(E)-4-[(2-Hydroxy­benzyl­idene)amino]benzene­sulfonic acid

The title mol­ecule, C₁₃H₁₁NO₄S, displays a trans configuration with respect to the imine C=N double bond. The central benzene ring directly linked to N and the hydroxyl group are disordered over two orientations [occupancies of 0.510 (16)/0.490 (16) and 0.528 (8)/0.472 (8), respectively]. The dihedral angle between the two aromatic rings is 23.3 (5)° for the major component and 18.3 (5)° for the minor component. There is an intra­molecular O—H...N hydrogen bond and mol­ecules are linked into chains along the a axis by O—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.009 Å
• Disorder in main residue
• R factor = 0.050
• wR factor = 0.121
• Data-to-parameter ratio = 9.2

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for    S1     --  O2      ..       8.76 su
PLAT241_ALERT_2_B Check High      Ueq as Compared to Neighbors for        C13
PLAT432_ALERT_2_B Short Inter X...Y Contact  C2'    ..  C6'     ..       2.91 Ang.
PLAT432_ALERT_2_B Short Inter X...Y Contact  C3'    ..  C5'     ..       2.91 Ang.
PLAT432_ALERT_2_B Short Inter X...Y Contact  C3'    ..  C6'     ..       3.01 Ang.

Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.04 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C10
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C8
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C11
PLAT301_ALERT_3_C Main Residue  Disorder .........................      21.00 Perc.
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          9
PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond  C8     -   C9     ...       1.37 Ang.
PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond  C9     -   C10    ...       1.38 Ang.
PLAT410_ALERT_2_C Short Intra H...H Contact  H7     ..  H5'     ..       1.97 Ang.
PLAT432_ALERT_2_C Short Inter X...Y Contact  C3     ..  C12     ..       3.19 Ang.

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           25.01
           From the CIF: _reflns_number_total               1952
           Count of symmetry unique reflns         1133
           Completeness (_total/calc)            172.29%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       819
           Fraction of Friedel pairs measured     0.723
           Are heavy atom types Z>Si present        yes
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2

   0 ALERT level A = In general: serious problem
   5 ALERT level B = Potentially serious problem
  10 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  13 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Schiff base compounds have been of great interest for many years. These compounds play an important role in the development of coordination chemistry related to catalysis and enzymatic reactions, magnetism and molecular architectures. As an extension of the work on the structural characterization of Schiff base compounds, the crystal structure of the title compound is reported here.

The structure of the title molecule is shown in Fig. 1. The bond lengths and angles are within normal ranges (Allen et al., 1987). The C7═N1 bond length of 1.262 (7) Å conforms to the value for a double bond. The dihedral angle between C1—C6 and C8—C13 benzene rings is 23.3 (5)° and that between C1/C2'/C3'/C4/C5'/C6' and C8—C13 rings is 18.3 (5)°. The C7—N1—C4—C5, C7—N1—C4—C3, O1—S1—C1—C6, O3—S1—C1—C6 and O2—S1—C1—C6 torsion angles are 22.8 (12)°, -156.4 (9)°, 173.5 (9)°, -58.9 (9)° and 56.3 (9)°, respectively. The molecule adopts a trans configuration about the C7?N1 bond. There exists an intramolecular O4—H4···N1 hydrogen bond involving the hydroxyl group and the imine N atom (Table 1).

In the crystal structure, the molecules are linked into chains running along the a axis by O—H···O hydrogen bonds.

Related literature

For bond-length data, see: Allen et al. (1987).

S2. Experimental

Salicylaldehyde (0.1 mmol, 12.2 mg) and sulfamide (0.1 mmol, 17.2 mg) were dissolved in methanol (10 ml). The mixture was stirred at room temperature for 10 min and then filtered. The filtrate was allowed to stand in air for 3 d, after which time yellow block-shaped crystals of the title compound were formed by slow evaporation of the solvent. The crystals were collected, washed with methanol and dried in a vacuum desiccator using anhydrous CaCl₂ (yield 54%). Analysis found: C 48.88, H 3.20, N 4.07%; calculated for C₁₃H₁₁NO₄S: C 48.9, H 3.20, N 4.08%.

S3. Refinement

The central benzene ring is disordered over two orientations (C1—C6/C1,C2',C3',C4,C5',C6') with refined occupancies of 0.510 (16) and 0.490 (16). The –OH group is also disordered over two positions with refined occupancies of 0.528 (8) and 0.472 (8). H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with O—H = 0.82 Å, C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C) and 1.5U_eq(O).

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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

Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. Both disorder components are shown.

(E)-4-[(2-Hydroxybenzylidene)amino]benzenesulfonic acid

Crystal data

C13H11NO4S	F(000) = 576
Mr = 277.29	Dx = 1.453 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 1329 reflections
a = 4.8711 (5) Å	θ = 2.7–23.9°
b = 29.022 (3) Å	µ = 0.27 mm^−1
c = 9.0356 (17) Å	T = 298 K
β = 97.223 (2)°	Block, yellow
V = 1267.2 (3) Å^3	0.42 × 0.31 × 0.15 mm
Z = 4

Data collection

Siemens SMART CCD area-detector diffractometer	1952 independent reflections
Radiation source: fine-focus sealed tube	1656 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ϕ and ω scans	θmax = 25.0°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −5→5
Tmin = 0.897, Tmax = 0.961	k = −34→31
3185 measured reflections	l = −9→10

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.050	H-atom parameters constrained
wR(F^2) = 0.121	w = 1/[σ^2(Fo^2) + (0.0495P)^2 + 1.7913P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.001
1952 reflections	Δρmax = 0.34 e Å^−3
213 parameters	Δρmin = −0.30 e Å^−3
2 restraints	Absolute structure: Flack (1983), 822 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.06 (14)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	0.75870 (18)	0.76105 (3)	0.47671 (13)	0.0372 (3)
N1	0.6129 (9)	0.96320 (13)	0.4070 (4)	0.0490 (10)
O1	0.6035 (6)	0.73963 (10)	0.3515 (3)	0.0470 (8)
O2	0.6306 (8)	0.74475 (13)	0.6247 (5)	0.0663 (11)
H2	0.4678	0.7526	0.6185	0.099*
O3	1.0490 (7)	0.75204 (11)	0.5021 (4)	0.0501 (8)
O4	0.387 (2)	1.0337 (3)	0.2463 (11)	0.0675 (18)	0.528 (8)
H4	0.4579	1.0080	0.2483	0.101*	0.528 (8)
O4'	0.285 (2)	1.0279 (4)	0.3133 (12)	0.0675 (18)	0.472 (8)
H4'	0.3138	1.0031	0.3557	0.101*	0.472 (8)
C1	0.7196 (9)	0.82135 (14)	0.4573 (5)	0.0365 (11)
C2	0.585 (3)	0.8377 (3)	0.3264 (16)	0.042 (3)	0.510 (16)
H2A	0.5178	0.8179	0.2493	0.051*	0.510 (16)
C3	0.554 (3)	0.8837 (3)	0.3133 (16)	0.045 (3)	0.510 (16)
H3	0.4598	0.8955	0.2254	0.055*	0.510 (16)
C2'	0.470 (3)	0.8413 (3)	0.3925 (16)	0.042 (3)	0.490 (16)
H2'	0.3224	0.8223	0.3586	0.051*	0.490 (16)
C3'	0.439 (3)	0.8887 (3)	0.3777 (16)	0.044 (3)	0.490 (16)
H3'	0.2733	0.9015	0.3339	0.053*	0.490 (16)
C4	0.6589 (11)	0.91570 (17)	0.4298 (6)	0.0426 (11)
C5	0.805 (3)	0.8949 (4)	0.5579 (16)	0.046 (3)	0.510 (16)
H5	0.8868	0.9136	0.6346	0.056*	0.510 (16)
C6	0.829 (3)	0.8473 (4)	0.5726 (16)	0.043 (3)	0.510 (16)
H6	0.9179	0.8339	0.6592	0.052*	0.510 (16)
C5'	0.909 (3)	0.8993 (4)	0.4909 (19)	0.047 (3)	0.490 (16)
H5'	1.0547	0.9193	0.5213	0.056*	0.490 (16)
C6'	0.941 (3)	0.8522 (4)	0.5065 (17)	0.047 (3)	0.490 (16)
H6'	1.1100	0.8403	0.5497	0.057*	0.490 (16)
C7	0.7682 (15)	0.99282 (16)	0.4771 (9)	0.0655 (13)
H7	0.9180	0.9826	0.5429	0.079*
C8	0.7245 (14)	1.04208 (16)	0.4601 (8)	0.0570 (14)
C9	0.5144 (14)	1.0594 (2)	0.3606 (8)	0.0771 (19)
C10	0.488 (2)	1.1068 (2)	0.3501 (10)	0.107 (3)
H10	0.3437	1.1187	0.2843	0.129*
C11	0.6584 (18)	1.1363 (2)	0.4287 (9)	0.0768 (18)
H11	0.6321	1.1679	0.4172	0.092*
C12	0.863 (2)	1.1202 (2)	0.5224 (11)	0.102 (3)
H12	0.9840	1.1404	0.5776	0.122*
C13	0.8992 (19)	1.0729 (2)	0.5393 (10)	0.111 (3)
H13	1.0455	1.0618	0.6059	0.133*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0310 (6)	0.0410 (5)	0.0369 (5)	0.0050 (6)	−0.0055 (4)	−0.0024 (6)
N1	0.052 (3)	0.041 (2)	0.054 (3)	−0.0006 (18)	0.008 (2)	0.0014 (18)
O1	0.048 (2)	0.0473 (18)	0.0402 (19)	0.0021 (15)	−0.0139 (15)	−0.0081 (15)
O2	0.055 (2)	0.072 (2)	0.070 (3)	0.0037 (18)	0.0028 (19)	0.0086 (19)
O3	0.0328 (18)	0.057 (2)	0.060 (2)	0.0086 (14)	0.0027 (15)	−0.0050 (16)
O4	0.076 (6)	0.062 (3)	0.062 (5)	0.009 (3)	−0.001 (3)	0.008 (4)
O4'	0.076 (6)	0.062 (3)	0.062 (5)	0.009 (3)	−0.001 (3)	0.008 (4)
C1	0.032 (3)	0.040 (2)	0.037 (3)	0.002 (2)	0.003 (2)	0.000 (2)
C2	0.047 (8)	0.039 (6)	0.039 (7)	−0.008 (5)	−0.001 (6)	−0.005 (5)
C3	0.047 (7)	0.045 (6)	0.043 (7)	0.002 (5)	0.001 (6)	0.002 (5)
C2'	0.036 (7)	0.041 (6)	0.047 (8)	−0.004 (5)	−0.004 (6)	−0.004 (5)
C3'	0.044 (7)	0.042 (6)	0.046 (7)	0.005 (5)	0.004 (6)	0.000 (5)
C4	0.041 (3)	0.040 (3)	0.046 (3)	−0.002 (2)	0.005 (2)	−0.001 (2)
C5	0.057 (9)	0.041 (6)	0.042 (7)	0.002 (5)	0.007 (6)	−0.008 (5)
C6	0.048 (8)	0.042 (6)	0.036 (7)	0.002 (5)	−0.003 (6)	−0.007 (5)
C5'	0.041 (8)	0.042 (6)	0.056 (9)	−0.003 (5)	0.004 (7)	−0.008 (6)
C6'	0.037 (8)	0.046 (7)	0.057 (9)	0.003 (5)	0.000 (7)	−0.003 (6)
C7	0.069 (3)	0.048 (3)	0.075 (3)	−0.001 (4)	−0.010 (3)	0.009 (4)
C8	0.064 (4)	0.042 (2)	0.066 (4)	−0.006 (3)	0.013 (3)	0.002 (3)
C9	0.083 (5)	0.051 (3)	0.091 (5)	0.019 (3)	−0.014 (4)	−0.018 (3)
C10	0.125 (7)	0.058 (4)	0.126 (7)	0.030 (4)	−0.035 (6)	−0.003 (4)
C11	0.105 (6)	0.046 (3)	0.084 (5)	0.006 (4)	0.027 (4)	−0.004 (3)
C12	0.118 (7)	0.056 (4)	0.125 (7)	−0.021 (5)	−0.012 (6)	0.001 (5)
C13	0.120 (6)	0.058 (4)	0.139 (7)	−0.013 (4)	−0.042 (6)	0.010 (5)

Geometric parameters (Å, º)

S1—O1	1.422 (3)	C3'—H3'	0.93
S1—O3	1.428 (3)	C4—C5'	1.359 (15)
S1—O2	1.615 (4)	C4—C5	1.415 (14)
S1—C1	1.767 (4)	C5—C6	1.392 (15)
N1—C7	1.262 (7)	C5—H5	0.93
N1—C4	1.408 (6)	C6—H6	0.93
O2—H2	0.82	C5'—C6'	1.382 (15)
O4—C9	1.359 (10)	C5'—H5'	0.93
O4—H4	0.82	C6'—H6'	0.93
O4'—C9	1.465 (12)	C7—C8	1.451 (6)
O4'—H4'	0.82	C7—H7	0.93
C1—C6	1.340 (11)	C8—C9	1.370 (8)
C1—C2	1.363 (12)	C8—C13	1.372 (9)
C1—C2'	1.405 (12)	C9—C10	1.382 (8)
C1—C6'	1.430 (13)	C10—C11	1.333 (11)
C2—C3	1.348 (13)	C10—H10	0.93
C2—H2A	0.93	C11—C12	1.310 (10)
C3—C4	1.448 (13)	C11—H11	0.93
C3—H3	0.93	C12—C13	1.390 (9)
C2'—C3'	1.387 (14)	C12—H12	0.93
C2'—H2'	0.93	C13—H13	0.93
C3'—C4	1.364 (12)
O1—S1—O3	117.6 (2)	C5—C4—C3	114.6 (7)
O1—S1—O2	108.0 (2)	C6—C5—C4	122.0 (10)
O3—S1—O2	106.9 (2)	C6—C5—H5	119.0
O1—S1—C1	108.29 (19)	C4—C5—H5	119.0
O3—S1—C1	106.8 (2)	C1—C6—C5	117.5 (10)
O2—S1—C1	108.9 (2)	C1—C6—H6	121.2
C7—N1—C4	121.3 (4)	C5—C6—H6	121.2
S1—O2—H2	109.5	C4—C5'—C6'	118.2 (11)
C9—O4—H4	109.5	C4—C5'—H5'	120.9
C9—O4'—H4'	109.5	C6'—C5'—H5'	120.9
C6—C1—C2	125.4 (8)	C5'—C6'—C1	121.1 (11)
C6—C1—C2'	109.3 (8)	C5'—C6'—H6'	119.5
C2—C1—C6'	108.3 (7)	C1—C6'—H6'	119.5
C2'—C1—C6'	116.8 (7)	N1—C7—C8	123.2 (6)
C6—C1—S1	116.8 (6)	N1—C7—H7	118.4
C2—C1—S1	117.7 (5)	C8—C7—H7	118.4
C2'—C1—S1	121.8 (5)	C9—C8—C13	117.8 (6)
C6'—C1—S1	121.4 (5)	C9—C8—C7	121.3 (6)
C3—C2—C1	117.3 (10)	C13—C8—C7	120.9 (6)
C3—C2—H2A	121.4	O4—C9—C8	121.9 (6)
C1—C2—H2A	121.4	O4—C9—C10	117.7 (7)
C2—C3—C4	123.0 (10)	C8—C9—C10	117.7 (6)
C2—C3—H3	118.5	C8—C9—O4'	116.2 (6)
C4—C3—H3	118.5	C10—C9—O4'	122.7 (7)
C3'—C2'—C1	121.9 (9)	C11—C10—C9	123.8 (7)
C3'—C2'—H2'	119.0	C11—C10—H10	118.1
C1—C2'—H2'	119.0	C9—C10—H10	118.1
C4—C3'—C2'	117.6 (10)	C12—C11—C10	119.1 (7)
C4—C3'—H3'	121.2	C12—C11—H11	120.5
C2'—C3'—H3'	121.2	C10—C11—H11	120.5
C5'—C4—C3'	124.4 (8)	C11—C12—C13	119.9 (8)
C5'—C4—N1	121.3 (6)	C11—C12—H12	120.0
C3'—C4—N1	114.1 (6)	C13—C12—H12	120.0
