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In the title compound, C18H16N4O, the dihedral angle between the N3C2 ring and the central benzene ring is 12.62 (9)°. The dihedral angle between the central and terminal benzene rings is 36.14 (9)°. In the crystal structure, mol­ecules inter­act via N—H...N hydrogen bonds, resulting in infinite chains. There is also an intramolecular N—H...O hydrogen bond.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025986/hb2428sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025986/hb2428Isup2.hkl
Contains datablock I

CCDC reference: 652071

Key indicators

  • Single-crystal X-ray study
  • T = 294 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.044
  • wR factor = 0.106
  • Data-to-parameter ratio = 14.4

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT230_ALERT_2_C Hirshfeld Test Diff for C5 - C6 .. 5.27 su
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 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 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

Heterocyclic ketene aminals, also named cyclic 1,1-enediamines, are useful building blocks in organic synthesis, especially for the synthesis of more complex heterocycles (Huang & Wang, 1994). The title compound, (I) (Fig. 1), belongs to the family of 1, 2,3-triazole fused 1,3-diazoheterocles and its structure is described here.

The dihedral angle between the N3C2 ring and the C7—C12 benzene ring is 12.62 (9)°. The dihedral angle between the two bezene rings (C7—C12 and C13—C18) is 36.14 (9)°.

In the crystal, adjacent molecules interact by way of N—H···N hydrogen bonds (Table 1) to result in [100] chains. An intramolecular N—H···O link occurs at the same time.

Related literature top

For background, see: Huang & Wang, 1992; Huang & Wang, 1994.

Experimental top

The title compound was prepared according to the procedure reported by Huang & Wang (1992) and purified by recrystallization from ethyl acetate in 82.7% yield; mp 438–440 K; FT—IR (KBr): 3369.03, 1636.30, 1588.09, 1526.38, 1428.03 cm-1.1H NMR (CDCl3, δp.p.m.): 8.60–8.57 (d, 2H, aryl H), 7.74–7.71 (d, 2H, aryl H), 7.67–7.65 (d, 2H, aryl H), 7.49–7.44(t, 2H, aryl H), 7.41–7.36 (t, 1H, aryl H), 6.73 (s, 1H, NH), 4.41–4.36 (t, 2H, CH2); 3.56–3.51 (m, 2H, CH2), 2.25–2.18 (m, 2H, CH2); 13C NMR (CDCl3, δp.p.m.): 185.18, 146.12, 144.95, 140.35, 136.02, 130.60, 128.90, 128.74, 127.98, 127.33, 126.95, 43.23, 38.66, 20.60; MS (EI) m/z: 305([M+H]+), 304 ([M]+). Anal. Calcd. For C18H16N4O: C, 71.04; H, 5.30; N, 18.41. Found: C, 70.53; H, 5.23; N, 21.18.50.

Refinement top

The N-bound hydrogen atom was located in a difference map and its position and Uiso value were freely refined. The C-bound H atoms were geometrically placed (C—H = 0.95–1.00 Å) and refined as riding with Uiso(H) = 1.2Ueq(C).

Structure description top

Heterocyclic ketene aminals, also named cyclic 1,1-enediamines, are useful building blocks in organic synthesis, especially for the synthesis of more complex heterocycles (Huang & Wang, 1994). The title compound, (I) (Fig. 1), belongs to the family of 1, 2,3-triazole fused 1,3-diazoheterocles and its structure is described here.

The dihedral angle between the N3C2 ring and the C7—C12 benzene ring is 12.62 (9)°. The dihedral angle between the two bezene rings (C7—C12 and C13—C18) is 36.14 (9)°.

In the crystal, adjacent molecules interact by way of N—H···N hydrogen bonds (Table 1) to result in [100] chains. An intramolecular N—H···O link occurs at the same time.

For background, see: Huang & Wang, 1992; Huang & Wang, 1994.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. Molecular structure of (I) showing 30% displacement ellipsoids (arbirary spheres for the H atoms).
[Figure 2] Fig. 2. Packing diagram of (I) viewed down the a-axis.
3-(4-Phenylbenzoyl)-4,5,6,7-tetrahydro-1,2,3-triazolo[1,5-a]pyrimidine top
Crystal data top
C18H16N4ODx = 1.345 Mg m3
Mr = 304.35Melting point = 438–440 K
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
a = 12.923 (3) ÅCell parameters from 2403 reflections
b = 7.3253 (17) Åθ = 3.2–21.2°
c = 31.765 (7) ŵ = 0.09 mm1
V = 3007.0 (12) Å3T = 294 K
Z = 8Prism, colourless
F(000) = 12800.24 × 0.20 × 0.14 mm
Data collection top
Bruker SMART CCD
diffractometer
3066 independent reflections
Radiation source: fine-focus sealed tube1804 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.074
ω scansθmax = 26.4°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
h = 1616
Tmin = 0.979, Tmax = 0.988k = 99
16020 measured reflectionsl = 2639
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.106 w = 1/[σ2(Fo2) + (0.0465P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.001
3066 reflectionsΔρmax = 0.17 e Å3
213 parametersΔρmin = 0.13 e Å3
1 restraintExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0087 (8)
Crystal data top
C18H16N4OV = 3007.0 (12) Å3
Mr = 304.35Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 12.923 (3) ŵ = 0.09 mm1
b = 7.3253 (17) ÅT = 294 K
c = 31.765 (7) Å0.24 × 0.20 × 0.14 mm
Data collection top
Bruker SMART CCD
diffractometer
3066 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
1804 reflections with I > 2σ(I)
Tmin = 0.979, Tmax = 0.988Rint = 0.074
16020 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0441 restraint
wR(F2) = 0.106H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.17 e Å3
3066 reflectionsΔρmin = 0.13 e Å3
213 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
xyzUiso*/Ueq
O10.27429 (9)0.3111 (2)0.43106 (4)0.0629 (4)
N10.20844 (11)0.2160 (2)0.51324 (5)0.0447 (4)
H10.2688 (9)0.216 (3)0.4990 (5)0.064 (6)*
N20.02806 (9)0.23953 (18)0.50904 (4)0.0361 (4)
N30.04815 (10)0.2859 (2)0.48069 (5)0.0441 (4)
N40.00221 (10)0.3245 (2)0.44527 (5)0.0412 (4)
C10.20019 (13)0.1494 (3)0.55610 (5)0.0438 (5)
H1A0.26270.17910.57150.053*
H1B0.19230.01770.55600.053*
C20.10745 (12)0.2368 (3)0.57734 (5)0.0422 (5)
H2A0.11790.36770.57910.051*
H2B0.10100.18990.60580.051*
C30.00857 (12)0.1979 (2)0.55315 (5)0.0414 (5)
H3A0.01080.07070.55630.050*
H3B0.04740.27310.56380.050*
C40.12182 (11)0.2518 (2)0.49126 (5)0.0348 (4)
C50.10309 (12)0.3075 (2)0.45001 (5)0.0347 (4)
C60.18455 (13)0.3375 (2)0.41932 (5)0.0401 (5)
C70.16573 (13)0.3949 (2)0.37498 (5)0.0364 (4)
C80.24826 (13)0.3823 (3)0.34710 (6)0.0474 (5)
H80.31190.34040.35680.057*
C90.23771 (14)0.4304 (3)0.30551 (6)0.0496 (5)
H90.29440.42030.28760.059*
C100.14424 (13)0.4939 (2)0.28949 (6)0.0401 (5)
C110.06187 (13)0.5085 (2)0.31750 (6)0.0444 (5)
H110.00150.55170.30790.053*
C120.07241 (13)0.4601 (3)0.35947 (5)0.0421 (5)
H120.01610.47150.37750.050*
C130.13337 (14)0.5414 (2)0.24429 (6)0.0431 (5)
C140.21450 (16)0.6219 (3)0.22220 (6)0.0561 (6)
H140.27650.64620.23600.067*
C150.20419 (19)0.6662 (3)0.18004 (7)0.0658 (6)
H150.25920.71980.16570.079*
C160.11331 (19)0.6316 (3)0.15926 (7)0.0665 (6)
H160.10610.66300.13100.080*
C170.03321 (18)0.5504 (3)0.18044 (7)0.0697 (7)
H170.02830.52510.16640.084*
C180.04299 (16)0.5058 (3)0.22242 (6)0.0578 (6)
H180.01220.45080.23630.069*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0297 (8)0.1105 (13)0.0485 (8)0.0093 (7)0.0012 (6)0.0123 (8)
N10.0269 (8)0.0697 (11)0.0377 (9)0.0051 (7)0.0009 (7)0.0067 (8)
N20.0246 (8)0.0471 (9)0.0367 (8)0.0010 (6)0.0008 (6)0.0018 (7)
N30.0288 (8)0.0592 (10)0.0441 (9)0.0002 (7)0.0015 (7)0.0047 (8)
N40.0298 (8)0.0524 (9)0.0414 (9)0.0004 (7)0.0001 (7)0.0032 (8)
C10.0391 (11)0.0499 (11)0.0425 (11)0.0044 (9)0.0029 (9)0.0072 (9)
C20.0391 (11)0.0497 (11)0.0380 (11)0.0010 (9)0.0003 (8)0.0060 (9)
C30.0345 (10)0.0491 (11)0.0407 (11)0.0023 (8)0.0079 (9)0.0042 (9)
C40.0262 (9)0.0401 (10)0.0382 (10)0.0004 (8)0.0002 (8)0.0018 (9)
C50.0268 (10)0.0415 (10)0.0357 (10)0.0021 (7)0.0003 (8)0.0012 (9)
C60.0306 (10)0.0490 (11)0.0408 (11)0.0033 (8)0.0022 (8)0.0024 (9)
C70.0313 (10)0.0403 (10)0.0376 (10)0.0000 (8)0.0003 (8)0.0013 (8)
C80.0342 (10)0.0647 (13)0.0433 (12)0.0079 (9)0.0035 (9)0.0033 (10)
C90.0417 (11)0.0667 (14)0.0402 (12)0.0065 (10)0.0114 (9)0.0015 (10)
C100.0404 (11)0.0403 (11)0.0395 (11)0.0009 (8)0.0013 (9)0.0023 (9)
C110.0364 (11)0.0568 (13)0.0399 (11)0.0057 (9)0.0043 (9)0.0021 (10)
C120.0337 (10)0.0547 (12)0.0379 (11)0.0031 (9)0.0047 (8)0.0005 (9)
C130.0505 (12)0.0409 (10)0.0378 (11)0.0021 (9)0.0016 (9)0.0019 (9)
C140.0590 (13)0.0658 (14)0.0436 (13)0.0082 (11)0.0040 (10)0.0016 (11)
C150.0825 (17)0.0672 (15)0.0479 (14)0.0052 (12)0.0184 (12)0.0065 (12)
C160.0975 (19)0.0633 (15)0.0388 (13)0.0091 (13)0.0009 (13)0.0025 (11)
C170.0766 (17)0.0841 (17)0.0485 (15)0.0029 (14)0.0138 (12)0.0020 (13)
C180.0586 (14)0.0693 (15)0.0457 (13)0.0078 (11)0.0065 (10)0.0068 (11)
Geometric parameters (Å, º) top
O1—C61.2333 (19)C7—C81.389 (2)
N1—C41.345 (2)C8—C91.374 (2)
N1—C11.450 (2)C8—H80.9300
N1—H10.901 (9)C9—C101.391 (2)
N2—C41.3398 (18)C9—H90.9300
N2—N31.3772 (18)C10—C111.391 (2)
N2—C31.456 (2)C10—C131.484 (2)
N3—N41.3032 (19)C11—C121.386 (2)
N4—C51.3748 (19)C11—H110.9300
C1—C21.517 (2)C12—H120.9300
C1—H1A0.9700C13—C181.384 (2)
C1—H1B0.9700C13—C141.392 (2)
C2—C31.518 (2)C14—C151.384 (3)
C2—H2A0.9700C14—H140.9300
C2—H2B0.9700C15—C161.371 (3)
C3—H3A0.9700C15—H150.9300
C3—H3B0.9700C16—C171.370 (3)
C4—C51.394 (2)C16—H160.9300
C5—C61.452 (2)C17—C181.379 (3)
C6—C71.490 (2)C17—H170.9300
C7—C121.387 (2)C18—H180.9300
C4—N1—C1119.45 (14)C12—C7—C6125.08 (15)
C4—N1—H1117.4 (12)C8—C7—C6117.28 (15)
C1—N1—H1122.2 (12)C9—C8—C7121.30 (17)
C4—N2—N3110.76 (13)C9—C8—H8119.4
C4—N2—C3125.19 (14)C7—C8—H8119.4
N3—N2—C3123.87 (13)C8—C9—C10121.58 (17)
N4—N3—N2107.00 (13)C8—C9—H9119.2
N3—N4—C5109.68 (13)C10—C9—H9119.2
N1—C1—C2109.48 (14)C9—C10—C11117.15 (17)
N1—C1—H1A109.8C9—C10—C13120.98 (17)
C2—C1—H1A109.8C11—C10—C13121.87 (17)
N1—C1—H1B109.8C12—C11—C10121.33 (17)
C2—C1—H1B109.8C12—C11—H11119.3
H1A—C1—H1B108.2C10—C11—H11119.3
C1—C2—C3111.13 (15)C11—C12—C7120.99 (16)
C1—C2—H2A109.4C11—C12—H12119.5
C3—C2—H2A109.4C7—C12—H12119.5
C1—C2—H2B109.4C18—C13—C14117.54 (18)
C3—C2—H2B109.4C18—C13—C10121.41 (17)
H2A—C2—H2B108.0C14—C13—C10121.04 (17)
N2—C3—C2107.59 (13)C15—C14—C13120.9 (2)
N2—C3—H3A110.2C15—C14—H14119.5
C2—C3—H3A110.2C13—C14—H14119.5
N2—C3—H3B110.2C16—C15—C14120.3 (2)
C2—C3—H3B110.2C16—C15—H15119.8
H3A—C3—H3B108.5C14—C15—H15119.8
N2—C4—N1121.38 (15)C17—C16—C15119.4 (2)
N2—C4—C5105.01 (13)C17—C16—H16120.3
N1—C4—C5133.60 (15)C15—C16—H16120.3
N4—C5—C4107.54 (14)C16—C17—C18120.6 (2)
N4—C5—C6129.10 (15)C16—C17—H17119.7
C4—C5—C6123.35 (14)C18—C17—H17119.7
O1—C6—C5117.08 (16)C17—C18—C13121.2 (2)
O1—C6—C7118.91 (15)C17—C18—H18119.4
C5—C6—C7124.00 (15)C13—C18—H18119.4
C12—C7—C8117.64 (16)
C4—N2—N3—N40.80 (19)C5—C6—C7—C1212.9 (3)
C3—N2—N3—N4176.12 (15)O1—C6—C7—C811.9 (3)
N2—N3—N4—C51.06 (18)C5—C6—C7—C8167.19 (16)
C4—N1—C1—C235.0 (2)C12—C7—C8—C90.8 (3)
N1—C1—C2—C357.67 (19)C6—C7—C8—C9179.30 (17)
C4—N2—C3—C219.5 (2)C7—C8—C9—C100.0 (3)
N3—N2—C3—C2155.16 (15)C8—C9—C10—C110.7 (3)
C1—C2—C3—N248.84 (19)C8—C9—C10—C13178.63 (18)
N3—N2—C4—N1178.77 (15)C9—C10—C11—C120.6 (3)
C3—N2—C4—N13.5 (3)C13—C10—C11—C12178.66 (17)
N3—N2—C4—C50.22 (18)C10—C11—C12—C70.1 (3)
C3—N2—C4—C5175.46 (15)C8—C7—C12—C110.8 (3)
C1—N1—C4—N24.8 (3)C6—C7—C12—C11179.28 (17)
C1—N1—C4—C5176.54 (18)C9—C10—C13—C18143.17 (19)
N3—N4—C5—C40.94 (19)C11—C10—C13—C1836.1 (3)
N3—N4—C5—C6179.67 (17)C9—C10—C13—C1436.1 (3)
N2—C4—C5—N40.42 (18)C11—C10—C13—C14144.62 (19)
N1—C4—C5—N4179.23 (18)C18—C13—C14—C150.7 (3)
N2—C4—C5—C6179.84 (15)C10—C13—C14—C15179.97 (18)
N1—C4—C5—C61.3 (3)C13—C14—C15—C160.1 (3)
N4—C5—C6—O1179.20 (16)C14—C15—C16—C170.9 (3)
C4—C5—C6—O10.1 (3)C15—C16—C17—C180.9 (3)
N4—C5—C6—C70.1 (3)C16—C17—C18—C130.0 (3)
C4—C5—C6—C7179.24 (16)C14—C13—C18—C170.8 (3)
O1—C6—C7—C12167.97 (17)C10—C13—C18—C17179.95 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.90 (1)2.27 (2)2.833 (2)120 (1)
N1—H1···N3i0.90 (1)2.45 (1)3.152 (2)135 (1)
Symmetry code: (i) x+1/2, y+1/2, z+1.

Experimental details

Crystal data
Chemical formulaC18H16N4O
Mr304.35
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)294
a, b, c (Å)12.923 (3), 7.3253 (17), 31.765 (7)
V3)3007.0 (12)
Z8
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.24 × 0.20 × 0.14
Data collection
DiffractometerBruker SMART CCD
Absorption correctionMulti-scan
(SADABS; Bruker, 1997)
Tmin, Tmax0.979, 0.988
No. of measured, independent and
observed [I > 2σ(I)] reflections
16020, 3066, 1804
Rint0.074
(sin θ/λ)max1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.106, 1.03
No. of reflections3066
No. of parameters213
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.17, 0.13

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.902 (13)2.269 (17)2.833 (2)120.3 (12)
N1—H1···N3i0.902 (13)2.452 (12)3.152 (2)134.6 (13)
Symmetry code: (i) x+1/2, y+1/2, z+1.
 

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