supplementary materials
1,3-Phenylenediammonium dinitrate
In the title compound, C6H10N22+·2NO3-, the dication lies on a crystallographic twofold rotation axis. The nitrate ions are linked to the dications though N-H
O hydrogen bonds, forming a three-dimensional network.
To a solution of 1,3-phenylenediamine (0.1 g) in CH3OH (2 ml) was added a few
drop of nitric acid. The white precipitate formed immediately was filtered and
washed with diethyl ether. Yield: 80%. M.P. 150.5°C. 1H NMR (500 MHz,
D2O, TSP): δ 7.15 (m, J = 4 Hz,1H, ArH), 6.68
(d, J = 8 Hz, J = 2 Hz, 2H, ArH), 6.62 (t, J= 2 Hz, 1H, ArH). Crystals suitable for X-ray crystallography were obtained
by recystallization from a methanolic solution of the salt and isolated after
seven days keeping the solution under Et2O diffusion in a desiccator.
H atoms bonded to carbons were positioned geometrically and refined using a
riding model, with C-H = 0.99 Å and Uiso(H) = 1.2 Ueq(C).
H atoms bonded to N atoms were located in a difference map and their positional
parameters were refined, with Uiso(H) = 1.2 Ueq(N).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
1,3-Phenylenediammonium dinitrate
top
Crystal data top
| C6H10N22+·2NO3− | F(000) = 488 |
| Mr = 234.18 | Dx = 1.551 Mg m−3 |
| Monoclinic, C2/c | Cu Kα radiation, λ = 1.54178 Å |
| Hall symbol: -C 2yc | Cell parameters from 3468 reflections |
| a = 16.2548 (12) Å | θ = 5.5–69.5° |
| b = 9.6212 (8) Å | µ = 1.22 mm−1 |
| c = 7.1070 (6) Å | T = 100 K |
| β = 115.506 (6)° | Block, colorless |
| V = 1003.14 (14) Å3 | 0.53 × 0.50 × 0.24 mm |
| Z = 4 | |
Data collection top
Bruker APEX CCD area-detector
diffractometer | 942 independent reflections |
| Radiation source: fine-focus sealed tube | 882 reflections with I > 2σ(I) |
| graphite | Rint = 0.036 |
| φ and ω scans | θmax = 69.5°, θmin = 5.5° |
Absorption correction: multi-scan
(SADABS; Sheldrick, 2007) | h = −19→18 |
| Tmin = 0.562, Tmax = 0.761 | k = −11→11 |
| 5278 measured reflections | l = −8→8 |
Refinement top
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.033 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.092 | w = 1/[σ2(Fo2) + (0.054P)2 + 1.07P]
where P = (Fo2 + 2Fc2)/3 |
| S = 1.00 | (Δ/σ)max = 0.001 |
| 942 reflections | Δρmax = 0.26 e Å−3 |
| 84 parameters | Δρmin = −0.20 e Å−3 |
| 0 restraints | Extinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0046 (5) |
Crystal data top
| C6H10N22+·2NO3− | V = 1003.14 (14) Å3 |
| Mr = 234.18 | Z = 4 |
| Monoclinic, C2/c | Cu Kα radiation |
| a = 16.2548 (12) Å | µ = 1.22 mm−1 |
| b = 9.6212 (8) Å | T = 100 K |
| c = 7.1070 (6) Å | 0.53 × 0.50 × 0.24 mm |
| β = 115.506 (6)° | |
Data collection top
Bruker APEX CCD area-detector
diffractometer | 942 independent reflections |
Absorption correction: multi-scan
(SADABS; Sheldrick, 2007) | 882 reflections with I > 2σ(I) |
| Tmin = 0.562, Tmax = 0.761 | Rint = 0.036 |
| 5278 measured reflections | θmax = 69.5° |
Refinement top
| R[F2 > 2σ(F2)] = 0.033 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.092 | Δρmax = 0.26 e Å−3 |
| S = 1.00 | Δρmin = −0.20 e Å−3 |
| 942 reflections | Absolute structure: ? |
| 84 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top| | x | y | z | Uiso*/Ueq | |
| N1A | 0.16571 (7) | 0.19642 (12) | 1.08086 (17) | 0.0129 (3) | |
| O1A | 0.11343 (7) | 0.11334 (11) | 0.94063 (14) | 0.0171 (3) | |
| O2A | 0.17425 (7) | 0.31761 (10) | 1.03487 (16) | 0.0205 (3) | |
| O3A | 0.20794 (7) | 0.15171 (11) | 1.26369 (14) | 0.0170 (3) | |
| C1 | 0.0000 | 0.16909 (19) | 0.2500 | 0.0119 (4) | |
| H1 | 0.0000 | 0.0703 | 0.2500 | 0.014* | |
| C2 | 0.06684 (9) | 0.24329 (14) | 0.40956 (19) | 0.0125 (3) | |
| C3 | 0.06855 (9) | 0.38745 (15) | 0.4119 (2) | 0.0148 (3) | |
| H3 | 0.1156 | 0.4364 | 0.5218 | 0.018* | |
| C4 | 0.0000 | 0.4588 (2) | 0.2500 | 0.0167 (4) | |
| H4 | 0.0000 | 0.5575 | 0.2500 | 0.020* | |
| N5 | 0.13746 (8) | 0.16679 (12) | 0.58086 (17) | 0.0136 (3) | |
| H5A | 0.1261 (12) | 0.1620 (17) | 0.700 (3) | 0.016* | |
| H5B | 0.1409 (11) | 0.079 (2) | 0.535 (3) | 0.016* | |
| H5C | 0.1918 (13) | 0.2147 (19) | 0.624 (3) | 0.016* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| N1A | 0.0125 (6) | 0.0140 (6) | 0.0121 (6) | 0.0001 (4) | 0.0053 (4) | −0.0013 (4) |
| O1A | 0.0187 (5) | 0.0179 (5) | 0.0115 (5) | −0.0058 (4) | 0.0034 (4) | −0.0038 (4) |
| O2A | 0.0234 (6) | 0.0108 (5) | 0.0243 (6) | −0.0001 (4) | 0.0075 (4) | 0.0016 (4) |
| O3A | 0.0154 (5) | 0.0232 (6) | 0.0100 (5) | −0.0005 (4) | 0.0032 (4) | 0.0017 (4) |
| C1 | 0.0139 (9) | 0.0107 (9) | 0.0117 (9) | 0.000 | 0.0062 (7) | 0.000 |
| C2 | 0.0122 (7) | 0.0161 (7) | 0.0097 (6) | 0.0005 (5) | 0.0053 (5) | 0.0011 (5) |
| C3 | 0.0157 (7) | 0.0151 (7) | 0.0138 (7) | −0.0031 (5) | 0.0065 (6) | −0.0034 (5) |
| C4 | 0.0215 (10) | 0.0119 (9) | 0.0191 (9) | 0.000 | 0.0112 (8) | 0.000 |
| N5 | 0.0133 (6) | 0.0149 (6) | 0.0098 (6) | −0.0005 (4) | 0.0022 (5) | −0.0005 (4) |
Geometric parameters (Å, °) top
| N1A—O2A | 1.2348 (16) | C3—C4 | 1.3901 (16) |
| N1A—O3A | 1.2556 (15) | C3—H3 | 0.95 |
| N1A—O1A | 1.2747 (15) | C4—H4 | 0.95 |
| C1—C2 | 1.3838 (16) | N5—H5A | 0.943 (19) |
| C1—H1 | 0.95 | N5—H5B | 0.92 (2) |
| C2—C3 | 1.387 (2) | N5—H5C | 0.924 (19) |
| C2—N5 | 1.4621 (16) | | |
| | | |
| O2A—N1A—O3A | 121.59 (11) | C4—C3—H3 | 120.7 |
| O2A—N1A—O1A | 119.88 (11) | C3i—C4—C3 | 120.83 (18) |
| O3A—N1A—O1A | 118.53 (11) | C3—C4—H4 | 119.6 |
| C2i—C1—C2 | 117.89 (17) | C2—N5—H5A | 112.7 (10) |
| C2—C1—H1 | 121.1 | C2—N5—H5B | 108.4 (11) |
| C1—C2—C3 | 122.02 (12) | H5A—N5—H5B | 109.8 (14) |
| C1—C2—N5 | 118.72 (13) | C2—N5—H5C | 108.7 (11) |
| C3—C2—N5 | 119.26 (11) | H5A—N5—H5C | 104.8 (15) |
| C2—C3—C4 | 118.62 (12) | H5B—N5—H5C | 112.5 (15) |
| C2—C3—H3 | 120.7 | | |
| | | |
| C2i—C1—C2—C3 | −0.49 (9) | N5—C2—C3—C4 | −178.80 (10) |
| C2i—C1—C2—N5 | 179.28 (13) | C2—C3—C4—C3i | −0.47 (8) |
| C1—C2—C3—C4 | 0.97 (17) | | |
| Symmetry codes: (i) −x, y, −z+1/2. |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N5—H5A···O1A | 0.94 (2) | 1.87 (2) | 2.7955 (15) | 168 (2) |
| N5—H5B···O1Aii | 0.92 (2) | 1.95 (2) | 2.8416 (16) | 163 (2) |
| N5—H5C···O3Aiii | 0.92 (2) | 1.96 (2) | 2.8626 (16) | 167 (2) |
| Symmetry codes: (ii) x, −y, z−1/2; (iii) −x+1/2, −y+1/2, −z+2. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N5—H5A···O1A | 0.94 (2) | 1.87 (2) | 2.7955 (15) | 168 (2) |
| N5—H5B···O1Ai | 0.92 (2) | 1.95 (2) | 2.8416 (16) | 163 (2) |
| N5—H5C···O3Aii | 0.92 (2) | 1.96 (2) | 2.8626 (16) | 167 (2) |
| Symmetry codes: (i) x, −y, z−1/2; (ii) −x+1/2, −y+1/2, −z+2. |
This work was supported by the National Center for Research Resources (grant No.
G12RR013459) and the National Institutes of Health (NIH) Science Education
Partnership Award (SEPA) Program `Recovery Act Administrative Supplements
Providing Summer Research Research Experiences for Students and Science
Educators' under contract 5R25RR020405–04S1. Funds to purchase the
diffractometer used in this study were provided in part by the National
Science Foundation (grant No. CHE-0130835).
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![[Figure 1]](./ci2920fig1thm.gif)
![[Figure 2]](./ci2920fig2thm.gif)
Simple polyammonium ions are known as excellent hydrogen bond donors for a variety of anions in particular for oxoanions, forming supramolecular aggregates with hydrogen bonding networks (Ilioudis et al., 2002). Indeed, a difunctional or trifunctional polyamine is widely used as an essential building block for a macrocyclic based host, and acts as major binding components for a negatively charged anion (Bianchi et al., 1997; Hossain, 2008). In this study, we used a simple 1,3-phenylenediamine to prepare an adduct with nitric acid. We report, herein, the crystal structure of the title compound in which the nitrate anions are connected to the cationic units through hydrogen bonding interactions.
X-ray analysis of the nitrate salt reveals that both amino groups are protonated to form a dication and crystallized with two nitrate anions. In the crystal lattice, each diaction is surrounded by two symmetry related nitrate anions (Fig. 1). Each amino group is engaged in coordinating nitrate anions through N—H ···O bonds ranging from 2.7955 (15) to 2.8626 (16) Å (see Table 1). The crystal structure viewed along the b axis shows that the cations are arranged antiparallel to one another along the c axis in which two adjacent aromatic units are separated at 7.024 Å (Fig. 2). Therefore, there is no π-π stacking involved. The nitrates serve as linkers of the two adjacent aromatic units by hydrogen bonding networks along the b axis.