metal-organic compounds
Potassium 4-nitrophenylsulfonate monohydrate
aDepartment of Chemistry, University of Durham, South Road, Durham DH1 3LE, England, and bGlaxoSmithKline Pharmaceuticals, New Frontiers Science Park, Third Avenue, Harlow, Essex CM19 5AW, England
*Correspondence e-mail: a.s.batsanov@durham.ac.uk
The title compound, K+·C6H4NO5S−·H2O, forms a three-dimensional polymeric structure with an O8 coordination environment of the K+ cation.
Comment
As part of a programme aimed at developing new aza-Baeyer–Villiger reactions, we have examined the use of N-alkyl-O-arylsulfonylhydroxylamines as potential nitrene equivalents (Hoffman & Buntain, 1988; Hoffman & Salvador, 1989a, 1991). Attempts have therefore been made to prepare a range of N-alkyl-O-arylsulfonylhydroxylamines p-XC6H4SO2NHR by reacting RNH2 with sulfonyl p-XC6H4SO2OOSO2C6H4-p-X, which in turn are accessible from sulfonyl chlorides p-XC6H4SO2Cl by reaction with t-BuOOH (Hoffman & Cadena, 1977; Hoffman & Belfoure, 1983; Hoffman & Salvador, 1989b). The title compound, (I), was isolated as a by-product during this synthesis.
Numerous et al., 1994; Chan & Wong, 2002; Tamura et al., 2002). However, no salt or complex of any metal with this anion has been studied previously.
of 4-nitrophenylsulfonic acid have been structurally characterized, as well as some salts with organic cations (Russell(I) has a three-dimensional polymeric (catena) (Fig. 1). The comprises one formula unit. The potassium cation is coordinated by eight O atoms, viz. five from the sulfonate groups of four different anions, one from a nitro group of another anion, and two μ2-bridging water molecules. The can be described as a distorted monocapped pentagonal bipyramid. The anion links five K+ cations, four of them via one O atom each. There is only one case of the sulfonate atoms O1 and O2 coordinated to the same potassium ion, and even this one is highly asymmmetric. The K—O2 distance is 0.33 Å longer than K—O1 and is by far the longest in the structure.
The aqua bridge is highly asymmetric: the K—O distances differ by 0.176 Å and the stronger-bound potassium ion is practically coplanar with the H2O plane. The weakly coordinated O2 atom and the uncoordinated O5 atom of the nitro group act as acceptors of hydrogen bonds donated by the water molecules. Notwithstanding these differences, both N—O bond lengths are equal within experimental error (mean 1.233 (3) Å), as are the three S—O bond lengths (mean 1.453 (3) Å). The benzene ring and the nitro group of the anion form a dihedral angle of 11.2 (1)°, whereas the S—O2 bond is nearly coplanar with the ring: the dihedral angle C2—C1—S—O2 is 9.0 (3)°.
Experimental
4-Nitrobenzenesulfonyl peroxide p-O2NC6H4SO2OOSO2C6H4NO2-p (II) was prepared according to Dannley et al. (1970). To a solution of K2CO3 (5.10 g, 36.9 mmol) in water (76 ml), ethanol (38 ml) and hydrogen peroxide (35%, 8.75 g) at 253 K a cooled (253 K) solution of 4-nitrobenzenesulfonyl chloride (7.88 g, 35.6 mmol) in chloroform (10 ml) was added and the suspension was mixed at full power for 1 min using a Breville ClassiqueTM blender. Ethanol (80 ml) was added and the solution was mixed for 4 min at low power. The precipitate formed was filtered off, washed with distilled water and recrystallized from acetone to give (II) as a yellow solid (2.22 g, 31%). The filtrate was cooled at 253 K for 24 h, yielding (I) as yellow crystals (0.160 g, 1.2%), m.p. >593 K, IR, ν, cm−1: 3065 (CH aromatic stretch), 1529 (NO2), 1461 (SO2) 819 (p-disubstituted aromatic). 1H NMR (200 MHz, CDCl3): 8.20 (d, 2H, CH aromatic, J 8.6 Hz), 8.49 (d, 2H, CH aromatic, J = 8.4 Hz). 13C NMR (100 MHz, CDCl3): 123.5 (2 × PhCNO2), 126.0 (4 × CH aromatic), 140.0 (4 × CH aromatic), 148.0 (2 × PhCSO2). The properties of (I) agree with those reported by Kozlov & Davydov (1965) or Dietze et al. (1989).
Crystal data
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Data collection
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Refinement
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Water atoms H01 and H02 were located in a difference map and refined isotropically. Benzene H atoms were treated as riding on the C atoms, C—H 0.95 Å, Uiso(H) = 1.2Ueq(C).
Data collection: SMART (Bruker, 2001); cell SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Supporting information
https://doi.org/10.1107/S1600536806007835/kp2006sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806007835/kp2006Isup2.hkl
Data collection: SMART (Bruker, 2001); cell
SMART; data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.K+·C6H4NO5S−·H2O | F(000) = 528 |
Mr = 259.28 | Dx = 1.871 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2733 reflections |
a = 10.794 (1) Å | θ = 3.3–27.5° |
b = 7.1516 (6) Å | µ = 0.81 mm−1 |
c = 12.417 (1) Å | T = 120 K |
β = 106.15 (1)° | Block, colourless |
V = 920.70 (14) Å3 | 0.3 × 0.2 × 0.15 mm |
Z = 4 |
Siemens SMART 1K CCD area detector diffractometer | 1596 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.067 |
Graphite monochromator | θmax = 27.5°, θmin = 2.0° |
Detector resolution: 8 pixels mm-1 | h = −14→13 |
ω scans | k = −9→9 |
9859 measured reflections | l = −16→15 |
2117 independent reflections |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.095 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0364P)2 + 0.9635P] where P = (Fo2 + 2Fc2)/3 |
2117 reflections | (Δ/σ)max < 0.001 |
144 parameters | Δρmax = 0.39 e Å−3 |
0 restraints | Δρmin = −0.46 e Å−3 |
Experimental. The data collection nominally covered full sphere of reciprocal Space, by a combination of 5 sets of ω scans each set at different φ and/or 2θ angles and each scan (10 s exposure) covering 0.3° in ω. Crystal to detector distance 4.51 cm. |
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. |
x | y | z | Uiso*/Ueq | ||
K | 0.43521 (6) | 0.53657 (9) | 0.74392 (5) | 0.01343 (16) | |
S | 0.37624 (7) | 0.22064 (10) | 0.46669 (6) | 0.01054 (17) | |
O1 | 0.4524 (2) | 0.2686 (3) | 0.39107 (17) | 0.0140 (5) | |
O2 | 0.3285 (2) | 0.0291 (3) | 0.45242 (18) | 0.0159 (5) | |
O3 | 0.4386 (2) | 0.2697 (3) | 0.58251 (17) | 0.0149 (5) | |
O4 | −0.1962 (2) | 0.6461 (3) | 0.31470 (18) | 0.0192 (5) | |
O5 | −0.0704 (2) | 0.8883 (3) | 0.35935 (18) | 0.0188 (5) | |
