N-(Phenyl­sulfon­yl)-l-asparagine

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

doi:10.1107/S1600536809050247

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3229

doi:10.1107/S1600536809050247

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N-(Phenylsulfonyl)-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 22 November 2009; online 28 November 2009)

In the title compound, C₁₀H₁₂N₂O₅S, one of the sulfonyl O atoms is hydrogen bonded to the amido N atom of an adjacent molecule. There is also a weak hydrogen-bonding interaction between the other sulfonyl O atom and the secondary amino N atom. In addition, the amido O atom is also hydrogen bonded to a carboxyl O atom. These hydrogen-bonding interactions give rise to a layer structure parallel to the bc plane.

Related literature

For related compounds, see: Koroniak et al. (2003 ); Arshad et al. (2008 , 2009 ).

Experimental

Crystal data

C₁₀H₁₂N₂O₅S
M_r = 272.28
Monoclinic, P 2₁
a = 10.5479 (6) Å
b = 5.1587 (3) Å
c = 11.0157 (7) Å
β = 92.011 (3)°
V = 599.03 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 296 K
0.25 × 0.21 × 0.13 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.932, T_max = 0.964
6832 measured reflections
2732 independent reflections
2518 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.076
S = 1.06
2732 reflections
176 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.16 e Å⁻³
Absolute structure: Flack (1983 ), 1187 Friedel pairs
Flack parameter: −0.01 (6)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O1ⁱ	0.77 (2)	2.31 (2)	3.076 (2)	168.6 (19)
N2—H2A⋯O2ⁱⁱ	0.95 (3)	2.06 (3)	2.998 (3)	172 (3)
O4—H4A⋯O6ⁱⁱⁱ	0.82	1.82	2.5804 (18)	155
Symmetry codes: (i) x, y+1, z; (ii) $[-x+1, y-{\script{1\over 2}}, -z+1]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z]$ .

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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809050247/om2295sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809050247/om2295Isup2.hkl

checkCIF report

Comment top

Sulfonamides compounds have long been studied due to their biological activity. N-acylsufonamide derivatives of asparagine have synthesized and characterized (Koroniak et al., 2003). The title compound is also a sulfonamide derivative and synthesized in continuation of our studies for the synthesis of acyclic and cyclic sulfonamides (Arshad et al., 2008), (Arshad et al., 2009). In this sulfonamide derivative of L-asparagine (Fig. 1), the molecule is twisted due to the tetrahedral geometries at S1, C7 and C9. One of the sulfonyl oxygen O2 is hydrogen-bonded to the amido nitrogen atom N2 of an adjacent molecule. The amido oxygen O6 also forms hydrogen bond with the carboxylate oxygen O4 of an adjacent molecule. There is a weak hydrogen bonding interaction between the other sulfonyl oxygen O1 and the secondary amino nitrogen N1 (Fig. 2). No significant intramolecular hydrogen bonding interaction is found in the molecule.

Related literature top

For related compounds, see: Koroniak et al. (2003); Arshad et al. (2008, 2009).

Experimental top

Asparagine (0.175 g, 1.32 mmol) was dissolved in distilled water (10 ml) in a round bottom flask (25 ml). The pH of the solution was adjusted at 8–9 using 1M, Na₂CO₃ solution. Benzenesulfonyl chloride (0.169 ml, 0.234 g, 1.32 mmol) was suspended to the above solution and stirred at room temperature until all the benzenesulfonyl chloride was consumed. The completion of the reaction was achieved when the suspension turned to a clear solution. Upon completion of the reaction, the pH was adjusted 1–2, using 1 N HCl solution. The precipitate obtained was filtered, washed with distilled water, dried and recrystalized in 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of N-(benzenesulfonyl)-L-asparagine showing 70% probability displacement ellipsoids and the atom numbering scheme. Hydrogen atoms are drawn as spheres of arbitrary radius.
	Fig. 2. Crystal packing as viewed down the crystallographic b-axis showing the hydrogen bonding interactions. Symmetry code: ii = -x+1,y+1/2,-z.

N-(Phenylsulfonyl)-L-asparagine top

Crystal data top

C₁₀H₁₂N₂O₅S	F(000) = 284
M_r = 272.28	D_x = 1.510 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 3825 reflections
a = 10.5479 (6) Å	θ = 2.6–27.4°
b = 5.1587 (3) Å	µ = 0.29 mm⁻¹
c = 11.0157 (7) Å	T = 296 K
β = 92.011 (3)°	Block, colorless
V = 599.03 (6) Å³	0.25 × 0.21 × 0.13 mm
Z = 2

Data collection top

Bruker APEXII diffractometer	2732 independent reflections
Radiation source: fine-focus sealed tube	2518 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ω scans	θ_max = 27.6°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
T_min = 0.932, T_max = 0.964	k = −6→6
6832 measured reflections	l = −14→14

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)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.076	w = 1/[σ²(F_o²) + (0.0464P)² + 0.0133P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2732 reflections	Δρ_max = 0.33 e Å⁻³
176 parameters	Δρ_min = −0.16 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1187 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (6)

Crystal data top

C₁₀H₁₂N₂O₅S	V = 599.03 (6) Å³
M_r = 272.28	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 10.5479 (6) Å	µ = 0.29 mm⁻¹
b = 5.1587 (3) Å	T = 296 K
c = 11.0157 (7) Å	0.25 × 0.21 × 0.13 mm
β = 92.011 (3)°

Data collection top

Bruker APEXII diffractometer	2732 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2518 reflections with I > 2σ(I)
T_min = 0.932, T_max = 0.964	R_int = 0.023
6832 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.076	Δρ_max = 0.33 e Å⁻³
S = 1.06	Δρ_min = −0.16 e Å⁻³
2732 reflections	Absolute structure: Flack (1983), 1187 Friedel pairs
176 parameters	Absolute structure parameter: −0.01 (6)
1 restraint

