Download citation
Download citation
link to html
The title compound, [NO2C6H4SO2NHCH2CHOHCH2NH3]+[p-NO2C6H4SO3]- or C9H14N3O5S+·C6H4NO5S-, was isolated from the reaction between 1,3-di­amino-2-hydroxy­propane and p-nitro­benzene­sulfonyl chloride in CH2Cl2. The fairly extensive hydrogen-bond system involving all `active' H atoms links the ions in the crystal into layers normal to the b axis.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802015349/ya6126sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802015349/ya6126Isup2.hkl
Contains datablock I

CCDC reference: 198327

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.009 Å
  • R factor = 0.053
  • wR factor = 0.052
  • Data-to-parameter ratio = 7.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Amber Alert Alert Level B:
REFNR_01 Alert B Ratio of reflections to parameters is < 8 for a centrosymmetric structure sine(theta)/lambda 0.6497 Proportion of unique data used 0.4303 Ratio reflections to parameters 7.1143
0 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
0 Alert Level C = Please check

Comment top

Nitrobenzenesulfonamide is an efficient protecting reagent for preparing amine derivatives (Fukuyama et al., 1995; Hidai et al., 1999). Under controlled reaction conditions, mono-protected primary diamine was synthesized selectively and in high yield. The crystal of the title compound, (I), has an ionic structure, built of 2-hydroxy-3-(p-nitrobenzenesulfonylamino)propylammonium cations, [NO2C6H4SO2NHCH2CHOHCH2NH3]+, and p-nitrobenzenesulfonate anions, [p-NO2C6H4SO3], as shown in Fig. 1. The present X-ray diffraction study proved the successful formation of mono-substituted products and provided the first reported crystal structure with cationic mono protected diamine.

The S—O and S—N bond lengths in the cation, and the S—O and S—C bond lengths in the anion are comparable to those in the similar previously reported molecular fragments (Barrans & Cotrait, 1976; Brunzelle et al., 1999; Cook et al., 1971; Curtis & Pavkovic, 1983; Russell et al., 1994; Takahashi et al., 1998).

There are five `active' H atoms in the structure of (I), all of which participate in hydrogen bonds of the N—H···OS, N—H···O(H) and O—H···OS types (Table 2). The N—H···OS and N—H···O(H) bonds are in the range 2.809 (5)–3.038 (5) Å. O5—H5a···O10 is a fairly strong interaction, with an O···O distance of 2.791 (5) Å and an O—H···O angle of 164.85 (18)°, which is typical for `anionic' O—H···O hydrogen bonds in the crystal structures of salts (Jeffrey, 1997). These hydrogen bonds link cations and anions into the infinite two-dimensional aggregates, i.e. layers parallel to the [010] plane (Fig. 2).

Experimental top

1,3-Diamino-2-hydroxypropane (0.2 g) was stirred with p-nitrobenzenesulfonyl chloride (0.5 g) and pyridine in dry CH2Cl2 (10 ml) under N2 at room temperature for 5 h. The reaction mixture was extracted with 5% aqueous HCl solution. The organic phase was dried and purified by silica chromatography [elution with CH2Cl2–MeOH in 50:1 (v:v)]. The pale-yellow monosulfonylated diamine was obtained in 75% yield. X-Ray quality crystals were obtained by slow evaporation of a 10 ml mixture of CH2Cl2 and MeOH in a 3:1 (v:v) ratio at room temperature over a few days.

Refinement top

The positions of the H atoms were generated geometrically (C—H and N—H bond lengths fixed at 0.95 Å) with assigned isotropic displacement parameters and were allowed to ride on their respective parent C and N atoms before the final cycle of least-squares refinement.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 1999); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: TEXSAN (Molecular Structure Corporation, 1992); software used to prepare material for publication: TEXSAN.

