Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
The title compound, C15H12N6, is a tri- or multidentate ligand. The asymmetric unit contains one mol­ecule. The crystal packing is stabilized by inter­molecular N—H...N hydrogen-bond inter­actions, resulting in a three-dimensional supra­molecular network.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807032667/wk2069sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807032667/wk2069Isup2.hkl
Contains datablock I

CCDC reference: 657727

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.042
  • wR factor = 0.112
  • Data-to-parameter ratio = 8.8

checkCIF/PLATON results

No syntax errors found



Alert level C STRVA01_ALERT_2_C Chirality of atom sites is inverted? From the CIF: _refine_ls_abs_structure_Flack 10.000 From the CIF: _refine_ls_abs_structure_Flack_su 10.000 PLAT032_ALERT_4_C Std. Uncertainty in Flack Parameter too High ... 10.00 PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT147_ALERT_1_C su on Symmetry Constrained Cell Angle(s) ....... ? PLAT153_ALERT_1_C The su's on the Cell Axes are Equal (x 100000) 500 Ang.
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 28.31 From the CIF: _reflns_number_total 1670 Count of symmetry unique reflns 1695 Completeness (_total/calc) 98.53% 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 PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K 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 6 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 5 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 3 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

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).

Related literature top

For related literature, see: Peng et al. (2006); Pleier et al. (2001); Zheng et al. (2003).

Experimental top

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%.

Refinement top

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.

Structure description top

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).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the title compound with the atomic labeling scheme. Displacement ellipsoids are shown at the 50% probability level.
[Figure 2] Fig. 2. The packing of the title compound, viewed down the b axis, showing three-dimensional supramolecular network connected by N—H···N hydrogen bonds (dashed lines).
1,3,5-Tris(1H-pyrazol-3-yl)benzene top
Crystal data top
C15H12N6Dx = 1.427 Mg m3
Mr = 276.31Mo Kα radiation, λ = 0.71069 Å
Orthorhombic, Pna21Cell parameters from 864 reflections
a = 8.183 (5) Åθ = 3.7–22.8°
b = 17.128 (5) ŵ = 0.09 mm1
c = 9.173 (5) ÅT = 293 K
V = 1285.7 (11) Å3Block, yellow
Z = 40.43 × 0.28 × 0.27 mm
F(000) = 576
Data collection top
Bruker SMART APEX II CCD
diffractometer
1670 independent reflections
Radiation source: fine-focus sealed tube1342 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.037
φ and ω scansθmax = 28.3°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
h = 109
Tmin = 0.962, Tmax = 0.976k = 1921
7598 measured reflectionsl = 1211
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)] = 0.042H-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 reflectionsΔρmax = 0.26 e Å3
190 parametersΔρmin = 0.18 e Å3
1 restraintAbsolute structure: Flack (1983), Number of Friedel pairs?
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 10 (10)
Crystal data top
C15H12N6V = 1285.7 (11) Å3
Mr = 276.31Z = 4
Orthorhombic, Pna21Mo Kα radiation
a = 8.183 (5) ŵ = 0.09 mm1
b = 17.128 (5) ÅT = 293 K
c = 9.173 (5) Å0.43 × 0.28 × 0.27 mm
Data collection top
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 = 0.976Rint = 0.037
7598 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.042H-atom parameters constrained
wR(F2) = 0.112Δρmax = 0.26 e Å3
S = 1.03Δρmin = 0.18 e Å3
1670 reflectionsAbsolute structure: Flack (1983), Number of Friedel pairs?
190 parametersAbsolute structure parameter: 10 (10)
1 restraint
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
C10.3602 (3)0.18881 (14)0.5920 (3)0.0366 (5)
C20.3385 (3)0.26016 (13)0.5217 (3)0.0369 (5)
H20.30540.26120.42470.044*
C30.3662 (3)0.33028 (14)0.5959 (3)0.0374 (6)
C40.4121 (3)0.32782 (14)0.7426 (3)0.0383 (6)
H40.42910.37420.79290.046*
C50.4326 (3)0.25690 (13)0.8144 (3)0.0378 (6)
C60.4073 (3)0.18830 (14)0.7377 (3)0.0393 (6)
H60.42210.14070.78480.047*
C70.3371 (3)0.11425 (14)0.5129 (2)0.0359 (5)
C80.4001 (4)0.04043 (15)0.5471 (3)0.0473 (7)
H80.46870.02740.62410.057*
C90.3388 (4)0.00815 (16)0.4426 (3)0.0513 (7)
H90.35630.06170.43690.062*
C100.3529 (3)0.40462 (14)0.5151 (3)0.0372 (5)
C110.3294 (3)0.41669 (15)0.3655 (3)0.0446 (6)
H110.31310.37870.29450.053*
C120.3355 (4)0.49591 (16)0.3455 (3)0.0486 (7)
H120.32550.52210.25710.058*
C130.4818 (3)0.25235 (13)0.9689 (3)0.0373 (5)
C140.4694 (3)0.18895 (14)1.0637 (3)0.0435 (6)
H140.42650.14001.04270.052*
C150.5333 (3)0.21336 (15)1.1941 (3)0.0444 (6)
H150.54240.18371.27870.053*
N10.2498 (3)0.03384 (13)0.3505 (3)0.0482 (6)
H10.20040.01520.27540.058*
N20.2472 (3)0.11020 (12)0.3905 (2)0.0428 (5)
N30.3585 (3)0.52856 (13)0.4757 (3)0.0538 (6)
H30.36420.57800.49080.065*
N40.3717 (3)0.47320 (13)0.5816 (2)0.0478 (6)
N50.5799 (3)0.28760 (13)1.1773 (2)0.0469 (6)
H50.62330.31561.24480.056*
N60.5498 (3)0.31309 (11)1.0397 (2)0.0444 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0490 (13)0.0301 (12)0.0306 (12)0.0023 (10)0.0015 (10)0.0039 (10)
C20.0520 (14)0.0333 (13)0.0253 (11)0.0002 (10)0.0035 (10)0.0033 (10)
C30.0473 (13)0.0303 (12)0.0347 (13)0.0015 (10)0.0005 (11)0.0027 (10)
C40.0538 (14)0.0292 (13)0.0320 (12)0.0017 (10)0.0050 (11)0.0058 (10)
C50.0476 (13)0.0352 (14)0.0306 (13)0.0021 (10)0.0036 (11)0.0037 (9)
C60.0581 (15)0.0308 (13)0.0292 (12)0.0004 (10)0.0058 (11)0.0008 (10)
C70.0517 (13)0.0298 (12)0.0261 (11)0.0020 (10)0.0010 (10)0.0018 (10)
C80.0674 (17)0.0356 (13)0.0389 (14)0.0061 (12)0.0106 (13)0.0025 (11)
C90.0731 (18)0.0324 (14)0.0485 (17)0.0068 (13)0.0084 (14)0.0068 (13)
C100.0472 (13)0.0301 (12)0.0344 (12)0.0014 (10)0.0004 (11)0.0037 (10)
C110.0618 (16)0.0363 (14)0.0356 (13)0.0012 (11)0.0063 (13)0.0054 (11)
C120.0675 (17)0.0423 (15)0.0361 (13)0.0018 (13)0.0035 (12)0.0056 (12)
C130.0489 (13)0.0331 (13)0.0299 (12)0.0017 (10)0.0030 (11)0.0043 (9)
C140.0592 (16)0.0308 (12)0.0405 (15)0.0041 (11)0.0026 (12)0.0006 (11)
C150.0564 (15)0.0408 (14)0.0361 (14)0.0013 (12)0.0006 (12)0.0026 (12)
N10.0695 (15)0.0361 (13)0.0389 (11)0.0025 (10)0.0096 (11)0.0085 (9)
N20.0653 (14)0.0327 (11)0.0303 (11)0.0027 (10)0.0084 (10)0.0034 (9)
N30.0862 (17)0.0317 (12)0.0436 (13)0.0032 (11)0.0032 (13)0.0023 (10)
N40.0768 (16)0.0301 (11)0.0364 (12)0.0014 (10)0.0042 (12)0.0023 (9)
N50.0678 (15)0.0413 (12)0.0316 (11)0.0026 (10)0.0083 (11)0.0051 (10)
N60.0699 (15)0.0327 (10)0.0307 (11)0.0049 (10)0.0084 (11)0.0028 (9)
Geometric parameters (Å, º) top
C1—C61.392 (3)C10—N41.332 (3)
C1—C21.393 (3)C10—C111.401 (4)
C1—C71.481 (3)C11—C121.370 (3)
C2—C31.399 (3)C11—H110.9300
C2—H20.9300C12—N31.332 (4)
C3—C41.397 (3)C12—H120.9300
C3—C101.477 (3)C13—N61.347 (3)
C4—C51.392 (3)C13—C141.395 (3)
C4—H40.9300C14—C151.371 (4)
C5—C61.385 (3)C14—H140.9300
C5—C131.475 (4)C15—N51.337 (4)
C6—H60.9300C15—H150.9300
C7—N21.344 (3)N1—N21.358 (3)
C7—C81.401 (3)N1—H10.8600
C8—C91.365 (4)N3—N41.362 (3)
C8—H80.9300N3—H30.8600
C9—N11.327 (3)N5—N61.358 (3)
C9—H90.9300N5—H50.8600
C6—C1—C2119.0 (2)C11—C10—C3129.0 (2)
C6—C1—C7120.1 (2)C12—C11—C10105.8 (2)
C2—C1—C7120.9 (2)C12—C11—H11127.1
C1—C2—C3120.5 (2)C10—C11—H11127.1
C1—C2—H2119.8N3—C12—C11107.5 (3)
C3—C2—H2119.8N3—C12—H12126.3
C4—C3—C2119.1 (2)C11—C12—H12126.3
C4—C3—C10121.9 (2)N6—C13—C14109.3 (2)
C2—C3—C10118.9 (2)N6—C13—C5122.4 (2)
C5—C4—C3121.0 (2)C14—C13—C5128.4 (2)
C5—C4—H4119.5C15—C14—C13106.2 (2)
C3—C4—H4119.5C15—C14—H14126.9
C6—C5—C4118.8 (2)C13—C14—H14126.9
C6—C5—C13118.9 (2)N5—C15—C14107.4 (2)
C4—C5—C13122.3 (2)N5—C15—H15126.3
C5—C6—C1121.6 (2)C14—C15—H15126.3
C5—C6—H6119.2C9—N1—N2111.0 (2)
C1—C6—H6119.2C9—N1—H1124.5
N2—C7—C8110.0 (2)N2—N1—H1124.5
N2—C7—C1121.6 (2)C7—N2—N1105.46 (19)
C8—C7—C1128.4 (2)C12—N3—N4111.0 (2)
C9—C8—C7104.9 (2)C12—N3—H3124.5
C9—C8—H8127.5N4—N3—H3124.5
C7—C8—H8127.5C10—N4—N3106.1 (2)
N1—C9—C8108.6 (2)C15—N5—N6111.2 (2)
N1—C9—H9125.7C15—N5—H5124.4
C8—C9—H9125.7N6—N5—H5124.4
N4—C10—C11109.5 (2)C13—N6—N5106.0 (2)
N4—C10—C3121.4 (2)
C6—C1—C2—C31.0 (4)N4—C10—C11—C120.1 (3)
C7—C1—C2—C3177.7 (2)C3—C10—C11—C12176.5 (2)
C1—C2—C3—C41.6 (4)C10—C11—C12—N30.9 (3)
C1—C2—C3—C10175.9 (2)C6—C5—C13—N6162.0 (3)
C2—C3—C4—C51.0 (4)C4—C5—C13—N617.4 (4)
C10—C3—C4—C5176.4 (2)C6—C5—C13—C1417.5 (4)
C3—C4—C5—C60.2 (4)C4—C5—C13—C14163.0 (3)
C3—C4—C5—C13179.7 (3)N6—C13—C14—C150.4 (3)
C4—C5—C6—C10.8 (4)C5—C13—C14—C15179.2 (3)
C13—C5—C6—C1179.7 (3)C13—C14—C15—N50.4 (3)
C2—C1—C6—C50.2 (4)C8—C9—N1—N20.7 (3)
C7—C1—C6—C5178.9 (2)C8—C7—N2—N11.7 (3)
C6—C1—C7—N2159.7 (2)C1—C7—N2—N1178.7 (2)
C2—C1—C7—N221.6 (4)C9—N1—N2—C70.6 (3)
C6—C1—C7—C820.7 (4)C11—C12—N3—N41.4 (3)
C2—C1—C7—C8158.0 (3)C11—C10—N4—N30.7 (3)
N2—C7—C8—C92.1 (3)C3—C10—N4—N3177.6 (2)
C1—C7—C8—C9178.3 (2)C12—N3—N4—C101.3 (3)
C7—C8—C9—N11.7 (3)C14—C15—N5—N60.3 (3)
C4—C3—C10—N45.3 (4)C14—C13—N6—N50.2 (3)
C2—C3—C10—N4177.3 (2)C5—C13—N6—N5179.4 (2)
C4—C3—C10—C11171.0 (3)C15—N5—N6—C130.1 (3)
C2—C3—C10—C116.4 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N5—H5···N2i0.862.102.960 (3)173
N3—H3···N6ii0.862.042.875 (3)163
N1—H1···N4iii0.862.012.855 (3)169
Symmetry codes: (i) x+1/2, y+1/2, z+1; (ii) x+1, y+1, z1/2; (iii) x+1/2, y1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC15H12N6
Mr276.31
Crystal system, space groupOrthorhombic, Pna21
Temperature (K)293
a, b, c (Å)8.183 (5), 17.128 (5), 9.173 (5)
V3)1285.7 (11)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.43 × 0.28 × 0.27
Data collection
DiffractometerBruker SMART APEX II CCD
Absorption correctionMulti-scan
(SADABS; Bruker, 2004)
Tmin, Tmax0.962, 0.976
No. of measured, independent and
observed [I > 2σ(I)] reflections
7598, 1670, 1342
Rint0.037
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.112, 1.03
No. of reflections1670
No. of parameters190
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.26, 0.18
Absolute structureFlack (1983), Number of Friedel pairs?
Absolute structure parameter10 (10)

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SAINT, SHELXTL (Sheldrick, 2001), SHELXTL and local programs.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N5—H5···N2i0.862.102.960 (3)173.2
N3—H3···N6ii0.862.042.875 (3)162.5
N1—H1···N4iii0.862.012.855 (3)168.7
Symmetry codes: (i) x+1/2, y+1/2, z+1; (ii) x+1, y+1, z1/2; (iii) x+1/2, y1/2, z1/2.
 

Subscribe to Acta Crystallographica Section E: Crystallographic Communications

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds