The structure of the red form of Pt(bpy)Cl_2 (bpy = 2,2‘-bipyridine) has been studied by variable-temperature X-ray crystallography. The stack of square-planar Pt(bpy)Cl_2 units in the linear-chain material contracts with decreasing temperature; in the interval between 294 and 20 K, the platinum−platinum distance shortens from 3.449(1) to 3.370(2) Å. Both absorption and emission spectra of the red compound depend strikingly on temperature; as previously found for tetracyanoplatinate salts, the emission maximum red-shifts as the temperature drops (613 nm at 300 K; 651 nm at 10 K), with the peak energy decreasing linearly with the inverse cube of the metal−metal separation

Connick, William B.

Gray, Harry B.

Henling, Lawrence M.

Marsh, Richard E.

Caltech Authors - Main

Inorg. Chem., 1996, 35(21), 6261-6265, DOI:10.1021/ic960511f
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Copyright © 1996 American Chemical Society
C1996 American Chemical Society Inorganic Chemistry V35 Page 6261 Connick Supplemental Page 1
Table 1. Crystal and-Intensity Collection Data for
Pt(bpy)C12 at 298 K
Formula: C 1 0 C12 N 2 H8 Pt Formula weight:
Crystal color: Red Habit: Diamond-
Crystal Size: 0.10 x 0.11 x 0.23 mm pcj. = 2.57 g cm
Crystal System: Orthorhombic Space group: Cm
a = 17.669(5) A
b = 9.081(2) A
c = 6.804(2) A
V = 1091.7(5) A3  Z=4
Lattice parameters: 29 reflections 9.50 <0 < 10.50
p. = 134.5 cm- 1  Tansmission co
Variable-temperature P! diffractometer 0 - 20 scan
MoKa, A = 0.7107A Graphite mono
20 range: 20-600 -24 < h < 21,-
T = 294K
Number of reflections measured: 6993 Number of idei
Number with FO > 0: 868 Number with F.
Standard reflections: 3 every 97 data Variation: within
GOFmerge: 1.06 for 877 multiples Rmerge: 0.018 fo
Number used in refinement: 880 Criterion: All r~
Final R: 0.029 for 804 reflections with F 2 > 3o(F2)
Final R: 0.033 for 868 reflections with F.
Final weighted R: 0.067
Final HOF: 1.74 for 48 parameters and 880 reflections
.0in final least squares cycle: <0.01
Apmax: 1.2 eA-3 , Apmi: -1.7 eAT3 in final disference map
SecondaVy extinction parameter: 1.09(4) x 10w
shaped needle
-3
cm (no. 63)
fE. = 0.70 - 1.27
iromator
12 < k < 12, -9 < 1 < 9
endent reflections: 880
> 3o-(F ): 804
n counting statistics
r 97 duplicates
flections used
S
VI990 American fiemical Society Inorganic uthemistry V. D Iage 6261 onmick Supplemental Iage 2
Table 2. Final Heavy Atom Parameters for
Platinum (Bipyridyl)- bis-Chloride at 294 K
z,y,z and U, x 10"
Atom z Y z Ug
Pt 0 -313(.5) 2500 261(1)
Cl 914(1) -2119(3) 2500 452(5)
N 732(3) 1380(7) 2500 293(14)
C(1) 1494(5) 1258(10) 2500 455(22)
C(2) 1944(5) 2503(14) 2500 623(29)
C(3) 1625(6) 3863(13) 2500 646(30)
C(4) 850(6) 3974(10) 2500 527(27)
C(5) 408(4) 2729(9) 2500 343(18)
a != 1 .did
VI990 American Liemical Society Inorganic utiemistry V33 Fage 6261 onmick Supplemental Iage j
Table 3. Assigned Hydrogen Atom Parameters for
Platinum (Bipyridyl)- bi-Chloride at 294 K
X, y and z x 10"
Atom a Y z B
H(1) 1721 310 2500 4.1
H(2) 2480 2406 2500 5.7
H(3) 1932 4722 2500 5.9
H(4) 617 4917 2500 4.8
53
.... .... 
VI990 American fiemical Society Inorganic uthemistry V. D Iage 6261 onmick Supplemental Iage 4
Table 4. Heavy Atom Anisotropic Displacement Parameters for
Platinum(Bipyridyl)-bis-Chloride at 294 K
Atom Un1 U 2 2 U 3 3 U 1 2 U 1 3 U 2 3
Pt
Cl
N
C(1)
C(2)
C(3)
C(4)
C(5)
295(2)
529(12)
335(30)
305(38)
360(47)
552(58)
586(55)
419(42)
184(2)
302(11)
189(30)
381(52)
753(84)
469(65)
218(42)
241(40)
303('2)
524(14)
354(35)
678(64)
757(79)
918(89)
777(75)
369(44)
0
158(9)
-58(24)
-26(34)
-215(50)
-265(50)
-115(41)
-14(31)
0
0
0
0
0
0
0
0
Uij values have been multiplied by 10"
The form of the displacement factor is:
exp -27r2(Uih 2a* + U2 2 k2b*2 + U3 3 1 2c* + 2Ui2 hka*b* + 2Uk3 hla*c*
0
0
0
0
0
0
0
0
+ 2Uz ktb*c*)
Si'
VI990 American fiemical Society Inorganic uthemistry V33 Fage 6261 onmick Supplemental Page D
Table 5. Complete Distances and Angles for
Platinum (Bipyridyl)- bi-Chloride at 294 K
Pt -N
Pt -Cl
N -C(1)
N -C(5)
C(1) -C(2)
C(1) -H(1)
C(2) -C(3)
C(2) -H(2)
C(3) -C(4)
C(3) -H(3)
C(4) -0(5)
C(4) -H(4)
C(5) -C(5)'
Distance(A)
2.009(6)
2.302(2)
1.350(10)
1.352(10)
1.383(14)
0.950
1.358(15)
0.950
1.374(15)
0.950
1.373(12)
0.950
1.442(11)
Angle(')
N -Pt -Cl
N -Pt -N'
N -Pt -Cl'
Cl -Pt -Cl'
Pt -N -C(1)
Pt -N -C(5)
C(5) -N -0(1)
C(2) -C(1) -N
H(1) -C(1) -N
H(1) -C(1) -C(2)
C(3) -C(2) -C(1)
H(2) -C(2) -C(1)
H(2) -C(2) -C(3)
C(4) -C(3) -C(2)
H(3) -C(3) -C(2)
H(3) -C(3) -C(4)
C(5) -C(4) -C(3)
H(4) -C(4) -C(3)
H(4) -C(4) -C(5)
C(4) -C(5) -N
C(5)' -C(5) -N
C(5)' -C(5) -C(4)
Symmetry code: (') -Z, y, z
S5
95.4(2)
80.2(2)
175.5(2)
89.1(1)
125.4(5)
114.9(5)
119.8(7)
120.5(8)
119.8
119.8
120.3(10)
119.9
119.9
118.8(10)
120.6
120.6
120.4(9)
119.8
119.8
120.3(8)
115.1(7)
124.6(8)
(G1996 American Chemical Society Inorganic Chemistry V35 Page 6261 Connick Supplemental Page 6
Table 6. Intermolecular Distances Less
Platinum(Bipyridyl)- bi-Chloride
Distance(A)
Pt -Pt
Pt -N
Cl -C(3)
01 -C(4)
Cl -H(3)
Cl -H(4)
Cl -C(2)
Cl -H(2)
01 -H(4)
01 -N
01 -C(1)
01 -C(2)
01 -C(3)
01 -C(4)
01 -C(5)
C(1) -C(3)
C(1) -H(2)
C(1) -H(3)
C(1) -H(1)
C(2) -C(2)
C(2) -H(2)
C(2) -H(1)
C(2) -H(3)
C(3) -H(2)
C(3) -H(1)
C(3) -H(2)
C(3) -C(3)
C(3) -H(3)
C(3) -H(4)
C(4) -C(4)
C(4) -H(4)
H(1) -H(2)
H(1) -H(3)
H(1) -H(1)
H(2) -H(2)
H(2) -H(3)
H(3) -H(3)
H(4) -H(4)
Than 4.0 A for
at 294 K
3.4492(6)
3.766(6)
3.859(11)
3.550(10)
3.387
2.742
3.800(11)
2.871
3.816
3.482(6)
3.638(9)
3.875(11)
3.957(11)
3.798(10)
3.561(8)
3.973(14)
3.941
3.112
3.710
3.928(15)
3.552
3.473
3.212
3.925
3.204
3.585
3.980(15)
3.677
3.997
3.879(13)
3.572
2.991
2.439
3.448
3.407
2.650
3.439
3.405
LI)
Figure la. An ORTEP drawing of 10 
molecules with a unit cell outlined; atoms 
are
shown as 50% probablilitY ellipsoids; 
HI atoms are not shown. View is in 
bc plane
(projection down a).
C(G-Oy x CO-Ooeco-OD CG-OGE
Figure lb. An ORTEP drawing of 10 molecules with a 
unit cell outlined; atoms are
shown as 50% probablility ellipsoids; H atoms are 
not shown. View is in ac plane
(projection down b).
7\ZKk>
i,1 4,01ic-1-014,0D
-0-0 O-GeeoBD 01----
CTCz
Figure 1c. An ORTEP drawing of 10
molecules with a unit cell outlined; atoms
are shown as 50% probablility ellipsoids; H
atoms are not shown. View is in ab plane
(projection down c).
UI990 American fiemical Society Inorganic uthemistry V. D Iage 6261 onmick Supplemental Iage iu
Table 7. Crystal and Intensity Collection Data for
Pt(bpy)C12 at 20 K
Formula: Co 0Cl2 N2 H 8 Pt Formula weight: 
422.17
Crystal color: Red Habit: Diamond-shaped 
needle
Crystal Size: 0.10 x 0.11 x 0.23 mm Peal = 2.65 g cm-
3
Crystal System: Orthorhombic Space group: Cmcm (no. 63)
a = 17.598(10) A
b = 9.059(4) A
c = 6.643(3) A
V = 1059.0(9) A3  Z=4
Lattice parameters: 28 reflections 9.5- < 0 <10.50
P = 138.6 cm 1  Transmission coeff. = 0.70 - 1.27
Variable-temperature P! diffractometer 0 - 20 scan
MoKa, A = 0.7107, Graphite monochromator
20 range: 2-81.00 -32 < h < 29,-16 < k < 16,-12 
< 1 < 12
T = 20 K
Number of reflections measured: 7503 Number of independent reflections: 
1844
Number with F2 > 0: 1797 Number with F > 3o-(F ): 1714
Standard reflections: 3 every 97 data Variation: within counting 
statistics
GOFmerge: 1.30 for 1840 multiples Rmerge: 0.026 for 
174 duplicates
Number used in refinement: 1844 Criterion: All reflections used
Final R: 0.032 for 1714 reflections with F2 > 3o(F2)
Final R: 0.034 for 1797 reflections with F2 > 0
Final weighted R: 0.077
Final GOF: 2.19 for 48 parameters and 1844 reflections
(AX/o-)maz in final least squares cycle: < 0.01
Apmax: 4.3 eA~3 , Apmin: -4.3 eA-
3 in final difference map
Secondary extinction parameter: 1.28(4) x 10~'
510
( 1996 American Chemical Society Inorganic Chemistry V35 Page 6261 Connick Supplemental Page 11
Table 8. Final Heavy Atom Parameters for
Platinum (Bipyridyl)- bis-Chloride at 20 K
M, y, z and U,,' x 10'
Atom x y z
Pt 0 -314(.3) 2500 32(1)
Cl 921(1) -2127(1) 2500 70(2)
N 739(2) 1384(4) 2500 47(7)
C(1) 1501(3) 1273(6) 2500 93(7)
C(2) 1966(3) 2503(6) 2500 91(8)
C(3) 1638(3) 3889(6) 2500 94(8)
C(4) 850(3) 4016(6) 2500 84(7)
C(5) 415(3) 2746(5) 2500 66(9)
a~ j Ej Z[Uii (a a ) (a'i -d.
SO'
(G1996 American Chemical Society Inorganic Chemistry V35 Page 6261 Connick Supplemental Page 12
Table 9. Assigned Hydrogen Atom Parameters for
Platinum (Bipyridyl)- bij- Chloride at 20 K
z, y and z x 104
Atom x Y z B
H(1) 1726 320 2500 0.8
H(2) 2503 2397 2500 0.8
H(3) 1947 4748 2500 0.9
H(4) 615 4960 2500 0.8
5191
(G1996 American Chemical Society Inorganic Chemistry V35 Page 6261 Connick Supplemental Page 13
Table 10. Heavy Atom Anisotropic Displacement Parameters for
Platinum (Bipyridyl)- bis- Chloride at 20 K
Atom Ui1 U 2 2 U33 U 1 2 U 1 3 U 2 3
Pt
Cl
N
C(1)
C(2)
C(3)
C(4)
C(5)
42(1)
86(4)
68(13)
85(16)
57(15)
92(17)
89(16)
56(14)
14(1)
47(4)
22(13)
76(17)
101(19)
63(17)
56(16)
27(15)
39(1)
76(4)
51(14)
118(19)
114(19)
126(19)
107(18)
114(18)
0
13(3)
-9(10)
1(13)
-21(13)
-13(13)
-8(14)
-1(12)
0
0
0
0
0
0
0
0
Uii values have been multiplied by 104
The form of the displacement factor is:
exp -27r2 (Uih 2 a* + U 2 2 k2b*2 + U3 3 2c*2 + 2Ul2hka*b* + 2Uiahta*c*
0
0
0
0
0
0
0
0
+ 2U23kib*c*)
si5
vi o American onemicai 3ociety inorganic enemistry V ID rage OZOI k LOnmCK 3uppiemental rage 14
Table 11. Complete Distances and Angles for
Platinum (Bipyridyl)- bi-Chloride at 20 K
Distance(l) Angle(o)
Pt -Cl
Pt -N
N -C(1)
N -C(5)
C(1) -C(2)
C(1) -H(1)
C(2) -C(3)
C(2) -H(2)
C(3) -C(4)
C(3) -H(3)
C(4) -C(5)
C(4) -H(4)
C(5) -C(5)'
2.308(1)
2.015(4)
1.343(6)
1.360(6)
1.383(7)
0.950
1.382(7)
0.950
1.391(7)
0.950
1.382(7)
0.950
1.459(6)
N -Pt -Cl
N -Pt -N'
N -Pt -Cl'
C -Pt -CP
Pt -N -C(1)
Pt -N -C(5)
C(1) -N -C(5)
C(2) -C(1) -N
H(1) -C(1) -N
H(1) -C(1) -C(2)
C(3) -C(2) -C(1)
H(2) -C(2) -C(1)
H(2) -C(2) -C(3)
C(4) -C(3) -C(2)
H(3) -C(3) -C(2)
H(3) -C(3) -C(4)
C(5) -C(4) -C(3)
H(4) -C(4) -C(3)
H(4) -C(4) -C(5)
C(4) -C(5) -N
C(5)' -C(5) -N
C(5)' -C(5) -C(4)
Symmetry code: (') -X, y, z
514
95.2(1)
80.5(2)
175.6(1)
89.2(1)
125.9(3)
114.9(3)
119.2(4)
122.0(5)
119.0
119.0
119.0(5)
120.5
120.5
119.4(5)
120.3
120.3
118.9(4)
120.5
120.5
121.5(4)
114.9(4)
123.7(4)
(G1996 American Chemical Society Inorganic Chemistry V35 Page 6261 Connick Supplemental Page 15
Table 12. Intermolecular Distances Less Than 4.0 A for
Platinum (Bipyridyl)- bia- Chloride at 20 K
Distance(K)
Pt -Pt
Pt -N
01 -C(3)
Cl -C(4)
01 -H(3)
C1 -H(4)
Cl -C(2)
01 -H(2)
C1 -H(4)
Cl -N
Cl -C(1)
Cl -C(2)
C1 -C(3)
01 -C(4)
Cl -C(5)
C1 -H(1)
C(1) -H(2)
C(1) -C(3)
C(1) -H(2)
C(1) -H(3)
C(1) -H(1)
C(2) -C(2)
C(2) -H(2)
C(2) -H(3)
C(2) -H(1)
C(3) -H(2)
C(3) -H(1)
C(3) -H(2)
C(3) -C(3)
C(3) -H(3)
C(3) -H(4)
C(4) -C(4)
C(4) -H(4)
C(5) -H(4)
H(1) -H(2)
H(1) -H(3)
H(1) -H(1)
H(2) -H(2)
H(2) -H(3)
H(2) -H(3)
H(2) -H(4)
3.3697(3)
3.697(4)
3.823(5)
3.497(5)
3.358
2.693
3.734(5)
2.807
3.778
3.404(4)
3.560(5)
3.812(5)
3.895(5)
3.738(5)
3.484(5)
3.965
3.945
3.924(7)
3.924
3.061
3.643
3.817(7)
3.452
3.145
3.437
3.831
3.158
3.520
3.884(7)
3.585
3.919
3.770(7)
3.474
3.934
2.975
2.391
3.372
3.327
3.968
2.588
3.981
Distance(A)
H(3) -H(3)
H(4) -H(4)
H(4) -H(4)
3.353
3.965
3.322
I 2
(r
(O-~---o - (7-,'
Figure oa. An ORTEP drawing of 10 molecules with 
a unit cell outlined atoms are
shown as 50% probablility ellipsoids; atoms are not 
shown. View is in bc Plane
(projection down a).
-C--UIJ---O)
(r
Figure 2b. An ORTEP drawing of 10 molecules with a unit cell outlined; atoms are
shown as 50% probablility ellipsoids; H atoms are not shown. View is in ac plane
(projection down b).
-1
C--E-;D-Ci--- -I-, --CG-O
I
cU'
Figure 2c. An ORTEP drawing of 10
molecules with a unit cell outlined; atoms
are shown as 50% probablility ellipsoids; H
atoms are not shown. View is in ab plane
(projection down c).
Pt-Pt Distance vs. Temperature
* -all Pt-Pt distances (quadratic fit)
(error bars derived +/- esd;
estimated from cell esd)
(4 distances from structures;
6 calculated from unit cell
determinations)
I
Y - MO + M1*x + ... M8*x 8 + M9*x9
MO 3.3657
Ml 0.00016989
M2 3.7211e-07
R 0.99857
Pt*..Pt= 3.3657 + 0.00016989(T) +3.7211e-7 (T)2
-I I I I I I 
I I
50 100 150 200
Temperature (K)
3.46
3.44
(p
0
U
1'
I'
3.42
3.4
3.38
3.36
0 250 300


Emission Spectroscopic Properties of the Red Form of Dichloro(2,2‘-bipyridine)platinum(II). Role of Intermolecular Stacking Interactions

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Emission Spectroscopic Properties of the Red Form of Dichloro(2,2‘-bipyridine)platinum(II). Role of Intermolecular Stacking Interactions

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