Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801007814/bt6045sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801007814/bt6045Isup2.hkl |
CCDC reference: 170729
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.004 Å
- R factor = 0.039
- wR factor = 0.090
- Data-to-parameter ratio = 20.1
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
PLAT_369 Alert C Long C(sp2)-C(sp2) Bond C(1) - C(1)a = 1.54 Ang.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
N,N,N',N'-Tetramethylethane-1,2-diamine (0.3 ml, 2 mmol) was added slowly to copper nitrate trihydrate (483.2 mg, 2 mmol) dissolved in water (10 ml). To the deep-blue solution, an aqueous solution (10 ml) of potassium cyanate (162.6 mg, 2 mmol) was poured drop-by-drop with constant stirring and a blue crystalline compound separated out. An aqueous solution (10 ml) of sodium oxalate (134 mg, 1 mmol) was added slowly with vigorous stirring and a deep-blue solution was obtained. This was filtered and the filtrate was kept in a desiccator. After a few days, single crystals suitable for X-ray crystal structure analysis were obtained.
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SHELXTL (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. ORTEP drawing of the title complex. Atoms labeled with a prime are centrosymmetrically related to those without prime. The coordination bonds are hollow. |
[Cu2(NCO)2(C2O4)(C6H16N2)2] | F(000) = 552 |
Mr = 531.06 | Dx = 1.543 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.4943 (9) Å | Cell parameters from 25 reflections |
b = 14.5660 (17) Å | θ = 2.4–28.3° |
c = 10.8812 (13) Å | µ = 1.90 mm−1 |
β = 105.655 (2)° | T = 296 K |
V = 1143.8 (2) Å3 | Rectangular plate, blue |
Z = 2 | 0.23 × 0.10 × 0.10 mm |
CCD area detector diffractometer | 2734 independent reflections |
Radiation source: fine-focus sealed tube | 2367 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
ϕ and ω scans | θmax = 28.3°, θmin = 2.4° |
Absorption correction: empirical (using intensity measurements) (North et al., 1968) | h = −9→9 |
Tmin = 0.646, Tmax = 0.827 | k = −15→18 |
7265 measured reflections | l = −14→14 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.090 | H-atom parameters constrained |
S = 1.16 | w = 1/[σ2(Fo2) + (0.115P)2 + 0.612P] where P = (Fo2 + 2Fc2)/3 |
2734 reflections | (Δ/σ)max < 0.001 |
136 parameters | Δρmax = 0.37 e Å−3 |
1 restraint | Δρmin = −0.51 e Å−3 |
[Cu2(NCO)2(C2O4)(C6H16N2)2] | V = 1143.8 (2) Å3 |
Mr = 531.06 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.4943 (9) Å | µ = 1.90 mm−1 |
b = 14.5660 (17) Å | T = 296 K |
c = 10.8812 (13) Å | 0.23 × 0.10 × 0.10 mm |
β = 105.655 (2)° |
CCD area detector diffractometer | 2734 independent reflections |
Absorption correction: empirical (using intensity measurements) (North et al., 1968) | 2367 reflections with I > 2σ(I) |
Tmin = 0.646, Tmax = 0.827 | Rint = 0.032 |
7265 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 1 restraint |
wR(F2) = 0.090 | H-atom parameters constrained |
S = 1.16 | Δρmax = 0.37 e Å−3 |
2734 reflections | Δρmin = −0.51 e Å−3 |
136 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.01552 (4) | 0.05732 (2) | 0.76424 (3) | 0.03128 (11) | |
O1 | 0.1048 (3) | −0.04496 (12) | 0.88738 (19) | 0.0418 (5) | |
C1 | −0.0525 (4) | 0.04310 (16) | 1.0118 (3) | 0.0341 (6) | |
O2 | −0.0791 (3) | 0.10586 (12) | 0.93093 (18) | 0.0432 (5) | |
N1 | −0.0582 (3) | 0.17153 (15) | 0.6555 (2) | 0.0347 (5) | |
N2 | 0.2833 (3) | 0.10567 (16) | 0.8003 (2) | 0.0400 (5) | |
N3 | −0.1915 (4) | −0.01432 (19) | 0.6664 (3) | 0.0578 (7) | |
C2 | −0.2965 (4) | −0.0685 (2) | 0.6242 (3) | 0.0446 (7) | |
O3 | −0.4076 (4) | −0.1258 (2) | 0.5775 (3) | 0.0987 (11) | |
C3 | 0.2787 (4) | 0.1884 (2) | 0.7196 (3) | 0.0483 (7) | |
H3A | 0.2916 | 0.1706 | 0.6365 | 0.058* | |
H3B | 0.3803 | 0.2291 | 0.7593 | 0.058* | |
C4 | 0.0967 (4) | 0.23676 (19) | 0.7049 (3) | 0.0431 (7) | |
H4A | 0.0905 | 0.2608 | 0.7868 | 0.052* | |
H4B | 0.0864 | 0.2879 | 0.6463 | 0.052* | |
C5 | −0.2319 (4) | 0.2123 (2) | 0.6696 (3) | 0.0461 (7) | |
H5A | −0.2195 | 0.2252 | 0.7580 | 0.069* | |
H5B | −0.3321 | 0.1700 | 0.6385 | 0.069* | |
H5C | −0.2570 | 0.2683 | 0.6214 | 0.069* | |
C6 | −0.0820 (5) | 0.1523 (3) | 0.5184 (3) | 0.0565 (8) | |
H6A | 0.0297 | 0.1257 | 0.5070 | 0.085* | |
H6B | −0.1083 | 0.2085 | 0.4708 | 0.085* | |
H6C | −0.1830 | 0.1102 | 0.4884 | 0.085* | |
C7 | 0.3592 (5) | 0.1307 (3) | 0.9364 (3) | 0.0649 (10) | |
H7A | 0.2829 | 0.1772 | 0.9589 | 0.097* | |
H7B | 0.4831 | 0.1536 | 0.9500 | 0.097* | |
H7C | 0.3608 | 0.0774 | 0.9887 | 0.097* | |
C8 | 0.4017 (5) | 0.0342 (3) | 0.7662 (4) | 0.0641 (10) | |
H8A | 0.3529 | 0.0177 | 0.6781 | 0.096* | |
H8B | 0.4037 | −0.0190 | 0.8187 | 0.096* | |
H8C | 0.5254 | 0.0574 | 0.7798 | 0.096* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.03512 (18) | 0.02876 (17) | 0.03108 (18) | −0.00039 (13) | 0.01084 (12) | 0.00284 (12) |
O1 | 0.0592 (13) | 0.0313 (10) | 0.0426 (11) | 0.0108 (8) | 0.0269 (9) | 0.0056 (8) |
C1 | 0.0405 (14) | 0.0253 (13) | 0.0383 (14) | 0.0000 (10) | 0.0134 (11) | 0.0022 (10) |
O2 | 0.0631 (13) | 0.0294 (10) | 0.0425 (11) | 0.0084 (9) | 0.0233 (9) | 0.0074 (8) |
N1 | 0.0362 (11) | 0.0357 (11) | 0.0325 (11) | −0.0001 (9) | 0.0096 (9) | 0.0044 (9) |
N2 | 0.0337 (12) | 0.0414 (13) | 0.0444 (13) | 0.0014 (10) | 0.0098 (10) | 0.0085 (10) |
N3 | 0.0497 (16) | 0.0456 (16) | 0.072 (2) | −0.0114 (13) | 0.0065 (14) | −0.0049 (14) |
C2 | 0.0430 (16) | 0.0385 (16) | 0.0496 (17) | 0.0046 (13) | 0.0078 (13) | 0.0008 (13) |
O3 | 0.079 (2) | 0.0691 (19) | 0.124 (3) | −0.0270 (16) | −0.0129 (18) | −0.0185 (18) |
C3 | 0.0399 (16) | 0.0479 (18) | 0.0601 (19) | −0.0059 (13) | 0.0189 (14) | 0.0139 (14) |
C4 | 0.0456 (16) | 0.0304 (14) | 0.0537 (17) | −0.0019 (12) | 0.0143 (13) | 0.0083 (12) |
C5 | 0.0376 (15) | 0.0477 (17) | 0.0507 (17) | 0.0088 (13) | 0.0078 (13) | 0.0084 (14) |
C6 | 0.070 (2) | 0.065 (2) | 0.0338 (15) | 0.0010 (17) | 0.0125 (15) | 0.0078 (14) |
C7 | 0.058 (2) | 0.075 (2) | 0.0505 (19) | −0.0179 (18) | −0.0045 (16) | 0.0048 (18) |
C8 | 0.0485 (19) | 0.062 (2) | 0.089 (3) | 0.0177 (16) | 0.0297 (19) | 0.0132 (19) |
Cu1—N3 | 1.933 (3) | C3—C4 | 1.505 (4) |
Cu1—O1 | 1.9946 (19) | C3—H3A | 0.9700 |
Cu1—N1 | 2.030 (2) | C3—H3B | 0.9700 |
Cu1—N2 | 2.062 (2) | C4—H4A | 0.9700 |
Cu1—O2 | 2.2330 (19) | C4—H4B | 0.9700 |
O1—C1i | 1.261 (3) | C5—H5A | 0.9600 |
C1—O2 | 1.247 (3) | C5—H5B | 0.9600 |
C1—O1i | 1.261 (3) | C5—H5C | 0.9600 |
C1—C1i | 1.540 (5) | C6—H6A | 0.9600 |
N1—C5 | 1.476 (4) | C6—H6B | 0.9600 |
N1—C6 | 1.480 (4) | C6—H6C | 0.9600 |
N1—C4 | 1.484 (3) | C7—H7A | 0.9600 |
N2—C8 | 1.479 (4) | C7—H7B | 0.9600 |
N2—C7 | 1.482 (4) | C7—H7C | 0.9600 |
N2—C3 | 1.486 (4) | C8—H8A | 0.9600 |
N3—C2 | 1.122 (4) | C8—H8B | 0.9600 |
C2—O3 | 1.191 (4) | C8—H8C | 0.9600 |
N3—Cu1—O1 | 92.33 (11) | C4—C3—H3B | 110.0 |
N3—Cu1—N1 | 93.99 (11) | H3A—C3—H3B | 108.4 |
O1—Cu1—N1 | 173.19 (9) | N1—C4—C3 | 109.7 (2) |
N3—Cu1—N2 | 152.15 (12) | N1—C4—H4A | 109.7 |
O1—Cu1—N2 | 89.69 (9) | C3—C4—H4A | 109.7 |
N1—Cu1—N2 | 85.91 (9) | N1—C4—H4B | 109.7 |
N3—Cu1—O2 | 103.58 (11) | C3—C4—H4B | 109.7 |
O1—Cu1—O2 | 79.23 (7) | H4A—C4—H4B | 108.2 |
N1—Cu1—O2 | 96.78 (8) | N1—C5—H5A | 109.5 |
N2—Cu1—O2 | 104.09 (9) | N1—C5—H5B | 109.5 |
C1i—O1—Cu1 | 116.23 (16) | H5A—C5—H5B | 109.5 |
O2—C1—O1i | 124.8 (2) | N1—C5—H5C | 109.5 |
O2—C1—C1i | 118.2 (3) | H5A—C5—H5C | 109.5 |
O1i—C1—C1i | 117.1 (3) | H5B—C5—H5C | 109.5 |
C1—O2—Cu1 | 108.40 (16) | N1—C6—H6A | 109.5 |
C5—N1—C6 | 108.1 (2) | N1—C6—H6B | 109.5 |
C5—N1—C4 | 109.3 (2) | H6A—C6—H6B | 109.5 |
C6—N1—C4 | 110.9 (2) | N1—C6—H6C | 109.5 |
C5—N1—Cu1 | 112.21 (17) | H6A—C6—H6C | 109.5 |
C6—N1—Cu1 | 111.86 (19) | H6B—C6—H6C | 109.5 |
C4—N1—Cu1 | 104.48 (15) | N2—C7—H7A | 109.5 |
C8—N2—C7 | 109.2 (3) | N2—C7—H7B | 109.5 |
C8—N2—C3 | 110.1 (3) | H7A—C7—H7B | 109.5 |
C7—N2—C3 | 109.4 (3) | N2—C7—H7C | 109.5 |
C8—N2—Cu1 | 109.3 (2) | H7A—C7—H7C | 109.5 |
C7—N2—Cu1 | 111.4 (2) | H7B—C7—H7C | 109.5 |
C3—N2—Cu1 | 107.35 (17) | N2—C8—H8A | 109.5 |
C2—N3—Cu1 | 167.3 (3) | N2—C8—H8B | 109.5 |
N3—C2—O3 | 179.0 (4) | H8A—C8—H8B | 109.5 |
N2—C3—C4 | 108.6 (2) | N2—C8—H8C | 109.5 |
N2—C3—H3A | 110.0 | H8A—C8—H8C | 109.5 |
C4—C3—H3A | 110.0 | H8B—C8—H8C | 109.5 |
N2—C3—H3B | 110.0 | ||
N3—Cu1—O1—C1i | −95.2 (2) | O2—Cu1—N2—C8 | 138.9 (2) |
N2—Cu1—O1—C1i | 112.6 (2) | N3—Cu1—N2—C7 | −155.2 (3) |
O2—Cu1—O1—C1i | 8.2 (2) | O1—Cu1—N2—C7 | −60.8 (2) |
O1i—C1—O2—Cu1 | −173.8 (2) | N1—Cu1—N2—C7 | 114.0 (2) |
C1i—C1—O2—Cu1 | 6.6 (4) | O2—Cu1—N2—C7 | 18.0 (2) |
N3—Cu1—O2—C1 | 81.9 (2) | N3—Cu1—N2—C3 | 85.0 (3) |
O1—Cu1—O2—C1 | −7.89 (18) | O1—Cu1—N2—C3 | 179.4 (2) |
N1—Cu1—O2—C1 | 177.70 (18) | N1—Cu1—N2—C3 | −5.8 (2) |
N2—Cu1—O2—C1 | −94.84 (19) | O2—Cu1—N2—C3 | −101.76 (19) |
N3—Cu1—N1—C5 | 67.7 (2) | O1—Cu1—N3—C2 | −6.5 (14) |
N2—Cu1—N1—C5 | −140.25 (19) | N1—Cu1—N3—C2 | 176.1 (14) |
O2—Cu1—N1—C5 | −36.53 (19) | N2—Cu1—N3—C2 | 87.3 (14) |
N3—Cu1—N1—C6 | −54.0 (2) | O2—Cu1—N3—C2 | −85.9 (14) |
N2—Cu1—N1—C6 | 98.0 (2) | C8—N2—C3—C4 | 151.4 (3) |
O2—Cu1—N1—C6 | −158.2 (2) | C7—N2—C3—C4 | −88.5 (3) |
N3—Cu1—N1—C4 | −174.06 (19) | Cu1—N2—C3—C4 | 32.5 (3) |
N2—Cu1—N1—C4 | −21.99 (18) | C5—N1—C4—C3 | 166.9 (2) |
O2—Cu1—N1—C4 | 81.74 (18) | C6—N1—C4—C3 | −74.0 (3) |
N3—Cu1—N2—C8 | −34.3 (3) | Cu1—N1—C4—C3 | 46.7 (3) |
O1—Cu1—N2—C8 | 60.1 (2) | N2—C3—C4—N1 | −54.3 (3) |
N1—Cu1—N2—C8 | −125.1 (2) |
Symmetry code: (i) −x, −y, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [Cu2(NCO)2(C2O4)(C6H16N2)2] |
Mr | 531.06 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 7.4943 (9), 14.5660 (17), 10.8812 (13) |
β (°) | 105.655 (2) |
V (Å3) | 1143.8 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.90 |
Crystal size (mm) | 0.23 × 0.10 × 0.10 |
Data collection | |
Diffractometer | CCD area detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (North et al., 1968) |
Tmin, Tmax | 0.646, 0.827 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7265, 2734, 2367 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.090, 1.16 |
No. of reflections | 2734 |
No. of parameters | 136 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.37, −0.51 |
Computer programs: SMART (Bruker, 1998), SMART, SHELXTL (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL.
Cu1—N3 | 1.933 (3) | O1—C1i | 1.261 (3) |
Cu1—O1 | 1.9946 (19) | C1—O2 | 1.247 (3) |
Cu1—N1 | 2.030 (2) | C1—O1i | 1.261 (3) |
Cu1—N2 | 2.062 (2) | C1—C1i | 1.540 (5) |
Cu1—O2 | 2.2330 (19) | ||
N3—Cu1—O1 | 92.33 (11) | N1—Cu1—N2 | 85.91 (9) |
N3—Cu1—N1 | 93.99 (11) | N3—Cu1—O2 | 103.58 (11) |
O1—Cu1—N1 | 173.19 (9) | O1—Cu1—O2 | 79.23 (7) |
N3—Cu1—N2 | 152.15 (12) | N1—Cu1—O2 | 96.78 (8) |
O1—Cu1—N2 | 89.69 (9) | N2—Cu1—O2 | 104.09 (9) |
Symmetry code: (i) −x, −y, −z+2. |
Magnetic studies of oxalate-bridged metal complexes are well documented (Julve, Verdaguer et al., 1984; Julve, Faus et al., 1984; Kahn et al., 1985). Presently, this study is mainly concentrated on one-dimensional/two-dimensional systems having alternating bridging ligands, i.e. systems where more than one bridging ligand (Vicente et al., 1996). Recently, Ribas et al. (1998) designed a strategy for having NiII and CuII as central atom with the aim of combining oxalate and azide super-exchange pathways in the same compound. To get the desired compound, they replaced the water molecule in [L(H2O)M-ox-M(H2O)L]2+ [M = CuII(Vicente et al., 1997), L = diamine; M = NiII (Escuer et al., 1994), L = diamine or triamine] with a bridging azide ligand. Using the same strategy, we tried to synthesize a µ-oxalato-µ-cyanato-dicopper(II) alternating chain. Surprisingly, due to the lesser bridging tendency of the cyanate ion compared to azide, we did not get the desired one-dimensional alternating chain but instead obtained a dinuclear copper(II) oxalate-bridged complex with a pendant cyanate ligand in the fifth position of each copper(II) in a trans fashion. The coordination geometry about each Cu atom is distorted trigonal–bipyrimidal, with with N2, N3, O2 and Cu atoms in the equatorial plane of the bipyramid (r.m.s. deviation 0.019 Å); N1 and O1 are on the axial apices. The µ-oxalato chelate is shared by of the two centrosymmetry-related CuII ions. Several similiar oxalato-briging structures of CuII coordination complex with aqua instead of isocyanato have been reported (Julve, Verdaguer et al., 1984; Julve, Faus et al., 1984; Sletten, 1983).