2-[(5-Chloro-2-oxidobenzyl­idene)aza­nium­yl]-2-methyl­propane-1,3-diol

Wang, D.-Y.; Liu, M.; Ma, J.-J.

doi:10.1107/S1600536811055784

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page o295

doi:10.1107/S1600536811055784

Open

access

2-[(5-Chloro-2-oxidobenzylidene)azaniumyl]-2-methylpropane-1,3-diol

Dong-Yue Wang,^a Min Liu ^a and Jing-Jun Ma ^a ^*

^aHebei Key Laboratory of Bioinorganic Chemistry, College of Sciences, Agricultural University of Hebei, Baoding 071001, People's Republic of China
^*Correspondence e-mail: majingjun71@yahoo.cn

(Received 23 December 2011; accepted 26 December 2011; online 7 January 2012)

The title compound, C₁₁H₁₄ClNO₃, was prepared by the condensation of equimolar quantities of 5-chlorosalicylaldehyde and 2-amino-2-methylpropane-1,3-diol in methanol. In the crystal, it exists in the zwitterionic form, with nominal proton transfer from the phenol group to the imine N atom. This results in the formation of an intramolecular N—H⋯O hydrogen bond, which generates an S(6) ring. Intermolecular O—H⋯O hydrogen bonds arise from the hydroxy groups, forming (001) sheets.

Related literature

For a related structure we have reported recently and for background to Schiff bases, see: Wang et al. (2011 ). For standard bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₁H₁₄ClNO₃
M_r = 243.68
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.0019 (16) Å
b = 8.838 (3) Å
c = 21.555 (3) Å
V = 1143.4 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 298 K
0.13 × 0.12 × 0.10 mm

Data collection

Bruker SMART 1K CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.959, T_max = 0.968
5744 measured reflections
2105 independent reflections
1745 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.076
S = 1.05
2105 reflections
155 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.15 e Å⁻³
Absolute structure: Flack (1983 ), 842 Friedel pairs
Flack parameter: −0.06 (8)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.90 (1)	1.84 (2)	2.606 (3)	142 (2)
O4—H4⋯O3ⁱ	0.85 (1)	1.87 (1)	2.680 (2)	160 (3)
O3—H3A⋯O1ⁱⁱ	0.85 (1)	1.80 (1)	2.648 (2)	176 (3)
Symmetry codes: (i) x+1, y, z; (ii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811055784/hb6578sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811055784/hb6578Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811055784/hb6578Isup3.cml

checkCIF report

Comment top

Recently, we have reported the structures of a few Schiff base compounds (e.g. Wang et al., 2011). As a continuation of the work, we present here the crystal structure of the title compound, that was obtained as the product of the reaction of 5-chlorosalicylaldehyde with 2-amino-2-methylpropane-1,3-diol in methanol.

In the title compound, Fig. 1, there in an intramolecular N1—H1···O1 hydrogen bond (Table 1). The bond distances and angles are within normal ranges (Allen et al., 1987).

In the crystal of the compound, the Schiff base molecules are linked through intermolecular O—H···O hydrogen bond, to form (001) sheets. (Table 1 and Fig. 2).

Related literature top

For a related structure we have reported recently and for background to Schiff bases, see: Wang et al. (2011). For standard bond lengths, see: Allen et al. (1987).

Experimental top

To a methanol solution (10 ml) of 5-chlorosalicylaldehyde (0.1 mmol, 15.6 mg) and 2-amino-2-methylpropane-1,3-diol (0.1 mmol, 10.5 mg), a few drops of acetic acid were added. The mixture was refluxed for 1 h and then cooled to room temperature. The yellow crystalline solid was collected by filtration, washed with cold methanol and dried in air. Yellow blocks were obtained by slow evaporation of a methanol solution of the product in air.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. Intramolecular N—H···O hydrogen bond is drawn as a dashed line.
	Fig. 2. Fragments of (001) sheets moleucles of the title compound, viewed along the a axis.

2-[(5-Chloro-2-oxidobenzylidene)azaniumyl]-2-methylpropane-1,3-diol top

Crystal data top

C₁₁H₁₄ClNO₃	D_x = 1.416 Mg m⁻³
M_r = 243.68	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 1733 reflections
a = 6.0019 (16) Å	θ = 2.5–24.2°
b = 8.838 (3) Å	µ = 0.33 mm⁻¹
c = 21.555 (3) Å	T = 298 K
V = 1143.4 (5) Å³	Block, yellow
Z = 4	0.13 × 0.12 × 0.10 mm
F(000) = 512

Data collection top

Bruker SMART 1K CCD diffractometer	2105 independent reflections
Radiation source: fine-focus sealed tube	1745 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ω scan	θ_max = 25.5°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −5→7
T_min = 0.959, T_max = 0.968	k = −10→10
5744 measured reflections	l = −26→21

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)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.076	w = 1/[σ²(F_o²) + (0.0287P)² + 0.113P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
2105 reflections	Δρ_max = 0.17 e Å⁻³
155 parameters	Δρ_min = −0.15 e Å⁻³
3 restraints	Absolute structure: Flack (1983), 842 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.06 (8)

Crystal data top

C₁₁H₁₄ClNO₃	V = 1143.4 (5) Å³
M_r = 243.68	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.0019 (16) Å	µ = 0.33 mm⁻¹
b = 8.838 (3) Å	T = 298 K
c = 21.555 (3) Å	0.13 × 0.12 × 0.10 mm

Data collection top

Bruker SMART 1K CCD diffractometer	2105 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1745 reflections with I > 2σ(I)
T_min = 0.959, T_max = 0.968	R_int = 0.033
5744 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.076	Δρ_max = 0.17 e Å⁻³
S = 1.05	Δρ_min = −0.15 e Å⁻³
2105 reflections	Absolute structure: Flack (1983), 842 Friedel pairs
155 parameters	Absolute structure parameter: −0.06 (8)
3 restraints

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
Cl1	0.67835 (15)	−0.07637 (8)	−0.02077 (3)	0.0613 (2)
N1	0.8677 (3)	0.4851 (2)	0.15414 (9)	0.0356 (5)
O1	1.2095 (3)	0.30421 (19)	0.14623 (7)	0.0422 (4)
O3	0.5214 (3)	0.6832 (2)	0.27003 (8)	0.0462 (5)
O4	1.0926 (3)	0.6167 (2)	0.24842 (11)	0.0609 (6)
C1	1.0897 (4)	0.2197 (3)	0.11037 (11)	0.0350 (6)
C2	1.1701 (5)	0.0789 (3)	0.08645 (11)	0.0442 (6)
H2	1.3107	0.0449	0.0981	0.053*
C3	1.0452 (5)	−0.0064 (3)	0.04693 (12)	0.0470 (7)
H3	1.1032	−0.0965	0.0316	0.056*
C4	0.8320 (5)	0.0388 (3)	0.02898 (11)	0.0412 (6)
C5	0.7447 (4)	0.1709 (3)	0.05062 (10)	0.0366 (6)
H5	0.6031	0.2012	0.0383	0.044*
C6	0.8698 (4)	0.2620 (3)	0.09192 (10)	0.0315 (5)
C7	0.7671 (4)	0.3945 (3)	0.11616 (10)	0.0352 (6)
H7	0.6219	0.4170	0.1042	0.042*
C8	0.7731 (4)	0.6211 (3)	0.18423 (10)	0.0350 (6)
C9	0.6345 (6)	0.7147 (3)	0.13884 (12)	0.0603 (8)
H9A	0.7202	0.7341	0.1021	0.090*
H9B	0.5940	0.8089	0.1579	0.090*
H9C	0.5020	0.6598	0.1280	0.090*
C10	0.6293 (4)	0.5634 (3)	0.23840 (11)	0.0384 (6)
H10A	0.5181	0.4938	0.2226	0.046*
H10B	0.7229	0.5085	0.2674	0.046*
C11	0.9699 (4)	0.7115 (3)	0.20833 (12)	0.0462 (7)
H11A	1.0627	0.7446	0.1741	0.055*
H11B	0.9180	0.8002	0.2306	0.055*
H3A	0.603 (4)	0.720 (3)	0.2983 (10)	0.069*
H4	1.215 (3)	0.651 (3)	0.2621 (12)	0.069*
H1	1.005 (2)	0.452 (3)	0.1646 (11)	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0825 (6)	0.0435 (4)	0.0579 (4)	−0.0035 (4)	−0.0139 (4)	−0.0124 (3)
N1	0.0328 (13)	0.0364 (11)	0.0375 (11)	0.0047 (10)	−0.0019 (11)	−0.0049 (9)
O1	0.0355 (11)	0.0420 (10)	0.0492 (10)	0.0030 (8)	−0.0089 (9)	0.0012 (8)
O3	0.0260 (10)	0.0535 (11)	0.0593 (13)	0.0027 (9)	−0.0050 (9)	−0.0220 (9)
O4	0.0310 (11)	0.0618 (13)	0.0897 (15)	−0.0013 (10)	−0.0201 (11)	−0.0092 (12)
C1	0.0362 (16)	0.0340 (13)	0.0349 (13)	−0.0015 (11)	0.0023 (11)	0.0063 (11)
C2	0.0376 (15)	0.0406 (14)	0.0543 (15)	0.0119 (14)	0.0050 (14)	0.0048 (13)
C3	0.0590 (19)	0.0330 (13)	0.0491 (16)	0.0070 (14)	0.0076 (15)	−0.0023 (13)
C4	0.0514 (17)	0.0346 (13)	0.0376 (13)	−0.0026 (13)	−0.0027 (13)	−0.0006 (11)
C5	0.0362 (16)	0.0358 (13)	0.0377 (13)	−0.0003 (11)	0.0001 (12)	0.0000 (11)
C6	0.0285 (14)	0.0331 (12)	0.0329 (12)	0.0010 (11)	0.0026 (11)	0.0009 (11)
C7	0.0318 (14)	0.0378 (13)	0.0360 (13)	0.0002 (11)	0.0009 (11)	−0.0011 (11)
C8	0.0351 (15)	0.0286 (12)	0.0412 (13)	0.0039 (11)	−0.0039 (12)	−0.0041 (10)
C9	0.076 (2)	0.0487 (16)	0.0564 (17)	0.0194 (16)	−0.0117 (16)	0.0018 (14)
C10	0.0296 (14)	0.0332 (12)	0.0524 (15)	−0.0012 (12)	0.0023 (12)	−0.0090 (12)
C11	0.0412 (17)	0.0391 (14)	0.0585 (17)	−0.0131 (13)	0.0074 (15)	−0.0071 (13)

Geometric parameters (Å, º) top

Cl1—C4	1.743 (2)	C4—C5	1.362 (3)
N1—C7	1.294 (3)	C5—C6	1.416 (3)
N1—C8	1.479 (3)	C5—H5	0.9300
N1—H1	0.903 (10)	C6—C7	1.423 (3)
O1—C1	1.293 (3)	C7—H7	0.9300
O3—C10	1.416 (3)	C8—C11	1.517 (3)
O3—H3A	0.847 (10)	C8—C9	1.528 (3)
O4—C11	1.411 (3)	C8—C10	1.539 (3)
O4—H4	0.847 (10)	C9—H9A	0.9600
C1—C6	1.428 (3)	C9—H9B	0.9600
C1—C2	1.431 (3)	C9—H9C	0.9600
C2—C3	1.362 (3)	C10—H10A	0.9700
C2—H2	0.9300	C10—H10B	0.9700
C3—C4	1.395 (4)	C11—H11A	0.9700
C3—H3	0.9300	C11—H11B	0.9700

C7—N1—C8	126.9 (2)	C6—C7—H7	118.7
C7—N1—H1	112.7 (17)	N1—C8—C11	106.2 (2)
C8—N1—H1	120.1 (17)	N1—C8—C9	111.61 (19)
C10—O3—H3A	112 (2)	C11—C8—C9	111.0 (2)
C11—O4—H4	117 (2)	N1—C8—C10	106.20 (18)
O1—C1—C6	121.9 (2)	C11—C8—C10	110.55 (19)
O1—C1—C2	122.0 (2)	C9—C8—C10	111.1 (2)
C6—C1—C2	116.1 (2)	C8—C9—H9A	109.5
C3—C2—C1	121.4 (2)	C8—C9—H9B	109.5
C3—C2—H2	119.3	H9A—C9—H9B	109.5
C1—C2—H2	119.3	C8—C9—H9C	109.5
C2—C3—C4	121.3 (2)	H9A—C9—H9C	109.5
C2—C3—H3	119.3	H9B—C9—H9C	109.5
C4—C3—H3	119.3	O3—C10—C8	111.98 (19)
C5—C4—C3	120.2 (2)	O3—C10—H10A	109.2
C5—C4—Cl1	120.5 (2)	C8—C10—H10A	109.2
C3—C4—Cl1	119.27 (19)	O3—C10—H10B	109.2
C4—C5—C6	119.9 (2)	C8—C10—H10B	109.2
C4—C5—H5	120.0	H10A—C10—H10B	107.9
C6—C5—H5	120.0	O4—C11—C8	107.65 (19)
C5—C6—C7	118.0 (2)	O4—C11—H11A	110.2
C5—C6—C1	121.1 (2)	C8—C11—H11A	110.2
C7—C6—C1	120.9 (2)	O4—C11—H11B	110.2
N1—C7—C6	122.6 (2)	C8—C11—H11B	110.2
N1—C7—H7	118.7	H11A—C11—H11B	108.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.90 (1)	1.84 (2)	2.606 (3)	142 (2)
O4—H4···O3ⁱ	0.85 (1)	1.87 (1)	2.680 (2)	160 (3)
O3—H3A···O1ⁱⁱ	0.85 (1)	1.80 (1)	2.648 (2)	176 (3)

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₄ClNO₃
M_r	243.68
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	298
a, b, c (Å)	6.0019 (16), 8.838 (3), 21.555 (3)
V (Å³)	1143.4 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.33
Crystal size (mm)	0.13 × 0.12 × 0.10

Data collection
Diffractometer	Bruker SMART 1K CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.959, 0.968
No. of measured, independent and observed [I > 2σ(I)] reflections	5744, 2105, 1745
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.605

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.076, 1.05
No. of reflections	2105
No. of parameters	155
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.15
Absolute structure	Flack (1983), 842 Friedel pairs
Absolute structure parameter	−0.06 (8)

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.903 (10)	1.837 (18)	2.606 (3)	142 (2)
O4—H4···O3ⁱ	0.847 (10)	1.870 (14)	2.680 (2)	160 (3)
O3—H3A···O1ⁱⁱ	0.847 (10)	1.802 (11)	2.648 (2)	176 (3)

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

Acknowledgements

This project was sponsored by the Natural Development Foundation of Hebei Province (B2011204051), the Development Foundation of the Department of Education of Hebei Province (2010137) and the Research Development Foundation of the Agricultural University of Hebei.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orphen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, D.-Y., Meng, X.-F. & Ma, J.-J. (2011). Acta Cryst. E67, o3150. Web of Science CSD CrossRef IUCr Journals Google Scholar