Bis(guanidinium) cyananilate

Abstract

The asymmetric unit of the title compound, 2CH₆N₃ ⁺·C₈N₂O₄ ²⁻, contains one half of a centrosymmetric 2,5-di­cyano-3,6-dioxocyclo­hexa-1,4-diene-1,4-diolate (cyananil­ate) anion and one guanidinium cation, which are connected by N—H⋯O and N—H⋯N hydrogen bonds into a three-dimensional network.

Related literature

For the synthesis and structure of 2,5-dihy­droxy-3,6-dicyano-1,4-benzoquinone (cyananilic acid), see: Zaman et al. (1996 ▶). For related cyananilic acid structures and background references, see: Zaman & Ripmeester (2010 ▶).

Experimental

Crystal data

• 2CH₆N₃ ⁺·C₈N₂O₄ ²⁻

• M _r = 308.28

• Monoclinic,

• a = 19.4873 (17) Å

• b = 3.6611 (3) Å

• c = 20.2452 (18) Å

• β = 112.887 (2)°

• V = 1330.7 (2) ų

• Z = 4

• Mo Kα radiation

• μ = 0.12 mm⁻¹

• T = 173 K

• 0.35 × 0.30 × 0.20 mm

Data collection

• Bruker SMART 1000 CCD diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.958, T _max = 0.976

• 7261 measured reflections

• 1704 independent reflections

• 1379 reflections with I > 2σ(I)

• R _int = 0.026

Refinement

• R[F ² > 2σ(F ²)] = 0.044

• wR(F ²) = 0.131

• S = 1.08

• 1704 reflections

• 124 parameters

• 61 restraints

• All H-atom parameters refined

• Δρ_max = 0.44 e Å⁻³

• Δρ_min = −0.42 e Å⁻³

Data collection: SMART (Bruker 2003 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ATOMS (Dowty, 1999 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811028340/gk2374Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O2i	0.95 (2)	2.20 (2)	3.000 (2)	142 (2)
N2—H2⋯O1i	0.95 (2)	2.21 (2)	3.020 (2)	143 (2)
N2—H1⋯O2	0.95 (2)	2.27 (2)	3.062 (2)	140 (2)
N3—H4⋯N1ii	0.92 (2)	2.14 (2)	3.025 (2)	160 (2)
N3—H3⋯O2	0.93 (2)	2.02 (2)	2.900 (2)	156 (2)
N4—H6⋯N1ii	0.92 (2)	2.38 (2)	3.199 (2)	148 (3)
N4—H5⋯O1i	0.95 (2)	1.95 (2)	2.826 (2)	151 (3)

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

The reaction between cyananilic acid and guanidinium carbonate in methanol leads to the title compound. Since 1997, cyananilic acid (2,5-dicyano-3,6-dihydroxy-1,4-benzoquinone) has been explored due to its valuable physicochemical features. It is an organic acid that has Mott-insulator properties, and organic ferroelectricity (Zaman & Ripmeester, 2010). It forms three dimensional network through N-H···O and N-H···N hydrogen bonds (Fig. 2).

Experimental

Cyananilic acid has been synthesized according to our published method (Zaman et al., 1996) and purified by recrystallization from benzene. Light yellow compound was grown by slow evaporation of a methanol solution containing a 1:1 stoichiometric quantity of guanidinium carbonate (Aldrich, 98%) and cyananilic acid under ambient conditions. Compound decomposes at 593K.

Refinement

N-H distances were restrained to 0.95 (2) Å and all H atoms were refined isotropically. Non- hydrogen atoms were restrained to have the same Uij components with SHELXL97 (Sheldrick, 2008) instruction 'SIMU C1 < N4'.

Figures

Fig. 1.

Molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level. Fragments generated by symmetry codes: (a) 1/2 - x, 1,5 - y, 1 - z; (b) 1/2 - x, 1/2 + y, 1/2 - z; (c) 1/2 + x, 2.5 - y, 1/2 + z. Hydrogen bonds are shown with dashed lines.

Fig. 2.

Packing diagram of the hydrogen-bonded framework structure of the title compound viewed down the b axial direction of the unit cell, showing hydrogen-bonding associations as thin lines.

Crystal data

2CH6N3+·C8N2O42−	F(000) = 640
Mr = 308.28	Dx = 1.539 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: -C 2yc	Cell parameters from 280 reflections
a = 19.4873 (17) Å	θ = 5.0–26°
b = 3.6611 (3) Å	µ = 0.12 mm−1
c = 20.2452 (18) Å	T = 173 K
β = 112.887 (2)°	Block, colourless
V = 1330.7 (2) Å3	0.35 × 0.30 × 0.20 mm
Z = 4

Data collection

Bruker SMART 1000 CCD diffractometer	1704 independent reflections
Radiation source: fine-focus sealed tube	1379 reflections with I > 2σ(I)
graphite	Rint = 0.026
ω scans	θmax = 28.7°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −26→26
Tmin = 0.958, Tmax = 0.976	k = −4→4
7261 measured reflections	l = −27→27

Refinement

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.131	All H-atom parameters refined
S = 1.08	w = 1/[σ2(Fo2) + (0.078P)2 + 0.709P] where P = (Fo2 + 2Fc2)/3
1704 reflections	(Δ/σ)max < 0.001
124 parameters	Δρmax = 0.44 e Å−3
61 restraints	Δρmin = −0.42 e Å−3

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
C1	0.30409 (9)	0.9359 (5)	0.47852 (9)	0.0199 (4)
C2	0.23212 (9)	0.7966 (5)	0.42334 (8)	0.0194 (4)
C3	0.18096 (9)	0.6179 (5)	0.44716 (9)	0.0193 (4)
C4	0.11214 (10)	0.4852 (5)	0.39572 (9)	0.0213 (4)
C5	0.11254 (10)	0.8997 (5)	0.17992 (9)	0.0221 (4)
O1	0.34792 (8)	1.0991 (4)	0.45742 (7)	0.0288 (4)
O2	0.22010 (7)	0.8452 (4)	0.35861 (7)	0.0254 (3)
N1	0.05680 (9)	0.3773 (5)	0.35458 (9)	0.0297 (4)
N2	0.17845 (9)	0.7347 (5)	0.19774 (8)	0.0255 (4)
H2	0.1912 (16)	0.640 (8)	0.1606 (13)	0.044 (7)*
H1	0.2039 (15)	0.661 (8)	0.2463 (11)	0.046 (7)*
N3	0.08938 (9)	1.0023 (5)	0.23049 (9)	0.0279 (4)
H4	0.0455 (12)	1.133 (7)	0.2154 (13)	0.039 (7)*
H3	0.1219 (15)	0.963 (8)	0.2780 (11)	0.051 (8)*
N4	0.07052 (10)	0.9652 (5)	0.11139 (9)	0.0294 (4)
H6	0.0260 (13)	1.086 (8)	0.1016 (16)	0.057 (9)*
H5	0.0886 (17)	0.897 (8)	0.0757 (14)	0.048 (8)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0204 (8)	0.0214 (9)	0.0206 (8)	−0.0006 (6)	0.0110 (7)	0.0004 (6)
C2	0.0201 (8)	0.0210 (8)	0.0184 (8)	0.0008 (6)	0.0088 (6)	0.0004 (6)
C3	0.0172 (8)	0.0214 (8)	0.0192 (8)	−0.0015 (6)	0.0071 (6)	−0.0006 (6)
C4	0.0209 (8)	0.0229 (9)	0.0218 (8)	−0.0001 (7)	0.0102 (7)	0.0003 (7)
C5	0.0223 (9)	0.0237 (9)	0.0218 (8)	−0.0009 (7)	0.0103 (7)	−0.0002 (6)
O1	0.0267 (7)	0.0376 (8)	0.0259 (7)	−0.0090 (6)	0.0145 (6)	0.0012 (6)
O2	0.0250 (7)	0.0345 (8)	0.0173 (6)	−0.0013 (5)	0.0089 (5)	0.0023 (5)
N1	0.0226 (8)	0.0345 (10)	0.0293 (8)	−0.0045 (7)	0.0072 (7)	−0.0028 (7)
N2	0.0234 (8)	0.0307 (9)	0.0236 (8)	0.0043 (6)	0.0104 (6)	−0.0008 (7)
N3	0.0248 (8)	0.0394 (10)	0.0214 (8)	0.0070 (7)	0.0110 (7)	0.0005 (7)
N4	0.0261 (8)	0.0421 (10)	0.0206 (8)	0.0089 (7)	0.0099 (7)	0.0007 (7)

Geometric parameters (Å, °)

C1—O1	1.246 (2)	C5—N4	1.330 (2)
C1—C3i	1.431 (2)	C5—N2	1.336 (2)
C1—C2	1.502 (2)	N2—H2	0.95 (2)
C2—O2	1.251 (2)	N2—H1	0.95 (2)
C2—C3	1.424 (2)	N3—H4	0.923 (19)
C3—C4	1.426 (2)	N3—H3	0.93 (2)
C4—N1	1.146 (2)	N4—H6	0.92 (2)
C5—N3	1.324 (2)	N4—H5	0.95 (2)
O1—C1—C3i	122.71 (15)	N3—C5—N2	120.05 (17)
O1—C1—C2	118.30 (15)	N4—C5—N2	120.02 (17)
C3i—C1—C2	118.99 (14)	C5—N2—H2	118.3 (18)
O2—C2—C3	123.33 (15)	C5—N2—H1	117.9 (17)
O2—C2—C1	118.10 (15)	H2—N2—H1	122 (2)
C3—C2—C1	118.57 (14)	C5—N3—H4	116.2 (16)
C2—C3—C4	119.52 (15)	C5—N3—H3	117.0 (18)
C2—C3—C1i	122.44 (14)	H4—N3—H3	126 (2)
C4—C3—C1i	118.04 (15)	C5—N4—H6	117.1 (19)
N1—C4—C3	179.7 (2)	C5—N4—H5	119.0 (19)
N3—C5—N4	119.93 (17)	H6—N4—H5	124 (3)

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

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2ii	0.95 (2)	2.20 (2)	3.000 (2)	142 (2)
N2—H2···O1ii	0.95 (2)	2.21 (2)	3.020 (2)	143 (2)
N2—H1···O2	0.95 (2)	2.27 (2)	3.062 (2)	140 (2)
N2—H1···N2ii	0.95 (2)	2.64 (3)	3.319 (3)	129 (2)
N3—H4···N1iii	0.92 (2)	2.14 (2)	3.025 (2)	160 (2)
N3—H3···O2	0.93 (2)	2.02 (2)	2.900 (2)	156 (2)
N4—H6···N1iii	0.92 (2)	2.38 (2)	3.199 (2)	148 (3)
N4—H5···O1ii	0.95 (2)	1.95 (2)	2.826 (2)	151 (3)

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