C3'—C4—C5	109.2 (8)	C8—C13—C12	121.7 (8)
N1—C4—C5	126.3 (6)	C8—C13—H13	119.2
C5'—C4—C3	106.8 (8)	C12—C13—H13	119.2
N1—C4—C3	119.1 (6)
O1—S1—C1—C6	173.5 (9)	C3'—C4—C5—C6	34.7 (15)
O3—S1—C1—C6	−58.9 (9)	N1—C4—C5—C6	177.2 (9)
O2—S1—C1—C6	56.3 (9)	C3—C4—C5—C6	−3.6 (16)
O1—S1—C1—C2	−7.4 (9)	C2—C1—C6—C5	−0.2 (17)
O3—S1—C1—C2	120.2 (8)	C2'—C1—C6—C5	−37.8 (14)
O2—S1—C1—C2	−124.6 (8)	C6'—C1—C6—C5	71.4 (15)
O1—S1—C1—C2'	35.0 (9)	S1—C1—C6—C5	178.8 (9)
O3—S1—C1—C2'	162.6 (8)	C4—C5—C6—C1	3.0 (18)
O2—S1—C1—C2'	−82.2 (9)	C3'—C4—C5'—C6'	−2.4 (19)
O1—S1—C1—C6'	−144.8 (9)	N1—C4—C5'—C6'	−178.4 (10)
O3—S1—C1—C6'	−17.2 (9)	C5—C4—C5'—C6'	71.8 (15)
O2—S1—C1—C6'	98.0 (9)	C3—C4—C5'—C6'	−37.3 (15)
C6—C1—C2—C3	−1.7 (17)	C4—C5'—C6'—C1	1 (2)
C2'—C1—C2—C3	72.3 (14)	C6—C1—C6'—C5'	−86.4 (17)
C6'—C1—C2—C3	−38.2 (14)	C2—C1—C6'—C5'	39.1 (16)
S1—C1—C2—C3	179.3 (9)	C2'—C1—C6'—C5'	0.2 (17)
C1—C2—C3—C4	1.0 (18)	S1—C1—C6'—C5'	180.0 (10)
C6—C1—C2'—C3'	38.5 (15)	C4—N1—C7—C8	−178.4 (6)
C2—C1—C2'—C3'	−85.4 (15)	N1—C7—C8—C9	−2.7 (11)
C6'—C1—C2'—C3'	−0.5 (16)	N1—C7—C8—C13	179.9 (8)
S1—C1—C2'—C3'	179.7 (9)	C13—C8—C9—O4	159.1 (9)
C1—C2'—C3'—C4	−0.6 (17)	C7—C8—C9—O4	−18.5 (11)
C2'—C3'—C4—C5'	2.1 (17)	C13—C8—C9—C10	−1.8 (11)
C2'—C3'—C4—N1	178.4 (9)	C7—C8—C9—C10	−179.4 (8)
C2'—C3'—C4—C5	−34.2 (14)	C13—C8—C9—O4'	−161.6 (8)
C2'—C3'—C4—C3	71.5 (13)	C7—C8—C9—O4'	20.9 (11)
C7—N1—C4—C5'	−19.9 (12)	O4—C9—C10—C11	−160.3 (10)
C7—N1—C4—C3'	163.7 (9)	C8—C9—C10—C11	1.4 (14)
C7—N1—C4—C5	22.8 (12)	O4'—C9—C10—C11	159.7 (10)
C7—N1—C4—C3	−156.4 (9)	C9—C10—C11—C12	−0.2 (15)
C2—C3—C4—C5'	38.7 (16)	C10—C11—C12—C13	−0.4 (14)
C2—C3—C4—C3'	−87.5 (16)	C9—C8—C13—C12	1.3 (13)
C2—C3—C4—N1	−179.1 (10)	C7—C8—C13—C12	178.9 (9)
C2—C3—C4—C5	1.5 (17)	C11—C12—C13—C8	−0.2 (14)
C5'—C4—C5—C6	−88.1 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3^i	0.82	2.17	2.917 (5)	151
O4—H4···N1	0.82	2.01	2.665 (10)	136

Symmetry code: (i) x−1, y, z.