organic compounds
4-Nitrophenylhydrazinium picrate monohydrate
aSchool of Chemistry and Material Science, Ludong University, Yantai 264025, People's Republic of China
*Correspondence e-mail: honglan_cai@126.com
In the 6H8N3O2+·C6H2N3O7−·H2O, N—H⋯O and O—H⋯O hydrogen bonds link the components into a two-dimensional network parallel to (010). In addition, there are pairs of weak inversion-related C—H⋯O hydrogen bonds within the two-dimensional network. The three nitro groups are twisted by 1.6 (3), 7.8 (3) and 12.1 (3)° from the ring plane in the anion, while in the cation, the nitro group makes a dihedral angle of 4.6 (2)° with the ring.
of the title compound, CCCDC reference: 974388
Related literature
For the use of picric acid acid as a co-crystallization agent, see: Herbstein & Kaftory (1976); Dubost et al. (1981); Harrison et al. (2007); Peng et al. (2011); Zeng et al. (2011); Dey et al. (2011).
Experimental
Crystal data
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Data collection: SMART (Bruker, 2001); cell SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Supporting information
CCDC reference: 974388
https://doi.org/10.1107/S1600536813032479/lh5673sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813032479/lh5673Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536813032479/lh5673Isup3.cml
All the reagents and solvents were used as obtained without further purification. 1:1 molar amount of 4-nitrophenylhydrazine (0.2 mmol, 30.6 mg) and picric acid (0.2 mmol, 45.8 g) were dissolved in 95% methanol (20.0 ml). The mixture was stirred for half an hour at ambient temperature and then filtered. The resulting yellow solution was kept in air for one week. Yellow needles of (I) suitable for single-crystal X-ray
were grown by slow evaporation of the solution at the bottom of the vessel. The crystals were filtered and dried in air. Yield: 60.2 mg, 75% (based on picric acid or 4-nitrophenylhydrazine).H atoms bonded to C atoms were positioned geometrically with C–H = 0.93 Å (aromatic) and refined in a riding-model approximation with [Uiso(H) = 1.2Ueq(aromatic C)]. H atoms bonded to N and O atoms were found in difference Fourier maps and refined with the constraints of N—H = 0.86 (1)Å and O—H = 0.82 (1) Å. The N1-bonded H···H distances were constrained by using the SADI command in SHELXL (Sheldrick, 2008). The water O10-bonded H···H distance was constrained to be 1.35 (1) Å. The isotropic displacment parameters of of N-bonded and water O10-bonded hydrogen atoms were set 1.2 times and 1.5 times of their parent atoms, respectively.
Cocrystal strategy has been often used due to its application in the fields of drug chemistry, physical material chemistry and biological crystallography. Picric acid, as a strong organic acid, is very frequently adopted to facilitate the crystallization of some difficult-crystallized organic bases (Herbstein & Kaftory, 1976; Dubost et al., 1981; Harrison et al., 2007; Peng et al., 2011; Zeng et al., 2011; Dey et al., 2011). In this report, we report the 1:1 cocrystallized complex of 4-nitrophenylhydrazine and picric acid in 95% methanol solution.
In the title compound (I), the
consists of a 4-nitrophenyldrazinium cation, a picrate anion and a solvent water molecule (Fig.1). During the preparation of (I) the picric acid proton has been transferred to the terminal hydrazine atom N1. In the picrate molecule, the phenolate (O3—C7) bond distance is 1.245 (3) Å shows an indication of delocalization between the precursor single C—O bond and the benzene ring with three electron-withdrawing nitro groups. As a result, the neighbouring C7—C8 and C7—C12 bond lengths of 1.459 (3) Å and 1.452 (3) Å are longer by ca 0.08 Å than the mean distance of the other four C—C bonds. The C8—C7—C12 angle is about 10° smaller than the mean value (121.4°) of the other five benzene inner angles. The three nitro groups N4/O4/O5, N5/O6/O7 and N6/O8/O9 are twisted by 1.6 (3)°, 7.8 (3)° and 12.1 (3)° from the picrate benzene ring plane, respectively.In the crystal, N—H···O and O—H···O hydrogen bonds link the components of the structure into a two-dimensional network parallel to (010) (Fig. 2). In addition, there are pairs of weak inversion related C—H···O hydrogen bonds within the two-dimensional network.
For the use of picric acid acid as a co-crystallization agent, see: Herbstein & Kaftory (1976); Dubost et al. (1981); Harrison et al. (2007); Peng et al. (2011); Zeng et al. (2011); Dey et al. (2011).
Data collection: SMART (Bruker, 2001); cell
SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. Molecular structure of (I) showing displacement ellipsoids drawn at the 50% probability level. H-bonds are shown in dashed lines. | |
Fig. 2. Part of the crystal structure of (I) showing the formation of a two-dimensional network parallel to (010). Hydrogen bonds are shown as dashed lines. For the sake of clarity, H atoms not involved in the motif have been omitted. |
C6H8N3O2+·C6H2N3O7−·H2O | F(000) = 824 |
Mr = 400.28 | Dx = 1.669 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 924 reflections |
a = 4.8483 (3) Å | θ = 2.3–21.5° |
b = 28.798 (2) Å | µ = 0.15 mm−1 |
c = 11.6352 (8) Å | T = 299 K |
β = 101.360 (1)° | Needle, yellow |
V = 1592.70 (18) Å3 | 0.20 × 0.08 × 0.04 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 3643 independent reflections |
Radiation source: fine-focus sealed tube | 2487 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.045 |
φ and ω scans | θmax = 27.5°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997) | h = −6→6 |
Tmin = 0.971, Tmax = 0.994 | k = −37→36 |
16632 measured reflections | l = −14→15 |
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)] = 0.063 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.150 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0602P)2 + 0.5955P] where P = (Fo2 + 2Fc2)/3 |
3643 reflections | (Δ/σ)max = 0.001 |
271 parameters | Δρmax = 0.31 e Å−3 |
10 restraints | Δρmin = −0.31 e Å−3 |
C6H8N3O2+·C6H2N3O7−·H2O | V = 1592.70 (18) Å3 |
Mr = 400.28 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 4.8483 (3) Å | µ = 0.15 mm−1 |
b = 28.798 (2) Å | T = 299 K |
c = 11.6352 (8) Å | 0.20 × 0.08 × 0.04 mm |
β = 101.360 (1)° |
Bruker SMART CCD area-detector diffractometer | 3643 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997) | 2487 reflections with I > 2σ(I) |
Tmin = 0.971, Tmax = 0.994 | Rint = 0.045 |
16632 measured reflections |
R[F2 > 2σ(F2)] = 0.063 | 10 restraints |
wR(F2) = 0.150 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.31 e Å−3 |
3643 reflections | Δρmin = −0.31 e Å−3 |
271 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | −0.3571 (5) | 0.67096 (8) | 0.4377 (2) | 0.0427 (6) | |
C2 | −0.5710 (5) | 0.67706 (9) | 0.3408 (2) | 0.0473 (6) | |
H2 | −0.5922 | 0.6562 | 0.2786 | 0.057* | |
C3 | −0.7524 (6) | 0.71420 (9) | 0.3368 (3) | 0.0523 (7) | |
H3 | −0.8968 | 0.7186 | 0.2722 | 0.063* | |
C4 | −0.7169 (6) | 0.74447 (8) | 0.4294 (3) | 0.0505 (7) | |
C5 | −0.5048 (7) | 0.73915 (10) | 0.5256 (3) | 0.0603 (8) | |
H5 | −0.4836 | 0.7603 | 0.5870 | 0.072* | |
C6 | −0.3246 (6) | 0.70235 (10) | 0.5302 (3) | 0.0555 (7) | |
H6 | −0.1806 | 0.6983 | 0.5952 | 0.067* | |
C7 | 0.7836 (5) | 0.56180 (8) | 0.7388 (2) | 0.0365 (5) | |
C8 | 0.6275 (5) | 0.59770 (7) | 0.7872 (2) | 0.0344 (5) | |
C9 | 0.6776 (5) | 0.61004 (7) | 0.9025 (2) | 0.0361 (5) | |
H9 | 0.5682 | 0.6327 | 0.9287 | 0.043* | |
C10 | 0.8913 (5) | 0.58870 (8) | 0.9798 (2) | 0.0375 (5) | |
C11 | 1.0603 (5) | 0.55567 (8) | 0.9429 (2) | 0.0363 (5) | |
H11 | 1.2063 | 0.5420 | 0.9960 | 0.044* | |
C12 | 1.0107 (5) | 0.54316 (7) | 0.8270 (2) | 0.0345 (5) | |
N1 | −0.2290 (5) | 0.59509 (8) | 0.3776 (2) | 0.0543 (6) | |
H1A | −0.377 (3) | 0.5818 (9) | 0.394 (2) | 0.065* | |
H1B | −0.078 (3) | 0.5783 (8) | 0.399 (2) | 0.065* | |
H1C | −0.250 (4) | 0.6027 (10) | 0.3037 (11) | 0.065* | |
N2 | −0.1620 (5) | 0.63550 (8) | 0.4446 (2) | 0.0579 (6) | |
H2A | −0.069 (6) | 0.6290 (11) | 0.5132 (14) | 0.070* | |
N3 | −0.9135 (7) | 0.78313 (9) | 0.4265 (3) | 0.0711 (8) | |
N4 | 0.3991 (4) | 0.62195 (7) | 0.71219 (19) | 0.0419 (5) | |
N5 | 0.9370 (5) | 0.60035 (8) | 1.10213 (19) | 0.0481 (5) | |
N6 | 1.2004 (4) | 0.50850 (7) | 0.79502 (19) | 0.0403 (5) | |
O1 | −1.1132 (6) | 0.78583 (8) | 0.3443 (3) | 0.0885 (8) | |
O2 | −0.8693 (7) | 0.81070 (9) | 0.5084 (3) | 0.1111 (11) | |
O3 | 0.7262 (4) | 0.54803 (7) | 0.63542 (15) | 0.0569 (5) | |
O4 | 0.3387 (6) | 0.61246 (9) | 0.6108 (2) | 0.1019 (10) | |
O5 | 0.2717 (6) | 0.65136 (10) | 0.7518 (2) | 0.0989 (10) | |
O6 | 0.7656 (5) | 0.62597 (7) | 1.13576 (17) | 0.0648 (6) | |
O7 | 1.1385 (5) | 0.58370 (8) | 1.16900 (17) | 0.0676 (6) | |
O8 | 1.3571 (5) | 0.48802 (8) | 0.87253 (19) | 0.0694 (6) | |
O9 | 1.2022 (4) | 0.50150 (8) | 0.69233 (18) | 0.0697 (6) | |
O10 | 0.2853 (4) | 0.54747 (6) | 0.43546 (16) | 0.0545 (5) | |
H10B | 0.264 (7) | 0.5203 (5) | 0.413 (2) | 0.082* | |
H10A | 0.362 (7) | 0.5483 (10) | 0.5049 (12) | 0.082* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0376 (13) | 0.0414 (13) | 0.0506 (15) | 0.0074 (10) | 0.0123 (11) | 0.0029 (11) |
C2 | 0.0436 (14) | 0.0457 (14) | 0.0508 (15) | 0.0078 (11) | 0.0049 (12) | −0.0036 (12) |
C3 | 0.0426 (15) | 0.0480 (15) | 0.0648 (18) | 0.0083 (12) | 0.0067 (13) | 0.0059 (14) |
C4 | 0.0498 (15) | 0.0353 (13) | 0.0716 (19) | 0.0075 (11) | 0.0248 (14) | 0.0055 (13) |
C5 | 0.074 (2) | 0.0456 (15) | 0.066 (2) | 0.0037 (14) | 0.0243 (17) | −0.0121 (14) |
C6 | 0.0565 (17) | 0.0579 (17) | 0.0494 (16) | 0.0044 (13) | 0.0038 (13) | −0.0049 (13) |
C7 | 0.0354 (12) | 0.0358 (12) | 0.0376 (13) | 0.0002 (10) | 0.0059 (10) | −0.0009 (10) |
C8 | 0.0320 (11) | 0.0294 (11) | 0.0407 (13) | −0.0004 (9) | 0.0041 (10) | 0.0015 (9) |
C9 | 0.0375 (12) | 0.0301 (11) | 0.0423 (14) | −0.0018 (9) | 0.0120 (10) | −0.0013 (10) |
C10 | 0.0440 (13) | 0.0336 (12) | 0.0346 (13) | −0.0063 (10) | 0.0069 (10) | −0.0033 (9) |
C11 | 0.0354 (12) | 0.0349 (12) | 0.0363 (13) | −0.0043 (10) | 0.0011 (10) | 0.0038 (10) |
C12 | 0.0321 (12) | 0.0303 (11) | 0.0413 (13) | −0.0012 (9) | 0.0081 (10) | −0.0009 (9) |
N1 | 0.0623 (15) | 0.0477 (13) | 0.0567 (15) | 0.0216 (12) | 0.0210 (12) | 0.0058 (11) |
N2 | 0.0523 (14) | 0.0538 (14) | 0.0629 (16) | 0.0191 (11) | −0.0006 (12) | −0.0046 (12) |
N3 | 0.077 (2) | 0.0415 (14) | 0.105 (2) | 0.0169 (13) | 0.0438 (18) | 0.0148 (15) |
N4 | 0.0409 (11) | 0.0384 (11) | 0.0444 (13) | 0.0028 (9) | 0.0040 (9) | 0.0026 (9) |
N5 | 0.0614 (14) | 0.0457 (12) | 0.0366 (12) | −0.0035 (11) | 0.0087 (11) | −0.0022 (10) |
N6 | 0.0341 (10) | 0.0359 (10) | 0.0500 (13) | 0.0014 (8) | 0.0067 (9) | −0.0026 (9) |
O1 | 0.0673 (15) | 0.0633 (15) | 0.140 (2) | 0.0261 (12) | 0.0334 (16) | 0.0306 (15) |
O2 | 0.149 (3) | 0.0583 (15) | 0.135 (3) | 0.0392 (16) | 0.052 (2) | −0.0139 (16) |
O3 | 0.0600 (12) | 0.0658 (12) | 0.0397 (10) | 0.0221 (10) | −0.0030 (9) | −0.0134 (9) |
O4 | 0.128 (2) | 0.0933 (18) | 0.0613 (15) | 0.0675 (16) | −0.0387 (14) | −0.0269 (13) |
O5 | 0.0998 (19) | 0.121 (2) | 0.0703 (16) | 0.0799 (17) | 0.0031 (13) | −0.0105 (15) |
O6 | 0.0896 (16) | 0.0642 (13) | 0.0453 (11) | 0.0148 (11) | 0.0250 (11) | −0.0069 (9) |
O7 | 0.0718 (14) | 0.0810 (15) | 0.0410 (11) | 0.0095 (11) | −0.0104 (10) | −0.0080 (10) |
O8 | 0.0686 (13) | 0.0686 (13) | 0.0667 (14) | 0.0360 (11) | 0.0026 (11) | 0.0090 (11) |
O9 | 0.0672 (13) | 0.0888 (16) | 0.0532 (13) | 0.0298 (12) | 0.0125 (10) | −0.0155 (11) |
O10 | 0.0654 (13) | 0.0531 (11) | 0.0411 (11) | 0.0203 (10) | 0.0008 (9) | −0.0079 (9) |
C1—N2 | 1.384 (3) | C10—N5 | 1.437 (3) |
C1—C2 | 1.385 (4) | C11—C12 | 1.371 (3) |
C1—C6 | 1.391 (4) | C11—H11 | 0.9300 |
C2—C3 | 1.380 (4) | C12—N6 | 1.454 (3) |
C2—H2 | 0.9300 | N1—N2 | 1.403 (3) |
C3—C4 | 1.370 (4) | N1—H1A | 0.866 (10) |
C3—H3 | 0.9300 | N1—H1B | 0.873 (10) |
C4—C5 | 1.371 (4) | N1—H1C | 0.874 (10) |
C4—N3 | 1.462 (3) | N2—H2A | 0.857 (10) |
C5—C6 | 1.367 (4) | N3—O1 | 1.222 (4) |
C5—H5 | 0.9300 | N3—O2 | 1.227 (4) |
C6—H6 | 0.9300 | N4—O4 | 1.190 (3) |
C7—O3 | 1.245 (3) | N4—O5 | 1.193 (3) |
C7—C12 | 1.452 (3) | N5—O7 | 1.221 (3) |
C7—C8 | 1.459 (3) | N5—O6 | 1.231 (3) |
C8—C9 | 1.362 (3) | N6—O8 | 1.212 (3) |
C8—N4 | 1.448 (3) | N6—O9 | 1.213 (3) |
C9—C10 | 1.376 (3) | O10—H10B | 0.825 (10) |
C9—H9 | 0.9300 | O10—H10A | 0.820 (10) |
C10—C11 | 1.378 (3) | ||
N2—C1—C2 | 122.3 (2) | C12—C11—H11 | 120.4 |
N2—C1—C6 | 117.6 (2) | C10—C11—H11 | 120.4 |
C2—C1—C6 | 120.0 (2) | C11—C12—C7 | 124.0 (2) |
C3—C2—C1 | 119.7 (3) | C11—C12—N6 | 115.8 (2) |
C3—C2—H2 | 120.1 | C7—C12—N6 | 120.2 (2) |
C1—C2—H2 | 120.1 | N2—N1—H1A | 111 (2) |
C4—C3—C2 | 119.1 (3) | N2—N1—H1B | 102 (2) |
C4—C3—H3 | 120.4 | H1A—N1—H1B | 112.3 (15) |
C2—C3—H3 | 120.4 | N2—N1—H1C | 108 (2) |
C3—C4—C5 | 121.9 (2) | H1A—N1—H1C | 112.3 (15) |
C3—C4—N3 | 119.1 (3) | H1B—N1—H1C | 110.8 (15) |
C5—C4—N3 | 119.0 (3) | C1—N2—N1 | 119.9 (2) |
C6—C5—C4 | 119.3 (3) | C1—N2—H2A | 116 (2) |
C6—C5—H5 | 120.3 | N1—N2—H2A | 111 (2) |
C4—C5—H5 | 120.3 | O1—N3—O2 | 123.9 (3) |
C5—C6—C1 | 119.9 (3) | O1—N3—C4 | 118.6 (3) |
C5—C6—H6 | 120.0 | O2—N3—C4 | 117.5 (3) |
C1—C6—H6 | 120.0 | O4—N4—O5 | 120.0 (2) |
O3—C7—C12 | 124.0 (2) | O4—N4—C8 | 119.8 (2) |
O3—C7—C8 | 124.4 (2) | O5—N4—C8 | 120.2 (2) |
C12—C7—C8 | 111.6 (2) | O7—N5—O6 | 122.6 (2) |
C9—C8—N4 | 115.8 (2) | O7—N5—C10 | 119.2 (2) |
C9—C8—C7 | 124.1 (2) | O6—N5—C10 | 118.2 (2) |
N4—C8—C7 | 120.2 (2) | O8—N6—O9 | 121.8 (2) |
C8—C9—C10 | 119.5 (2) | O8—N6—C12 | 118.6 (2) |
C8—C9—H9 | 120.3 | O9—N6—C12 | 119.6 (2) |
C10—C9—H9 | 120.3 | C7—O3—H10A | 134.2 (9) |
C9—C10—C11 | 121.5 (2) | H1B—O10—H10B | 108 (3) |
C9—C10—N5 | 119.5 (2) | H1B—O10—H10A | 114 (2) |
C11—C10—N5 | 119.0 (2) | H10B—O10—H10A | 110.2 (17) |
C12—C11—C10 | 119.2 (2) | ||
N2—C1—C2—C3 | −177.3 (3) | C8—C7—C12—C11 | 3.9 (3) |
C6—C1—C2—C3 | −0.4 (4) | O3—C7—C12—N6 | 4.4 (4) |
C1—C2—C3—C4 | 0.1 (4) | C8—C7—C12—N6 | −177.02 (19) |
C2—C3—C4—C5 | 0.5 (4) | C2—C1—N2—N1 | −24.1 (4) |
C2—C3—C4—N3 | −178.4 (2) | C6—C1—N2—N1 | 159.0 (3) |
C3—C4—C5—C6 | −0.7 (4) | C3—C4—N3—O1 | 3.9 (4) |
N3—C4—C5—C6 | 178.3 (3) | C5—C4—N3—O1 | −175.0 (3) |
C4—C5—C6—C1 | 0.3 (4) | C3—C4—N3—O2 | −177.1 (3) |
N2—C1—C6—C5 | 177.3 (3) | C5—C4—N3—O2 | 3.9 (4) |
C2—C1—C6—C5 | 0.3 (4) | C9—C8—N4—O4 | −178.5 (3) |
O3—C7—C8—C9 | 174.6 (2) | C7—C8—N4—O4 | 0.1 (4) |
C12—C7—C8—C9 | −3.9 (3) | C9—C8—N4—O5 | 1.5 (4) |
O3—C7—C8—N4 | −3.9 (4) | C7—C8—N4—O5 | −179.9 (3) |
C12—C7—C8—N4 | 177.60 (19) | C9—C10—N5—O7 | −175.1 (2) |
N4—C8—C9—C10 | −179.9 (2) | C11—C10—N5—O7 | 6.1 (3) |
C7—C8—C9—C10 | 1.5 (3) | C9—C10—N5—O6 | 6.8 (3) |
C8—C9—C10—C11 | 1.3 (3) | C11—C10—N5—O6 | −172.1 (2) |
C8—C9—C10—N5 | −177.5 (2) | C11—C12—N6—O8 | 11.2 (3) |
C9—C10—C11—C12 | −1.3 (3) | C7—C12—N6—O8 | −167.9 (2) |
N5—C10—C11—C12 | 177.5 (2) | C11—C12—N6—O9 | −167.3 (2) |
C10—C11—C12—C7 | −1.6 (3) | C7—C12—N6—O9 | 13.6 (3) |
C10—C11—C12—N6 | 179.32 (19) | C12—C7—O3—H10A | 155.2 (11) |
O3—C7—C12—C11 | −174.6 (2) | C8—C7—O3—H10A | −23.2 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O10i | 0.87 (1) | 2.05 (1) | 2.916 (3) | 177 (2) |
N1—H1B···O10 | 0.87 (1) | 1.94 (1) | 2.809 (3) | 172 (2) |
N1—H1B···O9ii | 0.87 (1) | 2.56 (3) | 2.908 (3) | 105 (2) |
N1—H1C···O6iii | 0.87 (1) | 2.08 (1) | 2.947 (3) | 170 (2) |
N2—H2A···O4 | 0.86 (1) | 2.13 (2) | 2.868 (3) | 144 (3) |
O10—H10A···O3 | 0.82 (1) | 2.09 (2) | 2.832 (3) | 150 (3) |
O10—H10A···O4 | 0.82 (1) | 2.24 (2) | 2.743 (3) | 120 (2) |
O10—H10B···O3ii | 0.83 (1) | 2.05 (1) | 2.869 (3) | 171 (3) |
O10—H10B···O9ii | 0.83 (1) | 2.43 (3) | 2.898 (3) | 117 (3) |
C11—H11···O8iv | 0.93 | 2.51 | 3.433 (3) | 172 |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z+1; (iii) x−1, y, z−1; (iv) −x+3, −y+1, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O10i | 0.866 (10) | 2.051 (10) | 2.916 (3) | 177 (2) |
N1—H1B···O10 | 0.873 (10) | 1.942 (10) | 2.809 (3) | 172 (2) |
N1—H1B···O9ii | 0.873 (10) | 2.56 (3) | 2.908 (3) | 105 (2) |
N1—H1C···O6iii | 0.874 (10) | 2.081 (11) | 2.947 (3) | 170 (2) |
N2—H2A···O4 | 0.857 (10) | 2.13 (2) | 2.868 (3) | 144 (3) |
O10—H10A···O3 | 0.820 (10) | 2.09 (2) | 2.832 (3) | 150 (3) |
O10—H10A···O4 | 0.820 (10) | 2.24 (2) | 2.743 (3) | 120 (2) |
O10—H10B···O3ii | 0.825 (10) | 2.050 (12) | 2.869 (3) | 171 (3) |
O10—H10B···O9ii | 0.825 (10) | 2.43 (3) | 2.898 (3) | 117 (3) |
C11—H11···O8iv | 0.93 | 2.51 | 3.433 (3) | 172 |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z+1; (iii) x−1, y, z−1; (iv) −x+3, −y+1, −z+2. |
Acknowledgements
This work received financial support mainly from the National Key Fundamental Project (No. 20603030).
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Cocrystal strategy has been often used due to its application in the fields of drug chemistry, physical material chemistry and biological crystallography. Picric acid, as a strong organic acid, is very frequently adopted to facilitate the crystallization of some difficult-crystallized organic bases (Herbstein & Kaftory, 1976; Dubost et al., 1981; Harrison et al., 2007; Peng et al., 2011; Zeng et al., 2011; Dey et al., 2011). In this report, we report the 1:1 cocrystallized complex of 4-nitrophenylhydrazine and picric acid in 95% methanol solution.
In the title compound (I), the asymmetric unit consists of a 4-nitrophenyldrazinium cation, a picrate anion and a solvent water molecule (Fig.1). During the preparation of (I) the picric acid proton has been transferred to the terminal hydrazine atom N1. In the picrate molecule, the phenolate (O3—C7) bond distance is 1.245 (3) Å shows an indication of delocalization between the precursor single C—O bond and the benzene ring with three electron-withdrawing nitro groups. As a result, the neighbouring C7—C8 and C7—C12 bond lengths of 1.459 (3) Å and 1.452 (3) Å are longer by ca 0.08 Å than the mean distance of the other four C—C bonds. The C8—C7—C12 angle is about 10° smaller than the mean value (121.4°) of the other five benzene inner angles. The three nitro groups N4/O4/O5, N5/O6/O7 and N6/O8/O9 are twisted by 1.6 (3)°, 7.8 (3)° and 12.1 (3)° from the picrate benzene ring plane, respectively.
In the crystal, N—H···O and O—H···O hydrogen bonds link the components of the structure into a two-dimensional network parallel to (010) (Fig. 2). In addition, there are pairs of weak inversion related C—H···O hydrogen bonds within the two-dimensional network.