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
C1	0.91282 (16)	0.8736 (3)	0.28950 (15)	0.0323 (4)
C2	0.93349 (19)	0.7209 (4)	0.18909 (17)	0.0411 (4)
H2	0.8795	0.5838	0.1688	0.049*
C3	1.03713 (19)	0.7776 (5)	0.11920 (19)	0.0503 (5)
H3	1.0534	0.6766	0.0516	0.060*
C4	1.11535 (19)	0.9813 (5)	0.1493 (2)	0.0499 (5)
H4	1.1837	1.0187	0.1012	0.060*
C5	1.09413 (19)	1.1314 (5)	0.2501 (2)	0.0517 (5)
H5	1.1483	1.2683	0.2700	0.062*
C6	0.99250 (18)	1.0783 (4)	0.32109 (19)	0.0439 (4)
H6	0.9775	1.1783	0.3893	0.053*
C7	0.59899 (15)	0.9058 (3)	0.19546 (14)	0.0279 (3)
H7	0.6111	0.7183	0.1873	0.034*
C8	0.64948 (16)	1.0412 (3)	0.08415 (14)	0.0311 (3)
C9	0.45593 (16)	0.9649 (3)	0.20037 (16)	0.0333 (4)
H9A	0.4444	1.1370	0.2336	0.040*
H9B	0.4187	0.9630	0.1186	0.040*
C10	0.38860 (15)	0.7715 (3)	0.27662 (15)	0.0315 (4)
H1A	0.379 (3)	1.000 (7)	0.406 (3)	0.073 (9)*
H2A	0.312 (3)	0.722 (7)	0.433 (3)	0.090 (10)*
N1	0.66143 (14)	0.9939 (3)	0.30846 (13)	0.0300 (3)
H1B	0.6757 (17)	1.141 (5)	0.3130 (17)	0.027 (5)*
N2	0.3616 (2)	0.8376 (5)	0.38858 (16)	0.0575 (5)
O1	0.73791 (14)	0.5586 (3)	0.36312 (13)	0.0448 (3)
O2	0.79671 (14)	0.9371 (3)	0.49048 (11)	0.0458 (3)
O3	0.70376 (15)	1.2446 (3)	0.08654 (13)	0.0492 (4)
O4	0.61999 (16)	0.9065 (3)	−0.01409 (11)	0.0485 (4)
H4A	0.6403	0.9880	−0.0743	0.073*
O6	0.35901 (14)	0.5579 (3)	0.23573 (12)	0.0430 (3)
S1	0.77553 (4)	0.82468 (8)	0.37280 (3)	0.03153 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0338 (7)	0.0321 (10)	0.0308 (8)	0.0042 (6)	−0.0010 (6)	0.0009 (6)
C2	0.0425 (9)	0.0410 (10)	0.0399 (10)	0.0005 (8)	0.0027 (8)	−0.0079 (8)
C3	0.0454 (10)	0.0652 (15)	0.0407 (10)	0.0089 (10)	0.0084 (8)	−0.0096 (10)
C4	0.0310 (9)	0.0658 (14)	0.0532 (12)	0.0041 (9)	0.0049 (8)	0.0057 (10)
C5	0.0355 (10)	0.0530 (13)	0.0662 (14)	−0.0071 (9)	−0.0025 (9)	−0.0011 (11)
C6	0.0412 (9)	0.0438 (11)	0.0466 (11)	−0.0015 (8)	−0.0012 (8)	−0.0101 (9)
C7	0.0340 (8)	0.0237 (7)	0.0263 (8)	−0.0001 (6)	0.0039 (6)	0.0008 (6)
C8	0.0357 (8)	0.0312 (9)	0.0268 (8)	−0.0011 (7)	0.0059 (7)	0.0014 (6)
C9	0.0340 (8)	0.0315 (9)	0.0346 (9)	0.0006 (7)	0.0041 (7)	0.0053 (7)
C10	0.0326 (8)	0.0314 (10)	0.0306 (8)	0.0005 (6)	0.0049 (6)	0.0018 (6)
N1	0.0365 (7)	0.0248 (7)	0.0287 (7)	0.0013 (6)	0.0026 (6)	−0.0003 (6)
N2	0.0810 (13)	0.0565 (11)	0.0363 (9)	−0.0212 (12)	0.0216 (8)	−0.0110 (10)
O1	0.0570 (8)	0.0306 (7)	0.0472 (8)	0.0007 (6)	0.0059 (6)	0.0108 (6)
O2	0.0567 (8)	0.0564 (8)	0.0244 (6)	0.0107 (7)	0.0006 (6)	−0.0009 (6)
O3	0.0665 (9)	0.0457 (9)	0.0357 (7)	−0.0255 (7)	0.0061 (6)	0.0041 (6)
O4	0.0820 (10)	0.0388 (7)	0.0255 (6)	−0.0119 (7)	0.0105 (6)	−0.0018 (5)
O6	0.0593 (8)	0.0361 (7)	0.0345 (6)	−0.0074 (6)	0.0152 (6)	−0.0019 (5)
S1	0.0406 (2)	0.0300 (2)	0.02406 (18)	0.00257 (18)	0.00257 (14)	0.00307 (17)

Geometric parameters (Å, º) top

C1—C2	1.382 (3)	C7—H7	0.9800
C1—C6	1.386 (3)	C8—O3	1.195 (2)
C1—S1	1.7596 (18)	C8—O4	1.314 (2)
C2—C3	1.390 (3)	C9—C10	1.499 (2)
C2—H2	0.9300	C9—H9A	0.9700
C3—C4	1.370 (3)	C9—H9B	0.9700
C3—H3	0.9300	C10—O6	1.226 (2)
C4—C5	1.378 (3)	C10—N2	1.320 (2)
C4—H4	0.9300	N1—S1	1.6289 (15)
C5—C6	1.377 (3)	N1—H1B	0.77 (2)
C5—H5	0.9300	N2—H1A	0.88 (4)
C6—H6	0.9300	N2—H2A	0.95 (3)
C7—N1	1.460 (2)	O1—S1	1.4319 (14)
C7—C8	1.523 (2)	O2—S1	1.4304 (14)
C7—C9	1.542 (2)	O4—H4A	0.8200

C2—C1—C6	121.60 (18)	O3—C8—C7	124.44 (15)
C2—C1—S1	119.45 (14)	O4—C8—C7	109.93 (14)
C6—C1—S1	118.76 (14)	C10—C9—C7	111.80 (14)
C1—C2—C3	118.21 (19)	C10—C9—H9A	109.3
C1—C2—H2	120.9	C7—C9—H9A	109.3
C3—C2—H2	120.9	C10—C9—H9B	109.3
C4—C3—C2	120.39 (19)	C7—C9—H9B	109.3
C4—C3—H3	119.8	H9A—C9—H9B	107.9
C2—C3—H3	119.8	O6—C10—N2	120.99 (18)
C3—C4—C5	120.86 (19)	O6—C10—C9	120.76 (16)
C3—C4—H4	119.6	N2—C10—C9	118.24 (18)
C5—C4—H4	119.6	C7—N1—S1	120.55 (12)
C6—C5—C4	119.82 (19)	C7—N1—H1B	116.2 (14)
C6—C5—H5	120.1	S1—N1—H1B	110.9 (14)
C4—C5—H5	120.1	C10—N2—H1A	113.9 (19)
C5—C6—C1	119.11 (18)	C10—N2—H2A	117.8 (19)
C5—C6—H6	120.4	H1A—N2—H2A	127 (3)
C1—C6—H6	120.4	C8—O4—H4A	109.5
N1—C7—C8	112.54 (13)	O2—S1—O1	119.35 (9)
N1—C7—C9	108.73 (13)	O2—S1—N1	105.46 (8)
C8—C7—C9	107.92 (13)	O1—S1—N1	106.44 (8)
N1—C7—H7	109.2	O2—S1—C1	108.01 (9)
C8—C7—H7	109.2	O1—S1—C1	109.25 (8)
C9—C7—H7	109.2	N1—S1—C1	107.77 (8)
O3—C8—O4	125.58 (16)

C6—C1—C2—C3	−0.1 (3)	C7—C9—C10—O6	−79.6 (2)
S1—C1—C2—C3	174.80 (16)	C7—C9—C10—N2	100.7 (2)
C1—C2—C3—C4	−0.6 (3)	C8—C7—N1—S1	−99.21 (15)
C2—C3—C4—C5	0.9 (3)	C9—C7—N1—S1	141.28 (13)
C3—C4—C5—C6	−0.6 (3)	C7—N1—S1—O2	−168.94 (12)
C4—C5—C6—C1	−0.1 (3)	C7—N1—S1—O1	−41.22 (15)
C2—C1—C6—C5	0.5 (3)	C7—N1—S1—C1	75.87 (14)
S1—C1—C6—C5	−174.49 (16)	C2—C1—S1—O2	160.50 (14)
N1—C7—C8—O3	−21.2 (2)	C6—C1—S1—O2	−24.43 (17)
C9—C7—C8—O3	98.8 (2)	C2—C1—S1—O1	29.25 (17)
N1—C7—C8—O4	161.31 (14)	C6—C1—S1—O1	−155.68 (14)
C9—C7—C8—O4	−78.71 (17)	C2—C1—S1—N1	−86.01 (16)
N1—C7—C9—C10	−78.10 (18)	C6—C1—S1—N1	89.06 (15)
C8—C7—C9—C10	159.55 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O1ⁱ	0.77 (2)	2.31 (2)	3.076 (2)	168.6 (19)
N2—H2A···O2ⁱⁱ	0.95 (3)	2.06 (3)	2.998 (3)	172 (3)
O4—H4A···O6ⁱⁱⁱ	0.82	1.82	2.5804 (18)	155

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₂N₂O₅S
M_r	272.28
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	296
a, b, c (Å)	10.5479 (6), 5.1587 (3), 11.0157 (7)
β (°)	92.011 (3)
V (Å³)	599.03 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.25 × 0.21 × 0.13

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.932, 0.964
No. of measured, independent and observed [I > 2σ(I)] reflections	6832, 2732, 2518
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.076, 1.06
No. of reflections	2732
No. of parameters	176
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.16
Absolute structure	Flack (1983), 1187 Friedel pairs
Absolute structure parameter	−0.01 (6)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O1ⁱ	0.77 (2)	2.31 (2)	3.076 (2)	168.6 (19)
N2—H2A···O2ⁱⁱ	0.95 (3)	2.06 (3)	2.998 (3)	172 (3)
O4—H4A···O6ⁱⁱⁱ	0.82	1.82	2.5804 (18)	155

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

Acknowledgements

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

References

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