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Acta Cryst. (2007). E63, m1383-m1384    [ doi:10.1107/S1600536807016728 ]

Poly[([mu]4-chloranilato)bis(saccharin)disodium(I)]

M. S. Refat, H. A. Hashem, K. Gotoh and H. Ishida

Abstract top

In the title compound {systematic name: poly[([mu]4-2,5-dichloro-3,6-dihydroxy-1,4-benzoquinonato)bis[1,2-benzisothiazol-3(2H)-one 1,1-dioxide]disodium(I)]}, [Na2(C6Cl2O4)(C7H5NO3S)2]n, the NaI atom is coordinated by six O atoms from three chloranilate ions and two saccharin ligands in a distorted octahedral geometry. There is an intramolecular N-H...O hydrogen bond between the saccharin ligand and the chloranilate dianion. Each O atom of the chloranilate ion bonds to two NaI atoms, while the saccharin ligand bridges the NaI atoms via the carbonyl O atom and one of the sulfonyl O atoms. The Na atoms and bridging ligands form layers parallel to the ab plane at z = 0 and z = {1 \over 2}. The shortest Na...Na and Na...Cl distances in the layer are 3.6006 (12) and 3.0680 (7) Å, respectively.

Comment top

The NaI atom of the title compound is at the centre of a distorted octahedron and deviates by 0.3422 (8) Å from the mean plane of atoms O1, O2ii, O2iii and O5, which form the equatorial plane (Figs. 1 and 2) [symmetry codes: (ii) -x, -y + 2, -z + 1; (iii) x + 1/2, y + 1/2, z]. The Na—O bond lengths in this plane range from 2.3663 (11) to 2.4024 (11) Å. Atoms O1i and O3iv occupy the axial positions [Na—O1i = 2.4527 (12) and Na—O3iv = 2.5624 (13) Å; symmetry codes: (i) -x + 1/2, -y + 3/2, -z + 1; (iv) x, 1 + y, z].

There is an intermolecular N—H···O hydrogen bond (Table 2). The chloranilate and saccharin ligands bridge the NaI atoms, forming layers parallel to the ab plane at z = 0 and z = 1/2 (Fig. 3).

Related literature top

There are a large number of metal complexes coordinated by the saccharinate anion obtained by deprotonation of the N—H group of saccharin (Baran, 2005; Baran & Yilmaz, 2006; Gumus et al., 2007). However, no crystal data for the metal complex with neutral saccharin as a ligand are available in the Cambridge Structural Database (Version 5.28; Allen, 2002).

Experimental top

The title compound was prepared by mixing chloroform–methanol (1:1 v/v) solutions (20 and 20 ml, respectively) of saccharin sodium (1.0 mmol) and chloranilic acid (1.0 mmol). The combined solution was left at room temperature for 12 h to give red crystals, which were filtered and washed several times with dichloromethane and then dried.

