Pyrimidine, pyridazine, quinazoline, phthalazine, and triazine coordination polymers of copper(I) halides

Article abstract of DOI:10.1016/S0277-5387(02)01372-4

The coordination of diazine and triazine bridging ligands (B = pyrimidine (Pym), quinazoline (Qnz), pyridazine (Pdz), phthalazine (Ptz), and 1,3,5-triazine (Trz)) with CuX and CuXL (X = Cl, Br, I; L = PPh₃, P(OPh)₃) has been investigated. Products without phosphorus(III) ligands include [CuXB] (B = Qnz, Pdz, Ptz), [(CuX)₂B] (B = Pym, Qnz, Pdz, Ptz, Trz), [(CuX)₃B₂] (B = Ptz, Trz), and [(CuX)₃B] (B = Trz). Only CuX-Trz and CuI-Pdz afford more than one product stoichiometry. Products with phosphorus ligands are of the types [(CuXL)B] (B = Pdz, Ptz), [(CuXL)₂B] (B = Pym, Qnz, Pdz, Ptz, Trz), and [(CuXL)₃B] (B = Trz). Thermogravimetic analyses of the complexes typically show step-wise losses of B and L, ultimately yielding CuX. The X-ray crystal structure of [CuBr(Qnz)] features copper atoms bridged by Br and Qnz, forming 2D sheets of fused rectangular Cu₄Br₂(Qnz)₂ units. The X-ray structures of [(CuBr(PPh₃))₂B] (B = Pym, Trz) show 1D chains formed from rhomboidal (CuL)₂Br₂ units linked by the B ligand. The structure of [CuCl(PPh₃)(Pdz)] is shown by X-ray to be a simple halide-bridged dimer. The X-ray structure of [(CuCl(P(OPh)₃))₃(Trz)] is a hexamer, having an oblate spheroid core. The core is composed of a Cu₆Cl₆ macrocycle capped with two Trz ligands.

Full text of DOI:10.1016/S0277-5387(02)01372-4

Polyhedron 22 (2003) 419ꢁ431
/
www.elsevier.com/locate/poly
Pyrimidine, pyridazine, quinazoline, phthalazine, and triazine
coordination polymers of copper(I) halides
Jonathan T. Maeyer a, T. Jason Johnson a, Amy K. Smith a, Brian D. Borne a,
Robert D. Pike a,*, William T. Pennington b, Mariusz Krawiec b,
Arnold L. Rheingold c
a Department of Chemistry, College of William and Mary, Williamsburg, VA 23187, USA
b Department of Chemistry, Clemson University, Clemson, SC 29634, USA
c Department of Chemistry and Biochemistry, University of Delaware, Newark, DE 19716, USA
Received 19 August 2002; accepted 30 October 2002
Abstract
The coordination of diazine and triazine bridging ligands (Bꢀ
(Ptz), and 1,3,5-triazine (Trz)) with CuX and CuXL (XꢀCl, Br, I; Lꢀ
phosphorus(III) ligands include [CuXB] (BꢀQnz, Pdz, Ptz), [(CuX)2B] (Bꢀ
and [(CuX)3B] (BꢀTrz). Only CuXꢀTrz and CuIꢀPdz afford more than one product stoichiometry. Products with phosphorus
ligands are of the types [(CuXL)B] (BꢀPdz, Ptz), [(CuXL)2B] (BꢀPym, Qnz, Pdz, Ptz, Trz), and [(CuXL)3B] (BꢀTrz).
/
pyrimidine (Pym), quinazoline (Qnz), pyridazine (Pdz), phthalazine
PPh3, P(OPh)3) has been investigated. Products without
Pym, Qnz, Pdz, Ptz, Trz), [(CuX)3B2] (BꢀPtz, Trz),
/
/
/
/
/
/
/
/
/
/
/
Thermogravimetic analyses of the complexes typically show step-wise losses of B and L, ultimately yielding CuX. The X-ray crystal
structure of [CuBr(Qnz)] features copper atoms bridged by Br and Qnz, forming 2D sheets of fused rectangular Cu4Br2(Qnz)2 units.
The X-ray structures of [(CuBr(PPh3))2B] (BꢀPym, Trz) show 1D chains formed from rhomboidal (CuL)2Br2 units linked by the B
/
ligand. The structure of [CuCl(PPh3)(Pdz)] is shown by X-ray to be a simple halide-bridged dimer. The X-ray structure of
[(CuCl(P(OPh)3))3(Trz)] is a hexamer, having an oblate spheroid core. The core is composed of a Cu6Cl6 macrocycle capped with
two Trz ligands.
# 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Copper complexes; Crystal structures; Pyridazine ligands; Pyrimidine ligands; Thermogravimetric analysis; Triazine ligands
1. Introduction
Recently, we [1] and others [2ꢁ
dimensional (3D) atom arrangements can exist for a
given stoichiometry. Additionally, the use of monoden-
tate ‘capping’ ligands (L) has been shown to limit
polymer growth, lowering the dimensionality of the
/
4] have demonstrated
that copper(I) halides undergo self-assembly reactions
with bridging nitrogen ligands to produce metal-organic
polymers. Copper(I) halides (CuX) are notable for their
ability to form rhomboid Cu2X2 dimers, Cu4X4 cubane
tetramers, (Cu2X2)n stair step polymers, and (CuX)n
chains. These structures are linked together by bridging
aromatic nitrogen ligands (B), such as pyrazine (Pyz)
and 4,4?-bipyridine (Bpy), into a variety of polymeric
arrays. The most commonly encountered stoichiome-
tries are 1:1 CuXB and 2:1 (CuX)2B. Multiple three-
metal-organic polymer, e.g. 2D0/1D [1,5].
In the current contribution, we report the products
resulting from the reactions of the B ligands shown in
Chart 1 with CuXꢀ/CuCl, CuBr, and CuI, in the
absence or in the presence of Lꢀ/PPh3 and P(OPh)3.
These ligands are notable for their geometrically rigid
bridging angles of 120 or 608. Kromp and Sheldrick
have reported the binary complexes of pyridazine and
pyrimidine: [CuX(Pdz)] (Xꢀ
and [CuBr(Pym)] [3]. Hubberstey and coworkers have
described [(CuX)3(Trz)] and [(CuX)2(Trz)] (XꢀBr, I)
/Cl, Br, I), [(CuI)2(Pdz)]
/
* Corresponding author. Tel.: ꢂ
2715.
E-mail address: rdpike@wm.edu (R.D. Pike).
/
1-757-221-2555; fax: ꢂ1-757-221-
/
[4]. All of the aforementioned species form metal-
organic networks. In addition, halide-free networks of
0277-5387/02/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 2 7 7 - 5 3 8 7 ( 0 2 ) 0 1 3 7 2 - 4

