The title compounds, bis(ammonium) naphthalene-1,5-disulfonate, 2NH
4+·C
10H
6O
6S
22−, and bis[1-(hydroxymethyl)-3,5,7-triaza-1-azoniatricyclo[3.3.1.1
3,7]decane] 1,5-naphthalenedisulfonate, 2C
7H
15N
4O
+·C
10H
6O
6S
22−, were prepared from the acid-promoted reaction of hexamethylenetetramine. In both structures, the disulfonate anion is positioned on an inversion center, with each sulfonate group contributing to the supramolecular assemblies
via hydrogen bonds. The ammonium cations are linked to sulfonate groups by four distinct N
+—H
−O—S contacts [N
O = 2.846 (2)–2.898 (2) Å and N—H
O = 160 (2)–175 (2)°], whereas the 1-(hydroxymethyl)-3,5,7-triaza-1-azoniatricyclo[3.3.1.1
3,7]decane cations form one O—H
−O—S [O
O = 2.628 (2) Å and O—H
O = 176°] and three C—H
−O—S [C
O = 3.359 (2)–3.380 (2) Å and C—H
O = 148–155°] interactions to neighboring sulfonate groups.
Supporting information
CCDC references: 214408; 214409
Compounds (I) and (II) were obtained from the addition of equimolar quantities of 1,5-naphthalenedisulfonic acid and hexamethylenetetraamine to water or a 2:1 methanol–water solution, respectively. The resulting heterogeneous mixtures were stirred at 333 K for ~30 min until completely dissolved and the resulting solutions were allowed to recrystallize by slow evaporation at room temperature. After 5 d, crystals were retrieved and the sample quality assessed by polarized microscopy.
The H-atom positions for (I) and (II) were located from difference density maps or calculated using C—H distance criteria (methylene C—H = 0.99 Å, aryl C—H = 0.95 Å and O—H = 0.84 Å). H atoms were refined isotropically or using a riding model with fixed displacement parameters (Uiso = 1.2Ueq for the atom to which they are bonded). Each HN atom in structure (I) was located on difference maps and refined isotropically.
For both compounds, data collection: XSCANS (Bruker, 1999); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: X-SEED.
(I) bis(ammonium) naphthalene-1,5-disulfonate
top
Crystal data top
2NH4+·C10H6O6S22− | F(000) = 336 |
Mr = 322.36 | Dx = 1.648 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 29 reflections |
a = 11.3771 (7) Å | θ = 19.3–24.9° |
b = 7.3386 (4) Å | µ = 0.44 mm−1 |
c = 7.9974 (7) Å | T = 298 K |
β = 103.431 (6)° | Transparent plate, colorless |
V = 649.46 (8) Å3 | 0.56 × 0.44 × 0.08 mm |
Z = 2 | |
Data collection top
Siemens P4 diffractometer | 1334 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.013 |
Graphite monochromator | θmax = 27.5°, θmin = 3.3° |
θ/2θ\ scans | h = −14→14 |
Absorption correction: analytical (SHELXTL; Bruker, 1998) | k = −9→1 |
Tmin = 0.844, Tmax = 0.963 | l = −1→10 |
2078 measured reflections | 3 standard reflections every 97 reflections |
1495 independent reflections | intensity decay: <3% |
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.086 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0512P)2 + 0.2958P] where P = (Fo2 + 2Fc2)/3 |
1495 reflections | (Δ/σ)max < 0.001 |
107 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
Crystal data top
2NH4+·C10H6O6S22− | V = 649.46 (8) Å3 |
Mr = 322.36 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.3771 (7) Å | µ = 0.44 mm−1 |
b = 7.3386 (4) Å | T = 298 K |
c = 7.9974 (7) Å | 0.56 × 0.44 × 0.08 mm |
β = 103.431 (6)° | |
Data collection top
Siemens P4 diffractometer | 1334 reflections with I > 2σ(I) |
Absorption correction: analytical (SHELXTL; Bruker, 1998) | Rint = 0.013 |
Tmin = 0.844, Tmax = 0.963 | 3 standard reflections every 97 reflections |
2078 measured reflections | intensity decay: <3% |
1495 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.086 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | Δρmax = 0.30 e Å−3 |
1495 reflections | Δρmin = −0.37 e Å−3 |
107 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 | x | y | z | Uiso*/Ueq | |
S | 0.19300 (3) | 0.54277 (5) | 0.45424 (5) | 0.02419 (14) | |
O1 | 0.12795 (11) | 0.70256 (18) | 0.48991 (19) | 0.0386 (3) | |
O2 | 0.18437 (11) | 0.39108 (17) | 0.56914 (16) | 0.0316 (3) | |
O3 | 0.15911 (11) | 0.4867 (2) | 0.27507 (16) | 0.0347 (3) | |
C1 | 0.34900 (13) | 0.6017 (2) | 0.5021 (2) | 0.0231 (3) | |
C2 | 0.38150 (15) | 0.7680 (2) | 0.5753 (2) | 0.0270 (3) | |
C3 | 0.50450 (15) | 0.8166 (2) | 0.6251 (2) | 0.0281 (3) | |
C4 | 0.59205 (14) | 0.6991 (2) | 0.6030 (2) | 0.0260 (3) | |
C5 | 0.56227 (13) | 0.5257 (2) | 0.52650 (19) | 0.0216 (3) | |
N | 0.08994 (15) | 0.0731 (2) | 0.3672 (2) | 0.0319 (3) | |
H2 | 0.3212 | 0.8507 | 0.5926 | 0.032* | |
H3 | 0.5265 | 0.9329 | 0.6747 | 0.034* | |
H4 | 0.6745 | 0.7336 | 0.6394 | 0.031* | |
H1N | 0.114 (2) | 0.160 (4) | 0.442 (3) | 0.049 (7)* | |
H2N | 0.124 (2) | 0.083 (3) | 0.279 (3) | 0.044 (6)* | |
H3N | 0.109 (3) | −0.038 (4) | 0.406 (4) | 0.055 (8)* | |
H4N | 0.007 (3) | 0.072 (4) | 0.331 (3) | 0.058 (8)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S | 0.0182 (2) | 0.0262 (2) | 0.0277 (2) | −0.00048 (14) | 0.00430 (15) | 0.00070 (15) |
O1 | 0.0252 (6) | 0.0317 (7) | 0.0596 (9) | 0.0039 (5) | 0.0113 (6) | −0.0044 (6) |
O2 | 0.0308 (6) | 0.0323 (7) | 0.0334 (6) | −0.0036 (5) | 0.0112 (5) | 0.0041 (5) |
O3 | 0.0253 (6) | 0.0481 (8) | 0.0275 (6) | −0.0013 (5) | −0.0004 (5) | −0.0003 (6) |
C1 | 0.0191 (7) | 0.0267 (8) | 0.0230 (7) | −0.0018 (6) | 0.0039 (6) | 0.0008 (6) |
C2 | 0.0245 (7) | 0.0266 (8) | 0.0294 (8) | 0.0015 (6) | 0.0054 (6) | −0.0023 (7) |
C3 | 0.0299 (8) | 0.0248 (8) | 0.0287 (8) | −0.0050 (7) | 0.0052 (6) | −0.0071 (6) |
C4 | 0.0214 (7) | 0.0279 (8) | 0.0277 (7) | −0.0055 (6) | 0.0035 (6) | −0.0044 (6) |
C5 | 0.0203 (7) | 0.0239 (7) | 0.0203 (7) | −0.0023 (6) | 0.0040 (6) | 0.0000 (6) |
N | 0.0287 (8) | 0.0343 (9) | 0.0325 (8) | −0.0057 (7) | 0.0065 (6) | 0.0002 (7) |
Geometric parameters (Å, º) top
S—O1 | 1.4499 (13) | C3—H3 | 0.9500 |
S—O3 | 1.4540 (13) | C4—C5 | 1.418 (2) |
S—O2 | 1.4612 (13) | C4—H4 | 0.9500 |
S—C1 | 1.7798 (15) | C5—C1i | 1.432 (2) |
C1—C2 | 1.367 (2) | C5—C5i | 1.432 (3) |
C1—C5i | 1.432 (2) | N—H1N | 0.88 (3) |
C2—C3 | 1.409 (2) | N—H2N | 0.88 (3) |
C2—H2 | 0.9500 | N—H3N | 0.88 (3) |
C3—C4 | 1.360 (2) | N—H4N | 0.92 (3) |
| | | |
O1—S—O3 | 113.07 (8) | C2—C3—H3 | 119.6 |
O1—S—O2 | 112.36 (8) | C3—C4—C5 | 121.08 (14) |
O3—S—O2 | 111.30 (8) | C3—C4—H4 | 119.5 |
O1—S—C1 | 106.88 (8) | C5—C4—H4 | 119.5 |
O3—S—C1 | 107.66 (7) | C4—C5—C1i | 123.19 (14) |
O2—S—C1 | 105.02 (7) | C4—C5—C5i | 118.99 (18) |
C2—C1—C5i | 121.35 (14) | C1i—C5—C5i | 117.82 (18) |
C2—C1—S | 117.77 (12) | H1N—N—H2N | 111 (2) |
C5i—C1—S | 120.79 (12) | H1N—N—H3N | 115 (2) |
C1—C2—C3 | 119.95 (15) | H2N—N—H3N | 104 (2) |
C1—C2—H2 | 120.0 | H1N—N—H4N | 111 (2) |
C3—C2—H2 | 120.0 | H2N—N—H4N | 110 (2) |
C4—C3—C2 | 120.80 (15) | H3N—N—H4N | 105 (2) |
C4—C3—H3 | 119.6 | | |
| | | |
O1—S—C1—C2 | 6.03 (15) | C5i—C1—C2—C3 | −0.3 (2) |
O3—S—C1—C2 | 127.80 (13) | S—C1—C2—C3 | 176.20 (13) |
O2—S—C1—C2 | −113.51 (14) | C1—C2—C3—C4 | −0.7 (3) |
O1—S—C1—C5i | −177.45 (13) | C2—C3—C4—C5 | 1.2 (3) |
O3—S—C1—C5i | −55.68 (15) | C3—C4—C5—C5i | −0.6 (3) |
O2—S—C1—C5i | 63.01 (14) | C3—C4—C5—C1i | 178.96 (15) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N—H1N···O2 | 0.88 (3) | 2.04 (3) | 2.898 (2) | 166 (2) |
N—H2N···O2ii | 0.88 (3) | 1.98 (3) | 2.846 (2) | 175 (2) |
N—H3N···O1iii | 0.88 (3) | 2.01 (3) | 2.889 (2) | 172 (3) |
N—H4N···O3iv | 0.92 (3) | 1.98 (3) | 2.868 (2) | 160 (2) |
Symmetry codes: (ii) x, −y+1/2, z−1/2; (iii) x, y−1, z; (iv) −x, y−1/2, −z+1/2. |
(II) bis[1-(hydroxymethyl)-3,5,7-triaza-1-azoniatricyclo[3.3.1.1
3,7]decane] 1,5-naphthalenedisulfonate
top
Crystal data top
2C7H15N4O+·C10H6O6S22− | F(000) = 664 |
Mr = 628.73 | Dx = 1.548 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 52 reflections |
a = 6.0625 (4) Å | θ = 20.7–25.9° |
b = 19.282 (1) Å | µ = 0.26 mm−1 |
c = 11.6207 (7) Å | T = 298 K |
β = 96.72 (4)° | Transparent rhomboid, colorless |
V = 1349.09 (14) Å3 | 0.68 × 0.32 × 0.20 mm |
Z = 2 | |
Data collection top
Siemens P4 diffractometer | Rint = 0.012 |
Radiation source: fine-focus sealed tube | θmax = 27.5°, θmin = 2.1° |
Graphite monochromator | h = −1→7 |
θ/2θ scans | k = −1→25 |
4192 measured reflections | l = −15→15 |
3101 independent reflections | 3 standard reflections every 97 reflections |
2669 reflections with I > 2σ(I) | intensity decay: <3% |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.108 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0436P)2 + 0.6708P] where P = (Fo2 + 2Fc2)/3 |
3101 reflections | (Δ/σ)max < 0.001 |
194 parameters | Δρmax = 0.45 e Å−3 |
0 restraints | Δρmin = −0.33 e Å−3 |
Crystal data top
2C7H15N4O+·C10H6O6S22− | V = 1349.09 (14) Å3 |
Mr = 628.73 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.0625 (4) Å | µ = 0.26 mm−1 |
b = 19.282 (1) Å | T = 298 K |
c = 11.6207 (7) Å | 0.68 × 0.32 × 0.20 mm |
β = 96.72 (4)° | |
Data collection top
Siemens P4 diffractometer | Rint = 0.012 |
4192 measured reflections | 3 standard reflections every 97 reflections |
3101 independent reflections | intensity decay: <3% |
2669 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.108 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.45 e Å−3 |
3101 reflections | Δρmin = −0.33 e Å−3 |
194 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 | x | y | z | Uiso*/Ueq | |
S1 | 0.96360 (8) | 0.63082 (2) | 0.79756 (4) | 0.03112 (13) | |
O1 | 0.8084 (3) | 0.68882 (7) | 0.79220 (11) | 0.0425 (3) | |
O2 | 0.9268 (3) | 0.58632 (7) | 0.69695 (11) | 0.0475 (4) | |
O3 | 1.1913 (2) | 0.65381 (8) | 0.82176 (14) | 0.0504 (4) | |
O4 | 0.6460 (2) | 0.74012 (9) | 0.59037 (12) | 0.0484 (4) | |
H4O | 0.6929 | 0.7231 | 0.6552 | 0.080 (10)* | |
N1 | −0.0017 (2) | 0.63935 (8) | 0.37794 (13) | 0.0322 (3) | |
N2 | 0.3463 (3) | 0.63972 (8) | 0.29311 (13) | 0.0348 (3) | |
N3 | 0.3359 (2) | 0.68248 (7) | 0.48914 (11) | 0.0268 (3) | |
N4 | 0.2931 (3) | 0.55924 (8) | 0.44949 (13) | 0.0350 (3) | |
C1 | 0.9034 (3) | 0.58010 (8) | 0.91800 (13) | 0.0268 (3) | |
C2 | 0.7296 (3) | 0.60048 (10) | 0.97527 (15) | 0.0350 (4) | |
H2 | 0.6472 | 0.6409 | 0.9512 | 0.042* | |
C3 | 0.6729 (3) | 0.56148 (10) | 1.06994 (16) | 0.0381 (4) | |
H3 | 0.5528 | 0.5761 | 1.1097 | 0.046* | |
C4 | 0.7878 (3) | 0.50330 (10) | 1.10507 (14) | 0.0322 (4) | |
H4 | 0.7461 | 0.4775 | 1.1687 | 0.039* | |
C5 | 0.9693 (3) | 0.48048 (8) | 1.04797 (13) | 0.0250 (3) | |
C6 | 0.4384 (3) | 0.69054 (9) | 0.37553 (14) | 0.0310 (4) | |
H6A | 0.4078 | 0.7377 | 0.3438 | 0.037* | |
H6B | 0.6014 | 0.6845 | 0.3902 | 0.037* | |
C7 | 0.1045 (3) | 0.64892 (11) | 0.27153 (16) | 0.0370 (4) | |
H7A | 0.0423 | 0.6150 | 0.2125 | 0.044* | |
H7B | 0.0711 | 0.6961 | 0.2405 | 0.044* | |
C8 | 0.3842 (3) | 0.60881 (9) | 0.53451 (15) | 0.0338 (4) | |
H8A | 0.5466 | 0.6019 | 0.5511 | 0.041* | |
H8B | 0.3175 | 0.6020 | 0.6075 | 0.041* | |
C9 | 0.0520 (3) | 0.56952 (9) | 0.42432 (17) | 0.0359 (4) | |
H9A | −0.0183 | 0.5628 | 0.4962 | 0.043* | |
H9B | −0.0098 | 0.5344 | 0.3673 | 0.043* | |
C10 | 0.0845 (3) | 0.68992 (9) | 0.46219 (15) | 0.0305 (4) | |
H10A | 0.0140 | 0.6837 | 0.5342 | 0.037* | |
H10B | 0.0482 | 0.7371 | 0.4321 | 0.037* | |
C11 | 0.3930 (3) | 0.56973 (10) | 0.34126 (17) | 0.0393 (4) | |
