Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111054722/bi3027sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111054722/bi3027Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111054722/bi3027IIsup3.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S0108270111054722/bi3027sup4.pdf |
CCDC references: 727571; 731505
Adduct (I) was prepared by dissolving 2-hydroxybenzoic acid (13.8 g, 0.1 mol) in distilled water (50 ml), then neutralizing this solution with an aqueous solution of hydrazine hydrate (5 ml in 20 ml of water). The clear solution formed at pH 6 was concentrated to half its volume in a water bath at 353 K, then left to evaporate slowly. After 2 d, colourless needles of (I) were filtered off and washed with ethanol. After complete evaporation of the filtrate, the bulk product comprised the simple salt hydrazinium 2-hydroxybenzoate, which has already been reported (Kuppusamy et al., 1995).
Adduct (II) was prepared by dissolving stoichiometric quantities of hydrazine hydrate (99.98% pure; 0.05 ml, 1 mmol) and 3-hydroxy-2-napthoic acid (0.376 g, 2 mmol) in absolute ethanol (40 ml) at pH 4. The solution was left to evaporate to dryness, and colourless needles of (II) were formed after 3 d. These crystals were recrystallized from ethanol.
In both structures, C-bound H atoms were positioned geometrically and allowed to ride during subsequent refinement, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). The H atoms of the hydrazinium cations were located in difference Fourier maps and refined without restraint with isotropic displacement parameters.
For both compounds, data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
N2H5+·C7H5O3−·C7H6O3 | Z = 2 |
Mr = 308.29 | F(000) = 324 |
Triclinic, P1 | Dx = 1.408 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.3434 (2) Å | Cell parameters from 5800 reflections |
b = 7.9884 (2) Å | θ = 2.6–29.3° |
c = 12.7593 (4) Å | µ = 0.11 mm−1 |
α = 96.497 (2)° | T = 293 K |
β = 92.783 (2)° | Block, colourless |
γ = 101.303 (1)° | 0.25 × 0.20 × 0.20 mm |
V = 727.33 (4) Å3 |
Bruker Kappa APEXII CCD area-detector diffractometer | 4054 independent reflections |
Radiation source: fine-focus sealed tube | 2980 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
ω and ϕ scans | θmax = 29.6°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −10→10 |
Tmin = 0.973, Tmax = 0.978 | k = −11→11 |
17523 measured reflections | l = −17→17 |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.123 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.061P)2 + 0.090P] where P = (Fo2 + 2Fc2)/3 |
4053 reflections | (Δ/σ)max < 0.001 |
231 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
N2H5+·C7H5O3−·C7H6O3 | γ = 101.303 (1)° |
Mr = 308.29 | V = 727.33 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.3434 (2) Å | Mo Kα radiation |
b = 7.9884 (2) Å | µ = 0.11 mm−1 |
c = 12.7593 (4) Å | T = 293 K |
α = 96.497 (2)° | 0.25 × 0.20 × 0.20 mm |
β = 92.783 (2)° |
Bruker Kappa APEXII CCD area-detector diffractometer | 4054 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 2980 reflections with I > 2σ(I) |
Tmin = 0.973, Tmax = 0.978 | Rint = 0.025 |
17523 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.123 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.24 e Å−3 |
4053 reflections | Δρmin = −0.23 e Å−3 |
231 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.11688 (12) | 0.90155 (10) | 0.38561 (7) | 0.0481 (2) | |
O2 | 0.28699 (11) | 0.75805 (10) | 0.47500 (7) | 0.0432 (2) | |
O3 | 0.17889 (12) | 0.42868 (11) | 0.45566 (7) | 0.0464 (2) | |
H3 | 0.236 (2) | 0.538 (2) | 0.4808 (14) | 0.076 (5)* | |
C1 | 0.08807 (14) | 0.60392 (13) | 0.32973 (8) | 0.0340 (2) | |
C2 | 0.09687 (14) | 0.44382 (13) | 0.36105 (9) | 0.0362 (2) | |
C3 | 0.01800 (17) | 0.29354 (15) | 0.29527 (11) | 0.0488 (3) | |
H3A | 0.0217 | 0.1868 | 0.3169 | 0.059* | |
C4 | −0.06508 (19) | 0.30375 (19) | 0.19850 (11) | 0.0583 (4) | |
H4A | −0.1179 | 0.2032 | 0.1546 | 0.070* | |
C5 | −0.07172 (19) | 0.4607 (2) | 0.16503 (10) | 0.0585 (4) | |
H5A | −0.1264 | 0.4659 | 0.0985 | 0.070* | |
C6 | 0.00326 (17) | 0.60997 (17) | 0.23087 (9) | 0.0456 (3) | |
H6A | −0.0030 | 0.7159 | 0.2088 | 0.055* | |
C7 | 0.16895 (14) | 0.76583 (13) | 0.40108 (9) | 0.0347 (2) | |
O4 | 0.41211 (12) | 0.51034 (11) | 0.65033 (7) | 0.0481 (2) | |
O5 | 0.46778 (14) | 0.36107 (12) | 0.78022 (8) | 0.0545 (2) | |
H5 | 0.395 (3) | 0.266 (3) | 0.7252 (16) | 0.097 (6)* | |
O6 | 0.49556 (14) | 0.83926 (12) | 0.67909 (7) | 0.0531 (2) | |
H6 | 0.445 (3) | 0.729 (3) | 0.6520 (14) | 0.084 (6)* | |
C8 | 0.55767 (15) | 0.66335 (15) | 0.81202 (9) | 0.0403 (2) | |
C9 | 0.56545 (16) | 0.82352 (15) | 0.77658 (9) | 0.0425 (3) | |
C10 | 0.6461 (2) | 0.97329 (19) | 0.84192 (12) | 0.0613 (4) | |
H10A | 0.6514 | 1.0801 | 0.8185 | 0.074* | |
C11 | 0.7177 (3) | 0.9616 (2) | 0.94119 (13) | 0.0803 (5) | |
H11A | 0.7728 | 1.0616 | 0.9850 | 0.096* | |
C12 | 0.7099 (3) | 0.8044 (3) | 0.97778 (12) | 0.0789 (5) | |
H12A | 0.7580 | 0.7993 | 1.0459 | 0.095* | |
C13 | 0.6314 (2) | 0.6562 (2) | 0.91370 (10) | 0.0582 (4) | |
H13A | 0.6272 | 0.5503 | 0.9381 | 0.070* | |
C14 | 0.47353 (15) | 0.50631 (15) | 0.74049 (9) | 0.0405 (2) | |
N1 | 0.32233 (15) | 0.15602 (12) | 0.53020 (9) | 0.0416 (2) | |
H1A | 0.282 (2) | 0.254 (2) | 0.5219 (12) | 0.065 (4)* | |
H1B | 0.258 (2) | 0.070 (2) | 0.4734 (13) | 0.069 (5)* | |
H1C | 0.449 (2) | 0.1745 (18) | 0.5279 (12) | 0.055 (4)* | |
N2 | 0.28335 (16) | 0.10961 (13) | 0.63366 (9) | 0.0460 (3) | |
H2A | 0.314 (2) | 0.008 (2) | 0.6358 (13) | 0.067 (5)* | |
H2B | 0.160 (2) | 0.095 (2) | 0.6343 (12) | 0.064 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0475 (5) | 0.0316 (4) | 0.0636 (5) | 0.0077 (3) | −0.0115 (4) | 0.0064 (3) |
O2 | 0.0393 (4) | 0.0376 (4) | 0.0492 (5) | 0.0054 (3) | −0.0135 (3) | 0.0015 (3) |
O3 | 0.0541 (5) | 0.0326 (4) | 0.0512 (5) | 0.0088 (3) | −0.0106 (4) | 0.0061 (3) |
C1 | 0.0277 (5) | 0.0360 (5) | 0.0368 (5) | 0.0050 (4) | −0.0008 (4) | 0.0019 (4) |
C2 | 0.0307 (5) | 0.0345 (5) | 0.0415 (6) | 0.0050 (4) | 0.0005 (4) | 0.0005 (4) |
C3 | 0.0463 (7) | 0.0365 (6) | 0.0581 (7) | 0.0022 (5) | 0.0037 (6) | −0.0063 (5) |
C4 | 0.0522 (8) | 0.0564 (8) | 0.0548 (8) | 0.0000 (6) | −0.0027 (6) | −0.0198 (6) |
C5 | 0.0521 (8) | 0.0789 (10) | 0.0377 (6) | 0.0082 (7) | −0.0089 (5) | −0.0074 (6) |
C6 | 0.0408 (6) | 0.0549 (7) | 0.0406 (6) | 0.0094 (5) | −0.0031 (5) | 0.0068 (5) |
C7 | 0.0292 (5) | 0.0320 (5) | 0.0416 (5) | 0.0037 (4) | −0.0012 (4) | 0.0045 (4) |
O4 | 0.0572 (5) | 0.0424 (4) | 0.0418 (4) | 0.0074 (4) | −0.0077 (4) | 0.0029 (3) |
O5 | 0.0585 (6) | 0.0460 (5) | 0.0587 (6) | 0.0077 (4) | −0.0072 (4) | 0.0157 (4) |
O6 | 0.0669 (6) | 0.0417 (5) | 0.0470 (5) | 0.0052 (4) | −0.0138 (4) | 0.0081 (4) |
C8 | 0.0351 (5) | 0.0497 (6) | 0.0349 (5) | 0.0067 (4) | 0.0001 (4) | 0.0051 (4) |
C9 | 0.0407 (6) | 0.0466 (6) | 0.0381 (6) | 0.0074 (5) | −0.0019 (5) | 0.0013 (5) |
C10 | 0.0704 (9) | 0.0506 (7) | 0.0557 (8) | 0.0042 (6) | −0.0075 (7) | −0.0045 (6) |
C11 | 0.0980 (13) | 0.0757 (11) | 0.0524 (9) | 0.0012 (9) | −0.0170 (8) | −0.0160 (8) |
C12 | 0.0915 (13) | 0.0967 (13) | 0.0395 (7) | 0.0058 (10) | −0.0177 (8) | 0.0026 (8) |
C13 | 0.0594 (8) | 0.0715 (9) | 0.0417 (7) | 0.0062 (7) | −0.0048 (6) | 0.0151 (6) |
C14 | 0.0353 (5) | 0.0444 (6) | 0.0426 (6) | 0.0085 (4) | 0.0021 (4) | 0.0091 (5) |
N1 | 0.0388 (5) | 0.0288 (4) | 0.0560 (6) | 0.0072 (4) | −0.0070 (4) | 0.0044 (4) |
N2 | 0.0430 (6) | 0.0338 (5) | 0.0615 (7) | 0.0077 (4) | −0.0007 (5) | 0.0094 (4) |
O1—C7 | 1.2507 (13) | O6—H6 | 0.91 (2) |
O2—C7 | 1.2648 (12) | C8—C13 | 1.3928 (16) |
O3—C2 | 1.3511 (13) | C8—C9 | 1.3964 (16) |
O3—H3 | 0.906 (19) | C8—C14 | 1.4734 (16) |
C1—C6 | 1.3895 (15) | C9—C10 | 1.3877 (17) |
C1—C2 | 1.3947 (15) | C10—C11 | 1.368 (2) |
C1—C7 | 1.4948 (14) | C10—H10A | 0.9300 |
C2—C3 | 1.3904 (15) | C11—C12 | 1.380 (3) |
C3—C4 | 1.3684 (19) | C11—H11A | 0.9300 |
C3—H3A | 0.9300 | C12—C13 | 1.368 (2) |
C4—C5 | 1.378 (2) | C12—H12A | 0.9300 |
C4—H4A | 0.9300 | C13—H13A | 0.9300 |
C5—C6 | 1.3791 (18) | N1—N2 | 1.4380 (16) |
C5—H5A | 0.9300 | N1—H1A | 0.905 (18) |
C6—H6A | 0.9300 | N1—H1B | 0.971 (18) |
O4—C14 | 1.2212 (13) | N1—H1C | 0.915 (16) |
O5—C14 | 1.3119 (14) | N2—H2A | 0.891 (17) |
O5—H5 | 1.02 (2) | N2—H2B | 0.889 (17) |
O6—C9 | 1.3510 (14) | ||
C2—O3—H3 | 103.9 (11) | O6—C9—C10 | 117.71 (11) |
C6—C1—C2 | 118.74 (10) | O6—C9—C8 | 122.02 (10) |
C6—C1—C7 | 120.69 (10) | C10—C9—C8 | 120.28 (12) |
C2—C1—C7 | 120.58 (9) | C11—C10—C9 | 119.07 (14) |
O3—C2—C3 | 117.86 (10) | C11—C10—H10A | 120.5 |
O3—C2—C1 | 121.81 (9) | C9—C10—H10A | 120.5 |
C3—C2—C1 | 120.33 (11) | C10—C11—C12 | 121.42 (14) |
C4—C3—C2 | 119.54 (12) | C10—C11—H11A | 119.3 |
C4—C3—H3A | 120.2 | C12—C11—H11A | 119.3 |
C2—C3—H3A | 120.2 | C13—C12—C11 | 119.85 (14) |
C3—C4—C5 | 121.07 (12) | C13—C12—H12A | 120.1 |
C3—C4—H4A | 119.5 | C11—C12—H12A | 120.1 |
C5—C4—H4A | 119.5 | C12—C13—C8 | 120.27 (14) |
C4—C5—C6 | 119.56 (12) | C12—C13—H13A | 119.9 |
C4—C5—H5A | 120.2 | C8—C13—H13A | 119.9 |
C6—C5—H5A | 120.2 | O4—C14—O5 | 121.95 (11) |
C5—C6—C1 | 120.75 (12) | O4—C14—C8 | 122.50 (10) |
C5—C6—H6A | 119.6 | O5—C14—C8 | 115.55 (10) |
C1—C6—H6A | 119.6 | N2—N1—H1A | 109.1 (10) |
O1—C7—O2 | 123.16 (9) | N2—N1—H1B | 113.1 (9) |
O1—C7—C1 | 118.99 (9) | H1A—N1—H1B | 106.1 (14) |
O2—C7—C1 | 117.86 (9) | N2—N1—H1C | 106.2 (9) |
C14—O5—H5 | 106.5 (11) | H1A—N1—H1C | 110.0 (14) |
C9—O6—H6 | 103.1 (11) | H1B—N1—H1C | 112.3 (13) |
C13—C8—C9 | 119.10 (12) | N1—N2—H2A | 106.0 (10) |
C13—C8—C14 | 121.76 (11) | N1—N2—H2B | 104.3 (10) |
C9—C8—C14 | 119.14 (10) | H2A—N2—H2B | 108.2 (14) |
C6—C1—C2—O3 | 179.36 (10) | C13—C8—C9—O6 | −179.62 (12) |
C7—C1—C2—O3 | −0.44 (16) | C14—C8—C9—O6 | 1.02 (18) |
C6—C1—C2—C3 | −1.54 (16) | C13—C8—C9—C10 | 0.16 (19) |
C7—C1—C2—C3 | 178.66 (10) | C14—C8—C9—C10 | −179.19 (12) |
O3—C2—C3—C4 | −179.51 (11) | O6—C9—C10—C11 | 179.85 (15) |
C1—C2—C3—C4 | 1.35 (18) | C8—C9—C10—C11 | 0.0 (2) |
C2—C3—C4—C5 | 0.1 (2) | C9—C10—C11—C12 | −0.5 (3) |
C3—C4—C5—C6 | −1.3 (2) | C10—C11—C12—C13 | 0.8 (3) |
C4—C5—C6—C1 | 1.1 (2) | C11—C12—C13—C8 | −0.6 (3) |
C2—C1—C6—C5 | 0.31 (18) | C9—C8—C13—C12 | 0.1 (2) |
C7—C1—C6—C5 | −179.88 (11) | C14—C8—C13—C12 | 179.45 (13) |
C6—C1—C7—O1 | 19.57 (16) | C13—C8—C14—O4 | −178.31 (12) |
C2—C1—C7—O1 | −160.63 (10) | C9—C8—C14—O4 | 1.02 (18) |
C6—C1—C7—O2 | −160.77 (10) | C13—C8—C14—O5 | 2.06 (17) |
C2—C1—C7—O2 | 19.03 (15) | C9—C8—C14—O5 | −178.61 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2 | 0.906 (19) | 1.736 (18) | 2.5747 (11) | 152.7 (16) |
O5—H5···N2 | 1.02 (2) | 1.67 (2) | 2.6840 (14) | 177.9 (18) |
O6—H6···O4 | 0.91 (2) | 1.71 (2) | 2.5579 (12) | 153.6 (17) |
N1—H1A···O3 | 0.905 (18) | 1.963 (17) | 2.8335 (13) | 161.0 (15) |
N1—H1B···O1i | 0.971 (18) | 1.774 (18) | 2.7370 (13) | 170.7 (14) |
N1—H1B···O2i | 0.971 (18) | 2.546 (16) | 3.1341 (12) | 119.0 (11) |
N1—H1C···O2ii | 0.915 (15) | 1.911 (15) | 2.8219 (14) | 173.1 (13) |
N2—H2A···O6i | 0.891 (17) | 2.163 (17) | 2.9905 (14) | 154.1 (14) |
N2—H2B···O1iii | 0.889 (17) | 2.044 (18) | 2.9204 (14) | 168.1 (14) |
Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y+1, −z+1; (iii) −x, −y+1, −z+1. |
N2H5+·C11H7O3−·C11H8O3 | Z = 2 |
Mr = 408.40 | F(000) = 428 |
