(Cyclo­hexyl­idene­amino)­oxy­acetic acid and [chloro­(phenyl)­methyl­ene­amino]­oxy­acetic acid: hydrogen-bonded R_2^2(8) dimers and aromatic π–π stacking interactions

Glidewell, C.; Low, J.N.; Skakle, J.M.S.; Wardell, J.L.

doi:10.1107/S0108270104004299

organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 60| Part 4| April 2004| Pages o270-o272

doi:10.1107/S0108270104004299

(Cyclohexylideneamino)oxyacetic acid and [chloro(phenyl)methyleneamino]oxyacetic acid: hydrogen-bonded R(8) dimers and aromatic π–π stacking interactions

Christopher Glidewell,^a ^* John N. Low,^b Janet M. S. Skakle ^b and James L. Wardell ^c

^aSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland, ^bDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and ^cInstituto de Química, Departamento de Química Inorgânica, Universidade Federal do Rio de Janeiro, 21945-970 Rio de Janeiro, RJ, Brazil
^*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 12 February 2004; accepted 23 February 2004; online 20 March 2004)

Molecules of (cyclohexylideneamino)oxyacetic acid, C₈H₁₃NO₃, (I), are linked into centrosymmetric dimers by pairs of O—H⋯O hydrogen bonds [H⋯O = 1.84 Å, O⋯O = 2.6782 (12) Å and O—H⋯O = 178°]. In [chloro(phenyl)methyleneamino]oxyacetic acid, C₉H₈ClNO₃, (II), the molecules are similarly linked into centrosymmetric dimers by pairs of O—H⋯O hydrogen bonds [H⋯O = 1.79 Å, O⋯O = 2.6329 (17) Å and O—H⋯O = 176°], and these dimers are weakly linked into chains by a single type of aromatic π–π stacking interaction.

Comment

Persulfate oxidation of iminooxyacetic acids, R(R′)C=NOCH₂COOH, provides a useful route to iminyl radicals (Forrester et al., 1979 ). The subsequent reactions of the iminyl radicals thus generated depend greatly on the substituents, and important species including nitrogen-containing heterocycles can result. We report here the molecular and supramolecular structures of two representative examples of such

precursors, viz. (cyclohexylideneamino)oxyacetic acid, (I

), and [chloro(phenyl)methyleneamino]oxyacetic acid, (II

In both (I) and (II) (Figs. 1 and 2), the C—O distances in the carboxy groups (Tables 1 and 3) are consistent with the fully ordered locations of the carboxy H atoms as deduced from difference maps. In the side chains of (I) and (II), the corresponding distances show very similar values, apart from the O3—N4 distances, which are significantly different; for comparison, the mean value for the —O—N= bond in oximes is 1.416 Å (Allen et al., 1987 ). The other distances are typical for bonds of their types.

The conformations of the side chains both exhibit near-planar fragments, viz. O1—C1—C2—O3 and C2—O3—N4—Cn [n = 11 in (I) and n = 5 in (II); see Figs. 1 and 2], but while the intervening C1—C2—O3—N4 torsion angles have similar magnitudes in (I) and (II), they have opposite signs, and it is this difference that determines the different overall conformations of these two molecules. For the cyclohexylidene ring in (I), the ring-puckering parameters (Cremer & Pople, 1975 ) corresponding to the atom sequence C11–C16 [φ = 174.0 (2)° and θ = 12 (2)°] indicate a conformation close to the chair form (Evans & Boeyens, 1989 ), despite the planarity at atom C11.

In the structures of both (I) and (II), the molecules are linked into centrosymmetric R₂²(8) (Bernstein et al., 1995 ) dimers (Figs. 3 and 4) by paired O—H⋯O hydrogen bonds, which are fairly short and effectively linear (Tables 2 and 4). In each structure, the reference molecule has been selected so that the hydrogen-bonded dimer in which this molecule participates is centred at ( $[1 \over 2]$ , $[1 \over 2]$ , $[1 \over 2]$ ). In the structure of (I), there are no further direction-specific interactions between the molecules, but in (II), the R₂²(8) dimers are weakly linked into chains by a single aromatic π–π stacking interaction. The aryl rings in the molecules at (x, y, z) and (2 − x, 1 − y, 2 − z) are parallel, with an interplanar spacing of 3.422 (2) Å; the ring-centroid separation is 3.856 (2) Å, corresponding to a centroid offset of 1.777 (2) Å. The molecules at (x, y, z) and (2 − x, 1 − y, 2 − z) are components of hydrogen-bonded dimers centred at ( $[1 \over 2]$ , $[1 \over 2]$ , $[1 \over 2]$ ) and (1, $[1 \over 2]$ , 1), respectively, and propagation by inversion of the two intermolecular interactions generates a chain running parallel to the [101] direction (Fig. 5).

In neither (I) nor (II) do atoms O3 and N4 act as acceptors of C—H⋯X (X = O or N) hydrogen bonds; there are no intermolecular H⋯X contact distances involving O3 or N4 that are less than 2.60 Å in (I), and none of less than 2.70 Å in (II).

Figure 1
The molecule of (I

), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 2
The molecule of (II

), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 3
Part of the crystal structure of (I

), showing the formation of an R₂²(8) dimer centred at ( $[1 \over 2]$ , $[1 \over 2]$ , $[1 \over 2]$ ). For clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (1 − x, 1 − y, 1 − z).

Figure 4
Part of the crystal structure of (II

Figure 5
A stereoview of part of the crystal structure of (II

), showing the formation of a π-stacked [101] chain of hydrogen-bonded dimers. For clarity, H atoms bonded to C atoms have been omitted.

Experimental

Benzhydroxamoyl chloride, Cl(Ph)C=NOH, was prepared from H(Ph)C=NOH according to the method of Baruah et al. (1988 ). Compounds (I) and (II) were prepared by reaction of chloroacetic acid with either cyclohexanone oxime [for (I)] or Cl(Ph)C=NOH [for (II)], using the following modification of the procedure of Forrester et al. (1979). A solution of the oxime (0.10 mol), chloroacetic acid (0.20 mol) and sodium hydroxide (0.40 mol) in a mixture of water (100 ml) and ethanol (50 ml) was heated under reflux overnight. The cooled solution was poured on to ice and acidified with dilute hydrochloric acid. The precipitate was collected, washed with water and dissolved in NaHCO₃ solution (100 ml of 1 mol dm⁻³). This solution was extracted with diethyl ether and acidified with dilute hydrochloric acid. The resulting solid was collected, washed with water and recrystallized from ethanol, yielding crystals suitable for single-crystal X-ray diffraction; m.p: (I) 365–367 K, (II) 381–383 K.

Compound (I)

Crystal data

C₈H₁₃NO₃
M_r = 171.19
Triclinic, $[P\overline 1]$
a = 5.0776 (1) Å
b = 8.6533 (3) Å
c = 10.7804 (3) Å
α = 111.2609 (15)°
β = 102.437 (2)°
γ = 93.597 (2)°
V = 425.88 (2) Å³
Z = 2
D_x = 1.335 Mg m⁻³
Mo Kα radiation
Cell parameters from 1945 reflections
θ = 3.9–27.5°
μ = 0.10 mm⁻¹
T = 120 (2) K
Block, colourless
0.40 × 0.30 × 0.30 mm

Data collection

Nonius KappaCCD diffractometer
φ scans, and ω scans with κ offsets
Absorption correction: multi-scan (SORTAV; Blessing, 1995 , 1997 ) T_min = 0.917, T_max = 0.968
9176 measured reflections
1945 independent reflections
1621 reflections with I > 2σ(I)
R_int = 0.042
θ_max = 27.5°
h = −5 → 6
k = −11 → 11
l = −13 → 13

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.098
S = 1.04
1945 reflections
110 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0482P)² + 0.1199P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Selected geometric parameters (Å, °) for (I)

C1—O1	1.3186 (14)
C1—O2	1.2134 (14)
O3—N4	1.4331 (12)
N4—C11	1.2775 (15)

O1—C1—O2	124.23 (11)
O1—C1—C2	111.52 (10)
O2—C1—C2	124.24 (10)
C2—O3—N4	107.87 (8)
O3—N4—C11	111.71 (9)

O1—C1—C2—O3	−177.14 (9)
O2—C1—C2—O3	1.83 (17)
C1—C2—O3—N4	−83.62 (11)
C2—O3—N4—C11	−175.25 (9)
O3—N4—C11—C12	179.11 (9)
O3—N4—C11—C16	1.24 (16)

Table 2
Hydrogen-bonding geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	0.84	1.84	2.6782 (12)	178
Symmetry code: (i) 1-x,1-y,1-z.

Compound (II)

Crystal data

C₉H₈ClNO₃
M_r = 213.61
Triclinic, $[P\overline 1]$
a = 6.7961 (1) Å
b = 7.3857 (2) Å
c = 10.8173 (3) Å
α = 98.4852 (9)°
β = 93.4156 (10)°
γ = 117.0191 (12)°
V = 473.44 (2) Å³
Z = 2
D_x = 1.498 Mg m⁻³
Mo Kα radiation
Cell parameters from 2133 reflections
θ = 3.2–27.4°
μ = 0.38 mm⁻¹
T = 120 (2) K
Plate, colourless
0.28 × 0.20 × 0.05 mm

Data collection

Nonius KappaCCD diffractometer
φ scans, and ω scans with κ offsets
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) T_min = 0.922, T_max = 0.981
3988 measured reflections
2133 independent reflections
1980 reflections with I > 2σ(I)
R_int = 0.031
θ_max = 27.4°
h = −8 → 8
k = −9 → 9
l = −13 → 13

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.141
S = 1.20
2132 reflections
128 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0766P)² + 0.1738P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Table 3
Selected geometric parameters (Å, °) for (II)

C5—Cl1	1.738 (2)
C1—O1	1.311 (2)
C1—O2	1.226 (2)
O3—N4	1.405 (2)
N4—C5	1.273 (2)

O1—C1—O2	124.64 (16)
O1—C1—C2	112.36 (14)
O2—C1—C2	123.00 (16)
C2—O3—N4	107.45 (13)
O3—N4—C5	113.12 (14)

O1—C1—C2—O3	−171.61 (14)
C1—C2—O3—N4	75.87 (17)
C2—O3—N4—C5	−173.61 (14)

Table 4
Hydrogen-bonding geometry (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	0.84	1.79	2.6329 (17)	176
Symmetry code: (i) 1-x,1-y,1-z.

Crystals of (I) and (II) are triclinic; space group $[P\overline 1]$ was selected for each and confirmed in both cases by the subsequent analyses. All H atoms were located from difference maps and then treated as riding atoms, with C—H distances of 0.95 (aromatic) or 0.99 Å (CH₂), and O—H distances of 0.84 Å.

For both compounds, data collection: KappaCCD Server Software (Nonius, 1997 ); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997 ); data reduction: DENZO–SMN; program(s) used to solve structure: OSCAIL (McArdle, 2003 ) and SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I, II. DOI: 10.1107/S0108270104004299/gg1209sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270104004299/gg1209Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S0108270104004299/gg1209IIsup3.hkl

Comment top

Persulfate oxidation of imino-oxyacetic acids, R(R^')C=NOCH₂COOH, provides a useful route to iminyl radicals (Forrester et al., 1979). The subsequent reactions of the iminyl radicals thus generated depend greatly on the substituents, and important species including nitrogen-containing heterocycles can result. We report here the molecular and supramolecular structures of two representative examples of such precursors, (cyclohexylideneamino)oxyacetic acid, (I), and [chloro(phenyl)methyleneamino]oxyacetic acid, (II).

In both (I) and (II) (Figs. 1 and 2), the C—O distances in the carboxy groups (Tables 1 and 3) are consistent with the fully ordered locations of the carboxy H atoms, as deduced from difference maps. In the side chains of (I) and (II), the corresponding distances show very similar values, apart from the O3—N4 distances, which are significantly different; for comparison, the mean value for –O—N= bonds in oximes is 1.416 Å (Allen et al., 1987). The other distances are typical for bonds of their types.

The conformations of the side chains both exhibit near-planar fragments, viz. O1—C1—C2—O3 and C2—O3—N4—Cn [n = 11 in (I) and n = 5 in (II), see Figs. 1 and 2], but while the intervening C1—C2—O3—N4 torsion angles have similar magnitudes in (I) and (II) they have opposite signs, and it is this difference that determines the different overall conformations of these two molecules. For the cyclohexylidene ring in (I), the ring-puckering parameters (Cremer & Pople, 1975) corresponding to the atom sequence C11–C16 [ϕ = 174.0 (2)° and θ = 12 (2) °] indicate a conformation close to the chair form (Evans & Boeyens, 1989), despite the planarity at atom C11.

In the structures of both (I) and (II), the molecules are linked into centrosymmetric R²₂(8) dimers (Figs. 3 and 4) by paired O—H···O hydrogen bonds, which are fairly short and effectively linear (Tables 2 and 4). In each structure, the reference molecule has been selected so that the hydrogen-bonded dimer in which this molecule participates is centred at (1/2, 1/2, 1/2). In the structure of (I), there are no further direction-specific interactions between the molecules, but in (II), the R²₂(8) dimers are weakly linked into chains by a single aromatic π–π stacking interaction. The aryl rings in the molecules at (x, y, z) and (2 − x, 1 − y, 2 − z) are parallel, with an interplanar spacing of 3.422 (2) Å; the ring-centroid separation is 3.856 (2) Å, corresponding to a centroid offset of 1.777 (2) Å. The molecules at (x, y, z) and (2 − x, 1 − y, 2 − z) are components of hydrogen-bonded dimers centred at (1/2, 1/2, 1/2) and (1, 1/2, 1), respectively, and propagation by inversion of the two intermolecular interactions generates a chain running parallel to the [101] direction (Fig. 5).

In neither (I) nor (II) do atoms O3 and N4 act as acceptors of C—H···X (X = O or N) hydrogen bonds; there are no intermolecular H···X contact distances involving O3 or N4 which are less than 2.60 Å in (I), and none of less than 2.70 Å in (II).

Experimental top

N-Hydroxybenzenecarboximidioyl chloride, Cl(Ph)C=NOH, was prepared from H(Ph)C=NOH according to the method of Baruah et al. (1988). Compounds (I) and (II) were prepared by reaction of chloroacetic acid with either cyclohexanone oxime [for (I)] or Cl(Ph)C=NOH [for (II)], using the following modification of the procedure of Forrester et al. (1979). A solution of the oxime (0.10 mol), chloroacetic acid (0.20 mol) and sodium hydroxide (0.40 mol) in a mixture of water (100 ml) and ethanol (50 ml) was heated under reflux overnight. The cooled solution was poured onto ice, and acidified with dilute hydrochloric acid. The precipitate was collected, washed with water and dissolved in Na[HCO₃] solution (100 ml of 1 mol dm⁻³). This solution was extracted with diethyl ether and acidified with dilute hydrochloric acid. The resulting solid was collected, washed with water and recrystallized from ethanol to give crystals suitable for single-crystal X-ray diffraction. M.p. (I) 365–367 K, (II) 381–383 K.

Computing details top

For both compounds, data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures top

	Fig. 1. The molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The molecule of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 3. Part of the crystal structure of (I), showing the formation of an R²₂(8) dimer centred at (1/2, 1/2, 1/2). For clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (1 − x, 1 − y, 1 − z).
	Fig. 4. Part of the crystal structure of (II), showing the formation of an R²₂(8) dimer centred at (1/2, 1/2, 1/2). For clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (1 − x, 1 − y, 1 − z).
	Fig. 5. A stereoview of part of the crystal structure of (II), showing the formation of a π-stacked [101] chain of hydrogen-bonded dimers. For clarity, H atoms bonded to C atoms have been omitted.

(I) (Cyclohexylideneamino)oxyacetic acid top

Crystal data top

C₈H₁₃NO₃	Z = 2
M_r = 171.19	F(000) = 184
Triclinic, P1	D_x = 1.335 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.0776 (1) Å	Cell parameters from 1945 reflections
b = 8.6533 (3) Å	θ = 3.9–27.5°
c = 10.7804 (3) Å	µ = 0.10 mm⁻¹
α = 111.2609 (15)°	T = 120 K
β = 102.437 (2)°	Block, colourless
γ = 93.597 (2)°	0.40 × 0.30 × 0.30 mm
V = 425.88 (2) Å³

Data collection top

Nonius KappaCCD diffractometer	1945 independent reflections
Radiation source: rotating anode	1621 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
ϕ scans, and ω scans with κ offsets	θ_max = 27.5°, θ_min = 3.9°
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997)	h = −5→6
T_min = 0.917, T_max = 0.968	k = −11→11
9176 measured reflections	l = −13→13

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.098	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0482P)² + 0.1199P] where P = (F_o² + 2F_c²)/3
1945 reflections	(Δ/σ)_max < 0.001
110 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₈H₁₃NO₃	γ = 93.597 (2)°
M_r = 171.19	V = 425.88 (2) Å³
Triclinic, P1	Z = 2
a = 5.0776 (1) Å	Mo Kα radiation
b = 8.6533 (3) Å	µ = 0.10 mm⁻¹
c = 10.7804 (3) Å	T = 120 K
α = 111.2609 (15)°	0.40 × 0.30 × 0.30 mm
β = 102.437 (2)°

Data collection top

Nonius KappaCCD diffractometer	1945 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997)	1621 reflections with I > 2σ(I)
T_min = 0.917, T_max = 0.968	R_int = 0.042
9176 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.098	H-atom parameters constrained
S = 1.04	Δρ_max = 0.25 e Å⁻³
1945 reflections	Δρ_min = −0.29 e Å⁻³
110 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.25509 (18)	0.43807 (11)	0.58143 (9)	0.0258 (2)
O2	0.63107 (18)	0.63065 (11)	0.66261 (9)	0.0253 (2)
O3	0.53648 (16)	0.75100 (10)	0.92037 (8)	0.0198 (2)
N4	0.76773 (19)	0.68931 (12)	0.97793 (10)	0.0191 (2)
C1	0.4331 (2)	0.56279 (14)	0.67960 (12)	0.0180 (2)
C2	0.3569 (2)	0.61259 (14)	0.81506 (11)	0.0197 (3)
C11	0.9316 (2)	0.80606 (14)	1.08118 (11)	0.0169 (2)
C12	1.1796 (2)	0.75439 (15)	1.15083 (13)	0.0229 (3)
C13	1.2053 (3)	0.81203 (15)	1.30557 (13)	0.0243 (3)
C14	1.1915 (2)	0.99871 (15)	1.36960 (12)	0.0202 (3)
C15	0.9271 (2)	1.03967 (15)	1.29856 (12)	0.0204 (3)
C16	0.9009 (2)	0.98760 (14)	1.14378 (11)	0.0188 (3)
H1	0.2940	0.4191	0.5059	0.031*
H2A	0.1694	0.6406	0.8025	0.024*
H2B	0.3569	0.5159	0.8435	0.024*
H12A	1.3448	0.8042	1.1357	0.027*
H12B	1.1665	0.6307	1.1098	0.027*
H13A	1.0561	0.7477	1.3210	0.029*
H13B	1.3810	0.7889	1.3509	0.029*
H14A	1.3495	1.0637	1.3611	0.024*
H14B	1.2017	1.0318	1.4688	0.024*
H15A	0.9237	1.1617	1.3408	0.024*
H15B	0.7696	0.9802	1.3122	0.024*
H16A	0.7204	1.0051	1.0985	0.023*
H16B	1.0435	1.0579	1.1294	0.023*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0266 (5)	0.0269 (5)	0.0144 (4)	−0.0078 (4)	0.0022 (3)	0.0008 (3)
O2	0.0272 (5)	0.0249 (5)	0.0169 (4)	−0.0064 (4)	0.0039 (4)	0.0027 (3)
O3	0.0203 (4)	0.0184 (4)	0.0150 (4)	0.0042 (3)	−0.0013 (3)	0.0030 (3)
N4	0.0183 (5)	0.0195 (5)	0.0178 (5)	0.0051 (4)	0.0020 (4)	0.0065 (4)
C1	0.0192 (5)	0.0148 (5)	0.0160 (6)	0.0016 (4)	0.0000 (4)	0.0041 (4)
C2	0.0190 (6)	0.0206 (6)	0.0149 (6)	−0.0002 (4)	0.0012 (4)	0.0037 (5)
C11	0.0185 (5)	0.0176 (5)	0.0147 (5)	0.0025 (4)	0.0047 (4)	0.0063 (4)
C12	0.0202 (6)	0.0181 (6)	0.0239 (6)	0.0033 (4)	0.0002 (5)	0.0037 (5)
C13	0.0222 (6)	0.0246 (6)	0.0245 (6)	−0.0012 (5)	−0.0034 (5)	0.0135 (5)
C14	0.0172 (5)	0.0263 (6)	0.0138 (5)	−0.0020 (5)	0.0013 (4)	0.0064 (5)
C15	0.0178 (6)	0.0244 (6)	0.0146 (5)	0.0024 (4)	0.0039 (4)	0.0027 (4)
C16	0.0234 (6)	0.0157 (5)	0.0145 (5)	0.0024 (4)	0.0016 (4)	0.0046 (4)

Geometric parameters (Å, º) top

C1—O1	1.3186 (14)	C12—H12B	0.99
C1—O2	1.2134 (14)	C13—C14	1.5221 (17)
C1—C2	1.5087 (17)	C13—H13A	0.99
O1—H1	0.84	C13—H13B	0.99
C2—O3	1.4092 (13)	C14—C15	1.5261 (16)
C2—H2A	0.99	C14—H14A	0.99
C2—H2B	0.99	C14—H14B	0.99
O3—N4	1.4331 (12)	C15—C16	1.5351 (16)
N4—C11	1.2775 (15)	C15—H15A	0.99
C11—C16	1.5015 (15)	C15—H15B	0.99
C11—C12	1.5022 (16)	C16—H16A	0.99
C12—C13	1.5309 (18)	C16—H16B	0.99
C12—H12A	0.99

O1—C1—O2	124.23 (11)	C12—C13—H13A	109.4
O1—C1—C2	111.52 (10)	C14—C13—H13B	109.4
O2—C1—C2	124.24 (10)	C12—C13—H13B	109.4
C1—O1—H1	109.5	H13A—C13—H13B	108.0
O3—C2—C1	112.73 (10)	C13—C14—C15	110.75 (10)
O3—C2—H2A	109.0	C13—C14—H14A	109.5
C1—C2—H2A	109.0	C15—C14—H14A	109.5
O3—C2—H2B	109.0	C13—C14—H14B	109.5
C1—C2—H2B	109.0	C15—C14—H14B	109.5
H2A—C2—H2B	107.8	H14A—C14—H14B	108.1
C2—O3—N4	107.87 (8)	C14—C15—C16	111.18 (10)
O3—N4—C11	111.71 (9)	C14—C15—H15A	109.4
N4—C11—C16	127.65 (10)	C16—C15—H15A	109.4
N4—C11—C12	116.10 (10)	C14—C15—H15B	109.4
C16—C11—C12	116.22 (10)	C16—C15—H15B	109.4
C11—C12—C13	110.86 (10)	H15A—C15—H15B	108.0
C11—C12—H12A	109.5	C11—C16—C15	109.79 (9)
C13—C12—H12A	109.5	C11—C16—H16A	109.7
C11—C12—H12B	109.5	C15—C16—H16A	109.7
C13—C12—H12B	109.5	C11—C16—H16B	109.7
H12A—C12—H12B	108.1	C15—C16—H16B	109.7
C14—C13—C12	111.15 (10)	H16A—C16—H16B	108.2
C14—C13—H13A	109.4

O1—C1—C2—O3	−177.14 (9)	C16—C11—C12—C13	51.20 (14)
O2—C1—C2—O3	1.83 (17)	C11—C12—C13—C14	−52.29 (13)
C1—C2—O3—N4	−83.62 (11)	C12—C13—C14—C15	57.08 (13)
C2—O3—N4—C11	−175.25 (9)	C13—C14—C15—C16	−58.22 (13)
O3—N4—C11—C12	179.11 (9)	N4—C11—C16—C15	126.14 (12)
O3—N4—C11—C16	1.24 (16)	C12—C11—C16—C15	−51.73 (13)
N4—C11—C12—C13	−126.92 (11)	C14—C15—C16—C11	53.91 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.84	1.84	2.6782 (12)	178

Symmetry code: (i) −x+1, −y+1, −z+1.

(II) [Chloro(phenyl)methyleneamino]oxyacetic acid top

Crystal data top

C₉H₈ClNO₃	Z = 2
M_r = 213.61	F(000) = 220
Triclinic, P1	D_x = 1.498 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.7961 (1) Å	Cell parameters from 2133 reflections
b = 7.3857 (2) Å	θ = 3.2–27.4°
c = 10.8173 (3) Å	µ = 0.38 mm⁻¹
α = 98.4852 (9)°	T = 120 K
β = 93.4156 (10)°	Plate, colourless
γ = 117.0191 (12)°	0.28 × 0.20 × 0.05 mm
V = 473.44 (2) Å³

Data collection top

Nonius KappaCCD diffractometer	2133 independent reflections
Radiation source: rotating anode	1980 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ϕ scans, and ω scans with κ offsets	θ_max = 27.4°, θ_min = 3.2°
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997)	h = −8→8
T_min = 0.922, T_max = 0.981	k = −9→9
3988 measured reflections	l = −13→13

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.141	H-atom parameters constrained
S = 1.20	w = 1/[σ²(F_o²) + (0.0766P)² + 0.1738P] where P = (F_o² + 2F_c²)/3
2132 reflections	(Δ/σ)_max < 0.001
128 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.48 e Å⁻³

Crystal data top

C₉H₈ClNO₃	γ = 117.0191 (12)°
M_r = 213.61	V = 473.44 (2) Å³
Triclinic, P1	Z = 2
a = 6.7961 (1) Å	Mo Kα radiation
b = 7.3857 (2) Å	µ = 0.38 mm⁻¹
c = 10.8173 (3) Å	T = 120 K
α = 98.4852 (9)°	0.28 × 0.20 × 0.05 mm
β = 93.4156 (10)°

Data collection top

Nonius KappaCCD diffractometer	2133 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997)	1980 reflections with I > 2σ(I)
T_min = 0.922, T_max = 0.981	R_int = 0.031
3988 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.141	H-atom parameters constrained
S = 1.20	Δρ_max = 0.34 e Å⁻³
2132 reflections	Δρ_min = −0.48 e Å⁻³
128 parameters

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

	x	y	z	U_iso*/U_eq
Cl1	0.82919 (7)	0.00737 (7)	0.78680 (4)	0.02459 (19)
O1	0.2370 (2)	0.27726 (19)	0.50408 (13)	0.0235 (3)
O2	0.5944 (2)	0.36247 (19)	0.56736 (12)	0.0229 (3)
O3	0.4685 (2)	0.00535 (19)	0.65729 (11)	0.0211 (3)
N4	0.5117 (3)	0.1192 (2)	0.78071 (14)	0.0197 (3)
C1	0.3942 (3)	0.2414 (3)	0.55267 (16)	0.0193 (4)
C2	0.3016 (3)	0.0310 (3)	0.58876 (17)	0.0219 (4)
C5	0.6749 (3)	0.1242 (2)	0.84810 (16)	0.0175 (4)
C11	0.7394 (3)	0.2326 (2)	0.98149 (16)	0.0183 (4)
C12	0.9281 (3)	0.2563 (3)	1.05444 (17)	0.0219 (4)
C13	0.9880 (3)	0.3636 (3)	1.17899 (18)	0.0264 (4)
C14	0.8604 (3)	0.4479 (3)	1.23152 (18)	0.0276 (4)
C15	0.6704 (3)	0.4242 (3)	1.15935 (19)	0.0272 (4)
C16	0.6092 (3)	0.3170 (3)	1.03528 (18)	0.0230 (4)
H1	0.2951	0.3949	0.4848	0.028*
H2A	0.1816	0.0141	0.6408	0.026*
H2B	0.2353	−0.0780	0.5113	0.026*
H12	1.0167	0.1987	1.0190	0.026*
H13	1.1172	0.3790	1.2281	0.032*
H14	0.9020	0.5217	1.3165	0.033*
H15	0.5823	0.4819	1.1954	0.033*
H16	0.4790	0.3007	0.9867	0.028*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0273 (3)	0.0281 (3)	0.0234 (3)	0.0181 (2)	0.00411 (19)	0.00161 (19)
O1	0.0176 (6)	0.0243 (7)	0.0273 (7)	0.0094 (5)	−0.0010 (5)	0.0045 (5)
O2	0.0174 (6)	0.0228 (6)	0.0254 (7)	0.0076 (5)	−0.0016 (5)	0.0039 (5)
O3	0.0230 (6)	0.0223 (6)	0.0172 (6)	0.0109 (5)	0.0008 (5)	0.0014 (5)
N4	0.0228 (7)	0.0193 (7)	0.0160 (7)	0.0091 (6)	0.0037 (6)	0.0030 (5)
C1	0.0188 (8)	0.0226 (8)	0.0149 (8)	0.0097 (7)	0.0009 (6)	−0.0004 (6)
C2	0.0176 (8)	0.0241 (8)	0.0216 (8)	0.0079 (7)	0.0005 (6)	0.0044 (7)
C5	0.0185 (8)	0.0143 (7)	0.0210 (8)	0.0078 (6)	0.0058 (6)	0.0053 (6)
C11	0.0211 (8)	0.0134 (7)	0.0193 (8)	0.0063 (6)	0.0050 (6)	0.0059 (6)
C12	0.0245 (9)	0.0174 (8)	0.0229 (9)	0.0092 (7)	0.0021 (7)	0.0043 (7)
C13	0.0287 (9)	0.0225 (9)	0.0241 (9)	0.0097 (7)	−0.0019 (7)	0.0036 (7)
C14	0.0360 (10)	0.0202 (9)	0.0196 (9)	0.0080 (8)	0.0038 (7)	0.0018 (7)
C15	0.0326 (10)	0.0246 (9)	0.0258 (10)	0.0145 (8)	0.0091 (8)	0.0029 (7)
C16	0.0243 (9)	0.0232 (8)	0.0232 (9)	0.0124 (7)	0.0050 (7)	0.0048 (7)

Geometric parameters (Å, º) top

C5—Cl1	1.738 (2)	C11—C12	1.390 (3)
C1—O1	1.311 (2)	C11—C16	1.402 (3)
C1—O2	1.226 (2)	C12—C13	1.391 (3)
C1—C2	1.510 (2)	C12—H12	0.95
O1—H1	0.84	C13—C14	1.381 (3)
C2—O3	1.418 (2)	C13—H13	0.95
C2—H2A	0.99	C14—C15	1.393 (3)
C2—H2B	0.99	C14—H14	0.95
O3—N4	1.405 (2)	C15—C16	1.386 (3)
N4—C5	1.273 (2)	C15—H15	0.95
C5—C11	1.477 (2)	C16—H16	0.95

O1—C1—O2	124.64 (16)	C16—C11—C5	119.14 (16)
O1—C1—C2	112.36 (14)	C11—C12—C13	120.46 (18)
O2—C1—C2	123.00 (16)	C11—C12—H12	119.8
C1—O1—H1	109.5	C13—C12—H12	119.8
O3—C2—C1	111.90 (14)	C14—C13—C12	120.27 (18)
O3—C2—H2A	109.2	C14—C13—H13	119.9
C1—C2—H2A	109.2	C12—C13—H13	119.9
O3—C2—H2B	109.2	C13—C14—C15	119.69 (18)
C1—C2—H2B	109.2	C13—C14—H14	120.2
H2A—C2—H2B	107.9	C15—C14—H14	120.2
C2—O3—N4	107.45 (13)	C16—C15—C14	120.40 (18)
O3—N4—C5	113.12 (14)	C16—C15—H15	119.8
N4—C5—C11	120.30 (15)	C14—C15—H15	119.8
N4—C5—Cl1	121.60 (14)	C15—C16—C11	120.00 (17)
C11—C5—Cl1	118.09 (13)	C15—C16—H16	120.0
C12—C11—C16	119.17 (17)	C11—C16—H16	120.0
C12—C11—C5	121.68 (16)

O2—C1—C2—O3	8.7 (2)	Cl1—C5—C11—C16	−176.09 (12)
O1—C1—C2—O3	−171.61 (14)	C16—C11—C12—C13	−0.5 (3)
C1—C2—O3—N4	75.87 (17)	C5—C11—C12—C13	178.41 (15)
C2—O3—N4—C5	−173.61 (14)	C11—C12—C13—C14	0.0 (3)
O3—N4—C5—C11	−178.38 (13)	C12—C13—C14—C15	0.3 (3)
O3—N4—C5—Cl1	2.2 (2)	C13—C14—C15—C16	−0.1 (3)
N4—C5—C11—C12	−174.38 (15)	C14—C15—C16—C11	−0.4 (3)
Cl1—C5—C11—C12	5.0 (2)	C12—C11—C16—C15	0.6 (3)
N4—C5—C11—C16	4.5 (2)	C5—C11—C16—C15	−178.26 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.84	1.79	2.6329 (17)	176

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

	(I)	(II)
Crystal data
Chemical formula	C₈H₁₃NO₃	C₉H₈ClNO₃
M_r	171.19	213.61
Crystal system, space group	Triclinic, P1	Triclinic, P1
Temperature (K)	120	120
a, b, c (Å)	5.0776 (1), 8.6533 (3), 10.7804 (3)	6.7961 (1), 7.3857 (2), 10.8173 (3)
α, β, γ (°)	111.2609 (15), 102.437 (2), 93.597 (2)	98.4852 (9), 93.4156 (10), 117.0191 (12)
V (Å³)	425.88 (2)	473.44 (2)
Z	2	2
Radiation type	Mo Kα	Mo Kα
µ (mm⁻¹)	0.10	0.38
Crystal size (mm)	0.40 × 0.30 × 0.30	0.28 × 0.20 × 0.05

Data collection
Diffractometer	Nonius KappaCCD diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SORTAV; Blessing, 1995, 1997)	Multi-scan (SORTAV; Blessing, 1995, 1997)
T_min, T_max	0.917, 0.968	0.922, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	9176, 1945, 1621	3988, 2133, 1980
R_int	0.042	0.031
(sin θ/λ)_max (Å⁻¹)	0.650	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.098, 1.04	0.040, 0.141, 1.20
No. of reflections	1945	2132
No. of parameters	110	128
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.29	0.34, −0.48

Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO–SMN (Otwinowski & Minor, 1997), OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997), OSCAIL and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).

Selected geometric parameters (Å, º) for (I) top

C1—O1	1.3186 (14)	O3—N4	1.4331 (12)
C1—O2	1.2134 (14)	N4—C11	1.2775 (15)

O1—C1—O2	124.23 (11)	C2—O3—N4	107.87 (8)
O1—C1—C2	111.52 (10)	O3—N4—C11	111.71 (9)
O2—C1—C2	124.24 (10)

O1—C1—C2—O3	−177.14 (9)	C2—O3—N4—C11	−175.25 (9)
O2—C1—C2—O3	1.83 (17)	O3—N4—C11—C12	179.11 (9)
C1—C2—O3—N4	−83.62 (11)	O3—N4—C11—C16	1.24 (16)

Hydrogen-bond geometry (Å, º) for (I) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.84	1.84	2.6782 (12)	178

Symmetry code: (i) −x+1, −y+1, −z+1.

Selected geometric parameters (Å, º) for (II) top

C5—Cl1	1.738 (2)	O3—N4	1.405 (2)
C1—O1	1.311 (2)	N4—C5	1.273 (2)
C1—O2	1.226 (2)

O1—C1—O2	124.64 (16)	C2—O3—N4	107.45 (13)
O1—C1—C2	112.36 (14)	O3—N4—C5	113.12 (14)
O2—C1—C2	123.00 (16)

O1—C1—C2—O3	−171.61 (14)	C2—O3—N4—C5	−173.61 (14)
C1—C2—O3—N4	75.87 (17)

Hydrogen-bond geometry (Å, º) for (II) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.84	1.79	2.6329 (17)	176

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

X-ray data were collected at the EPSRC X-ray Crystallographic Service, University of Southampton, England; the authors thank the staff for all their help and advice. JNL thanks NCR Self-Service, Dundee, for grants that have provided computing facilities for this work. JLW thanks CNPq and FAPERJ for financial support.

References

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Volume 60| Part 4| April 2004| Pages o270-o272

doi:10.1107/S0108270104004299

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

(Cyclo­hexyl­­idene­amino)­­oxy­acetic acid and [chloro­(phenyl)­methyl­ene­amino]­­oxy­acetic acid: hydrogen-bonded R(8) dimers and aromatic π–π stacking interactions

Comment

Experimental

Compound (I)

Crystal data

Data collection

Refinement

Compound (II)

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

(Cyclohexylideneamino)oxyacetic acid and [chloro(phenyl)methyleneamino]oxyacetic acid: hydrogen-bonded R(8) dimers and aromatic π–π stacking interactions