1-Methyl­hydrazinium picrate

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

doi:10.1107/S1600536811048677

1-Methylhydrazinium picrate

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

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 $\overline{1}$ ).

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536811048677/lh5375sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536811048677/lh5375Isup2.hkl Contains datablock I
	Chemical Markup Language (CML) file https://doi.org/10.1107/S1600536811048677/lh5375Isup3.cml Supplementary material

CCDC reference: 858458

checkCIF report

Key indicators

Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.002 Å
R factor = 0.037
wR factor = 0.103
Data-to-parameter ratio = 11.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.597          3

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT128_ALERT_4_G Alternate Setting of Space-group P21/c   .......      P21/n
PLAT432_ALERT_2_G Short Inter X...Y Contact  O2     ..  C8      ..       3.01 Ang.
PLAT432_ALERT_2_G Short Inter X...Y Contact  C4     ..  C6      ..       3.15 Ang.
PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still          65 Perc.

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   5 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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).