420
J.T. Maeyer et al. / Polyhedron 22 (2003) 419ꢁ431
/
Table 1
Synthetic and analytical data for CuX-B complexes
Compound
Yield Color
(%)
% (theory) % (experiment)
[(CuCl)2(Pym)] 67
[(CuBr)2(Pym)] 79
[(CuI)2(Pym)] 89
gold
yellowꢁ
bright yellow
Cu 45.70
Cu 34.63
Cu 27.57
C 10.42
H 0.87
45.87
33.93
27.28
10.59
0.89
/
olive
Chart 1.
N 6.08
6.06
[CuCl(Qnz)]
79
brick red
Cu 27.73
C 41.93
H 2.63
27.73
41.39
2.81
these ligands are known, including [CuSCN(Pym)] [6],
[CuCN(Pdz)] [7] [Cu(Pym)2]BF4 [8] dimeric [Cu2(Pdz)x-
(cnge)2]BF4 (xꢀ
/
2, 3; cngeꢀ
/
2-cyanoguanidine) [9] and
N 12.23
Cu 23.23
Cu 24.87
C 18.80
H 1.18
12.13
23.03
25.13
18.92
1.26
[CuBr(Qnz)]
[(CuI)2(Qnz)]
63
81
redꢁ
/
orange
[Cu2(Pdz)3(NCMe)2](PF6)2 and tetrameric [Cu4(Pdz)6]-
(ClO4)4 [10]. No copper(I) halide complexes of Qnz or
Ptz have yet been reported. Also novel are the phos-
redꢁ
/
orange
phorus(III) adducts of CuXꢀ
/B.
N 5.48
5.38
[CuCl(Pdz)]
[CuBr(Pdz)]
79
88
dark red
redꢁbrown
Cu 35.48
Cu 28.43
C 21.49
H 1.80
36.38
27.87
20.99
1.72
/
2. Experimental
N 12.53
Cu 23.49
C 17.76
H 1.49
12.12
22.65
17.83
1.45
[CuI(Pdz)]
86
95
orange
yellow
brown
orange
orange
amber
2.1. General methods
All syntheses were carried out under nitrogen atmo-
sphere. Microanalyses for C, H, and N were carried out
by Atlantic Microlab, Inc., Norcross, GA. Methods
used for thermogravimetric analysis (TGA) and atomic
absorption analyses have previously been described [1].
All ligands were purchased from Aldrich or Acros and
were used as received. Copper(I) chloride and bromide
were freshly recrystallized from aq. HCl or HBr.
Copper(I) iodide was used as received from Aldrich.
N 10.36
Cu 27.57
C 10.42
H 0.87
10.25
27.84
10.51
0.83
[(CuI)2(Pdz)]
N 6.08
5.93
[(CuCl)3(Ptz)2] 64
Cu 34.21
C 34.48
H 2.17
33.78
34.07
2.39
N 10.05
Cu 23.23
C 35.12
H 2.21
9.81
[CuBr(Ptz)]
[(CuI)2(Ptz)]
62
65
23.02
35.25
2.27
2.2. Syntheses
N 10.24
Cu 24.87
C 18.80
H 1.18
10.35
24.46
18.54
1.09
The following two descriptions are representative of
CuXꢀ
/
B and CuXꢀ
/
Lꢀ
/B syntheses, respectively. See
N 5.48
5.46
Tables 1 and 2 for complete synthetic results.
[(CuCl)2(Trz)] 70
[(CuCl)3(Trz)] 78
Cu 45.54
brown Cu 50.43
C 9.52
44.74
47.45
9.89
orangeꢁ
/
2.2.1. Synthesis of [CuCl(Qnz)]
H 0.80
N 11.12
1.00
Freshly recrystallized CuCl (0.492 g, 4.97 mmol) was
dissolved in 40 ml of CH3CN. The solution was filtered
through Celite to remove traces of Cu(II) species, and
was stirred under nitrogen at 25 8C. A solution of
quinazoline (0.646 g, 4.96 mmol) in 8 ml of CHCl3
was added to the CuCl solution via syringe. A blood red
precipitate rapidly developed. After stirring for 30 min
at 25 8C, the product was collected via filtration, washed
with Et2O, and then dried under vacuum (0.893 g, 3.90
mmol, 78.6%).
11.16
32.20
35.00
9.67
[(CuBr)3(Trz)2] 20
[(CuBr)2(Trz)] 78
redꢁ/brown
Cu 32.18
Cu 34.54
C 9.79
orange
H 0.82
0.92
N 11.42
Cu 37.28
Cu 27.51
C 7.80
10.99
37.19
27.58
8.12
[(CuBr)3(Trz)] 76
[(CuI)2(Trz)]
redꢁ/brown
94
bright yellow
H 0.65
N 9.10
0.62
9.11
2.2.2. Synthesis of [(CuI(PPh3))2(Pdz)]
ml of CH3CN was added by use of syringe. A yellow
solution containing a trace of orange powder resulted.
After stirring for 15 min, the orange powder, [CuI(Pdz)],
Copper(I) iodide (0.308 g, 1.62 mmol) and PPh3
(0.426 g, 1.63 mmol) were co-dissolved in 40 ml of
CHCl3 at 25 8C. Pyridazine (0.0680 g, 0.849 mmol) in 3

J.T. Maeyer et al. / Polyhedron 22 (2003) 419ꢁ
/431
421
Table 2
Synthetic and analytical data for CuXꢀ
/
Lꢀ
/
B complexes
Yield (%)
Compound
Color
% (theory)
% (experiment)
[(CuCl(PPh3))2(Pym)]
89
pale yellow
Cu 15.83
C 59.85
H 4.24
16.35
60.34
4.27
N 3.49
3.17
[(CuBr(PPh3))2(Pym)]
[(CuI(PPh3))2(Pym)]
98
36
yellow
bright yellow
Cu 14.26
Cu 12.90
C 48.74
H 3.48
14.64
13.11
47.87
3.45
N 2.84
2.78
[(CuCl(P(OPh)3))2(Pym)]
[(CuBr(P(OPh)3))2(Pym)]
42
71
pale yellow
pale yellow
Cu 14.14
Cu 12.87
C 48.64
H 3.44
13.53
12.94
48.04
3.57
N 2.84
3.05
[(CuCl(PPh3))2(Qnz)]
[(CuBr(PPh3))2(Qnz)]
[(CuI(PPh3))8(Qnz)]
67
68
82
bright orange
Cu 14.90
Cu 13.50
Cu 13.98
C 48.66
H 3.38
14.35
13.10
13.55
48.07
3.35
yellowꢁ/orange
golden
N 0.75
0.89
[(CuCl(P(OPh)3))2(Qnz)]
[(CuBr(P(OPh)3))2(Qnz)]
62
66
pale yellow
yellow
Cu 13.40
Cu 12.25
C 50.93
H 3.50
13.16
12.40
50.88
3.50
N 2.70
2.87
[(CuCl(PPh3))2(Pdz)]
[CuBr(PPh3)(Pdz)]
72
63
light yellow
Cu 15.83
C 59.86
H 4.27
14.99
59.20
4.23
N 3.49
4.07
yellowꢁ
/
orange
Cu 13.08
C 54.39
H 3.94
13.15
53.84
4.08
N 5.77
5.57
[CuI(PPh3)(Pdz)]
[CuCl(P(OPh)3)(Pdz)]
[CuBr(P(OPh)3)(Pdz)]
65
49
69
yellowꢁ
yellow
light yellow
/
orange
Cu 11.93
Cu 12.99
Cu 11.90
C 49.50
H 3.59
12.21
12.55
12.08
48.61
3.52
N 5.25
5.11
[(CuCl(PPh3))2(Ptz)]
[CuBr(PPh3)(Ptz)]
87
71
yellow
yellow
Cu 14.90
Cu 11.86
C 58.27
H 3.95
14.75
12.13
57.53
3.88
N 5.23
5.21
[CuI(PPh3)(Ptz)]
[CuCl(P(OPh)3)(Ptz)]
[(CuBr(P(OPh)3))2(Ptz)]
89
76
68
yellow
Cu 10.90
Cu 11.78
Cu 12.25
C 50.93
H 3.50
11.13
11.42
12.96
49.79
3.41
yellowꢁ
yellow
/orange
N 2.70
3.11
[(CuCl(PPh3))3(Trz)]
[(CuBr(PPh3))2(Trz)]
80
95
yellowꢁ
yellow
/orange
Cu 16.37
Cu 14.24
C 52.48
H 3.73
16.39
14.13
52.37
3.71
N 4.71
4.65
[(CuI(PPh3))2(Trz)]
92
82
pale orange
Cu 12.88
C 47.48
H 3.37
12.80
46.88
3.35
N 4.26
4.21
[(CuCl(P(OPh)3))3(Trz)]
yellow orange
Cu 14.56
C 52.30
H 3.70
14.50
50.19
3.64

422
J.T. Maeyer et al. / Polyhedron 22 (2003) 419ꢁ431
/
Table 2 (Continued)
Compound
Yield (%)
96
Color
% (theory)
% (experiment)
N 3.21
2.99
12.83
47.25
3.36
[(CuBr(P(OPh)3))2(Trz)]
[(CuI(P(OPh)3))3(Trz)]
orange
Cu 12.86
C 47.38
H 3.36
N 4.25
4.27
65
orange
Cu 12.04
C 43.24
H 3.06
11.77
44.00
3.34
N 2.65
2.79
was collected by filtration and discarded. The filtrate
was concentrated to 10 ml and the yellow solid product
precipitated upon addition of Et2O. The product was
collected via filtration, washed with Et2O, and then
dried under vacuum (0.521 g, 0.529 mmol, 65.3%).
the X-ray experiments and crystal data are summarized
in Table 3. Selected bond lengths and angles are given in
Table 4.
3. Results and discussion
2.3. X-ray data collection, structure soluitons and
refinements
3.1. Synthesis and characterization of products
The complexes were crystallized as follows.
[CuBr(Qnz)]: equal portions 20 mM Qnz and CuBr in
CH3CN were combined. The resulting yellow solution
was allowed to stand overnight, yielding large orange
Having previously reported the behavior of copper(I)
halides with ‘linear’ bridges, including Pyz, its benzo-
derivative, quinoxaline (Quin), and (Bpy) [1], herein is
reported the analogous coordination chemistry of the
‘bent’ bridging ligands, Pym, Qnz, Pdz, Ptz, and Trz
(Chart 1). The addition of the bridging ligand to CuX
solutions in CH3CN produced solid products within a
plate crystals.
[(CuBr(PPh3))2(Trz)],
[(CuBr(PPh3))2(Pym)],
[CuCl(PPh3)(Pdz)], and
[(CuCl(P(OPh)3))3(Trz)]: saturated solutions of the com-
plexes in CHCl3 were layered with ether in 5 mm tubes.
Crystals slowly formed over a period of 2 weeks. The
[CuCl(PPh3)(Pdz)] crystals were grown from a solution
of [(CuCl(PPh3))2(Pdz)].
few seconds to a few minutes. In the case of CuXꢀ
/
Trz
combinations, the products were soluble in CH3CN and
complete precipitation was ensured through the addition
of ether. A list of the CuXꢀ
/
B products prepared is
Crystals were mounted on glass fibers. Least-squares
refinement for all structures was carried out on F2. For
all structures except [CuBr(Qnz)], all measurements
shown in Table 1. Solutions of CuXL were formed by
addition of equimolar CuX and L in CHCl3. Subsequent
treatment with solutions of B produced solids or formed
solutions from which product could be precipitated
upon addition of ether. A list of the characterized
were made at ꢃ
ometer, equipped with a SMART APEX CCD detector.
Data for [CuBr(Qnz)] were collected at 2391 8C using a
/
1009
/
1 8C on a Bruker AXS diffract-
/
CuXLꢀ
/
B products is found in Table 2.
Mercury CCD detector coupled to a Rigaku AFC-8S
diffractometer. Initial space group determination was
based on a matrix of 60 frames. Data were collected in
10, 20, or 30 s frames. The data were reduced using
The formulations of the new compounds were deter-
mined through elemental analysis. These results were
confirmed via thermogravimetry and, where possible, X-
ray crystallography. For the phosphorus-free complexes
SAINT
ꢂ
/
[11] and empirical absorption correction ap-
of Pym, Qnz, Pdz, and Ptz, 1:1 and 2:1 CuXꢀ
/
B ratios
predominated (see Table 1). The pyrimidine species
plied using SADABS [12]. Data for [CuBr(Qnz)] were
collected and processed using CRYSTAL CLEAR [13].
Structures were solved using the Patterson method for
[(CuBr(PPh3))2(Pym)] and [(CuBr(PPh3))2(Trz)] and
direct methods for the other complexes. Rotational
twins were present for [(CuBr(PPh3))2(Trz)]. The GE-
MINI program [14] was used on 89 reflections to identify
the orientation matrices of the two twins (85 and 15%
occupancies). The non-hydrogen atoms were refined
anisotropically. Hydrogen atoms were placed in theore-
tical positions. Structure solution, refinement and the
calculation of derived results were performed using the
SHELXTL [15] package of computer programs. Details of
prepared were all novel 2:1 complexes, [(CuX)2(Pym)]
(XꢀCl, Br, I). Previously, only one Pym complex of
/
CuX had been reported [3]. This was a 1:1 Pym complex,
[CuBr(Pym)], prepared at high temperature. The closely
related Qnz ligand afforded new 1:1 products for CuCl
and CuBr, and a 2:1 product for CuI. The four
previously observed Pdz complexes [CuX(Pdz)] (Xꢀ
Cl, Br, I) and [(CuI)2(Pdz)] [3] were identified in the
current study. The closely related Ptz ligand yielded
/
three
[CuBr(Ptz)], and [(CuI)2(Ptz)]. The 3:2 ratio has not
distinct
stoichiometries,
[(CuCl)3(Ptz)2],
previously been observed in CuX complexes with