O6 | 0.3076 (2) | 0.8669 (3) | 0.6626 (2) | 0.0207 (5) | |
H01 | 0.315 (4) | 0.900 (5) | 0.605 (3) | 0.026 (11)* | |
H02 | 0.252 (4) | 0.945 (6) | 0.672 (3) | 0.039 (12)* | |
N | −0.0886 (2) | 0.7181 (4) | 0.3463 (2) | 0.0147 (5) | |
C1 | 0.2366 (3) | 0.3660 (4) | 0.4267 (2) | 0.0108 (6) | |
C2 | 0.1131 (3) | 0.2881 (4) | 0.4060 (2) | 0.0132 (6) | |
H2 | 0.1032 | 0.1568 | 0.4118 | 0.016* | |
C3 | 0.0058 (3) | 0.4025 (4) | 0.3772 (2) | 0.0136 (6) | |
H3 | −0.0787 | 0.3518 | 0.3622 | 0.016* | |
C4 | 0.0250 (3) | 0.5950 (4) | 0.3708 (2) | 0.0122 (6) | |
C5 | 0.1463 (3) | 0.6745 (4) | 0.3908 (2) | 0.0144 (6) | |
H5 | 0.1559 | 0.8060 | 0.3859 | 0.017* | |
C6 | 0.2534 (3) | 0.5582 (4) | 0.4183 (2) | 0.0139 (6) | |
H6 | 0.3376 | 0.6092 | 0.4312 | 0.017* |
U11 | U22 | U33 | U12 | U13 | U23 | |
K | 0.0157 (3) | 0.0116 (3) | 0.0132 (3) | −0.0007 (3) | 0.0043 (2) | 0.0000 (2) |
S | 0.0110 (4) | 0.0094 (3) | 0.0109 (4) | 0.0007 (3) | 0.0023 (3) | −0.0001 (3) |
O1 | 0.0159 (11) | 0.0149 (11) | 0.0126 (11) | 0.0009 (8) | 0.0063 (9) | 0.0003 (8) |
O2 | 0.0161 (11) | 0.0095 (10) | 0.0212 (12) | 0.0010 (9) | 0.0036 (9) | 0.0014 (9) |
O3 | 0.0169 (11) | 0.0159 (11) | 0.0097 (10) | 0.0022 (9) | 0.0000 (8) | −0.0016 (8) |
O4 | 0.0121 (12) | 0.0241 (12) | 0.0207 (12) | −0.0035 (9) | 0.0032 (9) | 0.0018 (9) |
O5 | 0.0191 (12) | 0.0150 (11) | 0.0217 (12) | 0.0042 (9) | 0.0046 (10) | 0.0011 (9) |
O6 | 0.0237 (14) | 0.0214 (13) | 0.0197 (13) | 0.0069 (10) | 0.0106 (11) | 0.0055 (10) |
N | 0.0137 (14) | 0.0205 (14) | 0.0107 (13) | 0.0018 (11) | 0.0047 (10) | 0.0033 (10) |
C1 | 0.0109 (14) | 0.0142 (15) | 0.0061 (14) | −0.0007 (12) | 0.0003 (11) | −0.0015 (11) |
C2 | 0.0177 (16) | 0.0117 (14) | 0.0110 (14) | −0.0015 (12) | 0.0055 (12) | −0.0023 (11) |
C3 | 0.0127 (15) | 0.0168 (15) | 0.0115 (15) | −0.0049 (12) | 0.0039 (12) | −0.0005 (11) |
C4 | 0.0126 (15) | 0.0154 (15) | 0.0070 (14) | 0.0023 (12) | 0.0002 (11) | 0.0002 (11) |
C5 | 0.0175 (16) | 0.0120 (14) | 0.0137 (15) | 0.0002 (12) | 0.0045 (12) | −0.0010 (11) |
C6 | 0.0129 (15) | 0.0164 (16) | 0.0128 (15) | 0.0002 (12) | 0.0041 (12) | 0.0009 (11) |
K—O1i | 2.712 (2) | O6—H01 | 0.78 (4) |
K—O3ii | 2.765 (2) | O6—H02 | 0.85 (4) |
K—O3 | 2.775 (2) | N—C4 | 1.471 (4) |
K—O6 | 2.779 (2) | C1—C6 | 1.395 (4) |
K—O4iii | 2.802 (2) | C1—C2 | 1.401 (4) |
K—O1iv | 2.819 (2) | C2—C3 | 1.382 (4) |
K—O6v | 2.955 (3) | C2—H2 | 0.9500 |
K—O2iv | 3.148 (2) | C3—C4 | 1.398 (4) |
