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Crystallization of the hexane reaction mixture after treatment of LiGe(OCH2CH2NMe2)3 with Ph3CN3 gives rise to a new triclinic (space group P\overline{1}) polymorph of triphenyl­methyl­amine, C19H17N, (I), containing dimers formed by N—H...N hydrogen bonds, whereas the structure of the known ortho­rhom­bic (space group P212121) polymorph of this compound, (II), consists of isolated mol­ecules. While the dimers in (I) lie across crystallographic inversion centres, the mol­ecules are not truly related by them. The centrosymmetric structure is due to the statistical disordering of the amino H atoms participating in the N—H...N hydrogen-bonding inter­actions, and thus the inversion centre is superpositional. The conformations and geometric parameters of the mol­ecules in (I) and (II) are very similar. It was found that the polarity of the solvent does not affect the capability of triphenyl­methyl­amine to crystallize in the different polymorphic modifications. The ortho­rhom­bic polymorph, (II), is more thermo­dynamically stable under normal conditions than the triclinic polymorph, (I). The experimental data indicate the absence of a phase transition in the temperature inter­val 120–293 K. The densities of (I) (1.235 Mg m−3) and (II) (1.231 Mg m−3) at 120 K are practically equal. It would seem that either the kinetic factors or the effects of the other products of the reaction facilitating the hydrogen-bonded dimerization of triphenyl­methyl­amine mol­ecules are the determining factor for the isolation of the triclinic polymorph (I) of triphenyl­methyl­amine.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108042911/gz3156sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108042911/gz3156Isup2.hkl
Contains datablock I

CCDC reference: 724197

Comment top

The design and preparation of materials with particular properties is one of the principal goals of chemists, physicists and structural biologists. Achieving that goal depends critically on understanding the relationship between the structure of a material and the properties in question. Polymorphic systems are a potential source of detailed information on structure–property relationships in organic solids, since the only variable among polymorphic forms is that of structure, and any variation in properties must therefore be due to structural differences. Moreover, the conditions and techniques required to obtain a particular polymorph, combined with knowledge of the crystal structures, can also provide information on the relative stability of the different structures (Bernstein, 2002).

On the other hand, the hydrogen bond is a subject that has attracted intense attention due to its importance in a vast number of chemical, biological and materials systems (Steiner, 2002). It has been widely used as a tool for the crystal engineering of organic and organometallic solids (Desiraju & Steiner, 1999; Braga & Grepioni, 2000; Nishio, 2004; Desiraju, 2005).

As a rule, the formation of hydrogen bonds of different types gives rise to a decrease in the total energy of a system and serves as its stabilizing factor. Taking this into consideration, it seemed surprising that triphenylmethylamine, possessing two active H atoms and a hydrogen-bond acceptor, forms only one polymorphic modification without hydrogen bonds (Glidewell & Ferguson, 1994; Clegg & Elsegood, 2005). Therefore, one could expect the existence of another polymorphic modification of this compound, which should contain N—H···N hydrogen bonds. A new triclinic polymorph, (I), of triphenylmethylamine was serendipitously obtained by crystallization of a hexane reaction mixture after treatment of LiGe(OCH2CH2NMe2)3 with Ph3CN3 and we report its structure here.

Polymorph (I) crystallizes in triclinic space group P1, rather than in the previously known orthorhombic modification of this compound (space group P212121), (II). The main difference between the two polymorphs is the formation of dimers via N—H···N hydrogen bonds in (I) (Fig. 1, Table 1), whereas (II) consists of isolated molecules. Despite the fact that the dimers lie across crystallographic inversion centres, the molecules are not really connected by them. The centrosymmetric structure is due to the statistical disordering of the amino H atoms participating in the N—H···N hydrogen bonds, and thus the inversion centre is superpositional.

The conformation of the molecules in (I) is such that there is an almost perfect staggering of the N—H and C—Ph bonds. A similar conformation is also characteristic of the molecules in polymorph (II) (Fig. 2). Nevertheless, the mutual disposition of the phenyl rings in the molecules of the two polymorphs is slightly different. In the orthorhombic structure, (II), the phenyl rings have a propeller-like arrangement, with dihedral N—C—C—C angles of -12.0 (1), -47.2 (2) and -60.3 (2)°, while in the triclinic structure, (I), the same dihedral N—C—C—C angles are -35.2 (2), -39.2 (1) and -53.2 (1)° (Fig. 2).

The aromatic C—C bond lengths in the phenyl rings and the C—Ph bond lengths of the central C atom of (I) fall in the narrow ranges of 1.377 (2)–1.400 (2) and 1.537 (2)–1.541 (2) Å, respectively, and are practically equal to the corresponding values in (II) [1.357 (5)–1.398 (3) and 1.539 (3)–1.541 (3) Å, respectively].

The crystal packings of the molecules in (I) and (II) are topologically similar. They both consist of stacks along the a axis and these stacks form layers parallel to the ab plane (Fig. 3a and b). However, the arrangements of the molecules relative to each other in neighbouring stacks, and consequently within the layers, differ considerably. In (I), molecules in neighbouring layers are oriented with the amino groups facing each other, which favours the formation of the aforementioned N—H···N hydrogen bonds, while in (II), the amino groups of neighbouring stacks both within and between the layers are oriented away from each other (Fig. 3c and d).

Since the orthorhombic polymorph was obtained by recrystallization from a solution in the polar solvent dichloromethane, while the triclinic polymorph was isolated from a nonpolar hexane solution, we decided to elucidate the influence of solvent polarity on the formation of the different polymophic modifications of triphenylmethylamine. For this purpose, we recrystallized commercially available triphenylmethylamine from solutions in the polar solvents ethanol, diethyl ether and dichloromethane, and the non-polar solvents hexane, heptane and benzene. It was found that only the orthorhombic modification of triphenylmethylamine is formed from all these solutions at room temperature. Thus, the polarity of solvent does not affect the capability of triphenylmethylamine to crystallize in the different polymorphic modifications. Moreover, the orthorhombic polymorph, (II), is more thermodynamically stable under normal conditions than the triclinic polymorph, (I). It is interesting to note that even the presence of hydrogen bonding in polymorph (I) does not result in its greater stability under ambient conditions compared with polymorph (II).

The possibility of a phase transition from the orthorhombic to the triclinic modification upon cooling was studied by X-ray diffraction analysis in the temperature interval 120–293 K. Our experimental data show that a phase transition does not occur. The densities of the orthorhombic (1.231 Mg m-3) and triclinic (1.235 Mg m-3) modifications at 120 K are practically equal. This result implies that factors other than thermodynamics might be responsible for their formation (Burger & Ramberger, 1979). In the present case, it would seem that either the kinetic factors or the effects of the other products of the reaction facilitating the hydrogen-bonded dimerization of triphenylmethylamine molecules were critical for the isolation of the triclinic polymorph of triphenylmethylamine, (I).

Experimental top

Single crystals of the new triclinic polymorph of triphenylmethylamine suitable for X-ray diffraction analysis were grown from the hexane reaction mixture of (Ph3CNLi)4 and Ge(OCH2CH2NMe2)2 at room temperature in air [Please give quantities etc.]. Triphenylmethylamine is formed by smooth hydrolysis of (Ph3CNLi)4in the presence of moisture (see second scheme).

Refinement top

The amino H atoms were objectively located in the difference Fourier map and refined in the isotropic approximation with fixed positional and displacement parameters [Uiso(H) = 1.2Ueq(N)]. One of the two amino H atoms is disordered over two sites with equal occupancies. The remaining H atoms were placed in calculated positions and refined in a riding model (C—H = 0.95 Å) with fixed displacement parameters [Uiso(H) = 1.2Ueq(C)].

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus (Bruker, 1998); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The dimer of (I) formed by the intermolecular N—H···N hydrogen bond, with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and only the amino H atoms are shown. The two alternative dispositions of the disordered amino H atoms within the dimer are depicted by heavy dashed and open lines. Thin dashed lines indicate the hydrogen bonds.
[Figure 2] Fig. 2. A comparison of the conformations of the molecules of the two polymorphs. The molecules of (I) and (II) are drawn with solid and open lines, respectively.
[Figure 3] Fig. 3. (a) A packing diagram of (I) along the a axis, indicating the columns of the dimers. (b) A packing diagram of (II) along the a axis, indicating the stacks of the molecules. (c) and (d) Projections of the crystal packing of (I) and (II), respectively, on the C2/C8/C14 plane of the basic molecule, demonstrating the differences in the mutual orientations of neighbouring molecules. Dashed lines in (c) indicate hydrogen bonds [Please check added text]. H atoms (except for the amino H atoms) have been omitted for clarity.
Triphenylmethylamine top
Crystal data top
C19H17NZ = 2
Mr = 259.34F(000) = 276
Triclinic, P1Dx = 1.235 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.7255 (8) ÅCell parameters from 3710 reflections
b = 8.9355 (9) Åθ = 2.7–29.9°
c = 10.6564 (10) ŵ = 0.07 mm1
α = 68.642 (2)°T = 120 K
β = 81.070 (2)°Plate, light-yellow
γ = 64.314 (2)°0.24 × 0.21 × 0.08 mm
V = 697.32 (12) Å3
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer
3309 independent reflections
Radiation source: normal-focus sealed tube2636 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.017
ϕ and ω scansθmax = 28.0°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1998)
h = 1111
Tmin = 0.984, Tmax = 0.992k = 1111
6598 measured reflectionsl = 1414
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.051Hydrogen site location: difference Fourier map
wR(F2) = 0.146H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.09P)2 + 0.18P]
where P = (Fo2 + 2Fc2)/3
3309 reflections(Δ/σ)max < 0.001
181 parametersΔρmax = 0.32 e Å3
0 restraintsΔρmin = 0.19 e Å3
Crystal data top
C19H17Nγ = 64.314 (2)°
Mr = 259.34V = 697.32 (12) Å3
Triclinic, P1Z = 2
a = 8.7255 (8) ÅMo Kα radiation
b = 8.9355 (9) ŵ = 0.07 mm1
c = 10.6564 (10) ÅT = 120 K
α = 68.642 (2)°0.24 × 0.21 × 0.08 mm
β = 81.070 (2)°
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer
3309 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1998)
2636 reflections with I > 2σ(I)
Tmin = 0.984, Tmax = 0.992Rint = 0.017
6598 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0510 restraints
wR(F2) = 0.146H-atom parameters constrained
S = 1.00Δρmax = 0.32 e Å3
3309 reflectionsΔρmin = 0.19 e Å3
181 parameters
Special details top

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 (Å2) top
xyzUiso*/UeqOcc. (<1)
N10.19683 (14)0.86986 (14)0.02960 (11)0.0277 (3)
H10.25780.92610.02700.033*
H20.08250.94700.01900.033*0.50
H2'0.21500.77250.00640.033*0.50
C10.24505 (15)0.82049 (15)0.17151 (13)0.0219 (3)
C20.27333 (15)0.97142 (15)0.18679 (12)0.0213 (3)
C30.14380 (16)1.14127 (16)0.14446 (13)0.0252 (3)
H30.04331.16090.10520.030*
C40.16077 (19)1.28118 (17)0.15934 (14)0.0305 (3)
H40.07171.39580.13040.037*
C50.3075 (2)1.25478 (18)0.21634 (14)0.0321 (3)
H50.31881.35080.22650.039*
C60.43611 (18)1.08797 (18)0.25786 (14)0.0309 (3)
H60.53661.06900.29670.037*
C70.41951 (16)0.94683 (17)0.24309 (14)0.0263 (3)
H70.50920.83250.27180.032*
C80.09703 (15)0.79298 (15)0.26171 (13)0.0237 (3)
C90.01051 (17)0.71027 (17)0.23139 (16)0.0304 (3)
H90.04030.67650.15310.037*
C100.11876 (18)0.67676 (18)0.31461 (18)0.0369 (4)
H100.17640.62040.29280.044*
C110.16363 (18)0.72511 (19)0.42886 (17)0.0368 (4)
H110.25250.70290.48520.044*
C120.07844 (19)0.8061 (2)0.46071 (15)0.0350 (3)
H120.10830.83900.53940.042*
C130.05118 (17)0.83940 (17)0.37746 (14)0.0284 (3)
H130.10910.89480.40030.034*
C140.40673 (16)0.64732 (16)0.20921 (13)0.0233 (3)
C150.5325 (2)0.6111 (2)0.11387 (15)0.0402 (4)
H150.51880.69430.02540.048*
C160.6780 (2)0.4548 (2)0.14613 (16)0.0459 (4)
H160.76230.43210.07930.055*
C170.70181 (18)0.33187 (18)0.27400 (15)0.0329 (3)
H170.80120.22480.29530.039*
C180.57911 (17)0.36717 (17)0.37006 (15)0.0313 (3)
H180.59410.28420.45860.038*
C190.43303 (16)0.52386 (17)0.33814 (14)0.0277 (3)
H190.34990.54670.40570.033*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0282 (6)0.0247 (5)0.0288 (6)0.0058 (4)0.0077 (5)0.0105 (4)
C10.0215 (6)0.0187 (5)0.0254 (6)0.0064 (4)0.0051 (5)0.0074 (4)
C20.0217 (6)0.0205 (6)0.0231 (6)0.0096 (5)0.0024 (5)0.0085 (4)
C30.0237 (6)0.0228 (6)0.0269 (6)0.0079 (5)0.0010 (5)0.0085 (5)
C40.0374 (7)0.0216 (6)0.0289 (7)0.0091 (5)0.0005 (6)0.0084 (5)
C50.0481 (8)0.0274 (7)0.0286 (7)0.0215 (6)0.0009 (6)0.0107 (5)
C60.0345 (7)0.0335 (7)0.0318 (7)0.0195 (6)0.0024 (6)0.0107 (6)
C70.0241 (6)0.0251 (6)0.0301 (7)0.0095 (5)0.0009 (5)0.0099 (5)
C80.0203 (6)0.0178 (5)0.0295 (6)0.0058 (4)0.0057 (5)0.0044 (5)
C90.0243 (6)0.0231 (6)0.0455 (8)0.0081 (5)0.0065 (6)0.0125 (6)
C100.0248 (7)0.0274 (7)0.0590 (10)0.0123 (6)0.0070 (6)0.0102 (6)
C110.0266 (7)0.0313 (7)0.0461 (9)0.0142 (6)0.0008 (6)0.0033 (6)
C120.0342 (7)0.0351 (7)0.0328 (8)0.0160 (6)0.0014 (6)0.0063 (6)
C130.0278 (7)0.0272 (6)0.0311 (7)0.0135 (5)0.0029 (5)0.0065 (5)
C140.0244 (6)0.0191 (6)0.0279 (6)0.0070 (5)0.0054 (5)0.0096 (5)
C150.0417 (8)0.0320 (8)0.0260 (7)0.0035 (6)0.0020 (6)0.0092 (6)
C160.0412 (9)0.0406 (9)0.0338 (8)0.0066 (7)0.0005 (7)0.0174 (7)
C170.0284 (7)0.0239 (6)0.0419 (8)0.0017 (5)0.0091 (6)0.0135 (6)
C180.0270 (7)0.0239 (6)0.0360 (8)0.0086 (5)0.0071 (6)0.0016 (5)
C190.0229 (6)0.0254 (6)0.0312 (7)0.0094 (5)0.0014 (5)0.0056 (5)
Geometric parameters (Å, º) top
N1—C11.4863 (16)C9—C101.392 (2)
N1—H10.9010C9—H90.9500
N1—H20.9304C10—C111.382 (2)
N1—H2'0.9316C10—H100.9500
C1—C21.5385 (16)C11—C121.384 (2)
C1—C81.5396 (18)C11—H110.9500
C1—C141.5417 (16)C12—C131.394 (2)
C2—C71.3905 (17)C12—H120.9500
C2—C31.3989 (17)C13—H130.9500
C3—C41.3864 (18)C14—C151.388 (2)
C3—H30.9500C14—C191.3899 (18)
C4—C51.392 (2)C15—C161.389 (2)
C4—H40.9500C15—H150.9500
C5—C61.379 (2)C16—C171.381 (2)
C5—H50.9500C16—H160.9500
C6—C71.3951 (18)C17—C181.377 (2)
C6—H60.9500C17—H170.9500
C7—H70.9500C18—C191.3933 (18)
C8—C131.3889 (19)C18—H180.9500
C8—C91.3978 (17)C19—H190.9500
C1—N1—H1110.2C10—C9—C8120.75 (14)
C1—N1—H2107.8C10—C9—H9119.6
H1—N1—H2108.3C8—C9—H9119.6
C1—N1—H2'112.5C11—C10—C9120.32 (13)
H1—N1—H2'108.0C11—C10—H10119.8
H2—N1—H2'110.0C9—C10—H10119.8
N1—C1—C2108.86 (10)C10—C11—C12119.62 (13)
N1—C1—C8107.56 (10)C10—C11—H11120.2
C2—C1—C8110.08 (10)C12—C11—H11120.2
N1—C1—C14109.70 (10)C11—C12—C13120.05 (14)
C2—C1—C14111.20 (9)C11—C12—H12120.0
C8—C1—C14109.37 (10)C13—C12—H12120.0
C7—C2—C3118.42 (11)C8—C13—C12121.10 (12)
C7—C2—C1123.31 (11)C8—C13—H13119.4
C3—C2—C1118.25 (10)C12—C13—H13119.4
C4—C3—C2120.61 (12)C15—C14—C19117.81 (12)
C4—C3—H3119.7C15—C14—C1120.24 (11)
C2—C3—H3119.7C19—C14—C1121.95 (12)
C3—C4—C5120.43 (13)C14—C15—C16120.83 (14)
C3—C4—H4119.8C14—C15—H15119.6
C5—C4—H4119.8C16—C15—H15119.6
C6—C5—C4119.38 (12)C17—C16—C15120.90 (15)
C6—C5—H5120.3C17—C16—H16119.6
C4—C5—H5120.3C15—C16—H16119.6
C5—C6—C7120.36 (12)C18—C17—C16118.87 (13)
C5—C6—H6119.8C18—C17—H17120.6
C7—C6—H6119.8C16—C17—H17120.6
C2—C7—C6120.79 (12)C17—C18—C19120.41 (13)
C2—C7—H7119.6C17—C18—H18119.8
C6—C7—H7119.6C19—C18—H18119.8
C13—C8—C9118.15 (12)C14—C19—C18121.17 (13)
C13—C8—C1122.17 (11)C14—C19—H19119.4
C9—C8—C1119.59 (12)C18—C19—H19119.4
N1—C1—C2—C7128.22 (13)C1—C8—C9—C10177.14 (11)
C8—C1—C2—C7114.12 (13)C8—C9—C10—C110.0 (2)
C14—C1—C2—C77.25 (17)C9—C10—C11—C120.4 (2)
N1—C1—C2—C353.18 (15)C10—C11—C12—C130.4 (2)
C8—C1—C2—C364.49 (14)C9—C8—C13—C120.56 (19)
C14—C1—C2—C3174.14 (11)C1—C8—C13—C12177.14 (12)
C7—C2—C3—C40.45 (19)C11—C12—C13—C80.2 (2)
C1—C2—C3—C4178.23 (11)N1—C1—C14—C1534.98 (16)
C2—C3—C4—C50.2 (2)C2—C1—C14—C1585.49 (15)
C3—C4—C5—C60.1 (2)C8—C1—C14—C15152.73 (13)
C4—C5—C6—C70.1 (2)N1—C1—C14—C19145.66 (12)
C3—C2—C7—C60.4 (2)C2—C1—C14—C1993.88 (14)
C1—C2—C7—C6178.17 (12)C8—C1—C14—C1927.91 (15)
C5—C6—C7—C20.2 (2)C19—C14—C15—C161.3 (2)
N1—C1—C8—C13144.21 (11)C1—C14—C15—C16179.34 (15)
C2—C1—C8—C1325.74 (15)C14—C15—C16—C170.4 (3)
C14—C1—C8—C1396.71 (13)C15—C16—C17—C180.5 (3)
N1—C1—C8—C939.26 (14)C16—C17—C18—C190.4 (2)
C2—C1—C8—C9157.73 (11)C15—C14—C19—C181.3 (2)
C14—C1—C8—C979.82 (13)C1—C14—C19—C18179.31 (11)
C13—C8—C9—C100.47 (19)C17—C18—C19—C140.5 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H2···N1i0.932.283.2069 (19)173
Symmetry code: (i) x, y+2, z.

Experimental details

Crystal data
Chemical formulaC19H17N
Mr259.34
Crystal system, space groupTriclinic, P1
Temperature (K)120
a, b, c (Å)8.7255 (8), 8.9355 (9), 10.6564 (10)
α, β, γ (°)68.642 (2), 81.070 (2), 64.314 (2)
V3)697.32 (12)
Z2
Radiation typeMo Kα
µ (mm1)0.07
Crystal size (mm)0.24 × 0.21 × 0.08
Data collection
DiffractometerBruker SMART 1000 CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1998)
Tmin, Tmax0.984, 0.992
No. of measured, independent and
observed [I > 2σ(I)] reflections
6598, 3309, 2636
Rint0.017
(sin θ/λ)max1)0.661
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.051, 0.146, 1.00
No. of reflections3309
No. of parameters181
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.32, 0.19

Computer programs: SMART (Bruker, 1998), SAINT-Plus (Bruker, 1998), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H2···N1i0.932.283.2069 (19)173
Symmetry code: (i) x, y+2, z.
 

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