3-Phenyl­pyrazole, a pseudosymmetric structure with Z′ = 6

Haghiri, A.; Lerner, H.-W.; Wagner, M.; Bats, J.W.

doi:10.1107/S1600536802020445

3-Phenylpyrazole, a pseudosymmetric structure with Z′ = 6

A. Haghiri, H.-W. Lerner, M. Wagner and J. W. Bats

The title compound, C₉H₈N₂, is triclinic (space group P $\overline 1$ with Z′ = 6). Six molecules are connected by N—H

N hydrogen bonds into centrosymmetric hexamers. The two independent hexamers are related by a pseudosymmetric glide plane.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802020445/na6180sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536802020445/na6180Isup2.hkl Contains datablock I

CCDC reference: 202333

checkCIF report

Key indicators

Single-crystal X-ray study
T = 148 K
Mean (C-C) = 0.002 Å
R factor = 0.049
wR factor = 0.124
Data-to-parameter ratio = 23.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

Comment top

Tris(1-pyrazolyl)borates (scorpionates) were invented more than 30 years ago and are today well established as ligands in coordination chemistry (Trofimenko, 1993). Scorpionates now find wide-ranging applications in chemistry, from modelling the active site of metal enzymes, through analytical chemistry and organic chemistry to catalysis and material science (Edelmann, 2001). Given this background, we became interested in the synthesis of transition metal complexes of hydrotri(3-phenylpyrazol-1-yl)borate. Therefore, we prepared 3-phenylpyrazole, (I). The synthesis of (I) was confirmed by a crystal structure determination.

The structure of (I) contains six independent molecules, labeled A to F (Fig. 1). The dimensions of the six molecules are very similar. The pyrazole and phenyl groups of each molecule are approximately planar. The angles between the planes of the pyrazole and phenyl groups are 9.21 (11), 8.10 (5), 9.38 (6), 27.62 (7), 6.21 (4) and 21.33 (4)° for molecules A–F, respectively. The crystal structure contains two independent clusters of six molecules connected by N—H.·N hydrogen bonds (Table 1). The six-membered clusters are centrosymmetric. One hexamer contains molecules A, B and C, while the other contains molecules D, E and F. Both hexamers have rather similar conformations (Fig. 2). Each is additionally stabilized by two symmetry-related C_pyrazole—H···π_pyrazole and C_pyrazole—H···π_phenyl interactions, with H···π distances between 2.64 and 2.83 Å, and C—H···π angles between 138 and 152° (π represents the centroid of the corresponding pyrazole or phenyl ring). Different hexamers are connected by seven additional intermolecular C—-H···π_pyrazole or C–H···π_phenyl interactions, with H···π distances between 2.76 and 3.14 Å, and C—H···π angles between 123 and 170°. One interaction is found between each of the symmetry-related hexamers, while five interactions connect symmetry-independent hexamers. The hexamer containing molecules A, B and C mainly occupies the section of the unit cell defined by 1/4 < z < 3/4 (Fig. 3). The hexamer containing molecules D, E and F is mainly confined to the section of the unit cell defined by −1/4 < z < 1/4. The crystal packing in both sections of the unit cell is very similar. The arrangement of the molecules in the latter section can approximately be obtained from the structure of the first section by interchanging the a and b axes. This shows the crystal structure of the title compound to be pseudosymmetric. The coordinates of the atoms in the two independent hexamers are related by the pseudosymmetry relations: x_ABC ~0.5 − y_DEF, y_ABC ~1 − x_DEF, z_ABC ~0.5 − z_DEF and x_ABC ~0.5 + y_DⁱEⁱFⁱ, y_ABC ~x_DⁱEⁱFⁱ, z_ABC ~0.5 + z_DⁱEⁱFⁱ [symmetry code: (i) 1 − x, −y, −z]. The latter pseudosymmetry relation corresponds to an approximate c-glide plane perpendicular to the a,¯b diagonal. A crystal structure with similar pseudosymmetric domains connected by C—H···π interactions has been reported by Bats et al. (1999).

Experimental top

3-Phenylpyrazole was synthesized as reported by Buchner & Hachumian (1902). Single crystals suitable for data collection were obtained by recrystallization from chloroform at ambient temperature.

Computing details top

Data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Sheldrick, 1996); software used to prepare material for publication: SHELXL97.

Figures top

	Fig. 1. The structure of molecule A shown with with 50% probability displacement ellipsoids. A similar numbering scheme is used for molecules B, C, D, E and F.
	Fig. 2. The hydrogen-bonded hexamer of molecules A, B, C, Aⁱ, Bⁱ and Cⁱ [symmetry code: (i) 1 − x, 1 − y, 1 − z].
	Fig. 3. The crystal packing of (I), viewed down c. A section with 1/4 < z < 3/4 containing only hexamers with molecules A, B and C is shown.

3-phenylpyrazole top

Crystal data top

C₉H₈N₂	Z = 12
M_r = 144.17	F(000) = 912
Triclinic, P1	D_x = 1.262 Mg m⁻³
a = 12.1514 (10) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.3120 (11) Å	Cell parameters from 324 reflections
c = 17.114 (2) Å	θ = 3–26°
α = 88.164 (11)°	µ = 0.08 mm⁻¹
β = 88.103 (12)°	T = 148 K
γ = 62.816 (6)°	Block, colorless
V = 2275.9 (4) Å³	0.50 × 0.48 × 0.40 mm

Data collection top

Siemens SMART CCD diffractometer	14026 independent reflections
Radiation source: normal-focus sealed tube	10303 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
ω scans	θ_max = 31.0°, θ_min = 1.9°
Absorption correction: numerical (SHELXTL; Sheldrick, 1996)	h = −17→17
T_min = 0.959, T_max = 0.975	k = −17→17
40438 measured reflections	l = −23→24

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)] = 0.049	H-atom parameters constrained
wR(F²) = 0.124	w = 1/[σ²(F_o²) + (0.04P)² + 0.9P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
14026 reflections	Δρ_max = 0.34 e Å⁻³
596 parameters	Δρ_min = −0.27 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0011 (3)

Crystal data top

C₉H₈N₂	γ = 62.816 (6)°
M_r = 144.17	V = 2275.9 (4) Å³
Triclinic, P1	Z = 12
a = 12.1514 (10) Å	Mo Kα radiation
b = 12.3120 (11) Å	µ = 0.08 mm⁻¹
c = 17.114 (2) Å	T = 148 K
α = 88.164 (11)°	0.50 × 0.48 × 0.40 mm
β = 88.103 (12)°

Data collection top

Siemens SMART CCD diffractometer	14026 independent reflections
Absorption correction: numerical (SHELXTL; Sheldrick, 1996)	10303 reflections with I > 2σ(I)
T_min = 0.959, T_max = 0.975	R_int = 0.038
40438 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.124	H-atom parameters constrained
S = 1.05	Δρ_max = 0.34 e Å⁻³
14026 reflections	Δρ_min = −0.27 e Å⁻³
596 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

	x	y	z	U_iso*/U_eq
N1A	0.26055 (10)	0.44741 (10)	0.47252 (6)	0.0248 (2)
N2A	0.20349 (10)	0.56046 (10)	0.50295 (6)	0.0272 (2)
H2NA	0.2181	0.6213	0.4868	0.033*
C1A	0.12195 (13)	0.56947 (13)	0.56055 (8)	0.0316 (3)
H1A	0.0720	0.6401	0.5899	0.038*
C2A	0.12483 (12)	0.45679 (12)	0.56871 (8)	0.0296 (3)
H2A	0.0776	0.4336	0.6046	0.036*
C3A	0.21228 (11)	0.38318 (11)	0.51294 (7)	0.0223 (2)
C4A	0.25082 (11)	0.25374 (11)	0.49731 (7)	0.0237 (2)
C5A	0.35027 (15)	0.18583 (14)	0.44807 (10)	0.0440 (4)
H5A	0.3970	0.2225	0.4241	0.053*
C6A	0.38200 (18)	0.06489 (15)	0.43349 (12)	0.0548 (5)
H6A	0.4494	0.0201	0.3988	0.066*
C7A	0.31724 (16)	0.00867 (14)	0.46848 (10)	0.0418 (4)
H7A	0.3399	−0.0744	0.4585	0.050*
C8A	0.21936 (15)	0.07459 (14)	0.51800 (10)	0.0407 (3)
H8A	0.1746	0.0365	0.5429	0.049*
C9A	0.18526 (13)	0.19654 (13)	0.53192 (9)	0.0347 (3)
H9A	0.1163	0.2414	0.5655	0.042*
N1B	0.30697 (10)	0.70842 (10)	0.42865 (6)	0.0259 (2)
N2B	0.42373 (10)	0.66906 (11)	0.45362 (7)	0.0290 (2)
H2NB	0.4462	0.6470	0.5023	0.035*
C1B	0.50110 (14)	0.66756 (15)	0.39560 (9)	0.0374 (3)
H1B	0.5869	0.6435	0.3998	0.045*
C2B	0.43328 (13)	0.70722 (15)	0.32898 (8)	0.0364 (3)
H2B	0.4620	0.7161	0.2780	0.044*
C3B	0.31204 (12)	0.73206 (11)	0.35213 (7)	0.0245 (2)
C4B	0.20062 (11)	0.77751 (11)	0.30429 (7)	0.0238 (2)
C5B	0.08326 (12)	0.81235 (12)	0.33827 (8)	0.0291 (3)
H5B	0.0747	0.8062	0.3934	0.035*
C6B	−0.02066 (13)	0.85566 (14)	0.29232 (9)	0.0341 (3)
H6B	−0.0998	0.8791	0.3162	0.041*
C7B	−0.00999 (13)	0.86495 (13)	0.21178 (9)	0.0337 (3)
H7B	−0.0813	0.8945	0.1804	0.040*
C8B	0.10556 (14)	0.83080 (13)	0.17754 (8)	0.0334 (3)
H8B	0.1135	0.8369	0.1224	0.040*
C9B	0.20978 (12)	0.78783 (12)	0.22310 (8)	0.0294 (3)
H9B	0.2885	0.7651	0.1988	0.035*
N1C	0.44277 (10)	0.65673 (10)	0.62598 (6)	0.0256 (2)
N2C	0.55701 (10)	0.59322 (10)	0.65585 (7)	0.0282 (2)
H2NC	0.6259	0.5675	0.6277	0.034*
C1C	0.55327 (13)	0.57385 (14)	0.73327 (8)	0.0325 (3)
H1C	0.6223	0.5314	0.7660	0.039*
C2C	0.43054 (12)	0.62703 (13)	0.75635 (8)	0.0304 (3)
H2C	0.3975	0.6287	0.8076	0.036*
C3C	0.36453 (11)	0.67838 (11)	0.68750 (7)	0.0235 (2)
C4C	0.22988 (11)	0.75014 (11)	0.67840 (7)	0.0233 (2)
C5C	0.17983 (12)	0.81181 (12)	0.60846 (8)	0.0278 (3)
H5C	0.2333	0.8092	0.5660	0.033*
C6C	0.05273 (13)	0.87690 (12)	0.60035 (9)	0.0317 (3)
H6C	0.0199	0.9176	0.5522	0.038*
C7C	−0.02701 (13)	0.88310 (13)	0.66198 (9)	0.0330 (3)
H7C	−0.1141	0.9272	0.6561	0.040*
C8C	0.02178 (13)	0.82440 (14)	0.73198 (9)	0.0343 (3)
H8C	−0.0321	0.8293	0.7747	0.041*
C9C	0.14889 (12)	0.75834 (13)	0.74044 (8)	0.0292 (3)
H9C	0.1811	0.7183	0.7889	0.035*
N1D	0.54292 (9)	0.25111 (10)	0.02935 (6)	0.0245 (2)
N2D	0.43726 (10)	0.29149 (10)	−0.01128 (7)	0.0273 (2)
H2ND	0.3775	0.2719	0.0007	0.033*
C1D	0.43390 (12)	0.36477 (13)	−0.07198 (8)	0.0299 (3)
H1D	0.3693	0.4024	−0.1084	0.036*
C2D	0.54199 (12)	0.37498 (12)	−0.07127 (8)	0.0279 (3)
H2D	0.5668	0.4214	−0.1064	0.033*
C3D	0.60770 (11)	0.30204 (11)	−0.00755 (7)	0.0224 (2)
C4D	0.73465 (11)	0.27131 (11)	0.01532 (7)	0.0230 (2)
C5D	0.81000 (12)	0.15966 (13)	0.05140 (8)	0.0303 (3)
H5D	0.7772	0.1049	0.0659	0.036*
C6D	0.93282 (13)	0.12792 (15)	0.06627 (9)	0.0374 (3)
H6D	0.9833	0.0519	0.0913	0.045*
C7D	0.98223 (13)	0.20627 (15)	0.04491 (9)	0.0367 (3)
H7D	1.0667	0.1837	0.0542	0.044*
C8D	0.90778 (13)	0.31742 (14)	0.00997 (9)	0.0355 (3)
H8D	0.9411	0.3718	−0.0043	0.043*
C9D	0.78459 (12)	0.35070 (13)	−0.00456 (8)	0.0297 (3)
H9D	0.7341	0.4279	−0.0282	0.036*
N1E	0.30245 (9)	0.17144 (10)	0.05880 (6)	0.0244 (2)
N2E	0.34159 (10)	0.05433 (10)	0.03747 (6)	0.0269 (2)
H2NE	0.3644	0.0283	−0.0105	0.032*
C1E	0.34147 (13)	−0.01718 (13)	0.09805 (8)	0.0318 (3)
H1E	0.3648	−0.1020	0.0965	0.038*
C2E	0.30139 (13)	0.05464 (12)	0.16290 (8)	0.0293 (3)
H2E	0.2917	0.0303	0.2148	0.035*
C3E	0.27782 (11)	0.17208 (11)	0.13579 (7)	0.0219 (2)
C4E	0.22847 (11)	0.28677 (11)	0.17925 (7)	0.0223 (2)
C5E	0.19739 (12)	0.39876 (12)	0.14094 (8)	0.0273 (3)
H5E	0.2108	0.4010	0.0860	0.033*
C6E	0.14723 (12)	0.50671 (13)	0.18213 (9)	0.0318 (3)
H6E	0.1271	0.5820	0.1554	0.038*
C7E	0.12634 (12)	0.50495 (13)	0.26217 (9)	0.0329 (3)
H7E	0.0914	0.5789	0.2903	0.040*
C8E	0.15679 (13)	0.39476 (13)	0.30076 (8)	0.0320 (3)
H8E	0.1424	0.3932	0.3556	0.038*
C9E	0.20830 (12)	0.28622 (13)	0.25977 (8)	0.0279 (3)
H9E	0.2299	0.2110	0.2870	0.034*
N1F	0.35696 (10)	0.02490 (10)	−0.13406 (6)	0.0253 (2)
N2F	0.41541 (10)	−0.08788 (10)	−0.16458 (6)	0.0275 (2)
H2NF	0.4435	−0.1558	−0.1363	0.033*
C1F	0.42582 (13)	−0.08467 (13)	−0.24280 (8)	0.0313 (3)
H1F	0.4634	−0.1531	−0.2760	0.038*
C2F	0.37204 (13)	0.03594 (13)	−0.26583 (8)	0.0302 (3)
H2F	0.3647	0.0682	−0.3176	0.036*
C3F	0.33003 (11)	0.10171 (12)	−0.19607 (7)	0.0242 (2)
C4F	0.26381 (11)	0.23455 (12)	−0.18656 (7)	0.0242 (2)
C5F	0.19203 (11)	0.28561 (12)	−0.11925 (7)	0.0262 (3)
H5F	0.1853	0.2338	−0.0790	0.031*
C6F	0.13088 (12)	0.41101 (13)	−0.11092 (8)	0.0300 (3)
H6F	0.0834	0.4444	−0.0647	0.036*
C7F	0.13799 (12)	0.48874 (13)	−0.16928 (8)	0.0313 (3)
H7F	0.0952	0.5748	−0.1633	0.038*
C8F	0.20818 (14)	0.43944 (13)	−0.23626 (8)	0.0334 (3)
H8F	0.2138	0.4919	−0.2764	0.040*
C9F	0.27046 (13)	0.31354 (13)	−0.24499 (8)	0.0304 (3)
H9F	0.3182	0.2807	−0.2913	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1A	0.0271 (5)	0.0256 (5)	0.0245 (5)	−0.0145 (4)	0.0019 (4)	0.0002 (4)
N2A	0.0321 (6)	0.0249 (5)	0.0285 (6)	−0.0167 (5)	0.0018 (4)	0.0004 (4)
C1A	0.0361 (7)	0.0297 (7)	0.0314 (7)	−0.0172 (6)	0.0085 (6)	−0.0062 (5)
C2A	0.0326 (7)	0.0310 (7)	0.0291 (6)	−0.0183 (6)	0.0094 (5)	−0.0039 (5)
C3A	0.0227 (5)	0.0260 (6)	0.0202 (5)	−0.0130 (5)	−0.0012 (4)	0.0018 (4)
C4A	0.0252 (6)	0.0248 (6)	0.0218 (6)	−0.0121 (5)	−0.0014 (4)	0.0018 (5)
C5A	0.0445 (9)	0.0289 (7)	0.0555 (10)	−0.0157 (7)	0.0233 (7)	−0.0030 (7)
C6A	0.0592 (11)	0.0301 (8)	0.0651 (12)	−0.0132 (8)	0.0305 (9)	−0.0094 (8)
C7A	0.0515 (9)	0.0251 (7)	0.0477 (9)	−0.0166 (7)	−0.0004 (7)	−0.0017 (6)
C8A	0.0451 (8)	0.0326 (8)	0.0524 (9)	−0.0250 (7)	0.0023 (7)	0.0006 (7)
C9A	0.0358 (7)	0.0300 (7)	0.0427 (8)	−0.0193 (6)	0.0090 (6)	−0.0040 (6)
N1B	0.0298 (5)	0.0270 (5)	0.0239 (5)	−0.0158 (5)	0.0018 (4)	0.0003 (4)
N2B	0.0318 (6)	0.0347 (6)	0.0238 (5)	−0.0180 (5)	−0.0028 (4)	0.0032 (4)
C1B	0.0306 (7)	0.0550 (10)	0.0314 (7)	−0.0238 (7)	0.0003 (6)	0.0030 (7)
C2B	0.0307 (7)	0.0562 (9)	0.0265 (7)	−0.0239 (7)	0.0031 (5)	0.0023 (6)
C3B	0.0285 (6)	0.0246 (6)	0.0238 (6)	−0.0153 (5)	0.0046 (5)	−0.0024 (5)
C4B	0.0278 (6)	0.0215 (6)	0.0249 (6)	−0.0137 (5)	0.0030 (5)	−0.0025 (5)
C5B	0.0304 (6)	0.0314 (7)	0.0277 (6)	−0.0164 (6)	0.0046 (5)	−0.0006 (5)
C6B	0.0287 (7)	0.0368 (8)	0.0399 (8)	−0.0179 (6)	0.0028 (6)	0.0012 (6)
C7B	0.0331 (7)	0.0318 (7)	0.0378 (8)	−0.0160 (6)	−0.0069 (6)	0.0012 (6)
C8B	0.0397 (8)	0.0320 (7)	0.0256 (7)	−0.0137 (6)	−0.0016 (6)	−0.0018 (5)
C9B	0.0297 (6)	0.0302 (7)	0.0261 (6)	−0.0118 (5)	0.0046 (5)	−0.0030 (5)
N1C	0.0247 (5)	0.0279 (5)	0.0255 (5)	−0.0133 (4)	0.0033 (4)	−0.0011 (4)
N2C	0.0229 (5)	0.0320 (6)	0.0295 (6)	−0.0127 (5)	0.0042 (4)	0.0006 (4)
C1C	0.0280 (6)	0.0385 (8)	0.0297 (7)	−0.0144 (6)	−0.0013 (5)	0.0052 (6)
C2C	0.0287 (6)	0.0364 (7)	0.0247 (6)	−0.0141 (6)	0.0032 (5)	0.0014 (5)
C3C	0.0264 (6)	0.0233 (6)	0.0243 (6)	−0.0146 (5)	0.0037 (5)	−0.0021 (5)
C4C	0.0261 (6)	0.0215 (6)	0.0253 (6)	−0.0134 (5)	0.0025 (5)	−0.0031 (5)
C5C	0.0314 (6)	0.0243 (6)	0.0287 (6)	−0.0136 (5)	0.0041 (5)	−0.0007 (5)
C6C	0.0334 (7)	0.0249 (6)	0.0350 (7)	−0.0119 (6)	−0.0034 (6)	0.0042 (5)
C7C	0.0256 (6)	0.0288 (7)	0.0434 (8)	−0.0115 (5)	0.0002 (6)	−0.0013 (6)
C8C	0.0281 (6)	0.0407 (8)	0.0359 (7)	−0.0175 (6)	0.0064 (6)	−0.0025 (6)
C9C	0.0274 (6)	0.0346 (7)	0.0275 (6)	−0.0160 (6)	0.0027 (5)	−0.0002 (5)
N1D	0.0230 (5)	0.0257 (5)	0.0261 (5)	−0.0125 (4)	0.0024 (4)	−0.0006 (4)
N2D	0.0215 (5)	0.0316 (6)	0.0311 (6)	−0.0142 (4)	0.0029 (4)	−0.0008 (4)
C1D	0.0238 (6)	0.0322 (7)	0.0309 (7)	−0.0106 (5)	−0.0016 (5)	0.0033 (5)
C2D	0.0258 (6)	0.0282 (6)	0.0292 (6)	−0.0122 (5)	0.0020 (5)	0.0040 (5)
C3D	0.0224 (5)	0.0210 (5)	0.0244 (6)	−0.0105 (5)	0.0039 (4)	−0.0022 (4)
C4D	0.0229 (5)	0.0258 (6)	0.0216 (6)	−0.0123 (5)	0.0028 (4)	−0.0030 (5)
C5D	0.0283 (6)	0.0334 (7)	0.0307 (7)	−0.0157 (6)	−0.0006 (5)	0.0052 (5)
C6D	0.0281 (7)	0.0443 (8)	0.0348 (8)	−0.0125 (6)	−0.0053 (6)	0.0070 (6)
C7D	0.0254 (6)	0.0560 (10)	0.0324 (7)	−0.0214 (7)	−0.0008 (5)	−0.0051 (7)
C8D	0.0351 (7)	0.0430 (8)	0.0393 (8)	−0.0272 (7)	0.0052 (6)	−0.0083 (6)
C9D	0.0301 (6)	0.0278 (6)	0.0349 (7)	−0.0165 (5)	0.0030 (5)	−0.0032 (5)
N1E	0.0251 (5)	0.0286 (5)	0.0228 (5)	−0.0151 (4)	0.0011 (4)	−0.0018 (4)
N2E	0.0297 (5)	0.0296 (6)	0.0236 (5)	−0.0153 (5)	0.0044 (4)	−0.0062 (4)
C1E	0.0379 (7)	0.0261 (6)	0.0314 (7)	−0.0147 (6)	0.0061 (6)	−0.0034 (5)
C2E	0.0357 (7)	0.0273 (6)	0.0248 (6)	−0.0146 (6)	0.0043 (5)	−0.0002 (5)
C3E	0.0192 (5)	0.0262 (6)	0.0221 (6)	−0.0120 (5)	−0.0005 (4)	−0.0004 (5)
C4E	0.0193 (5)	0.0262 (6)	0.0235 (6)	−0.0121 (5)	−0.0012 (4)	−0.0018 (5)
C5E	0.0259 (6)	0.0291 (6)	0.0274 (6)	−0.0131 (5)	−0.0014 (5)	0.0011 (5)
C6E	0.0278 (6)	0.0261 (6)	0.0415 (8)	−0.0121 (5)	−0.0039 (6)	0.0005 (6)
C7E	0.0276 (6)	0.0312 (7)	0.0402 (8)	−0.0130 (6)	0.0007 (6)	−0.0113 (6)
C8E	0.0341 (7)	0.0380 (7)	0.0263 (6)	−0.0182 (6)	0.0013 (5)	−0.0083 (6)
C9E	0.0307 (6)	0.0304 (7)	0.0247 (6)	−0.0156 (5)	0.0000 (5)	−0.0023 (5)
N1F	0.0274 (5)	0.0269 (5)	0.0236 (5)	−0.0143 (4)	0.0011 (4)	0.0000 (4)
N2F	0.0299 (5)	0.0272 (5)	0.0272 (5)	−0.0146 (5)	0.0013 (4)	0.0000 (4)
C1F	0.0349 (7)	0.0334 (7)	0.0270 (7)	−0.0169 (6)	0.0038 (5)	−0.0050 (5)
C2F	0.0344 (7)	0.0351 (7)	0.0218 (6)	−0.0165 (6)	0.0020 (5)	−0.0001 (5)
C3F	0.0233 (6)	0.0310 (6)	0.0220 (6)	−0.0156 (5)	−0.0005 (4)	0.0012 (5)
C4F	0.0220 (5)	0.0298 (6)	0.0230 (6)	−0.0137 (5)	−0.0032 (4)	0.0027 (5)
C5F	0.0247 (6)	0.0310 (6)	0.0247 (6)	−0.0145 (5)	0.0001 (5)	0.0023 (5)
C6F	0.0251 (6)	0.0324 (7)	0.0321 (7)	−0.0127 (5)	0.0021 (5)	−0.0023 (5)
C7F	0.0283 (6)	0.0279 (7)	0.0377 (7)	−0.0128 (5)	−0.0058 (5)	0.0030 (5)
C8F	0.0397 (7)	0.0342 (7)	0.0297 (7)	−0.0202 (6)	−0.0060 (6)	0.0085 (6)
C9F	0.0354 (7)	0.0345 (7)	0.0242 (6)	−0.0189 (6)	0.0007 (5)	0.0028 (5)

Geometric parameters (Å, º) top

N1A—C3A	1.3453 (15)	N1D—C3D	1.3432 (15)
N1A—N2A	1.3528 (15)	N1D—N2D	1.3538 (15)
N2A—C1A	1.3444 (17)	N2D—C1D	1.3431 (18)
N2A—H2NA	0.8800	N2D—H2ND	0.8800
C1A—C2A	1.3744 (19)	C1D—C2D	1.3759 (18)
C1A—H1A	0.9500	C1D—H1D	0.9500
C2A—C3A	1.4036 (17)	C2D—C3D	1.4046 (19)
C2A—H2A	0.9500	C2D—H2D	0.9500
C3A—C4A	1.4724 (17)	C3D—C4D	1.4742 (17)
C4A—C5A	1.3871 (19)	C4D—C5D	1.3937 (19)
C4A—C9A	1.3915 (18)	C4D—C9D	1.3951 (17)
C5A—C6A	1.386 (2)	C5D—C6D	1.3896 (19)
C5A—H5A	0.9500	C5D—H5D	0.9500
C6A—C7A	1.377 (2)	C6D—C7D	1.384 (2)
C6A—H6A	0.9500	C6D—H6D	0.9500
C7A—C8A	1.374 (2)	C7D—C8D	1.379 (2)
C7A—H7A	0.9500	C7D—H7D	0.9500
C8A—C9A	1.390 (2)	C8D—C9D	1.3887 (19)
C8A—H8A	0.9500	C8D—H8D	0.9500
C9A—H9A	0.9500	C9D—H9D	0.9500
N1B—C3B	1.3380 (16)	N1E—C3E	1.3409 (16)
N1B—N2B	1.3525 (16)	N1E—N2E	1.3542 (15)
N2B—C1B	1.3393 (17)	N2E—C1E	1.3390 (18)
N2B—H2NB	0.8800	N2E—H2NE	0.8800
C1B—C2B	1.370 (2)	C1E—C2E	1.3727 (18)
C1B—H1B	0.9500	C1E—H1E	0.9500
C2B—C3B	1.4066 (18)	C2E—C3E	1.4055 (18)
C2B—H2B	0.9500	C2E—H2E	0.9500
C3B—C4B	1.4724 (18)	C3E—C4E	1.4734 (17)
C4B—C9B	1.3967 (18)	C4E—C9E	1.3921 (17)
C4B—C5B	1.3992 (17)	C4E—C5E	1.3987 (18)
C5B—C6B	1.386 (2)	C5E—C6E	1.3879 (19)
C5B—H5B	0.9500	C5E—H5E	0.9500
C6B—C7B	1.386 (2)	C6E—C7E	1.386 (2)
C6B—H6B	0.9500	C6E—H6E	0.9500
C7B—C8B	1.383 (2)	C7E—C8E	1.383 (2)
C7B—H7B	0.9500	C7E—H7E	0.9500
C8B—C9B	1.385 (2)	C8E—C9E	1.3916 (18)
C8B—H8B	0.9500	C8E—H8E	0.9500
C9B—H9B	0.9500	C9E—H9E	0.9500
N1C—C3C	1.3429 (15)	N1F—C3F	1.3429 (16)
N1C—N2C	1.3526 (16)	N1F—N2F	1.3514 (15)
N2C—C1C	1.3417 (18)	N2F—C1F	1.3414 (17)
N2C—H2NC	0.8800	N2F—H2NF	0.8800
C1C—C2C	1.3762 (18)	C1F—C2F	1.371 (2)
C1C—H1C	0.9500	C1F—H1F	0.9500
C2C—C3C	1.4082 (19)	C2F—C3F	1.4091 (18)
C2C—H2C	0.9500	C2F—H2F	0.9500
C3C—C4C	1.4727 (17)	C3F—C4F	1.4680 (18)
C4C—C5C	1.3953 (19)	C4F—C9F	1.3987 (18)
C4C—C9C	1.3975 (17)	C4F—C5F	1.4007 (17)
C5C—C6C	1.3867 (19)	C5F—C6F	1.3838 (19)
C5C—H5C	0.9500	C5F—H5F	0.9500
C6C—C7C	1.388 (2)	C6F—C7F	1.389 (2)
C6C—H6C	0.9500	C6F—H6F	0.9500
C7C—C8C	1.382 (2)	C7F—C8F	1.384 (2)
C7C—H7C	0.9500	C7F—H7F	0.9500
C8C—C9C	1.3884 (19)	C8F—C9F	1.390 (2)
C8C—H8C	0.9500	C8F—H8F	0.9500
C9C—H9C	0.9500	C9F—H9F	0.9500

C3A—N1A—N2A	104.79 (10)	C3D—N1D—N2D	104.79 (10)
C1A—N2A—N1A	112.49 (11)	C1D—N2D—N1D	112.41 (10)
C1A—N2A—H2NA	123.8	C1D—N2D—H2ND	123.8
N1A—N2A—H2NA	123.8	N1D—N2D—H2ND	123.8
N2A—C1A—C2A	106.74 (12)	N2D—C1D—C2D	106.90 (12)
N2A—C1A—H1A	126.6	N2D—C1D—H1D	126.6
C2A—C1A—H1A	126.6	C2D—C1D—H1D	126.6
C1A—C2A—C3A	105.49 (11)	C1D—C2D—C3D	105.24 (11)
C1A—C2A—H2A	127.3	C1D—C2D—H2D	127.4
C3A—C2A—H2A	127.3	C3D—C2D—H2D	127.4
N1A—C3A—C2A	110.49 (11)	N1D—C3D—C2D	110.66 (11)
N1A—C3A—C4A	121.87 (11)	N1D—C3D—C4D	121.32 (11)
C2A—C3A—C4A	127.64 (11)	C2D—C3D—C4D	127.79 (11)
C5A—C4A—C9A	118.08 (12)	C5D—C4D—C9D	118.71 (12)
C5A—C4A—C3A	122.31 (12)	C5D—C4D—C3D	121.25 (11)
C9A—C4A—C3A	119.60 (11)	C9D—C4D—C3D	119.86 (12)
C6A—C5A—C4A	120.57 (14)	C6D—C5D—C4D	120.38 (13)
C6A—C5A—H5A	119.7	C6D—C5D—H5D	119.8
C4A—C5A—H5A	119.7	C4D—C5D—H5D	119.8
C7A—C6A—C5A	120.97 (15)	C7D—C6D—C5D	120.49 (14)
C7A—C6A—H6A	119.5	C7D—C6D—H6D	119.8
C5A—C6A—H6A	119.5	C5D—C6D—H6D	119.8
C8A—C7A—C6A	119.00 (14)	C8D—C7D—C6D	119.40 (13)
C8A—C7A—H7A	120.5	C8D—C7D—H7D	120.3
C6A—C7A—H7A	120.5	C6D—C7D—H7D	120.3
C7A—C8A—C9A	120.54 (14)	C7D—C8D—C9D	120.67 (13)
C7A—C8A—H8A	119.7	C7D—C8D—H8D	119.7
C9A—C8A—H8A	119.7	C9D—C8D—H8D	119.7
C8A—C9A—C4A	120.82 (13)	C8D—C9D—C4D	120.34 (13)
C8A—C9A—H9A	119.6	C8D—C9D—H9D	119.8
C4A—C9A—H9A	119.6	C4D—C9D—H9D	119.8
C3B—N1B—N2B	105.21 (10)	C3E—N1E—N2E	105.08 (10)
C1B—N2B—N1B	112.05 (11)	C1E—N2E—N1E	111.98 (10)
C1B—N2B—H2NB	124.0	C1E—N2E—H2NE	124.0
N1B—N2B—H2NB	124.0	N1E—N2E—H2NE	124.0
N2B—C1B—C2B	107.18 (12)	N2E—C1E—C2E	107.39 (12)
N2B—C1B—H1B	126.4	N2E—C1E—H1E	126.3
C2B—C1B—H1B	126.4	C2E—C1E—H1E	126.3
C1B—C2B—C3B	105.29 (12)	C1E—C2E—C3E	105.05 (12)
C1B—C2B—H2B	127.4	C1E—C2E—H2E	127.5
C3B—C2B—H2B	127.4	C3E—C2E—H2E	127.5
N1B—C3B—C2B	110.27 (12)	N1E—C3E—C2E	110.50 (11)
N1B—C3B—C4B	120.95 (11)	N1E—C3E—C4E	120.46 (11)
C2B—C3B—C4B	128.77 (12)	C2E—C3E—C4E	129.00 (11)
C9B—C4B—C5B	118.16 (12)	C9E—C4E—C5E	118.34 (12)
C9B—C4B—C3B	120.34 (11)	C9E—C4E—C3E	120.31 (12)
C5B—C4B—C3B	121.50 (11)	C5E—C4E—C3E	121.33 (11)
C6B—C5B—C4B	120.67 (13)	C6E—C5E—C4E	120.83 (12)
C6B—C5B—H5B	119.7	C6E—C5E—H5E	119.6
C4B—C5B—H5B	119.7	C4E—C5E—H5E	119.6
C5B—C6B—C7B	120.48 (13)	C7E—C6E—C5E	120.20 (13)
C5B—C6B—H6B	119.8	C7E—C6E—H6E	119.9
C7B—C6B—H6B	119.8	C5E—C6E—H6E	119.9
C8B—C7B—C6B	119.35 (13)	C8E—C7E—C6E	119.53 (13)
C8B—C7B—H7B	120.3	C8E—C7E—H7E	120.2
C6B—C7B—H7B	120.3	C6E—C7E—H7E	120.2
C7B—C8B—C9B	120.49 (13)	C7E—C8E—C9E	120.42 (13)
C7B—C8B—H8B	119.8	C7E—C8E—H8E	119.8
C9B—C8B—H8B	119.8	C9E—C8E—H8E	119.8
C8B—C9B—C4B	120.84 (12)	C8E—C9E—C4E	120.67 (13)
C8B—C9B—H9B	119.6	C8E—C9E—H9E	119.7
C4B—C9B—H9B	119.6	C4E—C9E—H9E	119.7
C3C—N1C—N2C	105.03 (10)	C3F—N1F—N2F	104.84 (10)
C1C—N2C—N1C	112.30 (10)	C1F—N2F—N1F	112.44 (11)
C1C—N2C—H2NC	123.9	C1F—N2F—H2NF	123.8
N1C—N2C—H2NC	123.9	N1F—N2F—H2NF	123.8
N2C—C1C—C2C	107.09 (12)	N2F—C1F—C2F	107.10 (12)
N2C—C1C—H1C	126.5	N2F—C1F—H1F	126.5
C2C—C1C—H1C	126.5	C2F—C1F—H1F	126.5
C1C—C2C—C3C	105.11 (12)	C1F—C2F—C3F	105.14 (12)
C1C—C2C—H2C	127.4	C1F—C2F—H2F	127.4
C3C—C2C—H2C	127.4	C3F—C2F—H2F	127.4
N1C—C3C—C2C	110.46 (11)	N1F—C3F—C2F	110.48 (12)
N1C—C3C—C4C	121.06 (11)	N1F—C3F—C4F	121.19 (11)
C2C—C3C—C4C	128.45 (11)	C2F—C3F—C4F	128.32 (12)
C5C—C4C—C9C	118.33 (12)	C9F—C4F—C5F	118.26 (12)
C5C—C4C—C3C	121.37 (11)	C9F—C4F—C3F	120.61 (11)
C9C—C4C—C3C	120.30 (12)	C5F—C4F—C3F	121.12 (11)
C6C—C5C—C4C	120.62 (12)	C6F—C5F—C4F	120.42 (12)
C6C—C5C—H5C	119.7	C6F—C5F—H5F	119.8
C4C—C5C—H5C	119.7	C4F—C5F—H5F	119.8
C5C—C6C—C7C	120.59 (13)	C5F—C6F—C7F	120.90 (13)
C5C—C6C—H6C	119.7	C5F—C6F—H6F	119.5
C7C—C6C—H6C	119.7	C7F—C6F—H6F	119.5
C8C—C7C—C6C	119.19 (13)	C8F—C7F—C6F	119.24 (13)
C8C—C7C—H7C	120.4	C8F—C7F—H7F	120.4
C6C—C7C—H7C	120.4	C6F—C7F—H7F	120.4
C7C—C8C—C9C	120.59 (13)	C7F—C8F—C9F	120.28 (13)
C7C—C8C—H8C	119.7	C7F—C8F—H8F	119.9
C9C—C8C—H8C	119.7	C9F—C8F—H8F	119.9
C8C—C9C—C4C	120.65 (13)	C8F—C9F—C4F	120.89 (13)
C8C—C9C—H9C	119.7	C8F—C9F—H9F	119.6
C4C—C9C—H9C	119.7	C4F—C9F—H9F	119.6

C3A—N1A—N2A—C1A	0.06 (14)	C3D—N1D—N2D—C1D	0.29 (14)
N1A—N2A—C1A—C2A	−0.11 (16)	N1D—N2D—C1D—C2D	−0.75 (15)
N2A—C1A—C2A—C3A	0.10 (16)	N2D—C1D—C2D—C3D	0.86 (15)
N2A—N1A—C3A—C2A	0.01 (14)	N2D—N1D—C3D—C2D	0.28 (13)
N2A—N1A—C3A—C4A	−179.98 (11)	N2D—N1D—C3D—C4D	−174.61 (10)
C1A—C2A—C3A—N1A	−0.07 (16)	C1D—C2D—C3D—N1D	−0.72 (15)
C1A—C2A—C3A—C4A	179.92 (12)	C1D—C2D—C3D—C4D	173.76 (12)
N1A—C3A—C4A—C5A	9.0 (2)	N1D—C3D—C4D—C5D	25.81 (18)
C2A—C3A—C4A—C5A	−170.94 (15)	C2D—C3D—C4D—C5D	−148.14 (13)
N1A—C3A—C4A—C9A	−170.16 (13)	N1D—C3D—C4D—C9D	−159.16 (12)
C2A—C3A—C4A—C9A	9.9 (2)	C2D—C3D—C4D—C9D	26.89 (19)
C9A—C4A—C5A—C6A	0.6 (3)	C9D—C4D—C5D—C6D	−0.8 (2)
C3A—C4A—C5A—C6A	−178.58 (16)	C3D—C4D—C5D—C6D	174.30 (12)
C4A—C5A—C6A—C7A	−1.2 (3)	C4D—C5D—C6D—C7D	−0.5 (2)
C5A—C6A—C7A—C8A	0.5 (3)	C5D—C6D—C7D—C8D	1.2 (2)
C6A—C7A—C8A—C9A	0.7 (3)	C6D—C7D—C8D—C9D	−0.6 (2)
C7A—C8A—C9A—C4A	−1.3 (3)	C7D—C8D—C9D—C4D	−0.7 (2)
C5A—C4A—C9A—C8A	0.6 (2)	C5D—C4D—C9D—C8D	1.37 (19)
C3A—C4A—C9A—C8A	179.80 (14)	C3D—C4D—C9D—C8D	−173.78 (12)
C3B—N1B—N2B—C1B	0.12 (15)	C3E—N1E—N2E—C1E	0.34 (14)
N1B—N2B—C1B—C2B	−0.19 (18)	N1E—N2E—C1E—C2E	−0.41 (16)
N2B—C1B—C2B—C3B	0.18 (18)	N2E—C1E—C2E—C3E	0.30 (15)
N2B—N1B—C3B—C2B	0.00 (14)	N2E—N1E—C3E—C2E	−0.14 (13)
N2B—N1B—C3B—C4B	−179.97 (11)	N2E—N1E—C3E—C4E	−177.97 (10)
C1B—C2B—C3B—N1B	−0.11 (17)	C1E—C2E—C3E—N1E	−0.10 (15)
C1B—C2B—C3B—C4B	179.86 (13)	C1E—C2E—C3E—C4E	177.49 (12)
N1B—C3B—C4B—C9B	−172.27 (12)	N1E—C3E—C4E—C9E	−177.07 (11)
C2B—C3B—C4B—C9B	7.8 (2)	C2E—C3E—C4E—C9E	5.55 (19)
N1B—C3B—C4B—C5B	8.26 (18)	N1E—C3E—C4E—C5E	4.80 (17)
C2B—C3B—C4B—C5B	−171.70 (14)	C2E—C3E—C4E—C5E	−172.58 (12)
C9B—C4B—C5B—C6B	0.10 (19)	C9E—C4E—C5E—C6E	−0.26 (18)
C3B—C4B—C5B—C6B	179.58 (12)	C3E—C4E—C5E—C6E	177.90 (11)
C4B—C5B—C6B—C7B	0.1 (2)	C4E—C5E—C6E—C7E	−0.47 (19)
C5B—C6B—C7B—C8B	−0.1 (2)	C5E—C6E—C7E—C8E	0.5 (2)
C6B—C7B—C8B—C9B	−0.1 (2)	C6E—C7E—C8E—C9E	0.1 (2)
C7B—C8B—C9B—C4B	0.3 (2)	C7E—C8E—C9E—C4E	−0.9 (2)
C5B—C4B—C9B—C8B	−0.32 (19)	C5E—C4E—C9E—C8E	0.94 (18)
C3B—C4B—C9B—C8B	−179.81 (12)	C3E—C4E—C9E—C8E	−177.24 (11)
C3C—N1C—N2C—C1C	0.32 (14)	C3F—N1F—N2F—C1F	−0.12 (14)
N1C—N2C—C1C—C2C	−0.03 (16)	N1F—N2F—C1F—C2F	0.12 (15)
N2C—C1C—C2C—C3C	−0.26 (16)	N2F—C1F—C2F—C3F	−0.06 (15)
N2C—N1C—C3C—C2C	−0.48 (14)	N2F—N1F—C3F—C2F	0.08 (13)
N2C—N1C—C3C—C4C	177.87 (11)	N2F—N1F—C3F—C4F	179.18 (10)
C1C—C2C—C3C—N1C	0.47 (15)	C1F—C2F—C3F—N1F	−0.01 (15)
C1C—C2C—C3C—C4C	−177.72 (12)	C1F—C2F—C3F—C4F	−179.03 (12)
N1C—C3C—C4C—C5C	−8.77 (18)	N1F—C3F—C4F—C9F	159.25 (12)
C2C—C3C—C4C—C5C	169.26 (13)	C2F—C3F—C4F—C9F	−21.82 (19)
N1C—C3C—C4C—C9C	171.53 (12)	N1F—C3F—C4F—C5F	−21.07 (17)
C2C—C3C—C4C—C9C	−10.4 (2)	C2F—C3F—C4F—C5F	157.85 (13)
C9C—C4C—C5C—C6C	−1.63 (19)	C9F—C4F—C5F—C6F	−0.78 (18)
C3C—C4C—C5C—C6C	178.67 (12)	C3F—C4F—C5F—C6F	179.54 (11)
C4C—C5C—C6C—C7C	0.8 (2)	C4F—C5F—C6F—C7F	0.81 (19)
C5C—C6C—C7C—C8C	0.6 (2)	C5F—C6F—C7F—C8F	−0.5 (2)
C6C—C7C—C8C—C9C	−1.0 (2)	C6F—C7F—C8F—C9F	0.2 (2)
C7C—C8C—C9C—C4C	0.1 (2)	C7F—C8F—C9F—C4F	−0.2 (2)
C5C—C4C—C9C—C8C	1.19 (19)	C5F—C4F—C9F—C8F	0.46 (19)
C3C—C4C—C9C—C8C	−179.10 (12)	C3F—C4F—C9F—C8F	−179.85 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2A—H2NA···N1B	0.88	2.06	2.8905 (17)	158
N2B—H2NB···N1C	0.88	2.12	2.9601 (16)	159
N2C—H2NC···N1Aⁱ	0.88	2.12	2.9540 (18)	157
N2D—H2ND···N1E	0.88	2.06	2.8767 (18)	154
N2E—H2NE···N1F	0.88	2.12	2.9587 (15)	159
N2F—H2NF···N1Dⁱⁱ	0.88	2.11	2.9157 (15)	152

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

Experimental details

Crystal data
Chemical formula	C₉H₈N₂
M_r	144.17
Crystal system, space group	Triclinic, P1
Temperature (K)	148
a, b, c (Å)	12.1514 (10), 12.3120 (11), 17.114 (2)
α, β, γ (°)	88.164 (11), 88.103 (12), 62.816 (6)
V (Å³)	2275.9 (4)
Z	12
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.50 × 0.48 × 0.40

Data collection
Diffractometer	Siemens SMART CCD diffractometer
Absorption correction	Numerical (SHELXTL; Sheldrick, 1996)
T_min, T_max	0.959, 0.975
No. of measured, independent and observed [I > 2σ(I)] reflections	40438, 14026, 10303
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.725

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.124, 1.05
No. of reflections	14026
No. of parameters	596
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.27

Computer programs: SMART (Siemens, 1995), SMART, SAINT (Siemens, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL (Sheldrick, 1996), SHELXL97.