Acta Cryst.(2003). E59, m1041±m1043 DOI: 10.1107/S1600536803023304 Christian NaÈtheret al. [Cu2I2(C2H3N)2(C18H15O3P)2]
m1041
metal-organic papers
Acta Crystallographica Section E Structure Reports Online
ISSN 1600-5368
Di-
l
-iodo-bis[(acetonitrile-
j
N
)(triphenyl-phosphite-
j
P
)copper(I)]
Christian NaÈther,* Tobias Steinhoff and Inke Jeû
Institut fuÈr Anorganische Chemie, Christian-Albrechts-UniversitaÈt Kiel, Olshausenstraûe 40, D-24098 Kiel, Germany
Correspondence e-mail: cnaether@ac.uni-kiel.de
Key indicators
Single-crystal X-ray study
T= 293 K
Mean(C±C) = 0.004 AÊ
Rfactor = 0.026
wRfactor = 0.066
Data-to-parameter ratio = 16.6
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2003 International Union of Crystallography Printed in Great Britain ± all rights reserved
In the title compound, [Cu2I2(C2H3N)2(C18H15O3P)2], (CuI)2
rings are found in which each Cu atom is coordinated by one triphenylphosphite ligand and one acetonitrile ligand within a slightly distorted tetrahedron. All atoms are located in general positions and the (CuI)2 rings are located on centres of
inversion. In the crystal structure, the Cu and I atoms are packed in a layer-like arrangement.
Comment
We are interested in the synthesis, crystal structure and thermal properties of coordination polymers built up of copper(I) halides and aromatic N-donor ligands. For one speci®c copper(I) halide and one speci®c N-donor ligand several compounds of different stoichiometry are observed. We have found that most of the amine-rich coordination polymers can be transformed into new amine-poorer coord-ination polymers by a well directed thermal decomposition (NaÈther & Jeû, 2002, 2003; NaÈther, Greve & Jeû, 2002; NaÈther, Wriedt & Jeû, 2002). To continue this work, we have started investigations on ternary coordination polymers based on copper(I) halides, N-donor ligands and triphenylphosphite. Some of these compounds with CuCl and CuBr have been investigated (Grahamet al., 2000; Pikeet al., 1999, 2002), but with copper(I) iodide, no compounds have been structurally characterized. During our own investigations on such coord-ination polymers we have isolated crystals of the title compound, (I).
In the structure of (I), (CuI)2-four-membered coplanar
rings are found in which the copper cations are connected by the iodide anions via 2 coordination. Each Cu atom is
coordinated by two I atoms, one P atom of the triphenyl-phosphite ligand and one N atom of the acetonitrile ligand, forming discrete molecular complexes. All atoms are located in general positions and the (CuI)2rings are located on centres
of inversion. The CuÐI bond lengths of 2.6427 (4) and 2.6477 (4) AÊ, the CuÐN bond length of 2.018 (2) AÊ and the
metal-organic papers
m1042
Christian NaÈtheret al. [Cu2I2(C2H3N)2(C18H15O3P)2] Acta Cryst.(2003). E59, m1041±m1043CuÐP bond length of 2.2011 (7) AÊ are in the normal ranges for related compounds retrieved from the Cambridge Struc-tural Database (Allen, 2002). The coordination of the Cu atoms can be described as slightly distorted tetrahedra, with
XÐCuÐX angles (X = I, N, P) between 106.68 (8) and 113.93 (2).
In the crystal structure, the (CuI)2rings are stacked in the
direction of the crystallographiccaxis. The Cu and I atoms are arranged in layers, which are parallel to the ac plane. In contrast to the previously reported compounds with CuBr, and 4,40-bipyridine or pyrazine (Grahamet al., 2000), which
are polymeric, the title compound forms only discrete mole-cular complexes because the acetonitrile ligand cannot bridge different Cu atoms.
Experimental
The title compound was prepared by the reaction of 189.9 mg (1 mmol) CuI and 0.263 ml (1 mmol) triphenylphosphite in about 2 ml acetonitrile in a glass container. After about 4 d, large colourless crystals had grown which decompose in air within a few hours.