J.T. Maeyer et al. / Polyhedron 22 (2003) 419ꢁ
/431
423
Table 3
Crystal and structure refinement data
Complex
[CuBr(Qnz)]
[(CuBr(PPh3))2(Pym)]
[CuCl(PPh3)(Pdz)]2
[(CuBr(PPh3))2(Trz)]
[(CuCl(P(OPh)3))6(Trz)2]
Empirical formula
Formula weight
Temperature (8C)
Radiation
C8H6BrCuN2
273.60
23
C40H34Br2Cu2N2P2
891.53
C44H38Cl2Cu2N4P2
882.70
C39H33Br2Cu2N3P2
892.52
C116H98Cl12Cu6N6O18P6
2856.64
ꢃ
/
100
Mo Ka
(lꢀ0.71073 A)
Yellow needle
ꢃ
/
100
Mo Ka
(lꢀ0.71073 A)
yellow block
ꢃ
/
100
Mo Ka
(lꢀ0.71073 A)
yellow needle
ꢃ
/
100
Mo Ka
(lꢀ0.71073 A)
orange block
Mo Ka
˚
0.71073 A)
˚
˚
˚
˚
(lꢀ
/
/
/
/
/
Color and habit
Space group
orange platelet
Pca21 (#29)
21.752(10)
3.876(2)
9.511(5)
90
¯
P1 (#2)
¯
P1 (#2)
¯
P1 (#2)
¯
P1 (#2)
/
/
/
/
˚
a (A)
10.2411(17)
12.647(2)
14.897(3)
98.630(3)
99.884(3)
104.433(3)
1802.7(5)
2
8.4658(7)
9.3699(8)
14.3898(12)
78.967(2)
73.6040(10)
64.2990(10)
983.56(14)
1
10.4465(13)
12.1583(15)
14.7891(18)
95.289(2)
103.401(2)
101.887(2)
1768.6(4)
2
14.1489(7)
15.7470(8)
29.6572(14)
76.4330(10)
79.5120(10)
72.2260(10)
6088.5(5)
2
˚
b (A)
˚
c (A)
a (8)
b (8)
g (8)
Volume (A )
Z
rcalc (g cmꢃ3
90
90
3
˚
801.8(5)
4
2.266
)
1.642
3.517
892
1.490
1.336
452
1.676
3.586
892
1.558
1.438
2896
m(Mo Ka) (mmꢃ1
F(000)
)
7.655
528
Crystal size (mm)
Residuals: R; Rw
Goodness-of-fit
0.45ꢄ
0.095; 0.154
1.930
/
0.3ꢄ
/
0.1
a
0.3ꢄ
0.055; 0.167
1.328
/
0.05ꢄ
/
0.02
b
0.3ꢄ
0.030; 0.083
1.132
/
0.2ꢄ
/
0.1
b
0.5ꢄ
0.035; 0.087
1.023
/
0.05ꢄ
/
0.05
b
0.4ꢄ
0.039; 0.083
1.054
/
0.3ꢄ0.1
/
b
a
Rꢀ
/
R1ꢀ
a jjFojꢃ
/
a jjFojꢃ
/
jFcjj/a jFoj for observed data only. Rwꢀ
/
wR2ꢀ
/
{a [w(Fo2ꢃ
/
Fc2)2]/a [w(Fo2)2]}1/2 for all data.
b
Rꢀ
/
/
jFcjj/a jFoj for observed data only. Rwꢀ
/
{a [w(Fo2ꢃ
/
Fc2)2]/a [w(Fo2)2]}1/2 for observed data only.
bridging ligands. An X-ray structure was determined for
[CuBr(Qnz)] (see below), however none of the new 2:1 or
3:2 materials was successfully crystallized. In general,
more copper-rich materials exhibit systems of fused
The reactions of CuX with triazine provided very
complex results. Previously, it has been reported that
CuBr and CuI form both 3:1 and 2:1 complexes with Trz
[4]. These products were reproduced, with the notable
exception of [(CuI)3(Trz)]. In addition, an apparent 3:2
complex, [(CuBr)3(Trz)2], was produced. However, an
(CuX)n rings (nꢀ
[(CuCl)2(Pyz)] [16], [(CuX)2(Bpy)] (Xꢀ
[17,18], [(CuI)2(Quin)] [1], [(CuI)2(Pdz)]
[(CuX)3(Trz)] (Xꢀ
/
2 or 3), such as those found in
Cl, Br, I)
[3],
/
apparent decoupling of CuBrꢀ
/
Trz mixing stoichiometry
to product stoichiometry was noted. For example, the
/Br, I) [4], and [(CuBr)2(Trz)] [4].
Table 4
˚
Selected bond distances (A) and angles (8)
[CuBr(Qnz)]
[(CuBr(PPh3))2(Pym)]
[CuCl(PPh3)(Pdz)]2
2.0657(14)
[(CuBr(PPh3))2(Trz)]
[(CuCl(P(OPh)3))6(Trz)2]
Bond distances
a
Cuꢀ
Cuꢀ
/
N
2.116(6), 2.020(6)
2.451(2), 2.540(2)
2.050(5), 2.056(5)
2.5053(10), 2.5367(11), 2.3492(5), 2.4334(5)
2.5332(10), 2.4987(10)
2.065(2), 2.075(2)
2.0583(18)ꢁ
/
2.1058(18)
b
/X
2.4846(5), 2.5109(5),
2.5510(6), 2.5353(6)
2.2136(9), 2.2117(9)
2.8545(8), 3.0348(8)
2.3215(6)ꢁ
/
2.4297(6)
a
a
Cuꢀ
/
P
2.2100(18), 2.2075(18) 2.1902(5)
2.8193(16), 2.9342(16) 2.303
2.1544(6)ꢁ
/
2.1629(7)
Cuꢀ ꢀ ꢀCu
Bond angles
3.876(2)
(ꢀ4)
/
Xꢀ
/
Cuꢀ
Cuꢀ
/
X
101.88(6)
111.95(3), 108.72(3)
95.058(15)
110.951(16), 106.063(16)
102.85(7), 101.41(7),
99.30(7), 101.14(7)
110.41(2)ꢁ
/
113.97(2)
b
Xꢀ
/
/N
103.7(4), 97.7(4),
122.8(7), 113.8(7)
113.5(2)
102.60(14), 100.51(15), 106.62(4), 103.80(4)
101.55(14), 103.62(14)
94.07(5)ꢁ
/
98.75(5)
Nꢀ
PꢀCuꢀ
/
CuꢀN
/
b
/
/
X
107.39(6), 110.01(6),
106.78(6), 110.20(6)
124.678(18),
112.785(17)
110.51(3), 114.52(3),
105.63(3), 111.31(3)
126.77(7), 120.65(7)
69.049(16), 73.937(16)
108.31(2)ꢁ/121.53(2)
a
a
Pꢀ
Cuꢀ
/
Cuꢀ
/
N
126.37(15), 123.13(15) 111.19(4)
68.05(3), 71.28(3) 84.942(15)
121.97(5)ꢁ
/
126.42(5)
/
Xꢀ
/
Cu 101.88(6)
127.81(3)ꢁ
/
133.58(3)
a
Range of six values.
Range of 12 values.
b

424
J.T. Maeyer et al. / Polyhedron 22 (2003) 419ꢁ431
/
3:2, 2:1, and 3:1 CuBrꢀ
/
Trz products were synthesized
3.2. X-ray crystallography
from 3:1, 3:2, and 1:1 mixing ratios, respectively. Mixing
studies of CuCl with Trz provided a variety of products
exhibiting many, often ambiguous, stoichiometric ra-
tios, which also seemed unrelated to the mixing ratio.
3.2.1. [CuBr(Qnz)]
The molecular structure and sheet arrangement of
[CuBr(Qnz)] are shown in Figs. 1 and 2 and represented
schematically in Chart 2. The structure is composed of
approximately tetrahedral copper atoms linked along
the c-direction by Qnz rings and along the b-direction
by Br atoms to form infinite 2D sheets, which stack
along the a-axis to complete the structure. p-Stacking is
also evident along the b-axis. The structure can be
regarded as a series of zigzag (CuBr)ꢁ polymers, which
are cross-linked by Qnz ligands projecting alternately
above and below the plane of the sheet. In contrast to
the current structure, [CuX(Pdz)] structures are com-
posed of (CuX)2 dimer units linked together by pairs of
Pdz ligands, and [CuBr(Pym)] is composed of both
chains and dimers [3]. These arrangements are illu-
The situation for CuClꢀ
the relative instability of products toward oxidation.
All of the complexes containing LꢀPPh3 and
/Trz was further complicated by
/
P(OPh)3 were novel. Elemental analysis data confirmed
three stoichiometric ratios: [(CuXL)B] (1:1:1),
[(CuXL)2B], (2:2:1), and [(CuXL)3B] (3:3:1). Only the
products of CuIꢀ
porate B ligand. The 1:1:1 products were found in
several instances for BꢀPdz and Ptz. An example was
/
P(OPh)3ꢀ/B reactions failed to incor-
/
demonstrated by X-ray crystallography (see below) to
be a rhomboid dimer with terminal B ligands. Examples
of 2:2:1 products were obtained for all five B ligands,
but appeared to predominate for BꢀPym and Qnz.
/
These compounds were shown by X-ray to consist of 1D
chains of linked rhomboid dimers. The few 2:2:1
complexes of Pdz and Ptz that were isolated appeared
to be metastable. Thus in many cases, recrystallization
was found to produce the 1:1:1 material, along with
‘CuXL’ (which typically exists as a tetramer [19]),
according to reaction (1).
strated in Chart 2. The copperꢀ
[CuBr(Qnz)] are significantly displaced from coplanarity
with the heteroaromatic ring (10.98ꢁ16.98). The spacing
between adjacent sheets corresponds to half of the a-cell
/
nitrogen bonds in
/
˚
dimension, about 10.9 A.
3.2.2. [(CuBr(PPh3))2(Pym)],
[(CuBr(PPh3))2(Trz)]
(CuXL)2B 0 CuXLꢂ(CuXL)B
The 3:3:1 products were found only for Bꢀ
(1)
The complexes [(CuBr(PPh3))2(Pym)] and [(CuBr-
(PPh3))2(Trz)] were isostructural. Molecular structure
diagrams for these molecules are given in Figs. 3 and 4.
The complexes are composed of quasi-1D polymer
chains. This structural type is similar to that found for
2:2:1 complexes of CuBr(P(OPh)3) [1], and CuCl(PPh3)
[5], with Pyz and Bpy. Each chain is composed of
(CuL)2Br2 dimers linked by B ligands. The zigzag chains
/
Trz. A
structure of one such complex exhibited an unusual
hexameric arrangement. A unique result was the forma-
tion of an apparent 8:8:1 complex, [(CuI(PPh3))8(Qnz)].
This formulation was confirmed by elemental analysis
and thermogravimetry. Unfortunately, X-ray quality
crystals of this compound could not be grown.
Fig. 1. Molecular structure of [CuBr(Qnz)]. Thermal ellipsoids shown at 50%.

J.T. Maeyer et al. / Polyhedron 22 (2003) 419ꢁ
/431
425
Fig. 2. Sheet arrangement of [CuBr(Qnz)].
3.2.3. [CuCl(PPh3)(Pdz)]
Crystallization of
the
2:2:1
complex,
[(CuCl(PPh3))2(Pdz)] from CHCl3 and ether produced
the dimeric 1:1:1 complex, [CuCl(PPh3)(Pdz)] and color-
less crystals of [CuCl(PPh3)]4. The molecular structure
diagram for the Pdz complex is shown in Fig. 5. The
structure reveals monodentate Pdz and PPh3 ligands
distributed around a rhomboid Cu2Cl2 core. This
arrangement is commonplace in the chemistry of CuX
with monodentate ligands [20]. The molecule lies on a
crystallographic inversion center. There are no unchar-
acteristically close contacts or other unusual packing
features. This is the first reported Cu(I)ꢀ
/
Pdz structure
showing monodentate, rather than bidentate, Pdz
ligands [3,7,10].
3.2.4. [(CuCl(P(OPh)3))3(Trz)]
An X-ray structure of the 3:3:1 complex,
[(CuCl(P(OPh)3))3(Trz)] confirmed the expected stoi-
chiometry. However, instead of revealing a polymeric
structure, such as those suggested in Chart 3, the
hexameric form (Chart 3) was found. A preliminary
report of this unique structure has appeared [21]. The
molecular structure diagram is presented in Fig. 6. There
are two independent molecules located on crystallo-
graphic inversion centers in the unit cell. The oblate
spheroid molecular core is formed by a puckered 12-
membered Cu6Cl6 ring capped by two m3-triazine
ligands. The core is remarkably symmetrical, showing
D3d symmetry and consisting of seven parallel planes:
phosphorus, triazine, copper, chloride, copper, triazine
and phosphorus. These planes are parallel to one
another to within about 1.68, 2.68 (for the two indepen-
dent molecules). As is the case for [CuBr(Qnz)], the
metal atoms are displaced from the ring plane. In the
Chart 2.
run parallel to the c-axis and pack in the other
directions through molecular interactions to complete
the structures. The bulky phosphine ligands fill the space
on either side of the polymer chains. However, devia-
tions from tetrahedral angles around the copper atoms
are relatively small.

426
J.T. Maeyer et al. / Polyhedron 22 (2003) 419ꢁ431
/
Fig. 3. Molecular structure of [(CuBr(PPh3))2(Pym)]. Thermal ellipsoids shown at 50%. Hydrogen atoms omitted for clarity.
Fig. 4. Molecular structure of [(CuBr(PPh3))2(Trz)]. Thermal ellipsoids shown at 50%. Hydrogen atoms omitted for clarity.
Fig. 5. Molecular structure of [CuCl(PPh)3(Pdz)]. Thermal ellipsoids
shown at 50%. Hydrogen atoms omitted for clarity.
hexamer structure, the Cuꢀ
/
N bonds form angles of
9.68ꢁ16.98 with the triazine planes. The six copper
/
atoms form a trigonally distorted octahedron, as do
the six nitrogen and the six phosphorus atoms, respec-
tively. The ‘top’ and ‘bottom’ Cu3 planes are separated
Chart 3.
˚
by only 2.654, 2.610 A; other pairings of Cu3 planes lie
˚
about 4.63 A apart. A central void, roughly 7.3 A across
˚
by 3.0 A high, is apparent in space filling projection of
the hexamer core. Presumably, a combination of the
˚
trigonal templating effect of the triazine molecules and
size of the triphenyl phosphite ligands results in the
formation of a compact core with peripheral phosphites.

J.T. Maeyer et al. / Polyhedron 22 (2003) 419ꢁ
/431
427
Fig. 6. Molecular structure of [(CuCl(P(OPh)3))3(Trz)]. Thermal ellipsoids shown at 50%. Phenyl rings and hydrogen atoms omitted for clarity.
percentage following formation of CuX remains essen-
tially constant, regardless of the original source.
The results of TGA for complexes without L are
provided in Table 5 and several representative TGA
traces are shown in Figs. 8 and 9. The 1:1 complexes all
showed an initial mass loss corresponding to loss of half
an equivalent of B ligand. This loss occurred at modest
temperatures, commencing at about 100ꢁ140 8C, and
/
resulted in a stoichiometry (CuXB1/2), which corre-
sponds well to that of the 2:1 complexes, (CuX)2B. In
the 185ꢁ205 8C range, the 2:1 intermediates further
/
decomposed to form CuX. Similar behavior has been
observed for Pyz and Bpy complexes [1,17,22]. Although
shallow plateaus suggest the possible existence of
metastable intermediate phases, [(CuX)4(Pdz)] (XꢀCl,
/
Br), careful studies of Bpy complexes by Nather et al.
[17] have afforded no evidence for such 4:1 species. The
overall sequence for the 1:1 complexes is illustrated by
reactions (2) and (3).
Fig. 7. Thermogravimetric mass loss profiles of CuX (XꢀCl, Br, I).
/
Triazine templating is also evident in the channelled
structure of [(CuBr)2(Trz)] [4].
CuXB 0 1=2 (CuX)2Bꢂ1=2 B
(CuX)2B 0 2CuXꢂB
(2)
(3)
3.3. Thermogravimetry
In general, the TGA results for the 2:1 complexes of
the bidentate B ligands reflected decomposition steps
corresponding to the later stages of the 1:1 sequence
(reaction (3)). Thus, the TGA results for [(CuI)2(Pdz)]
were roughly identical to those of [CuI(Pdz)] following
the initial loss of 1/2 equiv. of Pdz (Fig. 8). Also
consistent with Eq. (3), most of the 2:1 complexes
TGA (58 minꢃ1, 25ꢁ
proved to be a very effective tool for confirming the
stoichiometry of CuXꢀB complexes, as well as aiding in
the identification of metastable, more copper-rich
phases [1,17,22]. For comparison purposes, the thermal
behavior of the CuX salts was examined (see Fig. 7). The
TGA decomposition of these materials does not produce
copper metal or other identifiable material. The final
mass percent (6% for CuCl, 9% for CuBr, and 42% for
CuI) lies between that of CuX and Cu, suggesting a
probable mixture of the two. Nevertheless, the mass loss
/
900 8C, 40 ml minꢃ1 N2) has
/
decomposed directly to CuX, beginning 125ꢁ220 8C.
/
The thermal behavior of the unique complex
[(CuCl)3(Ptz)2] was complicated. However, possible
intermediates [(CuCl)2(Ptz)] and [(CuCl)3(Ptz)] were
suggested by the data. The 3:20
/
2:10/3:1 sequence is

428
J.T. Maeyer et al. / Polyhedron 22 (2003) 419ꢁ431
/
Table 5
Thermogravimetric decomposition results for CuXꢀ
/B complexes
Complex
Temperature (8C)
Product
wt.% (theory)
wt.% (actual)
[(CuCl)2(Pym)]
[(CuBr)2(Pym)]
[(CuI)2(Pym)]
[CuCl(Qnz)]
135ꢁ
145ꢁ
155ꢁ
135ꢁ
205ꢁ
140ꢁ
195ꢁ
170ꢁ
100ꢁ
185ꢁ
230ꢁ
120ꢁ
195ꢁ
260ꢁ
110ꢁ
200ꢁ
170ꢁ
130ꢁ
235ꢁ
205ꢁ
245ꢁ
220ꢁ
110ꢁ
160ꢁ
120ꢁ
175ꢁ
90ꢁ
145ꢁ
175ꢁ
105ꢁ
165ꢁ
75ꢁ
150ꢁ
125ꢁ
/
210
255
235
205
260
195
270
265
185
230
425
195
260
470
200
250
250
235
305
245
315
310
160
230
175
250
150
175
250
165
220
150
235
200
CuCl
CuBr
CuI
71
78
83
72
43
76
52
75
78
66
55
82
73
64
85
70
83
88
77
76
71
78
83
73
46
77
54
75
78
69
55
83
74
68
83
71
83
89
75
81
70
86
90
72
96
77
94
89
77
93
79
95
82
82
/
/
/
[(CuCl)2(Qnz)]
CuCl
/
[CuBr(Qnz)]
/
[(CuBr)2(Qnz)]
CuBr
/
[(CuI)2(Qnz)]
[CuCl(Pdz)]
/
CuI
/
[(CuCl)2(Pdz)]
[(CuCl)4(Pdz)]?
CuCl
/
/
[CuBr(Pdz)]
[CuI(Pdz)]
/
[(CuBr)2(Pdz)]
[(CuBr)4(Pdz)]?
CuBr
/
/
/
[(CuI)2(Pdz)]
CuI
/
[(CuI)2(Pdz)]
/
CuI
[(CuCl)3(Ptz)2]
/
[(CuCl)2(Ptz)]
[(CuCl)3(Ptz)]
[(CuBr)2(Ptz)]
??
/
[CuBr(Ptz)]
/
/
[(CuI)2(Ptz)]
[(CuCl)2(Trz)]
/
[(CuI)4(Ptz)]?
[(CuCl)3(Trz)]
CuCl
87
91
71
95
79
97
92
78
93
78
92
84
82
/
/
[(CuCl)3(Trz)]
[(CuBr)3(Trz)2]
/
[(CuCl)4(Trz)]?
CuCl
/
/
[(CuBr)2(Trz)]
[(CuBr)3(Trz)]
CuBr
/
/
[(CuBr)2(Trz)]
[(CuBr)3(Trz)]
[(CuI)2(Trz)]
/
[(CuBr)3(Trz)]
CuBr
/
/
[(CuBr)6(Trz)]?
CuBr
/
/
CuI
Fig. 8. Thermogravimetric mass loss profiles of selected Pym, Qnz,
and Pdz complexes.
Fig. 9. Thermogravimetric mass loss profiles of selected Trz com-
plexes.