Triclinic, P1 | Dx = 1.411 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.376 (5) Å | Cell parameters from 7727 reflections |
b = 7.915 (5) Å | θ = 2.4–27.4° |
c = 16.778 (5) Å | µ = 0.10 mm−1 |
α = 89.248 (5)° | T = 293 K |
β = 86.963 (5)° | Block, colourless |
γ = 100.609 (5)° | 0.30 × 0.25 × 0.20 mm |
V = 961.2 (9) Å3 |
Bruker Kappa APEXII CCD area-detector diffractometer | 4362 independent reflections |
Radiation source: fine-focus sealed tube | 3408 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ω and ϕ scans | θmax = 27.4°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −9→9 |
Tmin = 0.970, Tmax = 0.980 | k = −10→10 |
20463 measured reflections | l = −21→21 |
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)] = 0.037 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.117 | w = 1/[σ2(Fo2) + (0.0636P)2 + 0.1183P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
4362 reflections | Δρmax = 0.27 e Å−3 |
304 parameters | Δρmin = −0.18 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.013 (2) |
N2H5+·C11H7O3−·C11H8O3 | γ = 100.609 (5)° |
Mr = 408.40 | V = 961.2 (9) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.376 (5) Å | Mo Kα radiation |
b = 7.915 (5) Å | µ = 0.10 mm−1 |
c = 16.778 (5) Å | T = 293 K |
α = 89.248 (5)° | 0.30 × 0.25 × 0.20 mm |
β = 86.963 (5)° |
Bruker Kappa APEXII CCD area-detector diffractometer | 4362 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 3408 reflections with I > 2σ(I) |
Tmin = 0.970, Tmax = 0.980 | Rint = 0.026 |
20463 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.117 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.27 e Å−3 |
4362 reflections | Δρmin = −0.18 e Å−3 |
304 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.13779 (11) | 0.92904 (9) | 0.41504 (5) | 0.0427 (2) | |
O2 | 0.29469 (11) | 0.76482 (10) | 0.48039 (5) | 0.0403 (2) | |
O3 | 0.18565 (12) | 0.43761 (10) | 0.47036 (5) | 0.0414 (2) | |
H3 | 0.237 (2) | 0.534 (2) | 0.4865 (10) | 0.071 (5)* | |
C1 | 0.18963 (14) | 0.78972 (13) | 0.42607 (6) | 0.0317 (2) | |
C2 | 0.12546 (14) | 0.64283 (13) | 0.37236 (6) | 0.0304 (2) | |
C3 | 0.06926 (15) | 0.67270 (14) | 0.29829 (7) | 0.0359 (2) | |
H3A | 0.0689 | 0.7852 | 0.2816 | 0.043* | |
C4 | 0.01141 (15) | 0.53689 (16) | 0.24609 (7) | 0.0399 (3) | |
C5 | −0.04166 (19) | 0.5665 (2) | 0.16811 (8) | 0.0557 (4) | |
H5A | −0.0381 | 0.6783 | 0.1494 | 0.067* | |
C6 | −0.0983 (2) | 0.4304 (3) | 0.12017 (9) | 0.0693 (5) | |
H6A | −0.1322 | 0.4502 | 0.0688 | 0.083* | |
C7 | −0.1055 (2) | 0.2625 (2) | 0.14790 (9) | 0.0688 (5) | |
H7A | −0.1464 | 0.1714 | 0.1149 | 0.083* | |
C8 | −0.05434 (19) | 0.2295 (2) | 0.22167 (9) | 0.0560 (4) | |
H8A | −0.0594 | 0.1164 | 0.2388 | 0.067* | |
C9 | 0.00744 (15) | 0.36674 (15) | 0.27341 (7) | 0.0404 (3) | |
C10 | 0.06631 (16) | 0.33703 (14) | 0.34944 (7) | 0.0386 (3) | |
H10A | 0.0640 | 0.2249 | 0.3674 | 0.046* | |
C11 | 0.12711 (14) | 0.47123 (13) | 0.39757 (6) | 0.0320 (2) | |
O4 | 0.37960 (13) | 0.47294 (10) | 0.61522 (5) | 0.0460 (2) | |
O5 | 0.40530 (13) | 0.29446 (10) | 0.71466 (5) | 0.0493 (2) | |
H5 | 0.345 (3) | 0.212 (3) | 0.6722 (12) | 0.098 (6)* | |
O6 | 0.46208 (13) | 0.79770 (11) | 0.63173 (5) | 0.0466 (2) | |
H6 | 0.415 (3) | 0.694 (2) | 0.6133 (10) | 0.086 (6)* | |
C12 | 0.42173 (15) | 0.44921 (14) | 0.68334 (7) | 0.0366 (3) | |
C13 | 0.49233 (15) | 0.59234 (14) | 0.73570 (7) | 0.0347 (2) | |
C14 | 0.54130 (16) | 0.56337 (16) | 0.81142 (7) | 0.0418 (3) | |
H14A | 0.5319 | 0.4509 | 0.8303 | 0.050* | |
C15 | 0.60566 (17) | 0.70036 (18) | 0.86147 (7) | 0.0459 (3) | |
C16 | 0.6557 (2) | 0.6732 (2) | 0.94031 (8) | 0.0649 (4) | |
H16A | 0.6479 | 0.5619 | 0.9604 | 0.078* | |
C17 | 0.7153 (3) | 0.8101 (3) | 0.98679 (10) | 0.0877 (6) | |
H17A | 0.7474 | 0.7916 | 1.0386 | 0.105* | |
C18 | 0.7285 (3) | 0.9773 (3) | 0.95727 (11) | 0.0901 (6) | |
H18A | 0.7702 | 1.0691 | 0.9897 | 0.108* | |
C19 | 0.6820 (2) | 1.0091 (2) | 0.88229 (10) | 0.0689 (4) | |
H19A | 0.6911 | 1.1219 | 0.8639 | 0.083* | |
C20 | 0.61941 (17) | 0.87077 (17) | 0.83168 (7) | 0.0463 (3) | |
C21 | 0.57106 (17) | 0.89896 (15) | 0.75377 (7) | 0.0434 (3) | |
H21A | 0.5814 | 1.0109 | 0.7340 | 0.052* | |
C22 | 0.50890 (15) | 0.76404 (14) | 0.70643 (7) | 0.0363 (3) | |
N1 | 0.31600 (14) | 0.14701 (12) | 0.52578 (6) | 0.0363 (2) | |
H1A | 0.2770 (19) | 0.250 (2) | 0.5193 (8) | 0.052 (4)* | |
H1B | 0.266 (2) | 0.074 (2) | 0.4842 (9) | 0.066 (5)* | |
H1C | 0.444 (2) | 0.1652 (17) | 0.5227 (8) | 0.049 (4)* | |
N2 | 0.25397 (15) | 0.07702 (12) | 0.60419 (6) | 0.0398 (2) | |
H2A | 0.2839 (19) | −0.028 (2) | 0.6051 (8) | 0.053 (4)* | |
H2B | 0.131 (2) | 0.0661 (19) | 0.6032 (9) | 0.056 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0490 (5) | 0.0272 (4) | 0.0537 (5) | 0.0077 (3) | −0.0172 (4) | −0.0060 (3) |
O2 | 0.0418 (5) | 0.0361 (4) | 0.0446 (5) | 0.0064 (3) | −0.0191 (4) | −0.0066 (3) |
O3 | 0.0546 (5) | 0.0302 (4) | 0.0415 (5) | 0.0094 (4) | −0.0170 (4) | −0.0019 (3) |
C1 | 0.0302 (5) | 0.0288 (5) | 0.0352 (6) | 0.0023 (4) | −0.0060 (4) | −0.0027 (4) |
C2 | 0.0269 (5) | 0.0300 (5) | 0.0341 (6) | 0.0041 (4) | −0.0050 (4) | −0.0037 (4) |
C3 | 0.0346 (6) | 0.0381 (5) | 0.0350 (6) | 0.0052 (4) | −0.0062 (4) | 0.0005 (4) |
C4 | 0.0308 (6) | 0.0557 (7) | 0.0321 (6) | 0.0037 (5) | −0.0038 (4) | −0.0078 (5) |
C5 | 0.0475 (7) | 0.0821 (10) | 0.0365 (7) | 0.0071 (7) | −0.0102 (6) | −0.0052 (6) |
C6 | 0.0543 (9) | 0.1166 (15) | 0.0353 (7) | 0.0075 (9) | −0.0119 (6) | −0.0219 (8) |
C7 | 0.0567 (9) | 0.0924 (12) | 0.0531 (9) | −0.0013 (8) | −0.0071 (7) | −0.0387 (9) |
C8 | 0.0485 (8) | 0.0617 (8) | 0.0534 (8) | −0.0022 (6) | −0.0009 (6) | −0.0280 (6) |
C9 | 0.0308 (6) | 0.0470 (6) | 0.0410 (6) | 0.0005 (5) | −0.0001 (5) | −0.0162 (5) |
C10 | 0.0397 (6) | 0.0300 (5) | 0.0452 (7) | 0.0035 (4) | −0.0021 (5) | −0.0076 (4) |
C11 | 0.0303 (5) | 0.0314 (5) | 0.0346 (6) | 0.0059 (4) | −0.0040 (4) | −0.0033 (4) |
O4 | 0.0597 (6) | 0.0397 (4) | 0.0396 (5) | 0.0080 (4) | −0.0149 (4) | −0.0080 (3) |
O5 | 0.0602 (6) | 0.0358 (4) | 0.0528 (5) | 0.0074 (4) | −0.0156 (4) | −0.0015 (4) |
O6 | 0.0626 (6) | 0.0372 (4) | 0.0406 (5) | 0.0062 (4) | −0.0188 (4) | −0.0008 (4) |
C12 | 0.0339 (6) | 0.0365 (5) | 0.0401 (6) | 0.0071 (4) | −0.0055 (5) | −0.0035 (5) |
C13 | 0.0306 (5) | 0.0393 (5) | 0.0344 (6) | 0.0058 (4) | −0.0052 (4) | −0.0037 (4) |
C14 | 0.0376 (6) | 0.0473 (6) | 0.0390 (6) | 0.0036 (5) | −0.0047 (5) | 0.0024 (5) |
C15 | 0.0368 (6) | 0.0650 (8) | 0.0336 (6) | 0.0022 (5) | −0.0044 (5) | −0.0048 (5) |
C16 | 0.0593 (9) | 0.0931 (12) | 0.0391 (7) | 0.0035 (8) | −0.0115 (6) | 0.0004 (7) |
C17 | 0.0923 (14) | 0.1295 (18) | 0.0380 (8) | 0.0060 (12) | −0.0223 (8) | −0.0164 (10) |
C18 | 0.1048 (15) | 0.1045 (15) | 0.0572 (10) | 0.0013 (12) | −0.0247 (10) | −0.0376 (10) |
C19 | 0.0750 (11) | 0.0710 (10) | 0.0577 (9) | 0.0004 (8) | −0.0143 (8) | −0.0274 (7) |
C20 | 0.0394 (6) | 0.0561 (7) | 0.0414 (7) | 0.0016 (5) | −0.0047 (5) | −0.0141 (5) |
C21 | 0.0443 (7) | 0.0384 (6) | 0.0467 (7) | 0.0037 (5) | −0.0073 (5) | −0.0060 (5) |
C22 | 0.0338 (6) | 0.0399 (6) | 0.0356 (6) | 0.0066 (4) | −0.0060 (4) | −0.0038 (4) |
N1 | 0.0392 (6) | 0.0269 (4) | 0.0447 (6) | 0.0076 (4) | −0.0132 (4) | −0.0056 (4) |
N2 | 0.0420 (6) | 0.0291 (5) | 0.0489 (6) | 0.0062 (4) | −0.0093 (5) | −0.0026 (4) |
O1—C1 | 1.2465 (14) | O6—H6 | 0.894 (19) |
O2—C1 | 1.2635 (13) | C12—C13 | 1.4777 (16) |
O3—C11 | 1.3558 (13) | C13—C14 | 1.3670 (16) |
O3—H3 | 0.844 (18) | C13—C22 | 1.4206 (18) |
C1—C2 | 1.5026 (15) | C14—C15 | 1.4081 (18) |
C2—C3 | 1.3621 (15) | C14—H14A | 0.9300 |
C2—C11 | 1.4197 (17) | C15—C16 | 1.4162 (18) |
C3—C4 | 1.4142 (16) | C15—C20 | 1.416 (2) |
C3—H3A | 0.9300 | C16—C17 | 1.364 (3) |
C4—C9 | 1.412 (2) | C16—H16A | 0.9300 |
C4—C5 | 1.4141 (17) | C17—C18 | 1.391 (3) |
C5—C6 | 1.369 (2) | C17—H17A | 0.9300 |
C5—H5A | 0.9300 | C18—C19 | 1.354 (2) |
C6—C7 | 1.393 (3) | C18—H18A | 0.9300 |
C6—H6A | 0.9300 | C19—C20 | 1.4189 (18) |
C7—C8 | 1.349 (2) | C19—H19A | 0.9300 |
C7—H7A | 0.9300 | C20—C21 | 1.3988 (18) |
C8—C9 | 1.4235 (16) | C21—C22 | 1.3646 (16) |
C8—H8A | 0.9300 | C21—H21A | 0.9300 |
C9—C10 | 1.3998 (17) | N1—N2 | 1.4391 (15) |
C10—C11 | 1.3663 (15) | N1—H1A | 0.917 (15) |
C10—H10A | 0.9300 | N1—H1B | 0.957 (17) |
O4—C12 | 1.2213 (14) | N1—H1C | 0.926 (15) |
O5—C12 | 1.3088 (16) | N2—H2A | 0.896 (15) |
O5—H5 | 1.03 (2) | N2—H2B | 0.895 (16) |
O6—C22 | 1.3534 (14) | ||
C11—O3—H3 | 104.6 (11) | C14—C13—C22 | 119.41 (10) |
O1—C1—O2 | 123.35 (9) | C14—C13—C12 | 121.63 (11) |
O1—C1—C2 | 118.98 (10) | C22—C13—C12 | 118.96 (10) |
O2—C1—C2 | 117.67 (9) | C13—C14—C15 | 121.34 (12) |
C3—C2—C11 | 119.17 (9) | C13—C14—H14A | 119.3 |
C3—C2—C1 | 120.55 (10) | C15—C14—H14A | 119.3 |
C11—C2—C1 | 120.26 (10) | C14—C15—C16 | 122.25 (14) |
C2—C3—C4 | 121.62 (11) | C14—C15—C20 | 118.52 (12) |
C2—C3—H3A | 119.2 | C16—C15—C20 | 119.22 (13) |
C4—C3—H3A | 119.2 | C17—C16—C15 | 120.06 (17) |
C9—C4—C5 | 119.49 (11) | C17—C16—H16A | 120.0 |
C9—C4—C3 | 118.32 (11) | C15—C16—H16A | 120.0 |
C5—C4—C3 | 122.20 (12) | C16—C17—C18 | 120.50 (16) |
C6—C5—C4 | 119.92 (15) | C16—C17—H17A | 119.7 |
C6—C5—H5A | 120.0 | C18—C17—H17A | 119.7 |
C4—C5—H5A | 120.0 | C19—C18—C17 | 121.38 (15) |
C5—C6—C7 | 120.43 (14) | C19—C18—H18A | 119.3 |
C5—C6—H6A | 119.8 | C17—C18—H18A | 119.3 |
C7—C6—H6A | 119.8 | C18—C19—C20 | 120.15 (17) |
C8—C7—C6 | 121.29 (13) | C18—C19—H19A | 119.9 |
C8—C7—H7A | 119.4 | C20—C19—H19A | 119.9 |
C6—C7—H7A | 119.4 | C21—C20—C15 | 119.66 (11) |
C7—C8—C9 | 120.36 (15) | C21—C20—C19 | 121.66 (13) |
C7—C8—H8A | 119.8 | C15—C20—C19 | 118.68 (13) |
C9—C8—H8A | 119.8 | C22—C21—C20 | 120.71 (11) |
C10—C9—C4 | 119.73 (10) | C22—C21—H21A | 119.6 |
C10—C9—C8 | 121.77 (12) | C20—C21—H21A | 119.6 |
C4—C9—C8 | 118.50 (12) | O6—C22—C21 | 118.58 (11) |
C11—C10—C9 | 120.60 (11) | O6—C22—C13 | 121.08 (10) |
C11—C10—H10A | 119.7 | C21—C22—C13 | 120.33 (11) |
C9—C10—H10A | 119.7 | N2—N1—H1A | 108.7 (9) |
O3—C11—C10 | 118.94 (10) | N2—N1—H1B | 112.5 (9) |
O3—C11—C2 | 120.57 (9) | H1A—N1—H1B | 107.1 (13) |
C10—C11—C2 | 120.48 (11) | N2—N1—H1C | 107.5 (8) |
C12—O5—H5 | 105.6 (11) | H1A—N1—H1C | 109.8 (12) |
C22—O6—H6 | 104.1 (11) | H1B—N1—H1C | 111.2 (13) |
O4—C12—O5 | 121.73 (10) | N1—N2—H2A | 104.9 (9) |
O4—C12—C13 | 122.40 (10) | N1—N2—H2B | 102.4 (9) |
O5—C12—C13 | 115.87 (11) | H2A—N2—H2B | 109.2 (13) |
O1—C1—C2—C3 | 22.85 (16) | O4—C12—C13—C14 | −179.06 (11) |
O2—C1—C2—C3 | −156.98 (10) | O5—C12—C13—C14 | 1.52 (16) |
O1—C1—C2—C11 | −158.72 (10) | O4—C12—C13—C22 | 1.15 (17) |
O2—C1—C2—C11 | 21.44 (15) | O5—C12—C13—C22 | −178.27 (10) |
C11—C2—C3—C4 | 0.41 (16) | C22—C13—C14—C15 | 0.84 (18) |
C1—C2—C3—C4 | 178.85 (10) | C12—C13—C14—C15 | −178.96 (10) |
C2—C3—C4—C9 | 1.94 (17) | C13—C14—C15—C16 | 179.49 (12) |
C2—C3—C4—C5 | −177.94 (11) | C13—C14—C15—C20 | −0.14 (19) |
C9—C4—C5—C6 | 0.74 (19) | C14—C15—C16—C17 | −179.26 (15) |
C3—C4—C5—C6 | −179.38 (12) | C20—C15—C16—C17 | 0.4 (2) |
C4—C5—C6—C7 | 0.5 (2) | C15—C16—C17—C18 | −0.3 (3) |
C5—C6—C7—C8 | −1.2 (2) | C16—C17—C18—C19 | 0.4 (3) |
C6—C7—C8—C9 | 0.5 (2) | C17—C18—C19—C20 | −0.4 (3) |
C5—C4—C9—C10 | 177.65 (11) | C14—C15—C20—C21 | −0.63 (18) |
C3—C4—C9—C10 | −2.24 (17) | C16—C15—C20—C21 | 179.73 (12) |
C5—C4—C9—C8 | −1.39 (17) | C14—C15—C20—C19 | 179.22 (12) |
C3—C4—C9—C8 | 178.72 (10) | C16—C15—C20—C19 | −0.4 (2) |
C7—C8—C9—C10 | −178.21 (12) | C18—C19—C20—C21 | −179.69 (15) |
C7—C8—C9—C4 | 0.80 (19) | C18—C19—C20—C15 | 0.5 (2) |
C4—C9—C10—C11 | 0.19 (17) | C15—C20—C21—C22 | 0.70 (19) |
C8—C9—C10—C11 | 179.19 (11) | C19—C20—C21—C22 | −179.15 (13) |
C9—C10—C11—O3 | −179.02 (10) | C20—C21—C22—O6 | 179.37 (11) |
C9—C10—C11—C2 | 2.23 (17) | C20—C21—C22—C13 | 0.00 (18) |
C3—C2—C11—O3 | 178.74 (10) | C14—C13—C22—O6 | 179.87 (10) |
C1—C2—C11—O3 | 0.29 (15) | C12—C13—C22—O6 | −0.32 (16) |
C3—C2—C11—C10 | −2.54 (16) | C14—C13—C22—C21 | −0.78 (17) |
C1—C2—C11—C10 | 179.02 (10) | C12—C13—C22—C21 | 179.03 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2 | 0.844 (18) | 1.795 (18) | 2.5771 (19) | 153.3 (16) |
O5—H5···N2 | 1.03 (2) | 1.66 (2) | 2.6905 (15) | 178.5 (18) |
O6—H6···O4 | 0.894 (19) | 1.723 (19) | 2.5525 (19) | 153.0 (17) |
N1—H1A···O3 | 0.917 (15) | 1.934 (15) | 2.8164 (18) | 160.9 (13) |
N1—H1B···O1i | 0.957 (17) | 1.819 (17) | 2.7684 (15) | 171.1 (14) |
N1—H1B···O2i | 0.957 (17) | 2.496 (16) | 3.107 (2) | 121.7 (11) |
N1—H1C···O2ii | 0.927 (15) | 1.903 (15) | 2.824 (2) | 172.0 (12) |
N2—H2A···O6i | 0.896 (15) | 2.134 (15) | 2.9590 (19) | 152.7 (12) |
N2—H2B···O1iii | 0.895 (16) | 2.030 (17) | 2.916 (2) | 170.1 (13) |
Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y+1, −z+1; (iii) −x, −y+1, −z+1. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | N2H5+·C7H5O3−·C7H6O3 | N2H5+·C11H7O3−·C11H8O3 |
Mr | 308.29 | 408.40 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 7.3434 (2), 7.9884 (2), 12.7593 (4) | 7.376 (5), 7.915 (5), 16.778 (5) |
α, β, γ (°) | 96.497 (2), 92.783 (2), 101.303 (1) | 89.248 (5), 86.963 (5), 100.609 (5) |
V (Å3) | 727.33 (4) | 961.2 (9) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.11 | 0.10 |
Crystal size (mm) | 0.25 × 0.20 × 0.20 | 0.30 × 0.25 × 0.20 |
Data collection | ||
Diffractometer | Bruker Kappa APEXII CCD area-detector diffractometer | Bruker Kappa APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2004) | Multi-scan (SADABS; Bruker, 2004) |
Tmin, Tmax | 0.973, 0.978 | 0.970, 0.980 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17523, 4054, 2980 | 20463, 4362, 3408 |
Rint | 0.025 | 0.026 |
(sin θ/λ)max (Å−1) | 0.694 | 0.648 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.123, 1.03 | 0.037, 0.117, 1.03 |
No. of reflections | 4053 | 4362 |
No. of parameters | 231 | 304 |
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) | 0.24, −0.23 | 0.27, −0.18 |
Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT and XPREP (Bruker, 2004), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2 | 0.906 (19) | 1.736 (18) | 2.5747 (11) | 152.7 (16) |
O5—H5···N2 | 1.02 (2) | 1.67 (2) | 2.6840 (14) | 177.9 (18) |
O6—H6···O4 | 0.91 (2) | 1.71 (2) | 2.5579 (12) | 153.6 (17) |
N1—H1A···O3 | 0.905 (18) | 1.963 (17) | 2.8335 (13) | 161.0 (15) |
N1—H1B···O1i | 0.971 (18) | 1.774 (18) | 2.7370 (13) | 170.7 (14) |
N1—H1B···O2i | 0.971 (18) | 2.546 (16) | 3.1341 (12) | 119.0 (11) |
N1—H1C···O2ii | 0.915 (15) | 1.911 (15) | 2.8219 (14) | 173.1 (13) |
N2—H2A···O6i | 0.891 (17) | 2.163 (17) | 2.9905 (14) | 154.1 (14) |
N2—H2B···O1iii | 0.889 (17) | 2.044 (18) | 2.9204 (14) | 168.1 (14) |
Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y+1, −z+1; (iii) −x, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2 | 0.844 (18) | 1.795 (18) | 2.5771 (19) | 153.3 (16) |
O5—H5···N2 | 1.03 (2) | 1.66 (2) | 2.6905 (15) | 178.5 (18) |
O6—H6···O4 | 0.894 (19) | 1.723 (19) | 2.5525 (19) | 153.0 (17) |
N1—H1A···O3 | 0.917 (15) | 1.934 (15) | 2.8164 (18) | 160.9 (13) |
N1—H1B···O1i | 0.957 (17) | 1.819 (17) | 2.7684 (15) | 171.1 (14) |
N1—H1B···O2i | 0.957 (17) | 2.496 (16) | 3.107 (2) | 121.7 (11) |
N1—H1C···O2ii | 0.927 (15) | 1.903 (15) | 2.824 (2) | 172.0 (12) |
N2—H2A···O6i | 0.896 (15) | 2.134 (15) | 2.9590 (19) | 152.7 (12) |
N2—H2B···O1iii | 0.895 (16) | 2.030 (17) | 2.916 (2) | 170.1 (13) |
Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y+1, −z+1; (iii) −x, −y+1, −z+1. |
Acid adducts comprise a combination of an acid and a salt of that acid held together in a single crystal stabilized by hydrogen bonds. Structurally characterized examples include 8-hydroxyquinoline salicylate salicylic acid (Jebamony & Thomas Muthiah, 1998), pyridinium 3,5-dinitrosalicylate 3,5-dinitrosalicylic acid (Smith et al., 2003) and tetra-n-butylammonium 2,6-dihydroxybenzoate 2,6-dihydroxybenzoic acid (Almeida Paz et al., 2003). Hydrazine, a diacidic base, forms many crystalline salts with carboxylic acids and their structures have been studied (Nilsson et al., 1968; Hady et al., 1969; Thomas, 1973; Thomas & Liminga, 1978; Gajapathy et al., 1983; Chevrier et al., 1987; Fun et al., 1995; Bhogala et al., 2005; Starosta & Leciejewicz, 2008). Amongst hydroxy-substituted aromatic acids, the formation of hydrazinium 2-hydroxybenzoate has been reported (Kuppusamy et al., 1995), although its crystal structure has not been determined. In this paper, we report the crystal structure of the acid adduct hydrazinium 2-hydroxybenzoate–2-hydroxybenzoic acid (1/1), (I), and the closely related adduct hydrazinium 3-hydroxy-2-naphthoate–3-hydroxy-2-naphthoic acid (1/1), (II).
The asymmetric units of (I) and (II) contain one acid anion and one neutral acid molecule linked by the N2H5+ cation (Figs. 1 and 2). After transferring its proton to hydrazine, the deprotonated carboxylate group shows closely comparable bond lengths: C7—O1 = 1.2507 (13) Å and C7—O2 = 1.2648 (12) Å in (I), and C1—O1 = 1.2465 (14) Å and C1—O2 = 1.2635 (13) Å in (II). The C2—C1—C7—O2 torsion angle in (I) is 19.03 (15)°, while the comparable angle in (II), C11—C2—C1—O2, is 21.44 (15)°. Thus, the deprotonated carboxylate group is twisted from the plane of the aromatic ring in both structures. By contrast, the protonated carboxylic acid group remains essentially coplanar with the aromatic ring, as shown by the torsion angles C13—C8—C14—O5 = 2.06 (17)° in (I) and O5—C12—C13—C14 = 1.52 (16)° in (II). For the hydrazinium cation, the N1—N2 bond length [1.4380 (16) Å in (I) and 1.4391 (15) Å in (II)] is statistically equivalent in the two structures, and in good agreement with the mean value of 1.442 (11) Å derived from 49 hydrazinium salts identified in the Cambridge Structural Database (Version 5.32 plus updates; Allen, 2002; see Supplementary material).
Hydrogen bonding plays a major role in the construction of acid adducts. The title adducts (I) and (II) contain two types of intermolecular hydrogen bond (Tables 1 and 2), with N2H5+ acting as either a donor or an acceptor (Fig. 3). Intramolecular O—H···O hydrogen bonds are also evident within the acid molecules (Fig. 1 and 2). The hydrogen bonding is essentially identical in the two structures, defining closely comparable two-dimensional layers parallel to the (001) planes (Figs. 4 and 5). In order to highlight the similarity in the (001) planes, adduct (II) is reported using an unconventional nonreduced unit cell. The corresponding reduced cell is: a = 7.376 (5), b = 7.915 (5), c = 16.778 (5) Å, α = 90.752 (5), β = 93.037 (5) and γ = 100.609 (5)°. The planes of the aromatic rings within both structures are approximately parallel [interplanar angle = 5.3 (1)° in (I) and 3.6 (1)° in (II)], and the layers are stacked with closely comparable intermolecular interactions between the aromatic rings [Cg1···Cg1iv = 4.86 (1) Å in (I) and 4.83 (1) Å in (II), where Cg1 is the centroid of atoms C8–C13 in (I) and atoms C15–C20 in (II); symmetry code: (iv) -x + 1, -y + 2, -z + 2].