Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025998/hb2429sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025998/hb2429Isup2.hkl |
CCDC reference: 654514
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (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
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.
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).
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.
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.
Fig. 1. Molecular structure of (I) showing 30% displacement ellipsoids (arbitrary spheres for the H atoms). | |
Fig. 2. Packing diagram of (I) viewed down the b-axis. |
C13H14N4O | Dx = 1.274 Mg m−3 |
Mr = 242.28 | Melting point = 376–377 K |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
a = 14.644 (5) Å | Cell parameters from 2603 reflections |
b = 7.597 (3) Å | θ = 2.8–21.8° |
c = 22.711 (8) Å | µ = 0.09 mm−1 |
V = 2526.7 (16) Å3 | T = 294 K |
Z = 8 | Prism, very pale green |
F(000) = 1024 | 0.22 × 0.20 × 0.10 mm |
Bruker SMART CCD diffractometer | 2576 independent reflections |
Radiation source: fine-focus sealed tube | 1602 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.057 |
ω scans | θmax = 26.4°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | h = −17→18 |
Tmin = 0.982, Tmax = 0.992 | k = −8→9 |
13257 measured reflections | l = −28→13 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.041 | H-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 reflections | Δρmax = 0.15 e Å−3 |
165 parameters | Δρmin = −0.17 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0109 (11) |
C13H14N4O | V = 2526.7 (16) Å3 |
Mr = 242.28 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 14.644 (5) Å | µ = 0.09 mm−1 |
b = 7.597 (3) Å | T = 294 K |
c = 22.711 (8) Å | 0.22 × 0.20 × 0.10 mm |
Bruker SMART CCD diffractometer | 2576 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | 1602 reflections with I > 2σ(I) |
Tmin = 0.982, Tmax = 0.992 | Rint = 0.057 |
13257 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.15 e Å−3 |
2576 reflections | Δρmin = −0.17 e Å−3 |
165 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 | ||
O1 | 0.38429 (8) | 0.38641 (18) | 0.35194 (6) | 0.0657 (4) | |
N1 | 0.33793 (9) | 0.18589 (19) | 0.47987 (6) | 0.0504 (4) | |
N2 | 0.48321 (9) | 0.23988 (18) | 0.52259 (6) | 0.0445 (4) | |
N3 | 0.56950 (10) | 0.2989 (2) | 0.50826 (7) | 0.0521 (4) | |
N4 | 0.56915 (9) | 0.33018 (19) | 0.45181 (6) | 0.0484 (4) | |
C1 | 0.29124 (12) | 0.1074 (3) | 0.42903 (9) | 0.0663 (6) | |
H1A | 0.2966 | 0.1845 | 0.3957 | 0.099* | |
H1B | 0.2279 | 0.0903 | 0.4383 | 0.099* | |
H1C | 0.3187 | −0.0041 | 0.4199 | 0.099* | |
C2 | 0.30857 (12) | 0.1198 (3) | 0.53793 (9) | 0.0605 (6) | |
H2A | 0.3229 | −0.0045 | 0.5408 | 0.073* | |
H2B | 0.2429 | 0.1327 | 0.5415 | 0.073* | |
C3 | 0.35475 (14) | 0.2177 (3) | 0.58799 (8) | 0.0635 (6) | |
H3A | 0.3341 | 0.1704 | 0.6254 | 0.076* | |
H3B | 0.3381 | 0.3412 | 0.5865 | 0.076* | |
C4 | 0.45787 (13) | 0.1995 (2) | 0.58340 (8) | 0.0559 (5) | |
H4A | 0.4877 | 0.2805 | 0.6102 | 0.067* | |
H4B | 0.4764 | 0.0806 | 0.5934 | 0.067* | |
C5 | 0.42705 (11) | 0.2381 (2) | 0.47487 (7) | 0.0396 (4) | |
C6 | 0.48354 (11) | 0.2968 (2) | 0.42818 (7) | 0.0402 (4) | |
C7 | 0.46293 (11) | 0.3477 (2) | 0.36725 (7) | 0.0447 (4) | |
C8 | 0.53960 (11) | 0.3549 (2) | 0.32287 (7) | 0.0437 (4) | |
C9 | 0.61735 (12) | 0.2493 (2) | 0.32667 (8) | 0.0519 (5) | |
H9 | 0.6254 | 0.1766 | 0.3592 | 0.062* | |
C10 | 0.68318 (13) | 0.2516 (3) | 0.28232 (8) | 0.0629 (6) | |
H10 | 0.7344 | 0.1798 | 0.2852 | 0.075* | |
C11 | 0.67223 (15) | 0.3606 (3) | 0.23396 (9) | 0.0721 (6) | |
H11 | 0.7162 | 0.3629 | 0.2044 | 0.087* | |
C12 | 0.59586 (17) | 0.4655 (3) | 0.23000 (9) | 0.0830 (7) | |
H12 | 0.5886 | 0.5393 | 0.1977 | 0.100* | |
C13 | 0.52960 (14) | 0.4623 (3) | 0.27367 (8) | 0.0667 (6) | |
H13 | 0.4780 | 0.5327 | 0.2700 | 0.080* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0450 (8) | 0.0844 (10) | 0.0677 (9) | 0.0147 (7) | −0.0028 (6) | 0.0087 (7) |
N1 | 0.0361 (8) | 0.0526 (9) | 0.0624 (10) | −0.0028 (7) | 0.0089 (7) | 0.0014 (8) |
N2 | 0.0411 (8) | 0.0449 (8) | 0.0475 (9) | 0.0026 (6) | 0.0055 (7) | 0.0017 (6) |
N3 | 0.0411 (9) | 0.0620 (10) | 0.0532 (10) | −0.0024 (7) | 0.0012 (7) | −0.0023 (7) |
N4 | 0.0390 (9) | 0.0558 (9) | 0.0504 (9) | −0.0043 (7) | 0.0021 (7) | −0.0024 (7) |
C1 | 0.0427 (11) | 0.0700 (13) | 0.0861 (15) | −0.0115 (10) | −0.0008 (10) | −0.0117 (12) |
C2 | 0.0456 (11) | 0.0546 (12) | 0.0811 (15) | 0.0029 (9) | 0.0196 (10) | 0.0172 (11) |
C3 | 0.0694 (13) | 0.0589 (12) | 0.0621 (13) | 0.0159 (10) | 0.0259 (11) | 0.0127 (10) |
C4 | 0.0680 (13) | 0.0503 (11) | 0.0496 (11) | 0.0059 (9) | 0.0084 (9) | 0.0045 (9) |
C5 | 0.0351 (9) | 0.0332 (9) | 0.0506 (10) | 0.0041 (7) | 0.0025 (8) | −0.0007 (7) |
C6 | 0.0342 (9) | 0.0389 (9) | 0.0475 (10) | 0.0001 (7) | 0.0031 (8) | −0.0016 (7) |
C7 | 0.0420 (10) | 0.0385 (9) | 0.0536 (11) | 0.0028 (8) | 0.0004 (8) | −0.0013 (8) |
C8 | 0.0444 (10) | 0.0433 (9) | 0.0435 (10) | −0.0003 (8) | 0.0011 (8) | −0.0019 (8) |
C9 | 0.0506 (11) | 0.0543 (11) | 0.0510 (11) | 0.0040 (9) | 0.0035 (9) | 0.0022 (8) |
C10 | 0.0514 (12) | 0.0749 (14) | 0.0624 (13) | 0.0048 (10) | 0.0088 (10) | −0.0115 (11) |
C11 | 0.0734 (15) | 0.0853 (16) | 0.0576 (14) | −0.0081 (12) | 0.0215 (11) | −0.0015 (12) |
C12 | 0.0946 (18) | 0.0908 (17) | 0.0637 (14) | 0.0118 (14) | 0.0208 (13) | 0.0282 (12) |
C13 | 0.0709 (14) | 0.0689 (13) | 0.0603 (12) | 0.0157 (11) | 0.0070 (10) | 0.0172 (11) |
O1—C7 | 1.2385 (19) | C3—H3B | 0.9700 |
N1—C5 | 1.369 (2) | C4—H4A | 0.9700 |
N1—C1 | 1.469 (2) | C4—H4B | 0.9700 |
N1—C2 | 1.475 (2) | C5—C6 | 1.417 (2) |
N2—C5 | 1.360 (2) | C6—C7 | 1.468 (2) |
N2—N3 | 1.3798 (19) | C7—C8 | 1.510 (2) |
N2—C4 | 1.463 (2) | C8—C13 | 1.391 (2) |
N3—N4 | 1.3039 (19) | C8—C9 | 1.395 (2) |
N4—C6 | 1.387 (2) | C9—C10 | 1.394 (2) |
C1—H1A | 0.9600 | C9—H9 | 0.9300 |
C1—H1B | 0.9600 | C10—C11 | 1.385 (3) |
C1—H1C | 0.9600 | C10—H10 | 0.9300 |
C2—C3 | 1.518 (3) | C11—C12 | 1.376 (3) |
C2—H2A | 0.9700 | C11—H11 | 0.9300 |
C2—H2B | 0.9700 | C12—C13 | 1.388 (3) |
C3—C4 | 1.520 (3) | C12—H12 | 0.9300 |
C3—H3A | 0.9700 | C13—H13 | 0.9300 |
C5—N1—C1 | 119.77 (14) | C3—C4—H4B | 110.2 |
C5—N1—C2 | 116.80 (15) | H4A—C4—H4B | 108.5 |
C1—N1—C2 | 115.39 (15) | N2—C5—N1 | 120.87 (15) |
C5—N2—N3 | 111.66 (13) | N2—C5—C6 | 103.89 (14) |
C5—N2—C4 | 126.63 (14) | N1—C5—C6 | 135.23 (16) |
N3—N2—C4 | 121.55 (14) | N4—C6—C5 | 107.20 (14) |
N4—N3—N2 | 106.70 (13) | N4—C6—C7 | 120.15 (14) |
N3—N4—C6 | 110.53 (13) | C5—C6—C7 | 131.93 (15) |
N1—C1—H1A | 109.5 | O1—C7—C6 | 121.22 (15) |
N1—C1—H1B | 109.5 | O1—C7—C8 | 119.70 (15) |
H1A—C1—H1B | 109.5 | C6—C7—C8 | 119.07 (14) |
N1—C1—H1C | 109.5 | C13—C8—C9 | 118.21 (16) |
H1A—C1—H1C | 109.5 | C13—C8—C7 | 118.63 (16) |
H1B—C1—H1C | 109.5 | C9—C8—C7 | 123.00 (15) |
N1—C2—C3 | 111.89 (15) | C8—C9—C10 | 120.83 (17) |
N1—C2—H2A | 109.2 | C8—C9—H9 | 119.6 |
C3—C2—H2A | 109.2 | C10—C9—H9 | 119.6 |
N1—C2—H2B | 109.2 | C11—C10—C9 | 120.00 (19) |
C3—C2—H2B | 109.2 | C11—C10—H10 | 120.0 |
H2A—C2—H2B | 107.9 | C9—C10—H10 | 120.0 |
C2—C3—C4 | 110.29 (15) | C12—C11—C10 | 119.49 (18) |
C2—C3—H3A | 109.6 | C12—C11—H11 | 120.3 |
C4—C3—H3A | 109.6 | C10—C11—H11 | 120.3 |
C2—C3—H3B | 109.6 | C11—C12—C13 | 120.76 (19) |
C4—C3—H3B | 109.6 | C11—C12—H12 | 119.6 |
H3A—C3—H3B | 108.1 | C13—C12—H12 | 119.6 |
N2—C4—C3 | 107.33 (15) | C12—C13—C8 | 120.69 (19) |
N2—C4—H4A | 110.2 | C12—C13—H13 | 119.7 |
C3—C4—H4A | 110.2 | C8—C13—H13 | 119.7 |
N2—C4—H4B | 110.2 | ||
C5—N2—N3—N4 | −1.57 (18) | N1—C5—C6—N4 | −179.97 (17) |
C4—N2—N3—N4 | −177.20 (14) | N2—C5—C6—C7 | −170.36 (16) |
N2—N3—N4—C6 | 1.27 (18) | N1—C5—C6—C7 | 10.1 (3) |
C5—N1—C2—C3 | 35.7 (2) | N4—C6—C7—O1 | −150.75 (16) |
C1—N1—C2—C3 | −175.54 (15) | C5—C6—C7—O1 | 18.2 (3) |
N1—C2—C3—C4 | −58.9 (2) | N4—C6—C7—C8 | 28.4 (2) |
C5—N2—C4—C3 | −19.4 (2) | C5—C6—C7—C8 | −162.64 (16) |
N3—N2—C4—C3 | 155.57 (15) | O1—C7—C8—C13 | 23.3 (2) |
C2—C3—C4—N2 | 48.38 (19) | C6—C7—C8—C13 | −155.89 (16) |
N3—N2—C5—N1 | −179.16 (14) | O1—C7—C8—C9 | −151.94 (17) |
C4—N2—C5—N1 | −3.8 (2) | C6—C7—C8—C9 | 28.8 (2) |
N3—N2—C5—C6 | 1.18 (17) | C13—C8—C9—C10 | 0.0 (3) |
C4—N2—C5—C6 | 176.55 (14) | C7—C8—C9—C10 | 175.28 (16) |
C1—N1—C5—N2 | −151.85 (16) | C8—C9—C10—C11 | 0.6 (3) |
C2—N1—C5—N2 | −4.5 (2) | C9—C10—C11—C12 | −0.4 (3) |
C1—N1—C5—C6 | 27.7 (3) | C10—C11—C12—C13 | −0.4 (3) |
C2—N1—C5—C6 | 175.05 (17) | C11—C12—C13—C8 | 0.9 (3) |
N3—N4—C6—C5 | −0.57 (18) | C9—C8—C13—C12 | −0.7 (3) |
N3—N4—C6—C7 | 170.82 (14) | C7—C8—C13—C12 | −176.24 (19) |
N2—C5—C6—N4 | −0.39 (17) |
Experimental details
Crystal data | |
Chemical formula | C13H14N4O |
Mr | 242.28 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 294 |
a, b, c (Å) | 14.644 (5), 7.597 (3), 22.711 (8) |
V (Å3) | 2526.7 (16) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.22 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 1997) |
Tmin, Tmax | 0.982, 0.992 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13257, 2576, 1602 |
Rint | 0.057 |
(sin θ/λ)max (Å−1) | 0.626 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.116, 1.01 |
No. of reflections | 2576 |
No. of parameters | 165 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.15, −0.17 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- If you have already subscribed, you may need to register
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)°.