Poly[aqua­[μ-4-(4-chloro­phen­yl)-2-thioxo-2,3-dihydro­thia­zol-3-olato]­sodium(I)]

Hartung, J.; Bachmann, J.; Svoboda, I.; Fuess, H.

doi:10.1107/S1600536807067736

Poly[aqua[μ-4-(4-chlorophenyl)-2-thioxo-2,3-dihydrothiazol-3-olato]sodium(I)]

J. Hartung, J. Bachmann, I. Svoboda and H. Fuess

The packing of the title compound, [Na(C₉H₅ClNOS₂)(H₂O)]_n, in the crystal structure occurs by pairwise attachment of +sc- and −sc-arranged 4-(4-chlorophenyl)-2-thioxo-2,3-dihydrothiazol-3-olate subunits via S to sodium. Water molecules that are bound in the axial position of the distorted octahedral coordination octahedron give rise to a stereogenic center at sodium.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807067736/sj2452sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807067736/sj2452Isup2.hkl Contains datablock I

CCDC reference: 677405

checkCIF report

Key indicators

Single-crystal X-ray study
T = 300 K
Mean (C-C) = 0.013 Å
R factor = 0.080
wR factor = 0.173
Data-to-parameter ratio = 15.2

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT213_ALERT_2_B Atom C4      has ADP max/min Ratio .............       5.00 oblat
PLAT340_ALERT_3_B Low Bond Precision on C-C Bonds (x 1000) Ang ...         13
PLAT731_ALERT_1_B Bond    Calc    3.578(5), Rep  3.5780(10) ......       5.00 su-Ra
              NA1  -NA1     1.555   3.454
PLAT731_ALERT_1_B Bond    Calc    3.578(5), Rep  3.5780(10) ......       5.00 su-Ra
              NA1  -NA1     1.555   3.455
PLAT731_ALERT_1_B Bond    Calc    4.168(5), Rep  4.1680(10) ......       5.00 su-Ra
              NA1  -NA1     1.555   1.565
PLAT731_ALERT_1_B Bond    Calc    4.168(5), Rep  4.1680(10) ......       5.00 su-Ra
              NA1  -NA1     1.555   1.545

Alert level C
SHFSU01_ALERT_2_C  The absolute value of parameter shift to su ratio > 0.05
            Absolute value of the parameter shift to su ratio given   0.069
            Additional refinement cycles may be required.
PLAT080_ALERT_2_C Maximum Shift/Error ............................       0.07
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.38 Ratio

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           26.37
           From the CIF: _reflns_number_total               2288
           Count of symmetry unique reflns         1290
           Completeness (_total/calc)            177.36%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       998
           Fraction of Friedel pairs measured     0.774
           Are heavy atom types Z>Si present        yes
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         10

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

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

Comment top

Neutralization of 4(4-chlorophenyl)-3-hydroxythiazole-2(3H)-thione (Hartung et al., 1999) with sodium hydroxide in CH₃OH furnishes sodium 4-(4-chlorophenyl)-2-thiooxo-2,3-dihydrothiazole-3-olate. The compound crystallizes as monohydrate, (I), from a saturated solution of CH₃CN/hexane as yellowish prisms. The compound was investigated by X-ray diffraction in order to explore the structural chemistry of an alkali metal thiohydroxamate. The results of the study are summarized in the following section.

Fundamental differences between heterocyclic subunits of sodium 4-(4-chlorophenyl)-2-thiooxo-2,3-dihydrothiazole-3-olate monohydrate, (I) (Fig. 1), and the parent acid, i.e., 4(4-chlorophenyl)-3-hydroxythiazole-2(3H)-thione (Hartung et al., 1999) originate from a shortening of the N3—O3 distance from 1.379 (2) Å to 1.329 (8) Å and a lengthening of C2—S2 from 1.684 (2) Å to 1.699 (8) Å. The N3—O1 distance in (I) is closer to values reported for heterocyclic N– oxides than for thiohydroxamic acids (Hartung et al., 1996, 1999, 2007). The C2—S2 bond length lies in between typical values of C—S single and double bonds (Allen et al., 1987, Hartung et al., 1999). The distance C2—N3 [1.33 (1) Å] in sodium salt (I) agrees with the corresponding bond length of 4(4-chlorophenyl)-3-hydroxythiazole-2(3H)-thione (Hartung et al., 1999).

The parameters of the thiohydroxamate functional group in (I) are distinctively different from distances reported for 4(4-chlorophenyl)-3-isopropoxy-thiazole-2(3H)-thione [N3—O1 = 1.369 (3) Å, C2—S2 = 1.658 (3) Å, C2—N3 = 1.353 (3) Å] and further N-alkoxy derivatives thereof (Hartung et al., 1999). One possible explanation for this finding is associated with a significant contribution of the N-oxidothiolato formulae for the description of ground state properties of (I) apart from the well established thione resonance formulae. Support for this argumentation comes from sodium atom positioning in the unit cell of (I). The proximity to the metal is in line with 4-(4-chlorophenyl)-2-thiooxo-2,3-dihydrothiazole-3-olate binding as monodentate S-donor ligand to sodium [Na1—S1 = 3.001 (4) Å, S2—Na1A= 2.998 (4) Å, S2—Na1B = 2.958 (4) Å, S2—Na1A = 2.961 (4) Å]. The N-oxide oxygen atom O1 forms hydrogen bonds toward the hydrate water that is attached at either side of the apex of a octahedrally distorted coordination polyhedron at sodium [N3—O1···H2 = 162.2 (3) °, O1···O2A = 2.770 (4) Å] (Figure 2). O1 therefore does not participate in a chelate type of interaction with the metal atom [Na1···O1 = 3.855 (5) A].

The p-chlorophenyl substituent is characterized by two different arrangements with respect to the heterocyclic core, i.e. positive (+) and negative (-) synclinal [N3—C4—C6—C7 = ± 42 (1) °]. The sodium atom is offset from the heterocyclic plane by Na1—S2—C2—N3 = 53.9 (8) °. A pairwise +sc and –sc arrangement of 4-(4-chlorophenyl)-2-thiooxo-2,3-dihydrothiazole-3-olate entities in the equatorial plane in association with a non linearity of the O2—Na1—O2A axis [162.1 (3) °] gives rise to a stereogenic center at sodium (Fig. 2). Chirality thus originates from the packing of individual components of (I) in the solid state.

Related literature top

For related literature, see: Allen et al. (1987); Hartung et al. (1996, 1999, 2007); Nardelli (1999).

Experimental top

Sodium hydroxide (40.0 mg, 1.00 mmol, 1 equiv) was added to a solution of 4-(4-chlorphenyl)-3-hydroxythiazol-2(3H)-thione (244 mg, 1.00 mmol) in CH₃OH (5 ml) at 294 K. The reaction mixture was stirred at this temperature for 1.5 h. The volatiles were subsequently removed to afford a yellowish powder. The material was freeze-dried and subsequently dissolved in CH₃CN/hexane [1/1 (v/v)]. Yellowish prisms suitable for X-ray diffraction were grown by slowly allowing the solvent to evaporate at 293 K. Analysis calculated for C₉H₇ClNNaO₂S₂ (283.7 g/mol): C 38.10, H 2.49, N 4.94%; found C 38.15, H 2.39, N 4.92%; ¹H NMR (400 MHz, DMSO, p.p.m.): 7.06 (s, 1 H), 7.44 (d, J = 8.52 Hz, 2 H), 8.01 (d, J = 8.52 Hz, 2 H); ¹³C (150 MHz, DMSO, p.p.m.): 104.5, 127.9, 129.5, 130.3, 132.8, 142.0, 162.2.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997; program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top

	Fig. 1. Molecular structure of (I). Displacement ellipsoids are plotted at the 50% probability level.
	Fig. 2. Packing and hydrogen bonding (dashed lines) of (I) in the solid state. S atoms are depicted in yellow, Cl in green, O in red, N in blue, and Na in gray).

poly[aqua[µ-4-(4-chlorophenyl)-2-thioxo-2,3-dihydrothiazol-\3-olato]sodium(I)] top

Crystal data top

[Na(C₉H₅ClNOS₂)(H₂O)]	F(000) = 576
M_r = 283.72	D_x = 1.623 Mg m⁻³
Orthorhombic, Pca2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 1313 reflections
a = 39.264 (5) Å	θ = 2.1–23.1°
b = 4.168 (1) Å	µ = 0.71 mm⁻¹
c = 7.097 (1) Å	T = 300 K
V = 1161.4 (4) Å³	Prism, light yellow
Z = 4	0.60 × 0.28 × 0.02 mm

Data collection top

Oxford Diffraction Xcalibur with Sapphire CCD detector diffractometer	2288 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1860 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
Detector resolution: 8.4012 pixels mm^-1	θ_max = 26.4°, θ_min = 3.1°
Rotation method data acquisition using ω and ϕ scans	h = −47→48
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	k = −2→5
T_min = 0.677, T_max = 0.986	l = −8→8
5052 measured reflections

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)] = 0.081	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.173	w = 1/[σ²(F_o²) + 10.6487P] where P = (F_o² + 2F_c²)/3
S = 1.20	(Δ/σ)_max = 0.069
2288 reflections	Δρ_max = 0.61 e Å⁻³
151 parameters	Δρ_min = −0.83 e Å⁻³
10 restraints	Absolute structure: Flack (1983), 1009 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.1 (2)

Crystal data top

[Na(C₉H₅ClNOS₂)(H₂O)]	V = 1161.4 (4) Å³
M_r = 283.72	Z = 4
Orthorhombic, Pca2₁	Mo Kα radiation
a = 39.264 (5) Å	µ = 0.71 mm⁻¹
b = 4.168 (1) Å	T = 300 K
c = 7.097 (1) Å	0.60 × 0.28 × 0.02 mm

Data collection top

Oxford Diffraction Xcalibur with Sapphire CCD detector diffractometer	2288 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	1860 reflections with I > 2σ(I)
T_min = 0.677, T_max = 0.986	R_int = 0.036
5052 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.081	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.173	w = 1/[σ²(F_o²) + 10.6487P] where P = (F_o² + 2F_c²)/3
S = 1.20	Δρ_max = 0.61 e Å⁻³
2288 reflections	Δρ_min = −0.83 e Å⁻³
151 parameters	Absolute structure: Flack (1983), 1009 Friedel pairs
10 restraints	Absolute structure parameter: 0.1 (2)

Special details top

Experimental. empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm]

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
C2	−0.1784 (2)	−0.0666 (19)	0.0522 (12)	0.0262 (19)
C4	−0.1251 (2)	0.049 (2)	0.1720 (12)	0.028 (2)
C5	−0.1183 (3)	0.058 (3)	−0.0110 (13)	0.049 (3)
H5	−0.0969	0.1047	−0.0602	0.059*
C6	−0.1010 (2)	0.136 (2)	0.3269 (12)	0.030 (2)
C7	−0.0672 (2)	0.018 (3)	0.3149 (14)	0.041 (3)
H7	−0.0608	−0.1245	0.2202	0.049*
C8	−0.0438 (2)	0.122 (3)	0.4503 (16)	0.043 (3)
H8	−0.0211	0.0592	0.4419	0.051*
C9	−0.0540 (2)	0.314 (3)	0.5942 (14)	0.038 (3)
C10	−0.0872 (2)	0.429 (2)	0.6068 (15)	0.037 (2)
H10	−0.0936	0.5677	0.7031	0.044*
C11	−0.1107 (2)	0.330 (2)	0.4701 (12)	0.030 (2)
H11	−0.1332	0.3973	0.4781	0.036*
N3	−0.15955 (17)	−0.031 (2)	0.2072 (9)	0.0271 (18)
O1	−0.17113 (14)	−0.0646 (14)	0.3820 (7)	0.0230 (13)
O2	−0.28942 (14)	0.4205 (16)	−0.0027 (9)	0.0314 (15)
H2A	−0.302 (2)	0.266 (16)	−0.047 (12)	0.038*
H2B	−0.299 (2)	0.587 (15)	−0.058 (12)	0.038*
S1	−0.15330 (7)	−0.0274 (8)	−0.1467 (3)	0.0431 (7)
S2	−0.22082 (5)	−0.1443 (5)	0.0407 (3)	0.0271 (4)
Cl1	−0.02523 (8)	0.4352 (8)	0.7662 (5)	0.0758 (11)
Na1	−0.25584 (8)	0.3625 (9)	0.2703 (5)	0.0320 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C2	0.034 (4)	0.021 (5)	0.023 (4)	−0.004 (3)	0.002 (4)	0.015 (5)
C4	0.030 (4)	0.022 (5)	0.033 (5)	−0.001 (4)	0.006 (3)	0.024 (4)
C5	0.042 (6)	0.076 (9)	0.031 (5)	−0.010 (6)	0.009 (4)	−0.007 (6)
C6	0.030 (4)	0.023 (5)	0.037 (5)	−0.004 (4)	−0.001 (4)	−0.002 (4)
C7	0.037 (5)	0.041 (6)	0.045 (7)	−0.004 (5)	0.003 (4)	−0.005 (5)
C8	0.027 (5)	0.034 (6)	0.067 (7)	−0.005 (5)	−0.005 (5)	0.010 (6)
C9	0.033 (5)	0.032 (6)	0.050 (7)	−0.008 (5)	−0.016 (4)	0.022 (5)
C10	0.044 (6)	0.028 (6)	0.039 (5)	−0.004 (5)	−0.003 (4)	−0.003 (4)
C11	0.031 (5)	0.024 (5)	0.034 (5)	−0.002 (4)	0.002 (4)	0.000 (4)
N3	0.021 (3)	0.035 (5)	0.026 (4)	0.006 (3)	0.001 (3)	0.007 (4)
O1	0.032 (3)	0.018 (3)	0.018 (3)	−0.002 (3)	0.006 (2)	0.000 (3)
O2	0.025 (3)	0.032 (4)	0.037 (4)	0.005 (3)	−0.008 (3)	0.003 (3)
S1	0.0447 (14)	0.0600 (19)	0.0245 (11)	−0.0061 (14)	0.0058 (11)	0.0009 (15)
S2	0.0295 (10)	0.0234 (10)	0.0283 (10)	−0.0021 (9)	−0.0025 (10)	0.0016 (12)
Cl1	0.070 (2)	0.061 (2)	0.097 (3)	−0.0061 (17)	−0.048 (2)	−0.006 (2)
Na1	0.037 (2)	0.0337 (18)	0.0253 (17)	0.0020 (17)	−0.0014 (16)	0.0000 (19)

Geometric parameters (Å, º) top

C2—N3	1.334 (10)	C11—H11	0.9300
C2—S2	1.699 (8)	N3—O1	1.329 (8)
C2—S1	1.729 (9)	O2—Na1	2.356 (7)
C4—C5	1.326 (13)	O2—Na1ⁱ	2.411 (7)
C4—N3	1.415 (10)	O2—H2A	0.88 (5)
C4—C6	1.495 (12)	O2—H2B	0.89 (5)
C5—S1	1.716 (10)	S2—Na1ⁱⁱ	2.958 (4)
C5—H5	0.9300	S2—Na1ⁱⁱⁱ	2.961 (4)
C6—C11	1.352 (12)	S2—Na1ⁱ	2.998 (4)
C6—C7	1.420 (12)	S2—Na1	3.001 (4)
C7—C8	1.398 (13)	Na1—O2^iv	2.411 (7)
C7—H7	0.9300	Na1—S2^v	2.958 (4)
C8—C9	1.359 (14)	Na1—S2^vi	2.961 (4)
C8—H8	0.9300	Na1—S2^iv	2.998 (4)
C9—C10	1.389 (13)	Na1—Na1ⁱ	3.5780 (10)
C9—Cl1	1.738 (9)	Na1—Na1^iv	3.5780 (10)
C10—C11	1.402 (12)	Na1—Na1^vi	4.1680 (10)
C10—H10	0.9300	Na1—Na1ⁱⁱⁱ	4.1680 (10)

N3—C2—S2	127.2 (6)	Na1ⁱ—S2—Na1	73.23 (9)
N3—C2—S1	110.3 (6)	O2—Na1—O2^iv	162.1 (3)
S2—C2—S1	122.5 (5)	O2—Na1—S2^v	106.8 (2)
C5—C4—N3	111.8 (9)	O2^iv—Na1—S2^v	74.03 (18)
C5—C4—C6	125.8 (8)	O2—Na1—S2^vi	74.71 (19)
N3—C4—C6	122.1 (7)	O2^iv—Na1—S2^vi	87.46 (18)
C4—C5—S1	112.5 (8)	S2^v—Na1—S2^vi	91.06 (13)
C4—C5—H5	123.8	O2—Na1—S2^iv	115.3 (2)
S1—C5—H5	123.8	O2^iv—Na1—S2^iv	82.42 (17)
C11—C6—C7	121.1 (8)	S2^v—Na1—S2^iv	88.82 (11)
C11—C6—C4	121.3 (8)	S2^vi—Na1—S2^iv	169.51 (13)
C7—C6—C4	117.6 (8)	O2—Na1—S2	83.24 (19)
C8—C7—C6	117.7 (9)	O2^iv—Na1—S2	95.48 (18)
C8—C7—H7	121.2	S2^v—Na1—S2	169.51 (13)
C6—C7—H7	121.2	S2^vi—Na1—S2	88.70 (11)
C9—C8—C7	120.4 (9)	S2^iv—Na1—S2	89.52 (12)
C9—C8—H8	119.8	O2—Na1—Na1ⁱ	41.94 (16)
C7—C8—H8	119.8	O2^iv—Na1—Na1ⁱ	124.6 (2)
C8—C9—C10	121.9 (9)	S2^v—Na1—Na1ⁱ	133.11 (9)
C8—C9—Cl1	120.4 (8)	S2^vi—Na1—Na1ⁱ	52.77 (9)
C10—C9—Cl1	117.7 (9)	S2^iv—Na1—Na1ⁱ	132.39 (9)
C9—C10—C11	118.1 (10)	S2—Na1—Na1ⁱ	53.34 (9)
C9—C10—H10	120.9	O2—Na1—Na1^iv	152.5 (2)
C11—C10—H10	120.9	O2^iv—Na1—Na1^iv	40.77 (15)
C6—C11—C10	120.7 (9)	S2^v—Na1—Na1^iv	52.85 (8)
C6—C11—H11	119.6	S2^vi—Na1—Na1^iv	119.08 (11)
C10—C11—H11	119.7	S2^iv—Na1—Na1^iv	53.43 (8)
O1—N3—C2	124.6 (7)	S2—Na1—Na1^iv	118.65 (11)
O1—N3—C4	121.1 (6)	Na1ⁱ—Na1—Na1^iv	165.3 (2)
C2—N3—C4	114.2 (7)	O2—Na1—Na1^vi	84.11 (18)
Na1—O2—Na1ⁱ	97.3 (2)	O2^iv—Na1—Na1^vi	84.24 (18)
Na1—O2—H2A	123 (6)	S2^v—Na1—Na1^vi	45.98 (8)
Na1ⁱ—O2—H2A	97 (6)	S2^vi—Na1—Na1^vi	46.04 (8)
Na1—O2—H2B	134 (6)	S2^iv—Na1—Na1^vi	134.80 (8)
Na1ⁱ—O2—H2B	96 (6)	S2—Na1—Na1^vi	134.74 (8)
H2A—O2—H2B	100 (6)	Na1ⁱ—Na1—Na1^vi	90.0
C5—S1—C2	91.0 (4)	Na1^iv—Na1—Na1^vi	90.0
C2—S2—Na1ⁱⁱ	117.9 (3)	O2—Na1—Na1ⁱⁱⁱ	95.89 (18)
C2—S2—Na1ⁱⁱⁱ	124.2 (3)	O2^iv—Na1—Na1ⁱⁱⁱ	95.76 (18)
Na1ⁱⁱ—S2—Na1ⁱⁱⁱ	74.38 (9)	S2^v—Na1—Na1ⁱⁱⁱ	134.02 (8)
C2—S2—Na1ⁱ	101.3 (3)	S2^vi—Na1—Na1ⁱⁱⁱ	133.96 (8)
Na1ⁱⁱ—S2—Na1ⁱ	88.82 (11)	S2^iv—Na1—Na1ⁱⁱⁱ	45.20 (8)
Na1ⁱⁱⁱ—S2—Na1ⁱ	134.38 (7)	S2—Na1—Na1ⁱⁱⁱ	45.26 (8)
C2—S2—Na1	106.8 (3)	Na1ⁱ—Na1—Na1ⁱⁱⁱ	90.0
Na1ⁱⁱ—S2—Na1	134.38 (7)	Na1^iv—Na1—Na1ⁱⁱⁱ	90.0
Na1ⁱⁱⁱ—S2—Na1	88.70 (11)	Na1^vi—Na1—Na1ⁱⁱⁱ	180.000 (1)

N3—C4—C5—S1	0.3 (14)	Na1ⁱ—O2—Na1—S2	−39.9 (2)
C6—C4—C5—S1	−174.8 (8)	Na1ⁱ—O2—Na1—Na1^iv	175.14 (18)
C5—C4—C6—C11	133.0 (12)	Na1ⁱ—O2—Na1—Na1^vi	96.6 (2)
N3—C4—C6—C11	−41.7 (13)	Na1ⁱ—O2—Na1—Na1ⁱⁱⁱ	−83.4 (2)
C5—C4—C6—C7	−45.0 (15)	C2—S2—Na1—O2	129.3 (3)
N3—C4—C6—C7	140.3 (10)	Na1ⁱⁱ—S2—Na1—O2	−38.8 (3)
C11—C6—C7—C8	−3.5 (15)	Na1ⁱⁱⁱ—S2—Na1—O2	−105.24 (18)
C4—C6—C7—C8	174.5 (9)	Na1ⁱ—S2—Na1—O2	32.28 (18)
C6—C7—C8—C9	4.0 (16)	C2—S2—Na1—O2^iv	−32.8 (3)
C7—C8—C9—C10	−3.7 (16)	Na1ⁱⁱ—S2—Na1—O2^iv	159.16 (19)
C7—C8—C9—Cl1	178.3 (8)	Na1ⁱⁱⁱ—S2—Na1—O2^iv	92.68 (18)
C8—C9—C10—C11	2.7 (15)	Na1ⁱ—S2—Na1—O2^iv	−129.80 (19)
Cl1—C9—C10—C11	−179.2 (7)	C2—S2—Na1—S2^v	−34.2 (10)
C7—C6—C11—C10	2.7 (14)	Na1ⁱⁱ—S2—Na1—S2^v	157.7 (7)
C4—C6—C11—C10	−175.2 (8)	Na1ⁱⁱⁱ—S2—Na1—S2^v	91.2 (9)
C9—C10—C11—C6	−2.2 (14)	Na1ⁱ—S2—Na1—S2^v	−131.3 (9)
S2—C2—N3—O1	3.1 (13)	C2—S2—Na1—S2^vi	54.6 (3)
S1—C2—N3—O1	−176.2 (7)	Na1ⁱⁱ—S2—Na1—S2^vi	−113.52 (17)
S2—C2—N3—C4	−177.0 (7)	Na1ⁱⁱⁱ—S2—Na1—S2^vi	180.0
S1—C2—N3—C4	3.7 (10)	Na1ⁱ—S2—Na1—S2^vi	−42.48 (9)
C5—C4—N3—O1	177.3 (9)	C2—S2—Na1—S2^iv	−115.1 (3)
C6—C4—N3—O1	−7.4 (14)	Na1ⁱⁱ—S2—Na1—S2^iv	76.8 (2)
C5—C4—N3—C2	−2.7 (13)	Na1ⁱⁱⁱ—S2—Na1—S2^iv	10.34 (13)
C6—C4—N3—C2	172.7 (8)	Na1ⁱ—S2—Na1—S2^iv	147.86 (14)
C4—C5—S1—C2	1.5 (10)	C2—S2—Na1—Na1ⁱ	97.1 (3)
N3—C2—S1—C5	−2.9 (8)	Na1ⁱⁱ—S2—Na1—Na1ⁱ	−71.04 (19)
S2—C2—S1—C5	177.7 (6)	Na1ⁱⁱⁱ—S2—Na1—Na1ⁱ	−137.52 (9)
N3—C2—S2—Na1ⁱⁱ	−135.5 (7)	C2—S2—Na1—Na1^iv	−68.2 (3)
S1—C2—S2—Na1ⁱⁱ	43.7 (6)	Na1ⁱⁱ—S2—Na1—Na1^iv	123.7 (2)
N3—C2—S2—Na1ⁱⁱⁱ	−46.0 (9)	Na1ⁱⁱⁱ—S2—Na1—Na1^iv	57.21 (18)
S1—C2—S2—Na1ⁱⁱⁱ	133.2 (4)	Na1ⁱ—S2—Na1—Na1^iv	−165.27 (19)
N3—C2—S2—Na1ⁱ	129.8 (8)	C2—S2—Na1—Na1^vi	54.6 (3)
S1—C2—S2—Na1ⁱ	−51.0 (6)	Na1ⁱⁱ—S2—Na1—Na1^vi	−113.52 (17)
N3—C2—S2—Na1	54.1 (8)	Na1ⁱⁱⁱ—S2—Na1—Na1^vi	180.0
S1—C2—S2—Na1	−126.7 (5)	Na1ⁱ—S2—Na1—Na1^vi	−42.48 (9)
Na1ⁱ—O2—Na1—O2^iv	47.1 (12)	C2—S2—Na1—Na1ⁱⁱⁱ	−125.4 (3)
Na1ⁱ—O2—Na1—S2^v	137.05 (17)	Na1ⁱⁱ—S2—Na1—Na1ⁱⁱⁱ	66.48 (17)
Na1ⁱ—O2—Na1—S2^vi	50.6 (2)	Na1ⁱ—S2—Na1—Na1ⁱⁱⁱ	137.52 (9)
Na1ⁱ—O2—Na1—S2^iv	−126.10 (17)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1ⁱ	0.88 (5)	1.80 (5)	2.675 (8)	175 (9)
O2—H2A···N3ⁱ	0.88 (5)	2.61 (6)	3.434 (9)	156 (8)
O2—H2B···O1^vii	0.89 (5)	1.91 (6)	2.770 (8)	164 (9)

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

Experimental details

Crystal data
Chemical formula	[Na(C₉H₅ClNOS₂)(H₂O)]
M_r	283.72
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	300
a, b, c (Å)	39.264 (5), 4.168 (1), 7.097 (1)
V (Å³)	1161.4 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.71
Crystal size (mm)	0.60 × 0.28 × 0.02

Data collection
Diffractometer	Oxford Diffraction Xcalibur with Sapphire CCD detector diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2007)
T_min, T_max	0.677, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	5052, 2288, 1860
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.081, 0.173, 1.20
No. of reflections	2288
No. of parameters	151
No. of restraints	10
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
	w = 1/[σ²(F_o²) + 10.6487P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	0.61, −0.83
Absolute structure	Flack (1983), 1009 Friedel pairs
Absolute structure parameter	0.1 (2)

Computer programs: CrysAlis CCD (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 1997, SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003) and ORTEP-3 (Farrugia, 1997).