Crystal data
[Cu2I2(C2H3N)2(C18H15O3P)2]
Mr= 1083.53 Monoclinic,P21=c
a= 9.0239 (6) AÊ
b= 30.1204 (16) AÊ
c= 8.4220 (5) AÊ
= 112.139 (7)
V= 2120.4 (2) AÊ3
Z= 2
Dx= 1.697 Mg mÿ3 MoKradiation Cell parameters from 8000
re¯ections
= 14±23 = 2.58 mmÿ1
T= 293 (2) K Block, colourless 0.10.10.1 mm
Data collection
Stoe IPDS diffractometer
'scans
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1998)
Tmin= 0.760,Tmax= 0.771 17645 measured re¯ections 4082 independent re¯ections
3559 re¯ections withI> 2(I)
Rint= 0.031
max= 25.9
h=ÿ11!11
k=ÿ36!37
l=ÿ10!9
Re®nement
Re®nement onF2
R[F2> 2(F2)] = 0.026
wR(F2) = 0.066
S= 1.04 4082 re¯ections 246 parameters
H-atom parameters constrained
w= 1/[2(F
o2) + (0.0453P)2 + 0.0308P]
whereP= (Fo2+ 2Fc2)/3 (/)max= 0.001
max= 0.65 e AÊÿ3
min=ÿ0.66 e AÊÿ3
Extinction correction:SHELXL97 Extinction coef®cient: 0.0043 (3)
Table 1
Selected geometric parameters (AÊ,).
Cu1ÐN1 2.018 (2)
Cu1ÐP1 2.2011 (7) Cu1ÐI1
i 2.6427 (4)
Cu1ÐI1 2.6477 (4)
N1ÐCu1ÐP1 109.56 (7) N1ÐCu1ÐI1i 108.07 (8) P1ÐCu1ÐI1i 113.93 (2) N1ÐCu1ÐI1 106.68 (8)
P1ÐCu1ÐI1 112.24 (2) I1iÐCu1ÐI1 106.011 (12) Cu1iÐI1ÐCu1 73.989 (12)
Symmetry code: (i)ÿx;ÿy;1ÿz.
The aromatic H atoms were positioned with idealized geometry (CÐH = 0.93 AÊ) and re®ned with ®xed isotropic displacement parameters [Uiso(H) = 1.2Ueq(C)], using a riding model. The positions
of the methyl H atoms were idealized (CÐH = 0.96 AÊ), then re®ned with ®xed isotropic displacement parameters [Uiso(H) = 1.5Ueq(C)] as
rigid groups allowed to rotate but not tip.
Data collection:IPDS(Stoe & Cie, 1998); cell re®nement:IPDS; data reduction: IPDS; program(s) used to solve structure:
SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure:
SHELXL97 (Sheldrick, 1997); molecular graphics:XPinSHELXTL
(Bruker, 1998); software used to prepare material for publication:
CIFTABinSHELXTL.
This work is supported by the State of Schleswig-Holstein. We are very thankful to Professor Dr Wolfgang Bensch for ®nancial support and the opportunity to use his experimental equipment.
Figure 2
The crystal structure of the title compound, viewed along the crystal-lographiccaxis.
Figure 1
References
Allen, F. H. (2002).Acta Cryst.B58, 380±388.
Bruker (1998). SHELXTL. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.
Graham, P. M., Pike, R. D., Sabat, M., Bailey, R. D. & Pennington, W. T. (2000).
Inorg. Chem.39, 5121±5132.
NaÈther, C., Greve, J. & Jeû, I. (2002).Solid State Sci.4, 813±820. NaÈther, C. & Jeû, I. (2002).J. Solid State Chem.169, 103±112.
NaÈther, C. & Jeû, I. (2003).Inorg. Chem.42, 2968±2976.
NaÈther, C., Wriedt, M. & Jeû, I. (2002).Z. Anorg. Allg. Chem. 628, 394± 400.
Pike, R. D., Borne, B. D., Maeyer, J. T. & Rheingold, A. L. (2002).Inorg. Chem.
41, 631±633.
Pike, R. D., Starnes, W. H. & Carpenter, G. B. (1999).Acta Cryst.C55, 162±165. Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of
GoÈttingen, Germany.
Stoe & Cie (1998).IPDS(Version 2.89) andX-SHAPE(Version 1.03). Stoe & Cie, Darmstadt, Germany.
supporting information
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Acta Cryst. (2003). E59, m1041–m1043
supporting information
Acta Cryst. (2003). E59, m1041–m1043 [https://doi.org/10.1107/S1600536803023304]
Di-
µ
-iodo-bis[(acetonitrile-
κ
N
)(triphenylphosphite-
κ
P
)copper(I)]
Christian N
ä
ther, Tobias Steinhoff and Inke Je
ß
Di-µ-iodo-bis[(acetonitrile-κN)(triphenylphosphite-κP)copper(I)]
Crystal data
[Cu2I2(C2H3N)2(C18H15O3P)2] Mr = 1083.53
Monoclinic, P21/c a = 9.0239 (6) Å b = 30.1204 (16) Å c = 8.4220 (5) Å β = 112.139 (7)° V = 2120.4 (2) Å3 Z = 2
F(000) = 1064 Dx = 1.697 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 8000 reflections θ = 14–23°
µ = 2.58 mm−1 T = 293 K Block, colourless 0.1 × 0.1 × 0.1 mm
Data collection Stoe IPDS
diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
φ scans
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1998) Tmin = 0.760, Tmax = 0.771
17645 measured reflections 4082 independent reflections 3559 reflections with I > 2σ(I) Rint = 0.031
θmax = 25.9°, θmin = 2.5° h = −11→11
k = −36→37 l = −10→9
Refinement Refinement on F2
Least-squares matrix: full R[F2 > 2σ(F2)] = 0.026 wR(F2) = 0.066 S = 1.04 4082 reflections 246 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-atom parameters constrained w = 1/[σ2(F
o2) + (0.0453P)2 + 0.0308P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 0.65 e Å−3
Δρmin = −0.66 e Å−3
Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Extinction coefficient: 0.0043 (3)
Special details
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Acta Cryst. (2003). E59, m1041–m1043
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)
x y z Uiso*/Ueq
Cu1 0.11001 (3) 0.040175 (10) 0.60058 (4) 0.02639 (10)
I1 −0.00005 (2) 0.025384 (6) 0.26613 (2) 0.03119 (8)
P1 0.04610 (7) 0.10669 (2) 0.66251 (8) 0.02220 (15)
O1 −0.0147 (2) 0.14483 (6) 0.5173 (2) 0.0284 (4)
C1 0.0873 (3) 0.17001 (8) 0.4615 (3) 0.0235 (5)
C2 0.0743 (3) 0.21552 (9) 0.4677 (4) 0.0329 (6)
H2 0.0057 0.2283 0.5139 0.039*
C3 0.1652 (4) 0.24196 (9) 0.4038 (4) 0.0395 (7)
H3 0.1562 0.2727 0.4053 0.047*
C4 0.2684 (4) 0.22281 (10) 0.3383 (4) 0.0383 (7)
H4 0.3294 0.2407 0.2963 0.046*
C5 0.2818 (3) 0.17702 (9) 0.3345 (4) 0.0332 (6)
H5 0.3518 0.1643 0.2901 0.040*
C6 0.1909 (3) 0.15012 (8) 0.3970 (3) 0.0274 (5)
H6 0.1996 0.1194 0.3955 0.033*
O2 0.1801 (2) 0.13650 (6) 0.8069 (2) 0.0256 (4)
C11 0.3018 (3) 0.11841 (8) 0.9511 (3) 0.0223 (5)
C12 0.4532 (3) 0.13632 (10) 0.9948 (4) 0.0328 (6)
H12 0.4724 0.1584 0.9279 0.039*
C13 0.5761 (3) 0.12070 (11) 1.1404 (4) 0.0415 (7)
H13 0.6784 0.1324 1.1706 0.050*
C14 0.5485 (3) 0.08803 (10) 1.2407 (4) 0.0384 (7)
H14 0.6317 0.0776 1.3373 0.046*
C15 0.3958 (3) 0.07098 (9) 1.1963 (4) 0.0323 (6)
H15 0.3763 0.0493 1.2648 0.039*
C16 0.2709 (3) 0.08585 (8) 1.0500 (3) 0.0253 (5)
H16 0.1686 0.0741 1.0195 0.030*
O3 −0.1047 (2) 0.10662 (6) 0.7197 (2) 0.0272 (4)
C21 −0.1642 (3) 0.14504 (8) 0.7717 (3) 0.0241 (5)
C22 −0.1033 (3) 0.15657 (9) 0.9433 (3) 0.0280 (5)
H22 −0.0206 0.1403 1.0219 0.034*
C23 −0.1673 (3) 0.19273 (9) 0.9963 (4) 0.0320 (6)
H23 −0.1271 0.2009 1.1112 0.038*
C24 −0.2907 (3) 0.21681 (9) 0.8794 (4) 0.0324 (6)
H24 −0.3323 0.2413 0.9156 0.039*
C25 −0.3525 (3) 0.20444 (10) 0.7081 (4) 0.0370 (6)
H25 −0.4368 0.2204 0.6299 0.044*
C26 −0.2887 (3) 0.16832 (10) 0.6532 (4) 0.0331 (6)
H26 −0.3292 0.1600 0.5385 0.040*
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Acta Cryst. (2003). E59, m1041–m1043
C41 0.4840 (3) 0.03922 (10) 0.7510 (4) 0.0330 (6)
C42 0.6553 (4) 0.04523 (12) 0.8394 (6) 0.0614 (11)
H42A 0.6779 0.0760 0.8687 0.092*
H42B 0.7092 0.0361 0.7659 0.092*
H42C 0.6922 0.0276 0.9420 0.092*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
Cu1 0.02212 (16) 0.02615 (17) 0.02937 (19) 0.00179 (12) 0.00796 (13) −0.00245 (12)
I1 0.04037 (12) 0.03117 (12) 0.02448 (12) −0.00781 (7) 0.01501 (8) −0.00324 (6)
P1 0.0227 (3) 0.0229 (3) 0.0206 (3) 0.0011 (2) 0.0077 (2) −0.0008 (2)
O1 0.0265 (9) 0.0346 (10) 0.0243 (10) 0.0087 (7) 0.0096 (7) 0.0080 (7)
C1 0.0292 (12) 0.0241 (12) 0.0140 (12) 0.0040 (10) 0.0044 (9) 0.0025 (9)
C2 0.0431 (16) 0.0260 (13) 0.0250 (14) 0.0098 (11) 0.0076 (11) −0.0007 (11)
C3 0.0537 (18) 0.0212 (13) 0.0324 (16) 0.0002 (12) 0.0036 (13) 0.0013 (11)
C4 0.0426 (16) 0.0381 (16) 0.0258 (15) −0.0137 (12) 0.0032 (12) 0.0067 (12)
C5 0.0335 (14) 0.0399 (16) 0.0269 (15) −0.0027 (11) 0.0124 (11) −0.0018 (11)
C6 0.0348 (14) 0.0227 (13) 0.0253 (14) 0.0026 (10) 0.0119 (11) −0.0007 (10)
O2 0.0292 (9) 0.0219 (9) 0.0235 (10) −0.0015 (7) 0.0075 (7) 0.0034 (7)
C11 0.0231 (12) 0.0218 (12) 0.0222 (13) 0.0003 (9) 0.0088 (9) −0.0017 (9)
C12 0.0310 (14) 0.0398 (15) 0.0316 (16) −0.0109 (11) 0.0164 (12) −0.0011 (11)
C13 0.0242 (14) 0.0590 (19) 0.0405 (18) −0.0079 (13) 0.0112 (12) −0.0068 (14)
C14 0.0302 (14) 0.0460 (18) 0.0314 (16) 0.0092 (12) 0.0030 (12) −0.0007 (12)
C15 0.0385 (15) 0.0248 (13) 0.0322 (15) 0.0032 (11) 0.0118 (12) 0.0043 (11)
C16 0.0253 (12) 0.0228 (12) 0.0293 (14) −0.0027 (9) 0.0122 (10) 0.0008 (10)
O3 0.0264 (9) 0.0256 (9) 0.0327 (11) −0.0014 (7) 0.0146 (8) −0.0045 (7)
C21 0.0229 (12) 0.0260 (12) 0.0253 (14) −0.0060 (9) 0.0114 (10) −0.0037 (10)
C22 0.0254 (12) 0.0338 (14) 0.0225 (13) −0.0017 (10) 0.0065 (10) 0.0002 (10)
C23 0.0329 (14) 0.0387 (16) 0.0240 (14) −0.0074 (11) 0.0102 (11) −0.0099 (11)
C24 0.0333 (14) 0.0299 (14) 0.0399 (17) −0.0030 (11) 0.0205 (12) −0.0081 (12)
C25 0.0347 (15) 0.0432 (17) 0.0329 (16) 0.0113 (12) 0.0126 (12) 0.0044 (12)
C26 0.0323 (14) 0.0433 (16) 0.0202 (14) 0.0044 (12) 0.0059 (11) −0.0036 (11)
N1 0.0245 (13) 0.0351 (13) 0.0480 (16) 0.0018 (9) 0.0102 (11) −0.0031 (11)
C41 0.0259 (15) 0.0272 (13) 0.0481 (18) 0.0007 (10) 0.0163 (13) −0.0023 (11)
C42 0.0241 (15) 0.049 (2) 0.105 (3) −0.0066 (14) 0.0175 (18) −0.019 (2)
Geometric parameters (Å, º)
Cu1—N1 2.018 (2) C13—C14 1.380 (5)
Cu1—P1 2.2011 (7) C13—H13 0.9300
Cu1—I1i 2.6427 (4) C14—C15 1.383 (4)
Cu1—I1 2.6477 (4) C14—H14 0.9300
I1—Cu1i 2.6427 (4) C15—C16 1.394 (4)
P1—O3 1.6054 (18) C15—H15 0.9300
P1—O1 1.6159 (18) C16—H16 0.9300
P1—O2 1.6247 (18) O3—C21 1.413 (3)
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Acta Cryst. (2003). E59, m1041–m1043
C1—C2 1.379 (4) C21—C22 1.383 (4)
C1—C6 1.382 (4) C22—C23 1.383 (4)
C2—C3 1.389 (4) C22—H22 0.9300
C2—H2 0.9300 C23—C24 1.382 (4)
C3—C4 1.375 (5) C23—H23 0.9300
C3—H3 0.9300 C24—C25 1.387 (4)
C4—C5 1.386 (4) C24—H24 0.9300
C4—H4 0.9300 C25—C26 1.389 (4)
C5—C6 1.390 (4) C25—H25 0.9300
C5—H5 0.9300 C26—H26 0.9300
C6—H6 0.9300 N1—C41 1.131 (3)
O2—C11 1.404 (3) C41—C42 1.452 (4)
C11—C16 1.381 (3) C42—H42A 0.9600
C11—C12 1.384 (3) C42—H42B 0.9600
C12—C13 1.389 (4) C42—H42C 0.9600
C12—H12 0.9300
N1—Cu1—P1 109.56 (7) C14—C13—C12 120.9 (3)
N1—Cu1—I1i 108.07 (8) C14—C13—H13 119.5
P1—Cu1—I1i 113.93 (2) C12—C13—H13 119.5
N1—Cu1—I1 106.68 (8) C13—C14—C15 119.4 (3)
P1—Cu1—I1 112.24 (2) C13—C14—H14 120.3
I1i—Cu1—I1 106.011 (12) C15—C14—H14 120.3
Cu1i—I1—Cu1 73.989 (12) C14—C15—C16 120.8 (3)
O3—P1—O1 98.26 (9) C14—C15—H15 119.6
O3—P1—O2 104.62 (10) C16—C15—H15 119.6
O1—P1—O2 96.80 (10) C11—C16—C15 118.8 (2)
O3—P1—Cu1 113.40 (7) C11—C16—H16 120.6
O1—P1—Cu1 120.81 (7) C15—C16—H16 120.6
O2—P1—Cu1 119.52 (7) C21—O3—P1 123.79 (15)
C1—O1—P1 124.00 (15) C26—C21—C22 121.5 (2)
C2—C1—C6 121.7 (2) C26—C21—O3 119.5 (2)
C2—C1—O1 116.7 (2) C22—C21—O3 118.8 (2)
C6—C1—O1 121.6 (2) C23—C22—C21 119.0 (2)
C1—C2—C3 119.0 (3) C23—C22—H22 120.5
C1—C2—H2 120.5 C21—C22—H22 120.5
C3—C2—H2 120.5 C24—C23—C22 120.4 (3)
C4—C3—C2 120.2 (3) C24—C23—H23 119.8
C4—C3—H3 119.9 C22—C23—H23 119.8
C2—C3—H3 119.9 C23—C24—C25 120.0 (3)
C3—C4—C5 120.3 (3) C23—C24—H24 120.0
C3—C4—H4 119.8 C25—C24—H24 120.0
C5—C4—H4 119.8 C24—C25—C26 120.1 (3)
C4—C5—C6 120.1 (3) C24—C25—H25 119.9
C4—C5—H5 119.9 C26—C25—H25 119.9
C6—C5—H5 119.9 C21—C26—C25 118.9 (3)
C1—C6—C5 118.6 (2) C21—C26—H26 120.5
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Acta Cryst. (2003). E59, m1041–m1043
C5—C6—H6 120.7 C41—N1—Cu1 165.8 (2)
C11—O2—P1 123.49 (15) N1—C41—C42 178.2 (4)
C16—C11—C12 121.3 (2) C41—C42—H42A 109.5
C16—C11—O2 121.8 (2) C41—C42—H42B 109.5
C12—C11—O2 116.8 (2) H42A—C42—H42B 109.5
C11—C12—C13 118.9 (3) C41—C42—H42C 109.5
C11—C12—H12 120.6 H42A—C42—H42C 109.5
C13—C12—H12 120.6 H42B—C42—H42C 109.5