N,N′-Bis(9H-fluoren-9-yl­idene)benzene-1,4-diamine

Mol­ecules of the title compound, C₃₂H₂₀N₂, synthesized by the p-toluene­sulfonic acid-assisted Schiff base reaction between 9-fluorenone and p-phenyl­enediamine, are located on centers of inversion.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.038
• wR factor = 0.102
• Data-to-parameter ratio = 14.7

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low .......       0.90

Author Response: ... The best crystal was chosen for analysis.

Alert level B
REFLT03_ALERT_3_B  Reflection count < 90% complete (theta max?)
           From the CIF: _diffrn_reflns_theta_max           29.83
           From the CIF: _diffrn_reflns_theta_full          29.83
           From the CIF: _reflns_number_total               2844
           TEST2: Reflns within _diffrn_reflns_theta_max
           Count of symmetry unique reflns         3174
           Completeness (_total/calc)             89.60%

Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.98

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

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

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Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2005); cell refinement: CrysAlis RED (Oxford Diffraction, 2005); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

N,N'-bis(9H-fluoren-9-ylidene)benzene-1,4-diamine

Crystal data

C32H20N2	F(000) = 452
Mr = 432.50	Dx = 1.300 Mg m^−3
Monoclinic, P21/c	Melting point: 566 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.7107 Å
a = 5.1360 (3) Å	Cell parameters from 5041 reflections
b = 14.6772 (10) Å	θ = 3.9–29.8°
c = 15.0469 (9) Å	µ = 0.08 mm^−1
β = 103.154 (5)°	T = 298 K
V = 1104.51 (12) Å^3	Plate, orange
Z = 2	0.55 × 0.30 × 0.20 mm

Data collection

Sapphire3 diffractometer	2844 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2225 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.014
Detector resolution: 16.1790 pixels mm^-1	θmax = 29.8°, θmin = 3.9°
ω scans	h = −6→6
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2005)	k = −19→20
Tmin = 0.991, Tmax = 1.007	l = −20→19
8876 measured reflections

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.102	All H-atom parameters refined
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0548P)^2 + 0.0927P] where P = (Fo^2 + 2Fc^2)/3
2844 reflections	(Δ/σ)max = 0.010
194 parameters	Δρmax = 0.18 e Å^−3
0 restraints	Δρmin = −0.15 e Å^−3

Special details

Experimental. H atoms were found from difference maps.

R_f 0.48 (SiO₂, 90% hexanes/10% ethyl acetate/10% CH₂Cl₂); m.p. 566; IR (KBr) 3077, 3056, 1875, 1760, 1639, 1610, 1451, 842 cm^-1; ¹H NMR (400 MHz, CDCl₃) δ 7.947 (d, 2H, J = 7.3 Hz), 7.627 (d, 4H, J = 7.3 Hz), 7.487 (dt, 2H, J = 7.3 Hz, 0.9 Hz), 7.371 (tt, 4H, J = 7.9 Hz, 0.9 Hz), 7.100 (s, 4H), 7.235 (dq, 4H, J = 7.9 Hz, 0.9 Hz); ¹³C NMR (400 MHz, CDCl₃) δ 163.63, 148.16, 143.98, 142.00, 137.58, 132.01, 131.34, 128.58, 127.85, 127.41, 123.32, 120.39, 119.76, 119.73; UV/Vis (CH₂Cl₂; λmax, logε) 430 nm, 4817; ESI-MS obsd 432.9, calcd 433 [(M + H)⁺, M = C₃₂H₂₀N₂].

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
C1	0.2396 (2)	0.33475 (7)	0.35367 (6)	0.0341 (2)
C2	0.0787 (2)	0.37572 (7)	0.26715 (7)	0.0359 (2)
C3	−0.1301 (2)	0.43804 (8)	0.25083 (8)	0.0445 (3)
C4	−0.2466 (3)	0.46181 (9)	0.16080 (9)	0.0533 (3)
C5	−0.1562 (3)	0.42411 (9)	0.08869 (9)	0.0568 (3)
C6	0.0476 (3)	0.36003 (9)	0.10388 (8)	0.0500 (3)
C7	0.1635 (2)	0.33520 (7)	0.19319 (7)	0.0382 (2)
C8	0.3741 (2)	0.26766 (7)	0.22876 (7)	0.0370 (2)
C9	0.5265 (2)	0.21216 (8)	0.18554 (8)	0.0482 (3)
C10	0.7210 (3)	0.15740 (9)	0.23942 (9)	0.0526 (3)
C11	0.7612 (3)	0.15601 (8)	0.33381 (9)	0.0495 (3)
C12	0.6065 (2)	0.21070 (7)	0.37765 (8)	0.0424 (3)
C13	0.4147 (2)	0.26602 (7)	0.32418 (7)	0.0351 (2)
C14	0.1175 (2)	0.42526 (7)	0.46663 (6)	0.0353 (2)
C15	−0.0703 (2)	0.41180 (7)	0.51916 (7)	0.0388 (2)
C16	0.1890 (2)	0.51391 (7)	0.44911 (7)	0.0394 (2)
N1	0.25043 (19)	0.34960 (6)	0.43846 (6)	0.0397 (2)
H3	−0.202 (3)	0.4643 (9)	0.3011 (9)	0.053 (4)*
H4	−0.390 (3)	0.5047 (9)	0.1484 (10)	0.060 (4)*
H5	−0.250 (3)	0.4433 (9)	0.0246 (10)	0.065 (4)*
H6	0.117 (3)	0.3325 (9)	0.0522 (9)	0.059 (4)*
H9	0.496 (2)	0.2119 (9)	0.1184 (9)	0.054 (4)*
H10	0.837 (3)	0.1198 (10)	0.2101 (10)	0.066 (4)*
H11	0.901 (3)	0.1168 (10)	0.3703 (10)	0.065 (4)*
H12	0.636 (3)	0.2121 (9)	0.4467 (9)	0.053 (3)*
H15	−0.124 (2)	0.3478 (8)	0.5312 (8)	0.049 (3)*
H16	0.328 (2)	0.5238 (8)	0.4145 (8)	0.047 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0385 (5)	0.0320 (5)	0.0330 (5)	0.0005 (4)	0.0110 (4)	−0.0024 (4)
C2	0.0376 (5)	0.0348 (5)	0.0344 (5)	−0.0035 (4)	0.0066 (4)	−0.0021 (4)
C3	0.0427 (6)	0.0407 (6)	0.0476 (6)	0.0011 (4)	0.0049 (5)	−0.0028 (5)
C4	0.0497 (7)	0.0455 (6)	0.0565 (7)	0.0038 (5)	−0.0050 (5)	0.0024 (5)
C5	0.0643 (8)	0.0551 (7)	0.0416 (6)	−0.0040 (6)	−0.0071 (5)	0.0043 (5)
C6	0.0583 (7)	0.0559 (7)	0.0332 (5)	−0.0062 (6)	0.0051 (5)	−0.0021 (5)
C7	0.0409 (5)	0.0404 (5)	0.0328 (5)	−0.0068 (4)	0.0075 (4)	−0.0041 (4)
C8	0.0401 (5)	0.0384 (5)	0.0336 (5)	−0.0046 (4)	0.0107 (4)	−0.0072 (4)
C9	0.0544 (7)	0.0535 (7)	0.0401 (6)	−0.0023 (5)	0.0177 (5)	−0.0142 (5)
C10	0.0550 (7)	0.0503 (7)	0.0567 (7)	0.0069 (5)	0.0217 (6)	−0.0159 (6)
C11	0.0521 (7)	0.0415 (6)	0.0546 (7)	0.0113 (5)	0.0117 (5)	−0.0073 (5)
C12	0.0511 (6)	0.0375 (5)	0.0387 (5)	0.0062 (5)	0.0103 (5)	−0.0038 (4)
C13	0.0400 (5)	0.0326 (5)	0.0344 (5)	−0.0008 (4)	0.0118 (4)	−0.0052 (4)
C14	0.0429 (5)	0.0363 (5)	0.0274 (4)	0.0065 (4)	0.0097 (4)	−0.0016 (4)
C15	0.0492 (6)	0.0336 (5)	0.0360 (5)	0.0004 (4)	0.0148 (4)	0.0002 (4)
C16	0.0456 (6)	0.0417 (6)	0.0352 (5)	0.0032 (4)	0.0183 (4)	0.0012 (4)
N1	0.0510 (5)	0.0373 (4)	0.0333 (4)	0.0078 (4)	0.0145 (4)	−0.0018 (3)

Geometric parameters (Å, º)

C1—N1	1.2830 (12)	C9—C10	1.3902 (18)
C1—C13	1.4846 (13)	C9—H9	0.987 (13)
C1—C2	1.4999 (14)	C10—C11	1.3881 (18)
C2—C3	1.3882 (15)	C10—H10	0.985 (15)
C2—C7	1.4151 (14)	C11—C12	1.3962 (15)
C3—C4	1.3951 (17)	C11—H11	0.985 (16)
C3—H3	0.991 (13)	C12—C13	1.3844 (15)
C4—C5	1.389 (2)	C12—H12	1.015 (13)
C4—H4	0.954 (15)	C14—C16	1.3932 (14)
C5—C6	1.3869 (19)	C14—C15	1.3934 (14)
C5—H5	1.015 (15)	C14—N1	1.4179 (12)
C6—C7	1.3889 (15)	C15—C16^i	1.3860 (14)
C6—H6	1.010 (14)	C15—H15	1.007 (12)
C7—C8	1.4749 (15)	C16—C15^i	1.3859 (14)
C8—C9	1.3896 (15)	C16—H16	0.988 (12)
C8—C13	1.4034 (13)
N1—C1—C13	121.37 (9)	C10—C9—H9	121.4 (7)
N1—C1—C2	133.28 (9)	C8—C9—H9	120.4 (7)
C13—C1—C2	105.34 (8)	C9—C10—C11	121.66 (11)
C3—C2—C7	120.09 (10)	C9—C10—H10	119.3 (9)
C3—C2—C1	131.96 (10)	C11—C10—H10	119.0 (9)
C7—C2—C1	107.86 (9)	C10—C11—C12	120.46 (11)
C2—C3—C4	118.69 (11)	C10—C11—H11	119.9 (8)
C2—C3—H3	121.8 (8)	C12—C11—H11	119.6 (8)
C4—C3—H3	119.5 (8)	C13—C12—C11	117.96 (10)
C5—C4—C3	120.88 (12)	C13—C12—H12	120.2 (7)
C5—C4—H4	119.4 (9)	C11—C12—H12	121.8 (7)
C3—C4—H4	119.8 (9)	C12—C13—C8	121.67 (9)
C6—C5—C4	121.03 (11)	C12—C13—C1	128.61 (9)
C6—C5—H5	121.5 (8)	C8—C13—C1	109.58 (9)
C4—C5—H5	117.4 (8)	C16—C14—C15	119.07 (9)
C5—C6—C7	118.59 (12)	C16—C14—N1	120.63 (9)
C5—C6—H6	121.9 (8)	C15—C14—N1	120.07 (9)
C7—C6—H6	119.5 (8)	C16^i—C15—C14	119.95 (10)
C6—C7—C2	120.65 (11)	C16^i—C15—H15	120.7 (7)
C6—C7—C8	130.15 (10)	C14—C15—H15	119.3 (7)
C2—C7—C8	109.18 (9)	C15^i—C16—C14	120.95 (9)
C9—C8—C13	120.03 (10)	C15^i—C16—H16	119.6 (7)
C9—C8—C7	131.98 (10)	C14—C16—H16	119.4 (7)
C13—C8—C7	107.98 (9)	C1—N1—C14	121.03 (9)
C10—C9—C8	118.20 (11)
N1—C1—C2—C3	−6.8 (2)	C8—C9—C10—C11	1.23 (19)
C13—C1—C2—C3	174.54 (11)	C9—C10—C11—C12	−0.42 (19)
N1—C1—C2—C7	176.71 (11)	C10—C11—C12—C13	−0.28 (18)
C13—C1—C2—C7	−1.93 (11)	C11—C12—C13—C8	0.17 (17)
C7—C2—C3—C4	−2.19 (16)	C11—C12—C13—C1	−175.10 (10)
C1—C2—C3—C4	−178.30 (11)	C9—C8—C13—C12	0.65 (16)
C2—C3—C4—C5	−0.04 (18)	C7—C8—C13—C12	−178.22 (9)
C3—C4—C5—C6	1.7 (2)	C9—C8—C13—C1	176.73 (10)
C4—C5—C6—C7	−1.08 (19)	C7—C8—C13—C1	−2.14 (11)
C5—C6—C7—C2	−1.17 (17)	N1—C1—C13—C12	−0.59 (17)
C5—C6—C7—C8	177.72 (11)	C2—C1—C13—C12	178.25 (10)
C3—C2—C7—C6	2.83 (16)	N1—C1—C13—C8	−176.32 (10)
C1—C2—C7—C6	179.80 (10)	C2—C1—C13—C8	2.52 (11)
C3—C2—C7—C8	−176.26 (9)	C16—C14—C15—C16^i	1.89 (17)
C1—C2—C7—C8	0.70 (11)	N1—C14—C15—C16^i	176.40 (10)
C6—C7—C8—C9	3.2 (2)	C15—C14—C16—C15^i	−1.91 (17)
C2—C7—C8—C9	−177.80 (11)	N1—C14—C16—C15^i	−176.39 (10)
C6—C7—C8—C13	−178.09 (11)	C13—C1—N1—C14	169.16 (9)
C2—C7—C8—C13	0.89 (12)	C2—C1—N1—C14	−9.30 (18)
C13—C8—C9—C10	−1.32 (17)	C16—C14—N1—C1	−62.68 (14)
C7—C8—C9—C10	177.23 (11)	C15—C14—N1—C1	122.90 (11)

Symmetry code: (i) −x, −y+1, −z+1.