1-(2-Methyl-5-nitro-phenyl)guanidinium picrate.

In the crystal structure of the title salt, C(8)H(11)N(4)O(2) (+)·C(6)H(2)N(3)O(7) (-), the pictrate anion participates in extensive hydrogen bonding with the guanidinium ion group of the cation, linking the mol-ecules through N(+)-H⋯O(-) hydrogen bonds and inter-molecular N-H⋯O and C-H⋯O inter-actions. These hydrogen-bonding configurations involve two three-centre/bifurcated bonds [N-H⋯(O,O)] that are observed between two N atoms from the guanidinium ion group of the cation and the o-NO(2) and phenolate O atoms of the picrate anion. In addition, π-π inter-actions also contribute to the crystal packing, with a centroid-to-centroid distance of 3.693 (6) Å and a slippage angle of 1.614°. A significant number of conformational differences are observed between the salt in the crystal structure and the models obtained by density functional theory (DFT) calculations of the geometry-optimized structure.

Related literature

For background literature, see: Berlinck (2002 ▶); Heys et al. (2000 ▶); Ishikawa & Isobe (2002 ▶); Kelley et al. (2001 ▶); Laeckmann et al. (2002 ▶); Moroni et al. (2001 ▶); Orner & Hamilton (2001 ▶); Zyss et al. (1993 ▶). For related structures, see: Cunningham et al. (1997 ▶); Demir et al. (2006 ▶); Gupta & Dutta (1975 ▶); Moghimi et al. (2005 ▶); Murtaza et al. (2007 ▶, 2009 ▶); Pereira Silva et al. (2007 ▶); Pruszynski et al. (1992 ▶); Ren et al. (2007 ▶); Sonar et al. (2007 ▶); Smith et al. (2007 ▶, 2007a ▶); Stanford et al. (2007 ▶); Stępień & Grabowski (1977 ▶); Wang et al. (2009 ▶); Wei (2008 ▶). For density functional theory (DFT), see: Becke (1988 ▶, 1993 ▶); Frisch et al. (2004 ▶); Hehre et al. (1986 ▶); Lee et al. (1988 ▶); Schmidt & Polik (2007 ▶). For the Cambridge Structural Database, see: Allen (2002 ▶); Bruno et al. (2004 ▶).

Experimental

Crystal data

C8n class="Species">H11N4O2 +·C6class="Chemical">n class="Species">H2N3O7 −

M = 423.31

Triclinic,

a = 7.1318 (10) Å

b = 10.6239 (13) Å

c = 11.9564 (13) Å

α = 84.257 (10)°

β = 74.497 (11)°

γ = 77.559 (11)°

V = 851.58 (18) Å3

Z = 2

Cu Kα radiation

μ = 1.23 mm−1

T = 110 K

0.51 × 0.41 × 0.33 mm

Data collection

Oxford Xcalibur diffractometer with Ruby (Gemini Cu) detector

Absorption correction: multi-scan (CrysAlis Pro; Oxford Diffraction, 2009 ▶) T min = 0.431, T max = 1.000

6248 measun class="Disease">red reflectioclass="Chemical">ns

3344 independent reflections

2761 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.118

S = 1.07

3344 reflections

272 parameters

H-atom parameters constrained

Δρmax = 0.27 e Å−3

Δρmin = −0.29 e Å−3

Data collection: CrysAlis Pro (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis class="Disease">RED (Oxford Diffractioclass="Chemical">n, 2007 ▶); data class="Chemical">n class="Disease">reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809037647/kp2228sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809037647/kp2228Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C8H11N4O2+·C6H2N3O7−	Z = 2
Mr = 423.31	F(000) = 436
Triclinic, P1	Dx = 1.651 Mg m−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54184 Å
a = 7.1318 (10) Å	Cell parameters from 3632 reflections
b = 10.6239 (13) Å	θ = 4.3–73.8°
c = 11.9564 (13) Å	µ = 1.23 mm−1
α = 84.257 (10)°	T = 110 K
β = 74.497 (11)°	Chunk, pale yellow
γ = 77.559 (11)°	0.51 × 0.41 × 0.33 mm
V = 851.58 (18) Å3

Oxford Xcalibur diffractometer with Ruby (Gemini Cu) detector	3344 independent reflections
Radiation source: Enhance (Cu) X-ray Source	2761 reflections with I > 2σ(I)
graphite	Rint = 0.021
Detector resolution: 10.5081 pixels mm-1	θmax = 73.9°, θmin = 4.3°
ω scans	h = −7→8
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −13→13
Tmin = 0.431, Tmax = 1.000	l = −14→12
6248 measured reflections

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0696P)2 + 0.2349P] where P = (Fo2 + 2Fc2)/3
3344 reflections	(Δ/σ)max = 0.001
272 parameters	Δρmax = 0.27 e Å−3
0 restraints	Δρmin = −0.29 e Å−3

Experimental. CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.33.34d (release 27-02-2009 CrysAlis171 .NET) (compiled Feb 27 2009,15:38:38) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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
O1A	0.6186 (2)	0.42327 (13)	1.18314 (12)	0.0358 (3)
O2A	0.5417 (2)	0.62511 (13)	1.13392 (12)	0.0383 (3)
N1A	0.6304 (2)	0.51540 (14)	1.11228 (13)	0.0261 (3)
N2A	0.9515 (2)	0.68299 (13)	0.73199 (12)	0.0228 (3)
H2AA	1.0452	0.7222	0.7376	0.027*
N3A	0.7069 (2)	0.67430 (13)	0.64072 (12)	0.0236 (3)
H3AB	0.6416	0.7048	0.5877	0.028*
H3AC	0.6762	0.6076	0.6865	0.028*
N4A	0.8981 (2)	0.82883 (13)	0.58308 (12)	0.0225 (3)
H4AA	0.8336	0.8600	0.5299	0.027*
H4AB	0.9943	0.8644	0.5909	0.027*
C1A	1.0118 (2)	0.44934 (16)	0.77518 (15)	0.0229 (3)
C2A	0.9141 (2)	0.57363 (15)	0.80935 (14)	0.0208 (3)
C3A	0.7870 (2)	0.59582 (16)	0.91843 (14)	0.0221 (3)
H3AA	0.7204	0.6807	0.9400	0.026*
C4A	0.7597 (2)	0.49070 (16)	0.99526 (14)	0.0225 (3)
C5A	0.8533 (2)	0.36602 (16)	0.96653 (15)	0.0246 (4)
H5AA	0.8327	0.2956	1.0208	0.029*
C6A	0.9788 (3)	0.34633 (16)	0.85597 (15)	0.0254 (4)
H6AA	1.0437	0.2610	0.8347	0.030*
C7A	1.1495 (3)	0.42731 (18)	0.65702 (16)	0.0298 (4)
H7AA	1.0824	0.4706	0.5979	0.045*
H7AB	1.1880	0.3345	0.6445	0.045*
H7AC	1.2682	0.4624	0.6513	0.045*
C8A	0.8505 (2)	0.72837 (15)	0.65149 (14)	0.0202 (3)
O1B	0.59719 (17)	0.85654 (11)	0.47353 (10)	0.0254 (3)
O21B	0.84884 (19)	1.00632 (12)	0.36978 (12)	0.0319 (3)
O22B	0.7546 (2)	1.15265 (12)	0.24729 (12)	0.0324 (3)
O41B	0.3034 (2)	1.09649 (12)	0.03718 (11)	0.0318 (3)
O42B	0.1500 (3)	0.93647 (15)	0.08197 (15)	0.0518 (5)
O61B	0.2382 (2)	0.64362 (13)	0.39470 (12)	0.0351 (3)
O62B	0.3584 (2)	0.69013 (14)	0.52904 (12)	0.0353 (3)
N2B	0.7376 (2)	1.05245 (13)	0.30647 (12)	0.0236 (3)
N4B	0.2629 (2)	1.00057 (14)	0.09892 (13)	0.0292 (3)
N6B	0.3236 (2)	0.71124 (14)	0.43296 (12)	0.0243 (3)
C1B	0.5286 (2)	0.88544 (15)	0.38719 (14)	0.0206 (3)
C2B	0.5836 (2)	0.98569 (15)	0.29955 (14)	0.0211 (3)
C3B	0.4980 (2)	1.02404 (16)	0.20829 (14)	0.0224 (3)
H3BA	0.5364	1.0924	0.1555	0.027*
C4B	0.3543 (3)	0.96112 (16)	0.19447 (14)	0.0237 (3)
C5B	0.3011 (2)	0.85874 (16)	0.26861 (14)	0.0230 (3)
H5BA	0.2080	0.8137	0.2554	0.028*
C6B	0.3831 (2)	0.82270 (15)	0.36097 (14)	0.0217 (3)

	U11	U22	U33	U12	U13	U23
O1A	0.0411 (8)	0.0400 (8)	0.0270 (7)	−0.0189 (6)	−0.0048 (6)	0.0092 (6)
O2A	0.0393 (8)	0.0368 (8)	0.0319 (7)	−0.0027 (6)	−0.0007 (6)	−0.0020 (6)
N1A	0.0239 (7)	0.0325 (8)	0.0248 (7)	−0.0119 (6)	−0.0070 (6)	0.0014 (6)
N2A	0.0240 (7)	0.0239 (7)	0.0247 (7)	−0.0118 (6)	−0.0099 (6)	0.0048 (6)
N3A	0.0255 (7)	0.0248 (7)	0.0243 (7)	−0.0104 (6)	−0.0114 (6)	0.0063 (5)
N4A	0.0227 (7)	0.0246 (7)	0.0239 (7)	−0.0101 (5)	−0.0096 (6)	0.0042 (5)
C1A	0.0220 (8)	0.0269 (8)	0.0236 (8)	−0.0084 (6)	−0.0096 (6)	−0.0005 (6)
C2A	0.0211 (8)	0.0240 (8)	0.0216 (8)	−0.0101 (6)	−0.0099 (6)	0.0036 (6)
C3A	0.0206 (8)	0.0227 (8)	0.0262 (8)	−0.0064 (6)	−0.0103 (7)	0.0003 (6)
C4A	0.0214 (8)	0.0284 (9)	0.0211 (8)	−0.0105 (6)	−0.0076 (6)	0.0013 (6)
C5A	0.0277 (9)	0.0238 (8)	0.0275 (9)	−0.0126 (7)	−0.0121 (7)	0.0048 (6)
C6A	0.0286 (9)	0.0212 (8)	0.0298 (9)	−0.0073 (7)	−0.0115 (7)	−0.0011 (7)
C7A	0.0312 (9)	0.0307 (9)	0.0271 (9)	−0.0075 (7)	−0.0054 (7)	−0.0024 (7)
C8A	0.0195 (8)	0.0207 (8)	0.0193 (7)	−0.0032 (6)	−0.0031 (6)	−0.0018 (6)
O1B	0.0296 (6)	0.0253 (6)	0.0264 (6)	−0.0099 (5)	−0.0138 (5)	0.0039 (5)
O21B	0.0288 (7)	0.0328 (7)	0.0420 (7)	−0.0141 (5)	−0.0201 (6)	0.0092 (6)
O22B	0.0406 (7)	0.0278 (7)	0.0374 (7)	−0.0190 (6)	−0.0184 (6)	0.0089 (5)
O41B	0.0458 (8)	0.0249 (6)	0.0293 (7)	−0.0084 (5)	−0.0183 (6)	0.0044 (5)
O42B	0.0762 (11)	0.0455 (9)	0.0594 (10)	−0.0350 (8)	−0.0505 (9)	0.0193 (8)
O61B	0.0454 (8)	0.0334 (7)	0.0345 (7)	−0.0234 (6)	−0.0129 (6)	0.0028 (5)
O62B	0.0369 (7)	0.0442 (8)	0.0326 (7)	−0.0218 (6)	−0.0176 (6)	0.0158 (6)
N2B	0.0251 (7)	0.0224 (7)	0.0253 (7)	−0.0087 (6)	−0.0072 (6)	0.0005 (5)
N4B	0.0382 (8)	0.0246 (8)	0.0308 (8)	−0.0088 (6)	−0.0179 (7)	0.0015 (6)
N6B	0.0218 (7)	0.0248 (7)	0.0266 (7)	−0.0076 (6)	−0.0054 (6)	0.0020 (6)
C1B	0.0201 (8)	0.0194 (7)	0.0227 (8)	−0.0032 (6)	−0.0060 (6)	−0.0024 (6)
C2B	0.0209 (8)	0.0203 (8)	0.0237 (8)	−0.0061 (6)	−0.0062 (6)	−0.0024 (6)
C3B	0.0253 (8)	0.0197 (8)	0.0223 (8)	−0.0052 (6)	−0.0056 (6)	−0.0015 (6)
C4B	0.0281 (9)	0.0242 (8)	0.0224 (8)	−0.0060 (7)	−0.0116 (7)	−0.0020 (6)
C5B	0.0227 (8)	0.0227 (8)	0.0259 (8)	−0.0066 (6)	−0.0075 (7)	−0.0034 (6)
C6B	0.0209 (8)	0.0213 (8)	0.0233 (8)	−0.0057 (6)	−0.0055 (6)	0.0001 (6)