H11A | 0.3336 | 0.5346 | 0.2836 | 0.047* | |
H11B | 0.5557 | 0.5630 | 0.3565 | 0.047* | |
C12 | 0.4188 (3) | 0.73790 (11) | 0.57514 (17) | 0.0399 (4) | |
H12A | 0.3600 | 0.7835 | 0.5471 | 0.048* | |
H12B | 0.3633 | 0.7284 | 0.6504 | 0.048* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0428 (3) | 0.0244 (2) | 0.0264 (2) | −0.00076 (17) | 0.00464 (16) | 0.00141 (15) |
O1 | 0.0588 (9) | 0.0329 (7) | 0.0350 (7) | 0.0107 (6) | 0.0023 (6) | 0.0062 (5) |
O2 | 0.0789 (11) | 0.0386 (7) | 0.0257 (6) | 0.0012 (7) | 0.0083 (6) | −0.0043 (5) |
O3 | 0.0470 (8) | 0.0395 (8) | 0.0652 (10) | −0.0101 (7) | 0.0079 (7) | 0.0100 (7) |
O4 | 0.0427 (8) | 0.0590 (9) | 0.0400 (7) | −0.0121 (7) | −0.0062 (6) | 0.0078 (7) |
N1 | 0.0260 (7) | 0.0324 (8) | 0.0378 (8) | −0.0003 (6) | 0.0021 (6) | 0.0040 (6) |
N2 | 0.0349 (8) | 0.0422 (9) | 0.0283 (7) | −0.0022 (6) | 0.0075 (6) | −0.0015 (6) |
N3 | 0.0268 (7) | 0.0289 (7) | 0.0250 (6) | 0.0007 (5) | 0.0041 (5) | 0.0032 (5) |
N4 | 0.0356 (8) | 0.0289 (7) | 0.0408 (8) | 0.0055 (6) | 0.0056 (6) | 0.0033 (6) |
C1 | 0.0324 (8) | 0.0258 (7) | 0.0218 (7) | 0.0000 (6) | 0.0018 (6) | −0.0007 (6) |
C2 | 0.0398 (10) | 0.0318 (9) | 0.0337 (9) | 0.0098 (7) | 0.0054 (7) | 0.0018 (7) |
C3 | 0.0371 (9) | 0.0432 (10) | 0.0362 (9) | 0.0101 (8) | 0.0135 (7) | 0.0010 (8) |
C4 | 0.0336 (9) | 0.0369 (9) | 0.0274 (8) | 0.0013 (7) | 0.0085 (6) | 0.0013 (7) |
C5 | 0.0285 (8) | 0.0242 (7) | 0.0221 (7) | −0.0007 (6) | 0.0013 (6) | −0.0028 (6) |
C6 | 0.0274 (8) | 0.0383 (9) | 0.0281 (8) | −0.0039 (7) | 0.0068 (6) | 0.0035 (7) |
C7 | 0.0373 (9) | 0.0430 (10) | 0.0292 (8) | −0.0035 (8) | −0.0025 (7) | 0.0038 (7) |
C8 | 0.0359 (9) | 0.0325 (9) | 0.0325 (8) | 0.0062 (7) | 0.0022 (7) | 0.0085 (7) |
C9 | 0.0354 (9) | 0.0292 (9) | 0.0438 (10) | −0.0038 (7) | 0.0068 (7) | 0.0048 (7) |
C10 | 0.0252 (8) | 0.0305 (8) | 0.0367 (9) | 0.0056 (6) | 0.0068 (6) | 0.0040 (7) |
C11 | 0.0374 (10) | 0.0391 (10) | 0.0429 (10) | 0.0066 (8) | 0.0107 (8) | −0.0072 (8) |
C12 | 0.0433 (10) | 0.0395 (10) | 0.0364 (9) | −0.0011 (8) | 0.0021 (8) | −0.0040 (8) |
Geometric parameters (Å, º) top
S1—O3 | 1.4460 (15) | C2—H2 | 0.9500 |
S1—O2 | 1.4463 (14) | C3—C4 | 1.358 (3) |
S1—O1 | 1.4580 (14) | C3—H3 | 0.9500 |
S1—C1 | 1.7798 (16) | C4—C5 | 1.420 (2) |
O4—C12 | 1.369 (2) | C4—H4 | 0.9500 |
O4—H4O | 0.8400 | C5—C1i | 1.430 (2) |
N1—C10 | 1.436 (2) | C5—C5i | 1.430 (3) |
N1—C7 | 1.471 (2) | C6—H6A | 0.9900 |
N1—C9 | 1.472 (2) | C6—H6B | 0.9900 |
N2—C6 | 1.437 (2) | C7—H7A | 0.9900 |
N2—C7 | 1.468 (2) | C7—H7B | 0.9900 |
N2—C11 | 1.476 (2) | C8—H8A | 0.9900 |
N3—C12 | 1.508 (2) | C8—H8B | 0.9900 |
N3—C10 | 1.526 (2) | C9—H9A | 0.9900 |
N3—C6 | 1.531 (2) | C9—H9B | 0.9900 |
N3—C8 | 1.532 (2) | C10—H10A | 0.9900 |
N4—C8 | 1.438 (2) | C10—H10B | 0.9900 |
N4—C9 | 1.470 (2) | C11—H11A | 0.9900 |
N4—C11 | 1.472 (2) | C11—H11B | 0.9900 |
C1—C2 | 1.368 (2) | C12—H12A | 0.9900 |
C1—C5i | 1.430 (2) | C12—H12B | 0.9900 |
C2—C3 | 1.408 (3) | | |
| | | |
O3—S1—O2 | 113.10 (10) | N2—C6—H6B | 109.7 |
O3—S1—O1 | 111.70 (9) | N3—C6—H6B | 109.7 |
O2—S1—O1 | 112.51 (9) | H6A—C6—H6B | 108.2 |
O3—S1—C1 | 107.12 (9) | N2—C7—N1 | 111.57 (14) |
O2—S1—C1 | 106.46 (8) | N2—C7—H7A | 109.3 |
O1—S1—C1 | 105.34 (8) | N1—C7—H7A | 109.3 |
C12—O4—H4O | 109.5 | N2—C7—H7B | 109.3 |
C10—N1—C7 | 109.12 (14) | N1—C7—H7B | 109.3 |
C10—N1—C9 | 108.91 (14) | H7A—C7—H7B | 108.0 |
C7—N1—C9 | 108.82 (15) | N4—C8—N3 | 109.72 (13) |
C6—N2—C7 | 109.48 (15) | N4—C8—H8A | 109.7 |
C6—N2—C11 | 109.18 (14) | N3—C8—H8A | 109.7 |
C7—N2—C11 | 108.59 (15) | N4—C8—H8B | 109.7 |
C12—N3—C10 | 108.45 (13) | N3—C8—H8B | 109.7 |
C12—N3—C6 | 111.23 (13) | H8A—C8—H8B | 108.2 |
C10—N3—C6 | 108.03 (12) | N4—C9—N1 | 111.61 (14) |
C12—N3—C8 | 113.18 (13) | N4—C9—H9A | 109.3 |
C10—N3—C8 | 107.70 (13) | N1—C9—H9A | 109.3 |
C6—N3—C8 | 108.08 (13) | N4—C9—H9B | 109.3 |
C8—N4—C9 | 109.89 (15) | N1—C9—H9B | 109.3 |
C8—N4—C11 | 109.40 (15) | H9A—C9—H9B | 108.0 |
C9—N4—C11 | 108.09 (15) | N1—C10—N3 | 110.55 (13) |
C2—C1—C5i | 121.43 (15) | N1—C10—H10A | 109.5 |
C2—C1—S1 | 117.71 (13) | N3—C10—H10A | 109.5 |
C5i—C1—S1 | 120.85 (12) | N1—C10—H10B | 109.5 |
C1—C2—C3 | 119.93 (16) | N3—C10—H10B | 109.5 |
C1—C2—H2 | 120.0 | H10A—C10—H10B | 108.1 |
C3—C2—H2 | 120.0 | N4—C11—N2 | 111.69 (14) |
C4—C3—C2 | 120.85 (16) | N4—C11—H11A | 109.3 |
C4—C3—H3 | 119.6 | N2—C11—H11A | 109.3 |
C2—C3—H3 | 119.6 | N4—C11—H11B | 109.3 |
C3—C4—C5 | 120.91 (16) | N2—C11—H11B | 109.3 |
C3—C4—H4 | 119.5 | H11A—C11—H11B | 107.9 |
C5—C4—H4 | 119.5 | O4—C12—N3 | 111.09 (16) |
C4—C5—C1i | 123.13 (15) | O4—C12—H12A | 109.4 |
C4—C5—C5i | 119.21 (18) | N3—C12—H12A | 109.4 |
C1i—C5—C5i | 117.66 (18) | O4—C12—H12B | 109.4 |
N2—C6—N3 | 109.90 (13) | N3—C12—H12B | 109.4 |
N2—C6—H6A | 109.7 | H12A—C12—H12B | 108.0 |
N3—C6—H6A | 109.7 | | |
| | | |
O3—S1—C1—C2 | 122.35 (15) | C9—N4—C8—N3 | −59.14 (18) |
O2—S1—C1—C2 | −116.38 (15) | C11—N4—C8—N3 | 59.38 (18) |
O1—S1—C1—C2 | 3.30 (16) | C12—N3—C8—N4 | 177.87 (14) |
O3—S1—C1—C5i | −58.70 (15) | C10—N3—C8—N4 | 58.00 (17) |
O2—S1—C1—C5i | 62.57 (15) | C6—N3—C8—N4 | −58.49 (17) |
O1—S1—C1—C5i | −177.76 (13) | C8—N4—C9—N1 | 60.47 (19) |
C5i—C1—C2—C3 | 0.0 (3) | C11—N4—C9—N1 | −58.85 (19) |
S1—C1—C2—C3 | 178.96 (14) | C10—N1—C9—N4 | −60.18 (19) |
C1—C2—C3—C4 | −0.5 (3) | C7—N1—C9—N4 | 58.67 (19) |
C2—C3—C4—C5 | 0.5 (3) | C7—N1—C10—N3 | −59.01 (17) |
C3—C4—C5—C1i | 179.55 (17) | C9—N1—C10—N3 | 59.65 (17) |
C3—C4—C5—C5i | −0.1 (3) | C12—N3—C10—N1 | 178.39 (14) |
C7—N2—C6—N3 | 59.38 (17) | C6—N3—C10—N1 | 57.72 (17) |
C11—N2—C6—N3 | −59.38 (18) | C8—N3—C10—N1 | −58.80 (16) |
C12—N3—C6—N2 | −176.54 (14) | C8—N4—C11—N2 | −60.71 (19) |
C10—N3—C6—N2 | −57.62 (17) | C9—N4—C11—N2 | 58.92 (19) |
C8—N3—C6—N2 | 58.65 (17) | C6—N2—C11—N4 | 60.62 (19) |
C6—N2—C7—N1 | −61.13 (19) | C7—N2—C11—N4 | −58.69 (19) |
C11—N2—C7—N1 | 57.99 (19) | C10—N3—C12—O4 | −171.48 (14) |
C10—N1—C7—N2 | 60.62 (19) | C6—N3—C12—O4 | −52.8 (2) |
C9—N1—C7—N2 | −58.10 (19) | C8—N3—C12—O4 | 69.09 (19) |
Symmetry code: (i) −x+2, −y+1, −z+2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4O···O1 | 0.84 | 1.79 | 2.628 (2) | 176 |
C6—H6A···O3ii | 0.99 | 2.47 | 3.380 (2) | 153 |
C9—H9A···O2iii | 0.99 | 2.44 | 3.359 (2) | 155 |
C10—H10B···O1ii | 0.99 | 2.50 | 3.376 (2) | 148 |
Symmetry codes: (ii) x−1, −y+3/2, z−1/2; (iii) x−1, y, z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | 2NH4+·C10H6O6S22− | 2C7H15N4O+·C10H6O6S22− |
Mr | 322.36 | 628.73 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 298 | 298 |
a, b, c (Å) | 11.3771 (7), 7.3386 (4), 7.9974 (7) | 6.0625 (4), 19.282 (1), 11.6207 (7) |
β (°) | 103.431 (6) | 96.72 (4) |
V (Å3) | 649.46 (8) | 1349.09 (14) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.44 | 0.26 |
Crystal size (mm) | 0.56 × 0.44 × 0.08 | 0.68 × 0.32 × 0.20 |
|
Data collection |
Diffractometer | Siemens P4 diffractometer | Siemens P4 diffractometer |
Absorption correction | Analytical (SHELXTL; Bruker, 1998) | – |
Tmin, Tmax | 0.844, 0.963 | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2078, 1495, 1334 | 4192, 3101, 2669 |
Rint | 0.013 | 0.012 |
(sin θ/λ)max (Å−1) | 0.650 | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.086, 1.09 | 0.038, 0.108, 1.08 |
No. of reflections | 1495 | 3101 |
No. of parameters | 107 | 194 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.30, −0.37 | 0.45, −0.33 |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N—H1N···O2 | 0.88 (3) | 2.04 (3) | 2.898 (2) | 166 (2) |
N—H2N···O2i | 0.88 (3) | 1.98 (3) | 2.846 (2) | 175 (2) |
N—H3N···O1ii | 0.88 (3) | 2.01 (3) | 2.889 (2) | 172 (3) |
N—H4N···O3iii | 0.92 (3) | 1.98 (3) | 2.868 (2) | 160 (2) |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, y−1, z; (iii) −x, y−1/2, −z+1/2. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4O···O1 | 0.84 | 1.79 | 2.628 (2) | 176 |
C6—H6A···O3i | 0.99 | 2.47 | 3.380 (2) | 153 |
C9—H9A···O2ii | 0.99 | 2.44 | 3.359 (2) | 155 |
C10—H10B···O1i | 0.99 | 2.50 | 3.376 (2) | 148 |
Symmetry codes: (i) x−1, −y+3/2, z−1/2; (ii) x−1, y, z. |
The 1,5-naphthalenedisulfonate moiety has been shown to be a versatile building block in the construction of supramolecular arrays (Russell et al., 1997). Because of the high affinity of the sulfonate group to form hydrogen bonds and the inflexible nature of the naphthyl fragment, patterns of association to neighboring moieties often follow predictable sets of intermolecular contacts. The focus of this investigation was to understand the crystal chemistry of a two-component system composed of 1,5-naphthalenedisulfonic acid and hexamethylenetetramine (HMTA). Similar to previous reports on the donor ability of disulfonates and various acceptor molecules, we anticipated cocrystallization of the disulfonate and HMTA molecules would form motifs linked via strong D—H.·A interactions (Holman et al., 2001). Our crystallographic experiments, however, revealed chemical products from the reaction of HMTA and the disulfonic acid. We observed that slow evaporation of HMTA and 1,5-naphthalenedisulfonic acid from aqueous and methanolic solutions gave the ammonium, (I), and N-(hydroxymethyl)HMTA, (II), salts, respectively. The acid-promoted degradation of HMTA to formaldehyde and ammonia has been known for some time (Baur & Ruetschi, 1941) with recent reports detailing its influence on the construction of HMTA cocrystalline frameworks (Duraisamy et al., 2000; Lough et al., 2000). The structures of (I) and (II) support such a chemical process by providing structural evidence of chemical species [i.e. ammonium and N-(hydroxymethyl)HMTA] along the HMTA reaction coordinate.
From inspection of Figs. 1 and 2, the asymmetric units of both title compounds contain a 1,5-naphthalenedisulfonate molecule positioned on an inversion center and either two ammonium [for (I)] or N-(hydroxymethyl)HMTA [for (II)] cations. Each of the three S—O− sulfonate acceptors and the four N+—H donor groups in compound (I) are utilized in the construction of hydrogen bonds. The disulfonate groups are linked to four adjacent ammonium molecules by N+—H···−O—S contacts (Table 1). The collection of these hydrogen bonds forms a complex network of sulfonate and ammonium associations as shown in Fig. 3. These intermolecular associations generate molecular alignment with alternating hydrophobic (disulfonate and ammonium ions) and hydrophilic (naphthyl) regions that extend in the bc plane. In the structure of (II), the disulfonate moiety is hydrogen bonded to two neighboring N-(hydroxymethyl)HMTA cations via O—H···−O—S close contacts (Table 2). From inspection of Fig. 4, this set of interactions forms a discrete centrosymmetric trimeric pattern with graph set D22(10) (Bernstein et al., 1995). Molecular alignment of complex (II) is further influenced by additional C—H···−O3S interactions between the HMTA and sulfonate moieties. Although such C—H.·O interactions are weak by comparison to conventional hydrogen bonds, recent reports suggest their contribution to crystal packing may play a significant role in the overall construction of molecular assemblages (Desiraju, 2002; Steiner, 2002; Desiraju & Steiner, 1999).