The title complex, [Na(C8H9O5S)]n, is polymeric and consists of broad layers parallel to (100) made up of an inner hydrophilic core of Na+ cations and polar SO3C(OH)– groups, padded on both sides by two hydrophobic layers of pendant methoxyphenyl groups. The Na+ cations in the inner core are six-coordinated into highly distorted NaO6 octahedra by four symmetry-related (hydroxy)(4-methoxyphenyl)methanesulfonate anions, leading to a tightly woven two-dimensional structure. While there are some hydrogen bonds providing interplanar cohesion, interactions between adjacent layers are weak hydrophobic ones. The present compound appears to be the first reported structure containing the (hydroxy)(4-methoxyphenyl)methanesulfonate ligand.
Supporting information
CCDC reference: 925263
Compound (I) was synthesized by mixing a saturated aqueous solution of NaHSO3
with 4-methoxybenzaldehyde at room temperature (molar ratio 2:1). The
resulting white precipitate was first washed with the same bisulfite solution
used in the preparation, then with ethanol (96%) and finally with diethyl
ether. The solid powder thus obtained was dissolved in H2O, and methanol was
added until saturation was achieved. After [evaporation at room temperature
for?] one month, a few crystals suitable for X-ray diffraction analysis
were obtained.
All H atoms were visible in a difference map. The H atom attached to atom O5
was freely refined, whereas H atoms bonded to C atoms were idealized and
allowed to ride, with C—H = 0.98 Å and Uiso(H) =
1.2Ueq(C) for tertiary, C—H = 0.93 Å and Uiso(H) =
1.2Ueq(C) for aromatic, and C—H = 0.98 Å and Uiso(H) =
1.5Ueq(C) for methyl H atoms.
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
Poly[[µ
4-(hydroxy)(4-methoxyphenyl)methanesulfonato]sodium]
top
Crystal data top
[Na(C8H9O5S)] | F(000) = 496 |
Mr = 240.20 | Dx = 1.635 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 6270 reflections |
a = 16.649 (3) Å | θ = 3.1–26.3° |
b = 6.0854 (10) Å | µ = 0.37 mm−1 |
c = 9.8244 (16) Å | T = 170 K |
β = 101.365 (3)° | Block, colourless |
V = 975.8 (3) Å3 | 0.25 × 0.18 × 0.15 mm |
Z = 4 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2152 independent reflections |
Radiation source: fine-focus sealed tube | 1553 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.068 |
ϕ and ω scans | θmax = 27.8°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | h = −20→20 |
Tmin = 0.92, Tmax = 0.95 | k = −7→7 |
9705 measured reflections | l = −12→12 |
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)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.132 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + 0.0255P] where P = (Fo2 + 2Fc2)/3 |
2152 reflections | (Δ/σ)max < 0.001 |
141 parameters | Δρmax = 0.53 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
Crystal data top
[Na(C8H9O5S)] | V = 975.8 (3) Å3 |
Mr = 240.20 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 16.649 (3) Å | µ = 0.37 mm−1 |
b = 6.0854 (10) Å | T = 170 K |
c = 9.8244 (16) Å | 0.25 × 0.18 × 0.15 mm |
β = 101.365 (3)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2152 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | 1553 reflections with I > 2σ(I) |
Tmin = 0.92, Tmax = 0.95 | Rint = 0.068 |
9705 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.132 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.53 e Å−3 |
2152 reflections | Δρmin = −0.36 e Å−3 |
141 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Na1 | 0.45801 (7) | 0.32081 (16) | 0.62318 (11) | 0.0248 (3) | |
O1 | 0.44313 (12) | 0.6727 (3) | 0.51144 (19) | 0.0262 (5) | |
O2 | 0.44279 (12) | 0.9413 (3) | 0.69395 (18) | 0.0271 (5) | |
O3 | 0.36365 (12) | 1.0086 (3) | 0.46680 (17) | 0.0255 (5) | |
O4 | 0.06777 (13) | 0.4579 (3) | 0.1499 (2) | 0.0334 (5) | |
O5 | 0.34392 (12) | 0.5072 (3) | 0.6900 (2) | 0.0255 (5) | |
H5 | 0.349 (2) | 0.519 (6) | 0.777 (4) | 0.046 (10)* | |
S1 | 0.39701 (4) | 0.84056 (10) | 0.56812 (7) | 0.0215 (2) | |
C1 | 0.31082 (18) | 0.6947 (4) | 0.6149 (3) | 0.0235 (7) | |
H1 | 0.2848 | 0.7885 | 0.6747 | 0.028* | |
C2 | 0.24889 (17) | 0.6321 (4) | 0.4888 (3) | 0.0228 (6) | |
C3 | 0.25539 (19) | 0.4371 (5) | 0.4182 (3) | 0.0305 (7) | |
H3 | 0.3003 | 0.3462 | 0.4485 | 0.037* | |
C4 | 0.1975 (2) | 0.3742 (4) | 0.3047 (3) | 0.0311 (7) | |
H4 | 0.2037 | 0.2435 | 0.2589 | 0.037* | |
C5 | 0.13000 (19) | 0.5066 (4) | 0.2593 (3) | 0.0273 (7) | |
C6 | 0.1230 (2) | 0.7047 (5) | 0.3257 (3) | 0.0319 (7) | |
H6 | 0.0787 | 0.7967 | 0.2935 | 0.038* | |
C7 | 0.18134 (19) | 0.7658 (5) | 0.4391 (3) | 0.0308 (7) | |
H7 | 0.1756 | 0.8984 | 0.4833 | 0.037* | |
C8 | 0.0712 (2) | 0.2521 (5) | 0.0810 (3) | 0.0394 (8) | |
H8A | 0.0241 | 0.2376 | 0.0075 | 0.059* | |
H8B | 0.0718 | 0.1344 | 0.1463 | 0.059* | |
H8C | 0.1200 | 0.2461 | 0.0430 | 0.059* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Na1 | 0.0314 (8) | 0.0149 (5) | 0.0276 (6) | 0.0011 (4) | 0.0047 (5) | 0.0005 (4) |
O1 | 0.0329 (13) | 0.0162 (9) | 0.0314 (11) | 0.0036 (8) | 0.0105 (10) | 0.0003 (8) |
O2 | 0.0348 (13) | 0.0199 (10) | 0.0239 (10) | −0.0050 (9) | −0.0008 (9) | −0.0014 (8) |
O3 | 0.0384 (13) | 0.0140 (9) | 0.0230 (10) | 0.0049 (8) | 0.0033 (9) | 0.0035 (7) |
O4 | 0.0322 (13) | 0.0284 (11) | 0.0362 (12) | −0.0011 (9) | −0.0015 (10) | 0.0006 (9) |
O5 | 0.0388 (13) | 0.0166 (9) | 0.0209 (11) | 0.0025 (8) | 0.0052 (10) | 0.0033 (8) |
S1 | 0.0297 (5) | 0.0119 (3) | 0.0229 (4) | 0.0013 (3) | 0.0050 (3) | 0.0009 (3) |
C1 | 0.0290 (18) | 0.0145 (12) | 0.0278 (15) | 0.0054 (12) | 0.0077 (13) | 0.0006 (11) |
C2 | 0.0253 (17) | 0.0156 (13) | 0.0268 (15) | 0.0012 (11) | 0.0030 (13) | 0.0021 (11) |
C3 | 0.0300 (19) | 0.0204 (14) | 0.0379 (18) | 0.0064 (13) | −0.0008 (14) | −0.0041 (13) |
C4 | 0.033 (2) | 0.0186 (14) | 0.0388 (18) | 0.0014 (13) | 0.0003 (15) | −0.0057 (13) |
C5 | 0.0272 (18) | 0.0239 (14) | 0.0293 (16) | −0.0022 (13) | 0.0018 (13) | 0.0052 (12) |
C6 | 0.0303 (19) | 0.0277 (15) | 0.0354 (18) | 0.0080 (13) | 0.0007 (15) | 0.0000 (13) |
C7 | 0.037 (2) | 0.0211 (14) | 0.0339 (17) | 0.0067 (13) | 0.0050 (15) | −0.0005 (12) |
C8 | 0.046 (2) | 0.0304 (16) | 0.0377 (19) | −0.0059 (16) | −0.0019 (16) | −0.0020 (14) |
Geometric parameters (Å, º) top
Na1—O1i | 2.3060 (19) | C1—H1 | 0.9800 |
Na1—O2ii | 2.307 (2) | C2—C3 | 1.390 (4) |
Na1—O1 | 2.397 (2) | C2—C7 | 1.396 (4) |
Na1—O5 | 2.412 (2) | C3—C4 | 1.377 (4) |
Na1—O2iii | 2.439 (2) | C3—H3 | 0.9300 |
Na1—O3iii | 2.736 (2) | C4—C5 | 1.383 (4) |
