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Acta Cryst. (2009). E65, o2339    [ doi:10.1107/S1600536809035090 ]

4-(4-Diethylamino-2-hydroxybenzylideneammonio)-3-methylbenzenesulfonate dihydrate

W. Zhang and Y.-T. Chen

Abstract top

In the crystal of the title compound, C18H22N2O4S·2H2O, molecules are linked into a one-dimensional chain structure by C-H...O, N-H...O, O-H...O and O-H...N hydrogen bonds.

Comment top

Schiff bases play an important role in the field of bioinorganic chemistry because they have remarkable wide biological and pharmacological activities, such as antitumor, antidiabetic, antitubercular activities [Ranford, et al., 1998; Bu, et al., 2001]. Therefore, investigating the synthesis and proper ties of hydrazone of these compounds seems to be a very interesting problem. as one part of our systematic work, In this paper, we report on the synthesis and crystal structure of the title compound, (I), (Fig. 1).

The dihedral angle between the aromatic ring planes (C1–C6) and (C9–C14) is 5.70 (12)°, showing that the whole compound is not a plane molecule. The bond distances of C8—N1 [1.311 (3) Å], S1—O2 [1.449 (2) Å] and S1—O3 [1.426 (3) Å] are consistent with the carbon-nitrogen and sulfur-oxygen double-bond lengths, respectively. In the crystal packing, the molecules form a one-dimensional chain structure by C—H···O, N—H···O, O—H···O and O—H···N hydrogen bonds (Table 1).

Related literature top

For the biological and pharmacological activities of Schiff base compounds, see: Bu et al. (2001); Ranford et al. (1998).

Experimental top

The solution of 1.0 mmol 4-(diethylamino)salicylaldehyde was added to a solution of 1.0 mmol 3-methyl-benzenesulfonic acid in 5 ml ethanol at room temperature. The mixture was refluxed for 4 h with stirring, then the resulting precipitate was filtered, washed, and dried in vacuo over P4O10 for 48 h. Single crystals suitable for X-ray structural analysis was obtained by slowly evaporating from methanol at room temperature.

Refinement top

All H atoms were included in the refinement at calculated positions, in the riding-model approximation, with C–H distances of 0.93 (ArH), 0.98 (CH3), 0.97Å (CH2), N–H = 0.86 Å (NH), O–H = 0.82 Å (OH) and 0.85 Å (H2O) . The isotropic displacement parameters for all H atoms were set equal to 1.2 or 1.5Ueq of the carrier atom.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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
[Figure 1] Fig. 1. The molecular structure of (I) showing 30% displacement ellipsoids.
4-(4-Diethylamino-2-hydroxybenzylideneammonio)-3-methylbenzenesulfonate dihydrate top
Crystal data top
C18H22N2O4S·2H2OF(000) = 1696
Mr = 398.47Dx = 1.390 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 4718 reflections
a = 21.690 (3) Åθ = 2.2–28.4°
b = 11.4142 (17) ŵ = 0.21 mm−1
c = 16.639 (2) ÅT = 273 K
β = 112.459 (2)°Block, colourless
V = 3806.9 (9) Å30.19 × 0.16 × 0.06 mm
Z = 8
Data collection top
Bruker SMART CCD area-detector
diffractometer		3379 independent reflections
Radiation source: fine-focus sealed tube2910 reflections with I > 2σ(I)
graphiteRint = 0.026
φ and ω scansθmax = 25.1°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −11→25
Tmin = 0.962, Tmax = 0.988k = −13→13
9821 measured reflectionsl = −19→19
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.054H-atom parameters constrained
wR(F2) = 0.171 w = 1/[σ2(Fo2) + (0.1015P)2 + 5.082P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
3379 reflectionsΔρmax = 0.73 e Å−3
246 parametersΔρmin = −0.41 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0019 (5)
Crystal data top
C18H22N2O4S·2H2OV = 3806.9 (9) Å3
Mr = 398.47Z = 8
Monoclinic, C2/cMo Kα radiation
a = 21.690 (3) ŵ = 0.21 mm−1
b = 11.4142 (17) ÅT = 273 K
c = 16.639 (2) Å0.19 × 0.16 × 0.06 mm
β = 112.459 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		3379 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2910 reflections with I > 2σ(I)
Tmin = 0.962, Tmax = 0.988Rint = 0.026
9821 measured reflectionsθmax = 25.1°
Refinement top
R[F2 > 2σ(F2)] = 0.054H-atom parameters constrained
wR(F2) = 0.171Δρmax = 0.73 e Å−3
S = 1.05Δρmin = −0.41 e Å−3
3379 reflectionsAbsolute structure: ?
246 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
S10.18156 (3)0.09473 (5)−0.21298 (4)0.0405 (3)
O10.17722 (12)0.1276 (2)−0.29916 (14)0.0750 (8)
O20.11837 (9)0.1127 (2)−0.20400 (13)0.0573 (6)
O30.20786 (13)−0.0203 (2)−0.1892 (2)0.0980 (11)
O40.18994 (19)0.6795 (4)0.0958 (2)0.1365 (14)
H160.22520.64200.12540.205*
H150.16300.66690.12090.205*
O50.276 (2)0.6202 (16)1.001 (2)0.81 (3)
H180.30310.56641.00161.213*
H170.25820.64260.94871.213*
O60.50747 (8)0.45092 (15)0.15864 (11)0.0392 (4)
H60.53920.44050.20470.059*
N10.39104 (9)0.41470 (17)0.02004 (12)0.0332 (5)
H10.41540.38910.07090.040*
N20.60480 (10)0.83477 (18)0.19161 (14)0.0404 (5)
C10.24039 (11)0.1925 (2)−0.13942 (15)0.0343 (5)
C20.28796 (12)0.1511 (2)−0.06245 (15)0.0345 (5)
H20.28630.0733−0.04680.041*
C30.33840 (11)0.2239 (2)−0.00783 (14)0.0306 (5)
C40.33861 (11)0.3409 (2)−0.03262 (14)0.0303 (5)
C50.28903 (12)0.3837 (2)−0.10848 (16)0.0387 (6)
H50.28860.4624−0.12300.046*
C60.24063 (12)0.3090 (2)−0.16183 (16)0.0412 (6)
H6A0.20810.3371−0.21290.049*
C70.39164 (13)0.1746 (2)0.07302 (16)0.0442 (6)
H7A0.38370.09250.07740.066*
H7B0.39050.21450.12320.066*
H7C0.43460.18530.07000.066*
C80.40592 (11)0.5183 (2)−0.00150 (15)0.0338 (5)
H80.37900.5459−0.05630.041*
C90.45786 (11)0.59191 (19)0.04893 (15)0.0322 (5)
C100.50910 (11)0.5615 (2)0.13088 (14)0.0304 (5)
C110.55669 (11)0.6412 (2)0.17671 (15)0.0343 (5)
H110.58910.61940.22990.041*
C120.55782 (11)0.7562 (2)0.14517 (16)0.0355 (5)
C130.50789 (13)0.7859 (2)0.06268 (17)0.0417 (6)
H130.50730.86050.04000.050*
C140.46131 (13)0.7060 (2)0.01705 (16)0.0412 (6)
H140.43030.7270−0.03740.049*
C150.65369 (14)0.8065 (3)0.27868 (18)0.0514 (7)
H15A0.69120.85980.29290.062*
H15B0.67020.72770.27820.062*
C160.6252 (3)0.8148 (4)0.3481 (2)0.0935 (13)
H16A0.58240.77710.32820.140*
H16B0.62030.89570.36030.140*
H16C0.65470.77680.40000.140*
C170.60749 (14)0.9541 (2)0.1600 (2)0.0490 (7)
H17A0.59440.95160.09730.059*
H17B0.65320.98180.18500.059*
C180.56346 (19)1.0404 (3)0.1815 (3)0.0720 (10)
H18A0.57911.04990.24340.108*
H18B0.51851.01160.15980.108*
H18C0.56481.11450.15490.108*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0310 (4)0.0404 (4)0.0444 (4)−0.0065 (2)0.0080 (3)−0.0132 (3)
O10.0836 (16)0.1016 (18)0.0462 (12)−0.0473 (14)0.0318 (12)−0.0338 (12)
O20.0341 (10)0.0851 (15)0.0515 (11)−0.0193 (9)0.0150 (8)−0.0287 (10)
O30.0664 (15)0.0437 (13)0.128 (2)0.0007 (11)−0.0253 (15)−0.0222 (14)
O40.102 (3)0.148 (3)0.120 (3)0.026 (2)−0.002 (2)0.010 (2)
O51.22 (7)0.36 (2)1.12 (5)−0.11 (3)0.75 (6)−0.22 (3)
O60.0317 (9)0.0359 (9)0.0378 (9)−0.0044 (7)−0.0004 (7)0.0086 (7)
N10.0283 (10)0.0372 (11)0.0262 (10)−0.0048 (8)0.0018 (8)0.0015 (8)
N20.0344 (11)0.0346 (11)0.0480 (12)−0.0076 (9)0.0112 (9)−0.0070 (9)
C10.0255 (11)0.0394 (13)0.0366 (12)−0.0036 (9)0.0101 (10)−0.0069 (10)
C20.0353 (12)0.0305 (12)0.0386 (13)−0.0035 (9)0.0150 (10)−0.0023 (9)
C30.0296 (11)0.0340 (12)0.0279 (11)0.0010 (9)0.0106 (9)0.0014 (9)
C40.0271 (11)0.0359 (12)0.0266 (11)−0.0046 (9)0.0087 (9)−0.0020 (9)
C50.0355 (13)0.0324 (12)0.0380 (13)−0.0030 (10)0.0027 (10)0.0054 (10)
C60.0332 (13)0.0428 (14)0.0363 (13)−0.0028 (10)0.0005 (10)0.0015 (10)
C70.0459 (15)0.0393 (14)0.0376 (13)0.0019 (11)0.0049 (11)0.0055 (10)
C80.0305 (12)0.0382 (13)0.0284 (11)−0.0007 (9)0.0066 (9)0.0026 (9)
C90.0278 (12)0.0349 (12)0.0304 (12)−0.0024 (9)0.0073 (9)0.0012 (9)
C100.0269 (11)0.0323 (11)0.0304 (11)−0.0003 (9)0.0091 (9)0.0022 (9)
C110.0279 (11)0.0361 (12)0.0332 (12)0.0001 (9)0.0053 (9)0.0001 (9)
C120.0309 (12)0.0356 (13)0.0417 (13)−0.0022 (10)0.0157 (10)−0.0053 (10)
C130.0430 (14)0.0343 (13)0.0427 (14)−0.0049 (10)0.0105 (11)0.0065 (10)
C140.0394 (14)0.0411 (14)0.0354 (13)−0.0014 (10)0.0056 (11)0.0078 (10)
C150.0443 (16)0.0477 (16)0.0514 (16)−0.0131 (12)0.0061 (13)−0.0089 (12)
C160.137 (4)0.091 (3)0.053 (2)0.004 (3)0.038 (2)−0.004 (2)
C170.0440 (15)0.0393 (14)0.0621 (17)−0.0096 (12)0.0185 (13)−0.0068 (13)
C180.072 (2)0.0533 (19)0.089 (3)0.0109 (17)0.0290 (19)−0.0022 (17)
Geometric parameters (Å, °) top
S1—O31.426 (2)C7—H7A0.9600
S1—O21.449 (2)C7—H7B0.9600
S1—O11.450 (2)C7—H7C0.9600
S1—C11.783 (2)C8—C91.399 (3)
O4—H160.8502C8—H80.9300
O4—H150.8505C9—C141.419 (3)
O5—H180.8491C9—C101.434 (3)
O5—H170.8505C10—C111.369 (3)
O6—C101.349 (3)C11—C121.417 (3)
O6—H60.8200C11—H110.9300
N1—C81.311 (3)C12—C131.427 (3)
N1—C41.417 (3)C13—C141.357 (3)
N1—H10.8600C13—H130.9300
N2—C121.356 (3)C14—H140.9300
N2—C151.467 (3)C15—C161.507 (5)
N2—C171.470 (3)C15—H15A0.9700
C1—C61.382 (4)C15—H15B0.9700
C1—C21.385 (3)C16—H16A0.9600
C2—C31.398 (3)C16—H16B0.9600
C2—H20.9300C16—H16C0.9600
C3—C41.399 (3)C17—C181.506 (4)
C3—C71.508 (3)C17—H17A0.9700
C4—C51.397 (3)C17—H17B0.9700
C5—C61.380 (3)C18—H18A0.9600
C5—H50.9300C18—H18B0.9600
C6—H6A0.9300C18—H18C0.9600
O3—S1—O2113.29 (17)C8—C9—C14118.2 (2)
O3—S1—O1112.40 (19)C8—C9—C10125.4 (2)
O2—S1—O1111.02 (14)C14—C9—C10116.4 (2)
O3—S1—C1106.26 (12)O6—C10—C11123.0 (2)
O2—S1—C1107.32 (11)O6—C10—C9116.08 (19)
O1—S1—C1106.02 (12)C11—C10—C9121.0 (2)
H16—O4—H15105.3C10—C11—C12121.7 (2)
H18—O5—H17105.4C10—C11—H11119.1
C10—O6—H6109.5C12—C11—H11119.1
C8—N1—C4126.16 (19)N2—C12—C11121.1 (2)
C8—N1—H1116.9N2—C12—C13121.4 (2)
C4—N1—H1116.9C11—C12—C13117.5 (2)
C12—N2—C15121.3 (2)C14—C13—C12120.5 (2)
C12—N2—C17122.2 (2)C14—C13—H13119.7
C15—N2—C17116.4 (2)C12—C13—H13119.7
C6—C1—C2120.0 (2)C13—C14—C9122.8 (2)
C6—C1—S1119.52 (18)C13—C14—H14118.6
C2—C1—S1120.39 (18)C9—C14—H14118.6
C1—C2—C3121.3 (2)N2—C15—C16112.9 (3)
C1—C2—H2119.3N2—C15—H15A109.0
C3—C2—H2119.3C16—C15—H15A109.0
C2—C3—C4117.8 (2)N2—C15—H15B109.0
C2—C3—C7120.1 (2)C16—C15—H15B109.0
C4—C3—C7122.1 (2)H15A—C15—H15B107.8
C5—C4—C3120.8 (2)C15—C16—H16A109.5
C5—C4—N1120.7 (2)C15—C16—H16B109.5
C3—C4—N1118.52 (19)H16A—C16—H16B109.5
C6—C5—C4119.9 (2)C15—C16—H16C109.5
C6—C5—H5120.0H16A—C16—H16C109.5
C4—C5—H5120.0H16B—C16—H16C109.5
C5—C6—C1120.1 (2)N2—C17—C18113.9 (3)
