Acta Cryst. (2008). E64, m1628 [ doi:10.1107/S1600536808039202 ]
In the title compound, Na+·C6H4IO3S-·H2O, the Na atom is hexacoordinated by O atoms, forming a two-dimensional sheet-like structure in the bc plane, with the iodobenzene rings protruding above and below. Na
O contact distances are in the range 2.419 (2)-2.7218 (18) Å and ONaO angles are in the range 73.70 (5)-158.64 (7)°. The crystal structure is stabilized by O-HO and C-HO hydrogen bonds and C-H![[pi]](/logos/entities/pi_rmgif.gif)
interactions. The I atom is disordered over two positions with occupancies of 0.78 (2) and 0.22 (2).
The title compound was prepared following the method used by Chau & Kice (1977). Suitable crystals for X-ray analysis were obtained from the reaction mixture.
The Iodine atom was disordered over two positions (I1A/I1B) with occupancies of 0.78 (2)/0.22 (2). The water H-atoms were located in a difference Fourier map and were refined with distance restraints: O-H = 0.82 (2) Å with Uiso(H) = 1.2Ueq(O). The C-bound H-atoms were positioned geometrically and treated as riding atoms: C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C).
Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003).
![[Figure 1]](./su2075fig1thm.gif)
| Fig. 1. Molecular structure of compound (I), with the atom numbering scheme. The thermal ellipsoids are drawn at the 50% probability level. |
![[Figure 2]](./su2075fig2thm.gif)
| Fig. 2. A view along the c axis of the crystal packing in compound (I), showing the coordination of the O-atoms with the sodium atom and the hydrogen bonding involving the water molecules (H-atoms not involved in hydrogen bonding have been removed for clarity). |
| Na+·C6H4IO3S−·H2O | F(000) = 616 |
| Mr = 324.06 | Dx = 2.285 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 2339 reflections |
| a = 13.6141 (4) Å | θ = 1.5–28.3° |
| b = 8.8233 (3) Å | µ = 3.64 mm−1 |
| c = 7.8493 (3) Å | T = 296 K |
| β = 92.171 (1)° | Prismatic, colorless |
| V = 942.19 (6) Å3 | 0.25 × 0.17 × 0.15 mm |
| Z = 4 |
| Bruker KAPPA APEXII CCD diffractometer | 2339 independent reflections |
| Radiation source: fine-focus sealed tube | 2135 reflections with I > 2σ(I) |
| graphite | Rint = 0.024 |
| Detector resolution: 7.40 pixels mm-1 | θmax = 28.3°, θmin = 1.5° |
| ω scans | h = −18→18 |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | k = −11→11 |
| Tmin = 0.482, Tmax = 0.580 | l = −10→10 |
| 10141 measured reflections |
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.019 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.047 | H-atom parameters constrained |
| S = 1.05 | w = 1/[σ2(Fo2) + (0.0176P)2 + 0.7234P] where P = (Fo2 + 2Fc2)/3 |
| 2339 reflections | (Δ/σ)max = 0.009 |
| 128 parameters | Δρmax = 0.42 e Å−3 |
| 0 restraints | Δρmin = −0.42 e Å−3 |
| Na+·C6H4IO3S−·H2O | V = 942.19 (6) Å3 |
| Mr = 324.06 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 13.6141 (4) Å | µ = 3.64 mm−1 |
| b = 8.8233 (3) Å | T = 296 K |
| c = 7.8493 (3) Å | 0.25 × 0.17 × 0.15 mm |
| β = 92.171 (1)° |
| Bruker KAPPA APEXII CCD diffractometer | 2339 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | 2135 reflections with I > 2σ(I) |
| Tmin = 0.482, Tmax = 0.580 | Rint = 0.024 |
| 10141 measured reflections | θmax = 28.3° |
| R[F2 > 2σ(F2)] = 0.019 | H-atom parameters constrained |
| wR(F2) = 0.047 | Δρmax = 0.42 e Å−3 |
| S = 1.05 | Δρmin = −0.42 e Å−3 |
| 2339 reflections | Absolute structure: ? |
| 128 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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. |
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| I1A | 0.19343 (9) | −0.1923 (2) | 0.55095 (18) | 0.0385 (2) | 0.78 (2) |
| I1B | 0.1984 (5) | −0.1716 (17) | 0.5644 (12) | 0.0628 (13) | 0.22 (2) |
| S1 | 0.37585 (3) | 0.02639 (5) | 0.34970 (6) | 0.0236 (1) | |
| Na | 0.51091 (7) | 0.29771 (10) | 0.49492 (12) | 0.0402 (3) | |
| O1 | 0.42883 (11) | 0.14214 (18) | 0.2606 (2) | 0.0369 (5) | |
| O2 | 0.38308 (12) | 0.0514 (2) | 0.53146 (19) | 0.0461 (6) | |
| O3 | 0.40017 (11) | −0.12539 (18) | 0.2976 (2) | 0.0390 (5) | |
| O4 | 0.39172 (13) | 0.4952 (2) | 0.38765 (19) | 0.0413 (5) | |
| C1 | 0.24956 (13) | 0.0530 (2) | 0.2877 (2) | 0.0227 (5) | |
| C2 | 0.17328 (14) | −0.0292 (2) | 0.3573 (2) | 0.0251 (5) | |
| C3 | 0.07722 (15) | −0.0064 (3) | 0.2991 (3) | 0.0328 (6) | |
| C4 | 0.05587 (16) | 0.0976 (3) | 0.1724 (3) | 0.0386 (7) | |
| C5 | 0.13033 (18) | 0.1803 (3) | 0.1044 (3) | 0.0412 (7) | |
| C6 | 0.22673 (16) | 0.1593 (3) | 0.1618 (3) | 0.0332 (6) | |
| H3 | 0.02673 | −0.06165 | 0.34590 | 0.0393* | |
| H4 | −0.00875 | 0.11181 | 0.13299 | 0.0463* | |
| H4A | 0.38645 | 0.48643 | 0.28018 | 0.0496* | |
| H4B | 0.33495 | 0.51683 | 0.41658 | 0.0496* | |
| H5 | 0.11586 | 0.25088 | 0.01914 | 0.0495* | |
| H6 | 0.27653 | 0.21667 | 0.11578 | 0.0398* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| I1A | 0.0425 (3) | 0.0384 (5) | 0.0345 (3) | −0.0046 (4) | 0.0010 (2) | 0.0146 (3) |
| I1B | 0.0625 (16) | 0.071 (3) | 0.0543 (18) | −0.0264 (19) | −0.0055 (11) | 0.0310 (15) |
| S1 | 0.0214 (2) | 0.0248 (2) | 0.0243 (2) | 0.0002 (2) | −0.0019 (2) | −0.0017 (2) |
| Na | 0.0466 (5) | 0.0325 (5) | 0.0407 (5) | 0.0011 (4) | −0.0087 (4) | −0.0053 (4) |
| O1 | 0.0285 (7) | 0.0346 (8) | 0.0478 (9) | −0.0059 (6) | 0.0027 (6) | 0.0055 (7) |
| O2 | 0.0349 (8) | 0.0784 (13) | 0.0245 (7) | −0.0004 (8) | −0.0055 (6) | −0.0061 (8) |
| O3 | 0.0301 (8) | 0.0252 (8) | 0.0612 (10) | 0.0051 (6) | −0.0043 (7) | −0.0076 (7) |
| O4 | 0.0447 (9) | 0.0519 (10) | 0.0274 (7) | 0.0000 (8) | 0.0018 (7) | −0.0009 (7) |
| C1 | 0.0224 (8) | 0.0227 (9) | 0.0227 (8) | 0.0025 (7) | −0.0012 (7) | −0.0016 (7) |
| C2 | 0.0277 (9) | 0.0240 (9) | 0.0234 (9) | 0.0001 (7) | −0.0006 (7) | −0.0011 (7) |
| C3 | 0.0261 (9) | 0.0349 (12) | 0.0373 (11) | −0.0030 (8) | 0.0008 (8) | −0.0037 (9) |
| C4 | 0.0283 (10) | 0.0430 (13) | 0.0438 (12) | 0.0083 (9) | −0.0091 (9) | −0.0036 (10) |
| C5 | 0.0405 (12) | 0.0413 (14) | 0.0413 (12) | 0.0096 (10) | −0.0066 (10) | 0.0141 (10) |
| C6 | 0.0333 (10) | 0.0316 (11) | 0.0346 (11) | 0.0019 (8) | 0.0017 (8) | 0.0091 (9) |
| I1A—C2 | 2.104 (2) | O4—H4B | 0.8400 |
| I1B—C2 | 2.073 (12) | O4—H4A | 0.8500 |
| S1—O1 | 1.4459 (16) | C1—C6 | 1.389 (3) |
| S1—O2 | 1.4433 (16) | C1—C2 | 1.395 (3) |
| S1—O3 | 1.4424 (16) | C2—C3 | 1.384 (3) |
| S1—C1 | 1.7846 (18) | C3—C4 | 1.376 (4) |
| Na—O1 | 2.5219 (18) | C4—C5 | 1.373 (3) |
| Na—O4 | 2.505 (2) | C5—C6 | 1.384 (3) |
| Na—O3i | 2.7218 (18) | C3—H3 | 0.9300 |
| Na—O3ii | 2.5060 (18) | C4—H4 | 0.9300 |
| Na—O4iii | 2.419 (2) | C5—H5 | 0.9300 |
| Na—O1iv | 2.4609 (18) | C6—H6 | 0.9300 |
| I1A···O2 | 3.368 (2) | O4···O1iv | 3.191 (2) |
| I1A···O3 | 3.557 (2) | O4···O1i | 3.036 (2) |
| I1A···C1v | 3.750 (2) | O1···H4Aviii | 2.8900 |
| I1A···I1Avi | 4.055 (2) | O1···H6 | 2.4200 |
| I1A···I1Av | 4.055 (2) | O2···H6iv | 2.6100 |
| I1A···C2v | 3.456 (2) | O2···H4Aiv | 1.9800 |
| I1A···C3v | 3.688 (3) | C1···I1Avi | 3.750 (2) |
| I1B···O3 | 3.540 (8) | C1···I1Bvi | 3.846 (14) |
| I1B···O2 | 3.211 (11) | C2···I1Avi | 3.456 (2) |
| I1B···C3v | 3.797 (13) | C2···I1Bvi | 3.526 (13) |
| I1B···C1v | 3.846 (14) | C3···I1Avi | 3.688 (3) |
| I1B···C2v | 3.526 (13) | C3···I1Bvi | 3.797 (13) |
| I1A···H4vii | 3.3300 | C4···C4x | 3.506 (3) |
| S1···O2ii | 3.4468 (17) | C2···H5iv | 2.8900 |
| O1···O3i | 3.149 (2) | C3···H5iv | 2.8800 |
| O1···O4viii | 3.036 (2) | C4···H4x | 3.0700 |
| O1···O4ix | 3.191 (2) | C6···H4Bix | 2.9200 |
| O2···S1ii | 3.4468 (17) | H4···I1Axi | 3.3300 |
| O2···I1B | 3.211 (11) | H4···C4x | 3.0700 |
| O2···I1A | 3.368 (2) | H4A···O2ix | 1.9800 |
| O2···O4iv | 2.824 (2) | H4B···C6iv | 2.9200 |
| O3···I1B | 3.540 (8) | H5···C2ix | 2.8900 |
| O3···O1viii | 3.149 (2) | H5···C3ix | 2.8800 |
| O3···I1A | 3.557 (2) | H6···O1 | 2.4200 |
| O4···O2ix | 2.824 (2) | H6···O2ix | 2.6100 |
| O1—S1—O2 | 110.70 (10) | Na—O4—Naiii | 93.37 (7) |
| O1—S1—O3 | 113.24 (9) | Naiii—O4—H4A | 118.00 |
| O1—S1—C1 | 105.56 (9) | Naiii—O4—H4B | 103.00 |
| O2—S1—O3 | 114.48 (10) | Na—O4—H4A | 107.00 |
| O2—S1—C1 | 106.16 (9) | Na—O4—H4B | 131.00 |
| O3—S1—C1 | 105.90 (9) | H4A—O4—H4B | 104.00 |
| O1—Na—O4 | 82.53 (6) | C2—C1—C6 | 118.68 (17) |
| O1—Na—O3i | 73.70 (5) | S1—C1—C6 | 118.04 (14) |
| O1—Na—O3ii | 109.48 (6) | S1—C1—C2 | 123.27 (13) |
| O1—Na—O4iii | 155.53 (7) | I1A—C2—C3 | 115.71 (15) |
| O1—Na—O1iv | 122.18 (6) | I1A—C2—C1 | 124.06 (14) |
| O3i—Na—O4 | 81.15 (6) | I1B—C2—C3 | 118.2 (2) |
| O3ii—Na—O4 | 158.64 (7) | C1—C2—C3 | 120.23 (17) |
| O4—Na—O4iii | 86.63 (6) | I1B—C2—C1 | 121.3 (2) |
| O1iv—Na—O4 | 79.96 (6) | C2—C3—C4 | 120.5 (2) |
| O3i—Na—O3ii | 118.69 (6) | C3—C4—C5 | 119.8 (2) |
| O3i—Na—O4iii | 83.01 (6) | C4—C5—C6 | 120.5 (2) |
| O1iv—Na—O3i | 153.11 (6) | C1—C6—C5 | 120.4 (2) |
| O3ii—Na—O4iii | 88.08 (6) | C2—C3—H3 | 120.00 |
| O1iv—Na—O3ii | 78.69 (6) | C4—C3—H3 | 120.00 |
| O1iv—Na—O4iii | 76.94 (6) | C3—C4—H4 | 120.00 |
| S1—O1—Na | 104.30 (8) | C5—C4—H4 | 120.00 |
| S1—O1—Naix | 144.40 (10) | C4—C5—H5 | 120.00 |
| Na—O1—Naix | 107.32 (6) | C6—C5—H5 | 120.00 |
| S1—O3—Naviii | 125.79 (9) | C1—C6—H6 | 120.00 |
| S1—O3—Naii | 119.31 (9) | C5—C6—H6 | 120.00 |
| Naviii—O3—Naii | 100.23 (6) | ||
| O2—S1—O1—Na | 4.83 (11) | O3i—Na—O4—Naiii | −83.44 (6) |
| O2—S1—O1—Naix | 156.95 (15) | O3ii—Na—O4—Naiii | 75.95 (19) |
| O3—S1—O1—Na | −125.30 (9) | O4iii—Na—O4—Naiii | 0.00 (7) |
| O3—S1—O1—Naix | 26.83 (19) | O1iv—Na—O4—Naiii | 77.33 (6) |
| C1—S1—O1—Na | 119.29 (8) | O1—Na—O3i—S1i | 136.29 (11) |
| C1—S1—O1—Naix | −88.58 (16) | O1—Na—O3i—Naix | −1.72 (6) |
| O1—S1—O3—Naviii | −18.05 (13) | O4—Na—O3i—S1i | 51.55 (11) |
| O1—S1—O3—Naii | 112.93 (10) | O4—Na—O3i—Naix | −86.47 (6) |
| O2—S1—O3—Naviii | −146.24 (10) | O1—Na—O3ii—S1ii | 19.44 (12) |
| O2—S1—O3—Naii | −15.26 (13) | O1—Na—O3ii—Naiv | −122.08 (6) |
| C1—S1—O3—Naviii | 97.16 (10) | O4—Na—O3ii—S1ii | 141.17 (16) |
| C1—S1—O3—Naii | −131.86 (9) | O4—Na—O3ii—Naiv | −0.4 (2) |
| O1—S1—C1—C2 | −174.65 (15) | O1—Na—O4iii—Naiii | 63.66 (18) |
| O1—S1—C1—C6 | 6.44 (18) | O4—Na—O4iii—Naiii | 0.00 (6) |
| O2—S1—C1—C2 | −57.08 (17) | O1—Na—O1iv—S1iv | −100.39 (17) |
| O2—S1—C1—C6 | 124.01 (17) | O1—Na—O1iv—Naiv | 107.94 (8) |
| O3—S1—C1—C2 | 65.01 (16) | O4—Na—O1iv—S1iv | −25.90 (16) |
| O3—S1—C1—C6 | −113.91 (17) | O4—Na—O1iv—Naiv | −177.57 (7) |
| O4—Na—O1—S1 | −111.84 (9) | S1—C1—C2—I1A | 2.0 (2) |
| O4—Na—O1—Naix | 84.73 (7) | S1—C1—C2—C3 | −177.78 (16) |
| O3i—Na—O1—S1 | 165.24 (9) | C6—C1—C2—I1A | −179.11 (16) |
| O3i—Na—O1—Naix | 1.81 (6) | C6—C1—C2—C3 | 1.1 (3) |
| O3ii—Na—O1—S1 | 49.96 (10) | S1—C1—C6—C5 | 177.54 (18) |
| O3ii—Na—O1—Naix | −113.48 (7) | C2—C1—C6—C5 | −1.4 (3) |
| O4iii—Na—O1—S1 | −176.30 (14) | I1A—C2—C3—C4 | −179.9 (2) |
| O4iii—Na—O1—Naix | 20.27 (19) | C1—C2—C3—C4 | −0.1 (3) |
| O1iv—Na—O1—S1 | −38.71 (11) | C2—C3—C4—C5 | −0.6 (4) |
| O1iv—Na—O1—Naix | 157.85 (7) | C3—C4—C5—C6 | 0.3 (4) |
| O1—Na—O4—Naiii | −158.02 (6) | C4—C5—C6—C1 | 0.7 (4) |
| Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, −y, −z+1; (iii) −x+1, −y+1, −z+1; (iv) x, −y+1/2, z+1/2; (v) x, −y−1/2, z+1/2; (vi) x, −y−1/2, z−1/2; (vii) −x, y−1/2, −z+1/2; (viii) −x+1, y−1/2, −z+1/2; (ix) x, −y+1/2, z−1/2; (x) −x, −y, −z; (xi) −x, y+1/2, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O4—H4A···O2ix | 0.85 | 1.98 | 2.824 (2) | 174 |
| C6—H6···O1 | 0.93 | 2.42 | 2.834 (3) | 107 |
| C5—H5···Cgix | 0.93 | 2.79 | 3.661 (3) | 156 |
| Symmetry codes: (ix) x, −y+1/2, z−1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O4—H4A···O2i | 0.85 | 1.98 | 2.824 (2) | 174 |
| C6—H6···O1 | 0.93 | 2.42 | 2.834 (3) | 107 |
| C5—H5···Cgi | 0.93 | 2.79 | 3.661 (3) | 156 |
| Symmetry codes: (i) x, −y+1/2, z−1/2. |
MNA greatfully acknowledges the Higher Education Commission, Islamabad, Pakistan, for providing him a Scholarship under the Indigenous PhD Program (PIN 042–120607-PS2–183).
Arshad, M. N., Khan, I. U., Ahmad, S., Shafiq, M. & Stoeckli-Evans, H. (2008). Acta Cryst. E64, m994.
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In the continuation to our research work on the synthesis of biologically active benzothiazine derivatives (Arshad et al., 2008; Shafiq, Khan, Tahir & Siddiqui, 2008; Shafiq, Tahir, Khan, Ahmad & Siddiqui, 2008; Tahir et al., 2008), we synthesized the title compound, (I).
The molecular structure of compound (I) is illustrated in Fig. 1. The bond lengths and bond angles, as far as the 2-iodobenzenesulfonate is concerned, are similar to those reported for the potassium salt analogue, reported on recently (Arshad et al., 2008). The Na-atom is hexa-coordinated with O-atoms, involving four from the sulfonic groups and two water molecules. The range of the Na···O distances is 2.419 (2)–2.7218 (18) Å, whereas the range of O···Na···O angles is 73.70 (5)–158.64 (7)°. In this way a two-dimensional sheet-like structure in the bc plane is formed, with the iodobenzene rings protruding above and below.
It is interesting that one of the O-atoms of the sulfonic group is not involved in coordination with the Na-atom, but makes an intermolecular hydrogen bond with a water molecule, similar to the situation on the potassium salt analogue mentioned above. Also, one of the H-atoms of the H2O molecule is not involved in intra or intermolecular H-bonding.
In the crystal structure of compound (I) a two dimensional polymeric network extending along the b axis is formed (Fig. 2). There exist O-H···O and C-H···O hydrogen bonds, and C-H···π-interactions involving the centroid, Cg, of the benzene ring, see Table 1 for details.