1-Methyl­hydrazinium picrate

Mu, X.-G.; Wang, X.-J.; Zhang, Y.; Gou, X.; Li, X.

doi:10.1107/S1600536811048677

organic compounds

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Volume 67| Part 12| December 2011| Page o3378

https://doi.org/10.1107/S1600536811048677

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1-Methylhydrazinium picrate

Xiao-Gang Mu,^a ^* Xuan-Jun Wang,^a Youzhi Zhang,^a Xiaoli Gou ^a and Xia Li ^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 7 November 2011; accepted 16 November 2011; online 19 November 2011)

In the title salt, CH₇N₂⁺·C₆H₂N₃O₇⁻, the dihedral angles between the three nitro groups and the plane of the benzene ring are 22.4 (2), 35.3 (2) and 2.8 (2)°. In the crystal, the components are linked by N—H⋯O and N—H⋯N hydrogen bonds into a two-dimensional network parallel to (10 $[\overline{1}]$ ).

Related literature

For related structures, see: Yang et al. (2002 ); Mu et al. (2011 ).

Experimental

Crystal data

CH₇N₂⁺·C₆H₂N₃O₇⁻
M_r = 275.19
Monoclinic, P 2₁ /n
a = 11.766 (3) Å
b = 6.785 (2) Å
c = 14.420 (4) Å
β = 110.526 (4)°
V = 1078.0 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.15 mm⁻¹
T = 296 K
0.33 × 0.25 × 0.14 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.952, T_max = 0.979
5196 measured reflections
1907 independent reflections
1562 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.103
S = 1.08
1907 reflections
173 parameters
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯O3ⁱ	0.88	2.03	2.7807 (19)	142
N4—H4A⋯O2ⁱ	0.88	2.25	2.963 (2)	138
N4—H4B⋯N5ⁱⁱ	0.85	2.13	2.954 (2)	161
N5—H5A⋯O3ⁱⁱⁱ	0.87	2.36	3.156 (2)	151
N5—H5B⋯O4^iv	0.90	2.59	3.377 (2)	146
Symmetry codes: (i) -x+1, -y, -z+1; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) x, y, z+1.

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/S1600536811048677/lh5375sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811048677/lh5375Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811048677/lh5375Isup3.cml

checkCIF report

Comment top

The molecular structure of the title compound is shown in Fig. 1. The dihedral angles between the three nitro groups and the plane of the benzene ring are 22.4 (2), 35.3 (2) and 2.8 (2)° for the groups containing N1, N2 and N3. In the crystal, the components are linked by N—H···O hydrogen bonds into a two-dimensional network paralell to (101).

Related literature top

For related structures, see: Yang et al. (2002); Mu et al. (2011).

Experimental top

1-methylhydrazine (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 0.6 h to afford the title compound. Single crystals suitable for X-ray structural analysis was obtained by slowly evaporating from distilled water at room temperature.

Structure description top

For related structures, see: Yang et al. (2002); Mu et al. (2011).

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 30% probability displacement ellipsoids.

1-Methylhydrazinium 2,4,6-trinitrophenolate top

Crystal data top

CH₇N₂⁺·C₆H₂N₃O₇⁻	F(000) = 568
M_r = 275.19	D_x = 1.696 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1614 reflections
a = 11.766 (3) Å	θ = 2.8–26.1°
b = 6.785 (2) Å	µ = 0.15 mm⁻¹
c = 14.420 (4) Å	T = 296 K
β = 110.526 (4)°	Block, yellow
V = 1078.0 (5) Å³	0.33 × 0.25 × 0.14 mm
Z = 4

Data collection top

Bruker APEXII diffractometer	1907 independent reflections
Radiation source: fine-focus sealed tube	1562 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
φ and ω scans	θ_max = 25.1°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→14
T_min = 0.952, T_max = 0.979	k = −8→7
5196 measured reflections	l = −17→12

Refinement top

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0537P)² + 0.153P] where P = (F_o² + 2F_c²)/3
1907 reflections	(Δ/σ)_max < 0.001
173 parameters	Δρ_max = 0.15 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

CH₇N₂⁺·C₆H₂N₃O₇⁻	V = 1078.0 (5) Å³
M_r = 275.19	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.766 (3) Å	µ = 0.15 mm⁻¹
b = 6.785 (2) Å	T = 296 K
c = 14.420 (4) Å	0.33 × 0.25 × 0.14 mm
β = 110.526 (4)°

Data collection top

Bruker APEXII diffractometer	1907 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1562 reflections with I > 2σ(I)
T_min = 0.952, T_max = 0.979	R_int = 0.023
5196 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.103	H-atom parameters constrained
S = 1.08	Δρ_max = 0.15 e Å⁻³
1907 reflections	Δρ_min = −0.26 e Å⁻³
173 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
N1	0.52167 (12)	0.1473 (2)	0.41558 (10)	0.0358 (4)
N2	0.31795 (13)	0.0736 (2)	0.04968 (10)	0.0359 (4)
N3	0.08521 (12)	0.1090 (2)	0.26709 (11)	0.0353 (4)
N4	0.26648 (12)	0.1526 (2)	0.69636 (10)	0.0335 (4)
H4A	0.3278	0.0814	0.6943	0.040*
H4B	0.2808	0.2764	0.7014	0.040*
N5	0.24219 (13)	0.0849 (2)	0.78250 (11)	0.0361 (4)
H5A	0.1824	0.1576	0.7857	0.043*
H5B	0.3089	0.1102	0.8361	0.043*
O1	0.50471 (11)	0.2240 (2)	0.48615 (9)	0.0523 (4)
O2	0.62224 (11)	0.0934 (3)	0.41872 (10)	0.0575 (4)
O3	0.53492 (10)	0.09419 (19)	0.22096 (8)	0.0365 (3)
O4	0.39264 (12)	0.1642 (3)	0.02613 (10)	0.0612 (5)
O5	0.23853 (12)	−0.0268 (2)	−0.00860 (9)	0.0536 (4)
O6	−0.00559 (11)	0.0933 (2)	0.19306 (11)	0.0578 (4)
O7	0.08063 (12)	0.1317 (2)	0.34954 (11)	0.0568 (4)
C1	0.41718 (13)	0.1197 (2)	0.32599 (11)	0.0268 (4)
C2	0.43426 (14)	0.1013 (2)	0.23195 (12)	0.0266 (4)
C3	0.31911 (14)	0.0895 (2)	0.15092 (11)	0.0275 (4)
C4	0.20832 (14)	0.0859 (2)	0.16195 (12)	0.0281 (4)
H4	0.1377	0.0719	0.1070	0.034*
C5	0.20249 (14)	0.1034 (2)	0.25554 (12)	0.0274 (4)
C6	0.30624 (14)	0.1220 (2)	0.33767 (12)	0.0285 (4)
H6	0.3013	0.1359	0.4003	0.034*
C8	0.16207 (17)	0.1100 (3)	0.60533 (14)	0.0435 (5)
H8A	0.1426	−0.0278	0.6032	0.065*
H8B	0.1825	0.1437	0.5484	0.065*
H8C	0.0933	0.1862	0.6052	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0281 (8)	0.0469 (10)	0.0311 (8)	−0.0041 (6)	0.0089 (6)	−0.0046 (7)
N2	0.0319 (8)	0.0462 (9)	0.0298 (8)	0.0034 (7)	0.0111 (7)	0.0037 (7)
N3	0.0277 (8)	0.0379 (9)	0.0427 (9)	−0.0019 (6)	0.0155 (7)	0.0004 (6)
N4	0.0337 (8)	0.0286 (8)	0.0433 (9)	0.0012 (6)	0.0200 (7)	0.0013 (6)
N5	0.0365 (8)	0.0383 (9)	0.0383 (8)	0.0033 (6)	0.0192 (7)	0.0011 (6)
O1	0.0407 (7)	0.0773 (11)	0.0365 (7)	−0.0070 (7)	0.0104 (6)	−0.0241 (7)
O2	0.0246 (7)	0.1020 (13)	0.0408 (8)	0.0096 (7)	0.0051 (6)	−0.0088 (8)
O3	0.0244 (6)	0.0512 (8)	0.0367 (7)	0.0023 (5)	0.0142 (5)	0.0039 (5)
O4	0.0478 (8)	0.1007 (13)	0.0388 (8)	−0.0176 (8)	0.0196 (7)	0.0114 (8)
O5	0.0514 (8)	0.0733 (11)	0.0330 (7)	−0.0126 (8)	0.0111 (6)	−0.0139 (7)
O6	0.0231 (7)	0.0945 (12)	0.0524 (9)	−0.0012 (7)	0.0092 (6)	−0.0003 (8)
O7	0.0425 (8)	0.0867 (12)	0.0515 (9)	−0.0072 (7)	0.0294 (7)	−0.0082 (8)
C1	0.0229 (8)	0.0294 (9)	0.0260 (8)	−0.0015 (6)	0.0057 (6)	−0.0015 (6)
C2	0.0249 (8)	0.0224 (9)	0.0329 (9)	0.0000 (6)	0.0105 (7)	0.0015 (6)
C3	0.0301 (9)	0.0281 (9)	0.0243 (8)	0.0009 (7)	0.0094 (7)	0.0028 (6)
C4	0.0235 (8)	0.0279 (9)	0.0294 (8)	0.0006 (6)	0.0050 (7)	0.0028 (7)
C5	0.0228 (8)	0.0253 (9)	0.0361 (9)	0.0008 (6)	0.0127 (7)	0.0018 (7)
C6	0.0304 (9)	0.0277 (9)	0.0291 (8)	−0.0002 (7)	0.0126 (7)	−0.0013 (7)
C8	0.0428 (11)	0.0478 (12)	0.0381 (10)	0.0078 (9)	0.0118 (9)	−0.0004 (8)

Geometric parameters (Å, º) top

N1—O1	1.2200 (18)	N5—H5B	0.9046
N1—O2	1.2240 (18)	O3—C2	1.2498 (19)
N1—C1	1.450 (2)	C1—C6	1.374 (2)
N2—O4	1.2143 (19)	C1—C2	1.444 (2)
N2—O5	1.2216 (19)	C2—C3	1.448 (2)
N2—C3	1.459 (2)	C3—C4	1.368 (2)
N3—O7	1.2186 (19)	C4—C5	1.380 (2)
N3—O6	1.2217 (19)	C4—H4	0.9300
N3—C5	1.447 (2)	C5—C6	1.376 (2)
N4—N5	1.4439 (19)	C6—H6	0.9300
N4—C8	1.478 (2)	C8—H8A	0.9600
N4—H4A	0.8777	C8—H8B	0.9600
N4—H4B	0.8546	C8—H8C	0.9600
N5—H5A	0.8732

O1—N1—O2	122.36 (14)	O3—C2—C1	124.91 (14)
O1—N1—C1	117.56 (14)	O3—C2—C3	123.77 (15)
O2—N1—C1	120.08 (14)	C1—C2—C3	111.31 (13)
O4—N2—O5	122.94 (15)	C4—C3—C2	124.57 (15)
O4—N2—C3	119.25 (15)	C4—C3—N2	116.12 (14)
O5—N2—C3	117.77 (14)	C2—C3—N2	119.28 (14)
O7—N3—O6	122.63 (15)	C3—C4—C5	119.24 (15)
O7—N3—C5	119.05 (14)	C3—C4—H4	120.4
O6—N3—C5	118.31 (15)	C5—C4—H4	120.4
N5—N4—C8	110.36 (14)	C6—C5—C4	121.05 (14)
N5—N4—H4A	105.5	C6—C5—N3	119.50 (15)
C8—N4—H4A	107.4	C4—C5—N3	119.41 (14)
N5—N4—H4B	109.4	C1—C6—C5	119.20 (15)
C8—N4—H4B	110.2	C1—C6—H6	120.4
H4A—N4—H4B	113.8	C5—C6—H6	120.4
N4—N5—H5A	105.7	N4—C8—H8A	109.5
N4—N5—H5B	107.5	N4—C8—H8B	109.5
H5A—N5—H5B	108.8	H8A—C8—H8B	109.5
C6—C1—C2	124.55 (14)	N4—C8—H8C	109.5
C6—C1—N1	115.77 (14)	H8A—C8—H8C	109.5
C2—C1—N1	119.61 (14)	H8B—C8—H8C	109.5

O1—N1—C1—C6	−20.3 (2)	O4—N2—C3—C2	−37.3 (2)
O2—N1—C1—C6	159.30 (16)	O5—N2—C3—C2	144.91 (16)
O1—N1—C1—C2	156.85 (16)	C2—C3—C4—C5	3.1 (3)
O2—N1—C1—C2	−23.5 (2)	N2—C3—C4—C5	−178.99 (14)
C6—C1—C2—O3	−178.15 (16)	C3—C4—C5—C6	−0.8 (2)
N1—C1—C2—O3	4.9 (2)	C3—C4—C5—N3	177.12 (15)
C6—C1—C2—C3	1.2 (2)	O7—N3—C5—C6	0.6 (2)
N1—C1—C2—C3	−175.74 (14)	O6—N3—C5—C6	179.60 (15)
O3—C2—C3—C4	176.18 (16)	O7—N3—C5—C4	−177.37 (15)
C1—C2—C3—C4	−3.1 (2)	O6—N3—C5—C4	1.7 (2)
O3—C2—C3—N2	−1.7 (2)	C2—C1—C6—C5	0.8 (2)
C1—C2—C3—N2	178.99 (14)	N1—C1—C6—C5	177.81 (14)
O4—N2—C3—C4	144.66 (17)	C4—C5—C6—C1	−1.1 (2)
O5—N2—C3—C4	−33.1 (2)	N3—C5—C6—C1	−178.97 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O3ⁱ	0.88	2.03	2.7807 (19)	142
N4—H4A···O2ⁱ	0.88	2.25	2.963 (2)	138
N4—H4B···N5ⁱⁱ	0.85	2.13	2.954 (2)	161
N5—H5A···O3ⁱⁱⁱ	0.87	2.36	3.156 (2)	151
N5—H5B···O4^iv	0.90	2.59	3.377 (2)	146

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1/2, y+1/2, −z+3/2; (iii) x−1/2, −y+1/2, z+1/2; (iv) x, y, z+1.

Experimental details

Crystal data
Chemical formula	CH₇N₂⁺·C₆H₂N₃O₇⁻
M_r	275.19
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	11.766 (3), 6.785 (2), 14.420 (4)
β (°)	110.526 (4)
V (Å³)	1078.0 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.15
Crystal size (mm)	0.33 × 0.25 × 0.14

Data collection
Diffractometer	Bruker APEXII
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.952, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	5196, 1907, 1562
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.103, 1.08
No. of reflections	1907
No. of parameters	173
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.26

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
N4—H4A···O3ⁱ	0.88	2.03	2.7807 (19)	142.3
N4—H4A···O2ⁱ	0.88	2.25	2.963 (2)	137.8
N4—H4B···N5ⁱⁱ	0.85	2.13	2.954 (2)	160.8
N5—H5A···O3ⁱⁱⁱ	0.87	2.36	3.156 (2)	151.1
N5—H5B···O4^iv	0.90	2.59	3.377 (2)	145.6

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1/2, y+1/2, −z+3/2; (iii) x−1/2, −y+1/2, z+1/2; (iv) x, y, z+1.

References

Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Mu, X.-G., Wang, X.-J., Liu, X.-X., Cui, H. & Wang, H. (2011). Acta Cryst. E67, o2749. 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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