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organic compounds
1,1-Dimethylhydrazin-1-ium picrate
aNo. 503 Faculty, Xi'an Research Institute of High Technology, Hongqing Town, Xi'an 710025, People's Republic of China
*Correspondence e-mail: zhouliyou111@163.com
In the title compound, C2H9N2+·C6H2N3O7−, the dihedral angles between the mean planes of the three nitro groups and the benzene ring are 63.5 (3), 10.5 (2) and 10.4 (2)°. In the crystal, molecules are linked by N—H⋯O hydrogen bonds into a two-dimensional network parallel to (001).
Experimental
Crystal data
|
Refinement
|
|
Data collection: APEX2 (Bruker, 2007); cell SAINT (Bruker, 2007
); data reduction: SAINT; 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
https://doi.org/10.1107/S1600536811038554/lh5325sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811038554/lh5325Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536811038554/lh5325Isup3.cml
1,1-dimethylhydrazine (0.02 mol) was added to a solution of picric acid (0.02 mol) in 30 ml ethanol at room temperature, the mixture was stirred for 0.5 h to afford the title compound. Single crystals suitable for X-ray structure analysis were obtained by slowly evaporating a distilled water solution of the title compound at room temperature.
H atoms bonded to C atoms were fixed geometrically and allowed to ride on their attached atoms, with C—H distances = 0.93–0.96 Å and with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(Cmethyl). H atoms bonded to N atoms were refined independently with isotropic displacement parameters.
The molecular structure of the title compound is shown in Fig. 1. Examples of related structures have already been published (Merkoulov et al., 2005; Yang et al., 2002).
For related structures, see: Merkoulov et al. (2005); Yang et al. (2002).
Data collection: APEX2 (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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. The molecular structure of the title compound showing 50% probability displacement ellipsoids. |
C2H9N2+·C6H2N3O7− | F(000) = 1200 |
Mr = 289.22 | Dx = 1.571 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 1401 reflections |
a = 14.2038 (17) Å | θ = 2.9–24.3° |
b = 8.1932 (10) Å | µ = 0.14 mm−1 |
c = 21.233 (3) Å | T = 296 K |
β = 98.298 (2)° | Block, yellow |
V = 2445.1 (5) Å3 | 0.37 × 0.25 × 0.15 mm |
Z = 8 |
Bruker APEXII CCD diffractometer | 2781 independent reflections |
Radiation source: fine-focus sealed tube | 1878 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
φ and ω scans | θmax = 27.6°, θmin = 2.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→18 |
Tmin = 0.951, Tmax = 0.980 | k = −10→10 |
6952 measured reflections | l = −27→26 |
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)] = 0.055 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.135 | w = 1/[σ2(Fo2) + (0.0553P)2 + 0.8977P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.002 |
