1,1-Dimethyl­hydrazin-1-ium picrate

Mu, X.-G.; Wang, X.-J.; Liu, X.-X.; Cui, H.; Wang, H.

doi:10.1107/S1600536811038554

organic compounds

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Volume 67| Part 10| October 2011| Page o2749

https://doi.org/10.1107/S1600536811038554

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1,1-Dimethylhydrazin-1-ium picrate

Xiao-Gang Mu,^a ^* Xuan-Jun Wang,^a Xiang-Xuan Liu,^a Hu Cui ^a and Huanchun Wang ^a

^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

(Received 23 August 2011; accepted 20 September 2011; online 30 September 2011)

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).

Related literature

For related structures, see: Merkoulov et al. (2005 ); Yang et al. (2002 ).

Experimental

Crystal data

C₂H₉N₂⁺·C₆H₂N₃O₇⁻
M_r = 289.22
Monoclinic, C 2/c
a = 14.2038 (17) Å
b = 8.1932 (10) Å
c = 21.233 (3) Å
β = 98.298 (2)°
V = 2445.1 (5) Å³
Z = 8
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 296 K
0.37 × 0.25 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.951, T_max = 0.980
6952 measured reflections
2781 independent reflections
1878 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.135
S = 1.08
2781 reflections
195 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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) $[-x+2, y, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: 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

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811038554/lh5325sup1.cif

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

checkCIF report

Comment top

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).

Related literature top

For related structures, see: Merkoulov et al. (2005); Yang et al. (2002).

Experimental top

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.

Structure description top

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).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: 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.

Figures top

Fig. 1. The molecular structure of the title compound showing 50% probability displacement ellipsoids.

1,1-Dimethylhydrazin-1-ium picrate top

Crystal data top

C₂H₉N₂⁺·C₆H₂N₃O₇⁻	F(000) = 1200
M_r = 289.22	D_x = 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

Data collection top

Bruker APEXII CCD diffractometer	2781 independent reflections
Radiation source: fine-focus sealed tube	1878 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
φ and ω scans	θ_max = 27.6°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→18
T_min = 0.951, T_max = 0.980	k = −10→10
6952 measured reflections	l = −27→26

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)] = 0.055	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.135	w = 1/[σ²(F_o²) + (0.0553P)² + 0.8977P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.002
2781 reflections	Δρ_max = 0.36 e Å⁻³
195 parameters	Δρ_min = −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)

Crystal data top

C₂H₉N₂⁺·C₆H₂N₃O₇⁻	V = 2445.1 (5) Å³
M_r = 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)°

Data collection top

Bruker APEXII CCD diffractometer	2781 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1878 reflections with I > 2σ(I)
T_min = 0.951, T_max = 0.980	R_int = 0.035
6952 measured reflections

Refinement top

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	Δρ_max = 0.36 e Å⁻³
2781 reflections	Δρ_min = −0.39 e Å⁻³
195 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	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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⁻
M_r	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)
T_min, T_max	0.951, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	6952, 2781, 1878
R_int	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
Δρ_max, Δρ_min (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.

Hydrogen-bond geometry (Å, º) top

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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