Di­phenyl­amine

Acta Crystallographica Section E

Structure Reports

Online

ISSN 1600-5368

Diphenylamine

Mark A. Rodrigueza_{* and}

Scott D. Bungeb

a_{PO Box 5800, MS 1411, Sandia National} Laboratories, Albuquerque, New Mexico 87185-1411, USA, andb_{PO Box 5800,} MS 1349, Sandia National Laboratories, Albuquerque, New Mexico 87185-1349, USA

Correspondence e-mail: [email protected]

Key indicators Single-crystal X-ray study

T= 168 K

Mean(C±C) = 0.005 AÊ

Rfactor = 0.049

wRfactor = 0.115

Data-to-parameter ratio = 13.2

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2003 International Union of Crystallography

In the title compound, C12H11N, two phenyl rings are bound to

a central N atom. These rings are rotated with respect to one another by an average dihedral angle of 43 (5)_{. There are}

eight unique molecules in the asymmetric unit and a total of 16 molecules in the unit cell. The compound displays an interesting packing structure, where phenyl rings display both layered packing to nearest neighbors as well as rotation of phenyl rings to pack perpendicular to one other.

Comment

Throughout the Periodic Table, the use of the diphenylamide ligand, NPh2ÿ, has played a central role in the synthesis and

characterization of metal and metalloid complexes with low coordination numbers (Depue & Collum, 1988; Hitchcocket al., 2002; Liet al., 2002). In an effort to purify HNPh2, (I), for

subsequent deprotonation, the recrystallization of commer-cially purchased diphenylamine was undertaken and the solid-state structural characterization of the secondary amine is presented here. Fig. 1 shows the appearance of a typical molecule of (I). This simple molecule displays a central N atom bound to two phenyl rings. The phenyl rings are tilted with respect to each other. There are eight HNPh2molecules

in the asymmetric unit and a total of 16 in the unit cell (the second set of eight are generated by theP1 symmetry). Each molecule in the asymmetric unit displays a different dihedral angle between the phenyl rings. Molecules, denoted by their N atom (N1±N8), show dihedral angles of 47, 40, 41, 47, 38, 48, 49 and 37_{for N1±N8, respectively. Dihedral angles were}

calcu-lated based on planes de®ned by each phenyl ring and the central N atom. The average dihedral angle is 43 (5)_{. The unit}

cell has angles approaching 90_{. Perhaps a more constant}

dihedral angle would generate a more ordered packing which could result in a higher symmetry cell such as a monoclinic or orthorhombic lattice.

The relatively simple HNPh2 molecule displays a rather

complex packing arrangement. Fig. 2 shows the packing arrangement in the unit cell, as viewed down theaaxis. Layers of phenyl rings can be seen running vertically in this ®gure (in theabplane). There are a total of eight phenyl-ring layers, of which four are unique and four are generated by symmetry. The unique phenyl layers are labeled 1±4 and the

that the phenyl rings in layers 2 and 3 are always rotated approximately 90 _{with respect to their nearest neighbors.}

Only layer 4 shows a planar packing in the direction of theb axis. If we rotate the cell to view along thebaxis, as shown in Fig. 3, we can see again the opposition of the phenyl rings in layers 2 and 3, but now layer 1 shows a planar stacking of phenyl rings. If we isolate the molecules that generate the third and fourth phenyl-ring layers (namely molecules N1±N4) and view these molecules down thecaxis, we can more easily see the relationship for the packing. Fig. 4 illustrates this view by plotting the molecules as viewed down the c axis from between phenyl-ring layers 4 and 4A. The phenyl H atoms have been omitted for clarity. In this plot, the front phenyl layer is layer 4 and the back layer is layer 3. We can see that in layer 4 the stacking is planar along theaaxis, while the phenyl

rings are rotated by approximately 90_{along thebaxis. Fig. 5}

shows a similar diagram for the ®rst and second phenyl layers. Phenyl H atoms have been omitted for clarity. In this case, the molecules are viewed down thecaxis from the end of the unit cell. Hence the top phenyl layer is layer 1 and the back layer is layer 2. The packing in this case is essentially the same as that observed in Fig. 4, with the distinction that the planar packing in layer 1 now runs along thebaxis. The unusual sequence of phenyl-ring packing leads to the longcaxis.

Bond lengths in the individual molecules are in agreement with literature values. The average NÐC bond length across all molecules is 1.400 (4) AÊ. The CÐC bonding of the phenyl rings appears to be in¯uenced by the coordinated N atom. The CÐC bonds associated with the ipso-C atom of the phenyl ring have an average bond length of 1.395 (4) AÊ, while the

Figure 2

Packing diagram for (I), as viewed down theaaxis of the cell. Numerical values denote phenyl-ring layers. Phenyl H atoms have been omitted for clarity.

Figure 1

Molecular structure of one molecule of the asymmetric unit of (I). Displacement ellipsoids are displayed at the 50% probability level.

Figure 3

Packing diagram for (I), as viewed down thebaxis of the cell. Numerical

Figure 4

Packing diagram showing phenyl-ring layers 3 (back) and 4 (front) (see text for details).

average bond length for all other CÐC bonds in the phenyl ring is only 1.382 (5) AÊ.

Crystal data C12H11N

Mr= 169.22

Triclinic,P1

a= 9.853 (3) AÊ

b= 9.882 (3) AÊ

c= 37.944 (11) AÊ

= 83.845 (6) = 88.531 (6) = 89.856 (5)

V= 3672.0 (19) AÊ3

Z= 16

Dx= 1.224 Mg mÿ3

MoKradiation Cell parameters from 250

re¯ections

= 2.1±25.1 = 0.07 mmÿ1

T= 168 (2) K Block, colorless 0.200.170.07 mm Data collection

Bruker SMART CCD area-detector diffractometer

'and!scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1999)

Tmin= 0.980,Tmax= 0.990

23 981 measured re¯ections

12 700 independent re¯ections 7298 re¯ections withI> 2(I)

Rint= 0.036

max= 25.1

h=ÿ11!11

k=ÿ11!11

l=ÿ45!44 Re®nement

Re®nement onF2

R[F2_{> 2(F}2_{)] = 0.049}

wR(F2_{) = 0.115}

S= 0.97 12 700 re¯ections 961 parameters

H atoms treated by a mixture of independent and constrained re®nement

w= 1/[2_(F2

o) + (0.045P)2]

whereP= (F2

o+ 2F2c)/3

(/)max= 0.001 max= 0.16 e AÊÿ3 min=ÿ0.20 e AÊÿ3

H-atom positions were idealized, with H atoms riding on the atoms to which they are attached. These idealized H atoms had their

isotropic displacement parameters ®xed at 1.2Ueq(C). The H atoms

bonded to the N atoms (H101±H108) were the exception. These were located in difference Fourier maps; their atomic positional para-meters were re®ned and isotropic displacement parapara-meters were ®xed at 1.2Ueq(N). There are no intermolecular interactions (such as

hydrogen bonding) based on calculated bond distances. The data set is 97% complete at the maximum angle of 25.1_{. This range is} adequate for structure solution and typical for a triclinic structure.

Data collection:SMART(Bruker, 1998); cell re®nement:SMART; data reduction:SAINT-Plus(Bruker, 2001) andSHELXTL(Bruker, 1998); program(s) used to solve structure:SHELXTL; program(s) used to re®ne structure:SHELXTL; molecular graphics:SHELXTL; software used to prepare material for publication:SHELXTL.

Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy under contract No. DE-AC04-94AL85000. MAR thanks Timothy Boyle (Sandia) for his help in reviewing the manuscript.

References

Bruker (1998).SMART(Version 5.054) andSHELXTL(Version 5.1). Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2001). SAINT-Plus. Version 6.02. Bruker AXS Inc., Madison, Wisconsin, USA.

Depue, J. & Collum, D. (1988).J. Am. Chem. Soc.110, 5518±5524.

Hitchcock, P., Khvostov, A., Lappert, M. & Protchenko, A. (2002). J. Organomet. Chem.647, 198±204.