C5—C6—H6A120.0N2—C17—H17A108.8
C1—C6—H6A120.0C18—C17—H17A108.8
C3—C7—H7A109.5N2—C17—H17B108.8
C3—C7—H7B109.5C18—C17—H17B108.8
H7A—C7—H7B109.5H17A—C17—H17B107.7
C3—C7—H7C109.5C17—C18—H18A109.5
H7A—C7—H7C109.5C17—C18—H18B109.5
H7B—C7—H7C109.5H18A—C18—H18B109.5
N1—C8—C9127.1 (2)C17—C18—H18C109.5
N1—C8—H8116.4H18A—C18—H18C109.5
C9—C8—H8116.4H18B—C18—H18C109.5
O3—S1—C1—C6159.2 (2)N1—C8—C9—C107.0 (4)
O2—S1—C1—C6−79.3 (2)C8—C9—C10—O62.7 (3)
O1—S1—C1—C639.4 (2)C14—C9—C10—O6−176.7 (2)
O3—S1—C1—C2−17.3 (3)C8—C9—C10—C11−177.9 (2)
O2—S1—C1—C2104.2 (2)C14—C9—C10—C112.7 (3)
O1—S1—C1—C2−137.1 (2)O6—C10—C11—C12178.9 (2)
C6—C1—C2—C3−2.6 (4)C9—C10—C11—C12−0.6 (4)
S1—C1—C2—C3173.88 (17)C15—N2—C12—C11−3.9 (4)
C1—C2—C3—C41.2 (3)C17—N2—C12—C11179.4 (2)
C1—C2—C3—C7−176.6 (2)C15—N2—C12—C13176.3 (2)
C2—C3—C4—C51.4 (3)C17—N2—C12—C13−0.4 (4)
C7—C3—C4—C5179.2 (2)C10—C11—C12—N2179.3 (2)
C2—C3—C4—N1−177.30 (19)C10—C11—C12—C13−1.0 (3)
C7—C3—C4—N10.5 (3)N2—C12—C13—C14179.9 (2)
C8—N1—C4—C5−12.5 (4)C11—C12—C13—C140.2 (4)
C8—N1—C4—C3166.3 (2)C12—C13—C14—C92.2 (4)
C3—C4—C5—C6−2.7 (4)C8—C9—C14—C13177.0 (2)
N1—C4—C5—C6176.0 (2)C10—C9—C14—C13−3.6 (4)
C4—C5—C6—C11.3 (4)C12—N2—C15—C16−78.0 (3)
C2—C1—C6—C51.3 (4)C17—N2—C15—C1698.9 (3)
S1—C1—C6—C5−175.2 (2)C12—N2—C17—C1885.9 (3)
C4—N1—C8—C9−179.1 (2)C15—N2—C17—C18−91.0 (3)
N1—C8—C9—C14−173.7 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O60.862.102.723 (3)129
N1—H1···O2i0.862.583.160 (3)125
O6—H6···O2ii0.821.912.709 (3)166
O4—H16···O3i0.852.002.828 (5)166
O5—H18···N1iii0.852.513.35 (3)174
C2—H2···O30.932.562.915 (4)103
C5—H5···O1iv0.932.553.392 (3)150
C7—H7B···O2i0.962.443.325 (3)154
C8—H8···O1iv0.932.433.353 (3)172
C15—H15B···O3ii0.972.503.444 (4)166
C16—H16C···O5v0.962.513.42 (3)160
Symmetry codes: (i) −x+1/2, −y+1/2, −z; (ii) x+1/2, −y+1/2, z+1/2; (iii) x, y, z+1; (iv) −x+1/2, y+1/2, −z−1/2; (v) −x+1, y, −z+3/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O60.862.102.723 (3)129
N1—H1···O2i0.862.583.160 (3)125
O6—H6···O2ii0.821.912.709 (3)166
O4—H16···O3i0.852.002.828 (5)166
O5—H18···N1iii0.852.513.35 (3)174
C2—H2···O30.932.562.915 (4)103
C5—H5···O1iv0.932.553.392 (3)150
C7—H7B···O2i0.962.443.325 (3)154
C8—H8···O1iv0.932.433.353 (3)172
C15—H15B···O3ii0.972.503.444 (4)166
C16—H16C···O5v0.962.513.42 (3)160
Symmetry codes: (i) −x+1/2, −y+1/2, −z; (ii) x+1/2, −y+1/2, z+1/2; (iii) x, y, z+1; (iv) −x+1/2, y+1/2, −z−1/2; (v) −x+1, y, −z+3/2.
Acknowledgements top

The authors thank the Program for New Century Excellent Talents in Universities for a research grant.

references
References top

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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.