S—O1 | 1.451 (2) | C3—H3 | 0.9500 |
S—O3 | 1.451 (2) | C4—C5 | 1.384 (4) |
S—O2 | 1.457 (2) | C5—C6 | 1.388 (4) |
S—C1 | 1.784 (3) | C5—H5 | 0.9500 |
O4—N | 1.230 (3) | C6—H6 | 0.9500 |
O5—N | 1.236 (3) | ||
O1i—K—O3ii | 87.93 (6) | S—O1—Kvi | 106.82 (10) |
O1i—K—O3 | 78.99 (6) | Ki—O1—Kvi | 87.55 (6) |
O3ii—K—O3 | 151.04 (3) | S—O2—Kvi | 92.42 (10) |
O1i—K—O6 | 66.46 (7) | S—O3—Kv | 128.22 (11) |
O3ii—K—O6 | 81.82 (7) | S—O3—K | 141.86 (12) |
O3—K—O6 | 115.27 (7) | Kv—O3—K | 87.38 (6) |
O1i—K—O4iii | 128.10 (7) | N—O4—Kiii | 175.69 (19) |
O3ii—K—O4iii | 134.60 (7) | K—O6—Kii | 83.67 (7) |
O3—K—O4iii | 71.80 (7) | K—O6—H01 | 115 (3) |
O6—K—O4iii | 88.53 (7) | Kii—O6—H01 | 85 (3) |
O1i—K—O1iv | 146.95 (5) | K—O6—H02 | 144 (3) |
O3ii—K—O1iv | 91.85 (6) | Kii—O6—H02 | 108 (3) |
O3—K—O1iv | 85.63 (6) | H01—O6—H02 | 100 (4) |
O6—K—O1iv | 146.11 (7) | O4—N—O5 | 123.7 (3) |
O4iii—K—O1iv | 72.37 (6) | O4—N—C4 | 118.3 (2) |
O1i—K—O6v | 85.46 (7) | O5—N—C4 | 118.0 (2) |
O3ii—K—O6v | 74.70 (7) | C6—C1—C2 | 121.0 (3) |
O3—K—O6v | 78.56 (7) | C6—C1—S | 118.5 (2) |
O6—K—O6v | 143.93 (7) | C2—C1—S | 120.4 (2) |
O4iii—K—O6v | 127.38 (7) | C3—C2—C1 | 119.9 (3) |
O1iv—K—O6v | 62.76 (7) | C3—C2—H2 | 120.0 |
O1i—K—O2iv | 156.06 (6) | C1—C2—H2 | 120.0 |
O3ii—K—O2iv | 70.29 (6) | C2—C3—C4 | 118.1 (3) |
O3—K—O2iv | 124.93 (6) | C2—C3—H3 | 121.0 |
O6—K—O2iv | 99.66 (7) | C4—C3—H3 | 121.0 |
O4iii—K—O2iv | 67.84 (6) | C5—C4—C3 | 122.8 (3) |
O1iv—K—O2iv | 47.52 (6) | C5—C4—N | 118.9 (3) |
O6v—K—O2iv | 97.73 (7) | C3—C4—N | 118.2 (3) |
O1—S—O3 | 113.22 (12) | C4—C5—C6 | 118.7 (3) |
O1—S—O2 | 112.87 (12) | C4—C5—H5 | 120.7 |
O3—S—O2 | 113.49 (13) | C6—C5—H5 | 120.7 |
O1—S—C1 | 105.61 (13) | C5—C6—C1 | 119.5 (3) |
O3—S—C1 | 104.94 (12) | C5—C6—H6 | 120.3 |
O2—S—C1 | 105.73 (13) | C1—C6—H6 | 120.3 |
S—O1—Ki | 162.38 (12) | ||
C2—C1—S—O2 | 9.0 (3) | C5—C4—N—O5 | −9.6 (4) |
C3—C4—N—O4 | −11.6 (4) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y+1/2, −z+3/2; (iii) −x, −y+1, −z+1; (iv) x, −y+1/2, z+1/2; (v) −x+1, y−1/2, −z+3/2; (vi) x, −y+1/2, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H01···O2vii | 0.78 (4) | 2.15 (4) | 2.922 (3) | 172 (4) |
O6—H02···O5viii | 0.85 (4) | 2.23 (4) | 3.050 (3) | 161 (4) |
Symmetry codes: (vii) x, y+1, z; (viii) −x, −y+2, −z+1. |
Acknowledgements
We thank both the EPSRC and GlaxoSmithKline Pharmaceuticals for a CASE award (to AJB).
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