Bis(guanidinium) chloranilate

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

doi:10.1107/S1600536811036373

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 10| October 2011| Page o2625

https://doi.org/10.1107/S1600536811036373

Open

access

Bis(guanidinium) chloranilate

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, K1A 0R6, Canada, 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 10 August 2011; accepted 6 September 2011; online 14 September 2011)

The asymmetric unit of the title co-crystal, 2CH₆N₃⁺·C₆Cl₂O₄²⁻, contains one half of a chloranilate anion and one guanidinium cation, which are connected by strong N—H⋯O hydrogen bonds into a two-dimensional network.

Related literature

For organic co-crystals containing 2,5-dihydroxy-3,6-dichloro-1,4-benzoquinone (chloranilic acid), see: Andersen & Andersen (1975 ); Horiuchi et al. (2005 , 2007 ); Zaman et al. (1999a ,b , 2010 ). For inorganic co-ordination polymers containing chloranilic acid, see: Kitagawa et al. (2002 ). For guanidine and guanidinium structures, see: Abrahams et al. (2004 , 2005 ); Best et al. (2003 ); Said et al. (2006 ); Smith & Wermuth (2010 , 2011 ).

Experimental

Crystal data

2CH₆N₃⁺·C₆Cl₂O₄²⁻
M_r = 327.14
Monoclinic, C 2/c
a = 19.5224 (14) Å
b = 3.7316 (3) Å
c = 18.4103 (14) Å
β = 116.087 (1)°
V = 1204.56 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.57 mm⁻¹
T = 173 K
0.45 × 0.40 × 0.30 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS, Sheldrick, 1996 ) T_min = 0.785, T_max = 0.849
6965 measured reflections
1674 independent reflections
1525 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.078
S = 1.08
1674 reflections
116 parameters
All H-atom parameters refined
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H2⋯O3	0.85 (2)	2.32 (2)	3.0504 (13)	144.4 (16)
N1—H1⋯O2ⁱ	0.901 (17)	2.117 (17)	2.8978 (13)	144.4 (15)
N1—H1⋯O3ⁱ	0.901 (17)	2.303 (18)	3.0555 (13)	140.9 (15)
N2—H3⋯O3	0.818 (19)	2.161 (19)	2.9337 (14)	157.7 (17)
N3—H6⋯O2ⁱ	0.79 (2)	2.21 (2)	2.9016 (14)	146.3 (18)
N3—H5⋯O2ⁱⁱ	0.88 (2)	2.14 (2)	2.9586 (13)	154.4 (17)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{5\over 2}}, -z]$ ; (ii) $[x, -y+3, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2003 ); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus; 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: https://doi.org/10.1107/S1600536811036373/vm2118sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811036373/vm2118Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811036373/vm2118Isup3.cml

checkCIF report

Comment top

The co-crystallization of chloranilic acid and guanidine was carried out in methanol resulting in the co-crystal 2CH₆N₃⁺.C₆O₄Cl₂^2- (Fig. 1). The chloranilic acid molecule is centro-symmetric and contains two hydrogen bond donors and two hydrogen bond acceptors and is, therefore, capable of participating in multiple hydrogen bonds. It forms 2D-sheet-like networks through N3—H5···O2 hydrogen bonds as shown in Figure 2. There are three N—H bonds in guanidine that connect with the O2 and O3 atoms of the chloranilic acid and form a one-dimensional molecular supramolecular structure. Two of these one-dimensional structures are again connected via N3—H5···O2 hydrogen bonds and form a two-dimensional network. Details of hydrogen-bonds are shown in Table 1.

Related literature top

For organic co-crystals containing 2,5-dihydroxy-3,6-dichloro-1,4-benzoquinone (chloranilic acid), see: Andersen & Andersen (1975); Horiuchi et al. (2005, 2007); Zaman et al. (1999a,b, 2010). For inorganic co-ordination polymers containing chloranilic acid, see: Kitagawa et al. (2002). For guanidine and guanidinium structures, see: Abrahams et al. (2004, 2005); Best et al. (2003); Said et al. (2006); Smith & Wermuth (2010, 2011).

Experimental top

Crystals were grown by slow evaporation of a methanol solution under ambient conditions containing a 1:1 stoichiometric quantity of guanidinium carbonate (Aldrich, 98%) and chloranilic acid (Aldrich, 99%).

Structure description top

For organic co-crystals containing 2,5-dihydroxy-3,6-dichloro-1,4-benzoquinone (chloranilic acid), see: Andersen & Andersen (1975); Horiuchi et al. (2005, 2007); Zaman et al. (1999a,b, 2010). For inorganic co-ordination polymers containing chloranilic acid, see: Kitagawa et al. (2002). For guanidine and guanidinium structures, see: Abrahams et al. (2004, 2005); Best et al. (2003); Said et al. (2006); Smith & Wermuth (2010, 2011).

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus (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 and atom naming scheme. Displacement ellipsoids are drawn at the 50% probability level. Grown fragment generated by symmetry codes: (a) - x, 2 - y, - z; (b) 1/2 - x, 2.5 - y, - z.
	Fig. 2. Packing diagram of the hydrogen-bonded framework structure of co-crystals viewed down the b axis, showing hydrogen-bonding associations as thin lines (H atoms are omitted).

Bis(guanidinium) 2,5-dichloro-3,6-dioxocyclohexa-1,4-diene-1,4-bis(olate) top

Crystal data top

2CH₆N₃⁺·C₆Cl₂O₄²⁻	F(000) = 672
M_r = 327.14	D_x = 1.804 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: -C 2yc	Cell parameters from 220 reflections
a = 19.5224 (14) Å	θ = 4.0–29.0°
b = 3.7316 (3) Å	µ = 0.57 mm⁻¹
c = 18.4103 (14) Å	T = 173 K
β = 116.087 (1)°	Block, yellow
V = 1204.56 (16) Å³	0.45 × 0.40 × 0.30 mm
Z = 4

Data collection top

Bruker SMART 1000 CCD diffractometer	1674 independent reflections
Radiation source: fine-focus sealed tube	1525 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ω scans	θ_max = 29.6°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS, Sheldrick, 1996)	h = −27→27
T_min = 0.785, T_max = 0.849	k = −5→5
6965 measured reflections	l = −25→25

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.078	All H-atom parameters refined
S = 1.08	w = 1/[σ²(F_o²) + (0.0494P)² + 0.7637P] where P = (F_o² + 2F_c²)/3
1674 reflections	(Δ/σ)_max < 0.001
116 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

2CH₆N₃⁺·C₆Cl₂O₄²⁻	V = 1204.56 (16) Å³
M_r = 327.14	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 19.5224 (14) Å	µ = 0.57 mm⁻¹
b = 3.7316 (3) Å	T = 173 K
c = 18.4103 (14) Å	0.45 × 0.40 × 0.30 mm
β = 116.087 (1)°

Data collection top

Bruker SMART 1000 CCD diffractometer	1674 independent reflections
Absorption correction: multi-scan (SADABS, Sheldrick, 1996)	1525 reflections with I > 2σ(I)
T_min = 0.785, T_max = 0.849	R_int = 0.020
6965 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.078	All H-atom parameters refined
S = 1.08	Δρ_max = 0.47 e Å⁻³
1674 reflections	Δρ_min = −0.25 e Å⁻³
116 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
Cl1	0.036370 (14)	0.71393 (8)	0.174949 (15)	0.01677 (10)
O2	0.14122 (4)	1.0852 (3)	0.12281 (5)	0.01823 (18)
O3	0.11119 (5)	1.3347 (3)	−0.02492 (5)	0.01949 (19)
N1	0.23429 (6)	1.5093 (3)	−0.07912 (6)	0.0213 (2)
H2	0.2183 (11)	1.461 (6)	−0.0438 (12)	0.037 (5)*
H1	0.2810 (10)	1.436 (5)	−0.0711 (10)	0.028 (4)*
N2	0.11581 (6)	1.7324 (3)	−0.16016 (7)	0.0201 (2)
H4	0.0871 (10)	1.852 (5)	−0.1996 (11)	0.024 (4)*
H3	0.1026 (10)	1.648 (5)	−0.1273 (11)	0.030 (5)*
N3	0.21154 (6)	1.7664 (3)	−0.20145 (7)	0.0211 (2)
H6	0.2549 (12)	1.736 (5)	−0.1912 (12)	0.034 (5)*
H5	0.1782 (11)	1.824 (6)	−0.2505 (13)	0.039 (5)*
C1	0.01581 (6)	0.8726 (3)	0.07862 (6)	0.0143 (2)
C2	0.07504 (6)	1.0395 (3)	0.06811 (6)	0.0140 (2)
C3	0.05815 (6)	1.1811 (3)	−0.01681 (6)	0.0139 (2)
C4	0.18720 (6)	1.6695 (3)	−0.14746 (7)	0.0154 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.01745 (15)	0.02061 (16)	0.01101 (15)	−0.00081 (9)	0.00514 (11)	0.00188 (9)
O2	0.0120 (3)	0.0267 (4)	0.0132 (4)	−0.0009 (3)	0.0030 (3)	0.0000 (3)
O3	0.0147 (4)	0.0274 (5)	0.0165 (4)	−0.0040 (3)	0.0069 (3)	0.0016 (3)
N1	0.0181 (5)	0.0293 (5)	0.0165 (5)	0.0044 (4)	0.0077 (4)	0.0056 (4)
N2	0.0150 (4)	0.0270 (5)	0.0191 (5)	0.0023 (4)	0.0082 (4)	0.0045 (4)
N3	0.0154 (5)	0.0326 (6)	0.0154 (5)	0.0012 (4)	0.0069 (4)	0.0049 (4)
C1	0.0139 (4)	0.0182 (5)	0.0099 (4)	−0.0003 (4)	0.0043 (4)	0.0014 (4)
C2	0.0133 (4)	0.0161 (5)	0.0119 (4)	0.0007 (4)	0.0051 (4)	−0.0008 (4)
C3	0.0129 (5)	0.0166 (5)	0.0120 (5)	0.0004 (4)	0.0053 (4)	0.0000 (4)
C4	0.0142 (5)	0.0168 (5)	0.0142 (5)	−0.0013 (4)	0.0052 (4)	−0.0015 (4)

Geometric parameters (Å, º) top

Cl1—C1	1.7409 (11)	N2—H3	0.818 (19)
O2—C2	1.2522 (13)	N3—C4	1.3267 (15)
O3—C3	1.2487 (13)	N3—H6	0.79 (2)
N1—C4	1.3297 (15)	N3—H5	0.88 (2)
N1—H2	0.85 (2)	C1—C2	1.3997 (14)
N1—H1	0.901 (17)	C1—C3ⁱ	1.4051 (14)
N2—C4	1.3287 (14)	C2—C3	1.5423 (15)
N2—H4	0.827 (18)	C3—C1ⁱ	1.4052 (14)

C4—N1—H2	118.9 (13)	C3ⁱ—C1—Cl1	118.10 (8)
C4—N1—H1	121.3 (11)	O2—C2—C1	124.91 (10)
H2—N1—H1	119.6 (17)	O2—C2—C3	116.98 (9)
C4—N2—H4	120.2 (12)	C1—C2—C3	118.10 (9)
C4—N2—H3	116.7 (13)	O3—C3—C1ⁱ	125.41 (10)
H4—N2—H3	123.1 (17)	O3—C3—C2	117.36 (9)
C4—N3—H6	118.7 (14)	C1ⁱ—C3—C2	117.23 (9)
C4—N3—H5	119.3 (13)	N3—C4—N2	120.90 (11)
H6—N3—H5	121.0 (18)	N3—C4—N1	120.33 (11)
C2—C1—C3ⁱ	124.66 (10)	N2—C4—N1	118.76 (11)
C2—C1—Cl1	117.24 (8)

Symmetry code: (i) −x, −y+2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H2···O3	0.85 (2)	2.32 (2)	3.0504 (13)	144.4 (16)
N1—H1···O2ⁱⁱ	0.901 (17)	2.117 (17)	2.8978 (13)	144.4 (15)
N1—H1···O3ⁱⁱ	0.901 (17)	2.303 (18)	3.0555 (13)	140.9 (15)
N2—H3···O3	0.818 (19)	2.161 (19)	2.9337 (14)	157.7 (17)
N3—H6···O2ⁱⁱ	0.79 (2)	2.21 (2)	2.9016 (14)	146.3 (18)
N3—H5···O2ⁱⁱⁱ	0.88 (2)	2.14 (2)	2.9586 (13)	154.4 (17)

Symmetry codes: (ii) −x+1/2, −y+5/2, −z; (iii) x, −y+3, z−1/2.

Experimental details

Crystal data
Chemical formula	2CH₆N₃⁺·C₆Cl₂O₄²⁻
M_r	327.14
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	173
a, b, c (Å)	19.5224 (14), 3.7316 (3), 18.4103 (14)
β (°)	116.087 (1)
V (Å³)	1204.56 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.57
Crystal size (mm)	0.45 × 0.40 × 0.30

Data collection
Diffractometer	Bruker SMART 1000 CCD
Absorption correction	Multi-scan (SADABS, Sheldrick, 1996)
T_min, T_max	0.785, 0.849
No. of measured, independent and observed [I > 2σ(I)] reflections	6965, 1674, 1525
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.695

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.078, 1.08
No. of reflections	1674
No. of parameters	116
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.25

Computer programs: SMART (Bruker, 2003), SAINT-Plus (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
N1—H2···O3	0.85 (2)	2.32 (2)	3.0504 (13)	144.4 (16)
N1—H1···O2ⁱ	0.901 (17)	2.117 (17)	2.8978 (13)	144.4 (15)
N1—H1···O3ⁱ	0.901 (17)	2.303 (18)	3.0555 (13)	140.9 (15)
N2—H3···O3	0.818 (19)	2.161 (19)	2.9337 (14)	157.7 (17)
N3—H6···O2ⁱ	0.79 (2)	2.21 (2)	2.9016 (14)	146.3 (18)
N3—H5···O2ⁱⁱ	0.88 (2)	2.14 (2)	2.9586 (13)	154.4 (17)

Symmetry codes: (i) −x+1/2, −y+5/2, −z; (ii) x, −y+3, z−1/2.

References

Abrahams, B. E., Haywood, M. G., Hudson, T. A. & Robson, R. (2004). Angew. Chem. Int. Ed. 43, 6157–6160. Web of Science CSD CrossRef CAS Google Scholar
Abrahams, B. F., Haywood, M. G. & Robson, R. (2005). J. Am. Chem. Soc. 127, 816–817. Web of Science CSD CrossRef PubMed CAS Google Scholar
Andersen, E. K. & Andersen, I. G. K. (1975). Acta Cryst. B31, 379–383. CSD CrossRef IUCr Journals Web of Science Google Scholar
Best, M. D., Tobey, S. L. & Anslyn, E. V. (2003). Coord. Chem. Rev. 240, 3–15. Web of Science CrossRef CAS Google Scholar
Bruker (2003). SMART and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dowty, E. (1999). ATOMS. Shape Software, Kingsport, Tennessee, USA. Google Scholar
Horiuchi, S., Ishii, F., Kumai, R., Okimoto, Y., Tachibana, H., Nagaosa, N. & Tokura, Y. (2005). Nat. Mater. 4, 163–166. Web of Science CrossRef PubMed CAS Google Scholar
Horiuchi, S., Kumaia, R. & Tokura, Y. (2007). Chem. Commun. pp. 2321–2329. Web of Science CrossRef Google Scholar
Kitagawa, S. & Kawata, S. (2002). Coord. Chem. Rev. 224, 11–34 Web of Science CrossRef CAS Google Scholar
Said, F. F., Ong, T.-G., Bazinet, P., Yap, G. P. A. & Richeson, D. S. (2006). Cryst. Growth Des. 6, 1848–1857. Web of Science CSD CrossRef CAS 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
Smith, G. & Wermuth, U. D. (2010). Acta Cryst. C66, o575–o580. Web of Science CSD CrossRef IUCr Journals Google Scholar
Smith, G. & Wermuth, U. D. (2011). Acta Cryst. E67, o1645. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zaman, M. B. & Ripmeester, J. A. (2010). Supramol. Chem. 22, 582–585. Web of Science CrossRef CAS Google Scholar
Zaman, M. B., Tomura, M. & Yamashita, Y. (1999a). Chem. Commun. pp. 999–1000. Web of Science CSD CrossRef Google Scholar
Zaman, M. B., Tomura, M., Yamashita, Y., Sayaduzzaman, M. & Chowdhury, A. M. S. (1999b). CrystEngComm, 1, 36–38. Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 10| October 2011| Page o2625

https://doi.org/10.1107/S1600536811036373

Open

access