N1,N4-Diphenyl-3,6-bis­(phenyl­imino)­cyclo­hexa-1,4-diene-1,4-di­amine

Ohno, K.; Maruyama, H.; Fujihara, T.; Nagasawa, A.

doi:10.1107/S1600536814002906

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 3| March 2014| Pages o303-o304

doi:10.1107/S1600536814002906

Open

access

N¹,N⁴-Diphenyl-3,6-bis(phenylimino)cyclohexa-1,4-diene-1,4-diamine

Keiji Ohno,^a Haruki Maruyama,^a Takashi Fujihara ^b ^* and Akira Nagasawa ^a

^aDepartment of Chemistry, Graduate School of Science and Engineering, Saitama University, Shimo-Okubo 255, Sakura-ku, Saitama 338-8570, Japan, and ^bComprehensive Analysis Center for Science, Saitama University, Shimo-Okubo 255, Sakura-ku, Saitama 338-8570, Japan
^*Correspondence e-mail: fuji@chem.saitama-u.ac.jp

(Received 22 January 2014; accepted 8 February 2014; online 15 February 2014)

In the title compound, C₃₀H₂₄N₄, the central benzoquinonediimine moiety is approximately planar, with a maximum deviation of 0.044 (14) Å. The four terminal phenyl rings are twisted by 44.95 (11), 54.90 (10), 44.98 (10) and 50.68 (11)° with respect to the mean plane the benzoquinonediimine unit. In the crystal, molecules are linked by weak C—H⋯π interactions into supramolecular chains running along the b-axis direction.

CCDC reference:

Related literature

For general background to the title compound, see: Kimish (1875 ); Rall et al. (1998 ); Frantz et al. (2004 ); Siri et al. (2005 ); Taquet et al. (2006 ); Schweinfurth et al. (2013 ); Jeon et al. (2013 ). For related structures, see: Hughes & Saunders (1956 ); Merchant et al. (1984 ); Siri & Braunstein (2000 ); Wenderski et al. (2004 ); Khramov et al. (2006 ); Boydston et al. (2006 ); Huang et al., (2008 ); Su et al. (2012 ).

Experimental

Crystal data

C₃₀H₂₄N₄
M_r = 440.53
Triclinic, $[P \overline 1]$
a = 8.8858 (12) Å
b = 10.0540 (13) Å
c = 13.2256 (18) Å
α = 93.343 (3)°
β = 106.760 (3)°
γ = 98.530 (3)°
V = 1112.4 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 173 K
0.30 × 0.20 × 0.10 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.977, T_max = 0.992
8166 measured reflections
5291 independent reflections
3273 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.172
S = 1.03
5291 reflections
315 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 and Cg4 are the centroids of the C7–C12 and C19–C24 benzene rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯Cg4ⁱ	0.95	2.84	3.675 (2)	148
C14—H14⋯Cg2ⁱⁱ	0.95	2.81	3.673 (3)	151
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+1, -y, -z+1.

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

CCDC reference:

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536814002906/xu5766sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814002906/xu5766Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814002906/xu5766Isup3.cml

checkCIF report

Comment top

N¹,N⁴-Diphenyl-3,6-bis(phenylimino)cyclohexa-1,4-diene-1,4-diamine (I) was synthesized as early as in 1875 (Kimish, 1875) and called azophenine. Then I and its derivatives were obtained from aniline or substituted anilines in various ways, e.g. the oxidation of N,N'-diphenyl-p-phenylenediamine with mercury(II) oxide to give p-benzoquinone diamine followed by heating with aniline (Hughes & Saunders, 1956), heating of anilines with dry copper(II) chloride on a steam bath (Merchant et al., 1984), and the Buchwald-Hartwig cross coupling reaction (Wenderski et al., 2004). The molecular structures of the derivatives except I have been investigated (Boydston et al., 2006; Khramov et al., 2006; Huang et al., 2008). This class of compounds forms various metal complexes (Rall et al., 1998; Siri & Braunstein, 2000; Frantz et al., 2004; Siri et al., 2005; Su et al., 2012), some of which exhibit novel properties (Taquet et al., 2006; Schweinfurth et al., 2013), e.g. one-electron reduced dinuclear Fe complex with I behaves as a single molecule magnet with the strongest exchange coupling (Jeon et al., 2013).

The crystals of I were obtained in the process of a preparation of V^IV complex using aniline and [V^IV(O)(η²-ox)(H₂O)₃] (ox^2- = oxalate) in air. The reaction occurs neither under an argon atmosphere nor when less than four equivalents of aniline to [V^IV(O)(η²-ox)(H₂O)₃] was used. These results suggest that the reaction proceeds through coordination of aniline to [V^IV(O)(η²-ox)(H₂O)₃], which may act as a catalyst of oxidation pentamerization of aniline to form I.

The red crystals contain only I, and the structure is in triclinic P-1 space group. The atoms of diamino-benzoquinonediimine moiety of I are coplanar. The bond lengths of C(1)–N(1) and C(4)–N(3) correspond to C–N single bond, and that of C(2)–N(2) and C(5)–N(4) correspond to C–N double bond. The bond angles of C(1)—N(1)—C(7) and C(4)—N(3)—C(19) are 128.74 (18) and 127.80 (19)°, respectively, and that of C(2)═N(2)—C(13) and C(5)═N(4)—C(25) are 121.28 (18) and 123.00 (19)°, respectively, indicating that N(1 and 3) and N(2 and 4) are attributed to amine (sp³) and imine (sp²) nitrogen atoms, respectively. The bond length of C(2)–C(3) is similar with that of C(5)–C(6), corresponding to that of a single bond, and those of C(3)–C(4) and C(1)–C(6) are similar with each other, corresponding to that of a double bond. The bond lengths of C(1)–C(2) and C(4)–C(5) are slightly longer than the above mentioned single bonds. These results indicate that each of two N–C–C–C–N zigzag shaped moieties shows a bond alternation, but no conjugation between them.

Related literature top

For general background to the title compound, see: Kimish (1875); Rall et al. (1998); Frantz et al. (2004); Siri et al. (2005); Taquet et al. (2006); Schweinfurth et al. (2013); Jeon et al. (2013). For related structures, see: Hughes & Saunders (1956); Merchant et al. (1984); Siri & Braunstein (2000); Wenderski et al. (2004); Khramov et al. (2006); Boydston et al. (2006); Huang et al., (2008); Su et al. (2012).

Experimental top

The V^IV complex [V^IV(O)(η²-ox)(H₂O)₃] was purchased as "VO(ox)^.nH₂O" from Wako Chemicals, and used without further purification. A solution of aniline (27.9 g, 300 mmol) in EtOH (50 cm³) was added to a solution of VO(ox)^.nH₂O (1.13 g, 3.00 mmol) in a mixture of EtOH (50 cm³) and H₂O (100 cm³). The reaction mixture was set aside for 2 weeks at room temperature in air. The precipitated crystals were filterd off, washed with H₂O and EtOH, successively, and dried. Yield 1.34 g. (5.1%). ¹H NMR / CDCl₃: δ 8.22 (s, 2H, NH), 7.41–6.88 (m, 20H, PhH), 6.21 (s, 2H, CH). MALDI TOF MS: 441 (M+1). UV-vis / CH₂Cl₂, λ/nm (ε/M^-1cm^-1): 290 (46000), 379 (30000).

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of I, with displacement ellipsoids drawn at the 50% probability level.

N¹,N⁴-Diphenyl-3,6-bis(phenylimino)cyclohexa-1,4-diene-1,4-diamine top

Crystal data top

C₃₀H₂₄N₄	Z = 2
M_r = 440.53	F(000) = 464
Triclinic, P1	D_x = 1.315 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.8858 (12) Å	Cell parameters from 1264 reflections
b = 10.0540 (13) Å	θ = 2.4–25.9°
c = 13.2256 (18) Å	µ = 0.08 mm⁻¹
α = 93.343 (3)°	T = 173 K
β = 106.760 (3)°	Plate, red
γ = 98.530 (3)°	0.30 × 0.20 × 0.10 mm
V = 1112.4 (3) Å³

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	5291 independent reflections
Radiation source: fine-focus sealed tube	3273 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
Detector resolution: 8.366 pixels mm^-1	θ_max = 28.0°, θ_min = 1.6°
φ and ω scans	h = −10→11
Absorption correction: multi-scan (SADABS; Bruker, 2001)	k = −12→13
T_min = 0.977, T_max = 0.992	l = −17→8
8166 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.172	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0775P)² + 0.0548P] where P = (F_o² + 2F_c²)/3
5291 reflections	(Δ/σ)_max < 0.001
315 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₃₀H₂₄N₄	γ = 98.530 (3)°
M_r = 440.53	V = 1112.4 (3) Å³
Triclinic, P1	Z = 2
a = 8.8858 (12) Å	Mo Kα radiation
b = 10.0540 (13) Å	µ = 0.08 mm⁻¹
c = 13.2256 (18) Å	T = 173 K
α = 93.343 (3)°	0.30 × 0.20 × 0.10 mm
β = 106.760 (3)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	5291 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	3273 reflections with I > 2σ(I)
T_min = 0.977, T_max = 0.992	R_int = 0.031
8166 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	0 restraints
wR(F²) = 0.172	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.32 e Å⁻³
5291 reflections	Δρ_min = −0.24 e Å⁻³
315 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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

5.6034 (0.0038) x + 5.0416 (0.0058) y + 12.9434 (0.0071) z = 8.2491 (0.0021)

* 0.0006 (0.0008) C10 * -0.0066 (0.0008) C11 * 0.0067 (0.0009) C12 * -0.0008 (0.0009) C13 * -0.0053 (0.0009) C14 * 0.0053 (0.0008) C15

Rms deviation of fitted atoms = 0.0049

- 7.4963 (0.0028) x + 1.7481 (0.0065) y + 10.6592 (0.0082) z = 4.5261 (0.0067)

Angle to previous plane (with approximate e.s.d.) = 86.71 (0.03)

* 0.0118 (0.0008) C4 * -0.0134 (0.0008) C5 * 0.0021 (0.0009) C6 * 0.0111 (0.0009) C7 * -0.0128 (0.0009) C8 * 0.0013 (0.0009) C9

Rms deviation of fitted atoms = 0.0101

- 4.5932 (0.0050) x + 6.9089 (0.0064) y + 12.6394 (0.0086) z = 6.3197 (0.0043)

Angle to previous plane (with approximate e.s.d.) = 30.79 (0.06)

* 0.0005 (0.0006) C1 * -0.0005 (0.0006) C2 * 0.0005 (0.0006) C3 * -0.0005 (0.0006) C1_$1 * 0.0005 (0.0006) C2_$1 * -0.0005 (0.0006) C3_$1 - 3.3572 (0.0015) C13_$2 - 3.6100 (0.0013) C14_$2 - 3.7830 (0.0014) C15_$2

Rms deviation of fitted atoms = 0.0005

- 4.5932 (0.0050) x + 6.9089 (0.0064) y + 12.6394 (0.0086) z = 6.3197 (0.0043)

Angle to previous plane (with approximate e.s.d.) = 0.00 (0.10)

* 0.0005 (0.0006) C1 * -0.0005 (0.0006) C2 * 0.0005 (0.0006) C3 * -0.0005 (0.0006) C1_$1 * 0.0005 (0.0006) C2_$1 * -0.0005 (0.0006) C3_$1 - 3.7228 (0.0017) C10_$2 - 3.4796 (0.0019) C11_$2 - 3.2849 (0.0018) C12_$2

Rms deviation of fitted atoms = 0.0005

- 5.6034 (0.0038) x + 5.0416 (0.0058) y + 12.9434 (0.0070) z = 2.9266 (0.0041)

Angle to previous plane (with approximate e.s.d.) = 10.70 (0.08)

* 0.0006 (0.0008) C10_$2 * -0.0066 (0.0008) C11_$2 * 0.0067 (0.0009) C12_$2 * -0.0008 (0.0009) C13_$2 * -0.0053 (0.0009) C14_$2 * 0.0053 (0.0008) C15_$2

Rms deviation of fitted atoms = 0.0049

- 4.5932 (0.0050) x + 6.9089 (0.0064) y + 12.6394 (0.0086) z = 6.3197 (0.0043)

Angle to previous plane (with approximate e.s.d.) = 10.70 (0.08)

* 0.0005 (0.0006) C1 * -0.0005 (0.0006) C2 * 0.0005 (0.0006) C3 * -0.0005 (0.0006) C1_$1 * 0.0005 (0.0006) C2_$1 * -0.0005 (0.0006) C3_$1

Rms deviation of fitted atoms = 0.0005

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.6215 (2)	0.1790 (2)	0.48956 (16)	0.0279 (5)
C2	0.5987 (2)	0.2013 (2)	0.59667 (16)	0.0272 (5)
C3	0.4786 (3)	0.2780 (2)	0.60555 (17)	0.0291 (5)
H3	0.4665	0.2981	0.6736	0.035*
C4	0.3815 (3)	0.3228 (2)	0.51985 (17)	0.0290 (5)
C5	0.3993 (2)	0.2946 (2)	0.41226 (16)	0.0272 (5)
C6	0.5248 (3)	0.2248 (2)	0.40391 (17)	0.0298 (5)
H6	0.5412	0.2100	0.3366	0.036*
C7	0.8056 (2)	0.0811 (2)	0.40583 (17)	0.0305 (5)
C8	0.8318 (3)	0.1764 (2)	0.33796 (17)	0.0340 (5)
H8	0.8037	0.2632	0.3456	0.041*
C9	0.8982 (3)	0.1449 (2)	0.26007 (18)	0.0377 (6)
H9	0.9168	0.2109	0.2144	0.045*
C10	0.9386 (3)	0.0192 (2)	0.24679 (19)	0.0392 (6)
H10	0.9830	−0.0019	0.1918	0.047*
C11	0.9138 (3)	−0.0753 (2)	0.31417 (19)	0.0368 (6)
H11	0.9405	−0.1624	0.3054	0.044*
C12	0.8501 (3)	−0.0439 (2)	0.39462 (18)	0.0336 (5)
H12	0.8368	−0.1084	0.4424	0.040*
C13	0.6813 (3)	0.1632 (2)	0.77728 (16)	0.0286 (5)
C14	0.5421 (3)	0.1153 (2)	0.80110 (18)	0.0340 (5)
H14	0.4491	0.0748	0.7456	0.041*
C15	0.5379 (3)	0.1259 (2)	0.90426 (19)	0.0400 (6)
H15	0.4413	0.0938	0.9191	0.048*
C16	0.6711 (3)	0.1823 (2)	0.98623 (19)	0.0396 (6)
H16	0.6666	0.1908	1.0572	0.048*
C17	0.8115 (3)	0.2265 (2)	0.96395 (18)	0.0381 (6)
H17	0.9048	0.2642	1.0202	0.046*
C18	0.8180 (3)	0.2163 (2)	0.86100 (17)	0.0339 (5)
H18	0.9159	0.2457	0.8469	0.041*
C19	0.2077 (3)	0.4243 (2)	0.60850 (18)	0.0324 (5)
C20	0.3155 (3)	0.4832 (2)	0.70564 (19)	0.0386 (6)
H20	0.4267	0.5000	0.7138	0.046*
C21	0.2614 (3)	0.5167 (2)	0.78905 (19)	0.0399 (6)
H21	0.3360	0.5538	0.8555	0.048*
C22	0.1014 (3)	0.4976 (2)	0.77844 (19)	0.0411 (6)
H22	0.0655	0.5217	0.8369	0.049*
C23	−0.0066 (3)	0.4433 (2)	0.68263 (19)	0.0373 (6)
H23	−0.1176	0.4322	0.6745	0.045*
C24	0.0450 (3)	0.4049 (2)	0.59809 (19)	0.0352 (5)
H24	−0.0305	0.3651	0.5327	0.042*
C25	0.2863 (2)	0.3163 (2)	0.22856 (17)	0.0284 (5)
C26	0.2740 (3)	0.1896 (2)	0.17692 (18)	0.0344 (5)
H26	0.2778	0.1129	0.2157	0.041*
C27	0.2564 (3)	0.1740 (3)	0.06994 (19)	0.0426 (6)
H27	0.2469	0.0863	0.0354	0.051*
C28	0.2524 (3)	0.2840 (3)	0.01207 (19)	0.0447 (6)
H28	0.2436	0.2729	−0.0613	0.054*
C29	0.2612 (3)	0.4105 (3)	0.06249 (19)	0.0401 (6)
H29	0.2575	0.4867	0.0232	0.048*
C30	0.2753 (3)	0.4270 (2)	0.16866 (17)	0.0327 (5)
H30	0.2777	0.5139	0.2019	0.039*
H1	0.777 (3)	0.075 (3)	0.551 (2)	0.049 (8)*
H2	0.197 (3)	0.394 (3)	0.453 (2)	0.057 (8)*
N1	0.7414 (2)	0.1088 (2)	0.48930 (15)	0.0334 (5)
N2	0.6936 (2)	0.15137 (18)	0.67317 (14)	0.0296 (4)
N3	0.2589 (2)	0.3886 (2)	0.52080 (15)	0.0361 (5)
N4	0.2966 (2)	0.34011 (18)	0.33658 (14)	0.0300 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0257 (11)	0.0305 (12)	0.0276 (11)	0.0063 (9)	0.0076 (9)	0.0019 (9)
C2	0.0260 (11)	0.0272 (11)	0.0268 (11)	0.0027 (9)	0.0064 (9)	0.0036 (9)
C3	0.0331 (12)	0.0324 (12)	0.0248 (11)	0.0103 (9)	0.0111 (9)	0.0036 (9)
C4	0.0299 (11)	0.0301 (12)	0.0297 (12)	0.0090 (9)	0.0108 (9)	0.0046 (9)
C5	0.0267 (11)	0.0277 (11)	0.0262 (11)	0.0043 (9)	0.0064 (9)	0.0053 (9)
C6	0.0302 (12)	0.0367 (13)	0.0238 (11)	0.0081 (9)	0.0087 (9)	0.0042 (9)
C7	0.0223 (11)	0.0398 (13)	0.0277 (11)	0.0074 (9)	0.0037 (9)	0.0035 (10)
C8	0.0327 (12)	0.0338 (13)	0.0340 (13)	0.0082 (10)	0.0060 (10)	0.0058 (10)
C9	0.0393 (13)	0.0411 (14)	0.0336 (13)	0.0088 (11)	0.0108 (10)	0.0070 (11)
C10	0.0383 (14)	0.0460 (15)	0.0375 (13)	0.0119 (11)	0.0163 (11)	0.0020 (11)
C11	0.0336 (13)	0.0325 (13)	0.0443 (14)	0.0100 (10)	0.0104 (11)	0.0005 (11)
C12	0.0250 (11)	0.0352 (13)	0.0377 (13)	0.0063 (9)	0.0042 (9)	0.0066 (10)
C13	0.0326 (12)	0.0269 (11)	0.0273 (12)	0.0129 (9)	0.0059 (9)	0.0068 (9)
C14	0.0286 (12)	0.0384 (13)	0.0326 (13)	0.0077 (10)	0.0039 (9)	0.0072 (10)
C15	0.0387 (14)	0.0473 (15)	0.0390 (14)	0.0117 (11)	0.0159 (11)	0.0127 (12)
C16	0.0507 (16)	0.0438 (14)	0.0272 (12)	0.0126 (12)	0.0136 (11)	0.0047 (11)
C17	0.0424 (14)	0.0383 (14)	0.0282 (12)	0.0047 (11)	0.0036 (10)	0.0010 (10)
C18	0.0331 (12)	0.0317 (12)	0.0343 (13)	0.0040 (10)	0.0067 (10)	0.0056 (10)
C19	0.0375 (13)	0.0299 (12)	0.0332 (12)	0.0106 (10)	0.0126 (10)	0.0082 (10)
C20	0.0344 (13)	0.0398 (14)	0.0403 (14)	0.0075 (11)	0.0080 (11)	0.0078 (11)
C21	0.0470 (15)	0.0392 (14)	0.0313 (13)	0.0135 (11)	0.0058 (11)	−0.0002 (11)
C22	0.0554 (17)	0.0390 (14)	0.0350 (14)	0.0135 (12)	0.0201 (12)	0.0060 (11)
C23	0.0391 (13)	0.0354 (13)	0.0445 (14)	0.0117 (10)	0.0196 (11)	0.0108 (11)
C24	0.0350 (13)	0.0337 (13)	0.0356 (13)	0.0082 (10)	0.0071 (10)	0.0066 (10)
C25	0.0220 (10)	0.0360 (13)	0.0271 (11)	0.0080 (9)	0.0058 (9)	0.0040 (10)
C26	0.0336 (12)	0.0318 (12)	0.0367 (13)	0.0095 (10)	0.0069 (10)	0.0053 (10)
C27	0.0419 (15)	0.0423 (15)	0.0397 (14)	0.0115 (11)	0.0061 (11)	−0.0066 (12)
C28	0.0493 (16)	0.0602 (18)	0.0269 (13)	0.0211 (13)	0.0095 (11)	0.0040 (12)
C29	0.0467 (15)	0.0441 (15)	0.0314 (13)	0.0148 (12)	0.0097 (11)	0.0120 (11)
C30	0.0329 (12)	0.0326 (12)	0.0326 (12)	0.0096 (10)	0.0074 (10)	0.0049 (10)
N1	0.0346 (11)	0.0441 (12)	0.0255 (10)	0.0177 (9)	0.0088 (8)	0.0089 (9)
N2	0.0285 (10)	0.0336 (10)	0.0264 (10)	0.0091 (8)	0.0059 (8)	0.0038 (8)
N3	0.0407 (12)	0.0476 (12)	0.0264 (11)	0.0233 (9)	0.0111 (9)	0.0085 (9)
N4	0.0299 (10)	0.0336 (10)	0.0275 (10)	0.0091 (8)	0.0075 (8)	0.0074 (8)

Geometric parameters (Å, º) top

C1—C6	1.360 (3)	C16—C17	1.380 (3)
C1—N1	1.363 (3)	C16—H16	0.9500
C1—C2	1.497 (3)	C17—C18	1.378 (3)
C2—N2	1.296 (3)	C17—H17	0.9500
C2—C3	1.433 (3)	C18—H18	0.9500
C3—C4	1.358 (3)	C19—C24	1.395 (3)
C3—H3	0.9500	C19—C20	1.397 (3)
C4—N3	1.358 (3)	C19—N3	1.409 (3)
C4—C5	1.492 (3)	C20—C21	1.368 (3)
C5—N4	1.302 (3)	C20—H20	0.9500
C5—C6	1.429 (3)	C21—C22	1.370 (3)
C6—H6	0.9500	C21—H21	0.9500
C7—C12	1.385 (3)	C22—C23	1.374 (4)
C7—C8	1.390 (3)	C22—H22	0.9500
C7—N1	1.412 (3)	C23—C24	1.381 (3)
C8—C9	1.370 (3)	C23—H23	0.9500
C8—H8	0.9500	C24—H24	0.9500
C9—C10	1.379 (3)	C25—C26	1.384 (3)
C9—H9	0.9500	C25—C30	1.402 (3)
C10—C11	1.377 (3)	C25—N4	1.409 (3)
C10—H10	0.9500	C26—C27	1.375 (3)
C11—C12	1.383 (3)	C26—H26	0.9500
C11—H11	0.9500	C27—C28	1.380 (3)
C12—H12	0.9500	C27—H27	0.9500
C13—C14	1.388 (3)	C28—C29	1.382 (4)
C13—C18	1.396 (3)	C28—H28	0.9500
C13—N2	1.412 (3)	C29—C30	1.371 (3)
C14—C15	1.374 (3)	C29—H29	0.9500
C14—H14	0.9500	C30—H30	0.9500
C15—C16	1.374 (3)	N1—H1	0.89 (3)
C15—H15	0.9500	N3—H2	0.91 (3)

C6—C1—N1	126.3 (2)	C18—C17—H17	119.6
C6—C1—C2	120.17 (19)	C16—C17—H17	119.6
N1—C1—C2	113.47 (17)	C17—C18—C13	120.3 (2)
N2—C2—C3	126.4 (2)	C17—C18—H18	119.8
N2—C2—C1	116.00 (19)	C13—C18—H18	119.8
C3—C2—C1	117.54 (18)	C24—C19—C20	118.5 (2)
C4—C3—C2	122.1 (2)	C24—C19—N3	119.7 (2)
C4—C3—H3	118.9	C20—C19—N3	121.8 (2)
C2—C3—H3	118.9	C21—C20—C19	120.1 (2)
N3—C4—C3	125.5 (2)	C21—C20—H20	119.9
N3—C4—C5	114.23 (18)	C19—C20—H20	119.9
C3—C4—C5	120.15 (19)	C20—C21—C22	121.1 (2)
N4—C5—C6	128.0 (2)	C20—C21—H21	119.4
N4—C5—C4	114.12 (19)	C22—C21—H21	119.4
C6—C5—C4	117.92 (18)	C21—C22—C23	119.5 (2)
C1—C6—C5	121.9 (2)	C21—C22—H22	120.2
C1—C6—H6	119.0	C23—C22—H22	120.2
C5—C6—H6	119.0	C22—C23—C24	120.5 (2)
C12—C7—C8	119.1 (2)	C22—C23—H23	119.7
C12—C7—N1	118.3 (2)	C24—C23—H23	119.7
C8—C7—N1	122.5 (2)	C23—C24—C19	120.1 (2)
C9—C8—C7	119.9 (2)	C23—C24—H24	119.9
C9—C8—H8	120.0	C19—C24—H24	119.9
C7—C8—H8	120.0	C26—C25—C30	118.5 (2)
C8—C9—C10	121.1 (2)	C26—C25—N4	124.02 (19)
C8—C9—H9	119.4	C30—C25—N4	117.3 (2)
C10—C9—H9	119.4	C27—C26—C25	120.4 (2)
C11—C10—C9	119.2 (2)	C27—C26—H26	119.8
C11—C10—H10	120.4	C25—C26—H26	119.8
C9—C10—H10	120.4	C26—C27—C28	120.9 (2)
C10—C11—C12	120.2 (2)	C26—C27—H27	119.5
C10—C11—H11	119.9	C28—C27—H27	119.5
C12—C11—H11	119.9	C27—C28—C29	119.0 (2)
C11—C12—C7	120.3 (2)	C27—C28—H28	120.5
C11—C12—H12	119.8	C29—C28—H28	120.5
C7—C12—H12	119.8	C30—C29—C28	120.6 (2)
C14—C13—C18	118.3 (2)	C30—C29—H29	119.7
C14—C13—N2	122.83 (19)	C28—C29—H29	119.7
C18—C13—N2	118.66 (19)	C29—C30—C25	120.4 (2)
C15—C14—C13	120.5 (2)	C29—C30—H30	119.8
C15—C14—H14	119.7	C25—C30—H30	119.8
C13—C14—H14	119.7	C1—N1—C7	128.76 (19)
C16—C15—C14	121.0 (2)	C1—N1—H1	111.5 (17)
C16—C15—H15	119.5	C7—N1—H1	119.7 (17)
C14—C15—H15	119.5	C2—N2—C13	121.28 (19)
C15—C16—C17	119.0 (2)	C4—N3—C19	127.73 (19)
C15—C16—H16	120.5	C4—N3—H2	110.8 (18)
C17—C16—H16	120.5	C19—N3—H2	120.5 (18)
C18—C17—C16	120.7 (2)	C5—N4—C25	123.01 (19)

C6—C1—C2—N2	178.4 (2)	C24—C19—C20—C21	2.0 (3)
N1—C1—C2—N2	−0.2 (3)	N3—C19—C20—C21	179.9 (2)
C6—C1—C2—C3	−3.3 (3)	C19—C20—C21—C22	−2.2 (4)
N1—C1—C2—C3	178.05 (19)	C20—C21—C22—C23	0.3 (4)
N2—C2—C3—C4	−178.1 (2)	C21—C22—C23—C24	1.7 (3)
C1—C2—C3—C4	3.8 (3)	C22—C23—C24—C19	−1.8 (3)
C2—C3—C4—N3	175.7 (2)	C20—C19—C24—C23	−0.1 (3)
C2—C3—C4—C5	−0.9 (3)	N3—C19—C24—C23	−178.0 (2)
N3—C4—C5—N4	1.4 (3)	C30—C25—C26—C27	2.0 (3)
C3—C4—C5—N4	178.4 (2)	N4—C25—C26—C27	176.7 (2)
N3—C4—C5—C6	−179.6 (2)	C25—C26—C27—C28	0.7 (4)
C3—C4—C5—C6	−2.6 (3)	C26—C27—C28—C29	−2.0 (4)
N1—C1—C6—C5	178.3 (2)	C27—C28—C29—C30	0.6 (4)
C2—C1—C6—C5	−0.1 (3)	C28—C29—C30—C25	2.1 (4)
N4—C5—C6—C1	−178.1 (2)	C26—C25—C30—C29	−3.4 (3)
C4—C5—C6—C1	3.1 (3)	N4—C25—C30—C29	−178.5 (2)
C12—C7—C8—C9	1.2 (3)	C6—C1—N1—C7	8.2 (4)
N1—C7—C8—C9	178.3 (2)	C2—C1—N1—C7	−173.3 (2)
C7—C8—C9—C10	0.6 (3)	C12—C7—N1—C1	−142.5 (2)
C8—C9—C10—C11	−1.0 (4)	C8—C7—N1—C1	40.4 (3)
C9—C10—C11—C12	−0.4 (3)	C3—C2—N2—C13	3.3 (3)
C10—C11—C12—C7	2.2 (3)	C1—C2—N2—C13	−178.59 (18)
C8—C7—C12—C11	−2.6 (3)	C14—C13—N2—C2	57.2 (3)
N1—C7—C12—C11	−179.8 (2)	C18—C13—N2—C2	−127.5 (2)
C18—C13—C14—C15	2.9 (3)	C3—C4—N3—C19	0.3 (4)
N2—C13—C14—C15	178.2 (2)	C5—C4—N3—C19	177.2 (2)
C13—C14—C15—C16	−0.8 (4)	C24—C19—N3—C4	−136.7 (2)
C14—C15—C16—C17	−1.2 (4)	C20—C19—N3—C4	45.4 (3)
C15—C16—C17—C18	1.0 (4)	C6—C5—N4—C25	5.4 (3)
C16—C17—C18—C13	1.1 (3)	C4—C5—N4—C25	−175.67 (18)
C14—C13—C18—C17	−3.0 (3)	C26—C25—N4—C5	51.4 (3)
N2—C13—C18—C17	−178.5 (2)	C30—C25—N4—C5	−133.8 (2)

Hydrogen-bond geometry (Å, º) top

Cg2 and Cg4 are the centroids of the C7–C12 and C19–C24 benzene rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···Cg4ⁱ	0.95	2.84	3.675 (2)	148
C14—H14···Cg2ⁱⁱ	0.95	2.81	3.673 (3)	151

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

Hydrogen-bond geometry (Å, º) top

Cg2 and Cg4 are the centroids of the C7–C12 and C19–C24 benzene rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···Cg4ⁱ	0.95	2.8347	3.675 (2)	148
C14—H14···Cg2ⁱⁱ	0.95	2.8113	3.673 (3)	151

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

Acknowledgements

This work has been supported by the programs of the Grants-in-Aid for Scientific Research (to TF, No. 23510115) from the Japan Society for the Promotion of Science.

References

Boydston, A. J., Khramoc, D. M. & Bielawski, C. W. (2006). Tetrahedron Lett. 47, 5123–5125. Web of Science CSD CrossRef CAS 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
Frantz, S., Rall, J., Hartenbach, J., Schleid, T., Záliś, S. & Kaim, W. (2004). Chem. Eur. J. 10, 149–154. Web of Science CSD CrossRef PubMed CAS Google Scholar
Huang, Y.-B., Tang, G.-R., Jin, G.-Y. & Jin, G.-X. (2008). Organometallics, 27, 259–269. Web of Science CSD CrossRef CAS Google Scholar
Hughes, G. M. K. & Saunders, B. C. (1956). J. Chem. Soc. pp. 3814–3820. CrossRef Web of Science Google Scholar
Jeon, I. R., Park, J. G., Xiao, D. J. & Harris, T. D. (2013). J. Am. Chem. Soc. 135, 16845–16848. Web of Science CSD CrossRef CAS PubMed Google Scholar
Khramov, D. M., Boydston, A. J. & Bielawski, C. W. (2006). Org. Lett. 8, 1831–1834. Web of Science CSD CrossRef PubMed CAS Google Scholar
Kimish, C. (1875). Ber. Dtsch. Chem. Ges. 8, 1026–1032. Google Scholar
Merchant, J. R., Martyres, G. & Shinde, N. M. (1984). Bull. Chem. Soc. Jpn, 57, 1405–1406. CrossRef CAS Web of Science Google Scholar
Rall, J., Stange, A. F., Hübler, K. & Kaim, W. (1998). Angew. Chem. Int. Ed. 37, 2681–2682. CrossRef CAS Google Scholar
Schweinfurth, D., Khusniyarov, M. M., Bubrin, D., Hohloch, S., Su, C. Y. & Srkar, B. (2013). Inorg. Chem. 52, 10332–10339. Web of Science CSD CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siri, O. & Braunstein, P. (2000). Chem. Commun. pp. 2223–2224. Web of Science CSD CrossRef Google Scholar
Siri, O., Taquet, J. P., Collin, J. P., Rohmer, M. M., Bénard, M. & Braunstein, P. (2005). Chem. Eur. J. 11, 7247–7253. Web of Science CSD CrossRef PubMed CAS Google Scholar
Su, Y., Zhao, Y., Gao, J., Dong, Q., Wu, B. & Yang, X.-J. (2012). Inorg. Chem. 51, 5889–5896. Web of Science CSD CrossRef CAS PubMed Google Scholar
Taquet, J. P., Siri, O. & Braunstein, P. (2006). Inorg. Chem. 45, 4668–4676. Web of Science CSD CrossRef PubMed CAS Google Scholar
Wenderski, T., Light, K. M., Ogrin, D., Bott, S. G. & Harlan, C. J. (2004). Tetrahedron Lett. 45, 6851–6853. Web of Science CSD CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 3| March 2014| Pages o303-o304

doi:10.1107/S1600536814002906

Open

access