O1A—N1A	1.2306 (19)	C7A—H7AA	0.9800
O2A—N1A	1.217 (2)	C7A—H7AB	0.9800
N1A—C4A	1.468 (2)	C7A—H7AC	0.9800
N2A—C8A	1.344 (2)	O1B—C1B	1.241 (2)
N2A—C2A	1.4363 (19)	O21B—N2B	1.2334 (18)
N2A—H2AA	0.8800	O22B—N2B	1.2278 (18)
N3A—C8A	1.317 (2)	O41B—N4B	1.2364 (19)
N3A—H3AB	0.8800	O42B—N4B	1.227 (2)
N3A—H3AC	0.8800	O61B—N6B	1.2250 (19)
N4A—C8A	1.325 (2)	O62B—N6B	1.2280 (19)
N4A—H4AA	0.8800	N2B—C2B	1.4534 (19)
N4A—H4AB	0.8800	N4B—C4B	1.445 (2)
C1A—C2A	1.398 (2)	N6B—C6B	1.463 (2)
C1A—C6A	1.401 (2)	C1B—C2B	1.457 (2)
C1A—C7A	1.497 (2)	C1B—C6B	1.460 (2)
C2A—C3A	1.384 (2)	C2B—C3B	1.374 (2)
C3A—C4A	1.386 (2)	C3B—C4B	1.390 (2)
C3A—H3AA	0.9500	C3B—H3BA	0.9500
C4A—C5A	1.381 (2)	C4B—C5B	1.385 (2)
C5A—C6A	1.391 (2)	C5B—C6B	1.368 (2)
C5A—H5AA	0.9500	C5B—H5BA	0.9500
C6A—H6AA	0.9500
O2A—N1A—O1A	123.73 (15)	C1A—C7A—H7AC	109.5
O2A—N1A—C4A	118.54 (14)	H7AA—C7A—H7AC	109.5
O1A—N1A—C4A	117.73 (15)	H7AB—C7A—H7AC	109.5
C8A—N2A—C2A	123.28 (13)	N3A—C8A—N4A	120.59 (14)
C8A—N2A—H2AA	118.4	N3A—C8A—N2A	120.75 (14)
C2A—N2A—H2AA	118.4	N4A—C8A—N2A	118.67 (14)
C8A—N3A—H3AB	120.0	O22B—N2B—O21B	122.00 (13)
C8A—N3A—H3AC	120.0	O22B—N2B—C2B	118.56 (13)
H3AB—N3A—H3AC	120.0	O21B—N2B—C2B	119.43 (13)
C8A—N4A—H4AA	120.0	O42B—N4B—O41B	122.85 (15)
C8A—N4A—H4AB	120.0	O42B—N4B—C4B	118.43 (14)
H4AA—N4A—H4AB	120.0	O41B—N4B—C4B	118.72 (14)
C2A—C1A—C6A	117.73 (16)	O61B—N6B—O62B	122.78 (14)
C2A—C1A—C7A	121.12 (15)	O61B—N6B—C6B	117.97 (14)
C6A—C1A—C7A	121.14 (16)	O62B—N6B—C6B	119.25 (13)
C3A—C2A—C1A	121.89 (14)	O1B—C1B—C2B	124.20 (14)
C3A—C2A—N2A	118.23 (15)	O1B—C1B—C6B	124.04 (15)
C1A—C2A—N2A	119.82 (15)	C2B—C1B—C6B	111.76 (14)
C2A—C3A—C4A	118.15 (15)	C3B—C2B—N2B	116.04 (14)
C2A—C3A—H3AA	120.9	C3B—C2B—C1B	124.33 (14)
C4A—C3A—H3AA	120.9	N2B—C2B—C1B	119.63 (14)
C5A—C4A—C3A	122.45 (16)	C2B—C3B—C4B	118.92 (15)
C5A—C4A—N1A	119.67 (14)	C2B—C3B—H3BA	120.5
C3A—C4A—N1A	117.86 (15)	C4B—C3B—H3BA	120.5
C4A—C5A—C6A	118.22 (15)	C5B—C4B—C3B	121.16 (15)
C4A—C5A—H5AA	120.9	C5B—C4B—N4B	119.33 (14)
C6A—C5A—H5AA	120.9	C3B—C4B—N4B	119.48 (14)
C5A—C6A—C1A	121.56 (16)	C6B—C5B—C4B	119.76 (15)
C5A—C6A—H6AA	119.2	C6B—C5B—H5BA	120.1
C1A—C6A—H6AA	119.2	C4B—C5B—H5BA	120.1
C1A—C7A—H7AA	109.5	C5B—C6B—C1B	123.85 (15)
C1A—C7A—H7AB	109.5	C5B—C6B—N6B	116.32 (14)
H7AA—C7A—H7AB	109.5	C1B—C6B—N6B	119.79 (14)
C6A—C1A—C2A—C3A	−0.7 (2)	O1B—C1B—C2B—C3B	−175.27 (16)
C7A—C1A—C2A—C3A	−179.70 (15)	C6B—C1B—C2B—C3B	4.9 (2)
C6A—C1A—C2A—N2A	176.60 (13)	O1B—C1B—C2B—N2B	4.3 (3)
C7A—C1A—C2A—N2A	−2.4 (2)	C6B—C1B—C2B—N2B	−175.56 (14)
C8A—N2A—C2A—C3A	−94.78 (19)	N2B—C2B—C3B—C4B	177.91 (15)
C8A—N2A—C2A—C1A	87.8 (2)	C1B—C2B—C3B—C4B	−2.5 (3)
C1A—C2A—C3A—C4A	0.8 (2)	C2B—C3B—C4B—C5B	−2.0 (3)
N2A—C2A—C3A—C4A	−176.51 (13)	C2B—C3B—C4B—N4B	179.95 (15)
C2A—C3A—C4A—C5A	−0.3 (2)	O42B—N4B—C4B—C5B	−4.7 (3)
C2A—C3A—C4A—N1A	177.78 (13)	O41B—N4B—C4B—C5B	176.06 (16)
O2A—N1A—C4A—C5A	−176.41 (15)	O42B—N4B—C4B—C3B	173.45 (18)
O1A—N1A—C4A—C5A	3.7 (2)	O41B—N4B—C4B—C3B	−5.8 (3)
O2A—N1A—C4A—C3A	5.4 (2)	C3B—C4B—C5B—C6B	3.5 (3)
O1A—N1A—C4A—C3A	−174.45 (14)	N4B—C4B—C5B—C6B	−178.40 (15)
C3A—C4A—C5A—C6A	−0.3 (2)	C4B—C5B—C6B—C1B	−0.7 (3)
N1A—C4A—C5A—C6A	−178.34 (14)	C4B—C5B—C6B—N6B	−178.21 (15)
C4A—C5A—C6A—C1A	0.4 (2)	O1B—C1B—C6B—C5B	176.90 (16)
C2A—C1A—C6A—C5A	0.1 (2)	C2B—C1B—C6B—C5B	−3.2 (2)
C7A—C1A—C6A—C5A	179.07 (15)	O1B—C1B—C6B—N6B	−5.6 (2)
C2A—N2A—C8A—N3A	1.0 (2)	C2B—C1B—C6B—N6B	174.21 (14)
C2A—N2A—C8A—N4A	−179.04 (15)	O61B—N6B—C6B—C5B	13.8 (2)
O22B—N2B—C2B—C3B	14.1 (2)	O62B—N6B—C6B—C5B	−165.22 (16)
O21B—N2B—C2B—C3B	−164.83 (15)	O61B—N6B—C6B—C1B	−163.84 (16)
O22B—N2B—C2B—C1B	−165.51 (15)	O62B—N6B—C6B—C1B	17.1 (2)
O21B—N2B—C2B—C1B	15.6 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N2A—H2AA···O22Bi	0.88	2.20	3.0737 (18)	171
N3A—H3AB···O1B	0.88	2.03	2.7866 (18)	143
N3A—H3AB···O62B	0.88	2.35	3.0882 (18)	142
N3A—H3AC···O1Aii	0.88	2.32	2.9808 (19)	132
N4A—H4AA···O1B	0.88	1.98	2.7499 (18)	145
N4A—H4AA···O21B	0.88	2.34	3.0683 (19)	141
N4A—H4AB···O21Bi	0.88	2.11	2.9572 (18)	163
C3A—H3AA···O41Biii	0.95	2.37	3.262 (2)	155
C7A—H7AB···O1Biv	0.98	2.56	3.447 (2)	151

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2A—H2AA⋯O22Bi	0.88	2.20	3.0737 (18)	171
N3A—H3AB⋯O1B	0.88	2.03	2.7866 (18)	143
N3A—H3AB⋯O62B	0.88	2.35	3.0882 (18)	142
N3A—H3AC⋯O1Aii	0.88	2.32	2.9808 (19)	132
N4A—H4AA⋯O1B	0.88	1.98	2.7499 (18)	145
N4A—H4AA⋯O21B	0.88	2.34	3.0683 (19)	141
N4A—H4AB⋯O21Bi	0.88	2.11	2.9572 (18)	163
C3A—H3AA⋯O41Biii	0.95	2.37	3.262 (2)	155
C7A—H7AB⋯O1Biv	0.98	2.56	3.447 (2)	151

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