2781 reflections | Δρmax = 0.36 e Å−3 |
195 parameters | Δρmin = −0.39 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0133 (15) |
C2H9N2+·C6H2N3O7− | V = 2445.1 (5) Å3 |
Mr = 289.22 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 14.2038 (17) Å | µ = 0.14 mm−1 |
b = 8.1932 (10) Å | T = 296 K |
c = 21.233 (3) Å | 0.37 × 0.25 × 0.15 mm |
β = 98.298 (2)° |
Bruker APEXII CCD diffractometer | 2781 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1878 reflections with I > 2σ(I) |
Tmin = 0.951, Tmax = 0.980 | Rint = 0.035 |
6952 measured reflections |
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.135 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.36 e Å−3 |
2781 reflections | Δρmin = −0.39 e Å−3 |
195 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 | ||
O1 | 1.04883 (15) | 0.9752 (3) | 0.34381 (11) | 0.0893 (7) | |
O2 | 1.00739 (14) | 0.7278 (2) | 0.33165 (10) | 0.0805 (6) | |
O3 | 1.00992 (13) | 0.6369 (2) | 0.57533 (9) | 0.0771 (6) | |
O4 | 0.87633 (13) | 0.7067 (2) | 0.60489 (8) | 0.0606 (5) | |
O5 | 0.67812 (11) | 1.0875 (2) | 0.48554 (8) | 0.0562 (4) | |
O6 | 0.71397 (12) | 1.2026 (2) | 0.40207 (9) | 0.0680 (5) | |
O7 | 0.84917 (10) | 1.06520 (17) | 0.34354 (6) | 0.0462 (4) | |
N1 | 1.00342 (12) | 0.8594 (2) | 0.35666 (9) | 0.0451 (5) | |
N2 | 0.93391 (14) | 0.7096 (2) | 0.56715 (9) | 0.0483 (5) | |
N3 | 0.72977 (12) | 1.1019 (2) | 0.44486 (9) | 0.0408 (4) | |
C1 | 0.94420 (13) | 0.8768 (2) | 0.40738 (9) | 0.0344 (4) | |
C2 | 0.96717 (13) | 0.7855 (2) | 0.46090 (9) | 0.0371 (5) | |
H2 | 1.0187 | 0.7143 | 0.4652 | 0.044* | |
C3 | 0.91097 (13) | 0.8022 (2) | 0.50884 (9) | 0.0361 (5) | |
C4 | 0.83413 (13) | 0.9051 (2) | 0.50215 (10) | 0.0365 (4) | |
H4 | 0.7965 | 0.9127 | 0.5344 | 0.044* | |
C5 | 0.81262 (13) | 0.9972 (2) | 0.44776 (9) | 0.0332 (4) | |
C6 | 0.86629 (13) | 0.9897 (2) | 0.39543 (9) | 0.0326 (4) | |
N4 | 0.69915 (12) | 0.8697 (2) | 0.19680 (8) | 0.0378 (4) | |
N5 | 0.78695 (15) | 0.8351 (3) | 0.23798 (11) | 0.0506 (5) | |
H5A | 0.7935 (19) | 0.919 (3) | 0.2626 (14) | 0.074 (9)* | |
H5B | 0.8288 (18) | 0.831 (3) | 0.2133 (13) | 0.064 (8)* | |
C7 | 0.62138 (17) | 0.8862 (3) | 0.23556 (13) | 0.0603 (7) | |
H7A | 0.6170 | 0.7882 | 0.2598 | 0.090* | |
H7B | 0.5624 | 0.9040 | 0.2081 | 0.090* | |
H7C | 0.6342 | 0.9771 | 0.2640 | 0.090* | |
C8 | 0.70463 (16) | 1.0116 (3) | 0.15431 (10) | 0.0478 (5) | |
H8A | 0.7128 | 1.1096 | 0.1793 | 0.072* | |
H8B | 0.6469 | 1.0189 | 0.1247 | 0.072* | |
H8C | 0.7577 | 0.9983 | 0.1314 | 0.072* | |
H7D | 0.6867 (16) | 0.779 (3) | 0.1733 (12) | 0.054 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0967 (15) | 0.0698 (13) | 0.1180 (18) | −0.0159 (11) | 0.0723 (13) | −0.0003 (12) |
O2 | 0.0916 (14) | 0.0776 (13) | 0.0813 (14) | −0.0073 (11) | 0.0424 (11) | −0.0351 (11) |
O3 | 0.0667 (12) | 0.0918 (14) | 0.0690 (13) | 0.0318 (11) | −0.0025 (9) | 0.0300 (11) |
O4 | 0.0776 (12) | 0.0632 (11) | 0.0426 (10) | −0.0001 (9) | 0.0139 (9) | 0.0113 (8) |