Figures top
[Figure 1] Fig. 1. An ORTEPII (Johnson, 1976) drawing of the cation and anion in the structure of (I), showing 50% probability displacement ellipsoids and the crystallographic labeling scheme.
[Figure 2] Fig. 2. The packing diagram showing the hydrogen-bonding system.
(I) top
Crystal data top
C9H14N3O5S+·C6H4NO5SF(000) = 992.00
Mr = 478.45Dx = 1.576 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.7107 Å
a = 6.7120 (8) ÅCell parameters from 46 reflections
b = 31.392 (1) Åθ = 2.5–14°
c = 9.8260 (9) ŵ = 0.33 mm1
β = 103.170 (5)°T = 298 K
V = 2015.9 (3) Å3Block, colourless
Z = 40.23 × 0.20 × 0.11 mm
Data collection top
Bruker SMART CCD Area detector
diffractometer
1992 reflections with I > 2σ(I)
Radiation source: X-ray tubeRint = 0.049
Graphite monochromatorθmax = 27.5°, θmin = 2.5°
ϕ and ω scansh = 85
12619 measured reflectionsk = 3840
4629 independent reflectionsl = 812
Refinement top
Refinement on F0 restraints
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.053 w = 1/[(σ)2(Fo) + (p/2)2(Fo)2]
where P = 0.041
wR(F2) = 0.052(Δ/σ)max < 0.001
S = 1.19Δρmax = 0.40 e Å3
1992 reflectionsΔρmin = 0.28 e Å3
280 parameters
Crystal data top
C9H14N3O5S+·C6H4NO5SV = 2015.9 (3) Å3
Mr = 478.45Z = 4
Monoclinic, P21/cMo Kα radiation
a = 6.7120 (8) ŵ = 0.33 mm1
b = 31.392 (1) ÅT = 298 K
c = 9.8260 (9) Å0.23 × 0.20 × 0.11 mm
β = 103.170 (5)°
Data collection top
Bruker SMART CCD Area detector
diffractometer
1992 reflections with I > 2σ(I)
12619 measured reflectionsRint = 0.049
4629 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0530 restraints
wR(F2) = 0.052H-atom parameters constrained
S = 1.19Δρmax = 0.40 e Å3
1992 reflectionsΔρmin = 0.28 e Å3
280 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.3248 (2)0.14269 (4)0.5080 (2)0.0522 (5)
S20.2987 (2)0.19924 (4)0.9308 (1)0.0450 (4)
O10.2129 (8)0.0668 (1)0.4951 (6)0.101 (2)
O20.3339 (9)0.0590 (1)0.7171 (6)0.109 (2)
O30.3156 (6)0.1473 (1)0.3628 (4)0.075 (1)
O40.4979 (5)0.1584 (1)0.6097 (4)0.071 (1)
O50.1228 (5)0.23851 (10)0.5015 (3)0.051 (1)
O60.3082 (7)0.0366 (1)0.9817 (5)0.106 (2)
O70.0373 (7)0.0160 (1)1.1292 (4)0.076 (2)
O80.1889 (6)0.2138 (1)0.7940 (3)0.059 (1)
O90.5115 (5)0.1895 (1)0.9395 (4)0.057 (1)
O100.2715 (5)0.2280 (1)1.0419 (3)0.052 (1)
N10.2738 (8)0.0449 (2)0.6001 (8)0.072 (2)
N20.1280 (7)0.1637 (1)0.5458 (4)0.052 (1)
N30.3619 (6)0.2535 (1)0.2239 (4)0.050 (1)
N40.1302 (9)0.0412 (2)1.0427 (6)0.068 (2)
C10.2834 (8)0.0019 (2)0.5782 (7)0.052 (2)
C20.2327 (8)0.0172 (2)0.4450 (6)0.054 (2)
C30.2454 (8)0.0607 (2)0.4242 (5)0.050 (2)
C40.3078 (7)0.0874 (2)0.5371 (5)0.042 (2)
C50.3552 (8)0.0706 (2)0.6710 (6)0.058 (2)
C60.3437 (9)0.0275 (2)0.6914 (6)0.062 (2)
C70.0727 (9)0.1644 (2)0.4501 (6)0.058 (2)
C80.1186 (8)0.2094 (2)0.3896 (6)0.057 (2)
C90.3160 (9)0.2109 (2)0.2878 (6)0.063 (2)
C100.0215 (9)0.0792 (2)1.0112 (6)0.053 (2)
C110.1330 (10)0.1126 (2)0.9460 (9)0.107 (3)
C120.0305 (10)0.1489 (2)0.9222 (8)0.099 (3)
C130.1789 (8)0.1510 (1)0.9604 (5)0.044 (2)
C140.2867 (8)0.1168 (2)1.0249 (5)0.050 (2)
C150.1885 (9)0.0801 (2)1.0494 (5)0.051 (2)
H20.18960.00160.36800.0649
H2a0.14230.17640.63520.0628
H30.21100.07210.33220.0597
H3a10.49150.25300.15990.0596
H3a20.25940.26110.17570.0596
H3a30.36430.27390.29500.0596
H50.39590.08900.74910.0695
H5a0.03710.25050.53550.0779
H60.37730.01580.78300.0741
H7a0.17390.15650.49890.0699
H7b0.07440.14490.37600.0699
H80.01340.21770.34480.0683
H9b0.42110.20340.33390.0758
H9a0.31340.19090.21580.0758
H110.27790.11090.91750.1279
H120.10590.17280.87890.1193
H140.43160.11851.05330.0598
H150.26380.05601.09160.0610
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0535 (9)0.0436 (8)0.063 (1)0.0084 (7)0.0207 (8)0.0065 (7)
S20.0486 (9)0.0407 (7)0.0441 (8)0.0016 (7)0.0075 (6)0.0005 (7)
O10.093 (4)0.053 (3)0.159 (5)0.000 (3)0.035 (4)0.002 (3)
O20.131 (5)0.082 (3)0.128 (4)0.035 (3)0.058 (4)0.043 (3)
O30.110 (4)0.059 (3)0.067 (3)0.012 (2)0.045 (2)0.002 (2)
O40.048 (2)0.059 (2)0.104 (3)0.017 (2)0.010 (2)0.026 (2)
O50.050 (2)0.044 (2)0.054 (2)0.001 (2)0.002 (2)0.006 (2)
O60.074 (4)0.101 (4)0.131 (4)0.043 (3)0.002 (3)0.010 (3)
O70.096 (4)0.068 (3)0.067 (3)0.015 (3)0.024 (3)0.008 (2)
O80.083 (3)0.053 (2)0.037 (2)0.010 (2)0.006 (2)0.002 (2)
O90.045 (2)0.058 (2)0.070 (3)0.001 (2)0.018 (2)0.009 (2)
O100.056 (2)0.051 (2)0.047 (2)0.004 (2)0.004 (2)0.011 (2)
N10.052 (4)0.056 (4)0.118 (6)0.015 (3)0.040 (4)0.008 (4)
N20.052 (3)0.046 (2)0.055 (3)0.007 (2)0.004 (2)0.009 (2)
N30.050 (3)0.051 (3)0.042 (3)0.002 (2)0.002 (2)0.005 (2)
N40.066 (4)0.067 (4)0.073 (4)0.019 (3)0.020 (3)0.004 (3)
C10.037 (3)0.047 (3)0.078 (4)0.005 (3)0.023 (3)0.004 (3)
C20.042 (3)0.049 (3)0.070 (4)0.002 (3)0.010 (3)0.014 (3)
C30.049 (4)0.051 (3)0.052 (3)0.002 (3)0.015 (3)0.001 (3)
C40.037 (3)0.045 (3)0.046 (3)0.001 (2)0.016 (3)0.002 (3)
C50.059 (4)0.066 (4)0.050 (4)0.004 (3)0.014 (3)0.007 (3)
C60.064 (4)0.069 (4)0.056 (4)0.004 (3)0.021 (3)0.011 (3)
C70.060 (4)0.039 (3)0.067 (4)0.004 (3)0.004 (3)0.000 (3)
C80.057 (4)0.039 (3)0.065 (4)0.000 (3)0.005 (3)0.006 (3)
C90.068 (4)0.050 (3)0.060 (4)0.000 (3)0.009 (3)0.001 (3)
C100.053 (4)0.047 (3)0.062 (4)0.009 (3)0.016 (3)0.002 (3)
C110.044 (4)0.071 (5)0.194 (8)0.014 (4)0.005 (5)0.028 (5)
C120.049 (4)0.062 (4)0.174 (7)0.012 (3)0.002 (4)0.035 (5)
C130.042 (3)0.039 (3)0.049 (3)0.003 (2)0.007 (3)0.003 (2)
C140.041 (3)0.053 (3)0.054 (3)0.002 (3)0.008 (3)0.003 (3)
C150.056 (4)0.049 (3)0.045 (3)0.004 (3)0.007 (3)0.005 (3)
Geometric parameters (Å, º) top
S1—O31.421 (4)C10—C111.360 (8)
S1—O41.436 (4)C10—C151.374 (7)
S1—N21.594 (4)C11—C121.378 (8)
S1—C41.767 (5)C12—C131.371 (7)
S2—O81.452 (3)C13—C141.365 (6)
S2—O91.444 (3)C14—C151.376 (7)
S2—O101.459 (3)O5—H5a1.11
S2—C131.770 (5)N3—H3a10.95
O1—N11.230 (7)N3—H3a30.95
O2—N11.212 (6)C3—H30.95
O5—C81.434 (6)C6—H60.95
O6—N41.217 (6)C7—H7b0.95
O7—N41.222 (6)C9—H9b0.95
N1—C11.488 (7)C11—H110.95
N2—C71.457 (6)C14—H140.95
N3—C91.481 (6)N2—H2a0.95
N4—C101.468 (7)N3—H3a20.95
C1—C21.362 (7)C2—H20.95
C1—C61.357 (7)C5—H50.95
C2—C31.387 (7)C7—H7a0.95
C3—C41.378 (6)C8—H80.95
C4—C51.385 (7)C9—H9a0.95
C5—C61.374 (7)C12—H120.95
C7—C81.535 (7)C15—H150.95
C8—C91.468 (7)
O3—S1—O4120.4 (2)C12—C13—C14119.4 (5)
O3—S1—N2110.0 (2)C13—C14—C15121.0 (5)
O3—S1—C4105.9 (2)C10—C15—C14118.1 (5)
O4—S1—N2106.1 (2)C8—O5—H5a105.0
O4—S1—C4107.3 (2)C7—N2—H2a118.3
N2—S1—C4106.3 (2)C9—N3—H3a2109.5
O8—S2—O9114.0 (2)H3a1—N3—H3a2109.5
O8—S2—O10112.0 (2)H3a2—N3—H3a3109.5
O8—S2—C13105.5 (2)C3—C2—H2120.7
O9—S2—O10112.2 (2)C4—C3—H3120.0
O9—S2—C13106.8 (2)C6—C5—H5119.8
O10—S2—C13105.5 (2)C5—C6—H6120.7
O1—N1—O2124.5 (6)N2—C7—H7b109.4
O1—N1—C1116.6 (6)C8—C7—H7b109.4
O2—N1—C1118.9 (6)O5—C8—H8109.1
S1—N2—C7123.3 (4)C9—C8—H8109.1
O6—N4—O7123.6 (5)N3—C9—H9a108.7
O6—N4—C10118.1 (6)C8—C9—H9a108.7
O7—N4—C10118.2 (5)C10—C11—H11120.8
N1—C1—C2118.5 (6)C11—C12—H12119.6
N1—C1—C6118.7 (6)C13—C14—H14119.5
C2—C1—C6122.8 (5)C10—C15—H15120.9
C1—C2—C3118.6 (5)S1—N2—H2a118.3
C2—C3—C4119.9 (5)C9—N3—H3a1109.5
S1—C4—C3119.1 (4)C9—N3—H3a3109.5
S1—C4—C5121.2 (4)H3a1—N3—H3a3109.5
C3—C4—C5119.7 (5)C1—C2—H2120.7
C4—C5—C6120.4 (5)C2—C3—H3120.0
C1—C6—C5118.7 (5)C4—C5—H5119.8
N2—C7—C8109.8 (4)C1—C6—H6120.7
O5—C8—C7109.0 (4)N2—C7—H7a109.4
O5—C8—C9109.3 (4)C8—C7—H7a109.4
C7—C8—C9111.3 (4)H7a—C7—H7b109.5
N3—C9—C8112.7 (4)C7—C8—H8109.1
N4—C10—C11118.6 (6)N3—C9—H9b108.7
N4—C10—C15119.2 (5)C8—C9—H9b108.7
C11—C10—C15122.2 (5)H9b—C9—H9a109.5
C10—C11—C12118.3 (6)C12—C11—H11120.8
C11—C12—C13120.9 (6)C13—C12—H12119.6
S2—C13—C12118.1 (4)C15—C14—H14119.5
S2—C13—C14122.4 (4)C14—C15—H15120.9
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2a···O80.951.922.852 (5)166
N3—H3a1···O10i0.951.912.809 (5)157
N3—H3a2···O5ii0.952.123.002 (5)154
N3—H3a3···O50.952.552.871 (5)100
N3—H3a3···O9iii0.952.143.038 (5)158
O5—H5a···O10ii1.111.702.791 (5)165
Symmetry codes: (i) x1, y, z1; (ii) x, y+1/2, z1/2; (iii) x1, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC9H14N3O5S+·C6H4NO5S
Mr478.45
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)6.7120 (8), 31.392 (1), 9.8260 (9)
β (°) 103.170 (5)
V3)2015.9 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.33
Crystal size (mm)0.23 × 0.20 × 0.11
Data collection
DiffractometerBruker SMART CCD Area detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
12619, 4629, 1992
Rint0.049
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.053, 0.052, 1.19
No. of reflections1992
No. of parameters280
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.40, 0.28

Computer programs: SMART (Bruker, 1998), SMART, SAINT-Plus (Bruker, 1999), SIR92 (Altomare et al., 1994), TEXSAN (Molecular Structure Corporation, 1992), TEXSAN.

Selected geometric parameters (Å, º) top
S1—O31.421 (4)S2—C131.770 (5)
S1—O41.436 (4)O5—C81.434 (6)
S1—N21.594 (4)N2—C71.457 (6)
S1—C41.767 (5)N3—C91.481 (6)
S2—O81.452 (3)C7—C81.535 (7)
S2—O91.444 (3)C8—C91.468 (7)
S2—O101.459 (3)
O3—S1—O4120.4 (2)S1—C4—C3119.1 (4)
O3—S1—N2110.0 (2)S1—C4—C5121.2 (4)
O3—S1—C4105.9 (2)N2—C7—C8109.8 (4)
O4—S1—N2106.1 (2)O5—C8—C7109.0 (4)
O4—S1—C4107.3 (2)O5—C8—C9109.3 (4)
N2—S1—C4106.3 (2)C7—C8—C9111.3 (4)
S1—N2—C7123.3 (4)N3—C9—C8112.7 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2a···O80.951.922.852 (5)166
N3—H3a1···O10i0.951.912.809 (5)157
N3—H3a2···O5ii0.952.123.002 (5)154
N3—H3a3···O50.952.552.871 (5)100
N3—H3a3···O9iii0.952.143.038 (5)158
O5—H5a···O10ii1.111.702.791 (5)165
Symmetry codes: (i) x1, y, z1; (ii) x, y+1/2, z1/2; (iii) x1, y+1/2, z1/2.
 

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds