THE CRYSTAL AND MOLECULAR
STRUCTURE ANALYSIS OF C22 H22 N2 O4 AND
C18 H15 Au Cl P
by
Funda DUR
September, 2004
İZMİR
Abstract
Molecular and crystal structure of “N,N’-dibutyl-1,4,5,8-naphthalenediimide”,
C22H22N2O4, and “Tristriphenylphosphinechlorogold(1)”, C18H15AuClP, have been
determined by X-ray diffraction technique. Crystallographic data for C22H22N2O4 :
Triclinic, P-1, a = 5.3085(7) Å, b = 8.0011(11) Å, c = 11.1097(15) Å, Z = 2, R1 =
0.0409 (for 2625 reflections with I>2σ(I) and 172 parameters), wR2 = 0.0673, GOF =
0.918. The crystal structure was solved by Direct methods. The non-hydrogen atoms
refined anisotropically. The molecule exhibits inversion symmetry relative to the
inversion centre between C3 and C3i atoms. Due to the π-π ring interactions the
naphthalenediimide part is nearly planar and molecules are arrange in a row through
a axes in the lattice. Dihedral angle between the naphthalenediimide plane and butyl
plane is 74.96(0.08)˚. There are intermolecular hidrogen bonds which is C-H..O.
Crystallographic data for C18H15AuClP: Orthorhombic, P 21 21 21, a =10.200(2) Å, b
= 12.396(3) Å, c = 13.126(3) Å, Z = 4, R1 = 0.0308 (for 3940 reflections with I>2σ(I)
and 191 atomic parameters), wR2 = 0.0333, GOF = 1.139. The crystal structure was
solved by Patterson method. The non-hydrogen atoms refined anisotropically. P atom
is in a distorted tetrahedral environment with three carbons of the triphenylphosphine
and the Au atom occupying vertices. The Au atom exhibits a linear geometry so that
the angle of Cl1-Au1-P1 is 179.73(6)˚. The aromatic phenyl rings are almost
symmetrically disposed as seen in the sequence of dihedral angles of 78.6(4)˚,
85.0(4)˚, 80.7(4)˚ for the C1-C6, C7-C12 and C13-C18 rings, respectively.
Key Words: Crystal structure, naphthalenediimide, triphenylphosphine, single
crystal X-ray diffraction technique
Özet
“N,N’-dibütil-1,4,5,8-naftelendiimid”,
C22H22N2O4,
ve
Tristrifenilfosfinkloraltın(1)”, C18H15AuClP moleküllerinin moleküler ve kristal
yapısı tek kristal X-ışını kırınımı yöntemiyle çözülmüştür. C22H22N2O4 kristali için
kristalografik veriler: Triclinic, P-1, a = 5.3085(7) Å, b =
8.0011(11) Å, c =
11.1097(15) Å, Z = 2, R1 = 0.0409 (I > 2 σ(I) koşulunu sağlayan 2625 yansıma ve
172 atomik paremetre için), wR2 = 0.0673, GOF = 0.918. Kristal yapı Direk
yöntemlerle çözülmüştür. Hidrojen atomları hariç bütün atomlar anizotropik olarak
arıtılmıştır. Molekül inversiyon simetrisiyle C3 ve C3i atomları arasındaki inversiyon
merkezine göre tamamlanmıştır. Molekülün naftelendiimid kısmı halkalar arası π-π
etkileşmeleri sebebiyle düzlemsel olup moleküller birim hücrenin a ekseni boyunca
uzanan bir sıra oluşturmaktadır. Naftelendiimid karbon atomları düzlemi ile bütil
grubu karbon atomları düzlemi arasındaki dihedral açı 74.96(0.08)˚ dir. Molekül CH..O tipi moleküller arası hidrojen bağları içermektedir. C18H15AuClP molekülü için
kristalografik veriler: Orthorhombic, P 21 21 21, a =10.200(2) Å, b = 12.396(3) Å, c
= 13.126(3) Å, Z = 4, R1 = 0.0308 (I > 2 σ(I) şartını sağlayan 3940 yansıma ve 191
tane atomik parametre için), wR2 = 0.0333, GOF = 1.139. Kristal yapı Patterson
methoduyla çözülmüştür. Hidrojen atomları dışındaki tüm atomlar anizotropik olarak
arıtılmıştır. Moleküldeki P atomu, üç tane karbon ve altın atomunun köşelerini
oluşturduğu bozulmuş bir tetrahedral çevre içindedir. Cl1-Au1-P1 atomları
arasındaki açı 179.73(6)˚ olduğundan moleküldeki Au atomu lineer bir geometri
göstermektedir. C1-C6, C7-C12 ve C13-C18 halkaları için 78.6(4)˚, 85.0(4)˚,
80.7(4)˚ dihedral açı sıralamasında da görüleceği gibi aromatik fenil halkaları
simetrik bir şekilde düzenlenmiştir.
Anahtar sözcükler: Kristal yapı, naftelendiimid, trifenilfosfin, tek kristal X-ışını
kırınımı yöntemi
1. Introduction
In this research, the crystal structure of N,N’-dibutyl-1,4,5,8-naphthalenediimide,
C22 H22 N2 O4, and Tristriphenylphosphinechlorogold(1), C18 H15 Au Cl P, were
determined and investigated by X-ray diffraction technique.
1,4,5,8-naphthalene diimides (NDI’s) are compounds of current interest of
biological and medical areas as well as in supramolecular chemistry and material
science. Although 1,4,5,8-naphthalene diimide derivatives are known for many
years, in recent times, these class of compounds gained importance due to their
electron acceptor properties (Barros et al.,1997, Wasielewski et al., 1995).
Figure 1.1 Chemical diagram of N,N’-dibutyl-1,4,5,8-naphthalenediimide, C22 H22 N2 O4
Photophysical characterization of naphthalene diimides are limited to a few
derivatives in literature. Politi and coworkers (Barros et al., 1997) reports the
absorption and fluorescence parameters of N,N’-dibutyl derivative of naphthyl
diimides. Naphthalene diimides are expected to form anion radical intermediate on
photo electron transfer processes. Photooxidation studies have proven that
naphthalene diimides exert electron transfer via singlet or triplet excited state (Alp et
al., 2000). Starting from simple phthalimides, and increasing the complexity of the
molecules from a photophysical point of view by enhancing the contribution of the π,
π‫ ٭‬transition via the introduction of larger aromatic rings vicinal to the imide moiety,
as in naphthalimide derivatives (Barros et al., 1997).
In addition to the biological interest, naphthalene diimides have also been used for
technological purposes such as preparation of electrically conducting materials,
formation of Langmuir-Blodgett films, tube-like nanostructures and Host-guest
Complexes etc. (Kwan et al., 1992, Guo et al., 2003).
Figure 1.2 Chemical diagram of Tristriphenylphosphinechlorogold(1), C18 H15 Au Cl P
Triphenylphosphine is an important ligand of homogeneous phase catalyzer in
petrochemical production, also is a basic raw materials of rhodium-phosphine type
catalyzer. It has important effect in the synthesis of VD, VA, cleocin and plant
pigment. Triphenylphosphine also can be used as the brightening agent in dyeware,
heat stabilizer, stabilizer, antioxidant, flame retardants, anlistatig, antiozonidate and
analytic reagent.
2. Experimental Details
2.1 Preparation of C22 H22 N2 O4
The mixture of 1,4,5,8-naphthalenedianhydride (1 g, 3.75 mmol) and nbutylamine (0.7 g, 10 mmol) was dissolved in 20 ml m-cresol and few drops of
isoquinoline was added. The temperature was gradually increased to 160˚C. The
mixture was kept at this temperature for 6 h under nitrogen. The viscous solution was
diluted with 20 ml m-cresol and poured slowly into 50 ml of methanol while stirring.
The precipitate was filtered and washed thoroughly with warm acetone. Crude
product was purified by column chromatography, using dichloromethane as eluent.
N,N-bis-n-butyl-1,4,5,8-naphthalenediimide, C22 H22 N2 O4, MW: 378.4 g/mol, was
obtained in 0.46 g, 32% yield (Alp et al., 2000).
2.2 Data Collection of C22 H22 N2 O4 Crystal
Before starting data collection, the suitable crystals were selected from the
synthesized crystals by using stereomicroscope and polarization microscope. Than a
sample of size 0.15 x 0.20 x 0.30 mm3 was selected for the crystallographic study.
The diffraction measurements were performed at room temperature (293K) on
Stoe IPDS-II diffractometer diffractometer using graphite-monochromated MoKα
radiation. Orientation matrix and unit cell parameters were obtained from the setting
angles of 4997 reflections at medium θ (0.00˚< θ < 29.47˚). The systematic absences
and intensity symmetries indicated the triclinic P-1 space group. A total of 9108
intensities with θmax = 29.56˚ were collected in the ω scan mode, as suggested by
peak-shape analyses. No considerable amount intensity decay was observed
throughout measurement under discussion. The intensities were corrected for Lorentz
and Polarization factors and also for absorption effect ( µ = 0.096 mm-1 ).
2.3 Structure Solution and Refinement of C22 H22 N2 O4 Crystal
The structure was solved by direct methods using SHELXS-97 for 1513 reflections
with I > 2σ ( I ) and The refinement (on F2 ) was carried out by fullmatrix leastsquares procedure using SHELXL-97. All atoms were refined anisotropically, except
for hydrogens. The structure was refined to R = 0.041for the observed reflections and
R = 0.0673 for all data. The maximum and minimum peaks, observed in the final ∆ρ
map, were 0.284 and -0.162. eÅ-3 , respectively. The scattering factors were taken
from SHELXL 97 . All of the H atoms were found in difference-Fourier maps, and
positions and isotropic thermal parameters were refined. Further details of single
crystal data measurement and refinement are given in Table 2.1. The atomic
coordinates and equivalent isotropic thermal parameters of all atoms are listed in
Table 2.2 Bond distances and angles are given Table 2.3 and Table 2.4 torsion angles
are listed in Table 2.5
Table 2.1 Crystallographic data for C22 H22 N2 O4
CRYSTAL DATA
Chemical Formula
C22 H22 N2 O4
Formula Weight (a.m.u)
378.42
Crystal System
Triclinic
Space group
P-1
a, b, c (Å)
5.3085(7), 8.0011(11), 11.1097(15)
α, β, γ(˚)
103.731(11), 94.422(11), 95.446(11)
Vcell (Å3)
453.89(11)
Z
1
D(calc) (g/cm3)
1.384
Mu(MoKα) ( /mm )
0.096
F000
200
Crystal Size (mm)
0.15 x 0.20 x 0.30
(No. 2)
DATA COLLECTION
Diffractometer
Stoe IPDS-II diffractometer
Temperature (K)
293
Scan type
ω scans
Radiation/Wavelenght (Å)
MoKα
Reflections measured
9108
Independent/Observed reflections
2526/1513
Range of h, k, l
-6→7, -11→11, -15→15
Absorption correction
Integration (X-RED32; Stoe & Cie, 2002)
0.71073
REFINEMENT
Data/Restraints/parameters
2625 / 0 /172
Extinction Coefficient
0.107(14)
Final R indices (I > 2 σ(I))
0.0409
R indices (all data)
0.0673
GOOF (on F2)
0.918
∆ρmin /∆ρmax (e/Å3)
-0.162 / 0.284
Weighting function
w = 1 σ 2 (F02 ) + (0.0558P ) , where P = (F02 + 2 Fc2 ) 3
[
2
]
Table 2.2 Atomic coordinates and equivalent isotropic thermal parameters (Å).
Atom
x
y
Ueq‫٭‬
z
O1
1.04200(17)
0.92866(12)
0.27138(9)
0.0537(3)
O2
0.33015(17)
0.55148(11)
0.12475(9)
0.0527(3)
N1
0.68343(18)
0.74215(12)
0.20130(9)
0.0401(3)
C1
0.8436(2)
0.89233(15)
0.20430(11)
0.0399(3)
C2
0.7612(2)
1.00300(14)
0.12257(10)
0.0367(3)
C3
0.5367(2)
0.94840(13)
0.04040(10)
0.0346(3)
C4
0.3840(2)
0.79252(14)
0.03703(10)
0.0368(3)
C5
0.4584(2)
0.68475(14)
0.12306(11)
0.0396(3)
C6
0.7681(3)
0.63420(17)
0.28507(12)
0.0463(4)
C7
0.7286(3)
0.70831(19)
0.41995(12)
0.0482(4)
C8
0.4542(3)
0.71287(19)
0.44564(12)
0.0491(4)
C9
0.4243(4)
0.7821(2)
0.58265(14)
0.0617(6)
C10
0.1677(2)
0.74189(16)
-0.04436(11)
0.0413(3)
C11
0.9053(2)
1.15597(15)
0.12433(11)
0.0414(3)
‫ ٭‬Ueq ne third of the trace of the orthogonalizedis defined as o Uij tensor.
Figure 2.1 An ORTEP3 drawing of the C22 H22 N2 O4 showing the atomic numbering
scheme. Displacement ellipsoids of non-H atoms are shown at % 50 probability
level; H atoms are shown as small spheres of arbitrary size.
Table 2.3 Bond distances (Å) in the title molecule.
Atoms
Bond distance
Atoms
Bond distance
O1-C1
1.2113(15)
C8-C9
1.517(2)
O2-C5
1.2143(15)
C10-C11i
1.3997(17)
N1-C1
1.3966(16)
C6-H8
0.999(16)
N1-C5
1.3927(15)
C6-H9
0.996(16)
N1-C6
1.4849(17)
C7-H6
0.975(15)
C1-C2
1.4812(17)
C7-H7
0.985(16)
C2-C3
1.4102(15)
C8-H4
1.010(16)
C2-C11
1.3756(17)
C8-H5
0.979(16)
C3-C4
1.4125(16)
C9-H1
0.98(2)
C3-C3i
1.4137(15)
C9-H2
0.96(2)
C4-C5
1.4868(16)
C9-H3
0.985(19)
C4-C10
1.3703(16)
C10-H10
0.936(16)
C6-C7
1.5137(19)
C11-H11
0.939(16)
C7-C8
1.508(2)
Symmetry code; i = 1-x, 2-y, -z and ARU code; i = [ 2675.01 ]
Table 2.4 Bond angles (°)
Atoms
Bond Angle
Atoms
Bond Angle
C1-N1-C5
124.85(10)
N1-C6-H9
106.8(8)
C1-N1-C6
116.55(10)
C7-C6-H8
112.6(9)
C5-N1-C6
118.55(10)
C7-C6-H9
110.3(8)
O1-C1-N1
120.54(11)
H8-C6-H9
109.1(12)
O1-C1-C2
122.03(11)
C6-C7-H6
106.4(9)
N1-C1-C2
117.43(10)
C6-C7-H7
111.1(9)
C1-C2-C3
119.51(10)
C8-C7-H6
109.4(9)
C1-C2-C11
120.43(10)
C8-C7-H7
108.7(9)
C3-C2-C11
120.04(10)
H6-C7-H7
106.1(13)
C2-C3-C4
121.33(10)
C7-C8-H4
108.7(9)
C2-C3-C3i
119.32(10)
C7-C8-H5
107.8(9)
C3i-C3-C4
119.35(10)
C9-C8-H4
110.0(9)
C3-C4-C5
119.56(10)
C9-C8-H5
110.8(9)
C3-C4-C10
120.13(11)
H4-C8-H5
106.5(13)
C5-C4-C10
120.31(11)
C8-C9-H1
111.2(11)
O2-C5-N1
121.13(11)
C8-C9-H2
112.1(12)
O2-C5-C4
121.68(10)
C8-C9-H3
109.8(11)
N1-C5-C4
117.19(10)
H1-C9-H2
109.3(16)
N1-C6-C7
113.19(12)
H1-C9-H3
107.8(16)
C6-C7-C8
114.79(12)
H2-C9-H3
106.4(17)
C7-C8-C9
112.80(13)
C4-C10-H10
120.1(10)
C4-C10-C11i
120.58(11)
C11i-C10-H10 119.3(10)
C2-C11-C10i
120.58(10)
C2-C11-H11
N1-C6-H8
104.5(9)
C10i-C11-H11 120.1(10)
119.3(10)
Symmetry code; i = 1-x, 2-y, -z and ARU code; i = [ 2675.01 ]
Table 2.5 Torsion angles (°)
Atoms
Torsion agles
Atoms
Torsion agles
C5-N1-C1-O1
-176.62(11)
C1-C2-C11-C10i
177.93(11)
C6-N1-C1-O1
0.93(16)
C3i-C3-C4-C5
-179.14(10)
C5-N1-C1-C2
3.17(16)
C3i-C3-C4-C10
0.33(16)
C6-N1-C1-C2
-179.28(10)
C2-C3-C4-C10
-179.54(11)
i
i
C5-N1-C6-C7
-105.67(13)
C4-C3-C3 -C2
0.13(16)
C1-N1-C5-C4
-0.28(16)
C4-C3-C3i-C4i
-180.00(10)
C1-N1-C5-O2
179.16(11)
C2-C3-C3i-C4i
-0.13(16)
C6-N1-C5-O2
1.65(17)
C2-C3-C4-C5
0.99(16)
C6-N1-C5-C4
-177.79(10)
C2-C3-C3i-C2i
180.00(10)
C1-N1-C6-C7
76.61(15)
C10-C4-C5-O2
-0.81(17)
O1-C1-C2-C11
-2.61(17)
C10-C4-C5-N1
178.63(10)
N1-C1-C2-C3
-3.98(15)
C3-C4-C10-C11i
-0.39(17)
O1-C1-C2-C3
175.81(11)
C5-C4-C10-C11i
179.08(10)
N1-C1-C2-C11
177.60(10)
C3-C4-C5-O2
178.67(11)
C1-C2-C3-C3i
-177.90(10)
C3-C4-C5-N1
-1.89(15)
C11-C2-C3-C4
-179.60(11)
N1-C6-C7-C8
65.79(16)
C11-C2-C3-C3i
0.53(16)
C6-C7-C8-C9
177.93(13)
C1-C2-C3-C4
1.97(16)
C4-C10-C11i-C2i
-0.02(18)
C3-C2-C11-C10
i
-0.48(17)
Symmetry code; i = 1-x, 2-y, -z and ARU code; i = [ 2675.01 ]
Table 2.6 Hidrogen bonds
D—H..A
D--H (Å)
H..A (Å)
D-A (Å)
Angle (°)
C6--H8..O2
0.999(16)
2.261(16)
2.7432(18)
108.3(11)
C10--H10..O2ii
0.936(16)
2.446(16)
3.2795(16)
148.3(13)
Symmetry code; ii = -x, 1-y, -z and ARU code; ii = [ 2565.01 ]
Figure 2.2 The unit cell packing diagram of C22 H22 N2 O4 with the scheme of one
type of intermolecular hidrojen bonds in the unit cell.
2.4 Preparation of C18 H15 Au Cl P
In this study, the crystal of C18 H15 Au Cl P was synthesised as described in the
reference (Baenziger et al., 1976).
2.5 Data Collection of C18 H15 Au Cl P Crystal
Before starting data collection, the suitable crystals were selected from the
synthesized crystals by using stereomicroscope and polarization microscope. Than a
sample of size 0.48 x 0.24 x 0.23 mm3 was selected for the crystallographic study.
The diffraction measurements were performed at room temperature (293K) on
Stoe IPDS-II diffractometer using graphite-monochromated MoKα radiation. The
systematic absences and intensity symmetries indicated the Orthorhombic P 21 21 21
space group. A total of 11565 intensities with θmax = 28.29˚ were collected in the ω
scan mode, as suggested by peak-shape analyses. No considerable amount intensity
decay was observed throughout measurement under discussion. The intensities were
corrected for Lorentz and Polarization factors and also for absorption effect ( µ =
9.111 mm-1 ).
2.6 Structure Solution and Refinement of C18 H15 Au Cl P Crystal
The structure was solved by Patterson using SHELXS-97 for 3738 reflections with
I > 2σ ( I ). The refinement (on F2) was carried out by fullmatrix least-squares
procedure using SHELXL-97. All atoms were refined anisotropically, except for
hydrogens. The structure was refined to R = 0.0308 for the observed reflections and
R = 0.0333 for all data. The maximum and minimum peaks, observed in the final ∆ρ
map, were 1.903 and -0.744. eÅ-3 , respectively. The scattering factors were taken
from SHELXL 97. All of the H atoms were found in difference-Fourier maps, and
positions and isotropic thermal parameters were refined. Further details of single
crystal data measurement and refinement are given in Table 2.7. The atomic
coordinates and equivalent isotropic thermal parameters of all atoms are listed in
Table 2.8. Bond distances and angles are given Table 2.9 and Table 2.10. Torsion
angles are listed in Table 2.11.
2.7 Experimental Results for C18 H15 Au Cl P
Table 2.7 Crystallographic data for C18 H15 Au Cl P
CRYSTAL DATA
Chemical Formula
C18 H15 Au Cl P
Formula Weight (a.m.u)
494.69
Crystal System
Orthorhombic
Space group
P 21 21 21
a, b, c (Å)
10.200(2)
α, β, γ(˚)
90.00 90.00 90.00
Vcell (Å3)
1659.6(6)
Z
4
D(calc) (g/cm3)
1.980
Mu(MoKα) ( /mm )
9.112
F000
936
Crystal Size (mm)
0.48 x 0.24 x 0.23
Crystal description / Crystal colour
Prizmatic / Collorless
(No. 19)
12.396(3)
DATA COLLECTION
Diffractometer
CCD area detector
Temperature (K)
293(2)
Scan type
ω scan
Radiation/Wavelenght (Å)
MoKα
Reflections measured
11565
Independent/Observed reflections
3940 / 3738
0.71073
13.126(3)
Range of h, k, l
-13→12, -15→16, -17→16
Absorption correction
Integration
Computing data collection and cell
Bruker SMART / Bruker SAINT
refinement / Computing data reduction
REFINEMENT
Data/Restraints/parameters
3940/ 0 /191
Extinction Coefficient
0.0021(2)
Final R indices (I > 2 σ(I))
0.0308
R indices (all data)
0.0333
GOOF (on F2)
1.139
∆ρmin /∆ρmax (e/Å3)
-0.744/ 1.903
Weighting function
w = 1 σ 2 (F02 ) + (0.0304 P ) + 0.6239 P
[
2
whereP = (F02 + 2 Fc2 ) 3
]
Table 2.8 Atomic coordinates and equivalent isotropic thermal parameters (Å).
Atom
x
y
z
Ueq‫٭‬
Au1
0.33706(2)
0.06936(2)
0.24067(2)
0.0399(1)
Cl1
0.13054(17)
0.01257(15)
0.20003(15)
0.0578(6)
P1
0.53874(14)
0.12572(11)
0.28031(12)
0.0363(4)
C1
0.8032(9)
0.2824(8)
0.1012(7)
0.075(3)
C2
0.7490(7)
0.2141(7)
0.1746(6)
0.059(3)
C3
0.6144(7)
0.2090(5)
0.1829(5)
0.0417(19)
C4
0.5362(9)
0.2724(5)
0.1213(6)
0.053(3)
C5
0.5912(10)
0.3424(7)
0.0503(7)
0.067(3)
C6
0.7263(11)
0.3449(7)
0.0401(7)
0.071(3)
C7
0.7243(7)
-0.0005(6)
0.3859(6)
0.053(2)
C8
0.8124(9)
-0.0874(6)
0.3904(8)
0.069(3)
C9
0.8271(8)
-0.1552(6)
0.3119(7)
0.065(3)
C10
0.6687(7)
-0.0564(5)
0.2168(6)
0.054(2)
C11
0.7563(7)
-0.1415(6)
0.2254(7)
0.063(3)
C12
0.6541(6)
0.0152(4)
0.2986(5)
0.0403(17)
C13
0.5411(6)
0.2052(5)
0.3963(5)
0.0377(17)
C14
0.6080(8)
0.3030(5)
0.4034(6)
0.053(2)
C15
0.6010(9)
0.3594(6)
0.4916(7)
0.064(3)
C16
0.5277(8)
0.3283(6)
0.5737(6)
0.054(2)
C17
0.4624(9)
0.2329(7)
0.5661(6)
0.064(3)
C18
0.4670(8)
0.1723(5)
0.4781(6)
0.055(2)
‫ ٭‬Ueq is defined as one third of the trace of the orthogonalized Uij tensor.
Figure 2.3 An ORTEP3 drawing of the C18 H15 Au Cl P showing the atomic
numbering scheme. Displacement ellipsoids of non-H atoms are shown at % 50
probability level; H atoms are shown as small spheres of arbitrary size.
Table 2.9 Bond distances (Å) in the title molecule
Atoms
Bond distance
Atoms
Bond distance
Au1-Cl1
2.2842(19)
C14-C15
1.354(12)
Au1-P1
2.2340(15)
C15-C16
1.367(12)
P1-C3
1.816(7)
C16-C17
1.361(12)
P1-C12
1.822(6)
C17-C18
1.379(11)
P1-C13
1.814(7)
C1-H1
0.9299
C1-C2
1.397(12)
C2-H2
0.9295
C1-C6
1.363(14)
C4-H3
0.9300
C2-C3
1.379(10)
C5-H4
0.9299
C3-C4
1.381(10)
C6-H5
0.9297
C4-C5
1.391(12)
C7-H6
0.9307
C5-C6
1.385(15)
C8-H7
0.9297
C7-C8
1.404(11)
C9-H8
0.9301
C7-C12
1.365(10)
C10-H10
0.9295
C8-C9
1.338(13)
C11-H9
0.9298
C9-C11
1.356(12)
C14-H15
0.9300
C10-C11
1.387(10)
C15-H14
0.9298
C10-C12
1.401(9)
C16-H13
0.9297
C13-C14
1.394(9)
C17-H12
0.9303
C13-C18
1.375(10)
C18-H11
0.9293
Table 2.10 Bond angles (°)
Atoms
Bond Angle
Atoms
Bond Angle
Cl1-Au1-P1
179.73(6)
C15-C16-C17
117.1(7)
Au1-P1-C3
113.9(2)
C16-C17-C18
121.2(8)
Au1-P1-C12
112.97(19)
C13-C18-C17
120.8(7)
Au1-P1-C13
112.2(2)
C2-C1-H1
119.24
C3-P1-C12
104.2(3)
C6-C1-H1
119.26
C3-P1-C13
106.1(3)
C1-C2-H2
120.80
C12-P1-C13
106.8(3)
C3-C2-H2
120.75
C2-C1-C6
121.5(9)
C3-C4-H3
119.55
C1-C2-C3
118.5(7)
C5-C4-H3
119.52
P1-C3-C2
120.3(5)
C4-C5-H4
120.69
P1-C3-C4
119.4(6)
C6-C5-H4
120.63
C2-C3-C4
120.2(7)
C1-C6-H5
119.87
C3-C4-C5
120.9(8)
C5-C6-H5
119.94
C4-C5-C6
118.7(8)
C8-C7-H6
120.68
C1-C6-C5
120.2(9)
C12-C7-H6
120.61
C8-C7-C12
118.7(7)
C7-C8-H7
119.29
C7-C8-C9
121.4(9)
C9-C8-H7
119.30
C8-C9-C11
120.4(8)
C8-C9-H8
119.82
C11-C10-C12
119.2(7)
C11-C9-H8
119.76
C9-C11-C10
120.4(8)
C11-C10-H10
120.38
P1-C12-C7
123.8(5)
C12-C10-H10
120.42
P1-C12-C10
116.4(5)
C9-C11-H9
119.78
C7-C12-C10
119.8(6)
C10-C11-H9
119.80
P1-C13-C14
122.3(5)
C13-C14-H15
120.61
P1-C13-C18
119.2(5)
C15-C14-H15
120.69
C14-C13-C18
118.3(6)
C14-C15-H14
118.04
C13-C14-C15
118.7(7)
C16-C15-H14
118.10
C14-C15-C16
123.9(7)
C15-C16-H13
121.46
C17-C16-H13
121.48
C13-C18-H11
119.62
C16-C17-H12
119.41
C17-C18-H11
119.63
C18-C17-H12
119.37
Table 2.11 Torsion Angles
Atoms
Torsion agles
Atoms
Torsion agles
Au1-P1-C13-C18
42.0(6)
C1-C2-C3-C4
1.6(11)
C3-P1-C13-C18
166.9(6)
C2-C3-C4-C5
0.2(11)
C12-P1-C13-C18
82.3(6)
P1-C3-C4-C5
75.8(6)
Au1-P1-C12-C10
56.8(5)
C3-C4-C5-C6
2.1(12)
Au1-P1-C3-C2
153.8(5)
C4-C5-C6-C1
2.2(13)
C12-P1-C3-C2
30.3(7)
C12-C7-C8-C9
1.0(12)
C13-P1-C3-C2
82.3(6)
C8-C7-C12-P1
178.7(6)
Au1-P1-C3-C4
30.2(6)
C8-C7-C12-C10
1.5(10)
C12-P1-C3-C4
153.7(5)
C7-C8-C9-C11
0.1(13)
C13-P1-C3-C4
93.7(6)
C8-C9-C11-C10
0.6(12)
C13-P1-C12-C7
0.8(6)
C11-C10-C12-P1
179.2(5)
C3-P1-C12-C10
67.4(5)
C11-C10-C12-C7
1.0(10)
C13-P1-C12-C10
179.4(5)
C12-C10-C11-C9
0.1(11)
Au1-P1-C13-C14
133.3(5)
P1-C13-C14-C15
177.6(6)
C3-P1-C13-C14
8.3(7)
C18-C13-C14-C15
2.3(11)
C12-P1-C13-C14
102.4(6)
P1-C13-C18-C17
177.5(6)
C3-P1-C12-C7
112.8(6)
C14-C13-C18-C17
2.0(11)
Au1-P1-C12-C7
123.0(5)
C13-C14-C15-C16
2.6(13)
C2-C1-C6-C5
0.5(14)
C14-C15-C16-C17
2.4(13)
C6-C1-C2-C3
1.4(13)
C15-C16-C17-C18
2.0(13)
C1-C2-C3-P1
177.5(6)
C16-C17-C18-C13
1.9(13)
Figure 2.4 Unit cell packing diagram of C18 H15 Au Cl P
3. Results and Discussion
In this study molecular and crystal structures of N,N’-dibutyl-1,4,5,8naphthalenediimide, C22 H22 N2 O4 and Tristriphenylphosphinechlorogold(1), C18
H15 Au Cl P have been determined by single X-ray diffraction technique and
following results have been concluded.