O5 | 0.0470 (9) | 0.0668 (11) | 0.0589 (10) | 0.0182 (8) | 0.0216 (8) | 0.0022 (8) |
O6 | 0.0584 (10) | 0.0697 (11) | 0.0795 (13) | 0.0305 (9) | 0.0219 (9) | 0.0322 (10) |
O7 | 0.0608 (9) | 0.0421 (8) | 0.0361 (8) | 0.0118 (7) | 0.0081 (7) | 0.0045 (6) |
N1 | 0.0369 (10) | 0.0530 (11) | 0.0471 (11) | 0.0065 (8) | 0.0113 (8) | −0.0010 (9) |
N2 | 0.0564 (12) | 0.0457 (10) | 0.0399 (11) | 0.0027 (9) | −0.0020 (9) | 0.0055 (8) |
N3 | 0.0350 (9) | 0.0401 (9) | 0.0479 (11) | 0.0073 (7) | 0.0073 (8) | 0.0004 (8) |
C1 | 0.0291 (9) | 0.0358 (10) | 0.0393 (11) | −0.0001 (8) | 0.0084 (8) | −0.0041 (8) |
C2 | 0.0303 (10) | 0.0358 (10) | 0.0437 (12) | 0.0031 (8) | 0.0004 (8) | −0.0007 (9) |
C3 | 0.0355 (10) | 0.0353 (10) | 0.0359 (11) | 0.0012 (8) | −0.0008 (8) | 0.0032 (8) |
C4 | 0.0341 (10) | 0.0401 (11) | 0.0355 (11) | −0.0017 (8) | 0.0063 (8) | −0.0033 (9) |
C5 | 0.0287 (9) | 0.0324 (10) | 0.0382 (11) | 0.0033 (7) | 0.0041 (8) | −0.0019 (8) |
C6 | 0.0348 (10) | 0.0297 (9) | 0.0326 (10) | −0.0012 (8) | 0.0018 (8) | −0.0027 (8) |
N4 | 0.0408 (10) | 0.0391 (9) | 0.0338 (10) | −0.0045 (7) | 0.0068 (7) | −0.0019 (8) |
N5 | 0.0497 (12) | 0.0603 (13) | 0.0397 (12) | −0.0013 (10) | −0.0004 (9) | 0.0047 (10) |
C7 | 0.0552 (14) | 0.0719 (16) | 0.0595 (16) | −0.0023 (12) | 0.0277 (12) | −0.0014 (13) |
C8 | 0.0555 (13) | 0.0428 (12) | 0.0443 (13) | −0.0024 (10) | 0.0052 (10) | 0.0033 (10) |
O1—N1 | 1.201 (2) | C4—C5 | 1.376 (3) |
O2—N1 | 1.207 (2) | C4—H4 | 0.9300 |
O3—N2 | 1.223 (2) | C5—C6 | 1.437 (3) |
O4—N2 | 1.225 (2) | N4—N5 | 1.444 (3) |
O5—N3 | 1.217 (2) | N4—C7 | 1.476 (3) |
O6—N3 | 1.224 (2) | N4—C8 | 1.480 (3) |
O7—C6 | 1.256 (2) | N4—H7D | 0.90 (2) |
N1—C1 | 1.466 (2) | N5—H5A | 0.86 (3) |
N2—C3 | 1.449 (3) | N5—H5B | 0.85 (3) |
N3—C5 | 1.450 (2) | C7—H7A | 0.9600 |
C1—C2 | 1.360 (3) | C7—H7B | 0.9600 |
C1—C6 | 1.437 (3) | C7—H7C | 0.9600 |
C2—C3 | 1.388 (3) | C8—H8A | 0.9600 |
C2—H2 | 0.9300 | C8—H8B | 0.9600 |
C3—C4 | 1.370 (3) | C8—H8C | 0.9600 |
O1—N1—O2 | 123.0 (2) | O7—C6—C5 | 126.88 (17) |
O1—N1—C1 | 118.33 (18) | O7—C6—C1 | 121.24 (17) |
O2—N1—C1 | 118.55 (18) | C5—C6—C1 | 111.84 (16) |
O3—N2—O4 | 123.84 (19) | N5—N4—C7 | 109.31 (19) |
O3—N2—C3 | 117.47 (19) | N5—N4—C8 | 113.98 (17) |
O4—N2—C3 | 118.69 (18) | C7—N4—C8 | 112.17 (18) |
O5—N3—O6 | 121.83 (17) | N5—N4—H7D | 104.9 (15) |
O5—N3—C5 | 118.77 (17) | C7—N4—H7D | 106.4 (15) |
O6—N3—C5 | 119.39 (17) | C8—N4—H7D | 109.6 (15) |
C2—C1—C6 | 125.98 (17) | N4—N5—H5A | 102.7 (19) |
C2—C1—N1 | 117.82 (17) | N4—N5—H5B | 104.7 (18) |
C6—C1—N1 | 116.20 (17) | H5A—N5—H5B | 112 (3) |
C1—C2—C3 | 117.66 (17) | N4—C7—H7A | 109.5 |
C1—C2—H2 | 121.2 | N4—C7—H7B | 109.5 |
C3—C2—H2 | 121.2 | H7A—C7—H7B | 109.5 |
C4—C3—C2 | 121.25 (18) | N4—C7—H7C | 109.5 |
C4—C3—N2 | 119.24 (18) | H7A—C7—H7C | 109.5 |
C2—C3—N2 | 119.52 (17) | H7B—C7—H7C | 109.5 |
C3—C4—C5 | 120.08 (18) | N4—C8—H8A | 109.5 |
C3—C4—H4 | 120.0 | N4—C8—H8B | 109.5 |
C5—C4—H4 | 120.0 | H8A—C8—H8B | 109.5 |
C4—C5—C6 | 123.18 (17) | N4—C8—H8C | 109.5 |
C4—C5—N3 | 116.11 (17) | H8A—C8—H8C | 109.5 |
C6—C5—N3 | 120.69 (17) | H8B—C8—H8C | 109.5 |
O1—N1—C1—C2 | −115.2 (2) | C3—C4—C5—C6 | 1.2 (3) |
O2—N1—C1—C2 | 61.8 (3) | C3—C4—C5—N3 | 179.71 (17) |
O1—N1—C1—C6 | 65.0 (3) | O5—N3—C5—C4 | −9.2 (3) |
O2—N1—C1—C6 | −118.1 (2) | O6—N3—C5—C4 | 170.30 (18) |
C6—C1—C2—C3 | −0.2 (3) | O5—N3—C5—C6 | 169.29 (18) |
N1—C1—C2—C3 | 179.97 (17) | O6—N3—C5—C6 | −11.2 (3) |
C1—C2—C3—C4 | 1.0 (3) | C4—C5—C6—O7 | 177.27 (18) |
C1—C2—C3—N2 | −178.88 (17) | N3—C5—C6—O7 | −1.1 (3) |
O3—N2—C3—C4 | −170.0 (2) | C4—C5—C6—C1 | −0.5 (3) |
O4—N2—C3—C4 | 10.8 (3) | N3—C5—C6—C1 | −178.87 (16) |
O3—N2—C3—C2 | 9.9 (3) | C2—C1—C6—O7 | −177.91 (18) |
O4—N2—C3—C2 | −169.33 (19) | N1—C1—C6—O7 | 1.9 (3) |
C2—C3—C4—C5 | −1.5 (3) | C2—C1—C6—C5 | 0.0 (3) |
N2—C3—C4—C5 | 178.38 (17) | N1—C1—C6—C5 | 179.75 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5A···O7 | 0.86 (3) | 2.15 (3) | 2.964 (3) | 158 (3) |
N5—H5B···O1i | 0.85 (3) | 2.55 (3) | 3.308 (3) | 150 (2) |
N4—H7D···O7ii | 0.90 (2) | 1.84 (2) | 2.694 (2) | 157 (2) |
N4—H7D···O6ii | 0.90 (2) | 2.36 (2) | 2.924 (2) | 120.3 (18) |
Symmetry codes: (i) −x+2, y, −z+1/2; (ii) −x+3/2, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C2H9N2+·C6H2N3O7− |
Mr | 289.22 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 296 |
a, b, c (Å) | 14.2038 (17), 8.1932 (10), 21.233 (3) |
β (°) | 98.298 (2) |
V (Å3) | 2445.1 (5) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.14 |
Crystal size (mm) | 0.37 × 0.25 × 0.15 |
Data collection | |
Diffractometer | Bruker APEXII CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.951, 0.980 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6952, 2781, 1878 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.653 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.135, 1.08 |
No. of reflections | 2781 |
No. of parameters | 195 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.36, −0.39 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008.
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5A···O7 | 0.86 (3) | 2.15 (3) | 2.964 (3) | 158 (3) |
N5—H5B···O1i | 0.85 (3) | 2.55 (3) | 3.308 (3) | 150 (2) |
N4—H7D···O7ii | 0.90 (2) | 1.84 (2) | 2.694 (2) | 157 (2) |
N4—H7D···O6ii | 0.90 (2) | 2.36 (2) | 2.924 (2) | 120.3 (18) |
Symmetry codes: (i) −x+2, y, −z+1/2; (ii) −x+3/2, y−1/2, −z+1/2. |
References
Bruker (2007). APEX2 and SAINT. Bruker AXS, Inc., Madison, Wisconsin, USA. Google Scholar
Merkoulov, A., Harms, K. & Sundermeyer, J. (2005). Acta Cryst. E61, o1800–o1801. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yang, L., Zhang, J.-G. & Zhang, T.-L. (2002). Chin. J. Explos. Propel. 3, 66–68. Google Scholar
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The molecular structure of the title compound is shown in Fig. 1. Examples of related structures have already been published (Merkoulov et al., 2005; Yang et al., 2002).