O1—S1 | 1.4533 (18) | C4—H4 | 0.9300 |
O2—S1 | 1.4538 (19) | C5—C6 | 1.387 (4) |
O3—S1 | 1.4584 (18) | C6—C7 | 1.377 (4) |
O4—C5 | 1.370 (4) | C6—H6 | 0.9300 |
O4—C8 | 1.430 (3) | C7—H7 | 0.9300 |
O5—C1 | 1.410 (3) | C8—H8A | 0.9600 |
O5—H5 | 0.85 (3) | C8—H8B | 0.9600 |
S1—C1 | 1.822 (3) | C8—H8C | 0.9600 |
C1—C2 | 1.497 (4) | | |
| | | |
Na1···Na1i | 3.729 (2) | Na1···Na1v | 4.939 (2) |
Na1···Na1ii | 4.006 (2) | Na1···Na1vi | 4.987 (2) |
Na1···Na1iv | 4.006 (2) | Na1···Na1vii | 4.987 (2) |
| | | |
O1i—Na1—O2ii | 87.64 (8) | O3—S1—C1 | 107.51 (12) |
O1i—Na1—O1 | 75.11 (7) | O5—C1—C2 | 111.2 (2) |
O2ii—Na1—O1 | 93.80 (8) | O5—C1—S1 | 106.27 (19) |
O1i—Na1—O5 | 146.87 (8) | C2—C1—S1 | 111.33 (17) |
O2ii—Na1—O5 | 96.88 (7) | O5—C1—H1 | 109.3 |
O1—Na1—O5 | 71.86 (7) | C2—C1—H1 | 109.3 |
O1i—Na1—O2iii | 107.80 (7) | S1—C1—H1 | 109.3 |
O2ii—Na1—O2iii | 100.23 (6) | C3—C2—C7 | 117.4 (3) |
O1—Na1—O2iii | 165.74 (9) | C3—C2—C1 | 121.5 (3) |
O5—Na1—O2iii | 103.65 (7) | C7—C2—C1 | 121.1 (2) |
O1i—Na1—O3iii | 94.91 (7) | C4—C3—C2 | 122.0 (3) |
O2ii—Na1—O3iii | 154.36 (7) | C4—C3—H3 | 119.0 |
O1—Na1—O3iii | 111.53 (7) | C2—C3—H3 | 119.0 |
O5—Na1—O3iii | 94.80 (7) | C3—C4—C5 | 119.6 (3) |
O2iii—Na1—O3iii | 54.71 (6) | C3—C4—H4 | 120.2 |
S1—O1—Na1i | 134.30 (11) | C5—C4—H4 | 120.2 |
S1—O1—Na1 | 117.86 (10) | O4—C5—C4 | 124.6 (3) |
Na1i—O1—Na1 | 104.89 (7) | O4—C5—C6 | 115.9 (3) |
S1—O2—Na1iv | 134.67 (12) | C4—C5—C6 | 119.6 (3) |
S1—O2—Na1viii | 102.91 (10) | C7—C6—C5 | 120.3 (3) |
Na1iv—O2—Na1viii | 115.10 (8) | C7—C6—H6 | 119.9 |
S1—O3—Na1viii | 90.25 (9) | C5—C6—H6 | 119.9 |
C5—O4—C8 | 117.8 (2) | C6—C7—C2 | 121.1 (3) |
C1—O5—Na1 | 119.04 (14) | C6—C7—H7 | 119.4 |
C1—O5—H5 | 114 (2) | C2—C7—H7 | 119.4 |
Na1—O5—H5 | 113 (2) | O4—C8—H8A | 109.5 |
O1—S1—O2 | 113.21 (12) | O4—C8—H8B | 109.5 |
O1—S1—O3 | 112.97 (10) | H8A—C8—H8B | 109.5 |
O2—S1—O3 | 110.49 (11) | O4—C8—H8C | 109.5 |
O1—S1—C1 | 104.83 (11) | H8A—C8—H8C | 109.5 |
O2—S1—C1 | 107.34 (11) | H8B—C8—H8C | 109.5 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y−1/2, −z+3/2; (iii) x, y−1, z; (iv) −x+1, y+1/2, −z+3/2; (v) −x+1, −y, −z+1; (vi) x, −y+1/2, z−1/2; (vii) x, −y+1/2, z+1/2; (viii) x, y+1, z. |
Hydrogen-bond geometry (Å, º) topCg1 is the centroid of the C2–C7 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5···O3ix | 0.85 (3) | 1.84 (3) | 2.676 (3) | 169 (3) |
C3—H3···O3iii | 0.93 | 2.30 | 3.152 (3) | 152 |
C1—H1···Cg1ix | 0.98 | 2.93 (3) | 3.818 (3) | 157 |
C8—H8C···Cg1vi | 0.96 | 2.92 (3) | 3.669 (5) | 131 |
Symmetry codes: (iii) x, y−1, z; (vi) x, −y+1/2, z−1/2; (ix) x, −y+3/2, z+1/2. |
Experimental details
Crystal data |
Chemical formula | [Na(C8H9O5S)] |
Mr | 240.20 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 170 |
a, b, c (Å) | 16.649 (3), 6.0854 (10), 9.8244 (16) |
β (°) | 101.365 (3) |
V (Å3) | 975.8 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.37 |
Crystal size (mm) | 0.25 × 0.18 × 0.15 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2001) |
Tmin, Tmax | 0.92, 0.95 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9705, 2152, 1553 |
Rint | 0.068 |
(sin θ/λ)max (Å−1) | 0.655 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.132, 1.05 |
No. of reflections | 2152 |
No. of parameters | 141 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.53, −0.36 |
Selected interatomic distances (Å) topNa1—O1i | 2.3060 (19) | Na1—O5 | 2.412 (2) |
Na1—O2ii | 2.307 (2) | Na1—O2iii | 2.439 (2) |
Na1—O1 | 2.397 (2) | Na1—O3iii | 2.736 (2) |
| | | |
Na1···Na1i | 3.729 (2) | Na1···Na1iv | 4.939 (2) |
Na1···Na1ii | 4.006 (2) | Na1···Na1v | 4.987 (2) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y−1/2, −z+3/2; (iii) x, y−1, z; (iv) −x+1, −y, −z+1; (v) x, −y+1/2, z−1/2. |
Hydrogen-bond geometry (Å, º) topCg1 is the centroid of the C2–C7 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5···O3vi | 0.85 (3) | 1.84 (3) | 2.676 (3) | 169 (3) |
C3—H3···O3iii | 0.93 | 2.30 | 3.152 (3) | 152 |
C1—H1···Cg1vi | 0.98 | 2.93 (3) | 3.818 (3) | 157 |
C8—H8C···Cg1v | 0.96 | 2.92 (3) | 3.669 (5) | 131 |
Symmetry codes: (iii) x, y−1, z; (v) x, −y+1/2, z−1/2; (vi) x, −y+3/2, z+1/2. |
Aldehydes and methyl ketones are known to undergo nucleophilic addition of NaHSO3 in aqueous solution (Clayden et al., 2012). The resulting derivatives could act as potentially good ligands in coordination complexes through the O atoms of the sulfite group, which normally exhibits several binding modes. In order to obtain these coordination compounds, we have first prepared and determined the crystal structure of the title compound, (I). A search of the Cambridge Structural Database (CSD, Version 5.33, August 2012 update; Allen, 2002) revealed that this is the first crystal structure containing this otherwise well known commercially available (hydroxy)(4-methoxyphenyl)methanesulfonate (mbs) derivative [Chemical Abstracts Service (CAS) number 33402-67-4]. However, a few closely related compounds have been published. Perhaps the most interesting one for comparison purposes is the potassium salt of (hydroxyphenyl)methanesulfonate, (II) (Kuroda et al., 1967), a ligand similar to mbs but lacking the terminal methoxy group. The two solids are almost isostructural, and here we shall analyse their similarities and differences.
The asymmetric unit of (I) consists of one Na+ cation and one mbs anion. Fig. 1 shows an ellipsoid plot of the structure, displaying a complete Na environment, while Table 1 presents Na—O coordination bond lengths and some Na···Na distances (see below). Compound (I) has a two-dimensional polymeric structure built up around the six-coordinated Na+ cations, which show a highly distorted NaO6 octahedral environment. This is provided by four symmetry-related mbs anions (Fig. 1), two of them through two different chelating bites (atoms O1 and O5, and O2iii and O3iii), and the remaining two by way of two of these O atoms (O1i and O2ii), acting now in a bridging mode [symmetry codes: (i) -x + 1, -y + 1, -z + 1; (ii) -x + 1, y - 1/2, -z + 3/2; (iii) x, y - 1, z]. The Na—O coordination bond lengths span a narrow range [2.306 (2)–2.439 (2) Å for five of the O-atom donors, the sixth being an outlier of 2.736 (2) Å]. The fact that all four O atoms of the SO3COH group are involved in coordination provides multiple bridging paths connecting the Na+ cations, though this is not necessarily reflected in particularly short Na···Na distances (see below).
The mbs anion presents a µ4η4 binding mode not shown by any previous ligand containing an SO3COH group. Fig 2 presents a summary of the different coordination modes found in the CSD, ranging from the very simple µ1 up to the extremely complex µ7η4. This diversity seems to confirm the potential of mbs in structural design.
The –SO3 group in the ligand is extremely regular, with completely delocalized double bonds [S—O = 1.4533 (18)–1.4594 (18) Å], and the very small angular deviations from regularity are due solely to chelation. Thus, the O2—S1—O3 angle of 110.49 (11)° is 3% smaller than the remaining two O—S—O analogues. A similar relationship is encountered between C1—S1—O1 [104.84 (11)°] and its corresponding C—S—O analogues.
The bonding scheme results in a tightly woven two-dimensional array which can be described as a three-layered sandwich-like structure parallel to (100), viz. the B—A—B motif shown in Fig. 3. The inner part (A) is a hydrophilic core centred at x ~0.50 and about a/4 wide, built up by Na+ cations and sulfite anions. The methoxyphenyl groups, in turn, evolve upwards and downwards to form two limiting hydrophobic layers (B) sandwiching the former one (Fig. 3). Fig. 4 displays a simplified version of the central type `A' layer, built up of Na+ cations and sulfite anions. The wide diversity of loops linking the cations is apparent, and, as expected, those involving direct (O-atom mediated) Na—O—Na bridges lead to the shortest Na···Na distances. In the following, we refer the reader to Fig. 4 for geometric details and to Table 1 for symmetry codes. The nearest approach appears between atoms Na1 and Na1i [dark-grey shaded loop; Na···Na = 3.729 (2) Å], built up around an inversion centre and, accordingly, this results in two such Na—O—Na bridges. The second nearest are those linking 21-related cations, Na1···Na1ii [light-grey shading; Na···Na = 4.006 (1) Å], with only one such bridge. The minimum approach distance in (I) is in the range of the average found in the CSD for normal Na—O networks [3.47 (18) Å in a sample of 220 cases] but appears rather long if compared with, for instance, that in pure Na2SO3 [Na···Na = 3.090 (2) Å; Larsson & Kierkegaard, 1969]. As expected, Na—O—S—O—Na bridges are noticeably less effective in promoting close Na···Na contacts (see Fig. 4 and Table 1 for details).
Regarding type `B' zones, they are linked internally by weaker noncovalent interactions (Table 2), where atoms O4 and O5 present quite different behaviours. Protonated atom O5 is not only involved in coordination but also takes part in a moderately strong O—H···O hydrogen bond (first entry in Table 2), while due to its isolation in the hydrophobic region, atom O4 is neither coordinated nor involved in any relevant secondary interaction. The intralayer links are completed by significantly weaker interactions, viz. a non-conventional C—H···O hydrogen bond (second entry in Table 2) and a couple of C—H···π interactions (third and fourth entries in Table 2).
The whole three-layered B—A—B array fills one complete unit cell along the [100] direction. As suggested by Fig. 3, the interaction between neighbouring B—A—B structures is governed by weak hydrophobic B···B interactions.
As stated, (I) and the closely related potassium analogue, (II), are quasi-isostructural, crystallizing in the same space group (P21/c) and having similar cell parameters, although with variable relative increase when going from (I) to (II) (1.7% in a, 0.2% in b and 7.1% in c). These values correlate closely with the influence of the bulky methoxy group in (I) in the direction of each lattice parameter; this group is mainly oriented along c, only slightly along a and has no significant component along b.
The crystal structure description in terms of B—A—B zones is applicable to both (I) and (II), although, strikingly, this is where the similarities end: the B···B interactions and alignments are different in the two structures, as are the cation–sulfonate interactions in the hydrophilic zones A. This is easily revealed by inspection of the coordination modes of the ligands shown in Fig. 2, in which the modes for (I) and (II) have been encircled for clarity.
In summary, the results concerning the ligand properties of the mbs anion are encouraging, and therefore a project aimed at the synthesis of possible transition metal complexes of this ligand is under way in our laboratory.