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The structural data for sodium 2-hydroxy-5-nitro­benzyl­sulfonate monohydrate, Na+·C7H6NO6S-·H2O, which mimics an artificial substrate for human aryl­sulfatase A, viz. p-­nitrocatechol sulfate, reveal that the geometric parameters of the substrate and its analogue are very similar. Two water mol­ecules, the phenolic O atom and three sulfonate O atoms form the coordination sphere of the Na+ ion, which is a distorted octahedron. The Na+ cations and the O atoms join to form a chain polymer.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102000069/av1096sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102000069/av1096Isup2.hkl
Contains datablock I

CCDC reference: 182970

Comment top

The enzyme human arylsulfatase A (ASA) catalyses the in vivo desulfatation of cerebroside 3-sulfate, and a lack of ASA activity causes the rare disease metachromatic leukodystrophy. In this inherited disorder of myelin metabolism, cerebroside sulfate accumulates in the white matter of the central nervous system and in peripheral nerves (Kolodny & Fluharty, 1995). p-Nitrocatechol sulfate (NCS; Baum et al., 1959) is used in the assay of ASA activity in vitro. Because of the structural similarity between NCS (Bülow & Usón, 2000) and 2-hydroxy-5-nitrobenzylsulfonic acid (NBSA), and the fact that ASA is not able to cleave the C—S bond, NBSA very strongly inhibits sulfatase activity (Zucker-Franklin & Nabi, 1985). The structure of sodium 2-hydroxy-5-nitrobenzylsulfonate monohydrate, (I), the sodium salt of NBSA, is reported here. \sch

The molecular structure of (I) is shown in Fig. 1. The geometric parameters of NBSA and NCS are very similar. Only the geometry of the –CH2SO3- and –OSO3- groups is slightly different, due to the replacement of carbon by oxygen (Table 1). A difference is also observed in the length of the bond between the phenolic O atom and the C atom belonging to the aromatic ring. In (I), the C2—O4 bond is longer than in NCS [1.350 (2) versus 1.285 (2) Å], indicating the different protonation state of the O atom, i.e. it is protonated in (I) and deprotonated in NCS.

Two water molecules, the phenolic O atom and three O atoms from the sulfonate groups form the coordination sphere of the Na+ ion. These six O atoms create a distorted octahedron, with Na—O distances in the range 2.376 (1)–2.557 (2) Å. The Na+ cations and the O atoms form a chain polymer, in which the Na+···Na+ distance is 3.927 (1) Å and atoms O1 and O7 belong to the coordination spheres of two neighbouring metal atoms.

There are no intramolecular hydrogen bonds, but contacts consistent with intermolecular hydrogen bonding (Table 2) are observed. The water molecule present in the structure bridges the Na+ ions and also forms hydrogen bonds to the nitro and sulfonate groups. These connections enrich a network of possible interactions and stabilize the structure.

In the crystal structure of (I), molecules of NBSA form layers parallel to the (100) plane (Fig. 2). The hydrophobic interior of the layer is filled by aromatic rings arranged in antiparallel pairs and linked by face-to-face π stacking, while sulfonate and carboxyl groups give the layer a polar surface. Contacts between the layers are stabilized by Na+ ions and water molecules.

Experimental top

Compound (I) was synthesized according the procedure of Kaiser & Lo (1969), except 2-hydroxy-5-nitrobenzyl bromide (purchased from Fluka) was used instead of 2-hydroxy-5-nitrobenzyl chloride. The substrate (5.0 g) was mixed with anhydrous sodium sulphite (7.9 g) and distilled water (100 ml). The colour of the mixture changed to yellow. The mixture was then heated under reflux for 1.5 h. Water was removed under reduced pressure and the residual sodium salts were dissolved in 0.1 M HCl. The solution was filtered and placed in Petri dishes. After evaporation of the water, two types of crystals were found in the dishes. A pale yellow crystal, which was expected to be the salt of NBSA, was taken for X-ray analysis. The crystals of the second type were colourless, and they were assumed to be crystals of sodium bromide.

