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In the title compound, C13H14N4O, the dihedral angle between the mean planes of the C2N3 heterocyclic ring and the phenyl ring is 49.51 (9)°.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025998/hb2429sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025998/hb2429Isup2.hkl
Contains datablock I

CCDC reference: 654514

Key indicators

  • Single-crystal X-ray study
  • T = 294 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.041
  • wR factor = 0.116
  • Data-to-parameter ratio = 15.6

checkCIF/PLATON results

No syntax errors found



Alert level C CRYSC01_ALERT_1_C The word below has not been recognised as a standard identifier. very PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ?
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 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 synthons in organic synthesis, especially for the synthesis of heterocycles (Huang & Wang, 1994). The title compound, (I) (Fig. 1), belongs to the family of 1, 2,3-triazole fused 1,3-diazoheterocles. These compounds are potentially useful in developing new pharmaceuticals and agrochemicals. The crystal structure was expected to provide unambiguous evidence for the determination of the chemical structure of the title compound.

In the structure of (I), the six-membered –N1—C2—C3—C4—N2—C5- ring takes on an envelope conformation with C3 in the flap position. The dihedral angle between the mean planes of the C2N3-heterocyclic ring and the pendant benzene ring is 49.51 (9)°.

Related literature top

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

Experimental top

The title compound (I) was prepared according to the procedure reported by Huang & Wang (1992) and purified by recrystallization from ethyl acetate to obtain (I) as very pale green crystals in 75.6% yield; mp 376–377 K; FT—IR (KBr): 3396.03, 1640.16, 1583.27, 1473.35 cm-1. 1H NMR (CDCl3, δp.p.m.): 8.00 (d, 2H, aryl H), 7.45–7.36 (m, 3H, aryl H), 4.24–4.20 (t, 2H, CH2), 3.25–3.23 (t, 2H, CH2), 3.16 (s, 3H, N—CH3), 2.13–2.11 (m, 2H, CH2); 13C NMR (CDCl3, δp.p.m.): 186.52, 145.92, 138.72, 132.11, 130.42, 129.31, 127.99, 49.24, 43.58, 40.53, 20.90; MS (EI) m/z (relative intensity, %): 243(16, [M+H]+), 242(100, [M]+), 213 (82), 186 (28), 185 (44). Anal. Calcd for C13H14N4O: C, 64.45; H, 5.82; N, 23.13. Found: C, 64.33; H, 5.78; N, 23.23.

Refinement top

All H atoms were placed in geometrically idealized positions (C—H = 0.95–1.00 Å) and refined as riding with Uiso(H) = 1.2Ueq(carrier) or Uiso(H) = 1.5Ueq(methyl carrier).

Structure description top

Heterocyclic ketene aminals, also named cyclic 1,1-enediamines, are useful synthons in organic synthesis, especially for the synthesis of heterocycles (Huang & Wang, 1994). The title compound, (I) (Fig. 1), belongs to the family of 1, 2,3-triazole fused 1,3-diazoheterocles. These compounds are potentially useful in developing new pharmaceuticals and agrochemicals. The crystal structure was expected to provide unambiguous evidence for the determination of the chemical structure of the title compound.

In the structure of (I), the six-membered –N1—C2—C3—C4—N2—C5- ring takes on an envelope conformation with C3 in the flap position. The dihedral angle between the mean planes of the C2N3-heterocyclic ring and the pendant benzene ring is 49.51 (9)°.

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 (arbitrary spheres for the H atoms).
[Figure 2] Fig. 2. Packing diagram of (I) viewed down the b-axis.
3-Benzoyl-4-methyl-5,6,7-tetrahydro-1,2,3-triazolo[1,5-a]pyrimidine top
Crystal data top
C13H14N4ODx = 1.274 Mg m3
Mr = 242.28Melting point = 376–377 K
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
a = 14.644 (5) ÅCell parameters from 2603 reflections
b = 7.597 (3) Åθ = 2.8–21.8°
c = 22.711 (8) ŵ = 0.09 mm1
V = 2526.7 (16) Å3T = 294 K
Z = 8Prism, very pale green
F(000) = 10240.22 × 0.20 × 0.10 mm
Data collection top
Bruker SMART CCD
diffractometer
2576 independent reflections
Radiation source: fine-focus sealed tube1602 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.057
ω scansθmax = 26.4°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
h = 1718
Tmin = 0.982, Tmax = 0.992k = 89
13257 measured reflectionsl = 2813
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)] = 0.041H-atom parameters constrained
wR(F2) = 0.116 w = 1/[σ2(Fo2) + (0.0529P)2 + 0.2472P]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max = 0.004
2576 reflectionsΔρmax = 0.15 e Å3
165 parametersΔρmin = 0.17 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0109 (11)
Crystal data top
C13H14N4OV = 2526.7 (16) Å3
Mr = 242.28Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 14.644 (5) ŵ = 0.09 mm1
b = 7.597 (3) ÅT = 294 K
c = 22.711 (8) Å0.22 × 0.20 × 0.10 mm
Data collection top
Bruker SMART CCD
diffractometer
2576 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
1602 reflections with I > 2σ(I)
Tmin = 0.982, Tmax = 0.992Rint = 0.057
13257 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.116H-atom parameters constrained
S = 1.01Δρmax = 0.15 e Å3
2576 reflectionsΔρmin = 0.17 e Å3
165 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
O10.38429 (8)0.38641 (18)0.35194 (6)0.0657 (4)
N10.33793 (9)0.18589 (19)0.47987 (6)0.0504 (4)
N20.48321 (9)0.23988 (18)0.52259 (6)0.0445 (4)
N30.56950 (10)0.2989 (2)0.50826 (7)0.0521 (4)
N40.56915 (9)0.33018 (19)0.45181 (6)0.0484 (4)
C10.29124 (12)0.1074 (3)0.42903 (9)0.0663 (6)
H1A0.29660.18450.39570.099*
H1B0.22790.09030.43830.099*
H1C0.31870.00410.41990.099*
C20.30857 (12)0.1198 (3)0.53793 (9)0.0605 (6)
H2A0.32290.00450.54080.073*
H2B0.24290.13270.54150.073*
C30.35475 (14)0.2177 (3)0.58799 (8)0.0635 (6)
H3A0.33410.17040.62540.076*
H3B0.33810.34120.58650.076*
C40.45787 (13)0.1995 (2)0.58340 (8)0.0559 (5)
H4A0.48770.28050.61020.067*
H4B0.47640.08060.59340.067*
C50.42705 (11)0.2381 (2)0.47487 (7)0.0396 (4)
C60.48354 (11)0.2968 (2)0.42818 (7)0.0402 (4)
C70.46293 (11)0.3477 (2)0.36725 (7)0.0447 (4)
C80.53960 (11)0.3549 (2)0.32287 (7)0.0437 (4)
C90.61735 (12)0.2493 (2)0.32667 (8)0.0519 (5)
H90.62540.17660.35920.062*
C100.68318 (13)0.2516 (3)0.28232 (8)0.0629 (6)
H100.73440.17980.28520.075*
C110.67223 (15)0.3606 (3)0.23396 (9)0.0721 (6)
H110.71620.36290.20440.087*
C120.59586 (17)0.4655 (3)0.23000 (9)0.0830 (7)
H120.58860.53930.19770.100*
C130.52960 (14)0.4623 (3)0.27367 (8)0.0667 (6)
H130.47800.53270.27000.080*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0450 (8)0.0844 (10)0.0677 (9)0.0147 (7)0.0028 (6)0.0087 (7)
N10.0361 (8)0.0526 (9)0.0624 (10)0.0028 (7)0.0089 (7)0.0014 (8)
N20.0411 (8)0.0449 (8)0.0475 (9)0.0026 (6)0.0055 (7)0.0017 (6)
N30.0411 (9)0.0620 (10)0.0532 (10)0.0024 (7)0.0012 (7)0.0023 (7)
N40.0390 (9)0.0558 (9)0.0504 (9)0.0043 (7)0.0021 (7)0.0024 (7)
C10.0427 (11)0.0700 (13)0.0861 (15)0.0115 (10)0.0008 (10)0.0117 (12)
C20.0456 (11)0.0546 (12)0.0811 (15)0.0029 (9)0.0196 (10)0.0172 (11)
C30.0694 (13)0.0589 (12)0.0621 (13)0.0159 (10)0.0259 (11)0.0127 (10)
C40.0680 (13)0.0503 (11)0.0496 (11)0.0059 (9)0.0084 (9)0.0045 (9)
C50.0351 (9)0.0332 (9)0.0506 (10)0.0041 (7)0.0025 (8)0.0007 (7)
C60.0342 (9)0.0389 (9)0.0475 (10)0.0001 (7)0.0031 (8)0.0016 (7)
C70.0420 (10)0.0385 (9)0.0536 (11)0.0028 (8)0.0004 (8)0.0013 (8)
C80.0444 (10)0.0433 (9)0.0435 (10)0.0003 (8)0.0011 (8)0.0019 (8)
C90.0506 (11)0.0543 (11)0.0510 (11)0.0040 (9)0.0035 (9)0.0022 (8)
C100.0514 (12)0.0749 (14)0.0624 (13)0.0048 (10)0.0088 (10)0.0115 (11)
C110.0734 (15)0.0853 (16)0.0576 (14)0.0081 (12)0.0215 (11)0.0015 (12)
C120.0946 (18)0.0908 (17)0.0637 (14)0.0118 (14)0.0208 (13)0.0282 (12)
C130.0709 (14)0.0689 (13)0.0603 (12)0.0157 (11)0.0070 (10)0.0172 (11)
Geometric parameters (Å, º) top
O1—C71.2385 (19)C3—H3B0.9700
N1—C51.369 (2)C4—H4A0.9700
N1—C11.469 (2)C4—H4B0.9700
N1—C21.475 (2)C5—C61.417 (2)
N2—C51.360 (2)C6—C71.468 (2)
N2—N31.3798 (19)C7—C81.510 (2)
N2—C41.463 (2)C8—C131.391 (2)
N3—N41.3039 (19)C8—C91.395 (2)
N4—C61.387 (2)C9—C101.394 (2)
C1—H1A0.9600C9—H90.9300
C1—H1B0.9600C10—C111.385 (3)
C1—H1C0.9600C10—H100.9300
C2—C31.518 (3)C11—C121.376 (3)
C2—H2A0.9700C11—H110.9300
C2—H2B0.9700C12—C131.388 (3)
C3—C41.520 (3)C12—H120.9300
C3—H3A0.9700C13—H130.9300
C5—N1—C1119.77 (14)C3—C4—H4B110.2
C5—N1—C2116.80 (15)H4A—C4—H4B108.5
C1—N1—C2115.39 (15)N2—C5—N1120.87 (15)
C5—N2—N3111.66 (13)N2—C5—C6103.89 (14)
C5—N2—C4126.63 (14)N1—C5—C6135.23 (16)
N3—N2—C4121.55 (14)N4—C6—C5107.20 (14)
N4—N3—N2106.70 (13)N4—C6—C7120.15 (14)
N3—N4—C6110.53 (13)C5—C6—C7131.93 (15)
N1—C1—H1A109.5O1—C7—C6121.22 (15)
N1—C1—H1B109.5O1—C7—C8119.70 (15)
H1A—C1—H1B109.5C6—C7—C8119.07 (14)
N1—C1—H1C109.5C13—C8—C9118.21 (16)
H1A—C1—H1C109.5C13—C8—C7118.63 (16)
H1B—C1—H1C109.5C9—C8—C7123.00 (15)
N1—C2—C3111.89 (15)C8—C9—C10120.83 (17)
N1—C2—H2A109.2C8—C9—H9119.6
C3—C2—H2A109.2C10—C9—H9119.6
N1—C2—H2B109.2C11—C10—C9120.00 (19)
C3—C2—H2B109.2C11—C10—H10120.0
H2A—C2—H2B107.9C9—C10—H10120.0
C2—C3—C4110.29 (15)C12—C11—C10119.49 (18)
C2—C3—H3A109.6C12—C11—H11120.3
C4—C3—H3A109.6C10—C11—H11120.3
C2—C3—H3B109.6C11—C12—C13120.76 (19)
C4—C3—H3B109.6C11—C12—H12119.6
H3A—C3—H3B108.1C13—C12—H12119.6
N2—C4—C3107.33 (15)C12—C13—C8120.69 (19)
N2—C4—H4A110.2C12—C13—H13119.7
C3—C4—H4A110.2C8—C13—H13119.7
N2—C4—H4B110.2
C5—N2—N3—N41.57 (18)N1—C5—C6—N4179.97 (17)
C4—N2—N3—N4177.20 (14)N2—C5—C6—C7170.36 (16)
N2—N3—N4—C61.27 (18)N1—C5—C6—C710.1 (3)
C5—N1—C2—C335.7 (2)N4—C6—C7—O1150.75 (16)
C1—N1—C2—C3175.54 (15)C5—C6—C7—O118.2 (3)
N1—C2—C3—C458.9 (2)N4—C6—C7—C828.4 (2)
C5—N2—C4—C319.4 (2)C5—C6—C7—C8162.64 (16)
N3—N2—C4—C3155.57 (15)O1—C7—C8—C1323.3 (2)
C2—C3—C4—N248.38 (19)C6—C7—C8—C13155.89 (16)
N3—N2—C5—N1179.16 (14)O1—C7—C8—C9151.94 (17)
C4—N2—C5—N13.8 (2)C6—C7—C8—C928.8 (2)
N3—N2—C5—C61.18 (17)C13—C8—C9—C100.0 (3)
C4—N2—C5—C6176.55 (14)C7—C8—C9—C10175.28 (16)
C1—N1—C5—N2151.85 (16)C8—C9—C10—C110.6 (3)
C2—N1—C5—N24.5 (2)C9—C10—C11—C120.4 (3)
C1—N1—C5—C627.7 (3)C10—C11—C12—C130.4 (3)
C2—N1—C5—C6175.05 (17)C11—C12—C13—C80.9 (3)
N3—N4—C6—C50.57 (18)C9—C8—C13—C120.7 (3)
N3—N4—C6—C7170.82 (14)C7—C8—C13—C12176.24 (19)
N2—C5—C6—N40.39 (17)

Experimental details

Crystal data
Chemical formulaC13H14N4O
Mr242.28
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)294
a, b, c (Å)14.644 (5), 7.597 (3), 22.711 (8)
V3)2526.7 (16)
Z8
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.22 × 0.20 × 0.10
Data collection
DiffractometerBruker SMART CCD
Absorption correctionMulti-scan
(SADABS; Bruker, 1997)
Tmin, Tmax0.982, 0.992
No. of measured, independent and
observed [I > 2σ(I)] reflections
13257, 2576, 1602
Rint0.057
(sin θ/λ)max1)0.626
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.116, 1.01
No. of reflections2576
No. of parameters165
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.15, 0.17

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

 

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