N-(p-Tolyl­sulfon­yl)-l-asparagine

Arshad, M.N.; Mubashar-ur-Rehman, H.; Khan, I.U.; Shafiq, M.; Lo, K.M.

doi:10.1107/S1600536810004034

organic compounds

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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Page o541

doi:10.1107/S1600536810004034

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N-(p-Tolylsulfonyl)-L-asparagine

Muhammad Nadeem Arshad,^a Hafiz Mubashar-ur-Rehman,^a Islam Ullah Khan,^a ^* Muhammad Shafiq ^a and Kong Mun Lo ^b ^*

^aMaterials Chemistry Laboratory, Department of Chemistry, GC University, Lahore 54000 Pakistan, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: iukhan.gcu@gmail.com, kmlo@um.edu.my

(Received 28 October 2009; accepted 1 February 2010; online 6 February 2010)

In the title compound, C₁₁H₁₄N₂O₅S, the amide O atom acts as a hydrogen-bond acceptor from a carboxylate O atom and a secondary amino N atom. In addition, one of the sulfonyl O atoms and the carbonyl O atom of the carboxyl group also form hydrogen bonds with the primary amido N atom. These intermolecular hydrogen-bonding interactions give rise to a layer structure, with the layers parallel to the ac plane.

Related literature

For the antibacterial and anticancer activity of L-asparagines, Wagastuma et al. (1983 ); Murphy & Stubbins (1980 ). For a related compound, see Arshad et al. (2009 ).

Experimental

Crystal data

C₁₁H₁₄N₂O₅S
M_r = 286.30
Orthorhombic, P 2₁ 2₁ 2
a = 8.7566 (6) Å
b = 22.900 (2) Å
c = 6.9692 (7) Å
V = 1397.5 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 296 K
0.37 × 0.11 × 0.07 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.914, T_max = 0.983
8388 measured reflections
3206 independent reflections
2451 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.099
S = 1.02
3206 reflections
174 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.27 e Å⁻³
Absolute structure: Flack (1983 ), 1338 Friedel pairs
Flack parameter: −0.03 (8)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯O5ⁱ	0.82	1.78	2.592 (2)	168
N1—H1⋯O5ⁱⁱ	0.86	2.06	2.852 (2)	154
N2—H2A⋯O3ⁱⁱⁱ	0.86	2.12	2.924 (2)	155
N2—H2B⋯O2ⁱⁱ	0.86	2.06	2.901 (2)	166
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ .

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810004034/bv2133sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810004034/bv2133Isup2.hkl

checkCIF report

Comment top

L-asparagine, amino acid derivatives of amino penicillin have been synthesized and reported as active antibacterial agents (Wagastuma et al., 1983). In another study, different derivatives of asparagine have been synthesized and evaluated for their anticancer activities (Murphy & Stubbins et al., 1980). Our group also involved in the synthesis of sulfonamide derivatives of different amino acids (Arshad et al., 2009). In this sulfonamide derivative of L-asparagine (Fig. 1), the tetrahedral geometries at S1, C8 and C10 resulted in a twisted molecule in order to reduce steric hindrance. The molecules are linked together by hydrogen bonding between the amido oxygen O5 with the hydrogen atoms of the carboxylate oxygen O4 and the secondary amino nitrogen N1. In addition, one of the sulfonyl oxygen O2 and the carbonyl oxygen O3 also form hydrogen bonds with the primary amido nitrogen N2. These hydrogen bonding interactions produce a layer structure, with the layers propagated parallel to the ac plane (Fig. 2).

Related literature top

For the antibacterial and anticancer activity of L-asparagines, Wagastuma et al. (1983); Murphy & Stubbins (1980). For a related compound, see Arshad et al. (2009).

Experimental top

Asparagine (.25 g, 1.89 mmol) was dissolved in distilled water (10 ml) in a round bottom flask (25 ml). The pH of the solution was maintained at 8–9 using 1 M Na₂CO₃ solution. 4-Toluenesulfonyl chloride (0.361 g, 1.89 mmol) was suspended in the above solution and stirred at room temperature until all the 4-toluenesulfonyl chloride was consumed. The reaction was completed when the suspension turned to a clear solution. Upon completion of the reaction, the pH was adjusted 1–2, using 1 M HCl solution. The precipitate obtained was filtered, washed with distilled water, dried and recrystalized from methanol to yield white crystals.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of N-(4-toluenesulfonyl)-L-asparagine showing 70% probability displacement ellipsoids and the atom numbering. Hydrogen atoms are drawn as spheres of arbitrary radius.
	Fig. 2. Crystal packing of the unit cell showing the hydrogen bonding interactions in the molecule.

