N-(Pyrazin-2-yl)-1,8-naphthyridin-2-amine

Duan, Y.-S.; Wang, W.-Z.; Wen, Y.-S.; Zhu, Y.-Q.; Peng, S.-M.

doi:10.1107/S160053681300319X

organic compounds

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ISSN: 2056-9890

Volume 69| Part 3| March 2013| Page o349

doi:10.1107/S160053681300319X

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N-(Pyrazin-2-yl)-1,8-naphthyridin-2-amine

Yan-Shan Duan,^a Wen-Zhen Wang,^a ^* Yuh-Sheng Wen,^b Yu-Qin Zhu ^a and Shie-Ming Peng ^c

^aSchool of Chemistry and Chemical Engineering, Xi'an Shiyou University, Xi'an 710065, People's Republic of China, ^bInstitute of Chemistry, Academia Sinica, Taipei, Taiwan, and ^cDepartment of Chemistry, National Taiwan University, Taipei 106, Taiwan
^*Correspondence e-mail: wzwang@xsyu.edu.cn, smpeng@ntu.edu.tw

(Received 30 November 2012; accepted 31 January 2013; online 6 February 2013)

There are two independent molecules in the asymmetric unit of the title compound, C₁₂H₉N₅, in which the C—N(amine)—C angles differ slightly [129.63 (11) and 132.02 (11)°]. In each independent molecule, an intramolecular C—H⋯N hydrogen bond stabilizes the molecular structure, forming an S(6) ring motif. The independent molecules are linked via an N—H⋯N hydrogen bond. Further N—H⋯N and C—H⋯N hydrogen bonds connect the molecules into chains along c axis. Pairs of C—H⋯π interactions between the chains lead to sheets parallel to the b axis. These are linked by π–π interactions between the naphthyridine and pyrazine rings [centroid–centroid separations of 3.553 (8) Å] into a three-dimensional supramolecular network.

Related literature

For related structures, see: Alvarez-Rua et al. (2004 ); Basato et al. (2006 ); Ghosh et al. (2010 ); Jin et al. (2010 , 2011 ). For graph-set analysis, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₂H₉N₅
M_r = 223.24
Triclinic, $[P \overline 1]$
a = 7.8608 (3) Å
b = 11.8200 (5) Å
c = 11.9356 (4) Å
α = 105.096 (2)°
β = 98.086 (2)°
γ = 101.854 (2)°
V = 1025.53 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.28 × 0.2 × 0.18 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.927, T_max = 0.991
16351 measured reflections
3606 independent reflections
2557 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.074
S = 0.93
3606 reflections
308 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the N22/C23–C25/C29/C30 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C27—H27⋯N33	0.93	2.33	2.9318 (17)	122
C17—H17⋯N1	0.93	2.24	2.8518 (17)	123
N31—H31⋯N2	0.86	2.14	2.9396 (15)	154
N11—H11⋯N22ⁱ	0.86	2.23	3.0766 (15)	171
C26—H26⋯N16ⁱⁱ	0.93	2.51	3.3608 (17)	152
C15—H15⋯Cg1ⁱⁱⁱ	0.93	2.74	3.472 (2)	136
Symmetry codes: (i) -x, -y+1, -z; (ii) -x, -y+1, -z+1; (iii) x, y+1, z.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681300319X/rk2390sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681300319X/rk2390Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681300319X/rk2390Isup3.cml

checkCIF report

Comment top

1,8-Naphthyridine, a simple heterocycle compound with two ring nitrogen atoms as hydrogen bond acceptors, has been widely used by various groups in the area of molecular recognition research as hydrogen bonding building block. Some interesting coordination polymers assembled with 1,8-naphthyridine have been reported, showing various structural motifs (Alvarez-Rua et al., 2004; Basato et al., 2006; Ghosh et al., 2010; Jin et al., 2010; Jin et al., 2011). The title compound, C₁₂H₉N₅, I, contains an array of hydrogen bond NH donors and N acceptors and therefore follow different hydrogen bonding packing patterns. In this paper, we report its crystal structure, which crystallizes with two unique molecules, A & B (Fig. 1), focusing on three-dimensional supramolecular network via weak noncovalent interactions.

The molecular structure of the title compound is shown in Fig. 1. The C—N(amine)—C angles of the two chemically equal molecules in the dimer are slightly diferent, showing 129.63 (11)° and 132.02 (11)°, for molecule A and B, respectively. Two intramolecular hydrogen bonds C27—H27···N33 and C17—H17···N1 (Table 1) stabilize the molecular structure and result in an S(6) ring motif (Bernstein et al., 1995). Two independent molecules in the title compound form a molecular pair via N31—H31···N2 hydrogen bonds (Fig. 1). N11—H11···N22ⁱ intermolecular hydrogen bonds link dimer molecules into rings as basic expanding units, which are joined into one-dimensional chains along c axis through C26—H26···N16ⁱⁱ hydrogen bonds (Fig. 2). Pairs of C15—H15···Cgⁱⁱⁱ interactions between the chains construct sheets parallel to b axis (Fig. 3). Extensive three dimensional supramolecular networks are formed by π–π interactions between the naphthyridine and pyrazine rings with centroid–centroid separations of 3.553 (8)Å propagating along a axis (Fig. 4). Symmetry codes: (i) -x, -y+1, -z; (ii) -x, -y+1, -z+1; (iii) x, y+1, z.

Related literature top

For related structures, see: Alvarez-Rua et al. (2004); Basato et al. (2006); Ghosh et al. (2010); Jin et al. (2010, 2011). For graph-set analysis, see: Bernstein et al. (1995).

Experimental top

A mixture of 2-chloro-1,8-naphthyridine (8.0 g, 40 mmol), pyrazin-2-amine (4.6 g, 48 mmol), Pd₂(dba)₃ (0.73 g, 0.80 mmol) (dba is dibenzylideneacetone), 1,3-bis(diphenylphosphino)propane (0.66 g, 1.6 mmol) and Bu^tOK (13.1 g, 136 mmol) in dry toluene (350 ml) was refluxed under argon with stirring for 4 days. The crude product was washed with water, benzene and methanol and recrystallized from acetone.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. The molecular structure of I with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as a small spheres of arbitrary radius. H bonds are indicated by dashed lines.
	Fig. 2. Chains parallel c axis in the crystal structure of I. H bonds are indicated with dashed lines. Symmetry codes: (i) -x, -y+1, -z; (ii) -x, -y+1, -z+1.
	Fig. 3. A sheet parallels b axis in the crystal structure of I. H bonds are indicated with dashed lines. Symmetry code: (iii) x, y+1, z.
	Fig. 4. Three dimensional network in the crystal structure of I via π–π interactions between the naphthyridine and pyrazine rings. H bonds are indicated with dashed lines. Naphthyridine and pyrazine rings paired with π–π interaction are presented as spacefilled.

N-(Pyrazin-2-yl)-1,8-naphthyridin-2-amine top

Crystal data top

C₁₂H₉N₅	Z = 4
M_r = 223.24	F(000) = 464
Triclinic, P1	D_x = 1.446 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8608 (3) Å	Cell parameters from 5652 reflections
b = 11.8200 (5) Å	θ = 2.7–29.1°
c = 11.9356 (4) Å	µ = 0.09 mm⁻¹
α = 105.096 (2)°	T = 100 K
β = 98.086 (2)°	Prism, yellow
γ = 101.854 (2)°	0.28 × 0.2 × 0.18 mm
V = 1025.53 (7) Å³

Data collection top

Bruker SMART APEX CCD diffractometer	3606 independent reflections
Radiation source: fine-focus sealed tube	2557 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −8→9
T_min = 0.927, T_max = 0.991	k = −14→14
16351 measured reflections	l = −14→14

Refinement top

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)] = 0.031	H-atom parameters constrained
wR(F²) = 0.074	w = 1/[σ²(F_o²) + (0.0411P)²] where P = (F_o² + 2F_c²)/3
S = 0.93	(Δ/σ)_max < 0.001
3606 reflections	Δρ_max = 0.18 e Å⁻³
308 parameters	Δρ_min = −0.20 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0042 (11)

Crystal data top

C₁₂H₉N₅	γ = 101.854 (2)°
M_r = 223.24	V = 1025.53 (7) Å³
Triclinic, P1	Z = 4
a = 7.8608 (3) Å	Mo Kα radiation
b = 11.8200 (5) Å	µ = 0.09 mm⁻¹
c = 11.9356 (4) Å	T = 100 K
α = 105.096 (2)°	0.28 × 0.2 × 0.18 mm
β = 98.086 (2)°

Data collection top

Bruker SMART APEX CCD diffractometer	3606 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2557 reflections with I > 2σ(I)
T_min = 0.927, T_max = 0.991	R_int = 0.037
16351 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.074	H-atom parameters constrained
S = 0.93	Δρ_max = 0.18 e Å⁻³
3606 reflections	Δρ_min = −0.20 e Å⁻³
308 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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

	x	y	z	U_iso*/U_eq
N1	0.22552 (13)	0.57902 (10)	0.04843 (9)	0.0189 (3)
N2	0.21678 (14)	0.40952 (10)	0.10986 (9)	0.0201 (3)
N11	0.22899 (14)	0.75053 (10)	−0.01282 (9)	0.0209 (3)
H11	0.2565	0.7845	−0.0656	0.025*
N13	0.14424 (14)	0.92338 (10)	0.06217 (10)	0.0222 (3)
N16	0.09496 (15)	0.86566 (11)	0.26882 (10)	0.0260 (3)
N21	−0.04515 (14)	0.29804 (9)	0.29392 (9)	0.0196 (3)
N22	−0.27965 (14)	0.13223 (10)	0.21168 (10)	0.0234 (3)
N31	0.18130 (14)	0.46608 (10)	0.35900 (9)	0.0213 (3)
H31	0.1625	0.4602	0.2847	0.026*
N33	0.36229 (14)	0.58552 (10)	0.54390 (10)	0.0238 (3)
N36	0.52942 (15)	0.73882 (10)	0.42486 (10)	0.0277 (3)
C3	0.23662 (17)	0.29818 (12)	0.09116 (12)	0.0230 (3)
H3	0.2164	0.2607	0.1493	0.028*
C4	0.28551 (17)	0.23258 (12)	−0.00894 (12)	0.0238 (3)
H4	0.2998	0.1550	−0.0162	0.029*
C5	0.31171 (17)	0.28572 (12)	−0.09594 (12)	0.0232 (3)
H5	0.3434	0.2444	−0.1642	0.028*
C6	0.31156 (17)	0.46677 (13)	−0.16631 (12)	0.0229 (3)
H6	0.3405	0.4303	−0.2376	0.027*
C7	0.28987 (17)	0.57976 (13)	−0.14393 (12)	0.0227 (3)
H7	0.3026	0.6219	−0.1993	0.027*
C8	0.24673 (16)	0.63419 (12)	−0.03287 (12)	0.0188 (3)
C9	0.24464 (16)	0.46328 (12)	0.02396 (11)	0.0177 (3)
C10	0.29047 (16)	0.40294 (12)	−0.08155 (11)	0.0190 (3)
C12	0.17354 (17)	0.82116 (12)	0.07953 (11)	0.0182 (3)
C14	0.08721 (18)	0.99392 (12)	0.14756 (12)	0.0237 (3)
H14	0.0626	1.0647	0.1374	0.028*
C15	0.06335 (18)	0.96630 (12)	0.24991 (12)	0.0235 (3)
H15	0.0243	1.0189	0.3072	0.028*
C17	0.14880 (18)	0.79278 (13)	0.18385 (11)	0.0234 (3)
H17	0.1705	0.7213	0.1939	0.028*
C23	−0.38828 (18)	0.03571 (13)	0.22223 (13)	0.0261 (4)
H23	−0.4718	−0.0141	0.1553	0.031*
C24	−0.38621 (19)	0.00346 (13)	0.32681 (13)	0.0281 (4)
H24	−0.4634	−0.0670	0.3282	0.034*
C25	−0.26920 (18)	0.07709 (12)	0.42639 (13)	0.0257 (4)
H25	−0.2672	0.0584	0.4975	0.031*
C26	−0.02570 (17)	0.26653 (12)	0.51840 (12)	0.0224 (3)
H26	−0.0175	0.2559	0.5933	0.027*
C27	0.08325 (18)	0.36368 (12)	0.50309 (12)	0.0223 (3)
H27	0.1639	0.4214	0.5670	0.027*
C28	0.07114 (17)	0.37501 (12)	0.38708 (12)	0.0191 (3)
C29	−0.15825 (17)	0.20387 (12)	0.31086 (12)	0.0194 (3)
C30	−0.15148 (18)	0.18136 (12)	0.42162 (12)	0.0201 (3)
C32	0.31538 (17)	0.56440 (12)	0.42761 (12)	0.0188 (3)
C34	0.49447 (18)	0.68540 (13)	0.60011 (13)	0.0268 (4)
H34	0.5317	0.7046	0.6818	0.032*
C35	0.57667 (19)	0.76004 (13)	0.54274 (13)	0.0291 (4)
H35	0.6679	0.8275	0.5865	0.035*
C37	0.39957 (17)	0.64185 (12)	0.36948 (13)	0.0228 (3)
H37	0.3617	0.6237	0.2880	0.027*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0177 (6)	0.0199 (7)	0.0191 (7)	0.0044 (5)	0.0036 (5)	0.0062 (6)
N2	0.0206 (7)	0.0181 (7)	0.0208 (7)	0.0028 (5)	0.0040 (5)	0.0064 (5)
N11	0.0256 (7)	0.0230 (7)	0.0192 (6)	0.0083 (5)	0.0100 (5)	0.0103 (6)
N13	0.0249 (7)	0.0188 (7)	0.0238 (7)	0.0058 (5)	0.0058 (6)	0.0072 (6)
N16	0.0345 (7)	0.0259 (7)	0.0207 (7)	0.0129 (6)	0.0076 (6)	0.0071 (6)
N21	0.0220 (7)	0.0188 (7)	0.0187 (6)	0.0062 (5)	0.0059 (5)	0.0051 (6)
N22	0.0243 (7)	0.0218 (7)	0.0230 (7)	0.0043 (6)	0.0071 (6)	0.0049 (6)
N31	0.0258 (7)	0.0228 (7)	0.0155 (6)	0.0050 (6)	0.0051 (5)	0.0067 (5)
N33	0.0217 (7)	0.0272 (7)	0.0213 (7)	0.0096 (6)	0.0043 (6)	0.0027 (6)
N36	0.0244 (7)	0.0252 (7)	0.0313 (8)	0.0060 (6)	0.0050 (6)	0.0049 (6)
C3	0.0210 (8)	0.0208 (9)	0.0249 (8)	0.0006 (7)	0.0022 (7)	0.0083 (7)
C4	0.0205 (8)	0.0186 (8)	0.0285 (9)	0.0038 (6)	0.0014 (7)	0.0034 (7)
C5	0.0179 (8)	0.0242 (9)	0.0227 (8)	0.0056 (7)	0.0026 (6)	−0.0006 (7)
C6	0.0208 (8)	0.0321 (9)	0.0157 (8)	0.0093 (7)	0.0056 (6)	0.0042 (7)
C7	0.0230 (8)	0.0291 (9)	0.0194 (8)	0.0085 (7)	0.0069 (7)	0.0098 (7)
C8	0.0136 (7)	0.0221 (8)	0.0201 (8)	0.0041 (6)	0.0016 (6)	0.0066 (7)
C9	0.0129 (7)	0.0193 (8)	0.0180 (8)	0.0011 (6)	0.0002 (6)	0.0046 (6)
C10	0.0134 (7)	0.0216 (8)	0.0186 (8)	0.0030 (6)	0.0007 (6)	0.0028 (7)
C12	0.0157 (7)	0.0184 (8)	0.0183 (8)	0.0031 (6)	0.0017 (6)	0.0040 (6)
C14	0.0252 (8)	0.0175 (8)	0.0269 (9)	0.0053 (7)	0.0039 (7)	0.0051 (7)
C15	0.0264 (8)	0.0209 (8)	0.0220 (8)	0.0082 (7)	0.0043 (7)	0.0031 (7)
C17	0.0302 (9)	0.0248 (9)	0.0188 (8)	0.0127 (7)	0.0063 (7)	0.0075 (7)
C23	0.0252 (8)	0.0226 (8)	0.0293 (9)	0.0052 (7)	0.0097 (7)	0.0041 (7)
C24	0.0302 (9)	0.0226 (9)	0.0349 (9)	0.0062 (7)	0.0147 (8)	0.0106 (8)
C25	0.0324 (9)	0.0271 (9)	0.0259 (9)	0.0132 (7)	0.0140 (7)	0.0132 (7)
C26	0.0276 (8)	0.0285 (9)	0.0184 (8)	0.0141 (7)	0.0097 (7)	0.0112 (7)
C27	0.0242 (8)	0.0269 (9)	0.0178 (8)	0.0108 (7)	0.0050 (6)	0.0064 (7)
C28	0.0208 (8)	0.0189 (8)	0.0218 (8)	0.0103 (7)	0.0080 (7)	0.0071 (7)
C29	0.0212 (8)	0.0182 (8)	0.0221 (8)	0.0092 (6)	0.0091 (7)	0.0059 (7)
C30	0.0228 (8)	0.0210 (8)	0.0219 (8)	0.0113 (7)	0.0100 (7)	0.0083 (7)
C32	0.0174 (8)	0.0183 (8)	0.0205 (8)	0.0086 (6)	0.0038 (6)	0.0023 (7)
C34	0.0210 (8)	0.0309 (9)	0.0245 (9)	0.0096 (7)	0.0024 (7)	0.0003 (7)
C35	0.0217 (8)	0.0259 (9)	0.0326 (10)	0.0058 (7)	0.0023 (7)	−0.0012 (7)
C37	0.0217 (8)	0.0228 (8)	0.0241 (8)	0.0081 (7)	0.0043 (7)	0.0059 (7)

Geometric parameters (Å, º) top

N1—C8	1.3134 (15)	C6—C7	1.3434 (18)
N1—C9	1.3669 (16)	C6—C10	1.4190 (17)
N2—C3	1.3218 (16)	C6—H6	0.9300
N2—C9	1.3596 (15)	C7—C8	1.4346 (18)
N11—C8	1.3727 (16)	C7—H7	0.9300
N11—C12	1.3810 (16)	C9—C10	1.4105 (18)
N11—H11	0.8600	C12—C17	1.4000 (17)
N13—C14	1.3321 (17)	C14—C15	1.3715 (17)
N13—C12	1.3368 (16)	C14—H14	0.9300
N16—C17	1.3286 (16)	C15—H15	0.9300
N16—C15	1.3316 (16)	C17—H17	0.9300
N21—C28	1.3211 (16)	C23—C24	1.3957 (19)
N21—C29	1.3534 (15)	C23—H23	0.9300
N22—C23	1.3234 (16)	C24—C25	1.3568 (19)
N22—C29	1.3628 (16)	C24—H24	0.9300
N31—C32	1.3748 (16)	C25—C30	1.4005 (18)
N31—C28	1.3812 (15)	C25—H25	0.9300
N31—H31	0.8600	C26—C27	1.3545 (18)
N33—C32	1.3277 (16)	C26—C30	1.4105 (18)
N33—C34	1.3456 (17)	C26—H26	0.9300
N36—C37	1.3143 (16)	C27—C28	1.4174 (17)
N36—C35	1.3459 (17)	C27—H27	0.9300
C3—C4	1.3947 (19)	C29—C30	1.4108 (17)
C3—H3	0.9300	C32—C37	1.4030 (17)
C4—C5	1.3645 (18)	C34—C35	1.3674 (19)
C4—H4	0.9300	C34—H34	0.9300
C5—C10	1.3987 (19)	C35—H35	0.9300
C5—H5	0.9300	C37—H37	0.9300

C8—N1—C9	117.38 (11)	C15—C14—H14	118.7
C3—N2—C9	117.13 (11)	N16—C15—C14	121.31 (13)
C8—N11—C12	129.63 (11)	N16—C15—H15	119.3
C8—N11—H11	115.2	C14—C15—H15	119.3
C12—N11—H11	115.2	N16—C17—C12	121.52 (13)
C14—N13—C12	116.49 (12)	N16—C17—H17	119.2
C17—N16—C15	117.14 (12)	C12—C17—H17	119.2
C28—N21—C29	117.94 (11)	N22—C23—C24	124.57 (14)
C23—N22—C29	116.70 (12)	N22—C23—H23	117.7
C32—N31—C28	132.02 (11)	C24—C23—H23	117.7
C32—N31—H31	114.0	C25—C24—C23	118.61 (13)
C28—N31—H31	114.0	C25—C24—H24	120.7
C32—N33—C34	115.12 (12)	C23—C24—H24	120.7
C37—N36—C35	115.33 (12)	C24—C25—C30	119.71 (13)
N2—C3—C4	125.08 (13)	C24—C25—H25	120.1
N2—C3—H3	117.5	C30—C25—H25	120.1
C4—C3—H3	117.5	C27—C26—C30	120.52 (12)
C5—C4—C3	117.96 (13)	C27—C26—H26	119.7
C5—C4—H4	121.0	C30—C26—H26	119.7
C3—C4—H4	121.0	C26—C27—C28	118.26 (13)
C4—C5—C10	119.43 (13)	C26—C27—H27	120.9
C4—C5—H5	120.3	C28—C27—H27	120.9
C10—C5—H5	120.3	N21—C28—N31	112.89 (11)
C7—C6—C10	120.20 (12)	N21—C28—C27	123.37 (12)
C7—C6—H6	119.9	N31—C28—C27	123.73 (13)
C10—C6—H6	119.9	N21—C29—N22	114.31 (11)
C6—C7—C8	118.70 (13)	N21—C29—C30	123.03 (12)
C6—C7—H7	120.7	N22—C29—C30	122.66 (12)
C8—C7—H7	120.7	C25—C30—C26	125.60 (12)
N1—C8—N11	119.77 (12)	C25—C30—C29	117.65 (13)
N1—C8—C7	123.49 (13)	C26—C30—C29	116.75 (12)
N11—C8—C7	116.74 (12)	N33—C32—N31	121.43 (12)
N2—C9—N1	114.86 (11)	N33—C32—C37	121.48 (13)
N2—C9—C10	121.80 (12)	N31—C32—C37	117.09 (12)
N1—C9—C10	123.33 (12)	N33—C34—C35	123.07 (13)
C5—C10—C9	118.57 (12)	N33—C34—H34	118.5
C5—C10—C6	124.57 (12)	C35—C34—H34	118.5
C9—C10—C6	116.86 (12)	N36—C35—C34	121.93 (14)
N13—C12—N11	113.96 (11)	N36—C35—H35	119.0
N13—C12—C17	120.91 (12)	C34—C35—H35	119.0
N11—C12—C17	125.13 (12)	N36—C37—C32	123.07 (13)
N13—C14—C15	122.60 (13)	N36—C37—H37	118.5
N13—C14—H14	118.7	C32—C37—H37	118.5

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the N22/C23–C25/C29/C30 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C27—H27···N33	0.93	2.33	2.9318 (17)	122
C17—H17···N1	0.93	2.24	2.8518 (17)	123
N31—H31···N2	0.86	2.14	2.9396 (15)	154
N11—H11···N22ⁱ	0.86	2.23	3.0766 (15)	171
C26—H26···N16ⁱⁱ	0.93	2.51	3.3608 (17)	152
C15—H15···Cg1ⁱⁱⁱ	0.93	2.74	3.472 (2)	136

Symmetry codes: (i) −x, −y+1, −z; (ii) −x, −y+1, −z+1; (iii) x, y+1, z.

Experimental details

Crystal data
Chemical formula	C₁₂H₉N₅
M_r	223.24
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	7.8608 (3), 11.8200 (5), 11.9356 (4)
α, β, γ (°)	105.096 (2), 98.086 (2), 101.854 (2)
V (Å³)	1025.53 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.28 × 0.2 × 0.18

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.927, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	16351, 3606, 2557
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.074, 0.93
No. of reflections	3606
No. of parameters	308
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.20

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), WinGX (Farrugia, 2012).

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the N22/C23–C25/C29/C30 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C27—H27···N33	0.93	2.33	2.9318 (17)	122.1
C17—H17···N1	0.93	2.24	2.8518 (17)	122.7
N31—H31···N2	0.86	2.14	2.9396 (15)	153.5
N11—H11···N22ⁱ	0.86	2.23	3.0766 (15)	170.5
C26—H26···N16ⁱⁱ	0.93	2.51	3.3608 (17)	152.3
C15—H15···Cg1ⁱⁱⁱ	0.93	2.74	3.472 (2)	136.0

Symmetry codes: (i) −x, −y+1, −z; (ii) −x, −y+1, −z+1; (iii) x, y+1, z.

Acknowledgements

Financial support for this study came from the National Science Council of the Republic of China, the Natural Science Foundation of Shaanxi Province (No. 2012JM2011) and the Education Department of Shaanxi Province special scientific research plan (No. 11JK0606).

References

Alvarez-Rua, C., García-Granda, S., Goswami, S., Mukherjee, R., Dey, S., Claramunt, R. M., María, M. D. S., Rozas, I., Jagerovic, N., Alkortae, I. & Elguero, J. (2004). New J. Chem. 28, 700–707. CAS Google Scholar
Basato, M., Biffis, A., Martinati, G., Tubaro, C., Graiff, C., Tiripicchio, A., Aronica, L. A. & Caporusso, A. M. (2006). J. Organomet. Chem. 691, 3464–3471. Web of Science CSD CrossRef CAS Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ghosh, K., Sen, T. & Fröhlich, R. (2010). J. Incl. Phenom. Macrocycl. Chem. 68, 193–199. Web of Science CSD CrossRef CAS Google Scholar
Jin, S.-W., Liu, L., Wang, D.-Q. & Guo, J.-Z. (2011). J. Mol. Struct. 1005, 59–69. Web of Science CSD CrossRef CAS Google Scholar
Jin, S.-W., Zhang, W.-B., Liu, L., Gao, H.-F., Wang, D.-Q., Chen, R.-P. & Xu, X.-L. (2010). J. Mol. Struct. 975, 128–136. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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