9-p-Toluidinoanthracene

Condensation of anthrone with p-toluidine affords 9-p-toluidinoanthracene, C₂₁H₁₇N. The aromatic ring systems enclose a dihedral angle of 79.97 (3)°. One short intermolecular contact from the amino H atom is found to an aromatic C atom can be found.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.049
• wR factor = 0.140
• Data-to-parameter ratio = 21.8

checkCIF results

No syntax errors found

Structure: I
------------

ADDSYM reports no extra symmetry


 Alert Level C:



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           30.76
         From the CIF: _reflns_number_total               4454
         TEST2: Reflns within _diffrn_reflns_theta_max
         Count of symmetry unique reflns         4712
         Completeness (_total/calc)             94.52%
          Alert C: < 95% complete

PLAT_420  Alert C D-H Without Acceptor       N(1)   -   H(1)              ?


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 2 Alert Level C = Please check

---

S1. Comment

Anthracene derivatives have been widely studied because of their important biological and photophysical properties (Seonkyung et al., 1997; Lahlou et al., 1998). In our reseach, we concentrated on alkyl and aryl anthracene derivatives. Recently, we described the preparation of diethyl 2-anthracen-9-ylmethylenemalonate (Elazami et al., 1999). In this paper we report on the synthesis and crystal structure of a new arylanthracene, incorporating nitrogen in the chain, N-(9-anthracene) p-toluidine, which was prepared by the condensation reaction of anthrone and p-toluidine. The title compound has a high stability at room temperature [confirmed by mass spectroscopy 283 (M+, 100%)]. Since NMR and mass spectroscopy did not provide sufficient information about the conformation of the reaction product, we have carried out the X-ray structure analysis.

Bond lengths and angles are in the usual ranges. The N atom deviates only slightly from the plane of the anthracene ring system [0.036 (2) Å] and of the plane of the phenyl ring [0.075 (2) Å]. Both aromatic rings enclose a dihedral angle of 79.97 (3)°. In absence of a classical hydrogen bond acceptor, only one intermolecular N—H···C contact less than 3 Å can be found.

S2. Experimental

In a 100 ml three-necked flask fitted with a reflux condenser were placed anthrone (5 g, 25 mmol), p-toluidine (8 g, 075 mmol), which had previously been dissolved in benzene (40 ml), and dichloromethane (50 ml). The mixture was stirred at room temperature. Then aluminium trichloride (1 ml), dissolved in ethyl ether (20 ml), was added. At the end of the addition, the mixture was stirred and refluxed for 24 h. The solution was extracted with dichloromethane and dried with the anhydrous sodium sulfate. The solvant was removed on a rotary evaporator and the residue was purified by flash column chromatography over silica (hexane). Recrystallization from ethyl ether/hexane (volume ratio: 3/1) led to flat yellow crystals.

S3. Refinement

All H atoms were located by difference Fourier synthesis and refined with fixed individual displacement parameters [U(H) = 1.2 U_eq(C) or U(H) = 1.5 U_eq(C_methyl)] using a riding model with aromatic C—H = 0.95 Å or methyl C—H = 0.98 Å, respectively. The H atom bonded to N was refined isotropically. The methyl group was allowed to rotate about its local threefold axis.

Computing details

Data collection: SMART (Siemens, 1995); cell refinement: SMART (Siemens, 1995); data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Siemens, 1991).

Figures

Fig. 1. A perspective view of the title compound with the atom-numbering scheme. Displacement ellipsoids are at the 50% probability level.

9-p-Toluidinoanthracene

Crystal data

C21H17N	F(000) = 600
Mr = 283.36	Dx = 1.248 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.367 (1) Å	Cell parameters from 6696 reflections
b = 6.343 (1) Å	θ = 2–25°
c = 23.361 (2) Å	µ = 0.07 mm^−1
β = 100.98 (1)°	T = 173 K
V = 1508.0 (3) Å^3	Plate, yellow
Z = 4	0.60 × 0.50 × 0.20 mm

Data collection

Siemens CCD three-circle diffractometer	4454 independent reflections
Radiation source: fine-focus sealed tube	2900 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.064
ω scans	θmax = 30.8°, θmin = 1.8°
Absorption correction: empirical SADABS (Sheldrick, 1996)	h = −14→14
Tmin = 0.958, Tmax = 0.986	k = −9→9
39404 measured reflections	l = −32→32

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.140	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0706P)^2 + 0.162P] where P = (Fo^2 + 2Fc^2)/3
4454 reflections	(Δ/σ)max = 0.004
204 parameters	Δρmax = 0.22 e Å^−3
0 restraints	Δρmin = −0.28 e Å^−3

Special details

Experimental. ;

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	0.36462 (11)	0.56711 (18)	0.66343 (5)	0.0234 (2)
C2	0.24206 (11)	0.47210 (19)	0.64251 (5)	0.0242 (3)
C3	0.14423 (13)	0.5656 (2)	0.59847 (5)	0.0332 (3)
H3	0.1623	0.6954	0.5813	0.040*
C4	0.02497 (14)	0.4707 (3)	0.58067 (6)	0.0424 (4)
H4	−0.0390	0.5360	0.5516	0.051*
C5	−0.00425 (14)	0.2767 (3)	0.60504 (6)	0.0438 (4)
H5	−0.0879	0.2135	0.5925	0.053*
C6	0.08592 (13)	0.1803 (2)	0.64613 (6)	0.0361 (3)
H6	0.0655	0.0482	0.6614	0.043*
C7	0.21157 (12)	0.27413 (19)	0.66697 (5)	0.0264 (3)
C8	0.30366 (12)	0.18068 (19)	0.71102 (5)	0.0278 (3)
H8	0.2833	0.0497	0.7269	0.033*
C9	0.42485 (12)	0.27501 (19)	0.73224 (5)	0.0266 (3)
C10	0.51831 (13)	0.1829 (2)	0.77869 (6)	0.0367 (3)
H10	0.5003	0.0499	0.7941	0.044*
C11	0.63273 (14)	0.2845 (3)	0.80095 (6)	0.0450 (4)
H11	0.6930	0.2229	0.8322	0.054*
C12	0.66229 (13)	0.4804 (3)	0.77791 (6)	0.0425 (4)
H12	0.7425	0.5492	0.7939	0.051*
C13	0.57786 (12)	0.5726 (2)	0.73321 (6)	0.0325 (3)
H13	0.6000	0.7042	0.7183	0.039*
C14	0.45601 (11)	0.47346 (19)	0.70845 (5)	0.0246 (3)
N1	0.39332 (11)	0.76511 (16)	0.64016 (5)	0.0296 (3)
H1	0.3538 (17)	0.871 (3)	0.6510 (7)	0.051 (5)*
C21	0.49141 (11)	0.79528 (18)	0.60721 (5)	0.0229 (2)
C22	0.54433 (13)	0.62953 (19)	0.58029 (6)	0.0294 (3)
H22	0.5170	0.4891	0.5856	0.035*
C23	0.63702 (12)	0.6683 (2)	0.54569 (5)	0.0299 (3)
H23	0.6724	0.5527	0.5279	0.036*
C24	0.67948 (11)	0.87104 (19)	0.53641 (5)	0.0256 (3)
C241	0.77658 (13)	0.9119 (2)	0.49704 (6)	0.0363 (3)
H24A	0.8662	0.9012	0.5197	0.054*
H24B	0.7624	1.0536	0.4803	0.054*
H24C	0.7642	0.8074	0.4656	0.054*
C25	0.62643 (12)	1.03506 (19)	0.56408 (6)	0.0290 (3)
H25	0.6539	1.1754	0.5588	0.035*
C26	0.53484 (12)	0.99975 (18)	0.59908 (5)	0.0275 (3)
H26	0.5013	1.1151	0.6177	0.033*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0281 (6)	0.0192 (5)	0.0256 (6)	0.0006 (4)	0.0121 (5)	0.0009 (4)
C2	0.0268 (6)	0.0253 (6)	0.0224 (6)	0.0008 (5)	0.0096 (5)	−0.0011 (5)
C3	0.0356 (7)	0.0391 (7)	0.0260 (6)	0.0033 (6)	0.0085 (5)	0.0035 (6)
C4	0.0327 (7)	0.0658 (10)	0.0270 (7)	0.0031 (7)	0.0018 (5)	−0.0030 (7)
C5	0.0338 (7)	0.0622 (10)	0.0356 (8)	−0.0144 (7)	0.0076 (6)	−0.0157 (7)
C6	0.0389 (7)	0.0372 (7)	0.0357 (7)	−0.0140 (6)	0.0161 (6)	−0.0108 (6)
C7	0.0325 (6)	0.0252 (6)	0.0246 (6)	−0.0042 (5)	0.0135 (5)	−0.0047 (5)
C8	0.0388 (7)	0.0190 (5)	0.0304 (6)	−0.0004 (5)	0.0187 (5)	0.0017 (5)
C9	0.0314 (6)	0.0257 (6)	0.0262 (6)	0.0066 (5)	0.0142 (5)	0.0036 (5)
C10	0.0398 (7)	0.0414 (8)	0.0333 (7)	0.0160 (6)	0.0181 (6)	0.0123 (6)
C11	0.0316 (7)	0.0714 (11)	0.0330 (7)	0.0208 (7)	0.0087 (6)	0.0110 (7)
C12	0.0244 (6)	0.0680 (11)	0.0355 (7)	0.0014 (7)	0.0071 (5)	−0.0003 (7)
C13	0.0255 (6)	0.0408 (7)	0.0333 (7)	−0.0030 (5)	0.0111 (5)	−0.0009 (6)
C14	0.0244 (6)	0.0259 (6)	0.0258 (6)	0.0013 (5)	0.0104 (5)	−0.0004 (5)
N1	0.0354 (6)	0.0179 (5)	0.0407 (6)	0.0021 (4)	0.0200 (5)	0.0036 (4)
C21	0.0247 (6)	0.0208 (6)	0.0235 (5)	−0.0012 (4)	0.0056 (4)	0.0022 (4)
C22	0.0386 (7)	0.0184 (6)	0.0342 (7)	−0.0029 (5)	0.0141 (5)	0.0006 (5)
C23	0.0366 (7)	0.0243 (6)	0.0317 (6)	0.0017 (5)	0.0137 (5)	−0.0015 (5)
C24	0.0254 (6)	0.0278 (6)	0.0243 (6)	−0.0005 (5)	0.0060 (5)	0.0036 (5)
C241	0.0376 (7)	0.0364 (7)	0.0384 (7)	−0.0014 (6)	0.0162 (6)	0.0054 (6)
C25	0.0317 (6)	0.0204 (6)	0.0360 (7)	−0.0050 (5)	0.0096 (5)	0.0041 (5)
C26	0.0315 (6)	0.0194 (6)	0.0332 (7)	0.0004 (5)	0.0098 (5)	−0.0005 (5)

Geometric parameters (Å, º)

C1—C14	1.4060 (16)	C11—H11	0.9500
C1—C2	1.4071 (16)	C12—C13	1.3603 (19)
C1—N1	1.4224 (15)	C12—H12	0.9500
C2—C3	1.4287 (17)	C13—C14	1.4309 (17)
C2—C7	1.4394 (17)	C13—H13	0.9500
C3—C4	1.367 (2)	N1—C21	1.4003 (15)
C3—H3	0.9500	N1—H1	0.851 (18)
C4—C5	1.413 (2)	C21—C22	1.3904 (16)
C4—H4	0.9500	C21—C26	1.3977 (15)
C5—C6	1.352 (2)	C22—C23	1.3904 (17)
C5—H5	0.9500	C22—H22	0.9500
C6—C7	1.4306 (18)	C23—C24	1.3897 (17)
C6—H6	0.9500	C23—H23	0.9500
C7—C8	1.3955 (18)	C24—C25	1.3921 (17)
C8—C9	1.3946 (18)	C24—C241	1.5098 (17)
C8—H8	0.9500	C241—H24A	0.9800
C9—C10	1.4343 (18)	C241—H24B	0.9800
C9—C14	1.4373 (17)	C241—H24C	0.9800
C10—C11	1.363 (2)	C25—C26	1.3842 (17)
C10—H10	0.9500	C25—H25	0.9500
C11—C12	1.411 (2)	C26—H26	0.9500
C14—C1—C2	120.94 (11)	C11—C12—H12	119.4
C14—C1—N1	119.92 (11)	C12—C13—C14	120.72 (13)
C2—C1—N1	119.09 (11)	C12—C13—H13	119.6
C1—C2—C3	122.86 (11)	C14—C13—H13	119.6
C1—C2—C7	119.19 (11)	C1—C14—C13	122.27 (11)
C3—C2—C7	117.94 (11)	C1—C14—C9	119.35 (11)
C4—C3—C2	120.88 (13)	C13—C14—C9	118.34 (11)
C4—C3—H3	119.6	C21—N1—C1	123.88 (10)
C2—C3—H3	119.6	C21—N1—H1	119.7 (12)
C3—C4—C5	120.79 (14)	C1—N1—H1	116.0 (12)
C3—C4—H4	119.6	C22—C21—C26	118.36 (11)
C5—C4—H4	119.6	C22—C21—N1	122.39 (10)
C6—C5—C4	120.52 (13)	C26—C21—N1	119.21 (10)
C6—C5—H5	119.7	C23—C22—C21	120.35 (11)
C4—C5—H5	119.7	C23—C22—H22	119.8
C5—C6—C7	121.01 (13)	C21—C22—H22	119.8
C5—C6—H6	119.5	C24—C23—C22	121.91 (11)
C7—C6—H6	119.5	C24—C23—H23	119.0
C8—C7—C6	121.67 (12)	C22—C23—H23	119.0
C8—C7—C2	119.48 (11)	C23—C24—C25	117.03 (11)
C6—C7—C2	118.84 (12)	C23—C24—C241	121.44 (11)
C9—C8—C7	121.56 (11)	C25—C24—C241	121.52 (11)
C9—C8—H8	119.2	C24—C241—H24A	109.5
C7—C8—H8	119.2	C24—C241—H24B	109.5
C8—C9—C10	121.82 (12)	H24A—C241—H24B	109.5
C8—C9—C14	119.46 (11)	C24—C241—H24C	109.5
C10—C9—C14	118.68 (12)	H24A—C241—H24C	109.5
C11—C10—C9	120.64 (13)	H24B—C241—H24C	109.5
C11—C10—H10	119.7	C26—C25—C24	121.96 (11)
C9—C10—H10	119.7	C26—C25—H25	119.0
C10—C11—C12	120.48 (13)	C24—C25—H25	119.0
C10—C11—H11	119.8	C25—C26—C21	120.36 (11)
C12—C11—H11	119.8	C25—C26—H26	119.8
C13—C12—C11	121.10 (14)	C21—C26—H26	119.8
C13—C12—H12	119.4
C14—C1—C2—C3	177.49 (11)	C2—C1—C14—C13	−175.93 (11)
N1—C1—C2—C3	0.18 (17)	N1—C1—C14—C13	1.36 (17)
C14—C1—C2—C7	−1.23 (17)	C2—C1—C14—C9	1.69 (17)
N1—C1—C2—C7	−178.55 (10)	N1—C1—C14—C9	178.98 (10)
C1—C2—C3—C4	−178.03 (12)	C12—C13—C14—C1	178.02 (12)
C7—C2—C3—C4	0.71 (18)	C12—C13—C14—C9	0.38 (18)
C2—C3—C4—C5	−0.5 (2)	C8—C9—C14—C1	−1.16 (16)
C3—C4—C5—C6	−0.6 (2)	C10—C9—C14—C1	−179.14 (11)
C4—C5—C6—C7	1.5 (2)	C8—C9—C14—C13	176.56 (11)
C5—C6—C7—C8	177.39 (12)	C10—C9—C14—C13	−1.42 (16)
C5—C6—C7—C2	−1.33 (18)	C14—C1—N1—C21	68.34 (16)
C1—C2—C7—C8	0.24 (16)	C2—C1—N1—C21	−114.32 (13)
C3—C2—C7—C8	−178.55 (11)	C1—N1—C21—C22	18.72 (19)
C1—C2—C7—C6	178.98 (11)	C1—N1—C21—C26	−163.70 (12)
C3—C2—C7—C6	0.20 (16)	C26—C21—C22—C23	−0.72 (18)
C6—C7—C8—C9	−178.43 (11)	N1—C21—C22—C23	176.88 (12)
C2—C7—C8—C9	0.28 (17)	C21—C22—C23—C24	−0.4 (2)
C7—C8—C9—C10	178.09 (11)	C22—C23—C24—C25	0.91 (19)
C7—C8—C9—C14	0.18 (17)	C22—C23—C24—C241	−177.80 (12)
C8—C9—C10—C11	−176.11 (12)	C23—C24—C25—C26	−0.38 (18)
C14—C9—C10—C11	1.82 (18)	C241—C24—C25—C26	178.33 (12)
C9—C10—C11—C12	−1.1 (2)	C24—C25—C26—C21	−0.70 (19)
C10—C11—C12—C13	0.0 (2)	C22—C21—C26—C25	1.24 (18)
C11—C12—C13—C14	0.3 (2)	N1—C21—C26—C25	−176.44 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···C8^i	0.851 (18)	2.523 (18)	3.3375 (17)	160.4 (15)

Symmetry code: (i) x, y+1, z.