The molecule C22 H22 N2 O4 which displays the inversion symmetry and has centre
of symmetry (inversion centre) between the C3 and C3i atoms is a centrosymmetric
molecule. When the structure was solved, half of the entire molecule has been
determined and then the structure was completed with the inversion symmetry
operation relative to the inversion centre.
Experimental X-ray evidence shows that there are π-π* interactions in the lattice.
Some important rings that exhibits π-π* interactions are Cg(2)-Cg(2)i (symmetry
code: i = 2-X, 2-Y, -Z), Cg(3) -Cg(3)ii (symmetry code: ii = -X, 2-Y, -Z), Cg(2) [1]Cg(3)iii (symmetry code: iii = 1+X, Y, Z), Cg(3)-Cg(2)iv (symmetry code: iv = 1+X, Y, Z) and the distances between the rings above are 3.9476(8)Å ( where Cg(2)
= C2, C3, C3i, C4i, C10i, C11 and Cg(3) = C3, C4, C10, C11i, C2i, C3i ). Due to the
π-π* interaction the naphthalenediimide moiety of the molecule is nearly planar and
in the lattice molecules are arrange in a row through a axes of the unit cell.
In our study it was seen that atoms of the naphthalenediimide moiety, except
oxygen atoms, form a plane and deviations of O1 and O2 atoms from the
naphthalenediimide ring are 0.1108 (0.0013) Å and -0.0476 (0.0013) Å respectively.
It is also observed that in the molecule carbon atoms of the butyl group constitute a
plane, too. So dihedral angle between the naphthalenediimide plane and butyl plane
is 74.96 (8)˚.
The molecule exhibits intermolecular hidrojen bonds of the same type which is CH..O. The hidrojen bond distances are d(C6-H8..O2) = 2.7432(18)Å and d(C10-
H10..O2ii) = 3.2795(16)Å (Symmetry code; ii = -x, 1-y, -z and ARU code; ii =
[2565.01]).
In C18 H15 Au Cl P molecule the P atom is in a distorted tetrahedral environment
with three carbons of the triphenylphosphine ligand and the Au atom occupying the
vertices so that the angles for
Au1-P1-C3, Au1-P1-C12 and Au1-P1-C13 are
113.9(2)˚, 112.2(2)˚ and 112.97(2)˚ respectively.
The Au atom in the title compound, Tristriphenylphosphinechlorogold(1), exhibits
a linear geometry so that the Au1-Cl1 bond lenght is 2.2842(19)Å, Au1-P1 is
2.2340(15)Å and the angle of Cl1-Au1-P1 is 179.73(6)˚
P-C bond lenghts in the triphenylphosphine ligand is d(P1-C3) = 1.816(7)Å, d(P1C12) = 1822(6)Å and d(P1-C13) = 1814(7)Å. Resembeling compounds in the
literature are in a good correlation with our results (HoÉmer et al., 2003). C-C bonds
in the phenyl rings are ranging from 1.354(12)Å to 1.404(11)Å.
The aromatic phenyl rings are almost symmetrically disposed as seen in the
sequence of dihedral angles of 78.6(4)˚, 85.0(4)˚, 80.7(4)˚ for the C1-C6, C7-C12
and C13-C18 rings, respectively.
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