Computing details top

Data collection: COLLECT (Nonius, 1997-2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL DENZO (Otwinowski & Minor 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 (Farrugia, 1997).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. A packing diagram for (I), showing the hydrophobic and hydrophilic layers. Na+ ions are shown as the largest spheres and H atoms have been omitted.
sodium 2-hydroxy-5-nitrobenzylsulfonate monohydrate top
Crystal data top
Na(C7H6NO6S)·H2OF(000) = 560
Mr = 273.19Dx = 1.741 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 12.4940 (1) ÅCell parameters from 2893 reflections
b = 12.0800 (3) Åθ = 1.0–30.0°
c = 7.1600 (3) ŵ = 0.38 mm1
β = 105.264 (1)°T = 293 K
V = 1042.52 (5) Å3Prism, pale yellow
Z = 40.3 × 0.2 × 0.1 mm
Data collection top
Nonius KappaCCD area-detector
diffractometer
2606 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.015
Horizonally mounted graphite crystal monochromatorθmax = 30.0°, θmin = 2.4°
Detector resolution: 9 pixels mm-1h = 017
ϕ scans, and ω scans with κ offsetsk = 1615
5291 measured reflectionsl = 109
3026 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035Hydrogen site location: difference Fourier map
wR(F2) = 0.094All H-atom parameters refined
S = 1.10Calculated w = 1/[σ2(Fo2) + (0.0318P)2 + 0.6053P]
where P = (Fo2 + 2Fc2)/3
3026 reflections(Δ/σ)max = 0.002
186 parametersΔρmax = 0.30 e Å3
0 restraintsΔρmin = 0.44 e Å3
Crystal data top
Na(C7H6NO6S)·H2OV = 1042.52 (5) Å3
Mr = 273.19Z = 4
Monoclinic, P21/cMo Kα radiation
a = 12.4940 (1) ŵ = 0.38 mm1
b = 12.0800 (3) ÅT = 293 K
c = 7.1600 (3) Å0.3 × 0.2 × 0.1 mm
β = 105.264 (1)°
Data collection top
Nonius KappaCCD area-detector
diffractometer
2606 reflections with I > 2σ(I)
5291 measured reflectionsRint = 0.015
3026 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.094All H-atom parameters refined
S = 1.10Δρmax = 0.30 e Å3
3026 reflectionsΔρmin = 0.44 e Å3
186 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
xyzUiso*/Ueq
Na0.51268 (6)0.68316 (5)0.25367 (9)0.02991 (16)
S0.63218 (3)0.57656 (3)0.22544 (5)0.02100 (10)
O10.58125 (11)0.66148 (10)0.08673 (16)0.0334 (3)
O20.55192 (10)0.50288 (10)0.27538 (19)0.0344 (3)
O30.70769 (10)0.62568 (11)0.39595 (15)0.0339 (3)
C70.71423 (13)0.49101 (13)0.1142 (2)0.0241 (3)
H10.6606 (17)0.4555 (18)0.005 (3)0.033 (5)*
H20.7453 (19)0.4345 (19)0.208 (3)0.041 (6)*
O40.68967 (9)0.58223 (11)0.25615 (16)0.0295 (3)
H50.698 (2)0.601 (2)0.369 (4)0.049 (7)*
C20.78967 (12)0.59583 (13)0.1285 (2)0.0229 (3)
C10.80549 (12)0.55308 (12)0.0590 (2)0.0227 (3)
C60.90826 (13)0.56561 (13)0.1910 (2)0.0260 (3)
H60.9210 (18)0.5351 (18)0.315 (3)0.036 (5)*
C50.99296 (13)0.61849 (13)0.1342 (2)0.0271 (3)
C40.97869 (14)0.65959 (14)0.0513 (3)0.0311 (3)
H41.0387 (19)0.689 (2)0.085 (3)0.046 (6)*
C30.87651 (13)0.64914 (14)0.1826 (2)0.0293 (3)
H30.8617 (17)0.6796 (18)0.314 (3)0.036 (5)*
N11.10174 (12)0.62824 (13)0.2711 (2)0.0358 (3)
O51.11698 (13)0.58883 (14)0.4319 (2)0.0538 (4)
O61.17458 (12)0.67840 (15)0.2188 (3)0.0583 (4)
O70.41280 (12)0.82522 (12)0.1144 (2)0.0373 (3)
H70.346 (3)0.828 (3)0.141 (4)0.072 (9)*
H80.430 (4)0.888 (4)0.154 (6)0.124 (15)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Na0.0338 (4)0.0292 (3)0.0269 (3)0.0001 (3)0.0083 (3)0.0027 (2)
S0.02316 (18)0.02339 (18)0.01724 (16)0.00021 (12)0.00672 (12)0.00101 (12)
O10.0422 (7)0.0327 (6)0.0260 (5)0.0126 (5)0.0101 (5)0.0070 (5)
O20.0320 (6)0.0336 (6)0.0432 (7)0.0068 (5)0.0200 (5)0.0000 (5)
O30.0387 (7)0.0440 (7)0.0190 (5)0.0101 (5)0.0072 (5)0.0069 (5)
C70.0263 (7)0.0244 (7)0.0231 (6)0.0015 (5)0.0088 (6)0.0009 (5)
O40.0235 (5)0.0456 (7)0.0183 (5)0.0036 (5)0.0037 (4)0.0023 (5)
C20.0207 (7)0.0263 (7)0.0213 (6)0.0018 (5)0.0048 (5)0.0005 (5)
C10.0224 (7)0.0255 (7)0.0212 (6)0.0029 (5)0.0075 (5)0.0001 (5)
C60.0257 (7)0.0288 (8)0.0224 (7)0.0047 (6)0.0041 (6)0.0010 (5)
C50.0206 (7)0.0262 (7)0.0309 (7)0.0024 (6)0.0007 (6)0.0027 (6)
C40.0250 (7)0.0310 (8)0.0378 (8)0.0022 (6)0.0094 (7)0.0031 (6)
C30.0279 (8)0.0336 (8)0.0269 (7)0.0023 (6)0.0082 (6)0.0053 (6)
N10.0262 (7)0.0327 (8)0.0425 (8)0.0030 (6)0.0015 (6)0.0043 (6)
O50.0438 (8)0.0631 (10)0.0414 (8)0.0011 (7)0.0121 (6)0.0073 (7)
O60.0259 (7)0.0713 (11)0.0701 (11)0.0125 (7)0.0010 (7)0.0078 (9)
O70.0287 (7)0.0392 (7)0.0425 (7)0.0061 (5)0.0066 (5)0.0044 (6)
Geometric parameters (Å, º) top
Na—O12.3756 (13)C7—H20.96 (2)
Na—O1i2.4652 (13)O4—C21.3500 (18)
Na—O2ii2.3791 (14)O4—H50.87 (3)
Na—O42.5293 (14)C2—C31.401 (2)
Na—O72.4804 (15)C2—C11.403 (2)
Na—O7i2.5573 (15)C1—C61.388 (2)
Na—Si3.2855 (8)C6—C51.386 (2)
Na—Naiii3.9273 (6)C6—H60.94 (2)
Na—Nai3.9273 (6)C5—C41.385 (2)
S—C71.7842 (15)N1—C51.456 (2)
C7—C11.502 (2)C4—C31.378 (2)
S—O11.4529 (12)C4—H40.92 (2)
S—O21.4541 (12)C3—H30.98 (2)
S—O31.4582 (11)N1—O51.213 (2)
S—Naiii3.2855 (8)N1—O61.231 (2)
O1—Naiii2.4652 (13)O7—Naiii2.5573 (15)
O2—Naii2.3791 (14)O7—H70.81 (3)
C7—H10.98 (2)O7—H80.86 (5)
O1—Na—O2ii89.28 (5)O3—S—C7106.76 (8)
O1—Na—O1i118.95 (5)O1—S—Naiii44.34 (5)
O2ii—Na—O1i147.37 (5)O2—S—Naiii100.28 (5)
O1—Na—O775.37 (5)O3—S—Naiii78.69 (6)
O2ii—Na—O7118.81 (5)C7—S—Naiii148.59 (5)
O1i—Na—O786.15 (5)S—O1—Na138.93 (8)
O1—Na—O482.77 (4)S—O1—Naiii111.33 (6)
O2ii—Na—O480.00 (5)S—O2—Naii143.72 (8)
O1i—Na—O487.28 (5)C1—C7—S113.17 (11)
O7—Na—O4150.42 (5)C1—C7—H1114.4 (12)
O1—Na—O7i168.52 (5)S—C7—H1104.8 (12)
O2ii—Na—O7i80.19 (5)C1—C7—H2110.0 (14)
O1i—Na—O7i72.47 (4)S—C7—H2105.9 (14)
O7—Na—O7i105.67 (6)H1—C7—H2108.1 (18)
O4—Na—O7i99.72 (5)C2—O4—Na126.27 (10)
O1—Na—Si95.66 (4)C2—O4—H5106.5 (16)
O2ii—Na—Si169.11 (4)Na—O4—H5101.1 (17)
O1i—Na—Si24.33 (3)O4—C2—C3120.97 (13)
O7—Na—Si71.93 (4)O4—C2—C1118.38 (13)
O4—Na—Si90.97 (3)C3—C2—C1120.63 (14)
O7i—Na—Si95.50 (4)C6—C1—C2118.93 (14)
O1—Na—Naiii36.55 (3)C6—C1—C7120.37 (13)
O2ii—Na—Naiii111.50 (4)C2—C1—C7120.66 (13)
O1i—Na—Naiii101.12 (4)C5—C6—C1119.43 (14)
O7—Na—Naiii39.49 (4)C5—C6—H6120.5 (13)
O4—Na—Naiii114.48 (3)C1—C6—H6119.9 (13)
O7i—Na—Naiii145.06 (4)C4—C5—C6122.11 (14)
Si—Na—Naiii77.72 (2)C4—C5—N1118.57 (15)
O1—Na—Nai153.38 (4)C6—C5—N1119.29 (14)
O2ii—Na—Nai114.22 (4)C3—C4—C5118.94 (15)
O1i—Na—Nai35.02 (3)C3—C4—H4121.9 (14)
O7—Na—Nai101.71 (4)C5—C4—H4119.1 (14)
O4—Na—Nai88.97 (3)C4—C3—C2119.95 (15)
O7i—Na—Nai38.08 (3)C4—C3—H3121.8 (12)
Si—Na—Nai59.08 (2)C2—C3—H3118.2 (12)
Naiii—Na—Nai131.44 (4)O5—N1—O6122.54 (16)
Na—O1—Naiii108.43 (5)O5—N1—C5119.50 (16)
Na—O7—Naiii102.43 (5)O6—N1—C5117.95 (16)
O1—S—O2113.21 (8)Na—O7—H7122 (2)
O1—S—O3110.81 (8)Naiii—O7—H7116 (2)
O2—S—O3112.29 (7)Na—O7—H8106 (3)
O1—S—C7107.67 (7)Naiii—O7—H8105 (3)
O2—S—C7105.65 (7)H7—O7—H8103 (3)
Symmetry codes: (i) x, y+3/2, z1/2; (ii) x+1, y+1, z; (iii) x, y+3/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H5···O3iv0.87 (3)1.74 (3)2.613 (2)174 (3)
O7—H7···O6v0.81 (3)2.11 (3)2.901 (2)165 (3)
O7—H8···O2i0.86 (5)2.17 (5)2.946 (2)151 (4)
Symmetry codes: (i) x, y+3/2, z1/2; (iv) x, y, z1; (v) x1, y+3/2, z1/2.

Experimental details

Crystal data
Chemical formulaNa(C7H6NO6S)·H2O
Mr273.19
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)12.4940 (1), 12.0800 (3), 7.1600 (3)
β (°) 105.264 (1)
V3)1042.52 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.38
Crystal size (mm)0.3 × 0.2 × 0.1
Data collection
DiffractometerNonius KappaCCD area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
5291, 3026, 2606
Rint0.015
(sin θ/λ)max1)0.704
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.094, 1.10
No. of reflections3026
No. of parameters186
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.30, 0.44

Computer programs: COLLECT (Nonius, 1997-2000), HKL SCALEPACK (Otwinowski & Minor 1997), HKL DENZO (Otwinowski & Minor 1997) and SCALEPACK, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 (Farrugia, 1997).

Selected geometric parameters (Å, º) top
Na—O12.3756 (13)C7—C11.502 (2)
Na—O1i2.4652 (13)S—O11.4529 (12)
Na—O2ii2.3791 (14)S—O21.4541 (12)
Na—O42.5293 (14)S—O31.4582 (11)
Na—O72.4804 (15)N1—C51.456 (2)
Na—O7i2.5573 (15)N1—O51.213 (2)
S—C71.7842 (15)N1—O61.231 (2)
O1—Na—O2ii89.28 (5)O1—S—C7107.67 (7)
O1—Na—O1i118.95 (5)O2—S—C7105.65 (7)
O1—Na—O775.37 (5)O3—S—C7106.76 (8)
O1—Na—O482.77 (4)C1—C7—S113.17 (11)
O1—Na—O7i168.52 (5)O5—N1—O6122.54 (16)
O7—Na—O7i105.67 (6)O5—N1—C5119.50 (16)
Na—O1—Naiii108.43 (5)O6—N1—C5117.95 (16)
Na—O7—Naiii102.43 (5)
Symmetry codes: (i) x, y+3/2, z1/2; (ii) x+1, y+1, z; (iii) x, y+3/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H5···O3iv0.87 (3)1.74 (3)2.613 (2)174 (3)
O7—H7···O6v0.81 (3)2.11 (3)2.901 (2)165 (3)
O7—H8···O2i0.86 (5)2.17 (5)2.946 (2)151 (4)
Symmetry codes: (i) x, y+3/2, z1/2; (iv) x, y, z1; (v) x1, y+3/2, z1/2.
 

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