4-Nitro-phenyl-hydrazinium picrate monohydrate.

In the crystal structure of the title compound, C6H8N3O2 (+)·C6H2N3O7 (-)·H2O, N-H⋯O and O-H⋯O hydrogen bonds link the components into a two-dimensional network parallel to (010). In addition, there are pairs of weak inversion-related C-H⋯O hydrogen bonds within the two-dimensional network. The three nitro groups are twisted by 1.6 (3), 7.8 (3) and 12.1 (3)° from the ring plane in the anion, while in the cation, the nitro group makes a dihedral angle of 4.6 (2)° with the ring.

Related literature

For the use of picric acid acid as a co-crystallization agent, see: Herbstein & Kaftory (1976 ▶); Dubost et al. (1981 ▶); Harrison et al. (2007 ▶); Peng et al. (2011 ▶); Zeng et al. (2011 ▶); Dey et al. (2011 ▶).

Experimental

Crystal data

C6H8N3O2 +·C6n class="Species">H2N3O7 −·H2O

M = 400.28

Monoclinic,

a = 4.8483 (3) Å

b = 28.798 (2) Å

c = 11.6352 (8) Å

β = 101.360 (1)°

V = 1592.70 (18) Å3

Z = 4

Mo Kα radiation

μ = 0.15 mm−1

T = 299 K

0.20 × 0.08 × 0.04 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ▶) T min = 0.971, T max = 0.994

16632 measured reflections

3643 independent reflections

2487 reflections with I > 2σ(I)

R int = 0.045

Refinement

R[F 2 > 2σ(F 2)] = 0.063

wR(F 2) = 0.150

S = 1.05

3643 reflections

271 parameters

10 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.31 e Å−3

Δρmin = −0.31 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; 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 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813032479/lh5673sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813032479/lh5673Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536813032479/lh5673Isup3.cml

Additional supporting information: crystallographic information; 3D view; checkCIF report

C6H8N3O2+·C6H2N3O7−·H2O	F(000) = 824
Mr = 400.28	Dx = 1.669 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 924 reflections
a = 4.8483 (3) Å	θ = 2.3–21.5°
b = 28.798 (2) Å	µ = 0.15 mm−1
c = 11.6352 (8) Å	T = 299 K
β = 101.360 (1)°	Needle, yellow
V = 1592.70 (18) Å3	0.20 × 0.08 × 0.04 mm
Z = 4

Bruker SMART CCD area-detector diffractometer	3643 independent reflections
Radiation source: fine-focus sealed tube	2487 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
φ and ω scans	θmax = 27.5°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −6→6
Tmin = 0.971, Tmax = 0.994	k = −37→36
16632 measured reflections	l = −14→15

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.150	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0602P)2 + 0.5955P] where P = (Fo2 + 2Fc2)/3
3643 reflections	(Δ/σ)max = 0.001
271 parameters	Δρmax = 0.31 e Å−3
10 restraints	Δρmin = −0.31 e Å−3