Refinement top

All H atoms were located in a difference map. The N-bound H atom was refined freely, while other H atoms were refined using a riding model, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: PROCESS-AUTO (Rigaku/MSC, 2004); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: CrystalStructure and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. The intermolecular hydrogen bond is indicated by a dashed line. [Symmetry code: (ii) -x, -y + 2, -z + 1.]
[Figure 2] Fig. 2. A view of the polymeric fragment of (I), showing the distorted octahedral coordination geometry. [Symmetry codes: (i) -x + 1/2, -y + 3/2, -z + 1; (ii) -x, -y + 2, -z + 1; (iii) x + 1/2, y + 1/2, z; (iv) x, 1 + y, z.]
[Figure 3] Fig. 3. The molecular packing of (I), viewed along the b axis. H atoms have been omitted for clarity.
poly[(µ42,5-dichloro-3,6-dihydroxy-1,4-benzoquinonato)bis[1,2- benzisothiazol-3(2H)-one 1,1-dioxide]disodium(I)] top
Crystal data top
[Na2(C6Cl2O4)(C7H5NO3S)2]F(000) = 1248
Mr = 619.30Dx = 1.818 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71075 Å
Hall symbol: -C 2ycCell parameters from 10738 reflections
a = 14.6795 (7) Åθ = 3.0–30.0°
b = 6.2247 (3) ŵ = 0.57 mm−1
c = 25.2114 (12) ÅT = 170 K
β = 99.9052 (16)°Platelet, red
V = 2269.36 (19) Å30.55 × 0.23 × 0.07 mm
Z = 4
Data collection top
Rigaku R-AXIS RAPID
diffractometer		2886 reflections with I > 2σ(I)
Detector resolution: 10.00 pixels mm-1Rint = 0.041
ω scansθmax = 30.0°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −20→20
Tmin = 0.704, Tmax = 0.961k = −8→8
12067 measured reflectionsl = −35→35
3306 independent reflections
Refinement top
Refinement on F20 restraints
R[F2 > 2σ(F2)] = 0.035H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.089 w = 1/[σ2(Fo2) + (0.0492P)2 + 1.5311P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
3306 reflectionsΔρmax = 0.35 e Å−3
176 parametersΔρmin = −0.57 e Å−3
Crystal data top
[Na2(C6Cl2O4)(C7H5NO3S)2]V = 2269.36 (19) Å3
Mr = 619.30Z = 4
Monoclinic, C2/cMo Kα radiation
a = 14.6795 (7) ŵ = 0.57 mm−1
b = 6.2247 (3) ÅT = 170 K
c = 25.2114 (12) Å0.55 × 0.23 × 0.07 mm
β = 99.9052 (16)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer		3306 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		2886 reflections with I > 2σ(I)
Tmin = 0.704, Tmax = 0.961Rint = 0.041
12067 measured reflectionsθmax = 30.0°
Refinement top
R[F2 > 2σ(F2)] = 0.035H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.089Δρmax = 0.35 e Å−3
S = 1.05Δρmin = −0.57 e Å−3
3306 reflectionsAbsolute structure: ?
176 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
Cl1−0.04269 (2)0.57417 (5)0.431471 (13)0.01939 (9)
S10.14374 (2)0.30306 (6)0.354874 (14)0.01869 (9)
Na10.27054 (4)0.99825 (9)0.46736 (2)0.01851 (13)
O10.14132 (7)0.76727 (16)0.47271 (4)0.01704 (19)
O2−0.17515 (7)0.85677 (17)0.47486 (4)0.0179 (2)
O30.13973 (8)0.14915 (19)0.39671 (5)0.0262 (2)
O40.06485 (8)0.3162 (2)0.31285 (5)0.0282 (3)
O50.29399 (8)0.77774 (18)0.39676 (5)0.0255 (2)
N10.17091 (9)0.5440 (2)0.38105 (5)0.0205 (2)
C10.07295 (9)0.8707 (2)0.48321 (5)0.0141 (2)
C2−0.01884 (9)0.8108 (2)0.46768 (5)0.0152 (2)
C3−0.09322 (9)0.9193 (2)0.48437 (5)0.0143 (2)
C40.25872 (10)0.6137 (2)0.37689 (6)0.0185 (3)
C50.30221 (10)0.4592 (2)0.34423 (6)0.0190 (3)
C60.38975 (11)0.4763 (3)0.33085 (6)0.0263 (3)
H60.42660.59620.34060.032*
C70.42019 (12)0.3072 (3)0.30234 (7)0.0329 (4)
H70.47920.31250.29360.039*
C80.36383 (13)0.1295 (3)0.28656 (7)0.0324 (4)
H80.38560.01960.26710.039*
C90.27599 (12)0.1142 (3)0.29944 (6)0.0256 (3)
H90.2379−0.00280.28870.031*
C100.24751 (10)0.2814 (2)0.32910 (6)0.0194 (3)
H10.1459 (17)0.599 (4)0.4051 (10)0.041 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.01556 (15)0.01872 (16)0.02493 (17)−0.00330 (12)0.00638 (12)−0.00676 (12)
S10.01455 (16)0.02209 (17)0.02003 (17)−0.00378 (12)0.00463 (12)0.00048 (12)
Na10.0136 (3)0.0178 (3)0.0256 (3)−0.0015 (2)0.0077 (2)−0.0026 (2)
O10.0108 (4)0.0185 (5)0.0231 (5)0.0011 (4)0.0067 (3)−0.0014 (4)
O20.0092 (4)0.0205 (5)0.0246 (5)−0.0033 (4)0.0051 (3)−0.0039 (4)
O30.0252 (6)0.0282 (6)0.0266 (5)−0.0036 (5)0.0081 (4)0.0057 (4)
O40.0175 (5)0.0391 (7)0.0265 (6)−0.0066 (5)−0.0003 (4)0.0015 (5)
O50.0258 (6)0.0227 (5)0.0303 (6)−0.0070 (4)0.0111 (4)−0.0061 (4)
N10.0148 (5)0.0229 (6)0.0257 (6)−0.0014 (5)0.0089 (5)−0.0050 (5)
C10.0111 (5)0.0152 (6)0.0172 (5)−0.0003 (5)0.0057 (4)0.0008 (5)
C20.0114 (5)0.0148 (6)0.0201 (6)−0.0020 (5)0.0044 (5)−0.0046 (5)
C30.0109 (5)0.0158 (6)0.0171 (5)−0.0009 (5)0.0047 (4)−0.0005 (5)
C40.0158 (6)0.0205 (6)0.0204 (6)−0.0010 (5)0.0065 (5)−0.0002 (5)
C50.0168 (6)0.0225 (6)0.0191 (6)−0.0012 (5)0.0069 (5)−0.0012 (5)
C60.0183 (7)0.0362 (8)0.0269 (7)−0.0025 (6)0.0104 (6)−0.0020 (6)
C70.0232 (8)0.0520 (11)0.0268 (8)0.0063 (7)0.0138 (6)−0.0025 (7)
C80.0338 (9)0.0409 (10)0.0245 (7)0.0117 (8)0.0107 (6)−0.0067 (7)
C90.0299 (8)0.0254 (7)0.0218 (7)0.0015 (6)0.0057 (6)−0.0041 (6)
C100.0181 (6)0.0230 (7)0.0180 (6)0.0004 (5)0.0060 (5)−0.0005 (5)
Geometric parameters (Å, °) top
Cl1—C21.7365 (13)N1—H10.84 (3)
S1—O31.4336 (12)C1—C21.3879 (18)
S1—O41.4312 (11)C1—C3ii1.5431 (18)
S1—N11.6595 (13)C2—C31.4085 (18)
S1—C101.7610 (15)C4—C51.480 (2)
Na1—O12.4024 (11)C5—C61.388 (2)
Na1—O1i2.4527 (12)C5—C101.382 (2)
Na1—O2ii2.3663 (11)C6—C71.391 (2)
Na1—O2iii2.3664 (12)C6—H60.93
Na1—O3iv2.5624 (13)C7—C81.398 (3)
Na1—O52.3198 (13)C7—H70.93
O1—C11.2582 (16)C8—C91.386 (3)
O2—C31.2475 (15)C8—H80.93
O5—C41.2134 (19)C9—C101.387 (2)
N1—C41.3810 (18)C9—H90.93
Na1···Cl1iii3.0680 (7)Na1···Na1i3.6006 (12)
Na1···C13.0986 (14)Na1···Na1v3.6381 (11)
Na1···C3ii3.0998 (14)
O4—S1—O3116.90 (7)S1—N1—H1123.7 (18)
O4—S1—N1110.57 (7)O1—C1—C2125.03 (12)
O3—S1—N1110.42 (7)O1—C1—C3ii117.17 (11)
O4—S1—C10111.86 (7)C2—C1—C3ii117.80 (11)
O3—S1—C10111.58 (7)C1—C2—C3123.49 (12)
N1—S1—C1092.98 (7)C1—C2—Cl1118.31 (10)
O1—Na1—O1i84.27 (4)C3—C2—Cl1117.86 (10)
O2ii—Na1—O168.72 (4)O2—C3—C2124.33 (12)
O2iii—Na1—O1144.92 (4)O2—C3—C1ii117.26 (11)
O2ii—Na1—O1i100.55 (4)C2—C3—C1ii118.41 (11)
O2iii—Na1—O1i116.84 (4)O5—C4—N1124.78 (14)
O5—Na1—O184.94 (4)O5—C4—C5125.61 (14)
O5—Na1—O1i86.66 (4)N1—C4—C5109.61 (12)
O2ii—Na1—O2iii79.52 (4)C10—C5—C6120.85 (14)
O5—Na1—O2ii151.60 (5)C10—C5—C4112.84 (13)
O5—Na1—O2iii121.79 (5)C6—C5—C4126.25 (14)
O1—Na1—O3iv75.75 (4)C5—C6—C7117.44 (16)
O1i—Na1—O3iv158.14 (4)C5—C6—H6121.3
O2ii—Na1—O3iv80.56 (4)C7—C6—H6121.3
O2iii—Na1—O3iv84.93 (4)C6—C7—C8121.27 (16)
O5—Na1—O3iv82.87 (5)C6—C7—H7119.4
Na1—O1—Na1i95.73 (4)C8—C7—H7119.4
C1—O1—Na1111.82 (9)C9—C8—C7121.09 (15)
C1—O1—Na1i124.80 (9)C9—C8—H8119.5
C3—O2—Na1ii114.55 (9)C7—C8—H8119.5
C3—O2—Na1vi127.60 (9)C8—C9—C10116.99 (15)
Na1ii—O2—Na1vi100.48 (4)C8—C9—H9121.5
S1—O3—Na1vii129.47 (7)C10—C9—H9121.5
C4—O5—Na1134.88 (10)C5—C10—C9122.33 (14)
C4—N1—S1114.67 (10)C5—C10—S1109.58 (11)
C4—N1—H1117.3 (17)C9—C10—S1128.06 (12)
O5—Na1—O1—C1−141.72 (9)Na1vi—O2—C3—C1ii−147.38 (9)
O2ii—Na1—O1—C127.46 (9)Na1vi—O2—C3—Na1ii−127.17 (13)
O2iii—Na1—O1—C10.86 (13)C1—C2—C3—O2−173.24 (13)
O1i—Na1—O1—C1131.15 (10)Cl1—C2—C3—O2−0.03 (19)
O3iv—Na1—O1—C1−57.80 (9)C1—C2—C3—C1ii6.5 (2)
O5—Na1—O1—Na1i87.14 (4)Cl1—C2—C3—C1ii179.74 (9)
O2ii—Na1—O1—Na1i−103.69 (4)C1—C2—C3—Na1ii−126.4 (2)
O2iii—Na1—O1—Na1i−130.29 (7)Cl1—C2—C3—Na1ii46.8 (3)
O1i—Na1—O1—Na1i0.0Na1—O5—C4—N122.3 (2)
O3iv—Na1—O1—Na1i171.05 (5)Na1—O5—C4—C5−158.35 (11)
O4—S1—O3—Na1vii164.12 (8)S1—N1—C4—O5−174.54 (12)
N1—S1—O3—Na1vii−68.34 (10)S1—N1—C4—C55.99 (16)
C10—S1—O3—Na1vii33.61 (11)O5—C4—C5—C10176.99 (14)
O2ii—Na1—O5—C4−26.6 (2)N1—C4—C5—C10−3.55 (18)
O2iii—Na1—O5—C4−160.78 (14)O5—C4—C5—C6−0.2 (3)
O1—Na1—O5—C4−5.05 (15)N1—C4—C5—C6179.24 (15)
O1i—Na1—O5—C479.49 (15)C10—C5—C6—C7−0.7 (2)
O3iv—Na1—O5—C4−81.28 (15)C4—C5—C6—C7176.30 (15)
O4—S1—N1—C4−120.06 (11)C5—C6—C7—C81.6 (3)
O3—S1—N1—C4108.99 (12)C6—C7—C8—C9−0.9 (3)
C10—S1—N1—C4−5.37 (12)C7—C8—C9—C10−0.8 (3)
Na1—O1—C1—C2151.68 (11)C6—C5—C10—C9−1.0 (2)
Na1i—O1—C1—C2−94.16 (15)C4—C5—C10—C9−178.39 (14)
Na1—O1—C1—C3ii−28.03 (14)C6—C5—C10—S1177.20 (12)
Na1i—O1—C1—C3ii86.12 (13)C4—C5—C10—S1−0.18 (16)
Na1i—O1—C1—Na1114.16 (11)C8—C9—C10—C51.7 (2)
O1—C1—C2—C3173.81 (13)C8—C9—C10—S1−176.12 (13)
C3ii—C1—C2—C3−6.5 (2)O4—S1—C10—C5116.60 (11)
O1—C1—C2—Cl10.62 (19)O3—S1—C10—C5−110.32 (11)
C3ii—C1—C2—Cl1−179.67 (9)N1—S1—C10—C53.03 (12)
Na1ii—O2—C3—C2159.56 (11)O4—S1—C10—C9−65.31 (16)
Na1vi—O2—C3—C232.39 (19)O3—S1—C10—C967.76 (15)
Na1ii—O2—C3—C1ii−20.21 (14)N1—S1—C10—C9−178.89 (14)
Symmetry codes: (i) −x+1/2, −y+3/2, −z+1; (ii) −x, −y+2, −z+1; (iii) x+1/2, y+1/2, z; (iv) x, y+1, z; (v) −x+1/2, −y+5/2, −z+1; (vi) x−1/2, y−1/2, z; (vii) x, y−1, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.84 (3)2.01 (2)2.7938 (16)156 (2)
Table 1
Selected geometric parameters (Å) top
Na1—O12.4024 (11)Na1—O2iii2.3664 (12)
Na1—O1i2.4527 (12)Na1—O3iv2.5624 (13)
Na1—O2ii2.3663 (11)Na1—O52.3198 (13)
Symmetry codes: (i) −x+1/2, −y+3/2, −z+1; (ii) −x, −y+2, −z+1; (iii) x+1/2, y+1/2, z; (iv) x, y+1, z.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.84 (3)2.01 (2)2.7938 (16)156 (2)
Acknowledgements top

This work was partly supported by a Grant-in-Aid for Scientific Research (C) (No. 16550014) from the Japanese Society for the Promotion of Science.

references
References top

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Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.