1,1-Dimethyl­hydrazin-1-ium picrate

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).

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.055
• wR factor = 0.135
• Data-to-parameter ratio = 14.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N1
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          1
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          2
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         75

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 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

---

S1. Comment

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

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

S2. Experimental

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.

S3. Refinement

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 U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C_methyl). H atoms bonded to N atoms were refined independently with isotropic displacement parameters.

Computing details

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

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

1,1-Dimethylhydrazin-1-ium picrate

Crystal data

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) Å^3	0.37 × 0.25 × 0.15 mm
Z = 8

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.055	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.135	w = 1/[σ^2(Fo^2) + (0.0553P)^2 + 0.8977P] where P = (Fo^2 + 2Fc^2)/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+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0133 (15)

Special details

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 (Ų)

	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)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

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···O1^i	0.85 (3)	2.55 (3)	3.308 (3)	150 (2)
N4—H7D···O7^ii	0.90 (2)	1.84 (2)	2.694 (2)	157 (2)
N4—H7D···O6^ii	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.