(Z)-N′-Hy­droxy-4-(trifluoro­meth­yl)benzimidamide

Liu, F.; Zhang, F.; Chen, Q.; Dong, M.

doi:10.1107/S1600536811005022

organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page o859

doi:10.1107/S1600536811005022

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(Z)-N′-Hydroxy-4-(trifluoromethyl)benzimidamide

Fei Liu,^a ^* Fang Zhang,^a Qifan Chen ^b and Mingdong Dong ^b

^aCollege of Chemical Engineering & Materials, Eastern Liaoning University, No. 325 Wenhua Road, Yuanbao District, Dandong City, Liaoning Province 118003, People's Republic of China, and ^bExperiment Center, Eastern Liaoning University, No. 325 Wenhua Road, Yuanbao District, Dandong City, Liaoning Province 118003, People's Republic of China
^*Correspondence e-mail: berylliu8090@sina.com

(Received 10 February 2011; accepted 10 February 2011; online 12 March 2011)

In the title compound, C₈H₇F₃N₂O, the OH and NH₂ substituents adopt a Z configuration with respect to the C=N bond. The hydroxyimidamide unit is almost planar (r.m.s. deviation = 0.007 Å) and subtends an angle of 26.25 (13)° with the benzene ring. The F atoms of the trifluoromethyl substituent are disordered over two sets of sites with an occupancy ratio of 0.783 (15):0.217 (15). In the crystal, O—H⋯N hydrogen bonds form centrosymmetric dimers. Additional N—H⋯O hydrogen bonds link the dimers into zigzag chains along the b axis. Weak intermolecular F⋯F contacts of 2.714 (5) Å are also observed.

Related literature

For the preparation of the title compound, see: Rai et al. (2010 ). For the use of oxime derivatives in crystal engineering, see: Aakeröy et al. (2000 ). For a related structure, see: Orama & Saarinen (1996 ).

Experimental

Crystal data

C₈H₇F₃N₂O
M_r = 204.16
Monoclinic, P 2₁ /c
a = 9.8706 (8) Å
b = 11.2540 (12) Å
c = 8.4033 (7) Å
β = 104.61 (2)°
V = 903.29 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 293 K
0.32 × 0.24 × 0.20 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.946, T_max = 0.972
8605 measured reflections
2058 independent reflections
1324 reflections with I > 2σ(I)
R_int = 0.077

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.183
S = 1.07
2058 reflections
164 parameters
42 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1ⁱ	0.84 (3)	2.36 (3)	3.165 (3)	161 (3)
O1—H1O⋯N2ⁱⁱ	0.86 (3)	1.98 (3)	2.766 (2)	152 (3)
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+2.

Data collection: PROCESS-AUTO (Rigaku, 2006 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku, 2007 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811005022/sj5105sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811005022/sj5105Isup2.hkl

checkCIF report

Comment top

The oxime functionality is well known in organic synthesis, analytical chemistry, and coordination chemistry, yet it has remained relatively unexplored as an intermolecular connector in crystal engineering (Aakeröy et al., 2000).

In the title compound, the oxime also carries an amine substituent and assumes a Z configuration with respect to the C8═N2 bond (Fig. 1). Atoms F1A:F3B, F2A:F1B, F3A: F2B are disordered over two positions and with site occupancies of 0.5:0.5. The C8,N1,N2,O1 hydroxyimidamide unit is almost planar (r.m.s. deviation 0.007 Å) and subtends an angle of 26.25 (13)° to the C2···C7 benzene ring. The torsion angle O1—N2—C8—C5 between the oxime unit and the ring system is -177.71 (15)°. In the crystal O1–H1O···N1 hydrogen bonds form centrosymmetric dimers. An additional N1–H1N···O1 hydrogen bond links these dimers into zigzag chains along b. Weak intermolecular F2A···F2Aⁱⁱⁱ contacts, 2.714 (5) Å, (ⁱⁱⁱ = -x, 1-y, -z) are also observed (Fig. 2).

Related literature top

For the preparation of the title compound, see: Rai et al. (2010). For the use of oxime derivatives in crystal engineering, see: Aakeröy et al. (2000). For a related structure, see: Orama & Saarinen (1996).

Experimental top

The compound was prepared by a reported procedure (Rai et al., 2010) To a solution of 4-(trifluoromethyl)benzonitrile (0.2 mol) in ethanol (20 mL) was added hydroxylamine hydrochloride (0.4 mol) in water (40 mL). Then anhydrous sodium carbonate(0.4 mol) in water (120 mL) was slowly added to the resulting solution and the mixture was stirred at 358k for 5 h and then concentrated under vacuum to evaporate some water. The resulting suspension was filtered, the solid that formed was washed with cold water and dried under vacuum. Block-shaped crystals suitable for X-ray diffraction were obtained from methanol.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 2006); cell refinement: PROCESS-AUTO (Rigaku, 2006); data reduction: CrystalStructure (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. Structure of the title compound with 50% probability displacement ellipsoids. For clarity, only one of the two equivalent disorder components is shown.
	Fig. 2. Crystal packing of the title compound viewed down the c axis. Hydrogen bonds and F···F contacts are drawn as dashed lines.

N'-hydroxy-4-(trifluoromethyl)benzene-1-carboximidamide top

Crystal data top

C₈H₇F₃N₂O	F(000) = 416
M_r = 204.16	D_x = 1.501 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4741 reflections
a = 9.8706 (8) Å	θ = 3.1–27.4°
b = 11.2540 (12) Å	µ = 0.14 mm⁻¹
c = 8.4033 (7) Å	T = 293 K
β = 104.61 (2)°	Irregular block, colorless
V = 903.29 (16) Å³	0.32 × 0.24 × 0.20 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	2058 independent reflections
Radiation source: fine-focus sealed tube	1324 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.077
Detector resolution: 10.0 pixels mm^-1	θ_max = 27.4°, θ_min = 3.1°
ω scans	h = −12→12
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −14→14
T_min = 0.946, T_max = 0.972	l = −10→10
8605 measured reflections