N-(p-Tolylsulfonyl)-L-asparagine top

Crystal data top

C₁₁H₁₄N₂O₅S	F(000) = 600
M_r = 286.30	D_x = 1.361 Mg m⁻³
Orthorhombic, P2₁2₁2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2 2ab	Cell parameters from 2600 reflections
a = 8.7566 (6) Å	θ = 2.5–24°
b = 22.900 (2) Å	µ = 0.25 mm⁻¹
c = 6.9692 (7) Å	T = 296 K
V = 1397.5 (2) Å³	Block, white
Z = 4	0.37 × 0.11 × 0.07 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	3206 independent reflections
Radiation source: fine-focus sealed tube	2451 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ω scans	θ_max = 27.5°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
T_min = 0.914, T_max = 0.983	k = −26→29
8388 measured reflections	l = −9→9

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)] = 0.042	H-atom parameters constrained
wR(F²) = 0.099	w = 1/[σ²(F_o²) + (0.0521P)² + ] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
3206 reflections	Δρ_max = 0.18 e Å⁻³
174 parameters	Δρ_min = −0.27 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1328 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.03 (8)

Crystal data top

C₁₁H₁₄N₂O₅S	V = 1397.5 (2) Å³
M_r = 286.30	Z = 4
Orthorhombic, P2₁2₁2	Mo Kα radiation
a = 8.7566 (6) Å	µ = 0.25 mm⁻¹
b = 22.900 (2) Å	T = 296 K
c = 6.9692 (7) Å	0.37 × 0.11 × 0.07 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	3206 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2451 reflections with I > 2σ(I)
T_min = 0.914, T_max = 0.983	R_int = 0.029
8388 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	H-atom parameters constrained
wR(F²) = 0.099	Δρ_max = 0.18 e Å⁻³
S = 1.02	Δρ_min = −0.27 e Å⁻³
3206 reflections	Absolute structure: Flack (1983), 1328 Friedel pairs
174 parameters	Absolute structure parameter: −0.03 (8)
0 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
S1	0.95716 (6)	0.62903 (3)	0.10823 (10)	0.04939 (18)
O1	0.9573 (2)	0.61117 (9)	−0.0862 (3)	0.0778 (6)
O2	1.09832 (17)	0.64258 (8)	0.2020 (3)	0.0636 (5)
O3	0.62170 (16)	0.68014 (8)	0.3996 (2)	0.0554 (4)
O4	0.76473 (19)	0.73119 (9)	0.6017 (2)	0.0629 (5)
H4	0.7019	0.7200	0.6808	0.094*
O5	1.08999 (14)	0.79700 (8)	0.1128 (2)	0.0493 (4)
N1	0.85411 (17)	0.68699 (8)	0.1208 (3)	0.0392 (4)
H1	0.7966	0.6960	0.0253	0.047*
N2	0.90525 (19)	0.82712 (9)	−0.0810 (3)	0.0522 (5)
H2A	0.9703	0.8367	−0.1680	0.063*
