Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805014509/gh6011sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805014509/gh6011Isup2.hkl |
CCDC reference: 274398
Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C4H3N3 | F(000) = 96 |
Mr = 93.09 | Dx = 1.440 Mg m−3 |
Monoclinic, Pc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P -2yc | Cell parameters from 5074 reflections |
a = 5.7230 (13) Å | θ = 4.0–36.3° |
b = 3.6965 (9) Å | µ = 0.10 mm−1 |
c = 10.244 (2) Å | T = 158 K |
β = 97.689 (7)° | Needle, colorless |
V = 214.76 (8) Å3 | 0.50 × 0.10 × 0.10 mm |
Z = 2 |
Bruker SMART 1K CCD area-detector diffractometer | 1011 independent reflections |
Radiation source: sealed tube | 977 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
φ and ω scans | θmax = 36.3°, θmin = 4.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −9→9 |
Tmin = 0.952, Tmax = 0.98 | k = −6→6 |
9453 measured reflections | l = −17→17 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.032 | All H-atom parameters refined |
wR(F2) = 0.079 | w = 1/[σ2(Fo2) + (0.0589P)2 + 0.0007P] where P = (Fo2 + 2Fc2)/3 |
S = 1.13 | (Δ/σ)max < 0.001 |
1011 reflections | Δρmax = 0.39 e Å−3 |
76 parameters | Δρmin = −0.19 e Å−3 |
2 restraints | Absolute structure: merged for light atom structure, Mo radiation |
Primary atom site location: structure-invariant direct methods |
Experimental. A 1000 ml round bottom flask was charged with 30.012 g of diaminomaleonitrile, DAMN (278 mmol), and 510 ml of mixed xylenes. The flask was fitted with a reflux condenser and a magnetic stir bar and set to stirring. To the suspension of DAMN was added 24.0 ml of 97% formic acid. The reaction was allowed to stir at room temperature for 0.5 h before being heated to reflux. The reaction was maintained at reflux temperature for 7.5 h, during which time the xylenes solution became yellow-green and a black tarry residue formed on the walls of the flask. Once cooled to room temperature, the xylenes were decanted off and discarded. The tarry residue was dried in vacuo and then extracted via Soxhlet extractor using a standard cellulose thimble and water. Removal of the solvent by rotary evaporator, followed by 24 h in vacuo yields the product as an orange powder in 55% yield. FW (calc) 136.11 g/mol; m.p. 277–279° C (273° C, lit.); 1H NMR (300 MHz; DMSO-d6) ? (p.p.m.) 8.02 (s, 1H, CH), 7.74 (s, 1H, NH2), 7.70 (s, 1H, NH2); IR (KBr pellet, cm-1) 3387, 3216, 2241, 1674. A 1000 ml round bottom flask equipped with a magnetic stir bar was charged with 45.322 g. of 4-cyano-5-imidazole carboxamide (330 mmol) and 450 ml of 10% HCl in water. The suspension was stirred at reflux for 22 h during which a black solution had formed. The solution was diluted with 500 ml of ice water and then suction filtered into an iced flask. Upon standing, a white precipitate formed. The solid was collected by gravity filtration and dried en vacuo to give a 67% yield. FW (calc) 137.10 g/mol; m.p. 229–234° C (230° C, lit.); 1H NMR (300 MHz; DMSO-d6) ? (p.p.m.) 8.04 (s, 1H, CH); IR (KBr pellet, cm-1) 3370, 3120, 3000–2400 hydrogen bonding complexity, 2245, 1697. A 50 ml round bottom flask equipped with a magnetic stir bar was charged with 2.622 g of 4-cyano-5-imidazole carboxylic acid (28 mmol) and 35 ml of nitrobenzene. The solution was stirred at reflux for 20 h. The resultant green solution was chilled and hexanes added until a precipitate formed. The precipitate was collected by vacuum filtration and dried en vacuo to give a 71% yield.9 FW (calc) 93.09 g/mol; m.p. 140° C (143.5–144.5° C, lit.); 1H NMR (300 MHz; DMSO-d6) ? (p.p.m.) 8.09 (s, 1H, CH), 7.89 (s, 1H, CH); IR (KBr pellet, cm-1) 3147, 2230, 1406, 618. Highly redundant full sphere of 6060 frames x 45 sec. @ 4.959 cm; 0.3 °. steps in omega & phi |
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. None |
x | y | z | Uiso*/Ueq | ||
N1 | 0.34806 (16) | 0.4084 (3) | 0.80576 (10) | 0.02359 (18) | |
N2 | 0.90835 (15) | 0.0054 (2) | 1.15348 (8) | 0.01802 (15) | |
H2 | 0.970 (7) | −0.033 (8) | 1.230 (2) | 0.067 (8)* | |
N3 | 0.88969 (13) | 0.0210 (2) | 0.93560 (8) | 0.01742 (15) | |
C1 | 0.49911 (15) | 0.2985 (2) | 0.88149 (9) | 0.01763 (16) | |
C2 | 0.68577 (14) | 0.1638 (2) | 0.97403 (8) | 0.01497 (14) | |
C3 | 0.69551 (16) | 0.1552 (2) | 1.10900 (9) | 0.01745 (16) | |
H3 | 0.596 (4) | 0.222 (5) | 1.161 (2) | 0.030 (5)* | |
C4 | 1.01795 (15) | −0.0715 (3) | 1.04734 (9) | 0.01856 (16) | |
H4 | 1.172 (4) | −0.185 (5) | 1.049 (2) | 0.030 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0211 (4) | 0.0285 (4) | 0.0202 (4) | −0.0012 (3) | −0.0006 (3) | 0.0042 (3) |
N2 | 0.0211 (3) | 0.0229 (3) | 0.0095 (3) | −0.0019 (2) | −0.0002 (2) | 0.0009 (2) |
N3 | 0.0170 (3) | 0.0244 (3) | 0.0111 (3) | 0.0002 (2) | 0.0026 (2) | 0.0003 (3) |
C1 | 0.0189 (3) | 0.0203 (3) | 0.0138 (3) | −0.0017 (3) | 0.0024 (2) | 0.0011 (3) |
C2 | 0.0163 (3) | 0.0182 (3) | 0.0103 (3) | −0.0012 (2) | 0.0016 (2) | 0.0004 (3) |
C3 | 0.0212 (4) | 0.0210 (3) | 0.0106 (3) | −0.0011 (3) | 0.0036 (2) | −0.0005 (3) |
C4 | 0.0170 (3) | 0.0250 (4) | 0.0133 (3) | −0.0004 (3) | 0.0010 (2) | 0.0010 (3) |
N1—C1 | 1.1553 (13) | N3—C2 | 1.3852 (12) |
N2—C4 | 1.3561 (13) | C1—C2 | 1.4201 (12) |
N2—C3 | 1.3600 (14) | C2—C3 | 1.3768 (12) |
N2—H2 | 0.828 (19) | C3—H3 | 0.86 (2) |
N3—C4 | 1.3196 (12) | C4—H4 | 0.97 (3) |
C4—N2—C3 | 107.84 (8) | N3—C2—C1 | 122.08 (8) |
C4—N2—H2 | 123 (3) | N2—C3—C2 | 105.07 (8) |
C3—N2—H2 | 129 (3) | N2—C3—H3 | 123.1 (15) |
C4—N3—C2 | 104.14 (8) | C2—C3—H3 | 131.9 (15) |
N1—C1—C2 | 179.65 (10) | N3—C4—N2 | 112.21 (9) |
C3—C2—N3 | 110.74 (8) | N3—C4—H4 | 121.9 (14) |
C3—C2—C1 | 127.18 (8) | N2—C4—H4 | 125.9 (14) |
C4—N3—C2—C3 | 0.12 (10) | N3—C2—C3—N2 | 0.06 (10) |
C4—N3—C2—C1 | 179.76 (8) | C1—C2—C3—N2 | −179.56 (9) |
N1—C1—C2—C3 | 156 (19) | C2—N3—C4—N2 | −0.27 (11) |
N1—C1—C2—N3 | −23 (19) | C3—N2—C4—N3 | 0.31 (11) |
C4—N2—C3—C2 | −0.22 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···N3i | 0.83 (2) | 2.21 (3) | 2.9080 (12) | 142 (4) |
Symmetry code: (i) x, −y, z+1/2. |