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
C1	−0.3571 (5)	0.67096 (8)	0.4377 (2)	0.0427 (6)
C2	−0.5710 (5)	0.67706 (9)	0.3408 (2)	0.0473 (6)
H2	−0.5922	0.6562	0.2786	0.057*
C3	−0.7524 (6)	0.71420 (9)	0.3368 (3)	0.0523 (7)
H3	−0.8968	0.7186	0.2722	0.063*
C4	−0.7169 (6)	0.74447 (8)	0.4294 (3)	0.0505 (7)
C5	−0.5048 (7)	0.73915 (10)	0.5256 (3)	0.0603 (8)
H5	−0.4836	0.7603	0.5870	0.072*
C6	−0.3246 (6)	0.70235 (10)	0.5302 (3)	0.0555 (7)
H6	−0.1806	0.6983	0.5952	0.067*
C7	0.7836 (5)	0.56180 (8)	0.7388 (2)	0.0365 (5)
C8	0.6275 (5)	0.59770 (7)	0.7872 (2)	0.0344 (5)
C9	0.6776 (5)	0.61004 (7)	0.9025 (2)	0.0361 (5)
H9	0.5682	0.6327	0.9287	0.043*
C10	0.8913 (5)	0.58870 (8)	0.9798 (2)	0.0375 (5)
C11	1.0603 (5)	0.55567 (8)	0.9429 (2)	0.0363 (5)
H11	1.2063	0.5420	0.9960	0.044*
C12	1.0107 (5)	0.54316 (7)	0.8270 (2)	0.0345 (5)
N1	−0.2290 (5)	0.59509 (8)	0.3776 (2)	0.0543 (6)
H1A	−0.377 (3)	0.5818 (9)	0.394 (2)	0.065*
H1B	−0.078 (3)	0.5783 (8)	0.399 (2)	0.065*
H1C	−0.250 (4)	0.6027 (10)	0.3037 (11)	0.065*
N2	−0.1620 (5)	0.63550 (8)	0.4446 (2)	0.0579 (6)
H2A	−0.069 (6)	0.6290 (11)	0.5132 (14)	0.070*
N3	−0.9135 (7)	0.78313 (9)	0.4265 (3)	0.0711 (8)
N4	0.3991 (4)	0.62195 (7)	0.71219 (19)	0.0419 (5)
N5	0.9370 (5)	0.60035 (8)	1.10213 (19)	0.0481 (5)
N6	1.2004 (4)	0.50850 (7)	0.79502 (19)	0.0403 (5)
O1	−1.1132 (6)	0.78583 (8)	0.3443 (3)	0.0885 (8)
O2	−0.8693 (7)	0.81070 (9)	0.5084 (3)	0.1111 (11)
O3	0.7262 (4)	0.54803 (7)	0.63542 (15)	0.0569 (5)
O4	0.3387 (6)	0.61246 (9)	0.6108 (2)	0.1019 (10)
O5	0.2717 (6)	0.65136 (10)	0.7518 (2)	0.0989 (10)
O6	0.7656 (5)	0.62597 (7)	1.13576 (17)	0.0648 (6)
O7	1.1385 (5)	0.58370 (8)	1.16900 (17)	0.0676 (6)
O8	1.3571 (5)	0.48802 (8)	0.87253 (19)	0.0694 (6)
O9	1.2022 (4)	0.50150 (8)	0.69233 (18)	0.0697 (6)
O10	0.2853 (4)	0.54747 (6)	0.43546 (16)	0.0545 (5)
H10B	0.264 (7)	0.5203 (5)	0.413 (2)	0.082*
H10A	0.362 (7)	0.5483 (10)	0.5049 (12)	0.082*

	U11	U22	U33	U12	U13	U23
C1	0.0376 (13)	0.0414 (13)	0.0506 (15)	0.0074 (10)	0.0123 (11)	0.0029 (11)
C2	0.0436 (14)	0.0457 (14)	0.0508 (15)	0.0078 (11)	0.0049 (12)	−0.0036 (12)
C3	0.0426 (15)	0.0480 (15)	0.0648 (18)	0.0083 (12)	0.0067 (13)	0.0059 (14)
C4	0.0498 (15)	0.0353 (13)	0.0716 (19)	0.0075 (11)	0.0248 (14)	0.0055 (13)
C5	0.074 (2)	0.0456 (15)	0.066 (2)	0.0037 (14)	0.0243 (17)	−0.0121 (14)
C6	0.0565 (17)	0.0579 (17)	0.0494 (16)	0.0044 (13)	0.0038 (13)	−0.0049 (13)
C7	0.0354 (12)	0.0358 (12)	0.0376 (13)	0.0002 (10)	0.0059 (10)	−0.0009 (10)
C8	0.0320 (11)	0.0294 (11)	0.0407 (13)	−0.0004 (9)	0.0041 (10)	0.0015 (9)
C9	0.0375 (12)	0.0301 (11)	0.0423 (14)	−0.0018 (9)	0.0120 (10)	−0.0013 (10)
C10	0.0440 (13)	0.0336 (12)	0.0346 (13)	−0.0063 (10)	0.0069 (10)	−0.0033 (9)
C11	0.0354 (12)	0.0349 (12)	0.0363 (13)	−0.0043 (10)	0.0011 (10)	0.0038 (10)
C12	0.0321 (12)	0.0303 (11)	0.0413 (13)	−0.0012 (9)	0.0081 (10)	−0.0009 (9)
N1	0.0623 (15)	0.0477 (13)	0.0567 (15)	0.0216 (12)	0.0210 (12)	0.0058 (11)
N2	0.0523 (14)	0.0538 (14)	0.0629 (16)	0.0191 (11)	−0.0006 (12)	−0.0046 (12)
N3	0.077 (2)	0.0415 (14)	0.105 (2)	0.0169 (13)	0.0438 (18)	0.0148 (15)
N4	0.0409 (11)	0.0384 (11)	0.0444 (13)	0.0028 (9)	0.0040 (9)	0.0026 (9)
N5	0.0614 (14)	0.0457 (12)	0.0366 (12)	−0.0035 (11)	0.0087 (11)	−0.0022 (10)
N6	0.0341 (10)	0.0359 (10)	0.0500 (13)	0.0014 (8)	0.0067 (9)	−0.0026 (9)
O1	0.0673 (15)	0.0633 (15)	0.140 (2)	0.0261 (12)	0.0334 (16)	0.0306 (15)
O2	0.149 (3)	0.0583 (15)	0.135 (3)	0.0392 (16)	0.052 (2)	−0.0139 (16)
O3	0.0600 (12)	0.0658 (12)	0.0397 (10)	0.0221 (10)	−0.0030 (9)	−0.0134 (9)
O4	0.128 (2)	0.0933 (18)	0.0613 (15)	0.0675 (16)	−0.0387 (14)	−0.0269 (13)
O5	0.0998 (19)	0.121 (2)	0.0703 (16)	0.0799 (17)	0.0031 (13)	−0.0105 (15)
O6	0.0896 (16)	0.0642 (13)	0.0453 (11)	0.0148 (11)	0.0250 (11)	−0.0069 (9)
O7	0.0718 (14)	0.0810 (15)	0.0410 (11)	0.0095 (11)	−0.0104 (10)	−0.0080 (10)
O8	0.0686 (13)	0.0686 (13)	0.0667 (14)	0.0360 (11)	0.0026 (11)	0.0090 (11)
O9	0.0672 (13)	0.0888 (16)	0.0532 (13)	0.0298 (12)	0.0125 (10)	−0.0155 (11)
O10	0.0654 (13)	0.0531 (11)	0.0411 (11)	0.0203 (10)	0.0008 (9)	−0.0079 (9)

