (2)	0.2032 (5)	0.92338 (11)	0.0317 (9)
H6A	0.9567	0.3001	0.8904	0.047*
H6B	0.9406	0.0969	0.9657	0.047*
H6C	0.7847	0.3310	0.9501	0.047*
C7	0.6005 (6)	−0.1336 (9)	0.9179 (2)	0.0300 (8)
H7A	0.5109	−0.0078	0.9411	0.045*
H7B	0.6735	−0.2291	0.9629	0.045*
H7C	0.5272	−0.2620	0.8823	0.045*
C8	0.8656 (5)	−0.1602 (7)	0.8176 (2)	0.0246 (8)
H8A	0.7860	−0.3046	0.7922	0.037*
H8B	0.9705	−0.2366	0.8542	0.037*
H8C	0.9207	−0.0549	0.7743	0.037*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0269 (12)	0.0135 (13)	0.0271 (14)	−0.0025 (11)	−0.0007 (10)	0.0009 (10)
O2	0.0192 (12)	0.0197 (14)	0.0342 (14)	0.0009 (10)	−0.0008 (10)	0.0023 (11)
O3	0.0372 (13)	0.0126 (13)	0.0370 (15)	−0.0006 (12)	−0.0138 (11)	0.0009 (11)
O4	0.0314 (12)	0.0113 (12)	0.0230 (12)	0.0012 (10)	−0.0066 (10)	0.0013 (10)
N1	0.0214 (14)	0.0213 (17)	0.0241 (15)	−0.0002 (12)	0.0013 (12)	−0.0001 (13)
N2	0.0235 (14)	0.0133 (13)	0.0225 (15)	−0.0017 (12)	0.0015 (11)	0.0000 (13)
N3	0.0231 (13)	0.0110 (14)	0.0272 (15)	−0.0018 (12)	−0.0031 (12)	−0.0014 (13)
C1	0.0143 (13)	0.0129 (16)	0.0266 (18)	0.0004 (13)	−0.0010 (12)	0.0017 (15)
C2	0.0182 (15)	0.0140 (17)	0.0215 (17)	−0.0020 (13)	−0.0032 (13)	−0.0013 (13)
C3	0.0225 (15)	0.0165 (16)	0.0252 (17)	−0.0019 (15)	0.0030 (13)	−0.0005 (14)
C4	0.0212 (15)	0.0121 (17)	0.0243 (18)	−0.0008 (14)	−0.0001 (13)	0.0004 (13)
C5	0.0291 (18)	0.0122 (16)	0.0231 (18)	0.0020 (15)	−0.0036 (14)	0.0027 (14)
C6	0.042 (2)	0.0165 (18)	0.033 (2)	0.0034 (17)	−0.0155 (17)	−0.0002 (17)
C7	0.0403 (19)	0.022 (2)	0.028 (2)	0.0061 (18)	0.0032 (16)	0.0026 (16)
C8	0.0285 (16)	0.0156 (19)	0.0296 (19)	0.0021 (15)	0.0011 (14)	0.0029 (15)

Geometric parameters (Å, °) top

O1—C1	1.236 (4)	C2—H2	1.0000
O2—C3	1.416 (3)	C3—H3A	0.9900
O2—H1O	0.84 (3)	C3—H3B	0.9900
O3—C4	1.216 (3)	C5—C8	1.523 (4)
O4—C4	1.355 (3)	C5—C6	1.523 (3)
O4—C5	1.482 (3)	C5—C7	1.525 (4)
N1—N2	1.421 (4)	C6—H6A	0.9800
N1—H1N	0.91 (3)	C6—H6B	0.9800
N1—H2N	0.911 (13)	C6—H6C	0.9800
N2—C1	1.336 (5)	C7—H7A	0.9800
N2—H3N	0.878 (18)	C7—H7B	0.9800
N3—C4	1.352 (3)	C7—H7C	0.9800
N3—C2	1.466 (4)	C8—H8A	0.9800
N3—H4N	0.883 (14)	C8—H8B	0.9800
C1—C2	1.531 (5)	C8—H8C	0.9800
C2—C3	1.523 (4)

C3—O2—H1O	102 (3)	O3—C4—O4	124.9 (2)
C4—O4—C5	119.0 (2)	N3—C4—O4	110.6 (2)
N2—N1—H1N	109 (3)	O4—C5—C8	109.80 (19)
N2—N1—H2N	107 (2)	O4—C5—C6	102.46 (12)
H1N—N1—H2N	114 (4)	C8—C5—C6	110.49 (15)
C1—N2—N1	122.7 (3)	O4—C5—C7	109.8 (2)
C1—N2—H3N	122 (3)	C8—C5—C7	113.7 (2)
N1—N2—H3N	114 (3)	C6—C5—C7	109.99 (17)
C4—N3—C2	119.3 (3)	C5—C6—H6A	109.5
C4—N3—H4N	124 (3)	C5—C6—H6B	109.5
C2—N3—H4N	110 (3)	H6A—C6—H6B	109.5
O1—C1—N2	123.9 (3)	C5—C6—H6C	109.5
O1—C1—C2	122.0 (3)	H6A—C6—H6C	109.5
N2—C1—C2	114.0 (3)	H6B—C6—H6C	109.5
N3—C2—C3	109.8 (2)	C5—C7—H7A	109.5
N3—C2—C1	109.9 (3)	C5—C7—H7B	109.5
C3—C2—C1	110.2 (2)	H7A—C7—H7B	109.5
N3—C2—H2	109.0	C5—C7—H7C	109.5
C3—C2—H2	109.0	H7A—C7—H7C	109.5
C1—C2—H2	109.0	H7B—C7—H7C	109.5
O2—C3—C2	109.54 (19)	C5—C8—H8A	109.5
O2—C3—H3A	109.8	C5—C8—H8B	109.5
C2—C3—H3A	109.8	H8A—C8—H8B	109.5
O2—C3—H3B	109.8	C5—C8—H8C	109.5
C2—C3—H3B	109.8	H8A—C8—H8C	109.5
H3A—C3—H3B	108.2	H8B—C8—H8C	109.5
O3—C4—N3	124.4 (2)

Hydrogen-bond geometry (Å, °) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1o···N1ⁱ	0.84 (3)	1.94 (3)	2.776 (4)	174 (5)
N1—H1n···O2ⁱ	0.91 (3)	2.24 (3)	3.121 (4)	162 (4)
N1—H2n···O1ⁱⁱ	0.911 (13)	2.29 (2)	3.070 (4)	144 (3)
N2—H3n···O1ⁱⁱⁱ	0.878 (18)	2.183 (18)	2.985 (4)	152 (3)
N3—H4n···O3^iv	0.883 (14)	2.015 (12)	2.892 (4)	172 (3)

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

Table 1
Hydrogen-bond geometry (Å, °) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1o···N1ⁱ	0.84 (3)	1.94 (3)	2.776 (4)	174 (5)
N1—H1n···O2ⁱ	0.91 (3)	2.24 (3)	3.121 (4)	162 (4)
N1—H2n···O1ⁱⁱ	0.911 (13)	2.29 (2)	3.070 (4)	144 (3)
N2—H3n···O1ⁱⁱⁱ	0.878 (18)	2.183 (18)	2.985 (4)	152 (3)
N3—H4n···O3^iv	0.883 (14)	2.015 (12)	2.892 (4)	172 (3)

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

supplementary materials

tert-Butyl N-[(S)-1-hydrazinecarbonyl-2-hydroxyethyl]carbamate

A. C. Pinheiro, M. V. N. de Souza, S. M. S. V. Wardell, J. L. Wardell and E. R. T. Tiekink

	Fig. 1. The molecular structure of (I) showing displacement ellipsoids at the 50% probability level.
	Fig. 2. A view of a supramolecular array in (I) in the ab plane. The O–H···N and N–H···O hydrogen bonding interactions are shown as orange and blue dashed lines, respectively. Colour code: O, red; N, blue; C, grey; and H, green.
	Fig. 3. A view of the crystal packing in (I) in projection down the b axis, showing the stacking of layers. The O–H···N and N–H···O hydrogen bonding interactions are shown as orange and blue dashed lines, respectively. Colour code: O, red; N, blue; C, grey; and H, green.