H2B	0.8093	0.8323	−0.1008	0.063*
C1	0.8685 (3)	0.57415 (11)	0.2442 (4)	0.0490 (6)
C2	0.8893 (3)	0.57211 (12)	0.4400 (4)	0.0619 (7)
H2	0.9511	0.5994	0.5013	0.074*
C3	0.8171 (4)	0.52899 (16)	0.5433 (5)	0.0807 (10)
H3	0.8303	0.5277	0.6757	0.097*
C4	0.7259 (4)	0.48771 (14)	0.4570 (6)	0.0796 (10)
C5	0.7061 (4)	0.49096 (16)	0.2613 (7)	0.0896 (11)
H5	0.6442	0.4637	0.2002	0.107*
C6	0.7762 (3)	0.53379 (13)	0.1549 (5)	0.0712 (9)
H6	0.7613	0.5355	0.0229	0.085*
C7	0.6559 (5)	0.43887 (16)	0.5732 (7)	0.1317 (18)
H7A	0.5955	0.4145	0.4908	0.198*
H7B	0.5921	0.4551	0.6719	0.198*
H7C	0.7355	0.4160	0.6309	0.198*
C8	0.8551 (2)	0.72435 (9)	0.2877 (3)	0.0357 (5)
H8	0.9551	0.7208	0.3497	0.043*
C9	0.7331 (2)	0.70850 (10)	0.4343 (3)	0.0375 (5)
C10	0.8332 (2)	0.78799 (10)	0.2275 (3)	0.0416 (5)
H10A	0.7319	0.7931	0.1735	0.050*
H10B	0.8420	0.8131	0.3389	0.050*
C11	0.9521 (2)	0.80490 (9)	0.0805 (3)	0.0362 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0400 (3)	0.0489 (3)	0.0592 (4)	0.0011 (3)	0.0150 (3)	−0.0021 (3)
O1	0.0992 (14)	0.0717 (13)	0.0624 (12)	0.0039 (11)	0.0320 (12)	−0.0157 (11)
O2	0.0324 (8)	0.0578 (11)	0.1005 (15)	0.0023 (7)	0.0067 (8)	0.0111 (11)
O3	0.0385 (8)	0.0806 (12)	0.0471 (9)	−0.0149 (8)	0.0005 (7)	0.0108 (10)
O4	0.0571 (10)	0.0946 (15)	0.0369 (9)	−0.0274 (9)	0.0162 (8)	−0.0073 (10)
O5	0.0301 (7)	0.0789 (12)	0.0388 (8)	−0.0034 (7)	−0.0020 (7)	0.0164 (10)
N1	0.0368 (8)	0.0467 (11)	0.0342 (9)	0.0025 (8)	0.0010 (8)	0.0005 (10)
N2	0.0325 (8)	0.0808 (15)	0.0432 (11)	0.0045 (9)	0.0011 (8)	0.0199 (11)
C1	0.0413 (11)	0.0409 (14)	0.0646 (16)	0.0019 (10)	0.0084 (11)	−0.0013 (13)
C2	0.0677 (16)	0.0459 (16)	0.072 (2)	−0.0084 (13)	−0.0039 (13)	0.0062 (14)
C3	0.096 (2)	0.067 (2)	0.079 (2)	−0.0022 (19)	0.0075 (17)	0.0203 (19)
C4	0.074 (2)	0.046 (2)	0.119 (3)	−0.0002 (16)	0.0206 (19)	0.017 (2)
C5	0.076 (2)	0.059 (2)	0.134 (3)	−0.0230 (16)	0.006 (2)	−0.010 (2)
C6	0.0749 (18)	0.0609 (19)	0.078 (2)	−0.0156 (16)	0.0060 (15)	−0.0088 (17)
C7	0.127 (3)	0.074 (3)	0.195 (5)	−0.013 (2)	0.033 (4)	0.059 (3)
C8	0.0277 (9)	0.0456 (13)	0.0338 (11)	−0.0016 (9)	0.0021 (8)	0.0037 (10)
C9	0.0315 (9)	0.0479 (14)	0.0332 (11)	0.0011 (9)	0.0000 (8)	0.0078 (10)
C10	0.0390 (11)	0.0457 (14)	0.0400 (12)	0.0033 (10)	0.0086 (9)	0.0032 (11)
C11	0.0339 (9)	0.0393 (11)	0.0353 (11)	−0.0010 (9)	0.0012 (9)	0.0021 (10)

Geometric parameters (Å, º) top

S1—O1	1.416 (2)	C3—C4	1.376 (5)
S1—O2	1.4322 (18)	C3—H3	0.9300
S1—N1	1.6074 (18)	C4—C5	1.377 (5)
S1—C1	1.755 (3)	C4—C7	1.511 (4)
O3—C9	1.197 (2)	C5—C6	1.374 (5)
O4—C9	1.307 (2)	C5—H5	0.9300
O4—H4	0.8200	C6—H6	0.9300
O5—C11	1.242 (2)	C7—H7A	0.9600
N1—C8	1.444 (3)	C7—H7B	0.9600
N1—H1	0.8600	C7—H7C	0.9600
N2—C11	1.302 (3)	C8—C9	1.522 (3)
N2—H2A	0.8600	C8—C10	1.529 (3)
N2—H2B	0.8600	C8—H8	0.9800
C1—C6	1.376 (4)	C10—C11	1.511 (3)
C1—C2	1.378 (4)	C10—H10A	0.9700
C2—C3	1.376 (4)	C10—H10B	0.9700
C2—H2	0.9300

O1—S1—O2	119.92 (11)	C5—C6—C1	119.8 (3)
O1—S1—N1	106.93 (11)	C5—C6—H6	120.1
O2—S1—N1	106.30 (10)	C1—C6—H6	120.1
O1—S1—C1	108.07 (13)	C4—C7—H7A	109.5
O2—S1—C1	106.91 (12)	C4—C7—H7B	109.5
N1—S1—C1	108.27 (10)	H7A—C7—H7B	109.5
C9—O4—H4	109.5	C4—C7—H7C	109.5
C8—N1—S1	122.00 (14)	H7A—C7—H7C	109.5
C8—N1—H1	119.0	H7B—C7—H7C	109.5
S1—N1—H1	119.0	N1—C8—C9	113.27 (17)
C11—N2—H2A	120.0	N1—C8—C10	110.06 (17)
C11—N2—H2B	120.0	C9—C8—C10	108.87 (17)
H2A—N2—H2B	120.0	N1—C8—H8	108.2
C6—C1—C2	120.2 (3)	C9—C8—H8	108.2
C6—C1—S1	119.8 (2)	C10—C8—H8	108.2
C2—C1—S1	120.0 (2)	O3—C9—O4	124.65 (19)
C3—C2—C1	118.8 (3)	O3—C9—C8	124.49 (19)
C3—C2—H2	120.6	O4—C9—C8	110.84 (17)
C1—C2—H2	120.6	C11—C10—C8	110.12 (17)
C4—C3—C2	122.1 (3)	C11—C10—H10A	109.6
C4—C3—H3	119.0	C8—C10—H10A	109.6
C2—C3—H3	119.0	C11—C10—H10B	109.6
C3—C4—C5	118.0 (3)	C8—C10—H10B	109.6
C3—C4—C7	120.7 (4)	H10A—C10—H10B	108.2
C5—C4—C7	121.3 (4)	O5—C11—N2	121.34 (19)
C6—C5—C4	121.1 (3)	O5—C11—C10	120.65 (19)
C6—C5—H5	119.4	N2—C11—C10	118.00 (17)
C4—C5—H5	119.4

O1—S1—N1—C8	−166.24 (16)	C7—C4—C5—C6	−176.8 (3)
O2—S1—N1—C8	−37.03 (17)	C4—C5—C6—C1	0.3 (5)
C1—S1—N1—C8	77.52 (17)	C2—C1—C6—C5	−0.7 (4)
O1—S1—C1—C6	−19.0 (3)	S1—C1—C6—C5	−179.7 (3)
O2—S1—C1—C6	−149.3 (2)	S1—N1—C8—C9	−91.79 (18)
N1—S1—C1—C6	96.5 (2)	S1—N1—C8—C10	146.07 (15)
O1—S1—C1—C2	162.1 (2)	N1—C8—C9—O3	−19.7 (3)
O2—S1—C1—C2	31.7 (3)	C10—C8—C9—O3	103.1 (2)
N1—S1—C1—C2	−82.4 (2)	N1—C8—C9—O4	161.76 (19)
C6—C1—C2—C3	0.3 (4)	C10—C8—C9—O4	−75.4 (2)
S1—C1—C2—C3	179.3 (2)	N1—C8—C10—C11	−54.8 (2)
C1—C2—C3—C4	0.5 (5)	C9—C8—C10—C11	−179.54 (17)
C2—C3—C4—C5	−1.0 (5)	C8—C10—C11—O5	−53.0 (3)
C2—C3—C4—C7	176.4 (3)	C8—C10—C11—N2	126.1 (2)
C3—C4—C5—C6	0.6 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O5ⁱ	0.82	1.78	2.592 (2)	168
N1—H1···O5ⁱⁱ	0.86	2.06	2.852 (2)	154
N2—H2A···O3ⁱⁱⁱ	0.86	2.12	2.924 (2)	155
N2—H2B···O2ⁱⁱ	0.86	2.06	2.901 (2)	166

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₄N₂O₅S
M_r	286.30
Crystal system, space group	Orthorhombic, P2₁2₁2
Temperature (K)	296
a, b, c (Å)	8.7566 (6), 22.900 (2), 6.9692 (7)
V (Å³)	1397.5 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.37 × 0.11 × 0.07

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.914, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	8388, 3206, 2451
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.099, 1.02
No. of reflections	3206
No. of parameters	174
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.27
Absolute structure	Flack (1983), 1328 Friedel pairs
Absolute structure parameter	−0.03 (8)

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O5ⁱ	0.82	1.78	2.592 (2)	168.2
N1—H1···O5ⁱⁱ	0.86	2.06	2.852 (2)	153.7
N2—H2A···O3ⁱⁱⁱ	0.86	2.12	2.924 (2)	154.6
N2—H2B···O2ⁱⁱ	0.86	2.06	2.901 (2)	165.9

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

Acknowledgements

We thank the Higher Education Commission of Pakistan, the GC University, Lahore-Pakistan, and the University of Malaya, Malaysia for supporting this study.

References

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