C1—N2	1.384 (3)	C10—N5	1.437 (3)
C1—C2	1.385 (4)	C11—C12	1.371 (3)
C1—C6	1.391 (4)	C11—H11	0.9300
C2—C3	1.380 (4)	C12—N6	1.454 (3)
C2—H2	0.9300	N1—N2	1.403 (3)
C3—C4	1.370 (4)	N1—H1A	0.866 (10)
C3—H3	0.9300	N1—H1B	0.873 (10)
C4—C5	1.371 (4)	N1—H1C	0.874 (10)
C4—N3	1.462 (3)	N2—H2A	0.857 (10)
C5—C6	1.367 (4)	N3—O1	1.222 (4)
C5—H5	0.9300	N3—O2	1.227 (4)
C6—H6	0.9300	N4—O4	1.190 (3)
C7—O3	1.245 (3)	N4—O5	1.193 (3)
C7—C12	1.452 (3)	N5—O7	1.221 (3)
C7—C8	1.459 (3)	N5—O6	1.231 (3)
C8—C9	1.362 (3)	N6—O8	1.212 (3)
C8—N4	1.448 (3)	N6—O9	1.213 (3)
C9—C10	1.376 (3)	O10—H10B	0.825 (10)
C9—H9	0.9300	O10—H10A	0.820 (10)
C10—C11	1.378 (3)
N2—C1—C2	122.3 (2)	C12—C11—H11	120.4
N2—C1—C6	117.6 (2)	C10—C11—H11	120.4
C2—C1—C6	120.0 (2)	C11—C12—C7	124.0 (2)
C3—C2—C1	119.7 (3)	C11—C12—N6	115.8 (2)
C3—C2—H2	120.1	C7—C12—N6	120.2 (2)
C1—C2—H2	120.1	N2—N1—H1A	111 (2)
C4—C3—C2	119.1 (3)	N2—N1—H1B	102 (2)
C4—C3—H3	120.4	H1A—N1—H1B	112.3 (15)
C2—C3—H3	120.4	N2—N1—H1C	108 (2)
C3—C4—C5	121.9 (2)	H1A—N1—H1C	112.3 (15)
C3—C4—N3	119.1 (3)	H1B—N1—H1C	110.8 (15)
C5—C4—N3	119.0 (3)	C1—N2—N1	119.9 (2)
C6—C5—C4	119.3 (3)	C1—N2—H2A	116 (2)
C6—C5—H5	120.3	N1—N2—H2A	111 (2)
C4—C5—H5	120.3	O1—N3—O2	123.9 (3)
C5—C6—C1	119.9 (3)	O1—N3—C4	118.6 (3)
C5—C6—H6	120.0	O2—N3—C4	117.5 (3)
C1—C6—H6	120.0	O4—N4—O5	120.0 (2)
O3—C7—C12	124.0 (2)	O4—N4—C8	119.8 (2)
O3—C7—C8	124.4 (2)	O5—N4—C8	120.2 (2)
C12—C7—C8	111.6 (2)	O7—N5—O6	122.6 (2)
C9—C8—N4	115.8 (2)	O7—N5—C10	119.2 (2)
C9—C8—C7	124.1 (2)	O6—N5—C10	118.2 (2)
N4—C8—C7	120.2 (2)	O8—N6—O9	121.8 (2)
C8—C9—C10	119.5 (2)	O8—N6—C12	118.6 (2)
C8—C9—H9	120.3	O9—N6—C12	119.6 (2)
C10—C9—H9	120.3	C7—O3—H10A	134.2 (9)
C9—C10—C11	121.5 (2)	H1B—O10—H10B	108 (3)
C9—C10—N5	119.5 (2)	H1B—O10—H10A	114 (2)
C11—C10—N5	119.0 (2)	H10B—O10—H10A	110.2 (17)
C12—C11—C10	119.2 (2)
N2—C1—C2—C3	−177.3 (3)	C8—C7—C12—C11	3.9 (3)
C6—C1—C2—C3	−0.4 (4)	O3—C7—C12—N6	4.4 (4)
C1—C2—C3—C4	0.1 (4)	C8—C7—C12—N6	−177.02 (19)
C2—C3—C4—C5	0.5 (4)	C2—C1—N2—N1	−24.1 (4)
C2—C3—C4—N3	−178.4 (2)	C6—C1—N2—N1	159.0 (3)
C3—C4—C5—C6	−0.7 (4)	C3—C4—N3—O1	3.9 (4)
N3—C4—C5—C6	178.3 (3)	C5—C4—N3—O1	−175.0 (3)
C4—C5—C6—C1	0.3 (4)	C3—C4—N3—O2	−177.1 (3)
N2—C1—C6—C5	177.3 (3)	C5—C4—N3—O2	3.9 (4)
C2—C1—C6—C5	0.3 (4)	C9—C8—N4—O4	−178.5 (3)
O3—C7—C8—C9	174.6 (2)	C7—C8—N4—O4	0.1 (4)
C12—C7—C8—C9	−3.9 (3)	C9—C8—N4—O5	1.5 (4)
O3—C7—C8—N4	−3.9 (4)	C7—C8—N4—O5	−179.9 (3)
C12—C7—C8—N4	177.60 (19)	C9—C10—N5—O7	−175.1 (2)
N4—C8—C9—C10	−179.9 (2)	C11—C10—N5—O7	6.1 (3)
C7—C8—C9—C10	1.5 (3)	C9—C10—N5—O6	6.8 (3)
C8—C9—C10—C11	1.3 (3)	C11—C10—N5—O6	−172.1 (2)
C8—C9—C10—N5	−177.5 (2)	C11—C12—N6—O8	11.2 (3)
C9—C10—C11—C12	−1.3 (3)	C7—C12—N6—O8	−167.9 (2)
N5—C10—C11—C12	177.5 (2)	C11—C12—N6—O9	−167.3 (2)
C10—C11—C12—C7	−1.6 (3)	C7—C12—N6—O9	13.6 (3)
C10—C11—C12—N6	179.32 (19)	C12—C7—O3—H10A	155.2 (11)
O3—C7—C12—C11	−174.6 (2)	C8—C7—O3—H10A	−23.2 (12)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O10i	0.87 (1)	2.05 (1)	2.916 (3)	177 (2)
N1—H1B···O10	0.87 (1)	1.94 (1)	2.809 (3)	172 (2)
N1—H1B···O9ii	0.87 (1)	2.56 (3)	2.908 (3)	105 (2)
N1—H1C···O6iii	0.87 (1)	2.08 (1)	2.947 (3)	170 (2)
N2—H2A···O4	0.86 (1)	2.13 (2)	2.868 (3)	144 (3)
O10—H10A···O3	0.82 (1)	2.09 (2)	2.832 (3)	150 (3)
O10—H10A···O4	0.82 (1)	2.24 (2)	2.743 (3)	120 (2)
O10—H10B···O3ii	0.83 (1)	2.05 (1)	2.869 (3)	171 (3)
O10—H10B···O9ii	0.83 (1)	2.43 (3)	2.898 (3)	117 (3)
C11—H11···O8iv	0.93	2.51	3.433 (3)	172

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O10i	0.87 (1)	2.05 (1)	2.916 (3)	177 (2)
N1—H1B⋯O10	0.87 (1)	1.94 (1)	2.809 (3)	172 (2)
N1—H1B⋯O9ii	0.87 (1)	2.56 (3)	2.908 (3)	105 (2)
N1—H1C⋯O6iii	0.87 (1)	2.08 (1)	2.947 (3)	170 (2)
N2—H2A⋯O4	0.86 (1)	2.13 (2)	2.868 (3)	144 (3)
O10—H10A⋯O3	0.82 (1)	2.09 (2)	2.832 (3)	150 (3)
O10—H10A⋯O4	0.82 (1)	2.24 (2)	2.743 (3)	120 (2)
O10—H10B⋯O3ii	0.83 (1)	2.05 (1)	2.869 (3)	171 (3)
O10—H10B⋯O9ii	0.83 (1)	2.43 (3)	2.898 (3)	117 (3)
C11—H11⋯O8iv	0.93	2.51	3.433 (3)	172

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .