metal-organic papers
Acta Cryst.(2004). E60, m1573±m1575 doi: 10.1107/S1600536804024249 Yoon-Bo Shimet al. [Cu(NO2)2(C15H26N2)]
m1573
Acta Crystallographica Section EStructure Reports
Online ISSN 1600-5368
[(6
R
,7
S
,8
S
,14
R
)-(±)-
a
-Isosparteine-
j
2N
,
N
000]-bis(nitrito-
j
2O
,
O
000)copper(II)
Yoon-Bo Shim,aSung-Nak Choi,a
Seung Jae Lee,bSung Kwon
Kangb and Yong-Min Leea*
aDepartment of Chemistry and Chemistry Institute for Functional Materials, Pusan National University, Pusan 609-735, South Korea, and bDepartment of Chemistry, Chungnam National University, Daejeon 305-764, South Korea
Correspondence e-mail: yomlee@pusan.ac.kr
Key indicators
Single-crystal X-ray study
T= 293 K
Mean(C±C) = 0.005 AÊ Disorder in main residue
Rfactor = 0.040
wRfactor = 0.083
Data-to-parameter ratio = 16.3
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2004 International Union of Crystallography Printed in Great Britain ± all rights reserved
In the title complex, [Cu(NO2)2(-C15H26N2)], chiral
(6R,7S,8S,14R)-(ÿ)--isosparteine acts as a bidentate ligand, with two nitrite ligands occupying the remaining coordination
sites as 2-chelating groups, producing a pseudo-octahedral
coordination complex. The molecule of the title complex possesses a crystallographic twofold axis of rotation along a
line through the central C atom of the (ÿ)--isosparteine
ligand and the CuIIatom. However, as a result of the Jahn±
Teller effect operating on the d9 con®guration of the
copper(II) ion, each nitrite ligand coordinates asymmetrically to the copper(II) centre in a bidentate fashion.
Comment
In recent years, a large number of copper(II) complexes with
(ÿ)-sparteine ligands have been reported. The copper(II)
(ÿ)-sparteine complexes are usually four-coordinate and
tetrahedrally distorted around the approximately square-planar copper(II) ion, as a result of the steric requirements imposed by the bulky chelating (ÿ)-sparteine ligand (Choiet al., 1995, 2004; Kimet al., 2001, 2002, 2003; Leeet al., 2000, 2003; Lopez et al., 1998). The chiral diamine alkaloid, (ÿ )-sparteine, has three diastereomers, namely (ÿ)-l-sparteine (C15H26N2), (ÿ)--isosparteine (-C15H26N2) and (ÿ)-
-isosparteine (-C15H26N2), and has been utilized extensively
in medicinal chemistry (Cadyet al., 1977), in the asymmetric
synthesis of chiral compounds (Beaket al., 1996) and in the
preparation of a model compound of the type I copper(II)
sites in copper proteins (Kim et al., 2001). Although
four-coordinate copper(II) compounds with (ÿ)-l-sparteine,
(ÿ)--isosparteine and (ÿ)--isosparteine have similar tetra-hedrally distorted square-planar structures, the different
conformations of three (ÿ)-sparteine diastereomers in these
compounds impose different degrees of steric effect on the geometry around the copper(II) centre. For example, in the crystal structure of [(ÿ)--isosparteine]dinitratocopper(II), [Cu(NO3)2(-C15H26N2)] (Choi et al., 2004), the degree of
distortion from planarity towards a perfect tetrahedron is not as severe as that found in the corresponding copper(II) (ÿ)-l
sparteine compound [Cu(NO3)2(C15H26N2)] (Choi et al.,
1995).
Whereas many structural studies of four-coordinate
copper(II) complexes with (ÿ)-sparteine have been reported,
to date, relatively little is known about the structural
char-acteristics of copper(II) (ÿ)-sparteine compounds with a
higher coordination number of ®ve or six. The compound [Cu(NO2)2(C15H26N2)] is one of the few copper(II) (ÿ
)-sparteine compounds reported to have a ®ve-coordinate square-pyramidal structure, in which (ÿ)-l-sparteine and one nitrite [CuÐO = 2.025 (5) and 2.402 (6) AÊ] act as bidentate ligands and the other nitrite [CuÐO = 2.002 (5) and
2.637 (5) AÊ] is bound only through one O atom (Lee et al.,
1998).
In this work, we introduced the (ÿ)--isosparteine ligand, instead of (ÿ)-l-sparteine, to the Cu(NO2)2salt to prepare the
title complex, (I) (Fig. 1), and determined its crystal structure. The purpose of this work was to compare the extent of the
steric effect imposed by the two different (ÿ)-sparteine
diastereomers in copper(II) (ÿ)-sparteine compounds with a
coordination number higher than four.
The (ÿ)--isosparteine ligand reacts with Cu(NO2)2 in
ethanol to form (I). Two nitrite groups and one (ÿ)-
-isosparteine group in (I) coordinate to the copper(II) ion in a bidentate fashion to produce a six-coordinate and pseudo-octahedral complex, (I). The bonding parameters and coor-dination geometry of (I) are quite different from those of the
previously reported ®ve-coordinate copper(II) (ÿ)-l
-spar-teine dinitrite [Cu(NO2)2(C15H26N2)] (Lee et al., 1998)
complex. One O atom of each nitrite ligand in (I) occupies an axial position, and the other two O atoms of the nitrite ligands
constitute, with two N atoms of (ÿ)--isosparteine, the
equatorial plane.
The conformation of the coordinated (ÿ)--isosparteine in (I) consists of both terminal rings folded down over the metal (endo±endo), identical to the conformation of the free ligand (Boschmannet al., 1974; Wrobleski & Long, 1977). The mol-ecule possesses a twofold axis of rotation along a line through
atom C9 of (ÿ)--isosparteine and the Cu atom. The CuÐO2
and CuÐO2idistances (see Table 1) are signi®cantly longer
than the CuÐO1 and CuÐO1i distances; each nitrite ion is
asymmetrically chelated to copper(II) as a result of the severe
JahnÐTeller effect operating on the d9 con®guration of
copper(II). The difference in the coordination structures of [Cu(NO2)2(C15H26N2)] and (I) is attributable to the different
ring conformations of the two (ÿ)-sparteine diastereomers;
the conformation of the coordinated (ÿ)-l-sparteine in
[Cu(NO2)2(C15H26N2)] consists of one terminal ring folded
down over the Cu atom (endo) and a second terminal ring
folded back away from the Cu atom (exo), whereas both
terminal rings in (I) are folded down over the Cu atom (endo
-endo). The nitrite in theendosite can coordinate to the Cu
atom in a bidentate fashion, but in the case of the nitrite in the
exosite, only one O atom can bond to the Cu atom. In theexo
site of the coordinated (ÿ)-l-sparteine, the H atoms bonded to atom C10 (see Fig. 2) do not allow the access of a second nitrite O atom to the Cu atom [2.637 (5) AÊ] within a bonding
distance. As a result, the copper(II) (ÿ)-l-sparteine
compound adopts a ®ve-coordinate square-pyramidal struc-ture, whereas (I) adopts a six-coordinate and pseudo-octahe-dral structure.
Experimental
(ÿ)--Isosparteine (±C15H26N2) was derived from commercially
available (ÿ)-l-sparteine (C15H26N2) according to the literature
method (Leonard & Beyler, 1950). The precursor copper(II) complex [Cu(NO3)2(-C15H26N2)] was prepared by mixing an ethanol±
triethylorthoformate (5:1, v/v) solution of copper(II) nitrate 2.5-hydrate with a stoichiometric amount of (ÿ)--isosparteine at room temperature for 3 h, as has been reported (Choiet al., 2004). The resulting blue precipitate was ®ltered off, washed with cold absolute ethanol and then dried in a vacuum. The title complex, (I), was prepared by the substitution reaction of [Cu(NO3)2(±C15H26N2)]
with a stoichiometric amount of NaNO2 in an
ethanol±triethyl-orthoformate (5:1,v/v) solution. Single crystals of (I) were obtained by recrystallization at 278 K from a dichloromethane±triethyl-orthoformate (5:1,v/v) solution under CCl4vapour. Analysis
calcu-metal-organic papers
m1574
Yoon-Bo Shimet al. [Cu(NO2)2(C15H26N2)] Acta Cryst.(2004). E60, m1573±m1575 Figure 1ORTEP-3 (Farrugia, 1997) diagram of (I), showing the atom-numbering scheme and 30% probability displacement ellipsoids. Atom O2 is disordered over two positions (O2 and O2A), but atom O2Ahas been omitted for clarity. [Symmetry code: (i)y,x,ÿz.]
Figure 2
lated for CuC15H26N4O4: C 46.20, H 6.72, N 14.37%; found: C 46.27,
H 6.75, N, 14.31%.
Crystal data [Cu(NO2)2(C15H26N2)]
Mr= 389.94
Tetragonal,P41212
a= 8.2446 (5) AÊ
c= 25.088 (4) AÊ
V= 1705.3 (3) AÊ3
Z= 4
Dx= 1.519 Mg mÿ3
MoKradiation Cell parameters from 22
re¯ections = 11.4±14.1 = 1.31 mmÿ1
T= 293 (2) K Block, dark green 0.300.230.23 mm Data collection
Enraf±Nonius CAD-4 diffractometer Non-pro®led!/2scans Absorption correction: scan
(Northet al., 1968)
Tmin= 0.622,Tmax= 0.730
4231 measured re¯ections 1956 independent re¯ections 1445 re¯ections withI> 2(I)
Rint= 0.061
max= 27.5
h=ÿ10!10
k= 0!10
l= 0!32
3 standard re¯ections every 400 re¯ections intensity decay: none
Refinement Re®nement onF2
R[F2> 2(F2)] = 0.040
wR(F2) = 0.083
S= 1.00 1956 re¯ections 120 parameters
H-atom parameters constrained
w= 1/[2(F
o2) + (0.0297P)2]
whereP= (Fo2+ 2Fc2)/3
(/)max< 0.001
max= 0.44 e AÊÿ3
min=ÿ0.23 e AÊÿ3
Absolute structure: Flack (1983), 737 Friedel pairs
Flack parameter = 0.01 (2)
Table 1
Selected geometric parameters (AÊ,).
CuÐN1 2.043 (3)
CuÐO1 2.019 (3)
CuÐO2 2.50 (3)
N2ÐO1 1.264 (4)
N2ÐO2 1.30 (5)
N1ÐCuÐN1i 89.01 (16)
N1ÐCuÐO1 162.78 (9) N1ÐCuÐO1i 95.43 (12)
N1ÐCuÐO2 107.8 (11) N1ÐCuÐO2i 104.2 (14)
O1ÐCuÐO1i 85.23 (18)
O1ÐCuÐO2 55.0 (11) O1ÐCuÐO2i 90.3 (15)
O2ÐCuÐO2i 135 (3)
O1ÐN2ÐO2 112.4 (13)
Symmetry code: (i)y;x;ÿz.
H atoms on the (ÿ)--isosparteine ligand were positioned geometrically and constrained to ride on their attached atoms at distances of 0.97±0.98 AÊ. TheUiso(H) values were ®xed at 1.2Ueqof
their parent atoms. Atom O2 was disordered over two positions (O2 and O2A). The ®nal occupancy factors for the disordered atom were
0.50 (2) for both sites. The absolute con®guration of (I) was known from the con®guration of the starting material and was con®rmed by the value [0.01 (2)] of the Flack (1983) parameter.
Data collection: CAD-4 EXPRESS (Enraf±Nonius, 1994); cell re®nement:CAD-4EXPRESS; data reduction:XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows
(Farrugia, 1997); software used to prepare material for publication:
WinGX(Farrugia, 1999).
This research was supported by the Ministry of Health and Welfare, Republic of Korea (02-PJ3-PG6-EV05-0001).
References
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Farrugia, L. J. (1997).J. Appl. Cryst.30, 565. Farrugia, L. J. (1999).J. Appl. Cryst.32, 837±838. Flack, H. D. (1983).Acta Cryst.A39, 876±881.
Harms, K. & Wocadlo, S. (1995).XCAD4. University of Marburg, Germany. Kim, B.-J., Lee, Y.-M., Kim, E. H., Kang, S. K. & Choi, S.-N. (2002).Acta Cryst.
C58, m361±m362.
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Kim, Y.-K., Kim, B.-J., Kang, S. K., Choi, S.-N. & Lee, Y.-M. (2003).Acta Cryst.
C59, m64±m66.
Lee, Y.-M., Choi, S.-N., Suh, I.-H. & Bereman, R. D. (1998).Acta Cryst.C54, 1582±1584.
Lee, Y.-M., Chung, G., Kwon, M.-A. & Choi, S.-N. (2000).Acta Cryst.C56, 67± 68.
Lee, Y.-M., Kwon, M.-A., Kang, S. K., Jeong, J. H. & Choi, S.-N. (2003).Inorg. Chem. Commun.6, 197±201.
Leonard, N. J. & Beyler, R. E. (1950).J. Am. Chem. Soc.72, 1316±1323. Lopez, S., Muravyov, I., Pulley, S. R. & Keller, S. W. (1998).Acta Cryst.C54,
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North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968).Acta Cryst.A24, 351± 359.
Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of GoÈttingen, Germany.
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metal-organic papers
supporting information
sup-1
Acta Cryst. (2004). E60, m1573–m1575
supporting information
Acta Cryst. (2004). E60, m1573–m1575 [https://doi.org/10.1107/S1600536804024249]
[(6
R
,7
S
,8
S
,14
R
)-(
–
)-
α
-Isosparteine-
κ
2N
,
N
′
]bis(nitrito-
κ
2O
,
O
′
)copper(II)
Yoon-Bo Shim, Sung-Nak Choi, Seung Jae Lee, Sung Kwon Kang and Yong-Min Lee
[(6R,7S,8S,14R)-(-)-α-Isosparteine-κ2N,N′]bis(nitrito-κ2O,O′)copper(II)
Crystal data
[Cu(NO2)2(C15H26N2)] Mr = 389.94
Tetragonal, P41212 Hall symbol: P 4abw 2nw
a = 8.2446 (5) Å
c = 25.088 (4) Å
V = 1705.3 (3) Å3 Z = 4
F(000) = 820
Dx = 1.519 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 22 reflections
θ = 11.4–14.1°
µ = 1.31 mm−1 T = 293 K Block, dark green 0.30 × 0.23 × 0.23 mm
Data collection
Enraf–Nonius CAD-4 diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
non–profiled ω/2θ scans Absorption correction: ψ scan
(North et al., 1968)
Tmin = 0.622, Tmax = 0.730 4231 measured reflections
1956 independent reflections 1445 reflections with I > 2σ(I)
Rint = 0.061
θmax = 27.5°, θmin = 2.6° h = −10→10
k = 0→10
l = 0→32
3 standard reflections every 400 reflections intensity decay: none
Refinement
Refinement on F2 Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.040 wR(F2) = 0.083 S = 1.00 1956 reflections 120 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) + (0.0297P)2] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max < 0.001
Δρmax = 0.44 e Å−3 Δρmin = −0.23 e Å−3
Absolute structure: Flack (1983), 737 Friedel pairs
supporting information
sup-2
Acta Cryst. (2004). E60, m1573–m1575 Special details
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)
x y z Uiso*/Ueq Occ. (<1)
Cu 0.22073 (5) 0.22073 (5) 0.0000 0.03224 (16) N1 −0.0235 (3) 0.2150 (3) 0.01373 (9) 0.0301 (6) N2 0.4899 (5) 0.2616 (5) 0.05914 (17) 0.0661 (11) O1 0.4632 (3) 0.2331 (4) 0.01043 (11) 0.0618 (8)
O2 0.360 (5) 0.247 (8) 0.0882 (13) 0.072 (6) 0.5 (2)
O2A 0.375 (6) 0.278 (11) 0.0838 (18) 0.075 (9) 0.5 (2) C2 −0.0917 (5) 0.3801 (4) 0.02421 (13) 0.0403 (9)
H2A −0.2092 0.3735 0.0249 0.048*
H2B −0.0611 0.4521 −0.0047 0.048*
C3 −0.0326 (5) 0.4506 (4) 0.07654 (14) 0.0479 (10)
H3A 0.0839 0.4666 0.0748 0.058*
H3B −0.0829 0.5555 0.0823 0.058*
C4 −0.0726 (5) 0.3395 (5) 0.12285 (14) 0.0497 (10)
H4A −0.1892 0.3354 0.1279 0.060*
H4B −0.0242 0.3817 0.1552 0.060*
C5 −0.0085 (5) 0.1698 (4) 0.11210 (13) 0.0421 (9)
H5A −0.0423 0.0977 0.1406 0.051*
H5B 0.1092 0.1720 0.1115 0.051*
C6 −0.0712 (4) 0.1056 (4) 0.05904 (12) 0.0329 (8)
H6 −0.1898 0.1089 0.0611 0.039*
C8 −0.1002 (4) 0.1528 (4) −0.03672 (13) 0.0365 (9)
H8A −0.0590 0.2152 −0.0666 0.044*
H8B −0.2163 0.1707 −0.0348 0.044*
C7 −0.0696 (4) −0.0255 (4) −0.04733 (13) 0.0361 (8)
H7 −0.1348 −0.0567 −0.0783 0.043*
C9 −0.1272 (4) −0.1272 (4) 0.0000 0.0425 (12)
H9 −0.2418 −0.1095 0.0066 0.051*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
supporting information
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Acta Cryst. (2004). E60, m1573–m1575
O2A 0.059 (8) 0.12 (2) 0.042 (9) −0.037 (13) −0.006 (8) −0.012 (11) C2 0.048 (2) 0.033 (2) 0.041 (2) 0.0057 (17) 0.0031 (17) −0.0038 (16) C3 0.057 (3) 0.042 (2) 0.045 (2) 0.0044 (18) 0.0098 (19) −0.0112 (18) C4 0.054 (3) 0.062 (3) 0.0335 (19) 0.0007 (19) 0.0068 (19) −0.0166 (18) C5 0.045 (2) 0.054 (3) 0.0275 (17) 0.0003 (17) 0.0052 (16) 0.0014 (16) C6 0.0271 (18) 0.044 (2) 0.0272 (16) −0.0026 (15) 0.0035 (14) 0.0013 (15) C8 0.035 (2) 0.045 (2) 0.0291 (17) 0.0063 (17) −0.0065 (15) −0.0014 (15) C7 0.037 (2) 0.038 (2) 0.0338 (17) −0.0040 (16) −0.0063 (14) −0.0048 (15) C9 0.0396 (17) 0.0396 (17) 0.048 (3) −0.012 (2) 0.004 (2) −0.004 (2)
Geometric parameters (Å, º)
Cu—N1 2.043 (3) C3—H3B 0.9700
Cu—N1i 2.043 (3) C4—C5 1.520 (5)
Cu—O1 2.019 (3) C4—H4A 0.9700
Cu—O1i 2.019 (3) C4—H4B 0.9700
Cu—O2 2.50 (3) C5—C6 1.523 (4)
Cu—O2i 2.50 (3) C5—H5A 0.9700
N1—C2 1.496 (4) C5—H5B 0.9700
N1—C6 1.503 (4) C6—C7i 1.521 (4)
N1—C8 1.505 (4) C6—H6 0.9800
N2—O2A 1.14 (5) C8—C7 1.515 (4)
N2—O1 1.264 (4) C8—H8A 0.9700
N2—O2 1.30 (5) C8—H8B 0.9700
C2—C3 1.517 (5) C7—C6i 1.521 (4)
C2—H2A 0.9700 C7—C9 1.529 (4)
C2—H2B 0.9700 C7—H7 0.9800
C3—C4 1.516 (5) C9—C7i 1.529 (4)
C3—H3A 0.9700 C9—H9 0.9700
N1—Cu—N1i 89.01 (16) C2—C3—H3B 109.4
N1—Cu—O1 162.78 (9) H3A—C3—H3B 108.0
N1—Cu—O1i 95.43 (12) C3—C4—C5 110.1 (3)
N1—Cu—O2 107.8 (11) C3—C4—H4A 109.6
N1—Cu—O2i 104.2 (14) C5—C4—H4A 109.6
O1—Cu—N1i 95.43 (12) C3—C4—H4B 109.6
O1—Cu—O1i 85.23 (18) C5—C4—H4B 109.6
O1—Cu—O2 55.0 (11) H4A—C4—H4B 108.1
O1—Cu—O2i 90.3 (15) C4—C5—C6 110.9 (3)
O2—Cu—N1i 104.2 (14) C4—C5—H5A 109.5
O2—Cu—O1i 90.3 (15) C6—C5—H5A 109.5
O2—Cu—O2i 135 (3) C4—C5—H5B 109.5
N1i—Cu—O1i 162.78 (9) C6—C5—H5B 109.5
N1i—Cu—O2i 107.8 (11) H5A—C5—H5B 108.0
O1i—Cu—O2i 55.0 (11) N1—C6—C7i 111.0 (2)
C2—N1—C6 108.3 (2) N1—C6—C5 111.3 (3)
C2—N1—C8 107.4 (2) C7i—C6—C5 114.5 (3)
supporting information
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Acta Cryst. (2004). E60, m1573–m1575
C2—N1—Cu 112.3 (2) C7i—C6—H6 106.5
C6—N1—Cu 113.52 (18) C5—C6—H6 106.5
C8—N1—Cu 106.28 (19) N1—C8—C7 114.1 (3)
O2A—N2—O1 113.9 (11) N1—C8—H8A 108.7
O2A—N2—O2 12 (5) C7—C8—H8A 108.7
O1—N2—O2 112.4 (13) N1—C8—H8B 108.7
N2—O1—Cu 107.9 (2) C7—C8—H8B 108.7
N2—O2—Cu 83.7 (14) H8A—C8—H8B 107.6
N1—C2—C3 112.3 (3) C8—C7—C6i 115.6 (3)
N1—C2—H2A 109.1 C8—C7—C9 110.1 (2)
C3—C2—H2A 109.1 C6i—C7—C9 108.0 (2)
N1—C2—H2B 109.1 C8—C7—H7 107.6
C3—C2—H2B 109.1 C6i—C7—H7 107.6
H2A—C2—H2B 107.9 C9—C7—H7 107.6
C4—C3—C2 111.2 (3) C7i—C9—C7 105.2 (3)
C4—C3—H3A 109.4 C7i—C9—H9 110.7
C2—C3—H3A 109.4 C7—C9—H9 110.7
C4—C3—H3B 109.4
