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The title compound, C4H3N3, was synthesized in three steps from di­amino­maleo­nitrile in an overall yield of 38%. Single-crystal X-ray analysis reveals that the compound crystallizes exclusively as the 1H-imidazole-4-carbo­nitrile isomer. This heterocycle forms a non-centrosymmetric crystal structure and packs with an appreciable dipole moment, making it a good candidate for non-linear optical applications.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805014509/gh6011sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805014509/gh6011Isup2.hkl
Contains datablock I

CCDC reference: 274398

Key indicators

  • Single-crystal X-ray study
  • T = 158 K
  • Mean [sigma](C-C) = 0.001 Å
  • R factor = 0.032
  • wR factor = 0.079
  • Data-to-parameter ratio = 13.3

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT230_ALERT_2_B Hirshfeld Test Diff for C1 - C2 .. 7.83 su
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97 PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 1.01 PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.10 PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C1 - C2 ... 1.42 Ang. PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 3 N1 -C1 -C2 -C3 156.00 19.00 1.555 1.555 1.555 1.555 PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 4 N1 -C1 -C2 -N3 -23.00 19.00 1.555 1.555 1.555 1.555
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 36.31 From the CIF: _reflns_number_total 1011 Count of symmetry unique reflns 1041 Completeness (_total/calc) 97.12% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present no
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 6 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 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 4 ALERT type 4 Improvement, methodology, query or suggestion

Computing details top

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.

1H-Imidazole-4-carbonitrile top
Crystal data top
C4H3N3F(000) = 96
Mr = 93.09Dx = 1.440 Mg m3
Monoclinic, PcMo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2ycCell parameters from 5074 reflections
a = 5.7230 (13) Åθ = 4.0–36.3°
b = 3.6965 (9) ŵ = 0.10 mm1
c = 10.244 (2) ÅT = 158 K
β = 97.689 (7)°Needle, colorless
V = 214.76 (8) Å30.50 × 0.10 × 0.10 mm
Z = 2
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer
1011 independent reflections
Radiation source: sealed tube977 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.039
φ and ω scansθmax = 36.3°, θmin = 4.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 99
Tmin = 0.952, Tmax = 0.98k = 66
9453 measured reflectionsl = 1717
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032All 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 reflectionsΔρmax = 0.39 e Å3
76 parametersΔρmin = 0.19 e Å3
2 restraintsAbsolute structure: merged for light atom structure, Mo radiation
Primary atom site location: structure-invariant direct methods
Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.34806 (16)0.4084 (3)0.80576 (10)0.02359 (18)
N20.90835 (15)0.0054 (2)1.15348 (8)0.01802 (15)
H20.970 (7)0.033 (8)1.230 (2)0.067 (8)*
N30.88969 (13)0.0210 (2)0.93560 (8)0.01742 (15)
C10.49911 (15)0.2985 (2)0.88149 (9)0.01763 (16)
C20.68577 (14)0.1638 (2)0.97403 (8)0.01497 (14)
C30.69551 (16)0.1552 (2)1.10900 (9)0.01745 (16)
H30.596 (4)0.222 (5)1.161 (2)0.030 (5)*
C41.01795 (15)0.0715 (3)1.04734 (9)0.01856 (16)
H41.172 (4)0.185 (5)1.049 (2)0.030 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0211 (4)0.0285 (4)0.0202 (4)0.0012 (3)0.0006 (3)0.0042 (3)
N20.0211 (3)0.0229 (3)0.0095 (3)0.0019 (2)0.0002 (2)0.0009 (2)
N30.0170 (3)0.0244 (3)0.0111 (3)0.0002 (2)0.0026 (2)0.0003 (3)
C10.0189 (3)0.0203 (3)0.0138 (3)0.0017 (3)0.0024 (2)0.0011 (3)
C20.0163 (3)0.0182 (3)0.0103 (3)0.0012 (2)0.0016 (2)0.0004 (3)
C30.0212 (4)0.0210 (3)0.0106 (3)0.0011 (3)0.0036 (2)0.0005 (3)
C40.0170 (3)0.0250 (4)0.0133 (3)0.0004 (3)0.0010 (2)0.0010 (3)
Geometric parameters (Å, º) top
N1—C11.1553 (13)N3—C21.3852 (12)
N2—C41.3561 (13)C1—C21.4201 (12)
N2—C31.3600 (14)C2—C31.3768 (12)
N2—H20.828 (19)C3—H30.86 (2)
N3—C41.3196 (12)C4—H40.97 (3)
C4—N2—C3107.84 (8)N3—C2—C1122.08 (8)
C4—N2—H2123 (3)N2—C3—C2105.07 (8)
C3—N2—H2129 (3)N2—C3—H3123.1 (15)
C4—N3—C2104.14 (8)C2—C3—H3131.9 (15)
N1—C1—C2179.65 (10)N3—C4—N2112.21 (9)
C3—C2—N3110.74 (8)N3—C4—H4121.9 (14)
C3—C2—C1127.18 (8)N2—C4—H4125.9 (14)
C4—N3—C2—C30.12 (10)N3—C2—C3—N20.06 (10)
C4—N3—C2—C1179.76 (8)C1—C2—C3—N2179.56 (9)
N1—C1—C2—C3156 (19)C2—N3—C4—N20.27 (11)
N1—C1—C2—N323 (19)C3—N2—C4—N30.31 (11)
C4—N2—C3—C20.22 (10)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···N3i0.83 (2)2.21 (3)2.9080 (12)142 (4)
Symmetry code: (i) x, y, z+1/2.
 

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