A co-crystal of nona­hydrated disodium(II) with mixed anions from m-chloro­benzoic acid and furosemide

London, B.K.; Claville, M.O.F.; Babu, S.; Fronczek, F.R.; Uppu, R.M.

doi:10.1107/S2056989015017430

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ISSN: 2056-9890

Volume 71| Part 10| October 2015| Pages 1266-1269

doi:10.1107/S2056989015017430

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A co-crystal of nonahydrated disodium(II) with mixed anions from m-chlorobenzoic acid and furosemide

Bianca King London,^a Michelle O. Fletcher Claville,^b Sainath Babu,^b Frank R. Fronczek ^c and Rao M. Uppu ^a ^*

^aEnvironmental Toxicology PhD Program and the Health Research Center, Southern University and A&M College, Baton Rouge, LA 70813, USA, ^bSchool of Science, Hampton University, Hampton, VA 23668, USA, and ^cDepartment of Chemistry, Louisiana State University, Baton Rouge, LA 70803-1804, USA
^*Correspondence e-mail: rao_uppu@subr.edu

Edited by S. Parkin, University of Kentucky, USA (Received 1 July 2015; accepted 17 September 2015; online 30 September 2015)

In the title compound, [Na₂(H₂O)₉](C₇H₄ClO₂)(C₁₂H₁₀ClN₂O₅S) {systematic name: catena-poly[[[triaquasodium(I)]-di-μ-aqua-[triaquasodium(I)]-μ-aqua] 3-chlorobenzoate 4-chloro-2-[(furan-2-ylmethyl)amino]-5-sulfamoylbenzoate]}, both the original m-chlorobenzoic acid and furosemide exist with deprotonated carboxylates, and the sodium cations and water molecules exist in chains with stoichiometry [Na₂(OH₂)₉]²⁺ that propagate in the [-110] direction. Each of the two independent Na⁺ ions is coordinated by three monodentate water molecules, two double-water bridges, and one single-water bridge. There is considerable cross-linking between the [Na₂(OH₂)₉]²⁺ chains and to furosemide sulfonamide and carboxylate by intermolecular O—H⋯O hydrogen bonds. All hydrogen-bond donors participate in a complex two-dimensional array parallel to the ab plane. The furosemide NH group donates an intramolecular hydrogen bond to the carboxylate group, and the furosemide NH₂ group donates an intramolecular hydrogen bond to the Cl atom and an intermolecular one to the m-chlorobenzoate O atom. The plethora of hydrogen-bond donors on the cation/water chain leads to many large rings, up to graph set R₄⁴(24), involving two chains and two furosemide anions. The chlorobenzoate is involved in only one R₂²(8) ring, with two water molecules cis-coordinated to Na. The furan O atom is not hydrogen bonded.

Keywords: crystal structure; loop diuretics; co-crystals; pharmaceutical formulations; hydrogen bonding.

CCDC reference: 1425658

1. Chemical context

Furosemide is a widely used diuretic for the treatment of hypertension and edema (Krumlovsky & del Greco, 1976 ; Musini et al., 2015 ), and to a lesser extent, hypercalcemia (Belen et al., 2014 ; Carvalhana et al., 2006 ). While this furan-containing compound is of interest, the toxicity elicited by these core compounds is not well understood. The free furan itself is a known hepato-carcinogen and toxicant, as studied in rats (Gill et al., 2010 ) and mice (Terrell et al., 2014 ). The epoxide metabolite of furans, formed in CYP450-mediated oxidations, can isomerize to highly reactive electrophilic intermediates such as cis-2-butene-1,4-dial (Chen et al., 1995 ; Peterson 2015 ; Vargas et al., 1998 ).

We have performed the oxidation of furosemide with m-chloroperbenzoic acid (m-CPBA), and isolated various epoxide and isomerized products in support of our efforts to understand this type of toxicity mechanism, and to also identify potential biomarkers for furosemide in humans. During the separation and drying of the products of the furosemide–m-CPBA reaction, we observed the formation of crystals in the mother liquor (the organic layer). Analysis of these crystals by X-ray crystallography revealed a disodium nonahydrate co-crystal with furosemide (starting material) and m-chlorobenzoic acid (an inadvertent contaminant or the reduced product of m-CPBA). Analogous to the known properties of co-crystals of furosemide with nicotinamide and their pharmaceutical importance (Aitipamula et al., 2012 ; Chadha et al., 2012 ; Goud et al., 2012 ; Stepanovs & Mishnev, 2012 ; Ueto et al., 2012 ), we believe that the co-crystals of furosemide with m-chlorobenzoic acid could have useful applications in drug development and may lead to formulations with improved potency, solubility, and stability. Therefore, this serendipitous finding may have important applications for improving furosemide bioavailability.

2. Structural commentary

The asymmetric unit is illustrated in Fig. 1. The furosemide moiety is present as the monoanion, with the COOH group deprotonated, N2 as NH and the primary amine nitrogen N1 as NH₂. The m-chlorobenzoic acid moiety is also deprotonated. Balancing the charge of the two types of anions are two independent sodium cations, both of which are hexacoordinate, with Na⋯O(water) distances in the range 2.3558 (13)–2.4500 (13) Å. Each Na⁺ cation is coordinated by three monodentate water molecules, two double-water bridge molecules, and one single-water bridge molecule, as shown in Fig. 2. Thus, centrosymmetric Na₂(OH₂)₈ units are linked by single water bridges, forming chains in the [ $[\overline{1}]$ 10] direction.

Figure 1
The asymmetric unit with 50% ellipsoids.

Figure 2
A portion of the Na–water chain, showing the centrosymmetric Na₂(OH₂)₂ bridges and the single water bridges.

