N,N,N',N'-Tetra­phenyl-1,1'-biphenyl-4,4'-diamine

The mol­ecule of the title compound, C₃₆H₂₈N₂, adopts a propeller-like shape and possesses crystallographically imposed twofold rotation symmetry. The N atom has an almost ideal trigonal geometry, indicating that the lone electron pair is involved in conjugation with the system of aromatic rings.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.012 Å
• Disorder in main residue
• R factor = 0.057
• wR factor = 0.158
• Data-to-parameter ratio = 7.5

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT201_ALERT_2_B Isotropic non-H Atoms in Main Residue(s) .......          3
PLAT340_ALERT_3_B Low Bond Precision on C-C bonds (x 1000) Ang ...         11

Alert level C
PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax .LT. 18) .....       7.50
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for       C10'
PLAT301_ALERT_3_C Main Residue  Disorder .........................      14.00 Perc.
PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond  C7     -   C8     ...       1.39 Ang.
PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond  C7     -   C12    ...       1.38 Ang.

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           25.00
           From the CIF: _reflns_number_total               1283
           Count of symmetry unique reflns         1283
           Completeness (_total/calc)            100.00%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: XSCANS (Bruker, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL.

N,N,N',N'-Tetraphenyl-1,1'-biphenyl-4,4'-diamine

Crystal data

C36H28N2	F(000) = 2064
Mr = 488.60	Dx = 1.191 Mg m^−3
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 35 reflections
a = 16.389 (2) Å	θ = 5.0–12.4°
b = 34.178 (4) Å	µ = 0.07 mm^−1
c = 9.729 (2) Å	T = 293 K
V = 5449.6 (15) Å^3	Plate, colourless
Z = 8	0.40 × 0.37 × 0.04 mm

Data collection

Bruker P4 diffractometer	684 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.022
Graphite monochromator	θmax = 25.0°, θmin = 2.4°
ω scans	h = −19→1
Absorption correction: ψ scan (XSCANS; Bruker, 1996)	k = −40→1
Tmin = 0.967, Tmax = 0.996	l = −11→1
1614 measured reflections	3 standard reflections every 97 reflections
1283 independent reflections	intensity decay: 0.3%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.057	H-atom parameters constrained
wR(F^2) = 0.158	w = 1/[σ^2(Fo^2) + (0.0691P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
1283 reflections	Δρmax = 0.24 e Å^−3
171 parameters	Δρmin = −0.16 e Å^−3
10 restraints	Extinction correction: SHELXTL (Bruker, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0014 (3)

Special details

Experimental. ¹H NMR (CDCl₃): 7.47 (d 4H), 7.28 (m 8H), 7.14 (m 12H), 7.04 (t 4H). ES–MS: m/z = 488.5 (M⁺). ¹H NMR spectra were measured with a Bruker Avance 600 MHz NMR spectrometer with tetramethylsilane as internal standard. The electrospray mass spectra (ES–MS) was recorded on an ABI 4000 mass spectrograph.

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. Successful refinement of the Flack parameter was not possible because the anomalous scattering was not observable. Friedel opposites were therefore merged before refinement. The atoms of the disordered group were refined with restrained bond distance to the reasonable values. Occupancy of both positions of disordered group was refined and converged to the values of 0.57 (3) and 0.43 (3) respectively. All H atoms placed in geometrically calculated positions and refined using a riding model with C—H = 0.93%A, their isotropic displacement parameters were set to 1.2 times the equivalent displacement parameter of their parent atoms.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.3929 (4)	0.15762 (17)	0.9364 (14)	0.0589 (16)
C2	0.3283 (4)	0.18197 (17)	0.9065 (14)	0.0726 (19)
H2	0.3175	0.1889	0.8159	0.087*
C3	0.2800 (4)	0.19601 (18)	1.0107 (15)	0.086 (2)
H3	0.2369	0.2128	0.9905	0.104*
C4	0.2951 (5)	0.1853 (2)	1.1455 (15)	0.093 (3)
H4	0.2611	0.1941	1.2156	0.112*
C5	0.3605 (5)	0.1618 (2)	1.1750 (14)	0.092 (2)
H5	0.3719	0.1552	1.2658	0.110*
C6	0.4091 (4)	0.14779 (18)	1.0716 (13)	0.0698 (18)
H6	0.4531	0.1316	1.0924	0.084*
C13	0.4604 (3)	0.10214 (14)	0.8229 (13)	0.0537 (15)
C14	0.3995 (4)	0.07583 (16)	0.8552 (14)	0.073 (2)
H14	0.3477	0.0849	0.8782	0.087*
C15	0.4149 (3)	0.03622 (15)	0.8534 (13)	0.0651 (19)
H15	0.3732	0.0190	0.8766	0.078*
C16	0.4919 (3)	0.02113 (14)	0.8174 (13)	0.0533 (14)
C17	0.5510 (4)	0.04814 (15)	0.7829 (13)	0.0558 (16)
H17	0.6022	0.0394	0.7554	0.067*
C18	0.5359 (3)	0.08803 (15)	0.7882 (13)	0.0568 (16)
H18	0.5776	0.1055	0.7679	0.068*
N1	0.4442 (3)	0.14303 (12)	0.8302 (12)	0.0634 (14)
C7	0.4838 (3)	0.16951 (14)	0.7413 (13)	0.0614 (18)
C8	0.5099 (4)	0.20580 (14)	0.7885 (11)	0.084 (2)
H8	0.5075	0.2136	0.8800	0.101*
C12	0.4971 (4)	0.16093 (19)	0.6044 (12)	0.074 (2)
H12	0.4806	0.1359	0.5796	0.088*
C9	0.5401 (9)	0.2291 (4)	0.6830 (7)	0.078 (5)*	0.57 (3)
H9	0.5525	0.2549	0.7061	0.094*	0.57 (3)
C10	0.5539 (10)	0.2186 (4)	0.5470 (9)	0.087 (5)*	0.57 (3)
H10	0.5797	0.2362	0.4885	0.104*	0.57 (3)
C11	0.5301 (9)	0.1823 (4)	0.4963 (9)	0.079 (5)*	0.57 (3)
H11	0.5353	0.1738	0.4059	0.095*	0.57 (3)
C9'	0.5586 (10)	0.2356 (3)	0.7365 (10)	0.074 (6)*	0.43 (3)
H9'	0.5811	0.2567	0.7837	0.089*	0.43 (3)
C10'	0.5658 (8)	0.2268 (4)	0.5976 (10)	0.047 (5)*	0.43 (3)
H10'	0.5882	0.2454	0.5389	0.056*	0.43 (3)
C11'	0.5408 (9)	0.1911 (3)	0.5431 (14)	0.062 (5)*	0.43 (3)
H11'	0.5556	0.1868	0.4520	0.074*	0.43 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.067 (4)	0.049 (3)	0.061 (4)	0.002 (3)	0.015 (4)	−0.003 (3)
C2	0.082 (4)	0.057 (4)	0.078 (5)	0.014 (3)	0.002 (4)	−0.008 (4)
C3	0.086 (5)	0.056 (4)	0.118 (7)	0.015 (4)	0.018 (5)	−0.022 (5)
C4	0.115 (7)	0.079 (5)	0.086 (6)	−0.004 (5)	0.036 (5)	−0.026 (5)
C5	0.121 (6)	0.087 (5)	0.066 (5)	−0.012 (5)	0.020 (5)	−0.009 (5)
C6	0.074 (4)	0.062 (4)	0.073 (5)	0.003 (3)	0.010 (4)	−0.003 (4)
C13	0.067 (4)	0.036 (3)	0.058 (4)	0.003 (3)	0.002 (4)	0.005 (3)
C14	0.060 (4)	0.046 (3)	0.113 (6)	0.003 (3)	0.013 (4)	−0.003 (4)
C15	0.062 (4)	0.042 (3)	0.092 (5)	−0.003 (3)	0.011 (4)	0.004 (3)
C16	0.054 (3)	0.042 (3)	0.064 (4)	−0.005 (3)	0.006 (4)	0.000 (3)
C17	0.061 (3)	0.043 (3)	0.063 (4)	0.009 (3)	0.008 (3)	0.004 (3)
C18	0.059 (3)	0.045 (3)	0.066 (4)	−0.002 (3)	0.017 (3)	0.009 (3)
N1	0.081 (3)	0.039 (2)	0.070 (3)	0.007 (2)	0.027 (3)	−0.002 (3)
C7	0.056 (4)	0.054 (4)	0.075 (5)	0.012 (3)	0.011 (4)	0.017 (4)
C8	0.088 (5)	0.056 (4)	0.107 (6)	−0.009 (4)	0.008 (5)	−0.003 (4)
C12	0.066 (4)	0.074 (4)	0.081 (5)	0.016 (4)	0.019 (4)	0.024 (4)

Geometric parameters (Å, º)

C1—C2	1.378 (8)	C17—H17	0.9300
C1—C6	1.384 (9)	C18—H18	0.9300
C1—N1	1.421 (7)	N1—C7	1.411 (7)
C2—C3	1.372 (9)	C7—C12	1.381 (17)
C2—H2	0.9300	C7—C8	1.390 (8)
C3—C4	1.384 (11)	C8—C9'	1.3897 (11)
C3—H3	0.9300	C8—C9	1.3907 (11)
C4—C5	1.372 (10)	C8—H8	0.9300
C4—H4	0.9300	C12—C11	1.3899 (11)
C5—C6	1.369 (9)	C12—C11'	1.3906 (11)
C5—H5	0.9300	C12—H12	0.9300
C6—H6	0.9300	C9—C10	1.3903 (11)
C13—C18	1.370 (7)	C9—H9	0.9300
C13—C14	1.379 (7)	C10—C11	1.3898 (11)
C13—N1	1.424 (6)	C10—H10	0.9300
C14—C15	1.377 (7)	C11—H11	0.9300
C14—H14	0.9300	C9'—C10'	1.3898 (11)
C15—C16	1.407 (7)	C9'—H9'	0.9300
C15—H15	0.9300	C10'—C11'	1.3902 (11)
C16—C17	1.380 (7)	C10'—H10'	0.9300
C16—C16^i	1.469 (9)	C11'—H11'	0.9300
C17—C18	1.387 (7)
C2—C1—C6	119.6 (6)	C17—C18—H18	119.4
C2—C1—N1	120.9 (6)	C7—N1—C1	119.5 (5)
C6—C1—N1	119.5 (6)	C7—N1—C13	120.9 (5)
C3—C2—C1	120.0 (7)	C1—N1—C13	119.4 (5)
C3—C2—H2	120.0	C12—C7—C8	117.3 (6)
C1—C2—H2	120.0	C12—C7—N1	121.8 (5)
C2—C3—C4	120.3 (7)	C8—C7—N1	120.8 (6)
C2—C3—H3	119.9	C9'—C8—C7	135.3 (9)
C4—C3—H3	119.9	C7—C8—C9	112.2 (10)
C5—C4—C3	119.6 (8)	C9'—C8—H8	99.4
C5—C4—H4	120.2	C7—C8—H8	123.9
C3—C4—H4	120.2	C9—C8—H8	123.9
C6—C5—C4	120.4 (8)	C7—C12—C11	132.8 (9)
C6—C5—H5	119.8	C7—C12—C11'	109.7 (10)
C4—C5—H5	119.8	C7—C12—H12	113.6
C5—C6—C1	120.2 (7)	C11—C12—H12	113.6
C5—C6—H6	119.9	C11'—C12—H12	136.2
C1—C6—H6	119.9	C10—C9—C8	127.7 (13)
C18—C13—C14	118.7 (5)	C10—C9—H9	116.2
C18—C13—N1	121.7 (5)	C8—C9—H9	116.2
C14—C13—N1	119.6 (5)	C11—C10—C9	121.6 (12)
C15—C14—C13	120.3 (5)	C11—C10—H10	119.2
C15—C14—H14	119.8	C9—C10—H10	119.2
C13—C14—H14	119.8	C10—C11—C12	108.0 (10)
C14—C15—C16	121.9 (5)	C10—C11—H11	126.0
C14—C15—H15	119.1	C12—C11—H11	126.0
C16—C15—H15	119.1	C8—C9'—C10'	104.0 (11)
C17—C16—C15	116.4 (5)	C8—C9'—H9'	128.0
C17—C16—C16^i	122.0 (6)	C10'—C9'—H9'	128.0
C15—C16—C16^i	121.5 (6)	C9'—C10'—C11'	122.5 (12)
C16—C17—C18	121.5 (5)	C9'—C10'—H10'	118.7
C16—C17—H17	119.2	C11'—C10'—H10'	118.7
C18—C17—H17	119.2	C10'—C11'—C12	129.6 (13)
C13—C18—C17	121.1 (5)	C10'—C11'—H11'	115.2
C13—C18—H18	119.4	C12—C11'—H11'	115.2
C6—C1—C2—C3	−0.6 (9)	C1—N1—C7—C12	−145.3 (6)
N1—C1—C2—C3	−179.5 (6)	C13—N1—C7—C12	40.3 (8)
C1—C2—C3—C4	−1.0 (10)	C1—N1—C7—C8	33.5 (9)
C2—C3—C4—C5	2.4 (11)	C13—N1—C7—C8	−140.9 (6)
C3—C4—C5—C6	−2.1 (12)	C12—C7—C8—C9'	−11.3 (16)
C4—C5—C6—C1	0.5 (10)	N1—C7—C8—C9'	169.8 (13)
C2—C1—C6—C5	0.9 (9)	C12—C7—C8—C9	4.9 (10)
N1—C1—C6—C5	179.7 (6)	N1—C7—C8—C9	−173.9 (8)
C18—C13—C14—C15	0.5 (10)	C8—C7—C12—C11	−2.7 (13)
N1—C13—C14—C15	−177.7 (6)	N1—C7—C12—C11	176.2 (10)
C13—C14—C15—C16	−0.8 (11)	C8—C7—C12—C11'	4.2 (10)
C14—C15—C16—C17	−0.5 (10)	N1—C7—C12—C11'	−176.9 (9)
C15—C16—C17—C18	2.2 (9)	C9'—C8—C9—C10	147 (3)
C14—C13—C18—C17	1.1 (10)	C7—C8—C9—C10	−7.4 (17)
N1—C13—C18—C17	179.3 (12)	C8—C9—C10—C11	7 (2)
C16—C17—C18—C13	−2.6 (10)	C9—C10—C11—C12	−2.9 (17)
C2—C1—N1—C7	56.2 (8)	C7—C12—C11—C10	1.4 (16)
C6—C1—N1—C7	−122.6 (6)	C11'—C12—C11—C10	−15 (2)
C2—C1—N1—C13	−129.3 (6)	C7—C8—C9'—C10'	14 (2)
C6—C1—N1—C13	51.9 (8)	C9—C8—C9'—C10'	−21.4 (15)
C18—C13—N1—C7	33.1 (9)	C8—C9'—C10'—C11'	−11 (2)
C14—C13—N1—C7	−148.7 (6)	C9'—C10'—C11'—C12	9 (2)
C18—C13—N1—C1	−141.3 (6)	C7—C12—C11'—C10'	−4.2 (19)
C14—C13—N1—C1	36.9 (9)	C11—C12—C11'—C10'	163 (4)

Symmetry code: (i) −x+1, −y, z.