



Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536811028340/gk2374sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536811028340/gk2374Isup2.hkl |
![]() | Chemical Markup Language (CML) file https://doi.org/10.1107/S1600536811028340/gk2374Isup3.cml |
CCDC reference: 845339
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean
(C-C) = 0.003 Å
- R factor = 0.044
- wR factor = 0.131
- Data-to-parameter ratio = 13.7
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings Differ ? PLAT480_ALERT_4_C Long H...A H-Bond Reported H1 .. N2 .. 2.64 Ang. PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 5
Alert level G PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite 11 PLAT003_ALERT_2_G Number of Uiso or Uij Restrained Atom Sites .... 11 PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF .... ? PLAT333_ALERT_2_G Check Large Av C6-Ring C-C Dist. C1 -C3_a 1.46 Ang. PLAT371_ALERT_2_G Long C(sp2)-C(sp1) Bond C3 - C4 ... 1.43 Ang. PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 61
0 ALERT level A = Most likely a serious problem - resolve or explain 0 ALERT level B = A potentially serious problem, consider carefully 3 ALERT level C = Check. Ensure it is not caused by an omission or oversight 6 ALERT level G = General information/check it is not something unexpected 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 4 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
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.
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'.
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).
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 |
Bruker SMART 1000 CCD diffractometer | 1704 independent reflections |
Radiation source: fine-focus sealed tube | 1379 reflections with I > 2σ(I) |
Graphite monochromator | 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 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 |
2CH6N3+·C8N2O42− | V = 1330.7 (2) Å3 |
Mr = 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)° |
Bruker SMART 1000 CCD diffractometer | 1704 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1379 reflections with I > 2σ(I) |
Tmin = 0.958, Tmax = 0.976 | Rint = 0.026 |
7261 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 61 restraints |
wR(F2) = 0.131 | All H-atom parameters refined |
S = 1.08 | Δρmax = 0.44 e Å−3 |
1704 reflections | Δρmin = −0.42 e Å−3 |
124 parameters |
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 | 0.30409 (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)* |
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) |
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. |
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− |
Mr | 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) |
Tmin, Tmax | 0.958, 0.976 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7261, 1704, 1379 |
Rint | 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 |
Δρmax, Δρmin (e Å−3) | 0.44, −0.42 |
Computer programs: SMART (Bruker 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ATOMS (Dowty, 1999).
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. |
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).