Crystal structure and luminescent properties of [1-(biphenyl-4-yl)-1H-imidazole-κN³]di­chloridozinc

A new imidazole-based zinc complex, synthesized using hydro­thermal methods, exhibits luminescent behaviour.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.037
• wR factor = 0.091
• Data-to-parameter ratio = 15.9

checkCIF/PLATON results

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PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         22 Report

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PLAT154_ALERT_1_G The su's on the Cell Angles are Equal ..........    0.00100 Degree
PLAT899_ALERT_4_G SHELXL97   is Deprecated and Succeeded by SHELXL       2014 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ...          1 Report
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         23 Note

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S1. Chemical context

Metal coordination polymers constructed from organic ligands and metal cations have received attention because of their structural diversity and inter­esting physical and chemical properties, including adsorption, molecular separation, heterogeneous catalysis and non-linear optics (Sumida et al., 2012; Colombo et al., 2012; Henke et al., 2012). The development of such materials for various applications is reliant on the functionalities and modulations of the inorganic central atom and the organic linker. Materials constructed from d¹⁰ metal ions can be promising photoactive candidates (Lan et al., 2009; Qin et al., 2014). For example, a series of zinc- and cadmium-based coordination polymers were reported to be luminescent sensors for the detection of small organic molecules (Yi et al., 2012; Wang et al., 2013). On the other hand, the choice of the organic ligand or linkers is important for the supra­molecular arrangement.

Among the various organic ligands used for the construction of coordination polymers, nitro­gen-donor species are dominant due to their strong affinities for binding metal atoms (Yang et al., 2013, 2014). In particular, imidazoles are of great inter­est for the construction of zeolite imidazolate frameworks, which exhibit high stability and practical applications (Phan et al., 2010). By further modification of imidazole ligands, various compounds with different structural set-ups have been reported, including one-dimensional, two-dimensional and three-dimensional architectures (Kan et al., 2012). Recently, two one-dimensional imidazole-based zinc complexes were synthesized by using 1,4-di(1H-imidazol-1-yl)benzene (dib), and 1,3,5-tri(1H-imidazol-1-yl)benzene (tib) as ligands (Wang et al., 2014). To obtain further effects on the final structure by modification of the substituent of the imidazoles, 1-(bi­phenyl-4-yl)-1H-imidazole (bpi) was chosen as ligand and reacted with Zn²⁺ ions in this work, yielding the title compound ZnCl₂(C₁₅H₁₂N₂)₂, (I). Apart from the structure determination, its photoluminescent properties are also reported.

S2. Structural commentary

As shown in Fig. 1, the asymmetric unit of (I) consists of one zinc(II) cation, two bpi ligands and two chlorine ligands. The cation has a distorted tetra­hedral coordination sphere defined by the free imidazole N atoms and two Cl atoms. The Zn—N and Zn—Cl bond lengths (Table 1) are typical for tetra­hedrally coordinated Zn^II. The dihedral angles between the two phenyl rings in the two bpi ligands are 37.52 (14) and 42.45 (14)°, respectively, while the dihedral angles between the phenyl rings and the attached imidazole rings are 37.13 (14) and 40.05 (14)°.

Zn^II-based compounds with metal-organic framework structures are well-known for their luminescence properties. The photoluminescence spectrum of compound (I) in the solid state is shown in Fig. 2. On excitation at 278 nm, the emission band is centred at 350 nm. Compared to the free bpi ligand, which exhibits one main fluorescent emission band around 400 nm when excited at 271 nm, the emission band of complex (I) is about 50 nm hypochromatically shifted. Considering metal atoms with a d¹⁰ electron configuration and the bonding inter­actions with the ligand, such broad emission bands may be assigned to a ligand-to-ligand charge transfer (LLCT), admixing with metal-to-ligand (MLCT) and ligand-to-metal (LMCT) charge transfers (Gong et al., 2011).

S3. Supra­molecular features

As mentioned before, the imidazole-based ligands dib and tib, featuring two and three imidazole rings, respectively, can adopt different structural dimensionalities. The bpi ligand used in this study, however, has only one available N-donor, thus preventing the formation of a polymeric structure. Nevertheless, there are weak inter­molecular π–π stacking inter­actions between single molecules in the crystal packing. The terminal phenyl ring and the imidazole ring of a neighbouring ligand are tilted to each other by 11.72 (17)°, with a centroid-to-centroid distance of 3.751 Å (Fig. 3).

S4. Synthesis and crystallization

All chemicals were purchased commercially and used without further purification. A mixture of ZnCl₂ (81.6 mg, 5 mmol), bpi (130 mg, 0.6 mmol), and de-ionized water (9 ml) was loaded into a 20 ml Teflon-lined stainless steel autoclave. The autoclave was sealed and heated at 423 K for 5 d, and then cooled to room temperature by switching off the furnace. Colourless block-shaped crystals were isolated, which were filtered off and washed with de-ionized water. The final product was dried at ambient temperature (yield 75% based on zinc). Analysis calculated (wt%) for ZnCl₂(C₁₅H₁₂N₂)₂: C, 62.47; H, 4.19; N, 9.71. Found: C, 62.45; H, 4.15; N, 9.79.

Elemental analyses of C, H, and N were conducted on a Perkin–Elmer 2400 elemental analyser. The photoluminescence (PL) excitation and emission spectra were recorded with an F-7000 luminescence spectrometer equipped with a xenon lamp of 450 W as an excitation light source. The photomultiplier tube voltage was 400 V, the scan speed was 1200 nm min^-1, both the excitation and the emission slit widths were 5.0 nm.

S5. Refinement

All hydrogen atoms were positioned geometrically with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C).

Related literature

For related literature, see: Colombo et al. (2012); Gong et al. (2011); Henke et al. (2012); Kan et al. (2012); Lan et al. (2009); Phan et al. (2010); Qin et al. (2014); Sumida et al. (2012); Wang et al. (2013, 2014); Yang et al. (2013, 2014); Yi et al. (2012).

Computing details

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. The molecular structure of compound (I). Displacement ellipsoids were drawn at the 30% probability level.
	Fig. 2. Excitation and emission spectra of compound (I) in the solid state.
	Fig. 3. View of the crystal structure along [010] emphasizing π–π interactions (dotted lines and inset).

[1-(Biphenyl-4-yl)-1H-imidazole-κN³]dichloridozinc

Crystal data

[ZnCl2(C15H12N2)2]	Z = 2
Mr = 576.80	F(000) = 592
Triclinic, P1	#Added by publCIF _symmetry_space_group_name_hall '-P 1' #Added by publCIF _audit_update_record
Hall symbol: -P 1	Dx = 1.429 Mg m^−3
a = 9.2410 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.2595 (5) Å	Cell parameters from 2594 reflections
c = 16.4106 (10) Å	θ = 2.3–24.3°
α = 87.770 (1)°	µ = 1.14 mm^−1
β = 88.819 (1)°	T = 296 K
γ = 72.823 (1)°	Block, colourless
V = 1340.50 (14) Å^3	0.40 × 0.30 × 0.30 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	5308 independent reflections
Radiation source: fine-focus sealed tube	4067 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
phi and ω scans	θmax = 26.1°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −11→11
Tmin = 0.658, Tmax = 0.726	k = −11→11
8564 measured reflections	l = −20→17

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.091	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0389P)^2 + 0.3283P] where P = (Fo^2 + 2Fc^2)/3
5308 reflections	(Δ/σ)max = 0.014
334 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.35 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Zn1	0.49124 (3)	1.09677 (3)	0.333749 (18)	0.04334 (11)
N3	0.5776 (2)	0.8683 (2)	0.33926 (13)	0.0451 (5)
N1	0.2746 (2)	1.1586 (2)	0.37469 (13)	0.0472 (5)
N2	0.0780 (2)	1.2196 (2)	0.45740 (13)	0.0452 (5)
N4	0.6993 (2)	0.6477 (2)	0.28944 (12)	0.0418 (5)
C28	0.6686 (3)	0.7984 (3)	0.28125 (16)	0.0466 (6)
H28A	0.7072	0.8475	0.2395	0.056*
C25	0.7889 (3)	0.5422 (3)	0.23310 (15)	0.0414 (6)
C10	−0.0104 (3)	1.2386 (3)	0.53170 (16)	0.0456 (6)
C7	−0.1776 (3)	1.2747 (3)	0.67615 (16)	0.0452 (6)
C22	0.9495 (3)	0.3553 (3)	0.11331 (15)	0.0420 (6)
C30	0.6209 (3)	0.6192 (3)	0.35697 (16)	0.0475 (6)
H30A	0.6190	0.5249	0.3778	0.057*
C26	0.7462 (3)	0.4182 (3)	0.21310 (17)	0.0476 (6)
H26A	0.6641	0.3970	0.2391	0.057*
C12	−0.0612 (3)	1.1433 (3)	0.66213 (17)	0.0506 (7)
H12A	−0.0385	1.0662	0.7021	0.061*
C27	0.8274 (3)	0.3254 (3)	0.15356 (17)	0.0487 (7)
H27A	0.7994	0.2407	0.1401	0.058*
C16	1.0323 (3)	0.2598 (3)	0.04652 (16)	0.0453 (6)
C24	0.9140 (3)	0.5714 (3)	0.19650 (16)	0.0483 (7)
H24A	0.9449	0.6530	0.2122	0.058*
C23	0.9918 (3)	0.4791 (3)	0.13708 (17)	0.0477 (6)
H23A	1.0750	0.4999	0.1120	0.057*
C6	−0.3160 (3)	1.4297 (3)	0.79101 (18)	0.0519 (7)
H6A	−0.2935	1.5135	0.7674	0.062*
C29	0.5470 (3)	0.7554 (3)	0.38738 (16)	0.0492 (6)
H29A	0.4851	0.7704	0.4336	0.059*
C11	0.0216 (3)	1.1242 (3)	0.59019 (17)	0.0523 (7)
H11A	0.0983	1.0349	0.5816	0.063*
C1	−0.2672 (3)	1.2918 (3)	0.75330 (16)	0.0447 (6)
C14	0.1475 (3)	1.2263 (3)	0.33028 (18)	0.0524 (7)
H14A	0.1455	1.2434	0.2740	0.063*
C8	−0.2076 (3)	1.3875 (3)	0.61520 (17)	0.0517 (7)
H8A	−0.2861	1.4759	0.6226	0.062*
C9	−0.1236 (3)	1.3713 (3)	0.54385 (17)	0.0509 (7)
H9A	−0.1432	1.4493	0.5044	0.061*
C2	−0.3043 (3)	1.1702 (3)	0.78962 (17)	0.0549 (7)
H2A	−0.2725	1.0767	0.7655	0.066*
C17	0.9543 (4)	0.2104 (3)	−0.01281 (18)	0.0578 (7)
H17A	0.8490	0.2377	−0.0108	0.069*
C15	0.2278 (3)	1.1556 (3)	0.45106 (17)	0.0511 (7)
H15A	0.2907	1.1144	0.4948	0.061*
C5	−0.3974 (3)	1.4436 (3)	0.86282 (19)	0.0605 (8)
H5A	−0.4282	1.5365	0.8876	0.073*
C4	−0.4337 (4)	1.3225 (4)	0.89823 (19)	0.0631 (8)
H4A	−0.4887	1.3327	0.9468	0.076*
C21	1.1894 (3)	0.2188 (3)	0.0417 (2)	0.0629 (8)
H21A	1.2441	0.2516	0.0802	0.075*
C13	0.0260 (3)	1.2647 (3)	0.38006 (17)	0.0550 (7)
H13A	−0.0737	1.3123	0.3650	0.066*
C3	−0.3876 (4)	1.1852 (3)	0.86102 (19)	0.0648 (8)
H3A	−0.4127	1.1025	0.8842	0.078*
C19	1.1853 (5)	0.0807 (4)	−0.0781 (2)	0.0785 (11)
H19A	1.2369	0.0203	−0.1197	0.094*
C18	1.0313 (5)	0.1212 (4)	−0.07452 (19)	0.0727 (10)
H18A	0.9780	0.0887	−0.1138	0.087*
C20	1.2645 (4)	0.1285 (4)	−0.0208 (2)	0.0775 (11)
H20A	1.3697	0.1002	−0.0237	0.093*
Cl2	0.62413 (8)	1.20582 (8)	0.41117 (4)	0.05347 (18)
Cl1	0.49053 (9)	1.16111 (8)	0.20162 (4)	0.05715 (19)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.04203 (18)	0.03878 (17)	0.04857 (19)	−0.01084 (13)	0.00502 (13)	−0.00512 (13)
N3	0.0478 (13)	0.0386 (11)	0.0492 (13)	−0.0136 (10)	0.0045 (10)	−0.0034 (10)
N1	0.0405 (12)	0.0491 (13)	0.0514 (14)	−0.0122 (10)	0.0002 (10)	−0.0024 (10)
N2	0.0361 (12)	0.0470 (12)	0.0510 (13)	−0.0098 (10)	0.0007 (10)	−0.0006 (10)
N4	0.0441 (12)	0.0333 (11)	0.0476 (12)	−0.0112 (9)	0.0013 (10)	0.0004 (9)
C28	0.0508 (16)	0.0366 (13)	0.0524 (16)	−0.0137 (12)	0.0069 (13)	0.0018 (12)
C25	0.0402 (14)	0.0333 (13)	0.0488 (15)	−0.0083 (11)	−0.0012 (11)	0.0006 (11)
C10	0.0345 (14)	0.0473 (15)	0.0549 (16)	−0.0118 (12)	0.0042 (12)	−0.0041 (12)
C7	0.0384 (14)	0.0457 (15)	0.0540 (16)	−0.0163 (12)	0.0006 (12)	−0.0039 (12)
C22	0.0388 (14)	0.0367 (13)	0.0499 (15)	−0.0105 (11)	−0.0033 (12)	0.0017 (11)
C30	0.0550 (16)	0.0392 (14)	0.0508 (16)	−0.0186 (13)	0.0026 (13)	0.0049 (12)
C26	0.0426 (15)	0.0400 (14)	0.0636 (18)	−0.0178 (12)	0.0088 (13)	−0.0035 (12)
C12	0.0483 (16)	0.0429 (15)	0.0568 (17)	−0.0083 (13)	0.0007 (13)	0.0026 (12)
C27	0.0476 (16)	0.0387 (14)	0.0646 (18)	−0.0195 (12)	0.0011 (13)	−0.0077 (12)
C16	0.0488 (16)	0.0374 (13)	0.0482 (15)	−0.0112 (12)	0.0033 (12)	0.0020 (11)
C24	0.0478 (16)	0.0431 (14)	0.0598 (17)	−0.0223 (13)	−0.0003 (13)	−0.0035 (13)
C23	0.0400 (14)	0.0460 (15)	0.0603 (17)	−0.0182 (12)	0.0048 (13)	−0.0004 (13)
C6	0.0478 (16)	0.0455 (15)	0.0633 (18)	−0.0151 (13)	0.0034 (14)	−0.0039 (13)
C29	0.0498 (16)	0.0513 (16)	0.0484 (16)	−0.0184 (13)	0.0058 (12)	−0.0016 (12)
C11	0.0436 (16)	0.0441 (15)	0.0628 (18)	−0.0031 (13)	0.0034 (13)	−0.0052 (13)
C1	0.0380 (14)	0.0466 (15)	0.0510 (16)	−0.0146 (12)	−0.0003 (12)	−0.0032 (12)
C14	0.0519 (17)	0.0507 (16)	0.0526 (16)	−0.0129 (14)	−0.0004 (14)	0.0039 (13)
C8	0.0433 (15)	0.0426 (15)	0.0662 (18)	−0.0085 (12)	0.0074 (14)	−0.0018 (13)
C9	0.0437 (15)	0.0459 (15)	0.0603 (18)	−0.0102 (13)	0.0029 (13)	0.0061 (13)
C2	0.0579 (18)	0.0512 (16)	0.0600 (18)	−0.0225 (14)	0.0058 (14)	−0.0088 (14)
C17	0.0657 (19)	0.0519 (17)	0.0575 (18)	−0.0206 (15)	−0.0001 (15)	0.0018 (14)
C15	0.0357 (14)	0.0621 (17)	0.0521 (17)	−0.0091 (13)	−0.0019 (12)	−0.0029 (13)
C5	0.0566 (18)	0.0575 (18)	0.067 (2)	−0.0145 (15)	0.0041 (15)	−0.0157 (15)
C4	0.065 (2)	0.072 (2)	0.0553 (18)	−0.0240 (17)	0.0111 (15)	−0.0064 (16)
C21	0.0498 (18)	0.0642 (19)	0.070 (2)	−0.0103 (15)	0.0076 (15)	0.0011 (16)
C13	0.0379 (15)	0.0604 (18)	0.0594 (18)	−0.0042 (13)	−0.0067 (13)	0.0069 (14)
C3	0.072 (2)	0.0609 (19)	0.066 (2)	−0.0288 (17)	0.0101 (17)	0.0021 (15)
C19	0.116 (3)	0.0500 (19)	0.064 (2)	−0.019 (2)	0.038 (2)	−0.0033 (16)
C18	0.112 (3)	0.0595 (19)	0.0515 (19)	−0.033 (2)	0.0074 (19)	−0.0057 (15)
C20	0.066 (2)	0.061 (2)	0.092 (3)	−0.0024 (18)	0.033 (2)	0.0075 (19)
Cl2	0.0559 (4)	0.0533 (4)	0.0553 (4)	−0.0217 (3)	−0.0010 (3)	−0.0073 (3)
Cl1	0.0716 (5)	0.0505 (4)	0.0496 (4)	−0.0188 (4)	0.0034 (3)	0.0002 (3)

Geometric parameters (Å, º)

Zn1—N1	2.021 (2)	C16—C17	1.391 (4)
Zn1—N3	2.028 (2)	C24—C23	1.368 (3)
Zn1—Cl1	2.2258 (7)	C24—H24A	0.9300
Zn1—Cl2	2.2447 (8)	C23—H23A	0.9300
N3—C28	1.314 (3)	C6—C5	1.374 (4)
N3—C29	1.377 (3)	C6—C1	1.388 (4)
N1—C15	1.319 (3)	C6—H6A	0.9300
N1—C14	1.367 (3)	C29—H29A	0.9300
N2—C15	1.339 (3)	C11—H11A	0.9300
N2—C13	1.372 (3)	C1—C2	1.381 (4)
N2—C10	1.441 (3)	C14—C13	1.343 (4)
N4—C28	1.341 (3)	C14—H14A	0.9300
N4—C30	1.371 (3)	C8—C9	1.380 (4)
N4—C25	1.434 (3)	C8—H8A	0.9300
C28—H28A	0.9300	C9—H9A	0.9300
C25—C26	1.373 (3)	C2—C3	1.377 (4)
C25—C24	1.384 (3)	C2—H2A	0.9300
C10—C11	1.370 (4)	C17—C18	1.379 (4)
C10—C9	1.376 (3)	C17—H17A	0.9300
C7—C12	1.389 (3)	C15—H15A	0.9300
C7—C8	1.388 (4)	C5—C4	1.367 (4)
C7—C1	1.486 (3)	C5—H5A	0.9300
C22—C27	1.388 (3)	C4—C3	1.379 (4)
C22—C23	1.388 (3)	C4—H4A	0.9300
C22—C16	1.486 (3)	C21—C20	1.388 (4)
C30—C29	1.353 (4)	C21—H21A	0.9300
C30—H30A	0.9300	C13—H13A	0.9300
C26—C27	1.382 (3)	C3—H3A	0.9300
C26—H26A	0.9300	C19—C18	1.361 (5)
C12—C11	1.382 (4)	C19—C20	1.366 (5)
C12—H12A	0.9300	C19—H19A	0.9300
C27—H27A	0.9300	C18—H18A	0.9300
C16—C21	1.390 (4)	C20—H20A	0.9300
N1—Zn1—N3	110.09 (9)	C5—C6—C1	120.7 (3)
N1—Zn1—Cl1	108.12 (7)	C5—C6—H6A	119.7
N3—Zn1—Cl1	105.05 (6)	C1—C6—H6A	119.7
N1—Zn1—Cl2	107.94 (7)	C30—C29—N3	109.4 (2)
N3—Zn1—Cl2	111.23 (7)	C30—C29—H29A	125.3
Cl1—Zn1—Cl2	114.33 (3)	N3—C29—H29A	125.3
C28—N3—C29	105.4 (2)	C10—C11—C12	119.2 (2)
C28—N3—Zn1	120.15 (17)	C10—C11—H11A	120.4
C29—N3—Zn1	133.74 (17)	C12—C11—H11A	120.4
C15—N1—C14	105.6 (2)	C2—C1—C6	118.0 (2)
C15—N1—Zn1	127.00 (18)	C2—C1—C7	120.7 (2)
C14—N1—Zn1	127.06 (19)	C6—C1—C7	121.3 (2)
C15—N2—C13	106.9 (2)	C13—C14—N1	109.8 (2)
C15—N2—C10	126.2 (2)	C13—C14—H14A	125.1
C13—N2—C10	126.9 (2)	N1—C14—H14A	125.1
C28—N4—C30	106.8 (2)	C9—C8—C7	121.5 (2)
C28—N4—C25	124.6 (2)	C9—C8—H8A	119.3
C30—N4—C25	128.4 (2)	C7—C8—H8A	119.3
N3—C28—N4	111.9 (2)	C10—C9—C8	119.3 (3)
N3—C28—H28A	124.0	C10—C9—H9A	120.3
N4—C28—H28A	124.0	C8—C9—H9A	120.3
C26—C25—C24	120.8 (2)	C3—C2—C1	121.1 (3)
C26—C25—N4	120.1 (2)	C3—C2—H2A	119.5
C24—C25—N4	119.0 (2)	C1—C2—H2A	119.5
C11—C10—C9	120.8 (2)	C18—C17—C16	120.7 (3)
C11—C10—N2	119.1 (2)	C18—C17—H17A	119.6
C9—C10—N2	120.0 (2)	C16—C17—H17A	119.6
C12—C7—C8	117.5 (2)	N1—C15—N2	111.3 (2)
C12—C7—C1	120.8 (2)	N1—C15—H15A	124.4
C8—C7—C1	121.7 (2)	N2—C15—H15A	124.4
C27—C22—C23	117.6 (2)	C4—C5—C6	120.8 (3)
C27—C22—C16	121.7 (2)	C4—C5—H5A	119.6
C23—C22—C16	120.6 (2)	C6—C5—H5A	119.6
C29—C30—N4	106.4 (2)	C5—C4—C3	119.2 (3)
C29—C30—H30A	126.8	C5—C4—H4A	120.4
N4—C30—H30A	126.8	C3—C4—H4A	120.4
C25—C26—C27	118.8 (2)	C16—C21—C20	119.7 (3)
C25—C26—H26A	120.6	C16—C21—H21A	120.2
C27—C26—H26A	120.6	C20—C21—H21A	120.2
C11—C12—C7	121.6 (3)	C14—C13—N2	106.4 (2)
C11—C12—H12A	119.2	C14—C13—H13A	126.8
C7—C12—H12A	119.2	N2—C13—H13A	126.8
C26—C27—C22	121.7 (2)	C2—C3—C4	120.2 (3)
C26—C27—H27A	119.1	C2—C3—H3A	119.9
C22—C27—H27A	119.1	C4—C3—H3A	119.9
C21—C16—C17	118.5 (3)	C18—C19—C20	120.3 (3)
C21—C16—C22	120.6 (3)	C18—C19—H19A	119.9
C17—C16—C22	120.8 (2)	C20—C19—H19A	119.9
C23—C24—C25	119.4 (2)	C19—C18—C17	120.1 (3)
C23—C24—H24A	120.3	C19—C18—H18A	119.9
C25—C24—H24A	120.3	C17—C18—H18A	119.9
C24—C23—C22	121.5 (2)	C19—C20—C21	120.7 (3)
C24—C23—H23A	119.2	C19—C20—H20A	119.7
C22—C23—H23A	119.2	C21—C20—H20A	119.7