3. Supramolecular features

Hydrogen bonding is extensive (Table 1), with all 21 hydrogen-bond donors involved. Notable features of the two-dimensional hydrogen-bonding pattern (Etter et al.. 1990 ) are sulfonamide N—H⋯O bonds to m-chlorobenzoate, secondary amine N—H⋯O hydrogen bonds to furosemide anion (carboxylate), and water O—H⋯O hydrogen bonds to the sulfonamide O atom, to both types of carboxylates, and to other water molecules. The direction of the normal to the hydrogen-bonding network is [001]. The furan oxygen atom O5 is not involved in the hydrogen bonding. A supramolecular layer in the ab plane is shown in Fig. 3.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H11N⋯Cl1	0.839 (18)	2.767 (17)	3.2848 (16)	121.6 (14)
N1—H12N⋯O6	0.872 (18)	1.920 (18)	2.7905 (17)	175.3 (17)
N2—H2N⋯O4	0.860 (18)	1.906 (18)	2.6199 (16)	139.4 (16)
O8—H81⋯O3ⁱ	0.83 (2)	2.07 (2)	2.8737 (16)	162 (2)
O8—H82⋯O15ⁱⁱ	0.82 (2)	2.00 (2)	2.8025 (16)	168 (2)
O9—H91⋯O16ⁱⁱⁱ	0.86 (2)	1.99 (2)	2.8499 (15)	172 (2)
O9—H92⋯O7	0.81 (2)	2.10 (2)	2.8867 (16)	167 (2)
O10—H101⋯O11ⁱⁱⁱ	0.78 (2)	1.96 (2)	2.7444 (16)	174 (2)
O10—H102⋯O3^iv	0.93 (2)	1.90 (2)	2.8271 (15)	171 (2)
O11—H111⋯O6	0.84 (2)	1.89 (2)	2.7296 (16)	176 (2)
O11—H112⋯O12	0.81 (2)	2.08 (2)	2.8641 (16)	162 (2)
O12—H121⋯O4ⁱ	0.85 (2)	1.96 (2)	2.7962 (16)	171 (2)
O12—H122⋯O2^v	0.76 (2)	2.12 (2)	2.8593 (15)	165 (2)
O13—H131⋯O7ⁱ	0.81 (2)	2.01 (2)	2.8082 (15)	169 (2)
O13—H132⋯O3ⁱ	0.85 (2)	1.97 (2)	2.7939 (15)	165 (2)
O14—H141⋯O4ⁱ	0.76 (2)	1.99 (2)	2.7265 (16)	164 (2)
O14—H142⋯O1	0.74 (2)	2.31 (2)	3.0019 (17)	156 (2)
O15—H151⋯O14^v	0.85 (2)	1.92 (2)	2.7766 (16)	178 (2)
O15—H152⋯O7ⁱ	0.80 (2)	2.14 (2)	2.8545 (16)	149 (2)
O16—H161⋯O10^v	0.798 (19)	1.990 (19)	2.7857 (16)	175.7 (18)
O16—H162⋯O1^v	0.80 (2)	2.20 (2)	2.9852 (15)	165.8 (17)
Symmetry codes: (i) x-1, y+1, z; (ii) -x-1, -y+2, -z+1; (iii) -x, -y+1, -z+1; (iv) -x+1, -y+1, -z+1; (v) x-1, y, z.

Figure 3
A supramolecular layer of the title compound in the ab plane.

4. Synthesis and crystallization

Furosemide (8.2 mmol; 2.71 g), dissolved in 3 ml of dichloromethane (DCM), was added dropwise over 5 min to a solution of 8.2 mmol of m-CPBA (1.84 g) and 10.5 mmol NaHCO₃ (0.88 g) in 20 ml of DCM on ice with rapid stirring (Fig. 4). After 2 h, an additional 4 mmol of m-CPBA in 10 ml of DCM was added to the reaction mixture. Upon removal from the ice bath, 4 ml of aqueous sodium sulfite solution (10%) was added with stirring for an additional 15 min. After partitioning the layers with deionized water (resistance 18.2 M Ω cm⁻¹), the organic layer was collected and the aqueous layer was extracted with another 10 ml of DCM. The combined mixture of the organic layer was washed with 10 ml of aqueous solution of NaHCO₃ (5%, w/v), dried over anhydrous Na₂SO₄, and then subjected to partial evaporation under low pressure (ca 4 psi) at 308 K. The partially evaporated sample was left at ambient pressure and temperature overnight. Crystals were formed with slow evaporation.

Figure 4
Proposed scheme of reactions of furosemide with m-chloroperoxybenzoic acid.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms on C were idealized with C—H distances of 0.95 Å for sp² C and 0.99 Å for CH₂. Those on N and O were assigned from difference maps, and their positions refined, with O—H distances restrained to be equal. U_iso(H) were assigned as 1.2 times U_eq of the attached atoms (1.5 for water). Six reflections with Fo<<Fc were omitted from the calculations.

Table 2
Experimental details

Crystal data
Chemical formula	[Na₂(OH₂)₉](C₇H₄ClO₂)(C₁₂H₁₀ClN₂O₅S)
M_r	693.41
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	7.908 (2), 10.224 (3), 19.631 (4)
α, β, γ (°)	85.46 (2), 81.80 (2), 74.96 (2)
V (Å³)	1515.7 (7)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.39
Crystal size (mm)	0.30 × 0.25 × 0.07

Data collection
Diffractometer	Nonius KappaCCD
Absorption correction	Multi-scan (SCALEPACK; Otwinowski & Minor, 1997 )
T_min, T_max	0.893, 0.974
No. of measured, independent and observed [I > 2s(I)] reflections	17752, 10267, 7760
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.751

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.107, 1.05
No. of reflections	10267
No. of parameters	442
No. of restraints	120
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.55
Computer programs: COLLECT (Nonius, 1999 ), HKL SCALEPACK and DENZO and SCALEPACK (Otwinowski & Minor 1997), SIR97 (Altomare et al., 1999 ), SHELXL97 (Sheldrick, 2008 ) and ORTEP-3 for Windows (Farrugia, 2012 ).

Supporting information

CCDC reference: 1425658

Crystal structure: contains datablocks New_Global_Publ_Block, I. DOI: 10.1107/S2056989015017430/pk2557sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015017430/pk2557Isup2.hkl

checkCIF report

Chemical context top

Furosemide is a widely used diuretic for the treatment of hypertension and edema (Krumlovsky & del Greco, 1976; Musini et al., 2015), and to a lesser extent, hypercalcemia (Belen et al., 2014; Carvalhana et al. (2006)). This furan-containing compound is of interest; however, the toxicity elicited by these core compounds is not well understood. The free furan itself is a known hepato-carcinogen and toxicant, as studied in rats (Gill et al., 2010) and mice (Terrell et al., 2014). The epoxide metabolite of furans, formed in CYP450-mediated oxidations, can isomerize to highly reactive electrophilic intermediates such as cis-2-butene-1,4-dial (Chen et al., 1995; Peterson 2015; Vargas et al., 1998).

We have performed the oxidation of furosemide with m-chloroperbenzoic acid (m-CPBA), and isolated various epoxide and isomerized products in support of our efforts to understand this type of toxicity mechanism, and to also identify potential biomarkers for furosemide in humans. During the separation and drying of the products of the furosemide–m-CPBA reaction, we observed the formation of crystals in the mother liquor (the organic layer). Analysis of these crystals by X-ray crystallography revealed a nonahydrate co-crystal of furosemide (starting material) with that of m-chlorobenzoic acid (an inadvertent contaminant or the reduced product of m-CPBA). Analogous to the known properties of co-crystals of furosemide with nicotinamide and their pharmaceutical importance (Aitipamula et al., 2012; Chadha et al., 2012; Goud et al., 2012; Stepanovs & Mishnev, 2012; Ueto et al., 2012), we believe that the co-crystals of furosemide with m-chlorobenzoic acid could have useful applications in drug development and may lead to formulations with improved potency, solubility, and stability. Therefore, this serendipitous finding may have important applications for improving furosemide bioavailability.

Structural commentary top

The asymmetric unit is illustrated in Fig. 1. The furosemide moiety is present as the monoanion, with the COOH group deprotonated, N2 as NH and the primary amine nitrogen N1 as NH₂. The m-chlorobenzoate moiety is also deprotonated. Balancing the charge of the two types of anions are two independent sodium cations, both of which are hexacoordinate, with Na···O(water) distances in the range 2.3558 (13)–2.4500 (13) Å. Each Na⁺ cation is coordinated by three monodentate water molecules, two double-water bridge molecules, and one single-water bridge molecules, as shown in Fig. 2. Thus, centrosymmetric Na₂(OH₂)₈ units are linked by single water bridges, forming chains in the [110] direction.

Supramolecular features top

Hydrogen bonding is extensive (Table 1), with all 21 hydrogen-bond donors involved. Notable features of the two-dimensional hydrogen-bonding pattern (Etter et al.. 1990) are sulfonamide N—H···O bonds to m-chlorobenzoate, secondary amine N—H···O hydrogen bonds to furosemide carboxylate, and water O—H···O hydrogen bonds to sulfonamide O, to both types of carboxylates, and to other water molecules. The direction of the normal to the hydrogen-bonding network is [001]. The furan oxygen atom O5 is not involved in the hydrogen bonding.

Synthesis and crystallization top

Furosemide (8.2 mmol; 2.71 g), dissolved in 3 ml of dichloromethane (DCM), was added dropwise over 5 min to a solution of 8.2 mmol of m-CPBA (1.84 g) and 10.5 mmol NaHCO₃ (0.88 g) in 20 ml of DCM on ice with rapid stirring (Fig. 3). After 2 h, an additional 4 mmol of m-CPBA in 10 ml of DCM was added to the reaction mixture. Upon removal from the ice bath, 4 ml of aqueous sodium sulfite solution (10%) was added with stirring for an additional 15 min. After partitioning the layers with deionized water (resistance ~18.2 M Ω cm^-1), the organic layer was collected and the aqueous layer was extracted with another 10 ml of DCM. The combined mixture of the organic layer was washed with 10 ml of aqueous solution of NaHCO₃ (5%, w/v), dried over anhydrous Na₂SO₄, and then subjected to partial evaporation under low pressure (ca 4 psi) at 308 K. The partially evaporated sample was left at ambient pressure and temperature overnight. Crystals were formed with slow evaporation.

Refinement top

Related literature top

For the origins and functions of furosemide, see: Belen et al. (2014); Carvalhana et al. (2006); Musini et al.. (2015); Krumlovsky & del Greco (1976); Vargas et al. (1998). For related structural studies, see: Aitipamula et al. (2012); Chadha et al. (2012); Goud et al. (2012); Stepanovs & Mishnev (2012); Ueto et al. (2012). For information supporting the reported structure and analogs, see: Chen et al. (1995); Gill et al. (2010); Peterson et al. (2015); Terrell et al. (2014). For graph sets of hydrogen bonding, see: Etter et al. (1990).

Computing details top

Data collection: COLLECT (Nonius, 1999); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit with 50% ellipsoids.
	Fig. 2. A portion of the Na–water chain, showing the centrosymmetric Na₂(OH₂)₂ bridges and the single water bridges.
	Fig. 3. Proposed scheme of reactions of furosemide with m-chloroperoxybenzoic acid.
	Fig. 4. A supramolecular layer of the title compound in the ab plane.

catena-Poly[[[triaquasodium(I)]-di-µ-aqua-[triaquasodium(I)]-µ-aqua] 3-chlorobenzoate 4-chloro-2-[(furan-2-ylmethyl)amino]-5-sulfamoylbenzoate] top

Crystal data top

[Na₂(OH₂)₉](C₇H₄ClO₂)(C₁₂H₁₀ClN₂O₅S)	Z = 2
M_r = 693.41	F(000) = 720
Triclinic, P1	D_x = 1.519 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.908 (2) Å	Cell parameters from 17752 reflections
b = 10.224 (3) Å	θ = 2.5–32.6°
c = 19.631 (4) Å	µ = 0.39 mm⁻¹
α = 85.46 (2)°	T = 100 K
β = 81.80 (2)°	Lath fragment, colorless
γ = 74.96 (2)°	0.30 × 0.25 × 0.07 mm
V = 1515.7 (7) Å³

Data collection top

Nonius KappaCCD diffractometer	10267 independent reflections
Radiation source: fine-focus sealed tube	7760 reflections with I > 2s(I)
Graphite monochromator	R_int = 0.035
ω and φ scans	θ_max = 32.3°, θ_min = 2.7°
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	h = −11→11
T_min = 0.893, T_max = 0.974	k = −13→15
17752 measured reflections	l = −29→29

Refinement top

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.058P)²] where P = (F_o² + 2F_c²)/3
10267 reflections	(Δ/σ)_max = 0.001
442 parameters	Δρ_max = 0.47 e Å⁻³
120 restraints	Δρ_min = −0.55 e Å⁻³

Crystal data top

[Na₂(OH₂)₉](C₇H₄ClO₂)(C₁₂H₁₀ClN₂O₅S)	γ = 74.96 (2)°
M_r = 693.41	V = 1515.7 (7) Å³
Triclinic, P1	Z = 2
a = 7.908 (2) Å	Mo Kα radiation
b = 10.224 (3) Å	µ = 0.39 mm⁻¹
c = 19.631 (4) Å	T = 100 K
α = 85.46 (2)°	0.30 × 0.25 × 0.07 mm
β = 81.80 (2)°

Data collection top

Nonius KappaCCD diffractometer	10267 independent reflections
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	7760 reflections with I > 2s(I)
T_min = 0.893, T_max = 0.974	R_int = 0.035
17752 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	120 restraints
wR(F²) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.47 e Å⁻³
10267 reflections	Δρ_min = −0.55 e Å⁻³
442 parameters

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
Cl1	0.62548 (4)	0.49926 (3)	0.089838 (16)	0.01988 (8)
S1	0.53103 (4)	0.56412 (3)	0.252718 (16)	0.01360 (7)
O1	0.49898 (12)	0.54858 (10)	0.32676 (5)	0.01772 (19)
O2	0.61708 (13)	0.66762 (9)	0.22345 (5)	0.0186 (2)
O3	0.86565 (12)	0.10830 (9)	0.36913 (5)	0.01511 (18)
O4	0.95416 (13)	−0.04844 (9)	0.29000 (5)	0.01778 (19)
O5	0.92982 (13)	−0.22550 (10)	0.12326 (6)	0.0250 (2)
N1	0.34022 (15)	0.59988 (12)	0.22586 (6)	0.0171 (2)
H11N	0.345 (2)	0.6226 (18)	0.1837 (10)	0.021*
H12N	0.282 (2)	0.5394 (18)	0.2404 (9)	0.021*
N2	0.97465 (16)	0.03032 (12)	0.15946 (6)	0.0191 (2)
H2N	1.009 (2)	−0.0258 (18)	0.1927 (9)	0.023*
C1	0.65991 (16)	0.40639 (13)	0.22332 (6)	0.0133 (2)
C2	0.70427 (17)	0.37919 (13)	0.15334 (7)	0.0149 (2)
C3	0.81105 (18)	0.25674 (13)	0.13183 (7)	0.0165 (2)
H3	0.8422	0.2422	0.0840	0.020*
C4	0.87486 (17)	0.15226 (13)	0.18053 (7)	0.0147 (2)
C5	0.83234 (16)	0.17957 (12)	0.25209 (6)	0.0128 (2)
C6	0.72692 (16)	0.30566 (13)	0.27139 (7)	0.0131 (2)
H6	0.6996	0.3237	0.3190	0.016*
C7	0.88889 (16)	0.07359 (13)	0.30778 (7)	0.0133 (2)
C8	1.0003 (2)	−0.01178 (14)	0.08920 (7)	0.0215 (3)
H8A	1.0944	0.0249	0.0619	0.026*
H8B	0.8900	0.0247	0.0682	0.026*
C9	1.05072 (18)	−0.16262 (14)	0.08795 (7)	0.0179 (3)
C10	1.19245 (19)	−0.25494 (14)	0.05907 (7)	0.0193 (3)
H10	1.2949	−0.2372	0.0325	0.023*
C11	1.1573 (2)	−0.38525 (14)	0.07659 (7)	0.0211 (3)
H11	1.2312	−0.4709	0.0634	0.025*
C12	0.9991 (2)	−0.36173 (15)	0.11544 (9)	0.0252 (3)
H12	0.9430	−0.4302	0.1348	0.030*
Cl2	0.28737 (6)	0.23829 (4)	0.026181 (19)	0.02904 (9)
O6	0.15314 (12)	0.41020 (9)	0.27976 (5)	0.01757 (19)
O7	0.25838 (13)	0.23500 (10)	0.35073 (5)	0.01731 (19)
C13	0.31680 (17)	0.20440 (13)	0.22941 (7)	0.0147 (2)
C14	0.27177 (18)	0.25472 (13)	0.16425 (7)	0.0162 (2)
H14	0.1917	0.3408	0.1589	0.019*
C15	0.34577 (19)	0.17705 (14)	0.10766 (7)	0.0191 (3)
C16	0.4648 (2)	0.05117 (14)	0.11350 (8)	0.0230 (3)
H16	0.5148	−0.0002	0.0740	0.028*
C17	0.5091 (2)	0.00209 (15)	0.17849 (8)	0.0243 (3)
H17	0.5903	−0.0836	0.1836	0.029*
C18	0.43507 (18)	0.07803 (14)	0.23614 (7)	0.0198 (3)
H18	0.4654	0.0434	0.2804	0.024*
C19	0.23698 (16)	0.28915 (13)	0.29148 (7)	0.0140 (2)
Na1	0.01996 (6)	0.65083 (5)	0.45870 (3)	0.01372 (11)
Na2	−0.44798 (7)	0.87445 (5)	0.44265 (3)	0.01394 (11)
O8	−0.15551 (12)	0.88218 (10)	0.46379 (5)	0.01546 (18)
H81	−0.126 (2)	0.9400 (19)	0.4362 (10)	0.023*
H82	−0.175 (2)	0.9155 (18)	0.5017 (10)	0.023*
O9	0.19980 (12)	0.42119 (10)	0.45986 (5)	0.01525 (18)
H91	0.295 (2)	0.4001 (18)	0.4793 (9)	0.023*
H92	0.217 (2)	0.3797 (19)	0.4253 (10)	0.023*
O10	0.18912 (12)	0.66647 (10)	0.54828 (5)	0.01560 (18)
H101	0.169 (2)	0.6053 (19)	0.5718 (10)	0.023*
H102	0.158 (2)	0.7401 (18)	0.5767 (9)	0.023*
O11	−0.10007 (13)	0.54861 (10)	0.37594 (5)	0.01550 (18)
H111	−0.026 (2)	0.5051 (18)	0.3452 (10)	0.023*
H112	−0.161 (2)	0.6123 (19)	0.3560 (9)	0.023*
O12	−0.30234 (14)	0.80747 (10)	0.33026 (5)	0.0182 (2)
H121	−0.221 (2)	0.8455 (19)	0.3142 (10)	0.027*
H122	−0.329 (2)	0.7843 (19)	0.2985 (10)	0.027*
O13	−0.47562 (13)	1.11930 (10)	0.43409 (5)	0.01560 (18)
H131	−0.543 (2)	1.1568 (19)	0.4070 (10)	0.023*
H132	−0.380 (2)	1.1303 (18)	0.4114 (10)	0.023*
O14	0.16422 (13)	0.76011 (10)	0.36697 (5)	0.01745 (19)
H141	0.108 (3)	0.802 (2)	0.3408 (10)	0.026*
H142	0.236 (3)	0.713 (2)	0.3462 (10)	0.026*
O15	−0.73738 (13)	0.97411 (10)	0.41518 (5)	0.01661 (19)
H151	−0.770 (2)	0.9090 (19)	0.4010 (9)	0.025*
H152	−0.753 (2)	1.0342 (19)	0.3861 (10)	0.025*
O16	−0.49332 (13)	0.65364 (10)	0.46360 (5)	0.01549 (18)
H161	−0.582 (2)	0.6532 (18)	0.4885 (10)	0.023*
H162	−0.494 (2)	0.6123 (18)	0.4305 (10)	0.023*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.02539 (17)	0.01556 (15)	0.01459 (14)	0.00207 (12)	−0.00343 (12)	0.00125 (11)
S1	0.01423 (14)	0.01061 (14)	0.01548 (15)	−0.00184 (11)	−0.00167 (11)	−0.00254 (11)
O1	0.0191 (5)	0.0175 (5)	0.0155 (4)	−0.0020 (4)	−0.0016 (4)	−0.0041 (4)
O2	0.0209 (5)	0.0136 (4)	0.0221 (5)	−0.0062 (4)	−0.0016 (4)	−0.0022 (4)
O3	0.0167 (4)	0.0147 (4)	0.0138 (4)	−0.0036 (4)	−0.0024 (3)	−0.0002 (3)
O4	0.0240 (5)	0.0108 (4)	0.0176 (5)	−0.0022 (4)	−0.0036 (4)	−0.0001 (3)
O5	0.0199 (5)	0.0182 (5)	0.0335 (6)	−0.0016 (4)	0.0032 (4)	−0.0038 (4)
N1	0.0153 (5)	0.0159 (5)	0.0194 (6)	−0.0022 (4)	−0.0036 (4)	0.0003 (4)
N2	0.0276 (6)	0.0118 (5)	0.0141 (5)	0.0027 (5)	−0.0032 (5)	−0.0016 (4)
C1	0.0137 (5)	0.0117 (6)	0.0144 (6)	−0.0022 (4)	−0.0020 (4)	−0.0027 (4)
C2	0.0170 (6)	0.0129 (6)	0.0146 (6)	−0.0027 (5)	−0.0039 (5)	0.0015 (4)
C3	0.0207 (6)	0.0137 (6)	0.0134 (6)	−0.0014 (5)	−0.0019 (5)	−0.0013 (4)
C4	0.0158 (6)	0.0120 (6)	0.0155 (6)	−0.0018 (5)	−0.0019 (5)	−0.0021 (4)
C5	0.0138 (5)	0.0108 (5)	0.0141 (6)	−0.0035 (5)	−0.0022 (4)	−0.0006 (4)
C6	0.0129 (5)	0.0128 (6)	0.0147 (6)	−0.0044 (5)	−0.0023 (4)	−0.0019 (4)
C7	0.0118 (5)	0.0137 (6)	0.0155 (6)	−0.0050 (5)	−0.0019 (4)	0.0002 (4)
C8	0.0317 (8)	0.0147 (6)	0.0144 (6)	0.0003 (6)	−0.0010 (5)	−0.0025 (5)
C9	0.0205 (6)	0.0153 (6)	0.0169 (6)	−0.0024 (5)	−0.0022 (5)	−0.0028 (5)
C10	0.0205 (6)	0.0173 (6)	0.0179 (6)	−0.0011 (5)	−0.0019 (5)	−0.0015 (5)
C11	0.0266 (7)	0.0137 (6)	0.0210 (7)	0.0011 (5)	−0.0064 (5)	−0.0033 (5)
C12	0.0252 (7)	0.0158 (7)	0.0351 (8)	−0.0059 (6)	−0.0027 (6)	−0.0037 (6)
Cl2	0.0479 (2)	0.02199 (18)	0.01606 (16)	−0.00506 (16)	−0.00745 (15)	−0.00001 (13)
O6	0.0176 (4)	0.0127 (4)	0.0196 (5)	0.0003 (4)	−0.0008 (4)	−0.0010 (4)
O7	0.0203 (5)	0.0165 (5)	0.0149 (4)	−0.0031 (4)	−0.0048 (4)	−0.0003 (3)
C13	0.0144 (6)	0.0130 (6)	0.0168 (6)	−0.0029 (5)	−0.0032 (5)	−0.0016 (4)
C14	0.0187 (6)	0.0114 (6)	0.0182 (6)	−0.0026 (5)	−0.0038 (5)	0.0002 (5)
C15	0.0268 (7)	0.0167 (6)	0.0146 (6)	−0.0067 (5)	−0.0036 (5)	0.0006 (5)
C16	0.0299 (7)	0.0166 (7)	0.0204 (7)	−0.0033 (6)	0.0017 (6)	−0.0047 (5)
C17	0.0282 (7)	0.0137 (6)	0.0257 (7)	0.0036 (6)	−0.0017 (6)	−0.0020 (5)
C18	0.0217 (7)	0.0156 (6)	0.0192 (6)	0.0000 (5)	−0.0031 (5)	0.0012 (5)
C19	0.0119 (5)	0.0137 (6)	0.0170 (6)	−0.0037 (5)	−0.0039 (4)	−0.0002 (4)
Na1	0.0119 (2)	0.0117 (2)	0.0173 (3)	−0.00179 (19)	−0.00343 (19)	−0.00038 (19)
Na2	0.0129 (2)	0.0116 (2)	0.0173 (3)	−0.00220 (19)	−0.00328 (19)	−0.00089 (19)
O8	0.0164 (4)	0.0126 (4)	0.0164 (5)	−0.0017 (4)	−0.0026 (4)	−0.0003 (4)
O9	0.0129 (4)	0.0153 (4)	0.0168 (5)	−0.0006 (4)	−0.0040 (4)	−0.0025 (3)
O10	0.0168 (4)	0.0128 (4)	0.0182 (5)	−0.0054 (4)	−0.0022 (4)	−0.0011 (4)
O11	0.0138 (4)	0.0139 (4)	0.0173 (5)	−0.0006 (4)	−0.0022 (4)	−0.0006 (4)
O12	0.0196 (5)	0.0178 (5)	0.0187 (5)	−0.0063 (4)	−0.0044 (4)	−0.0014 (4)
O13	0.0127 (4)	0.0158 (5)	0.0181 (5)	−0.0030 (4)	−0.0036 (4)	0.0012 (4)
O14	0.0142 (5)	0.0155 (5)	0.0207 (5)	−0.0006 (4)	−0.0008 (4)	−0.0025 (4)
O15	0.0168 (5)	0.0142 (5)	0.0205 (5)	−0.0047 (4)	−0.0065 (4)	−0.0005 (4)
O16	0.0138 (4)	0.0150 (5)	0.0184 (5)	−0.0041 (4)	−0.0020 (4)	−0.0031 (4)

Geometric parameters (Å, º) top

Cl1—C2	1.7411 (14)	C14—H14	0.9500
S1—O2	1.4418 (10)	C15—C16	1.391 (2)
S1—O1	1.4427 (10)	C16—C17	1.392 (2)
S1—N1	1.6120 (13)	C16—H16	0.9500
S1—C1	1.7604 (14)	C17—C18	1.393 (2)
O3—C7	1.2572 (16)	C17—H17	0.9500
O4—C7	1.2761 (16)	C18—H18	0.9500
O5—C9	1.3664 (17)	Na1—O14	2.3558 (13)
O5—C12	1.3703 (18)	Na1—O10	2.3946 (12)
N1—H11N	0.839 (18)	Na1—O9ⁱ	2.4090 (12)
N1—H12N	0.872 (18)	Na1—O9	2.4091 (13)
N2—C4	1.3512 (17)	Na1—O8	2.4134 (13)
N2—C8	1.4483 (18)	Na1—O11	2.4200 (12)
N2—H2N	0.860 (18)	Na2—O15	2.3709 (13)
C1—C6	1.3919 (18)	Na2—O16	2.3718 (13)
C1—C2	1.4001 (18)	Na2—O12	2.4016 (13)
C2—C3	1.3755 (19)	Na2—O13ⁱⁱ	2.4108 (12)
C3—C4	1.4163 (18)	Na2—O8	2.4294 (12)
C3—H3	0.9500	Na2—O13	2.4500 (13)
C4—C5	1.4295 (18)	O8—H81	0.83 (2)
C5—C6	1.3892 (18)	O8—H82	0.821 (19)
C5—C7	1.5066 (18)	O9—Na1ⁱ	2.4090 (12)
C6—H6	0.9500	O9—H91	0.862 (19)
C8—C9	1.4907 (19)	O9—H92	0.806 (19)
C8—H8A	0.9900	O10—H101	0.784 (19)
C8—H8B	0.9900	O10—H102	0.932 (18)
C9—C10	1.3501 (19)	O11—H111	0.842 (19)
C10—C11	1.436 (2)	O11—H112	0.811 (19)
C10—H10	0.9500	O12—H121	0.848 (19)
C11—C12	1.344 (2)	O12—H122	0.76 (2)
C11—H11	0.9500	O13—Na2ⁱⁱ	2.4108 (12)
C12—H12	0.9500	O13—H131	0.807 (19)
Cl2—C15	1.7510 (15)	O13—H132	0.848 (19)
O6—C19	1.2637 (16)	O14—H141	0.76 (2)
O7—C19	1.2623 (16)	O14—H142	0.74 (2)
C13—C18	1.3938 (19)	O15—H151	0.853 (19)
C13—C14	1.3995 (18)	O15—H152	0.803 (19)
C13—C19	1.5158 (19)	O16—H161	0.798 (19)
C14—C15	1.3857 (19)	O16—H162	0.80 (2)

O2—S1—O1	118.19 (6)	O7—C19—O6	124.65 (13)
O2—S1—N1	106.89 (7)	O7—C19—C13	118.41 (12)
O1—S1—N1	106.20 (7)	O6—C19—C13	116.94 (12)
O2—S1—C1	108.39 (6)	O14—Na1—O10	99.71 (4)
O1—S1—C1	106.54 (6)	O14—Na1—O9ⁱ	163.93 (4)
N1—S1—C1	110.57 (6)	O10—Na1—O9ⁱ	91.71 (4)
C9—O5—C12	106.30 (11)	O14—Na1—O9	103.75 (5)
S1—N1—H11N	112.4 (11)	O10—Na1—O9	81.57 (4)
S1—N1—H12N	112.1 (11)	O9ⁱ—Na1—O9	89.00 (4)
H11N—N1—H12N	116.8 (16)	O14—Na1—O8	77.59 (4)
C4—N2—C8	124.07 (12)	O10—Na1—O8	95.33 (4)
C4—N2—H2N	113.6 (12)	O9ⁱ—Na1—O8	90.19 (4)
C8—N2—H2N	121.6 (12)	O9—Na1—O8	176.78 (4)
C6—C1—C2	118.22 (12)	O14—Na1—O11	89.24 (4)
C6—C1—S1	118.85 (10)	O10—Na1—O11	159.01 (4)
C2—C1—S1	122.88 (10)	O9ⁱ—Na1—O11	83.87 (4)
C3—C2—C1	121.58 (12)	O9—Na1—O11	77.85 (4)
C3—C2—Cl1	117.22 (10)	O8—Na1—O11	105.17 (4)
C1—C2—Cl1	121.21 (10)	O15—Na2—O16	94.41 (4)
C2—C3—C4	120.46 (12)	O15—Na2—O12	99.60 (4)
C2—C3—H3	119.8	O16—Na2—O12	88.32 (4)
C4—C3—H3	119.8	O15—Na2—O13ⁱⁱ	96.08 (4)
N2—C4—C3	120.49 (12)	O16—Na2—O13ⁱⁱ	81.69 (4)
N2—C4—C5	121.12 (12)	O12—Na2—O13ⁱⁱ	162.00 (4)
C3—C4—C5	118.38 (12)	O15—Na2—O8	153.51 (4)
C6—C5—C4	119.11 (12)	O16—Na2—O8	111.98 (4)
C6—C5—C7	118.49 (11)	O12—Na2—O8	83.99 (4)
C4—C5—C7	122.30 (11)	O13ⁱⁱ—Na2—O8	85.91 (4)
C5—C6—C1	122.19 (12)	O15—Na2—O13	74.54 (4)
C5—C6—H6	118.9	O16—Na2—O13	166.06 (4)
C1—C6—H6	118.9	O12—Na2—O13	101.72 (4)
O3—C7—O4	123.35 (12)	O13ⁱⁱ—Na2—O13	90.90 (4)
O3—C7—C5	119.00 (11)	O8—Na2—O13	79.02 (4)
O4—C7—C5	117.62 (11)	Na1—O8—Na2	105.44 (4)
N2—C8—C9	110.13 (12)	Na1—O8—H81	118.9 (13)
N2—C8—H8A	109.6	Na2—O8—H81	106.7 (12)
C9—C8—H8A	109.6	Na1—O8—H82	116.0 (13)
N2—C8—H8B	109.6	Na2—O8—H82	102.7 (12)
C9—C8—H8B	109.6	H81—O8—H82	105.7 (17)
H8A—C8—H8B	108.1	Na1ⁱ—O9—Na1	91.00 (4)
C10—C9—O5	110.48 (12)	Na1ⁱ—O9—H91	105.6 (12)
C10—C9—C8	134.27 (13)	Na1—O9—H91	120.6 (12)
O5—C9—C8	115.26 (12)	Na1ⁱ—O9—H92	109.7 (13)
C9—C10—C11	106.27 (13)	Na1—O9—H92	118.4 (13)
C9—C10—H10	126.9	H91—O9—H92	108.7 (17)
C11—C10—H10	126.9	Na1—O10—H101	97.5 (13)
C12—C11—C10	106.22 (13)	Na1—O10—H102	122.0 (11)
C12—C11—H11	126.9	H101—O10—H102	105.4 (17)
C10—C11—H11	126.9	Na1—O11—H111	116.0 (11)
C11—C12—O5	110.72 (13)	Na1—O11—H112	104.5 (13)
C11—C12—H12	124.6	H111—O11—H112	105.9 (17)
O5—C12—H12	124.6	Na2—O12—H121	115.2 (13)
C18—C13—C14	119.61 (13)	Na2—O12—H122	135.5 (14)
C18—C13—C19	121.12 (12)	H121—O12—H122	103.8 (19)
C14—C13—C19	119.27 (12)	Na2ⁱⁱ—O13—Na2	89.10 (4)
C15—C14—C13	119.01 (12)	Na2ⁱⁱ—O13—H131	123.6 (13)
C15—C14—H14	120.5	Na2—O13—H131	111.3 (13)
C13—C14—H14	120.5	Na2ⁱⁱ—O13—H132	126.5 (12)
C14—C15—C16	122.04 (13)	Na2—O13—H132	106.2 (12)
C14—C15—Cl2	119.23 (11)	H131—O13—H132	98.4 (17)
C16—C15—Cl2	118.73 (11)	Na1—O14—H141	117.4 (14)
C15—C16—C17	118.54 (14)	Na1—O14—H142	113.1 (15)
C15—C16—H16	120.7	H141—O14—H142	104 (2)
C17—C16—H16	120.7	Na2—O15—H151	104.6 (12)
C16—C17—C18	120.34 (13)	Na2—O15—H152	119.8 (13)
C16—C17—H17	119.8	H151—O15—H152	106.5 (18)
C18—C17—H17	119.8	Na2—O16—H161	112.4 (13)
C17—C18—C13	120.46 (13)	Na2—O16—H162	117.0 (13)
C17—C18—H18	119.8	H161—O16—H162	106.8 (18)
C13—C18—H18	119.8

O2—S1—C1—C6	119.77 (10)	C10—C11—C12—O5	0.73 (17)
O1—S1—C1—C6	−8.40 (12)	C9—O5—C12—C11	−0.22 (17)
N1—S1—C1—C6	−123.38 (11)	C18—C13—C14—C15	0.23 (19)
O2—S1—C1—C2	−57.59 (12)	C19—C13—C14—C15	179.71 (12)
O1—S1—C1—C2	174.23 (10)	C13—C14—C15—C16	−0.7 (2)
N1—S1—C1—C2	59.26 (13)	C13—C14—C15—Cl2	179.03 (10)
C6—C1—C2—C3	−0.01 (19)	C14—C15—C16—C17	0.5 (2)
S1—C1—C2—C3	177.37 (10)	Cl2—C15—C16—C17	−179.18 (12)
C6—C1—C2—Cl1	179.75 (10)	C15—C16—C17—C18	0.1 (2)
S1—C1—C2—Cl1	−2.87 (16)	C16—C17—C18—C13	−0.5 (2)
C1—C2—C3—C4	2.1 (2)	C14—C13—C18—C17	0.3 (2)
Cl1—C2—C3—C4	−177.66 (10)	C19—C13—C18—C17	−179.15 (13)
C8—N2—C4—C3	−10.5 (2)	C18—C13—C19—O7	−10.56 (19)
C8—N2—C4—C5	170.04 (13)	C14—C13—C19—O7	169.97 (11)
C2—C3—C4—N2	177.67 (12)	C18—C13—C19—O6	169.39 (12)
C2—C3—C4—C5	−2.87 (19)	C14—C13—C19—O6	−10.09 (18)
N2—C4—C5—C6	−178.95 (12)	O14—Na1—O8—Na2	117.64 (5)
C3—C4—C5—C6	1.59 (18)	O10—Na1—O8—Na2	−143.56 (4)
N2—C4—C5—C7	−2.64 (19)	O9ⁱ—Na1—O8—Na2	−51.83 (5)
C3—C4—C5—C7	177.90 (11)	O11—Na1—O8—Na2	31.87 (5)
C4—C5—C6—C1	0.48 (19)	Na1ⁱ—Na1—O8—Na2	−54.90 (7)
C7—C5—C6—C1	−175.97 (11)	O15—Na2—O8—Na1	−165.17 (8)
C2—C1—C6—C5	−1.29 (18)	O16—Na2—O8—Na1	20.07 (6)
S1—C1—C6—C5	−178.78 (10)	O12—Na2—O8—Na1	−65.67 (5)
C6—C5—C7—O3	−12.06 (17)	O13ⁱⁱ—Na2—O8—Na1	99.40 (5)
C4—C5—C7—O3	171.61 (11)	O13—Na2—O8—Na1	−168.88 (5)
C6—C5—C7—O4	166.10 (11)	Na2ⁱⁱ—Na2—O8—Na1	145.27 (4)
C4—C5—C7—O4	−10.23 (18)	O14—Na1—O9—Na1ⁱ	−170.12 (4)
C4—N2—C8—C9	−156.88 (13)	O10—Na1—O9—Na1ⁱ	91.87 (4)
C12—O5—C9—C10	−0.43 (16)	O9ⁱ—Na1—O9—Na1ⁱ	0.0
C12—O5—C9—C8	179.48 (12)	O11—Na1—O9—Na1ⁱ	−83.94 (4)
N2—C8—C9—C10	−119.97 (17)	O15—Na2—O13—Na2ⁱⁱ	96.06 (4)
N2—C8—C9—O5	60.15 (16)	O16—Na2—O13—Na2ⁱⁱ	57.56 (17)
O5—C9—C10—C11	0.86 (16)	O12—Na2—O13—Na2ⁱⁱ	−167.08 (4)
C8—C9—C10—C11	−179.02 (15)	O13ⁱⁱ—Na2—O13—Na2ⁱⁱ	0.0
C9—C10—C11—C12	−0.96 (16)	O8—Na2—O13—Na2ⁱⁱ	−85.65 (4)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11N···Cl1	0.839 (18)	2.767 (17)	3.2848 (16)	121.6 (14)
N1—H12N···O6	0.872 (18)	1.920 (18)	2.7905 (17)	175.3 (17)
N2—H2N···O4	0.860 (18)	1.906 (18)	2.6199 (16)	139.4 (16)
O8—H81···O3ⁱⁱⁱ	0.83 (2)	2.07 (2)	2.8737 (16)	162 (2)
O8—H82···O15ⁱⁱ	0.82 (2)	2.00 (2)	2.8025 (16)	168 (2)
O9—H91···O16ⁱ	0.86 (2)	1.99 (2)	2.8499 (15)	172 (2)
O9—H92···O7	0.81 (2)	2.10 (2)	2.8867 (16)	167 (2)
O10—H101···O11ⁱ	0.78 (2)	1.96 (2)	2.7444 (16)	174 (2)
O10—H102···O3^iv	0.93 (2)	1.90 (2)	2.8271 (15)	171 (2)
O11—H111···O6	0.84 (2)	1.89 (2)	2.7296 (16)	176 (2)
O11—H112···O12	0.81 (2)	2.08 (2)	2.8641 (16)	162 (2)
O12—H121···O4ⁱⁱⁱ	0.85 (2)	1.96 (2)	2.7962 (16)	171 (2)
O12—H122···O2^v	0.76 (2)	2.12 (2)	2.8593 (15)	165 (2)
O13—H131···O7ⁱⁱⁱ	0.81 (2)	2.01 (2)	2.8082 (15)	169 (2)
O13—H132···O3ⁱⁱⁱ	0.85 (2)	1.97 (2)	2.7939 (15)	165 (2)
O14—H141···O4ⁱⁱⁱ	0.76 (2)	1.99 (2)	2.7265 (16)	164 (2)
O14—H142···O1	0.74 (2)	2.31 (2)	3.0019 (17)	156 (2)
O15—H151···O14^v	0.85 (2)	1.92 (2)	2.7766 (16)	178 (2)
O15—H152···O7ⁱⁱⁱ	0.80 (2)	2.14 (2)	2.8545 (16)	149 (2)
O16—H161···O10^v	0.798 (19)	1.990 (19)	2.7857 (16)	175.7 (18)
O16—H162···O1^v	0.80 (2)	2.20 (2)	2.9852 (15)	165.8 (17)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11N···Cl1	0.839 (18)	2.767 (17)	3.2848 (16)	121.6 (14)
N1—H12N···O6	0.872 (18)	1.920 (18)	2.7905 (17)	175.3 (17)
N2—H2N···O4	0.860 (18)	1.906 (18)	2.6199 (16)	139.4 (16)
O8—H81···O3ⁱ	0.83 (2)	2.07 (2)	2.8737 (16)	162.4 (17)
O8—H82···O15ⁱⁱ	0.821 (19)	1.995 (19)	2.8025 (16)	167.6 (17)
O9—H91···O16ⁱⁱⁱ	0.862 (19)	1.994 (19)	2.8499 (15)	171.8 (17)
O9—H92···O7	0.806 (19)	2.10 (2)	2.8867 (16)	167.3 (18)
O10—H101···O11ⁱⁱⁱ	0.784 (19)	1.964 (19)	2.7444 (16)	173.7 (18)
O10—H102···O3^iv	0.932 (18)	1.903 (18)	2.8271 (15)	170.6 (15)
O11—H111···O6	0.842 (19)	1.889 (19)	2.7296 (16)	175.6 (16)
O11—H112···O12	0.811 (19)	2.082 (19)	2.8641 (16)	161.9 (17)
O12—H121···O4ⁱ	0.848 (19)	1.96 (2)	2.7962 (16)	170.8 (18)
O12—H122···O2^v	0.76 (2)	2.12 (2)	2.8593 (15)	165 (2)
O13—H131···O7ⁱ	0.807 (19)	2.011 (19)	2.8082 (15)	169.4 (18)
O13—H132···O3ⁱ	0.848 (19)	1.966 (19)	2.7939 (15)	165.0 (17)
O14—H141···O4ⁱ	0.76 (2)	1.99 (2)	2.7265 (16)	164 (2)
O14—H142···O1	0.74 (2)	2.31 (2)	3.0019 (17)	155.7 (19)
O15—H151···O14^v	0.853 (19)	1.92 (2)	2.7766 (16)	177.8 (18)
O15—H152···O7ⁱ	0.803 (19)	2.135 (19)	2.8545 (16)	149.2 (17)
O16—H161···O10^v	0.798 (19)	1.990 (19)	2.7857 (16)	175.7 (18)
O16—H162···O1^v	0.80 (2)	2.20 (2)	2.9852 (15)	165.8 (17)

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

Experimental details

Crystal data
Chemical formula	[Na₂(OH₂)₉](C₇H₄ClO₂)(C₁₂H₁₀ClN₂O₅S)
M_r	693.41
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	7.908 (2), 10.224 (3), 19.631 (4)
α, β, γ (°)	85.46 (2), 81.80 (2), 74.96 (2)
V (Å³)	1515.7 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.39
Crystal size (mm)	0.30 × 0.25 × 0.07

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.893, 0.974
No. of measured, independent and observed [I > 2s(I)] reflections	17752, 10267, 7760
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.751

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.107, 1.05
No. of reflections	10267
No. of parameters	442
No. of restraints	120
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.55

Computer programs: COLLECT (Nonius, 1999), HKL SCALEPACK (Otwinowski & Minor 1997), HKL DENZO and SCALEPACK (Otwinowski & Minor 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012).

Acknowledgements

The research presented within was made possible by funding from the National Science Foundation (NSF) ACE Implementation (HRD-1043316) and CAREER (CHE-1230357) programs, and the US Department of Education (DoE) grant PO31B040030 (Title III, Part B - Strengthening Historically Black Graduate Institutions). The contents of this publication are solely the responsibility of the authors and do not necessarily represent the official views of the NSF or US DoE. The purchase of the diffractometer was made possible by grant No. LEQSF (1999–2000)-ENH-TR-13, administered by the Louisiana Board of Regents.

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

A co-crystal of nona­hydrated disodium(II) with mixed anions from m-chloro­benzoic acid and furosemide

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Synthesis and crystallization

5. Refinement

Supporting information

Acknowledgements

References

research communications

A co-crystal of nonahydrated disodium(II) with mixed anions from m-chlorobenzoic acid and furosemide

3. Supramolecular features