Bis(guanidinium) cyananilate

Udachin, K.A.; Zaman, M.B.; Ripmeester, J.A.

doi:10.1107/S1600536811028340

organic compounds

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doi:10.1107/S1600536811028340

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Bis(guanidinium) cyananilate

Konstantin A. Udachin,^a ^* Md. Badruz Zaman ^a,^b and John A. Ripmeester ^a

^aSteacie Institute for Molecular Sciences, National Research Council of Canada, 100 Sussex, Ottawa, Ontario, Canada K1A 0R6, and ^bCenter of Excellence for Research in Engineering Materials, Faculty of Engineering, King Saud University, Riyadh 11421, Saudi Arabia
^*Correspondence e-mail: Kostia.Oudatchin@nrc-cnrc.gc.ca

(Received 6 May 2011; accepted 14 July 2011; online 11 August 2011)

The asymmetric unit of the title compound, 2CH₆N₃⁺·C₈N₂O₄²⁻, 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⁺·C₈N₂O₄²⁻
M_r = 308.28
Monoclinic, C 2/c
a = 19.4873 (17) Å
b = 3.6611 (3) Å
c = 20.2452 (18) Å
β = 112.887 (2)°
V = 1330.7 (2) Å³
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[F² > 2σ(F²)] = 0.044
wR(F²) = 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

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) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x, y+1, -z+{\script{1\over 2}}]$ .

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811028340/gk2374sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811028340/gk2374Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811028340/gk2374Isup3.cml

checkCIF report

Comment top

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).

Related literature top

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 top

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.

Computing details top

Data collection: SMART (Bruker 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); 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 (Sheldrick, 2008).

Figures top

	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.

bis(guanidinium) 2,5-dicyano-3,6-dioxocyclohexa-1,4-diene-1,4-diolate top

Crystal data top

2CH₆N₃⁺·C₈N₂O₄²⁻	F(000) = 640
M_r = 308.28	D_x = 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 top

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

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.131	All H-atom parameters refined
S = 1.08	w = 1/[σ²(F_o²) + (0.078P)² + 0.709P] where P = (F_o² + 2F_c²)/3
1704 reflections	(Δ/σ)_max < 0.001
124 parameters	Δρ_max = 0.44 e Å⁻³
61 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

2CH₆N₃⁺·C₈N₂O₄²⁻	V = 1330.7 (2) Å³
M_r = 308.28	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 19.4873 (17) Å	µ = 0.12 mm⁻¹
b = 3.6611 (3) Å	T = 173 K
c = 20.2452 (18) Å	0.35 × 0.30 × 0.20 mm
β = 112.887 (2)°

Data collection top

Bruker SMART 1000 CCD diffractometer	1704 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1379 reflections with I > 2σ(I)
T_min = 0.958, T_max = 0.976	R_int = 0.026
7261 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	61 restraints
wR(F²) = 0.131	All H-atom parameters refined
S = 1.08	Δρ_max = 0.44 e Å⁻³
1704 reflections	Δρ_min = −0.42 e Å⁻³
124 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
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 (Å²) top

	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, º) top

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 code: (i) −x+1/2, −y+3/2, −z+1.

Hydrogen-bond geometry (Å, º) top

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.

Experimental details

Crystal data
Chemical formula	2CH₆N₃⁺·C₈N₂O₄²⁻
M_r	308.28
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	173
a, b, c (Å)	19.4873 (17), 3.6611 (3), 20.2452 (18)
β (°)	112.887 (2)
V (Å³)	1330.7 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.35 × 0.30 × 0.20

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.958, 0.976
No. of measured, independent and observed [I > 2σ(I)] reflections	7261, 1704, 1379
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.677

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.131, 1.08
No. of reflections	1704
No. of parameters	124
No. of restraints	61
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.42

Computer programs: SMART (Bruker 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ATOMS (Dowty, 1999).

Hydrogen-bond geometry (Å, º) top

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	0.923 (19)	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) −x+1/2, y−1/2, −z+1/2; (ii) −x, y+1, −z+1/2.

References

Bruker (2003). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dowty, E. (1999). ATOMS. Shape Software, Kingsport, Tennessee, USA. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zaman, M. B., Morita, Y., Toyoda, J., Yamochi, H., Sekizaki, S. & Nakasuji, K. (1996). Mol. Cryst. Liq. Cryst. 287, 249–257. CrossRef CAS Google Scholar
Zaman, M. B. & Ripmeester, J. A. (2010). Supramol. Chem. 22, 582–585. Web of Science CrossRef CAS Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page o2279

doi:10.1107/S1600536811028340

Open

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