Li, H., Yao, Y., Shen, Q. & Weng, L. (2002).Organometallics,21, 2529±2532. Sheldrick, G. M. (1999).SADABS.Version 2.03. University of GoÈttingen,

supporting information

Acta Cryst. (2003). E59, o1123–o1125 [https://doi.org/10.1107/S1600536803014788]

Diphenylamine

Mark A. Rodriguez and Scott D. Bunge

(I)

Crystal data C12H11N

Mr = 169.22

Triclinic, P1 Hall symbol: -P 1 a = 9.853 (3) Å b = 9.882 (3) Å c = 37.944 (11) Å α = 83.845 (6)° β = 88.531 (6)° γ = 89.856 (5)° V = 3672.0 (19) Å3

Z = 16 F(000) = 1440 Dx = 1.224 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 250 reflections θ = 2.1–25.1°

µ = 0.07 mm−1

T = 168 K Block, colorless 0.20 × 0.17 × 0.07 mm

Data collection CCD area detector

diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

phi and ω scans

Absorption correction: empirical (using intensity measurements)

(SADABS; Sheldrick, 1999) Tmin = 0.980, Tmax = 0.990

23981 measured reflections 12700 independent reflections 7298 reflections with I > 2s(I) Rint = 0.036

θmax = 25.1°, θmin = 2.1°

h = −11→11 k = −11→11 l = −45→44

Refinement Refinement on F2

Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.049}

wR(F2_{) = 0.115}

S = 0.97

12700 reflections 961 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H atoms treated by a mixture of independent and constrained refinement

w = 1/[σ2_(F

o2) + (0.045P)2]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max = 0.001

Δρmax = 0.16 e Å−3

Special details

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 F}2_,

conventional R-factors R are based

on F, with F set to zero for negative F2_{. The threshold expression of}

F2 _{> σ(F}2_{) 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 (Å2₎

x y z Uiso*/Ueq

C89 0.9202 (2) 0.9169 (2) 0.20044 (6) 0.0372 (6) H89 0.9348 0.9954 0.2123 0.045* C90 0.8924 (2) 0.9308 (2) 0.16474 (6) 0.0322 (5) H90 0.8885 1.0193 0.1522 0.039* C91 0.7586 (2) 0.7658 (2) 0.08992 (6) 0.0330 (5) C92 0.7531 (2) 0.8125 (2) 0.05406 (6) 0.0443 (6) H92 0.8071 0.8881 0.0447 0.053* C93 0.6696 (3) 0.7500 (3) 0.03204 (7) 0.0539 (7) H93 0.6662 0.7835 0.0077 0.065* C94 0.5907 (2) 0.6387 (3) 0.04506 (7) 0.0513 (7) H94 0.5336 0.5956 0.0298 0.062* C95 0.5970 (2) 0.5925 (2) 0.08037 (7) 0.0436 (6) H95 0.5438 0.5159 0.0895 0.052* C96 0.6788 (2) 0.6544 (2) 0.10315 (6) 0.0369 (6) H96 0.6805 0.6212 0.1276 0.044*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

C70 0.0474 (15) 0.0447 (15) 0.0456 (17) −0.0007 (12) −0.0126 (13) 0.0068 (13) C71 0.0358 (13) 0.0349 (14) 0.0483 (17) 0.0015 (10) −0.0035 (12) 0.0023 (12) C72 0.0327 (12) 0.0321 (13) 0.0348 (14) −0.0029 (10) −0.0026 (10) −0.0065 (11) C73 0.0294 (12) 0.0216 (11) 0.0367 (14) −0.0028 (9) −0.0010 (10) −0.0019 (10) C74 0.0240 (12) 0.0283 (12) 0.0394 (15) −0.0011 (9) −0.0023 (10) −0.0025 (10) C75 0.0298 (12) 0.0338 (13) 0.0397 (15) −0.0020 (10) 0.0033 (11) −0.0046 (11) C76 0.0402 (14) 0.0362 (13) 0.0338 (14) −0.0062 (10) −0.0040 (11) −0.0019 (11) C77 0.0290 (13) 0.0389 (14) 0.0422 (16) −0.0026 (10) −0.0055 (11) −0.0017 (11) C78 0.0260 (12) 0.0310 (13) 0.0405 (15) −0.0007 (9) 0.0023 (10) −0.0015 (10) C79 0.0270 (12) 0.0304 (12) 0.0331 (14) 0.0037 (9) 0.0000 (10) −0.0043 (10) C80 0.0443 (14) 0.0425 (15) 0.0353 (15) −0.0021 (11) 0.0024 (11) −0.0004 (11) C81 0.0582 (17) 0.0517 (16) 0.0332 (15) 0.0048 (13) −0.0061 (13) −0.0064 (12) C82 0.0480 (15) 0.0458 (15) 0.0455 (17) 0.0014 (12) −0.0127 (13) −0.0160 (13) C83 0.0325 (13) 0.0337 (13) 0.0490 (17) −0.0021 (10) −0.0037 (11) −0.0067 (12) C84 0.0295 (12) 0.0322 (13) 0.0346 (14) 0.0015 (10) −0.0026 (10) 0.0001 (10) C85 0.0257 (11) 0.0312 (13) 0.0350 (14) 0.0003 (9) 0.0000 (10) −0.0023 (10) C86 0.0381 (13) 0.0275 (13) 0.0440 (16) 0.0009 (10) −0.0030 (11) −0.0033 (11) C87 0.0398 (14) 0.0342 (14) 0.0493 (17) −0.0032 (11) −0.0059 (12) 0.0103 (12) C88 0.0330 (13) 0.0527 (16) 0.0376 (15) −0.0044 (11) −0.0056 (11) 0.0026 (12) C89 0.0290 (12) 0.0402 (14) 0.0433 (16) 0.0003 (10) −0.0034 (11) −0.0086 (12) C90 0.0294 (12) 0.0256 (12) 0.0409 (15) 0.0022 (9) −0.0017 (10) −0.0003 (10) C91 0.0320 (12) 0.0318 (13) 0.0365 (15) 0.0022 (10) −0.0010 (10) −0.0100 (11) C92 0.0503 (15) 0.0442 (15) 0.0380 (16) −0.0010 (12) −0.0029 (12) −0.0019 (12) C93 0.0635 (18) 0.0588 (18) 0.0410 (17) 0.0092 (14) −0.0112 (14) −0.0102 (14) C94 0.0475 (16) 0.0543 (17) 0.0566 (19) 0.0023 (13) −0.0130 (14) −0.0243 (14) C95 0.0340 (14) 0.0385 (14) 0.0604 (19) −0.0007 (11) −0.0005 (13) −0.0152 (13) C96 0.0350 (13) 0.0366 (14) 0.0396 (15) −0.0009 (10) 0.0005 (11) −0.0070 (11)

Geometric parameters (Å, º)

C23—H23 0.9500 C78—H78 0.9500 C24—H24 0.9500 C79—C84 1.393 (3) C25—C30 1.386 (3) C79—C80 1.394 (3) C25—C26 1.401 (3) C80—C81 1.382 (3) C26—C27 1.384 (3) C80—H80 0.9500 C26—H26 0.9500 C81—C82 1.388 (3) C27—C28 1.376 (3) C81—H81 0.9500 C27—H27 0.9500 C82—C83 1.371 (3) C28—C29 1.387 (3) C82—H82 0.9500 C28—H28 0.9500 C83—C84 1.391 (3) C29—C30 1.382 (3) C83—H83 0.9500 C29—H29 0.9500 C84—H84 0.9500 C30—H30 0.9500 C85—C86 1.393 (3) C31—C32 1.391 (3) C85—C90 1.399 (3) C31—C36 1.400 (3) C86—C87 1.376 (3) C32—C33 1.380 (3) C86—H86 0.9500 C32—H32 0.9500 C87—C88 1.379 (3) C33—C34 1.382 (3) C87—H87 0.9500 C33—H33 0.9500 C88—C89 1.382 (3) C34—C35 1.386 (3) C88—H88 0.9500 C34—H34 0.9500 C89—C90 1.381 (3) C35—C36 1.371 (3) C89—H89 0.9500 C35—H35 0.9500 C90—H90 0.9500 C36—H36 0.9500 C91—C92 1.392 (3) C37—C42 1.393 (3) C91—C96 1.395 (3) C37—C38 1.396 (3) C92—C93 1.380 (3) C38—C39 1.388 (3) C92—H92 0.9500 C38—H38 0.9500 C93—C94 1.387 (3) C39—C40 1.379 (3) C93—H93 0.9500 C39—H39 0.9500 C94—C95 1.372 (3) C40—C41 1.389 (3) C94—H94 0.9500 C40—H40 0.9500 C95—C96 1.386 (3) C41—C42 1.380 (3) C95—H95 0.9500 C41—H41 0.9500 C96—H96 0.9500