A new polymorph of sulfanilic acid monohydrate

Banu, A.; Golzar Hossain, G.M.

doi:10.1107/S1600536806016060

organic compounds

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ISSN: 2056-9890

Volume 62| Part 6| June 2006| Pages o2252-o2253

https://doi.org/10.1107/S1600536806016060

A new polymorph of sulfanilic acid monohydrate

Afroza Banu ^a and G. M. Golzar Hossain ^a ^*

^aSchool of Chemistry, Cardiff University, Cardiff CF10 3AT, Wales
^*Correspondence e-mail: acsbd@yahoo.com

(Received 29 March 2006; accepted 1 May 2006; online 10 May 2006)

An orthorhombic polymorph of sulfanilic acid monohydrate, C₆H₇NO₃S·H₂O, is described in which there are significant hydrogen-bonding interactions between the components of the structure.

Comment

The crystal structure of a monoclinic form (P2₁/n) of sulfanilic acid monohydrate, (II), has been described (Rae & Maslen, 1962 ). Here, the structure of an orthorhombic form, (I) (P2₁2₁2₁), obtained by recrystallization from a methanol solution of the compound, is described (Fig. 1 and Table 1).

The C—S and C—N bond lengths in (I) (Table 1) are close to the corresponding distances in (II) and O₃SC₆H₄NH–CH–N(CH₃)₂·H₂O (Hempel et al., 1999 ). The S—O bond distances in (I) are similar to those found in (II) (Rae & Maslen, 1962), in metanilic acid (Hall & Maslen, 1965 ), and in 2,5-dichlorobenzenesulfonic acid and 2,5-dibromobenzenesulfonic acid (Lundgren & Lundin, 1972 ). The C—S—O and O—S—O angles deviate from 109.5° in the expected manner.

The crystal structure of (I) is stabilized by intermolecular N—H⋯O and O—H⋯O hydrogen bonds (Table 2), which result in the formation of a hydrogen-bonded network (Fig. 2). The water molecule is hydrogen bonded to the amine group (N1/H1B). The distance between the two parallel structures, with symmetry (1 + x, y, z), in the packing diagram (Fig. 2) is 6.163 (3) Å.

Figure 1
The asymmetric unit of (I)

, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 35% probability level. The hydrogen bond is shown as a dashed line.

Figure 2
The molecular packing of (I)

, viewed approximately along the a axis. Dashed lines indicate the hydrogen-bonding interactions.

Experimental

Sulfanilic acid (1.732 g, 1 mmol) was dissolved in methanol (20 ml) and stirred for 1 h. After filtration, the clear solution was left for crystallization, and after two weeks, pale-yellow crystals were obtained.

Crystal data

C₆H₇NO₃S·H₂O
M_r = 191.20
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.1630 (6) Å
b = 6.9607 (5) Å
c = 18.3251 (10) Å
V = 786.12 (10) Å³
Z = 4
D_x = 1.616 Mg m⁻³
Mo Kα radiation
μ = 0.39 mm⁻¹
T = 150 (2) K
Block, pale yellow
0.25 × 0.22 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
ω/θ scans
Absorption correction: part of the refinement model (ΔF) (Walker & Stuart, 1983 ) T_min = 0.910, T_max = 0.927
1822 measured reflections
957 independent reflections
793 reflections with I > 2σ(I)
R_int = 0.024
θ_max = 26.3°
3 standard reflections every 134 reflections intensity decay: none

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.092
S = 1.04
957 reflections
114 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.0544P)² + 0.1313P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

S1—O1	1.448 (3)
S1—O2	1.459 (3)
S1—O3	1.446 (3)
S1—C1	1.773 (3)
N1—C4	1.468 (4)

O1—S1—O2	111.64 (19)
O1—S1—O3	113.77 (19)
O1—S1—C1	106.26 (15)
O2—S1—O3	112.15 (15)
O2—S1—C1	105.00 (15)
O3—S1—C1	107.36 (15)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4A⋯O1ⁱ	0.95	1.90	2.821 (3)	163
O4—H4B⋯O2ⁱⁱ	0.95	1.89	2.838 (4)	175
N1—H1A⋯O3ⁱⁱⁱ	0.94	1.97	2.846 (4)	154
N1—H1B⋯O4	0.93	1.84	2.738 (3)	160
N1—H1C⋯O2^iv	0.96	1.95	2.895 (4)	166
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+1, z-{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (iv) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

In the absence of significant anomalous scattering, Friedel pairs were merged before the final refinement. C-bound H atoms were included in the riding model approximation with C—H = 0.95 Å, and with U_iso(H) = 1.2U_eq(C). H atoms attached to N and O(water) were located from an electron density map, fixed in these positions and assigned individual isotropic displacement parameters; see Table 2 for bond distances.

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1992 ); cell refinement: CAD-4 EXPRESS; data reduction: CAD-4 Processing Program (Hursthouse, 1976 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ); 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: https://doi.org/10.1107/S1600536806016060/tk2027sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806016060/tk2027Isup2.hkl

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1992); cell refinement: CAD-4 EXPRESS; data reduction: CAD-4 Processing Program (Hursthouse, 1976); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

sulfanilic acid monohydrate top

Crystal data top

C₆H₇NO₃S·H₂O	F(000) = 400
M_r = 191.20	D_x = 1.616 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 957 reflections
a = 6.1630 (6) Å	θ = 2.9–26.3°
b = 6.9607 (5) Å	µ = 0.39 mm⁻¹
c = 18.3251 (10) Å	T = 150 K
V = 786.12 (10) Å³	Block, pale yellow
Z = 4	0.25 × 0.22 × 0.20 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	793 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.024
Graphite monochromator	θ_max = 26.3°, θ_min = 2.2°
ω/θ scans	h = −7→0
Absorption correction: part of the refinement model (ΔF) (Walker & Stuart, 1983)	k = −8→2
T_min = 0.910, T_max = 0.927	l = −22→22
3 measured reflections	1534 standard reflections every 134 reflections
957 independent reflections	intensity decay: none

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)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.092	w = 1/[σ²(F_o²) + (0.0544P)² + 0.1313P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
957 reflections	Δρ_max = 0.31 e Å⁻³
114 parameters	Δρ_min = −0.29 e Å⁻³
5 restraints	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods

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	−0.01053 (14)	0.48483 (12)	0.63841 (4)	0.0291 (2)
O1	0.2228 (4)	0.5066 (5)	0.63447 (13)	0.0463 (7)
O2	−0.1130 (5)	0.6505 (4)	0.67294 (13)	0.0386 (7)
O3	−0.0795 (5)	0.3055 (4)	0.67078 (13)	0.0428 (7)
O4	0.0515 (4)	0.6429 (5)	0.25576 (15)	0.0663 (11)
N1	−0.3138 (4)	0.5290 (4)	0.32896 (13)	0.0307 (7)
C1	−0.1055 (5)	0.4873 (4)	0.54710 (15)	0.0252 (7)
C2	−0.3124 (6)	0.5482 (5)	0.53154 (17)	0.0303 (8)
H2	−0.4084	0.5827	0.5699	0.036*
C3	−0.3807 (6)	0.5591 (5)	0.45936 (17)	0.0307 (8)
H3	−0.5234	0.6011	0.4480	0.037*
C4	−0.2392 (5)	0.5081 (5)	0.40465 (16)	0.0273 (7)
C5	−0.0359 (6)	0.4401 (5)	0.41925 (16)	0.0304 (8)
H5	0.0554	0.4006	0.3803	0.036*
C6	0.0381 (4)	0.4282 (4)	0.49055 (13)	0.0299 (8)
H6	0.1797	0.3823	0.5013	0.036*
H1A	−0.3781	0.4113	0.3158	0.053 (13)*
H1B	−0.1976	0.5436	0.2970	0.041 (11)*
H1C	−0.4142	0.6317	0.3197	0.059 (14)*
H4A	0.1434	0.6163	0.2156	0.12 (2)*
H4B	0.1615	0.7184	0.2777	0.15 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0329 (4)	0.0347 (4)	0.0195 (3)	0.0022 (5)	−0.0003 (3)	0.0014 (4)
O1	0.0293 (13)	0.079 (2)	0.0311 (12)	−0.0029 (16)	−0.0032 (10)	0.0047 (17)
O2	0.0500 (18)	0.0387 (13)	0.0270 (12)	0.0017 (14)	0.0012 (14)	−0.0070 (11)
O3	0.0549 (19)	0.0419 (14)	0.0315 (13)	0.0020 (14)	0.0023 (15)	0.0098 (11)
O4	0.052 (2)	0.096 (3)	0.0513 (16)	−0.025 (2)	0.0144 (17)	−0.0228 (18)
N1	0.0376 (16)	0.0327 (16)	0.0217 (12)	−0.0033 (15)	−0.0041 (13)	0.0000 (12)
C1	0.0299 (16)	0.0241 (15)	0.0216 (13)	−0.0018 (18)	0.0004 (12)	0.0007 (13)
C2	0.0306 (18)	0.0334 (18)	0.0268 (16)	0.0028 (16)	0.0057 (14)	−0.0008 (14)
C3	0.0296 (19)	0.0331 (17)	0.0294 (16)	0.0016 (16)	−0.0019 (14)	−0.0002 (14)
C4	0.0353 (17)	0.0254 (16)	0.0212 (15)	0.0001 (17)	−0.0030 (12)	−0.0001 (15)
C5	0.0321 (19)	0.0353 (17)	0.0237 (14)	0.0036 (15)	0.0054 (15)	−0.0067 (13)
C6	0.031 (2)	0.0305 (16)	0.0284 (15)	0.0041 (15)	0.0018 (15)	−0.0026 (13)

Geometric parameters (Å, º) top

S1—O1	1.448 (3)	C1—C2	1.374 (5)
S1—O2	1.459 (3)	C1—C6	1.424 (4)
S1—O3	1.446 (3)	C2—C3	1.390 (4)
S1—C1	1.773 (3)	C2—H2	0.9500
O4—H4A	0.9476	C3—C4	1.376 (5)
O4—H4B	0.9474	C3—H3	0.9500
N1—C4	1.468 (4)	C4—C5	1.366 (5)
N1—H1A	0.9415	C5—C6	1.386 (4)
N1—H1B	0.9315	C5—H5	0.9500
N1—H1C	0.9606	C6—H6	0.9500

O1—S1—O2	111.64 (19)	C1—C2—C3	119.7 (3)
O1—S1—O3	113.77 (19)	C1—C2—H2	120.2
O1—S1—C1	106.26 (15)	C3—C2—H2	120.2
O2—S1—O3	112.15 (15)	C4—C3—C2	119.2 (3)
O2—S1—C1	105.00 (15)	C4—C3—H3	120.4
O3—S1—C1	107.36 (15)	C2—C3—H3	120.4
H4A—O4—H4B	90.5	C5—C4—C3	121.9 (3)
C4—N1—H1A	106.8	C5—C4—N1	120.4 (3)
C4—N1—H1B	111.4	C3—C4—N1	117.7 (3)
H1A—N1—H1B	104.9	C4—C5—C6	120.5 (3)
C4—N1—H1C	116.3	C4—C5—H5	119.8
H1A—N1—H1C	109.3	C6—C5—H5	119.8
H1B—N1—H1C	107.6	C5—C6—C1	117.7 (3)
C2—C1—C6	121.0 (3)	C5—C6—H6	121.2
C2—C1—S1	120.4 (2)	C1—C6—H6	121.2
C6—C1—S1	118.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4a···O1ⁱ	0.95	1.90	2.821 (3)	163
O4—H4b···O2ⁱⁱ	0.95	1.89	2.838 (4)	175
N1—H1a···O3ⁱⁱⁱ	0.94	1.97	2.846 (4)	154
N1—H1b···O4	0.93	1.84	2.738 (3)	160
N1—H1c···O2^iv	0.96	1.95	2.895 (4)	166

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

Acknowledgements

GMGH acknowledges the Ministry of Science and Technology, The People's Republic of Bangladesh, for the award of a Bangabandhu Fellowship.

References

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 62| Part 6| June 2006| Pages o2252-o2253

https://doi.org/10.1107/S1600536806016060

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

A new polymorph of sulfanilic acid monohydrate

Comment

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds