Literature DB >> 24826185

An ortho-rhom-bic polymorph of N (1),N (4)-diphenyl-3,6-bis-(phenyl-imino)-cyclo-hexa-1,4-diene-1,4-di-amine.

Keiji Ohno¹, Takashi Fujihara², Akira Nagasawa¹.

Abstract

A new ortho-rhom-bic polymorph of the title compound, C30H24N4, with a density of 1.315 Mg m(-3), has been obtained. The mol-ecule is centrosymmetric with the centroid of the cyclo-hexa-1,4-diene ring located on an inversion center. The two unique benzene rings are almost perpendicular to each other [dihedral angle = 86.70 (6)°] and are oriented at dihedral angles of 30.79 (5) and 68.07 (5)° with respect to the central cyclo-hexa-diene ring. In the crystal, π-π stacking is observed between the central cyclo-hexa-1,4-diene-1,4-di-amine unit and a phenyl ring of a neighboring mol-ecule [centroid-centroid distance = 3.7043 (7) Å]. The crystal structure of the triclinic polymorph [Ohno et al. (2014 ▶). Acta Cryst. E70, o303-o304] showed chains running along the b-axis direction through weak C-H⋯π inter-actions.

Entities: Chemical Disease Gene

Year: 2014 PMID： 24826185 PMCID： PMC3998558 DOI： 10.1107/S1600536814006254

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

For general background to the title compound, see: Kimish (1875 ▶). For the triclinic polymorph of the title compound, see: Ohno et al. (2014 ▶). For related structures, see: Siri & Braunstein (2000 ▶); Khramov et al. (2006 ▶); Boydston et al. (2006 ▶); Huang et al. (2008 ▶); Su et al. (2012 ▶). A calculation using Gaussian98 indicates that the triclinic form of the title compound is more stable, see: Frisch et al. (2001 ▶).

Experimental

Crystal data

C30H24N4 M = 440.53 Orthorhombic, a = 9.1927 (5) Å b = 12.4711 (7) Å c = 18.9806 (11) Å V = 2176.0 (2) Å3 Z = 4 Mo Kα radiation μ = 0.08 mm−1 T = 173 K 0.35 × 0.30 × 0.10 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.97, T max = 0.99 14830 measured reflections 2591 independent reflections 2193 reflections with I > 2σ(I) R int = 0.116

Refinement

R[F 2 > 2σ(F 2)] = 0.046 wR(F 2) = 0.133 S = 1.09 2591 reflections 158 parameters H atoms treated by a mixture of independent and constrained refinement Δρmax = 0.31 e Å−3 Δρmin = −0.24 e Å−3 Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: SHELXTL. Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814006254/xu5776sup1.cif Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814006254/xu5776Isup2.hkl Click here for additional data file. Supporting information file. DOI: 10.1107/S1600536814006254/xu5776Isup3.cml CCDC reference: 992862 Additional supporting information: crystallographic information; 3D view; checkCIF report

C₃₀H₂₄N₄	F(000) = 928
M_r = 440.53	D_x = 1.345 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 6200 reflections
a = 9.1927 (5) Å	θ = 3.0–27.8°
b = 12.4711 (7) Å	µ = 0.08 mm⁻¹
c = 18.9806 (11) Å	T = 173 K
V = 2176.0 (2) Å³	Plate, orange
Z = 4	0.35 × 0.30 × 0.10 mm

Bruker SMART APEX CCD area-detector diffractometer	2591 independent reflections
Radiation source: fine-focus sealed tube	2193 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.116
Detector resolution: 8.366 pixels mm^-1	θ_max = 27.9°, θ_min = 2.2°
φ and ω scans	h = −12→11
Absorption correction: multi-scan (SADABS; Bruker, 2001)	k = −16→15
T_min = 0.97, T_max = 0.99	l = −16→24
14830 measured reflections

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.133	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.073P)² + 0.1882P] where P = (F_o² + 2F_c²)/3
2591 reflections	(Δ/σ)_max < 0.001
158 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

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)- 4.5932 (0.0050) x + 6.9089 (0.0064) y + 12.6394 (0.0086) z = 6.3197 (0.0043)* 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_$1Rms 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_$2Rms 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 - 3.7228 (0.0017) C10_$2 - 3.4796 (0.0019) C11_$2 - 3.2849 (0.0018) C12_$2Rms 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 - 3.3572 (0.0015) C13_$2 - 3.6100 (0.0013) C14_$2 - 3.7830 (0.0014) C15_$2Rms deviation of fitted atoms = 0.0005- 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.) = 30.79 (0.06)* 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) C9Rms deviation of fitted atoms = 0.01015.6034 (0.0038) x + 5.0416 (0.0058) y + 12.9434 (0.0071) z = 8.2491 (0.0021)Angle to previous plane (with approximate e.s.d.) = 86.71 (0.03)* 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) C15Rms deviation of fitted atoms = 0.004

	x	y	z	U_iso*/U_eq
C1	0.12006 (12)	−0.00788 (8)	0.54798 (6)	0.0209 (3)
C2	0.10916 (12)	0.08101 (8)	0.49535 (6)	0.0206 (3)
C3	−0.01449 (12)	0.08355 (9)	0.44911 (6)	0.0215 (3)
H3	−0.0224	0.1398	0.4156	0.026*
C4	0.29282 (12)	−0.06850 (9)	0.64289 (6)	0.0219 (3)
C5	0.27035 (13)	−0.17924 (10)	0.64288 (6)	0.0256 (3)
H5	0.2148	−0.2119	0.6065	0.031*
C6	0.32978 (14)	−0.24128 (10)	0.69630 (7)	0.0301 (3)
H6	0.3123	−0.3164	0.6968	0.036*
C7	0.41411 (15)	−0.19588 (10)	0.74902 (6)	0.0321 (3)
H7	0.4531	−0.2392	0.7856	0.039*
C8	0.44080 (15)	−0.08662 (10)	0.74762 (6)	0.0314 (3)
H8	0.5013	−0.0551	0.7825	0.038*
C9	0.37968 (13)	−0.02321 (9)	0.69556 (6)	0.0264 (3)
H9	0.3969	0.0519	0.6956	0.032*
C10	0.21200 (12)	0.24083 (9)	0.45179 (6)	0.0223 (3)
C11	0.11033 (13)	0.32190 (10)	0.46367 (6)	0.0262 (3)
H11	0.0366	0.3124	0.4982	0.031*
C12	0.11658 (14)	0.41614 (9)	0.42529 (7)	0.0280 (3)
H12	0.0483	0.4717	0.4343	0.034*
C13	0.22200 (14)	0.43007 (10)	0.37364 (7)	0.0288 (3)
H13	0.2254	0.4945	0.3469	0.035*
C14	0.32205 (14)	0.34921 (10)	0.36147 (7)	0.0291 (3)
H14	0.3940	0.3582	0.3260	0.035*
C15	0.31853 (13)	0.25534 (9)	0.40038 (6)	0.0254 (3)
H15	0.3887	0.2008	0.3921	0.031*
H1	0.2849 (18)	0.0610 (13)	0.5831 (8)	0.030 (4)*
N1	0.23876 (11)	0.00087 (8)	0.59090 (5)	0.0248 (2)
N2	0.21592 (10)	0.14848 (8)	0.49516 (5)	0.0236 (2)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0178 (5)	0.0226 (5)	0.0223 (5)	0.0024 (4)	−0.0001 (4)	−0.0009 (4)
C2	0.0181 (5)	0.0207 (5)	0.0231 (5)	0.0007 (4)	0.0008 (4)	−0.0010 (4)
C3	0.0197 (5)	0.0220 (5)	0.0229 (5)	0.0005 (4)	−0.0010 (4)	0.0020 (4)
C4	0.0160 (5)	0.0264 (6)	0.0234 (5)	0.0013 (4)	0.0005 (4)	0.0022 (4)
C5	0.0198 (6)	0.0265 (6)	0.0305 (6)	−0.0003 (4)	−0.0015 (4)	−0.0008 (4)
C6	0.0243 (6)	0.0266 (6)	0.0393 (7)	0.0012 (5)	0.0003 (5)	0.0055 (5)
C7	0.0288 (7)	0.0374 (7)	0.0302 (6)	0.0062 (5)	−0.0025 (5)	0.0084 (5)
C8	0.0267 (7)	0.0395 (7)	0.0279 (6)	0.0026 (5)	−0.0061 (5)	−0.0014 (5)
C9	0.0233 (6)	0.0267 (6)	0.0291 (6)	0.0007 (4)	−0.0032 (4)	−0.0007 (4)
C10	0.0183 (5)	0.0222 (5)	0.0264 (6)	−0.0041 (4)	−0.0045 (4)	0.0007 (4)
C11	0.0201 (6)	0.0287 (6)	0.0297 (6)	−0.0013 (4)	0.0015 (4)	0.0006 (4)
C12	0.0225 (6)	0.0250 (6)	0.0364 (7)	0.0025 (4)	−0.0017 (5)	−0.0001 (5)
C13	0.0282 (6)	0.0251 (6)	0.0330 (6)	−0.0032 (5)	−0.0028 (5)	0.0064 (5)
C14	0.0244 (6)	0.0326 (6)	0.0301 (6)	−0.0035 (5)	0.0032 (5)	0.0038 (5)
C15	0.0202 (6)	0.0264 (6)	0.0296 (6)	0.0006 (4)	−0.0014 (4)	−0.0002 (4)
N1	0.0217 (5)	0.0237 (5)	0.0290 (5)	−0.0051 (4)	−0.0059 (4)	0.0044 (4)
N2	0.0194 (5)	0.0227 (5)	0.0286 (5)	−0.0017 (4)	−0.0019 (4)	0.0021 (4)

C1—C3ⁱ	1.3547 (16)	C8—C9	1.3847 (17)
C1—N1	1.3662 (15)	C8—H8	0.9500
C1—C2	1.4957 (15)	C9—H9	0.9500
C2—N2	1.2927 (14)	C10—C15	1.3942 (17)
C2—C3	1.4365 (15)	C10—C11	1.3952 (17)
C3—C1ⁱ	1.3547 (16)	C10—N2	1.4160 (14)
C3—H3	0.9500	C11—C12	1.3840 (17)
C4—C5	1.3964 (16)	C11—H11	0.9500
C4—C9	1.3985 (16)	C12—C13	1.3893 (18)
C4—N1	1.4032 (15)	C12—H12	0.9500
C5—C6	1.3874 (17)	C13—C14	1.3842 (18)
C5—H5	0.9500	C13—H13	0.9500
C6—C7	1.3866 (19)	C14—C15	1.3846 (16)
C6—H6	0.9500	C14—H14	0.9500
C7—C8	1.3848 (19)	C15—H15	0.9500
C7—H7	0.9500	N1—H1	0.874 (17)

C3ⁱ—C1—N1	127.12 (10)	C8—C9—H9	119.6
C3ⁱ—C1—C2	119.71 (10)	C4—C9—H9	119.6
N1—C1—C2	113.12 (10)	C15—C10—C11	119.31 (10)
N2—C2—C3	125.78 (10)	C15—C10—N2	119.63 (10)
N2—C2—C1	115.69 (10)	C11—C10—N2	120.83 (10)
C3—C2—C1	118.51 (10)	C12—C11—C10	120.17 (11)
C1ⁱ—C3—C2	121.78 (10)	C12—C11—H11	119.9
C1ⁱ—C3—H3	119.1	C10—C11—H11	119.9
C2—C3—H3	119.1	C11—C12—C13	120.44 (11)
C5—C4—C9	118.94 (10)	C11—C12—H12	119.8
C5—C4—N1	123.87 (10)	C13—C12—H12	119.8
C9—C4—N1	117.12 (10)	C14—C13—C12	119.34 (11)
C6—C5—C4	119.55 (11)	C14—C13—H13	120.3
C6—C5—H5	120.2	C12—C13—H13	120.3
C4—C5—H5	120.2	C13—C14—C15	120.76 (11)
C7—C6—C5	121.32 (11)	C13—C14—H14	119.6
C7—C6—H6	119.3	C15—C14—H14	119.6
C5—C6—H6	119.3	C14—C15—C10	119.96 (11)
C8—C7—C6	119.14 (11)	C14—C15—H15	120.0
C8—C7—H7	120.4	C10—C15—H15	120.0
C6—C7—H7	120.4	C1—N1—C4	130.77 (10)
C9—C8—C7	120.25 (12)	C1—N1—H1	110.7 (10)
C9—C8—H8	119.9	C4—N1—H1	118.5 (10)
C7—C8—H8	119.9	C2—N2—C10	120.77 (10)
C8—C9—C4	120.74 (11)

C3ⁱ—C1—C2—N2	−178.63 (10)	N2—C10—C11—C12	173.81 (11)
N1—C1—C2—N2	3.91 (14)	C10—C11—C12—C13	1.35 (18)
C3ⁱ—C1—C2—C3	0.14 (17)	C11—C12—C13—C14	−0.79 (19)
N1—C1—C2—C3	−177.31 (10)	C12—C13—C14—C15	−0.37 (19)
N2—C2—C3—C1ⁱ	178.50 (11)	C13—C14—C15—C10	0.95 (18)
C1—C2—C3—C1ⁱ	−0.14 (17)	C11—C10—C15—C14	−0.38 (17)
C9—C4—C5—C6	2.39 (17)	N2—C10—C15—C14	−175.02 (10)
N1—C4—C5—C6	179.27 (11)	C3ⁱ—C1—N1—C4	7.7 (2)
C4—C5—C6—C7	−1.51 (18)	C2—C1—N1—C4	−175.09 (11)
C5—C6—C7—C8	−0.8 (2)	C5—C4—N1—C1	26.84 (19)
C6—C7—C8—C9	2.2 (2)	C9—C4—N1—C1	−156.22 (12)
C7—C8—C9—C4	−1.33 (19)	C3—C2—N2—C10	6.60 (17)
C5—C4—C9—C8	−1.00 (18)	C1—C2—N2—C10	−174.73 (9)
N1—C4—C9—C8	−178.09 (11)	C15—C10—N2—C2	−119.41 (12)
C15—C10—C11—C12	−0.76 (17)	C11—C10—N2—C2	66.04 (14)

4 in total

1. Highly efficient synthesis and solid-state characterization of 1,2,4,5-tetrakis(alkyl- and arylamino)benzenes and cyclization to their respective benzobis(imidazolium) salts.

Authors: Dimitri M Khramov; Andrew J Boydston; Christopher W Bielawski
Journal: Org Lett Date: 2006-04-27 Impact factor: 6.005