In the title compound, [Na(C9H6NO4S)], the sodium ion is coordinated by the N and O atoms of the quinolinol moiety (usual bidentate chelation) and three O atoms from three different sulfonate groups. The quinolinol O atom and one of the sulfonate O atoms are in the axial positions and the ring N atom and two O atoms from two different sulfonate groups lie in the equatorial positions of the trigonal bipyramid around sodium. Unlike other metal sulfoxinates, the quinolinol O atom is not deprotonated, but is involved in hydrogen bonding. Moreover, all three sulfonate O atoms are involved in coordination, leading to a supramolecular three-dimensional network structure.
Supporting information
CCDC reference: 187220
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.002 Å
- R factor = 0.031
- wR factor = 0.091
- Data-to-parameter ratio = 15.8
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
REFLT_03
From the CIF: _diffrn_reflns_theta_max 30.55
From the CIF: _reflns_number_total 2662
TEST2: Reflns within _diffrn_reflns_theta_max
Count of symmetry unique reflns 2826
Completeness (_total/calc) 94.20%
Alert C: < 95% complete
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
An aqueous solution of sodium diethyldithiocarbomate (0.113 g) and an aqueous solution of 8-hydroxyquinoline-5-sulfonic acid monohydrate were mixed and warmed over a water bath for 30 min. The product was then recrystallized from acetonitrile.
The H atoms were located in difference fourier maps and refined with isotropic displacement parameters. The C—H and O—H bond lengths are 0.883 (18)–0.98 (3) and 0.805 (18) Å, respectively.
Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1997); software used to prepare material for publication: PLATON.
(8-hydroxyquinoline-5-sulfonato-N
1,
O8)sodium(I)
top
Crystal data top
[Na(C9H6NO4S)] | F(000) = 504 |
Mr = 247.21 | Dx = 1.779 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2ybc | Cell parameters from 50 reflections |
a = 8.284 (2) Å | θ = 3.0–29.6° |
b = 10.488 (2) Å | µ = 0.39 mm−1 |
c = 10.916 (2) Å | T = 293 K |
β = 103.25 (2)° | Cubic, colourless |
V = 923.2 (3) Å3 | 0.34 × 0.26 × 0.17 mm |
Z = 4 | |
Data collection top
Bruker AXS SMART with CCD diffractometer | 2662 independent reflections |
Radiation source: fine-focus sealed tube | 2119 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
ω scans | θmax = 30.6°, θmin = 2.5° |
Absorption correction: ψ scan (SHELXTL-NT; Bruker, 1997) | h = −11→11 |
Tmin = 0.787, Tmax = 0.936 | k = −14→14 |
132007 measured reflections | l = −14→14 |
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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.091 | All H-atom parameters refined |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0587P)2] where P = (Fo2 + 2Fc2)/3 |
2662 reflections | (Δ/σ)max = 0.003 |
169 parameters | Δρmax = 0.35 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
0 constraints | |
Crystal data top
[Na(C9H6NO4S)] | V = 923.2 (3) Å3 |
Mr = 247.21 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.284 (2) Å | µ = 0.39 mm−1 |
b = 10.488 (2) Å | T = 293 K |
c = 10.916 (2) Å | 0.34 × 0.26 × 0.17 mm |
β = 103.25 (2)° | |
Data collection top
Bruker AXS SMART with CCD diffractometer | 2662 independent reflections |
Absorption correction: ψ scan (SHELXTL-NT; Bruker, 1997) | 2119 reflections with I > 2σ(I) |
Tmin = 0.787, Tmax = 0.936 | Rint = 0.032 |
132007 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.091 | All H-atom parameters refined |
S = 1.01 | Δρmax = 0.35 e Å−3 |
2662 reflections | Δρmin = −0.29 e Å−3 |
169 parameters | |
Special details top
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'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 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S | 0.62753 (4) | 0.20423 (3) | −0.04879 (3) | 0.0218 (1) | |
Na | 0.41137 (7) | −0.03354 (5) | −0.23651 (5) | 0.0289 (2) | |
O1 | 1.33869 (13) | 0.33975 (11) | 0.13065 (11) | 0.0312 (3) | |
O2 | 0.62324 (13) | 0.08738 (11) | −0.12015 (11) | 0.0340 (3) | |
O3 | 0.56791 (13) | 0.18555 (10) | 0.06713 (10) | 0.0289 (3) | |
O4 | 0.54382 (13) | 0.31155 (10) | −0.12117 (10) | 0.0317 (3) | |
N1 | 1.11475 (14) | 0.49135 (11) | 0.19225 (11) | 0.0246 (3) | |
C2 | 1.00318 (18) | 0.57073 (14) | 0.21803 (13) | 0.0268 (4) | |
C3 | 0.83086 (19) | 0.55232 (14) | 0.17862 (14) | 0.0273 (4) | |
C4 | 0.77215 (17) | 0.44641 (13) | 0.10996 (13) | 0.0243 (4) | |
C5 | 0.83967 (16) | 0.24662 (12) | 0.00206 (12) | 0.0205 (3) | |
C6 | 0.95901 (17) | 0.16969 (13) | −0.02792 (13) | 0.0242 (4) | |
C7 | 1.12987 (18) | 0.19806 (13) | 0.01441 (14) | 0.0260 (4) | |
C8 | 1.17851 (16) | 0.30424 (12) | 0.08708 (13) | 0.0225 (4) | |
C9 | 1.05738 (16) | 0.38597 (12) | 0.12076 (12) | 0.0203 (3) | |
C10 | 0.88590 (16) | 0.35824 (12) | 0.07735 (12) | 0.0196 (3) | |
H1 | 1.401 (2) | 0.2898 (18) | 0.1096 (17) | 0.035 (5)* | |
H2 | 1.049 (2) | 0.6485 (19) | 0.2615 (17) | 0.040 (5)* | |
H3 | 0.765 (2) | 0.6107 (18) | 0.1993 (16) | 0.032 (5)* | |
H4 | 0.657 (2) | 0.4366 (16) | 0.0846 (17) | 0.034 (5)* | |
H6 | 0.918 (2) | 0.0955 (18) | −0.0790 (16) | 0.035 (5)* | |
H7 | 1.208 (2) | 0.1434 (16) | −0.0072 (15) | 0.026 (4)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S | 0.0180 (2) | 0.0221 (2) | 0.0238 (2) | −0.0022 (1) | 0.0020 (1) | −0.0004 (1) |
Na | 0.0246 (3) | 0.0284 (3) | 0.0305 (3) | 0.0002 (2) | −0.0002 (2) | −0.0018 (2) |
O1 | 0.0169 (5) | 0.0344 (6) | 0.0404 (6) | 0.0006 (4) | 0.0027 (4) | −0.0065 (5) |
O2 | 0.0269 (5) | 0.0319 (6) | 0.0407 (6) | −0.0058 (4) | 0.0025 (5) | −0.0137 (5) |
O3 | 0.0248 (5) | 0.0329 (5) | 0.0308 (5) | −0.0004 (4) | 0.0099 (4) | 0.0048 (4) |
O4 | 0.0246 (5) | 0.0332 (6) | 0.0329 (6) | 0.0012 (4) | −0.0023 (4) | 0.0076 (4) |
N1 | 0.0239 (6) | 0.0254 (6) | 0.0229 (6) | −0.0031 (4) | 0.0020 (4) | −0.0025 (5) |
C2 | 0.0305 (7) | 0.0242 (7) | 0.0249 (7) | −0.0029 (5) | 0.0044 (6) | −0.0050 (5) |
C3 | 0.0279 (7) | 0.0261 (7) | 0.0284 (7) | 0.0036 (5) | 0.0076 (6) | −0.0035 (6) |
C4 | 0.0209 (6) | 0.0262 (7) | 0.0255 (7) | 0.0005 (5) | 0.0049 (5) | −0.0014 (5) |
C5 | 0.0189 (6) | 0.0212 (6) | 0.0203 (6) | −0.0016 (5) | 0.0023 (5) | 0.0006 (5) |
C6 | 0.0238 (7) | 0.0215 (6) | 0.0269 (7) | −0.0013 (5) | 0.0048 (5) | −0.0025 (5) |
C7 | 0.0219 (6) | 0.0251 (7) | 0.0312 (7) | 0.0035 (5) | 0.0064 (5) | −0.0017 (6) |
C8 | 0.0179 (6) | 0.0260 (7) | 0.0222 (6) | 0.0002 (5) | 0.0020 (5) | 0.0028 (5) |
C9 | 0.0199 (6) | 0.0210 (6) | 0.0192 (6) | −0.0010 (5) | 0.0028 (5) | 0.0009 (5) |
C10 | 0.0194 (6) | 0.0204 (6) | 0.0184 (6) | −0.0006 (4) | 0.0033 (5) | 0.0015 (5) |
Geometric parameters (Å, º) top
S—O2 | 1.4482 (12) | C3—C4 | 1.366 (2) |
S—O3 | 1.4731 (12) | C4—C10 | 1.423 (2) |
S—O4 | 1.4563 (12) | C5—C10 | 1.4312 (18) |
S—C5 | 1.7740 (15) | C5—C6 | 1.373 (2) |
Na—O2 | 2.2979 (14) | C6—C7 | 1.416 (2) |
Na—O4i | 2.3357 (13) | C7—C8 | 1.3730 (19) |
Na—O3ii | 2.4175 (13) | C8—C9 | 1.4304 (19) |
Na—O1iii | 2.4892 (14) | C9—C10 | 1.4207 (19) |
Na—N1iii | 2.4418 (15) | C2—H2 | 0.98 (2) |
O1—C8 | 1.3551 (18) | C3—H3 | 0.883 (18) |
O1—H1 | 0.805 (18) | C4—H4 | 0.936 (17) |
N1—C2 | 1.3213 (19) | C6—H6 | 0.972 (18) |
N1—C9 | 1.3735 (18) | C7—H7 | 0.934 (17) |
C2—C3 | 1.407 (2) | | |
| | | |
S···H1iv | 2.967 (18) | C7···C3vi | 3.423 (2) |
S···H4 | 2.821 (17) | C7···C2vi | 3.500 (2) |
O1···O3v | 2.7029 (17) | C8···C2vi | 3.575 (2) |
O1···N1 | 2.6445 (18) | C8···C4vi | 3.469 (2) |
O1···C4vi | 3.416 (2) | C8···C3vi | 3.252 (2) |
O2···C3vii | 3.415 (2) | C9···C10vi | 3.544 (2) |
O3···C4 | 3.1943 (19) | C9···C9vi | 3.525 (2) |
O3···O1iv | 2.7029 (17) | C10···N1vi | 3.3380 (19) |
O4···C4 | 3.1235 (19) | C10···C9vi | 3.544 (2) |
O4···C3viii | 3.343 (2) | C2···H6x | 3.027 (18) |
O2···H6 | 2.381 (17) | C3···H6x | 3.008 (18) |
O3···H1iv | 1.902 (18) | C5···H2xi | 2.735 (18) |
O3···H4 | 2.729 (17) | C6···H6xii | 3.097 (19) |
O4···H4 | 2.584 (18) | C6···H2xi | 2.933 (18) |
O4···H3viii | 2.634 (17) | C8···H3xi | 3.046 (18) |
N1···O1 | 2.6445 (18) | C9···H2xi | 3.025 (19) |
N1···C10vi | 3.3380 (19) | C10···H2xi | 2.791 (19) |
C2···C5ix | 3.551 (2) | H1···Sv | 2.967 (18) |
C2···C6ix | 3.483 (2) | H1···O3v | 1.902 (18) |
C2···C5vi | 3.545 (2) | H1···H7 | 2.37 (2) |
C2···C6vi | 3.481 (2) | H2···C5ix | 2.735 (18) |
C2···C7vi | 3.500 (2) | H2···C6ix | 2.933 (18) |
C2···C8vi | 3.575 (2) | H2···C9ix | 3.025 (19) |
C3···C8vi | 3.252 (2) | H2···C10ix | 2.791 (19) |
C3···O4viii | 3.343 (2) | H3···C8ix | 3.046 (18) |
C3···C7vi | 3.423 (2) | H3···O4viii | 2.634 (17) |
C3···O2x | 3.415 (2) | H4···S | 2.821 (17) |
C4···O4 | 3.1235 (19) | H4···O3 | 2.729 (17) |
C4···O1vi | 3.416 (2) | H4···O4 | 2.584 (18) |
C4···O3 | 3.1943 (19) | H6···O2 | 2.381 (17) |
C4···C8vi | 3.469 (2) | H6···C6xii | 3.097 (19) |
C5···C2xi | 3.551 (2) | H6···C2vii | 3.027 (18) |
C5···C2vi | 3.545 (2) | H6···C3vii | 3.008 (18) |
C6···C2vi | 3.481 (2) | H7···H1 | 2.37 (2) |
C6···C2xi | 3.483 (2) | | |
| | | |
O2—S—O3 | 112.20 (7) | C2—C3—C4 | 119.23 (14) |
O2—S—O4 | 114.35 (7) | C3—C4—C10 | 119.54 (13) |
O2—S—C5 | 106.31 (7) | C6—C5—C10 | 120.35 (13) |
O3—S—O4 | 110.92 (7) | S—C5—C10 | 120.01 (10) |
O3—S—C5 | 105.53 (7) | S—C5—C6 | 119.61 (10) |
O4—S—C5 | 106.88 (7) | C5—C6—C7 | 121.29 (13) |
O2—Na—O4i | 122.27 (5) | C6—C7—C8 | 119.86 (13) |
O2—Na—O3ii | 91.71 (5) | O1—C8—C9 | 115.68 (12) |
O1iii—Na—O2 | 85.61 (5) | O1—C8—C7 | 124.04 (13) |
O2—Na—N1iii | 131.41 (5) | C7—C8—C9 | 120.28 (13) |
O3ii—Na—O4i | 93.20 (5) | N1—C9—C10 | 122.93 (12) |
O1iii—Na—O4i | 103.57 (5) | C8—C9—C10 | 119.89 (12) |
O4i—Na—N1iii | 102.47 (5) | N1—C9—C8 | 117.16 (12) |
O1iii—Na—O3ii | 161.68 (5) | C5—C10—C9 | 118.32 (12) |
O3ii—Na—N1iii | 104.65 (5) | C4—C10—C5 | 124.75 (13) |
O1iii—Na—N1iii | 64.86 (4) | C4—C10—C9 | 116.90 (12) |
Naxiii—O1—C8 | 121.03 (9) | N1—C2—H2 | 114.7 (10) |
S—O2—Na | 133.30 (7) | C3—C2—H2 | 121.2 (10) |
S—O3—Naii | 139.97 (7) | C2—C3—H3 | 118.0 (12) |
S—O4—Naxiv | 140.35 (7) | C4—C3—H3 | 122.8 (11) |
Naxiii—O1—H1 | 127.8 (13) | C3—C4—H4 | 117.5 (11) |
C8—O1—H1 | 111.2 (13) | C10—C4—H4 | 122.9 (11) |
Naxiii—N1—C2 | 121.33 (10) | C5—C6—H6 | 115.5 (10) |
C2—N1—C9 | 117.40 (12) | C7—C6—H6 | 123.2 (10) |
Naxiii—N1—C9 | 121.24 (9) | C6—C7—H7 | 119.1 (10) |
N1—C2—C3 | 123.97 (13) | C8—C7—H7 | 121.0 (10) |
| | | |
O3—S—C5—C10 | −59.77 (12) | Naxiii—O1—C8—C7 | −179.42 (11) |
O4—S—C5—C10 | 58.38 (12) | Naxiii—O1—C8—C9 | 1.00 (16) |
O3—S—O2—Na | 70.79 (11) | C2—N1—C9—C8 | 176.52 (12) |
O4—S—O2—Na | −56.65 (11) | Naxiii—N1—C9—C8 | −1.68 (16) |
C5—S—O2—Na | −174.33 (9) | C9—N1—C2—C3 | 1.2 (2) |
O2—S—C5—C6 | −1.11 (13) | Naxiii—N1—C2—C3 | 179.35 (11) |
O2—S—O4—Naxiv | −80.24 (12) | Naxiii—N1—C9—C10 | −179.89 (9) |
O3—S—O4—Naxiv | 151.67 (9) | C2—N1—C9—C10 | −1.69 (19) |
C5—S—O4—Naxiv | 37.11 (12) | N1—C2—C3—C4 | 0.3 (2) |
O2—S—O3—Naii | 41.33 (12) | C2—C3—C4—C10 | −1.3 (2) |
O4—S—O3—Naii | 170.58 (9) | C3—C4—C10—C5 | −177.57 (13) |
C5—S—O3—Naii | −74.02 (11) | C3—C4—C10—C9 | 0.79 (19) |
O4—S—C5—C6 | −123.64 (11) | C10—C5—C6—C7 | 0.1 (2) |
O2—S—C5—C10 | −179.09 (11) | S—C5—C6—C7 | −177.91 (11) |
O3—S—C5—C6 | 118.21 (11) | C6—C5—C10—C9 | −0.64 (19) |
O4i—Na—O2—S | 164.24 (8) | C6—C5—C10—C4 | 177.71 (13) |
O3ii—Na—O2—S | −100.90 (10) | S—C5—C10—C9 | 177.32 (10) |
O1—Naxiii—N1—C2 | −176.60 (12) | S—C5—C10—C4 | −4.33 (18) |
O2xiii—Naxiii—N1—C2 | 125.17 (11) | C5—C6—C7—C8 | 0.1 (2) |
O1—Naxiii—N1—C9 | 1.53 (10) | C6—C7—C8—C9 | 0.3 (2) |
O2xiii—Naxiii—N1—C9 | −56.70 (12) | C6—C7—C8—O1 | −179.24 (13) |
O1iii—Na—O2—S | 60.95 (10) | C7—C8—C9—C10 | −0.9 (2) |
N1iii—Na—O2—S | 10.43 (13) | C7—C8—C9—N1 | −179.18 (13) |
O2xiv—Naxiv—O4—S | 166.12 (9) | O1—C8—C9—N1 | 0.42 (18) |
N1—Naxiii—O1—C8 | −1.31 (10) | O1—C8—C9—C10 | 178.68 (12) |
O2xiii—Naxiii—O1—C8 | 138.94 (11) | C8—C9—C10—C5 | 1.06 (19) |
O2ii—Naii—O3—S | −84.62 (11) | N1—C9—C10—C4 | 0.74 (19) |
O2xiii—Naxiii—O1—H1 | −39.0 (16) | N1—C9—C10—C5 | 179.22 (12) |
N1—Naxiii—O1—H1 | −179.2 (17) | C8—C9—C10—C4 | −177.42 (12) |
Symmetry codes: (i) −x+1, y−1/2, −z−1/2; (ii) −x+1, −y, −z; (iii) x−1, −y+1/2, z−1/2; (iv) x−1, y, z; (v) x+1, y, z; (vi) −x+2, −y+1, −z; (vii) x, −y+1/2, z−1/2; (viii) −x+1, −y+1, −z; (ix) −x+2, y+1/2, −z+1/2; (x) x, −y+1/2, z+1/2; (xi) −x+2, y−1/2, −z+1/2; (xii) −x+2, −y, −z; (xiii) x+1, −y+1/2, z+1/2; (xiv) −x+1, y+1/2, −z−1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3v | 0.805 (18) | 1.902 (18) | 2.7029 (17) | 173.4 (17) |
C4—H4···O4 | 0.936 (17) | 2.584 (18) | 3.1235 (19) | 117.1 (13) |
C6—H6···O2 | 0.972 (18) | 2.381 (17) | 2.8657 (19) | 110.2 (12) |
Symmetry code: (v) x+1, y, z. |
Experimental details
Crystal data |
Chemical formula | [Na(C9H6NO4S)] |
Mr | 247.21 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 8.284 (2), 10.488 (2), 10.916 (2) |
β (°) | 103.25 (2) |
V (Å3) | 923.2 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.39 |
Crystal size (mm) | 0.34 × 0.26 × 0.17 |
|
Data collection |
Diffractometer | Bruker AXS SMART with CCD diffractometer |
Absorption correction | ψ scan (SHELXTL-NT; Bruker, 1997) |
Tmin, Tmax | 0.787, 0.936 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 132007, 2662, 2119 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.715 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.091, 1.01 |
No. of reflections | 2662 |
No. of parameters | 169 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.35, −0.29 |
Selected geometric parameters (Å, º) topS—O2 | 1.4482 (12) | Na—O3ii | 2.4175 (13) |
S—O3 | 1.4731 (12) | Na—O1iii | 2.4892 (14) |
S—O4 | 1.4563 (12) | Na—N1iii | 2.4418 (15) |
S—C5 | 1.7740 (15) | O1—C8 | 1.3551 (18) |
Na—O2 | 2.2979 (14) | N1—C2 | 1.3213 (19) |
Na—O4i | 2.3357 (13) | N1—C9 | 1.3735 (18) |
| | | |
O2—S—O3 | 112.20 (7) | O1iii—Na—N1iii | 64.86 (4) |
O2—S—O4 | 114.35 (7) | Naiv—O1—C8 | 121.03 (9) |
O2—S—C5 | 106.31 (7) | S—O2—Na | 133.30 (7) |
O3—S—O4 | 110.92 (7) | S—O3—Naii | 139.97 (7) |
O3—S—C5 | 105.53 (7) | S—O4—Nav | 140.35 (7) |
O4—S—C5 | 106.88 (7) | Naiv—N1—C2 | 121.33 (10) |
O2—Na—O4i | 122.27 (5) | C2—N1—C9 | 117.40 (12) |
O2—Na—O3ii | 91.71 (5) | Naiv—N1—C9 | 121.24 (9) |
O1iii—Na—O2 | 85.61 (5) | N1—C2—C3 | 123.97 (13) |
O2—Na—N1iii | 131.41 (5) | S—C5—C10 | 120.01 (10) |
O3ii—Na—O4i | 93.20 (5) | S—C5—C6 | 119.61 (10) |
O1iii—Na—O4i | 103.57 (5) | O1—C8—C9 | 115.68 (12) |
O4i—Na—N1iii | 102.47 (5) | O1—C8—C7 | 124.04 (13) |
O1iii—Na—O3ii | 161.68 (5) | N1—C9—C10 | 122.93 (12) |
O3ii—Na—N1iii | 104.65 (5) | N1—C9—C8 | 117.16 (12) |
Symmetry codes: (i) −x+1, y−1/2, −z−1/2; (ii) −x+1, −y, −z; (iii) x−1, −y+1/2, z−1/2; (iv) x+1, −y+1/2, z+1/2; (v) −x+1, y+1/2, −z−1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3vi | 0.805 (18) | 1.902 (18) | 2.7029 (17) | 173.4 (17) |
C4—H4···O4 | 0.936 (17) | 2.584 (18) | 3.1235 (19) | 117.1 (13) |
C6—H6···O2 | 0.972 (18) | 2.381 (17) | 2.8657 (19) | 110.2 (12) |
Symmetry code: (vi) x+1, y, z. |
Oxine and its derivatives are well known analytical reagents and antiamoebic agents (Bambury, 1979). Oxine is a bidentate chelator forming complexes with many metal ions through the quinoline N and deprotonated quinolinol O atoms. Metal chelation has been implicated in the biological activity of oxine derivatives (Martel & Calvin, 1959). The incorporation of sulfonic acid in the oxine moiety provides additional metal-binding and potential hydrogen-bonding acceptor sites/modes. This type of ligand is called sulfoxine (sulfonic acid + oxine). In metal sulfoxinates, in addition to the usual bidentate chelation of the oxine moiety through the N and O atoms, sulfonic-O atoms also coordinate to the metal. Hydrogen-bonding patterns and metal-binding modes of sulfoxinates are of current interest (Cai, Chen, Liao, Feng & Chen, 2001; Cai, Chen, Liao, Yao et al., 2001; Cai, Chen, Feng et al., 2001). It has recently been demonstrated that the combination of coordination and the sulfonate group can result in the formation of strong supramolecular aggregates through hydrogen bonding and this represents a new strategy for the design of SHG (second harmonic generation) materials (Xie et al., 2002). Information on the structural chemistry of metal sulfoxinates is relatively rare due to the poor coordination strength of sulfoxinates compared with that of phosphonates. The various remarkable structural features of metal sulfoxinates have prompted us to investigate systematically the structural chemistry of these compounds. The crystal structures of 7-iodo-8-hydroxyquinoline-5-sulfonic acid (ferron; Balasubramanian & Muthiah, 1996a), 7-nitro-8-hydroxyquinoline-5-sulfonic acid monohydrate (Balasubramanian & Muthiah, 1996b), the cobalt complex of ferron (Balasubramanian, 1995), the nickel complex of 8-hydroxyquinoline-5-sulfonic acid (HQS; Baskar Raj et al., 2001), the nickel complex of ferron (Baskar Raj et al., 2002) and the lithium complex of HQS (Murugesan & Muthiah, 1997) have also been reported from our laboratory.
In metal sulfoxinates, the sulfonate motifs can be linked in two ways. In one type, in addition to the usual bidentate chelation of the oxine motif, two centrosymmetrically related monomers are bridged by one of the sulfonate O atoms involved in the coordination, forming a cage-like dimer, as observed in the copper–sulfoxinate complexes (Petit, Coquerel et al., 1993; Petit, Ammor et al., 1993), the cobalt complex of ferron (Balasubramanian, 1995), the nickel complex of ferron (Baskar Raj et al., 2002) and the lithium complex of HQS (Murugesan & Muthiah, 1997). In another type, in addition to the usual bidentate chelation, a sulfonic acid O atom of one molecule is coordinated to the metal atom of another molecule, leading to a one-dimensional polymeric arrangement, as observed in the copper–sulfoxinate complex (Petit, Coquerel et al., 1993).
In the sodium complex of HQS, (I), the coordination geometry around the sodium ion is distorted trigonal bipyramidal. In addition to the usual bidentate chelation involving the N and O atoms of the oxine moiety, three sulfonate O atoms from three different sulfonate groups are coordinated to the sodium ion. The O atom of the quinolinol moiety and one of the O atoms (O3) from the sulfonate group bind to the Na+ ion at the axial positions and two O atoms (O2 and O4) from two different sulfonate groups and the ring N atom lie in the equatorial positions. A view of the complex unit of (I), with the atom-labelling scheme, is shown in Fig. 1. One of the sulfonate O atoms bridges the two inversion-related monomers, leading to a cage-like dimeric unit (Fig. 2). The distance between two neighbouring Na atoms is 5.4718 (15) Å. A view of the packing is shown in Fig. 3. The present sodium complex is quite different from other metal sulfoxinates reported in the literature (Balasubramanian, 1996; Murugesan & Muthiah, 1997; Petit, Coquerel et al., 1993; Petit, Ammor et al., 1993; Baskar Raj et al., 2001, 2002) in the sense that all tthree sulfonate O atoms are involved in the coordination, leading to a supramolecular network structure. The smaller N—Na—O bite angle in (I) may be the result of longer coordination bonds than those in the Co and Ni complexes. The Na—O(quinolinol) and Na—N(ring) bond distances are not significantly different from one another. The Na—N(ring) distance [2.4418 (15) Å] in (I) agrees with the range of values [2.459 (7)–2.539 (6) Å] reported in the literature (Papadimitriou et al., 1998). Also, the Na—O(quinolinol) distance [2.4892 (14) Å] in (I) agrees with the corresponding distance [2.42 (9) Å] in small molecules (Harding, 2002) reported in the Cambridge Structural Database (Allen & Kennard, 1993). The Na—O(sulfonate) distances agree with the corresponding distance reported in the literature (Cai, Chen, Liao, Feng & Chen, 2001; Cai, Chen, Liao, Yao et al., 2001; Cai, Chen, Feng et al., 2001) and are significantly shorter than the Na—O(quinolinol) distance (Table 1).
Unlike other sulfoxinates, the quinolinol O atom is not deprotonated, but is involved in a hydrogen bond with a symmetry-related O atom of the sulfonic acid group [O1—H1···O3i: symmetry code: (i) 1 + x, y, z]. Atoms C4 and C6 are also involved in intramolecular hydrogen bonding with atoms O4 and O2 of the sulfonate group (Table 2), forming five-membered rings on both sides of the S—C bond. Intramolecular hydrogen bonding involving atom C6 with one of the sulfonate O atoms has also been observed in both 7-nitro-8-hydroxyquinoline-5-sulfonic acid monohydrate (Balasubramanian & Muthiah, 1996b) and ferron (Balasubramanian & Muthiah, 1996a). There is also a glide-related C—H···π interaction [H···Cg 2.6341 (6) Å and C2—H2···Cg 134.02 (5)°; atoms C2 is in the pyridine ring and Cg is the phenyl-ring centroid]. Stacking interactions between the pyridine and phenyl rings in adjacent complex units is observed. The centroid-to-centroid and interplanar distances are 3.499 (9) and 3.303 (4) Å, respectively. The slip angles (angle between the centroid vector and the normal to the plane) is 20.73 (3)°.