Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807032667/wk2069sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807032667/wk2069Isup2.hkl |
CCDC reference: 657727
All reagents were purchased (Aldrich) and used without further purification. The title compound was synthesized according to the literature method (Pleier et al., 2001). The title compound (0.552 g, 0.002 mol) was dissolved into 20 ml DMF. After heating at 70 °C for 20 min, the mixture was allowed to cool and evaporate naturally. Yellow block crystals suitable for single-crystal X-ray diffraction were obtained by evaporating the mixture at room temperature for a period of two weeks. Analysis found: C 65.3, H 4.4, N 30.3%; C15H12N6 requires: C 65.21, H 4.38, N 30.42%.
All H atoms were visible in difference Fourier maps but were placed in calculated positions with C—H= 0.93 Å (CH) or N—H= 0.90 Å (NH), Uiso(H)= 1.2 times Ueq(C) or Ueq(N) for CH or NH. All other non-H atoms were refined anisotropically. The maximum positive peak of 0.26 e Å-3 in the final difference electron density map was located 0.73 Å from atom C5. As the absolute structure cannot been determined for a light atom structure with Mo K-α radiation under normal circumstances, the Friedel-pair reflections have been merged before final refinement.
Recently, there has been much interest in the study of crystal engineering of supramolecular architectures using N-donor ligands (Zheng et al., 2003; Peng et al., 2006). The title compound, C15H12N6, can be an important organic tri- or polydentate ligand to form new metal complexes.
The asymmetric unit (Fig. 1), which contains one molecule. Molecules are linked together via intermolecular N—H···N hydrogen bond interactions (Table. 1). The intermolecular N—H···N contacts (2.856 (3)–2.961 (3) Å) satisfy the definition of standard hydrogen bonds and resulted in a three dimensional supramolecular network (Fig. 2). Interestingly, all of the non-H atoms in the title compound are not coplanar (the mean deviation of the atoms from the least-squares plane is 0.153 Å).
For related literature, see: Peng et al. (2006); Pleier et al. (2001); Zheng et al. (2003).
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.
C15H12N6 | Dx = 1.427 Mg m−3 |
Mr = 276.31 | Mo Kα radiation, λ = 0.71069 Å |
Orthorhombic, Pna21 | Cell parameters from 864 reflections |
a = 8.183 (5) Å | θ = 3.7–22.8° |
b = 17.128 (5) Å | µ = 0.09 mm−1 |
c = 9.173 (5) Å | T = 293 K |
V = 1285.7 (11) Å3 | Block, yellow |
Z = 4 | 0.43 × 0.28 × 0.27 mm |
F(000) = 576 |
Bruker SMART APEX II CCD diffractometer | 1670 independent reflections |
Radiation source: fine-focus sealed tube | 1342 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
φ and ω scans | θmax = 28.3°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −10→9 |
Tmin = 0.962, Tmax = 0.976 | k = −19→21 |
7598 measured reflections | l = −12→11 |
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)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.112 | w = 1/[σ2(Fo2) + (0.0717P)2 + 0.0158P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
1670 reflections | Δρmax = 0.26 e Å−3 |
190 parameters | Δρmin = −0.18 e Å−3 |
1 restraint | Absolute structure: Flack (1983), Number of Friedel pairs? |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 10 (10) |
C15H12N6 | V = 1285.7 (11) Å3 |
Mr = 276.31 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 8.183 (5) Å | µ = 0.09 mm−1 |
b = 17.128 (5) Å | T = 293 K |
c = 9.173 (5) Å | 0.43 × 0.28 × 0.27 mm |
Bruker SMART APEX II CCD diffractometer | 1670 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 1342 reflections with I > 2σ(I) |
Tmin = 0.962, Tmax = 0.976 | Rint = 0.037 |
7598 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.112 | Δρmax = 0.26 e Å−3 |
S = 1.03 | Δρmin = −0.18 e Å−3 |
1670 reflections | Absolute structure: Flack (1983), Number of Friedel pairs? |
190 parameters | Absolute structure parameter: 10 (10) |
1 restraint |
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 | ||
C1 | 0.3602 (3) | 0.18881 (14) | 0.5920 (3) | 0.0366 (5) | |
C2 | 0.3385 (3) | 0.26016 (13) | 0.5217 (3) | 0.0369 (5) | |
H2 | 0.3054 | 0.2612 | 0.4247 | 0.044* | |
C3 | 0.3662 (3) | 0.33028 (14) | 0.5959 (3) | 0.0374 (6) | |
C4 | 0.4121 (3) | 0.32782 (14) | 0.7426 (3) | 0.0383 (6) | |
H4 | 0.4291 | 0.3742 | 0.7929 | 0.046* | |
C5 | 0.4326 (3) | 0.25690 (13) | 0.8144 (3) | 0.0378 (6) | |
C6 | 0.4073 (3) | 0.18830 (14) | 0.7377 (3) | 0.0393 (6) | |
H6 | 0.4221 | 0.1407 | 0.7848 | 0.047* | |
C7 | 0.3371 (3) | 0.11425 (14) | 0.5129 (2) | 0.0359 (5) | |
C8 | 0.4001 (4) | 0.04043 (15) | 0.5471 (3) | 0.0473 (7) | |
H8 | 0.4687 | 0.0274 | 0.6241 | 0.057* | |
C9 | 0.3388 (4) | −0.00815 (16) | 0.4426 (3) | 0.0513 (7) | |
H9 | 0.3563 | −0.0617 | 0.4369 | 0.062* | |
C10 | 0.3529 (3) | 0.40462 (14) | 0.5151 (3) | 0.0372 (5) | |
C11 | 0.3294 (3) | 0.41669 (15) | 0.3655 (3) | 0.0446 (6) | |
H11 | 0.3131 | 0.3787 | 0.2945 | 0.053* | |
C12 | 0.3355 (4) | 0.49591 (16) | 0.3455 (3) | 0.0486 (7) | |
H12 | 0.3255 | 0.5221 | 0.2571 | 0.058* | |
C13 | 0.4818 (3) | 0.25235 (13) | 0.9689 (3) | 0.0373 (5) | |
C14 | 0.4694 (3) | 0.18895 (14) | 1.0637 (3) | 0.0435 (6) | |
H14 | 0.4265 | 0.1400 | 1.0427 | 0.052* | |
C15 | 0.5333 (3) | 0.21336 (15) | 1.1941 (3) | 0.0444 (6) | |
H15 | 0.5424 | 0.1837 | 1.2787 | 0.053* | |
N1 | 0.2498 (3) | 0.03384 (13) | 0.3505 (3) | 0.0482 (6) | |
H1 | 0.2004 | 0.0152 | 0.2754 | 0.058* | |
N2 | 0.2472 (3) | 0.11020 (12) | 0.3905 (2) | 0.0428 (5) | |
N3 | 0.3585 (3) | 0.52856 (13) | 0.4757 (3) | 0.0538 (6) | |
H3 | 0.3642 | 0.5780 | 0.4908 | 0.065* | |
N4 | 0.3717 (3) | 0.47320 (13) | 0.5816 (2) | 0.0478 (6) | |
N5 | 0.5799 (3) | 0.28760 (13) | 1.1773 (2) | 0.0469 (6) | |
H5 | 0.6233 | 0.3156 | 1.2448 | 0.056* | |
N6 | 0.5498 (3) | 0.31309 (11) | 1.0397 (2) | 0.0444 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0490 (13) | 0.0301 (12) | 0.0306 (12) | −0.0023 (10) | −0.0015 (10) | −0.0039 (10) |
C2 | 0.0520 (14) | 0.0333 (13) | 0.0253 (11) | −0.0002 (10) | −0.0035 (10) | −0.0033 (10) |
C3 | 0.0473 (13) | 0.0303 (12) | 0.0347 (13) | 0.0015 (10) | −0.0005 (11) | −0.0027 (10) |
C4 | 0.0538 (14) | 0.0292 (13) | 0.0320 (12) | −0.0017 (10) | −0.0050 (11) | −0.0058 (10) |
C5 | 0.0476 (13) | 0.0352 (14) | 0.0306 (13) | −0.0021 (10) | −0.0036 (11) | −0.0037 (9) |
C6 | 0.0581 (15) | 0.0308 (13) | 0.0292 (12) | −0.0004 (10) | −0.0058 (11) | −0.0008 (10) |
C7 | 0.0517 (13) | 0.0298 (12) | 0.0261 (11) | −0.0020 (10) | −0.0010 (10) | −0.0018 (10) |
C8 | 0.0674 (17) | 0.0356 (13) | 0.0389 (14) | 0.0061 (12) | −0.0106 (13) | −0.0025 (11) |
C9 | 0.0731 (18) | 0.0324 (14) | 0.0485 (17) | 0.0068 (13) | −0.0084 (14) | −0.0068 (13) |
C10 | 0.0472 (13) | 0.0301 (12) | 0.0344 (12) | 0.0014 (10) | −0.0004 (11) | −0.0037 (10) |
C11 | 0.0618 (16) | 0.0363 (14) | 0.0356 (13) | −0.0012 (11) | −0.0063 (13) | −0.0054 (11) |
C12 | 0.0675 (17) | 0.0423 (15) | 0.0361 (13) | −0.0018 (13) | −0.0035 (12) | 0.0056 (12) |
C13 | 0.0489 (13) | 0.0331 (13) | 0.0299 (12) | −0.0017 (10) | −0.0030 (11) | −0.0043 (9) |
C14 | 0.0592 (16) | 0.0308 (12) | 0.0405 (15) | −0.0041 (11) | −0.0026 (12) | −0.0006 (11) |
C15 | 0.0564 (15) | 0.0408 (14) | 0.0361 (14) | 0.0013 (12) | 0.0006 (12) | 0.0026 (12) |
N1 | 0.0695 (15) | 0.0361 (13) | 0.0389 (11) | −0.0025 (10) | −0.0096 (11) | −0.0085 (9) |
N2 | 0.0653 (14) | 0.0327 (11) | 0.0303 (11) | −0.0027 (10) | −0.0084 (10) | −0.0034 (9) |
N3 | 0.0862 (17) | 0.0317 (12) | 0.0436 (13) | −0.0032 (11) | 0.0032 (13) | 0.0023 (10) |
N4 | 0.0768 (16) | 0.0301 (11) | 0.0364 (12) | −0.0014 (10) | 0.0042 (12) | −0.0023 (9) |
N5 | 0.0678 (15) | 0.0413 (12) | 0.0316 (11) | −0.0026 (10) | −0.0083 (11) | −0.0051 (10) |
N6 | 0.0699 (15) | 0.0327 (10) | 0.0307 (11) | −0.0049 (10) | −0.0084 (11) | −0.0028 (9) |
C1—C6 | 1.392 (3) | C10—N4 | 1.332 (3) |
C1—C2 | 1.393 (3) | C10—C11 | 1.401 (4) |
C1—C7 | 1.481 (3) | C11—C12 | 1.370 (3) |
C2—C3 | 1.399 (3) | C11—H11 | 0.9300 |
C2—H2 | 0.9300 | C12—N3 | 1.332 (4) |
C3—C4 | 1.397 (3) | C12—H12 | 0.9300 |
C3—C10 | 1.477 (3) | C13—N6 | 1.347 (3) |
C4—C5 | 1.392 (3) | C13—C14 | 1.395 (3) |
C4—H4 | 0.9300 | C14—C15 | 1.371 (4) |
C5—C6 | 1.385 (3) | C14—H14 | 0.9300 |
C5—C13 | 1.475 (4) | C15—N5 | 1.337 (4) |
C6—H6 | 0.9300 | C15—H15 | 0.9300 |
C7—N2 | 1.344 (3) | N1—N2 | 1.358 (3) |
C7—C8 | 1.401 (3) | N1—H1 | 0.8600 |
C8—C9 | 1.365 (4) | N3—N4 | 1.362 (3) |
C8—H8 | 0.9300 | N3—H3 | 0.8600 |
C9—N1 | 1.327 (3) | N5—N6 | 1.358 (3) |
C9—H9 | 0.9300 | N5—H5 | 0.8600 |
C6—C1—C2 | 119.0 (2) | C11—C10—C3 | 129.0 (2) |
C6—C1—C7 | 120.1 (2) | C12—C11—C10 | 105.8 (2) |
C2—C1—C7 | 120.9 (2) | C12—C11—H11 | 127.1 |
C1—C2—C3 | 120.5 (2) | C10—C11—H11 | 127.1 |
C1—C2—H2 | 119.8 | N3—C12—C11 | 107.5 (3) |
C3—C2—H2 | 119.8 | N3—C12—H12 | 126.3 |
C4—C3—C2 | 119.1 (2) | C11—C12—H12 | 126.3 |
C4—C3—C10 | 121.9 (2) | N6—C13—C14 | 109.3 (2) |
C2—C3—C10 | 118.9 (2) | N6—C13—C5 | 122.4 (2) |
C5—C4—C3 | 121.0 (2) | C14—C13—C5 | 128.4 (2) |
C5—C4—H4 | 119.5 | C15—C14—C13 | 106.2 (2) |
C3—C4—H4 | 119.5 | C15—C14—H14 | 126.9 |
C6—C5—C4 | 118.8 (2) | C13—C14—H14 | 126.9 |
C6—C5—C13 | 118.9 (2) | N5—C15—C14 | 107.4 (2) |
C4—C5—C13 | 122.3 (2) | N5—C15—H15 | 126.3 |
C5—C6—C1 | 121.6 (2) | C14—C15—H15 | 126.3 |
C5—C6—H6 | 119.2 | C9—N1—N2 | 111.0 (2) |
C1—C6—H6 | 119.2 | C9—N1—H1 | 124.5 |
N2—C7—C8 | 110.0 (2) | N2—N1—H1 | 124.5 |
N2—C7—C1 | 121.6 (2) | C7—N2—N1 | 105.46 (19) |
C8—C7—C1 | 128.4 (2) | C12—N3—N4 | 111.0 (2) |
C9—C8—C7 | 104.9 (2) | C12—N3—H3 | 124.5 |
C9—C8—H8 | 127.5 | N4—N3—H3 | 124.5 |
C7—C8—H8 | 127.5 | C10—N4—N3 | 106.1 (2) |
N1—C9—C8 | 108.6 (2) | C15—N5—N6 | 111.2 (2) |
N1—C9—H9 | 125.7 | C15—N5—H5 | 124.4 |
C8—C9—H9 | 125.7 | N6—N5—H5 | 124.4 |
N4—C10—C11 | 109.5 (2) | C13—N6—N5 | 106.0 (2) |
N4—C10—C3 | 121.4 (2) | ||
C6—C1—C2—C3 | 1.0 (4) | N4—C10—C11—C12 | 0.1 (3) |
C7—C1—C2—C3 | −177.7 (2) | C3—C10—C11—C12 | −176.5 (2) |
C1—C2—C3—C4 | −1.6 (4) | C10—C11—C12—N3 | −0.9 (3) |
C1—C2—C3—C10 | 175.9 (2) | C6—C5—C13—N6 | 162.0 (3) |
C2—C3—C4—C5 | 1.0 (4) | C4—C5—C13—N6 | −17.4 (4) |
C10—C3—C4—C5 | −176.4 (2) | C6—C5—C13—C14 | −17.5 (4) |
C3—C4—C5—C6 | 0.2 (4) | C4—C5—C13—C14 | 163.0 (3) |
C3—C4—C5—C13 | 179.7 (3) | N6—C13—C14—C15 | −0.4 (3) |
C4—C5—C6—C1 | −0.8 (4) | C5—C13—C14—C15 | 179.2 (3) |
C13—C5—C6—C1 | 179.7 (3) | C13—C14—C15—N5 | 0.4 (3) |
C2—C1—C6—C5 | 0.2 (4) | C8—C9—N1—N2 | −0.7 (3) |
C7—C1—C6—C5 | 178.9 (2) | C8—C7—N2—N1 | 1.7 (3) |
C6—C1—C7—N2 | 159.7 (2) | C1—C7—N2—N1 | −178.7 (2) |
C2—C1—C7—N2 | −21.6 (4) | C9—N1—N2—C7 | −0.6 (3) |
C6—C1—C7—C8 | −20.7 (4) | C11—C12—N3—N4 | 1.4 (3) |
C2—C1—C7—C8 | 158.0 (3) | C11—C10—N4—N3 | 0.7 (3) |
N2—C7—C8—C9 | −2.1 (3) | C3—C10—N4—N3 | 177.6 (2) |
C1—C7—C8—C9 | 178.3 (2) | C12—N3—N4—C10 | −1.3 (3) |
C7—C8—C9—N1 | 1.7 (3) | C14—C15—N5—N6 | −0.3 (3) |
C4—C3—C10—N4 | −5.3 (4) | C14—C13—N6—N5 | 0.2 (3) |
C2—C3—C10—N4 | 177.3 (2) | C5—C13—N6—N5 | −179.4 (2) |
C4—C3—C10—C11 | 171.0 (3) | C15—N5—N6—C13 | 0.1 (3) |
C2—C3—C10—C11 | −6.4 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5···N2i | 0.86 | 2.10 | 2.960 (3) | 173 |
N3—H3···N6ii | 0.86 | 2.04 | 2.875 (3) | 163 |
N1—H1···N4iii | 0.86 | 2.01 | 2.855 (3) | 169 |
Symmetry codes: (i) x+1/2, −y+1/2, z+1; (ii) −x+1, −y+1, z−1/2; (iii) −x+1/2, y−1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C15H12N6 |
Mr | 276.31 |
Crystal system, space group | Orthorhombic, Pna21 |
Temperature (K) | 293 |
a, b, c (Å) | 8.183 (5), 17.128 (5), 9.173 (5) |
V (Å3) | 1285.7 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.43 × 0.28 × 0.27 |
Data collection | |
Diffractometer | Bruker SMART APEX II CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2004) |
Tmin, Tmax | 0.962, 0.976 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7598, 1670, 1342 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.112, 1.03 |
No. of reflections | 1670 |
No. of parameters | 190 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.26, −0.18 |
Absolute structure | Flack (1983), Number of Friedel pairs? |
Absolute structure parameter | 10 (10) |
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SAINT, SHELXTL (Sheldrick, 2001), SHELXTL and local programs.
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5···N2i | 0.86 | 2.10 | 2.960 (3) | 173.2 |
N3—H3···N6ii | 0.86 | 2.04 | 2.875 (3) | 162.5 |
N1—H1···N4iii | 0.86 | 2.01 | 2.855 (3) | 168.7 |
Symmetry codes: (i) x+1/2, −y+1/2, z+1; (ii) −x+1, −y+1, z−1/2; (iii) −x+1/2, y−1/2, z−1/2. |
Recently, there has been much interest in the study of crystal engineering of supramolecular architectures using N-donor ligands (Zheng et al., 2003; Peng et al., 2006). The title compound, C15H12N6, can be an important organic tri- or polydentate ligand to form new metal complexes.
The asymmetric unit (Fig. 1), which contains one molecule. Molecules are linked together via intermolecular N—H···N hydrogen bond interactions (Table. 1). The intermolecular N—H···N contacts (2.856 (3)–2.961 (3) Å) satisfy the definition of standard hydrogen bonds and resulted in a three dimensional supramolecular network (Fig. 2). Interestingly, all of the non-H atoms in the title compound are not coplanar (the mean deviation of the atoms from the least-squares plane is 0.153 Å).