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.183	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.101P)² + 0.058P] where P = (F_o² + 2F_c²)/3
2058 reflections	(Δ/σ)_max < 0.001
164 parameters	Δρ_max = 0.23 e Å⁻³
42 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₈H₇F₃N₂O	V = 903.29 (16) Å³
M_r = 204.16	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.8706 (8) Å	µ = 0.14 mm⁻¹
b = 11.2540 (12) Å	T = 293 K
c = 8.4033 (7) Å	0.32 × 0.24 × 0.20 mm
β = 104.61 (2)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	2058 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1324 reflections with I > 2σ(I)
T_min = 0.946, T_max = 0.972	R_int = 0.077
8605 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	42 restraints
wR(F²) = 0.183	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.23 e Å⁻³
2058 reflections	Δρ_min = −0.29 e Å⁻³
164 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	Occ. (<1)
C1	−0.0030 (2)	0.6553 (2)	0.2394 (3)	0.0759 (7)
F1A	−0.0355 (6)	0.7584 (3)	0.1633 (6)	0.1154 (16)	0.783 (15)
F2A	−0.0071 (5)	0.5782 (6)	0.1205 (6)	0.1246 (19)	0.783 (15)
F3A	−0.1063 (3)	0.6322 (8)	0.3082 (5)	0.1140 (18)	0.783 (15)
F2B	−0.082 (2)	0.564 (2)	0.260 (3)	0.133 (8)	0.217 (15)
F3B	−0.0726 (17)	0.7557 (13)	0.244 (4)	0.133 (8)	0.217 (15)
F1B	−0.0132 (15)	0.629 (2)	0.0833 (8)	0.119 (6)	0.217 (15)
C2	0.1369 (2)	0.65458 (19)	0.3615 (3)	0.0581 (6)
C3	0.2008 (2)	0.7593 (2)	0.4227 (3)	0.0620 (6)
H3	0.1607	0.8316	0.3828	0.074*
C4	0.3252 (2)	0.75674 (18)	0.5442 (3)	0.0575 (6)
H4	0.3685	0.8276	0.5857	0.069*
C5	0.3858 (2)	0.64908 (16)	0.6046 (2)	0.0484 (5)
C8	0.5128 (2)	0.64594 (16)	0.7435 (2)	0.0503 (5)
N1	0.6164 (2)	0.72612 (19)	0.7499 (3)	0.0731 (6)
H1N	0.620 (3)	0.764 (3)	0.665 (4)	0.088*
H2N	0.689 (3)	0.717 (2)	0.830 (4)	0.088*
N2	0.51210 (16)	0.56917 (14)	0.85708 (19)	0.0515 (5)
O1	0.63766 (15)	0.57836 (13)	0.98654 (18)	0.0622 (5)
H1O	0.618 (3)	0.532 (2)	1.059 (3)	0.093*
C6	0.3222 (2)	0.54448 (19)	0.5390 (3)	0.0622 (6)
H6	0.3633	0.4720	0.5765	0.075*
C7	0.1980 (2)	0.5470 (2)	0.4181 (3)	0.0679 (7)
H7	0.1554	0.4763	0.3747	0.081*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0610 (14)	0.104 (2)	0.0610 (14)	0.0069 (14)	0.0127 (11)	0.0105 (14)
F1A	0.099 (2)	0.128 (3)	0.101 (3)	0.0203 (16)	−0.0095 (18)	0.0460 (19)
F2A	0.105 (2)	0.156 (4)	0.085 (2)	0.026 (2)	−0.027 (2)	−0.034 (2)
F3A	0.0503 (12)	0.200 (5)	0.0912 (19)	0.0029 (18)	0.0178 (11)	0.032 (2)
F2B	0.071 (8)	0.173 (13)	0.131 (12)	−0.053 (8)	−0.019 (7)	0.066 (9)
F3B	0.075 (7)	0.144 (11)	0.154 (15)	0.039 (7)	−0.020 (8)	−0.008 (9)
F1B	0.061 (5)	0.216 (15)	0.075 (6)	0.026 (7)	0.010 (4)	0.049 (8)
C2	0.0521 (11)	0.0711 (14)	0.0523 (11)	0.0048 (10)	0.0152 (9)	0.0074 (10)
C3	0.0615 (13)	0.0589 (13)	0.0664 (13)	0.0101 (10)	0.0177 (11)	0.0179 (10)
C4	0.0622 (12)	0.0453 (11)	0.0645 (12)	−0.0022 (9)	0.0149 (10)	0.0077 (9)
C5	0.0508 (11)	0.0461 (11)	0.0500 (10)	0.0000 (8)	0.0161 (8)	0.0033 (8)
C8	0.0513 (11)	0.0430 (10)	0.0567 (11)	0.0002 (8)	0.0136 (9)	−0.0008 (8)
N1	0.0646 (12)	0.0725 (13)	0.0765 (14)	−0.0214 (10)	0.0071 (10)	0.0161 (11)
N2	0.0519 (9)	0.0474 (9)	0.0516 (9)	0.0000 (7)	0.0062 (7)	0.0021 (7)
O1	0.0586 (9)	0.0609 (10)	0.0585 (9)	−0.0033 (7)	−0.0009 (7)	0.0033 (7)
C6	0.0634 (13)	0.0451 (11)	0.0709 (14)	0.0038 (9)	0.0035 (11)	0.0016 (9)
C7	0.0663 (14)	0.0583 (13)	0.0718 (14)	−0.0050 (10)	0.0042 (11)	−0.0059 (10)

Geometric parameters (Å, º) top

C1—F2A	1.316 (3)	C4—H4	0.9300
C1—F3A	1.318 (3)	C5—C6	1.381 (3)
C1—F1B	1.323 (3)	C5—C8	1.483 (3)
C1—F1A	1.324 (3)	C8—N2	1.289 (2)
C1—F3B	1.328 (3)	C8—N1	1.354 (3)
C1—F2B	1.330 (3)	N1—H1N	0.84 (3)
C1—C2	1.498 (3)	N1—H2N	0.86 (3)
C2—C3	1.374 (3)	N2—O1	1.432 (2)
C2—C7	1.383 (3)	O1—H1O	0.86 (3)
C3—C4	1.385 (3)	C6—C7	1.382 (3)
C3—H3	0.9300	C6—H6	0.9300
C4—C5	1.389 (3)	C7—H7	0.9300

F2A—C1—F3A	108.9 (3)	C2—C3—C4	119.77 (18)
F2A—C1—F1B	28.5 (8)	C2—C3—H3	120.1
F3A—C1—F1B	121.1 (7)	C4—C3—H3	120.1
F2A—C1—F1A	104.7 (3)	C3—C4—C5	120.46 (18)
F3A—C1—F1A	105.3 (3)	C3—C4—H4	119.8
F1B—C1—F1A	76.5 (9)	C5—C4—H4	119.8
F2A—C1—F3B	131.8 (9)	C6—C5—C4	119.17 (19)
F3A—C1—F3B	72.1 (12)	C6—C5—C8	120.16 (17)
F1B—C1—F3B	107.9 (10)	C4—C5—C8	120.59 (17)
F1A—C1—F3B	37.4 (13)	N2—C8—N1	124.23 (19)
F2A—C1—F2B	71.5 (14)	N2—C8—C5	115.93 (16)
F3A—C1—F2B	41.1 (14)	N1—C8—C5	119.69 (18)
F1B—C1—F2B	93.3 (11)	C8—N1—H1N	120 (2)
F1A—C1—F2B	131.5 (9)	C8—N1—H2N	115.4 (18)
F3B—C1—F2B	109.3 (11)	H1N—N1—H2N	121 (3)
F2A—C1—C2	111.3 (3)	C8—N2—O1	110.41 (15)
F3A—C1—C2	112.3 (2)	N2—O1—H1O	100.9 (19)
F1B—C1—C2	120.3 (6)	C5—C6—C7	120.37 (19)
F1A—C1—C2	113.9 (2)	C5—C6—H6	119.8
F3B—C1—C2	112.2 (7)	C7—C6—H6	119.8
F2B—C1—C2	112.1 (6)	C6—C7—C2	120.0 (2)
C3—C2—C7	120.2 (2)	C6—C7—H7	120.0
C3—C2—C1	120.58 (19)	C2—C7—H7	120.0
C7—C2—C1	119.1 (2)

F2A—C1—C2—C3	137.2 (4)	C2—C3—C4—C5	0.0 (3)
F3A—C1—C2—C3	−100.5 (5)	C3—C4—C5—C6	1.6 (3)
F1B—C1—C2—C3	107.0 (12)	C3—C4—C5—C8	−175.20 (18)
F1A—C1—C2—C3	19.2 (4)	C6—C5—C8—N2	−41.5 (3)
F3B—C1—C2—C3	−21.5 (17)	C4—C5—C8—N2	135.3 (2)
F2B—C1—C2—C3	−145.0 (19)	C6—C5—C8—N1	142.6 (2)
F2A—C1—C2—C7	−46.0 (5)	C4—C5—C8—N1	−40.6 (3)
F3A—C1—C2—C7	76.4 (5)	N1—C8—N2—O1	−2.0 (3)
F1B—C1—C2—C7	−76.1 (12)	C5—C8—N2—O1	−177.71 (15)
F1A—C1—C2—C7	−164.0 (4)	C4—C5—C6—C7	−1.7 (3)
F3B—C1—C2—C7	155.3 (17)	C8—C5—C6—C7	175.06 (19)
F2B—C1—C2—C7	31.9 (19)	C5—C6—C7—C2	0.3 (4)
C7—C2—C3—C4	−1.5 (3)	C3—C2—C7—C6	1.3 (4)
C1—C2—C3—C4	175.34 (19)	C1—C2—C7—C6	−175.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.84 (3)	2.36 (3)	3.165 (3)	161 (3)
O1—H1O···N2ⁱⁱ	0.86 (3)	1.98 (3)	2.766 (2)	152 (3)

Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+1, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	C₈H₇F₃N₂O
M_r	204.16
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	9.8706 (8), 11.2540 (12), 8.4033 (7)
β (°)	104.61 (2)
V (Å³)	903.29 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.32 × 0.24 × 0.20

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.946, 0.972
No. of measured, independent and observed [I > 2σ(I)] reflections	8605, 2058, 1324
R_int	0.077
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.183, 1.07
No. of reflections	2058
No. of parameters	164
No. of restraints	42
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.29

Computer programs: PROCESS-AUTO (Rigaku, 2006), CrystalStructure (Rigaku, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.84 (3)	2.36 (3)	3.165 (3)	161 (3)
O1—H1O···N2ⁱⁱ	0.86 (3)	1.98 (3)	2.766 (2)	152 (3)

Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+1, −y+1, −z+2.

Acknowledgements

The authors gratefully acknowledge financial support from the Education Department of Liaoning Province (2009 A 265) and Liaoning University.

References

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