J.T. Maeyer et al. / Polyhedron 22 (2003) 419ꢁ
/431
429
Table 6
Thermogravimetric decomposition results for CuXꢀ
/
LꢀB complexes
/
Complex
Temperature (8C)
Product
wt.% (theory)
wt.% (actual)
[(CuCl(PPh3))2(Pym)]
115ꢁ
245ꢁ
75ꢁ
175ꢁ
145ꢁ
255ꢁ
105ꢁ
210ꢁ
100ꢁ
190ꢁ
120ꢁ
195ꢁ
160ꢁ
210ꢁ
120ꢁ
170ꢁ
125ꢁ
135ꢁ
115ꢁ
180ꢁ
65ꢁ
130ꢁ200
260ꢁ
70ꢁ
110ꢁ
200ꢁ
45ꢁ
85ꢁ
145ꢁ
220ꢁ
180ꢁ
210ꢁ
245ꢁ
165ꢁ
200ꢁ
260ꢁ
60ꢁ
130ꢁ260
165ꢁ
135ꢁ
115ꢁ
240ꢁ
120ꢁ
165ꢁ
40ꢁ
170ꢁ290
65ꢁ
185ꢁ
30ꢁ
150ꢁ
/
175
355
175
380
170
325
210
350
190
280
195
350
210
340
170
325
280
285
180
400
[(CuCl(PPh3))8(Pym)]?
CuCl
98
25
96
32
92
39
91
22
92
29
85
23
86
31
96
41
21
28
90
24
92
84
30
92
85
36
20
27
85
23
88
76
27
89
78
33
97
28
95
30
92
40
91
23
91
32
88
24
85
31
96
42
24
30
92
25
94
79
31
92
88
35
24
32
86
25
87
77
33
88
75
36
94
43
43
28
91
37
91
39
94
23
91
32
94
38
/
[(CuBr(PPh3))2(Pym)]
[(CuI(PPh3))2(Pym)]
[(CuCl(P(OPh)3))2(Pym)]
[(CuBr(P(OPh)3))2(Pym)]
[(CuCl(PPh3))2(Qnz)]
[(CuBr(PPh3))2(Qnz)]
[(CuI(PPh3))8(Qnz)]
/
[(CuBr(PPh3))4(Pym)]?
CuBr
/
/
[CuI(PPh3)]
CuI
/
/
[CuCl(P(OPh)3)]
CuCl
/
/
[CuBr(P(OPh)3)]
CuBr
/
/
[CuCl(PPh3)]
CuCl
/
/
[CuBr(PPh3)]
CuBr
/
/
[CuI(PPh3)]
CuI
/
[(CuCl(P(OPh)3))2(Qnz)]
[(CuBr(P(OPh)3))2(Qnz)]
[(CuCl(PPh3))2(Pdz)]
/
CuCl
CuBr
/
/
[CuCl(PPh3)]
CuCl
/
[CuBr(PPh3)(Pdz)]
[CuI(PPh3)(Pdz)]
/
95
[(CuBr(PPh3))2(Pdz)]
[CuBr(PPh3)]
CuBr
/
/
370
110
160
380
280
265
220
360
210
245
340
200
260
320
/
[(CuI(PPh3))2(Pdz)]
[CuI(PPh3)]
CuI
/
/
[CuCl(P(OPh)3)(Pdz)]
[CuBr(P(OPh)3)(Pdz)]
[(CuCl(PPh3))2(Ptz)]
/
CuCl
CuBr
/
/
[CuCl(PPh3)]
CuCl
/
[CuBr(PPh3)(Ptz)]
[CuI(PPh3)(Ptz)]
/
[(CuBr(PPh3))2(Ptz)]
[CuBr(PPh3)]
CuBr
/
/
/
[(CuI(PPh3))2(Ptz)]
[CuI(PPh3)]
CuI
/
/
[CuCl(P(OPh)3)(Ptz)]
/90
??
/
??
[(CuBr(P(OPh)3))2(Ptz)]
[(CuCl(PPh3))3(Trz)]
[(CuBr(PPh3))2(Trz)]
/
280
390
150
370
165
440
[(CuBr)2(Ptz)]
CuCl
40
25
91
32
92
39
94
23
92
29
95
36
/
/
[CuBr(PPh3)]
CuBr
/
[(CuI(PPh3))2(Trz)]
/
[CuI(PPh3)]
CuI
/
[(CuCl(P(OPh)3))3(Trz)]
[(CuBr(P(OPh)3))2(Trz)]
[(CuI(P(OPh)3))3(Trz)]
/90
[CuCl(P(OPh)3)]
CuCl
/
/
185
275
150
255
[CuBr(P(OPh)3)]
CuBr
/
/
[CuI(P(OPh)3)]
CuI
/
[(CuX)3(Trz)2] 0 3=2 [(CuX)2(Trz)]ꢂ1=2 Trz
[(CuX)2(Trz)] 0 2=3 [(CuX)3(Trz)]ꢂ1=3 Trz
[(CuX)3(Trz)] 0 3CuXꢂTrz
(4)
(5)
(6)
similar that of [(CuBr)3(Trz)2], shown below in Eqs. (4)
and (5).
The TGA data for the phosphorus-free complexes of
the Trz (Fig. 9) proved useful in supporting elemental
analysis data. A 3:2 complex, [(CuBr)3(Trz)2], showed
decomposition steps corresponding to those shown in
Similarly, the behavior of the isolated 2:1 complexes was
consistent with Eqs. (5) and (6). The isolated 3:1
Eqs. (4)ꢁ/(6).
materials (XꢀCl, Br) decomposed to form CuX (reac-
/

430
J.T. Maeyer et al. / Polyhedron 22 (2003) 419ꢁ431
/
tion (6)), but also showed evidence of shallow plateaus,
possibly corresponding to more copper-rich stoichiome-
tries.
Acknowledgements
We gratefully acknowledge support from the Henry
Dreyfus Teacher-Scholar Awards Program of the Ca-
mille and Henry Dreyfus Foundation (TH-99-010), the
Petroleum Research Fund of the American Chemical
Society (32226-B3), and the Thomas F. and Kate Miller
Jeffress Memorial Trust (J-440). We also acknowledge
the following partial support: a Verizon Summer
Research Fellowship (B.D.B.) and a semester research
assignment from the College of William & Mary
(R.D.P.). We are indebted to NSF (CHE-9808165) and
Clemson University for the purchase of CCD diffract-
ometer (W.T.P. and M.K.).
Thermogravimetry of complexes bearing Lꢀ
and P(OPh)3 suggested that the dimeric 1:1:1 species,
[(CuXL)B] (BꢀPdz, Ptz), usually underwent the se-
quence of reactions (7)ꢁ(9). The data are summarized in
Table 6. However, when LꢀP(OPh)3, intermediates
were not usually seen.
/
PPh3
/
/
/
(CuXL)B 0 1=2 (CuXL)2Bꢂ1=2 B
(CuXL)2B 0 2CuXLꢂB
CuXL 0 CuXꢂL
(7)
(8)
(9)
The 1:1:1 complex of CuClꢁ
/
P(OPh)3ꢁ/Ptz yielded TGA
traces that were not readily interpretible. As would be
expected, the 2:2:1 complexes, [(CuXL)2B] (BꢀPym,
/
Qnz, Pdz, Ptz, Trz), typically degraded according to
reactions (8) and (9). In two cases, shallow plateaus
References
corresponded
[(CuX(PPh3))4(Pym)] (Xꢀ
to
possible
metastable
species
Cl, Br) during step (8) de-
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/
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