Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680101460X/cv6054sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680101460X/cv6054Isup2.hkl |
CCDC reference: 175321
Physical methods and the synthesis of the compound were carried out as described in the literature (Riggio et al., 2001). Yield 72%; elemental analysis [found% (calculated%)] for C14H10CuN8O2: 43.4 (43.6) C, 2.3 (2.6) H, 28.8 (29.0) N. A crystal was selected for the X-ray measurements and mounted on the glass fiber using the oil-drop method (Kottke & Stalke, 1993) and data were collected at 193 K.
The intensity data were corrected for Lorentz and polarization effects and for absorption. The O17 atom was disordered and was refined in the two positions with population parameters 0.75 and 0.25. The H atoms were introduced in calculated positions and refined with fixed geometry with respect to their carrier atoms.
Data collection: CAD-4 Software (Enraf-Nonius, 1985); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1994); software used to prepare material for publication: SHELXL97.
[Cu(C2N3)2(C5H5NO)2] | Dx = 1.670 Mg m−3 |
Mr = 385.84 | Cu Kα radiation, λ = 1.54180 Å |
Orthorhombic, Pbca | Cell parameters from 25 reflections |
a = 7.266 (2) Å | θ = 12–27° |
b = 13.925 (3) Å | µ = 2.28 mm−1 |
c = 30.327 (6) Å | T = 193 K |
V = 3068.5 (12) Å3 | Prismatic, green |
Z = 8 | 0.50 × 0.20 × 0.08 mm |
F(000) = 1560 |
Enraf-nonius CAD-4 diffractometer | 2241 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.100 |
Graphite monochromator | θmax = 66.9°, θmin = 2.9° |
ω–2θ scans | h = −8→0 |
Absorption correction: ψ scan (North et al., 1968) | k = −16→0 |
Tmin = 0.755, Tmax = 1.000 | l = −36→11 |
2780 measured reflections | 3 standard reflections every 200 reflections |
2723 independent reflections | intensity decay: 0.0% |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 0.81 | Calculated w = 1/[σ2(Fo2) + (0.0878P)2 + 8.7618P] where P = (Fo2 + 2Fc2)/3 |
2723 reflections | (Δ/σ)max = 0.001 |
235 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.96 e Å−3 |
[Cu(C2N3)2(C5H5NO)2] | V = 3068.5 (12) Å3 |
Mr = 385.84 | Z = 8 |
Orthorhombic, Pbca | Cu Kα radiation |
a = 7.266 (2) Å | µ = 2.28 mm−1 |
b = 13.925 (3) Å | T = 193 K |
c = 30.327 (6) Å | 0.50 × 0.20 × 0.08 mm |
Enraf-nonius CAD-4 diffractometer | 2241 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.100 |
Tmin = 0.755, Tmax = 1.000 | 3 standard reflections every 200 reflections |
2780 measured reflections | intensity decay: 0.0% |
2723 independent reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 0.81 | Δρmax = 0.32 e Å−3 |
2723 reflections | Δρmin = −0.96 e Å−3 |
235 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 | Occ. (<1) | |
Cu1 | 0.11022 (6) | 0.14599 (3) | 0.130442 (13) | 0.01939 (17) | |
N11 | 0.1003 (4) | 0.19606 (19) | 0.06788 (8) | 0.0229 (6) | |
C12 | 0.0875 (4) | 0.1339 (2) | 0.03419 (10) | 0.0240 (7) | |
H12A | 0.0817 | 0.0670 | 0.0402 | 0.029* | |
C13 | 0.0826 (5) | 0.1652 (2) | −0.00915 (10) | 0.0258 (7) | |
H13A | 0.0744 | 0.1198 | −0.0330 | 0.031* | 0.25 |
C14 | 0.0892 (5) | 0.2626 (2) | −0.01816 (10) | 0.0288 (7) | |
H14A | 0.0864 | 0.2854 | −0.0477 | 0.035* | |
C15 | 0.0998 (5) | 0.3258 (2) | 0.01689 (11) | 0.0309 (8) | |
H15A | 0.1028 | 0.3941 | 0.0116 | 0.037* | 0.75 |
C16 | 0.1066 (5) | 0.2905 (2) | 0.05945 (10) | 0.0280 (7) | |
H16A | 0.1160 | 0.3343 | 0.0834 | 0.034* | |
O17 | 0.0654 (4) | 0.09604 (19) | −0.04008 (8) | 0.0261 (7) | 0.75 |
H17A | 0.0876 | 0.1193 | −0.0651 | 0.039* | 0.75 |
O171 | 0.1309 (19) | 0.4214 (8) | 0.0094 (4) | 0.057 (3) | 0.25 |
H171 | 0.1392 | 0.4312 | −0.0178 | 0.085* | 0.25 |
N21 | 0.1136 (3) | 0.09834 (19) | 0.19294 (8) | 0.0212 (5) | |
C22 | 0.0691 (4) | 0.0064 (2) | 0.20051 (10) | 0.0229 (6) | |
H22A | 0.0419 | −0.0340 | 0.1761 | 0.027* | |
C23 | 0.0611 (4) | −0.0321 (2) | 0.24258 (10) | 0.0241 (7) | |
C24 | 0.1007 (5) | 0.0281 (3) | 0.27804 (10) | 0.0282 (7) | |
H24A | 0.0942 | 0.0048 | 0.3074 | 0.034* | |
C25 | 0.1490 (5) | 0.1215 (3) | 0.26978 (11) | 0.0287 (7) | |
H25A | 0.1790 | 0.1630 | 0.2936 | 0.034* | |
C26 | 0.1544 (4) | 0.1556 (2) | 0.22707 (10) | 0.0230 (6) | |
H26A | 0.1875 | 0.2206 | 0.2218 | 0.028* | |
O27 | 0.0140 (4) | −0.12552 (15) | 0.24642 (8) | 0.0361 (6) | |
H27A | 0.0328 | −0.1439 | 0.2724 | 0.054* | |
N1 | −0.4039 (4) | 0.0225 (3) | 0.08212 (9) | 0.0368 (8) | |
C1 | −0.2654 (4) | 0.0571 (2) | 0.10424 (9) | 0.0215 (6) | |
N2 | −0.1348 (4) | 0.0875 (2) | 0.11995 (8) | 0.0255 (6) | |
C2 | −0.5689 (4) | 0.0191 (2) | 0.09899 (9) | 0.0221 (7) | |
N3 | −0.7200 (4) | 0.0127 (2) | 0.11002 (9) | 0.0289 (6) | |
N4 | 0.6075 (4) | 0.3220 (2) | 0.12620 (9) | 0.0260 (6) | |
C3 | 0.4645 (5) | 0.2703 (2) | 0.13617 (9) | 0.0215 (6) | |
N5 | 0.3280 (4) | 0.2293 (2) | 0.14094 (8) | 0.0276 (6) | |
C4 | 0.7622 (5) | 0.3143 (2) | 0.14901 (9) | 0.0224 (6) | |
N6 | 0.9038 (4) | 0.3123 (2) | 0.16638 (10) | 0.0334 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0201 (3) | 0.0245 (3) | 0.0135 (2) | −0.00362 (18) | −0.00160 (16) | 0.00089 (16) |
N11 | 0.0255 (14) | 0.0234 (13) | 0.0197 (12) | −0.0024 (11) | −0.0015 (10) | −0.0005 (10) |
C12 | 0.0307 (17) | 0.0210 (15) | 0.0202 (15) | −0.0040 (13) | −0.0007 (13) | 0.0019 (12) |
C13 | 0.0329 (18) | 0.0296 (17) | 0.0149 (14) | −0.0036 (14) | 0.0004 (13) | −0.0012 (13) |
C14 | 0.0420 (19) | 0.0276 (17) | 0.0170 (15) | −0.0014 (15) | −0.0018 (14) | 0.0034 (13) |
C15 | 0.048 (2) | 0.0218 (15) | 0.0226 (16) | −0.0003 (15) | −0.0041 (15) | 0.0026 (13) |
C16 | 0.0407 (19) | 0.0235 (15) | 0.0198 (16) | 0.0000 (14) | −0.0016 (14) | −0.0009 (13) |
O17 | 0.0506 (19) | 0.0192 (13) | 0.0085 (12) | −0.0036 (13) | 0.0039 (12) | −0.0028 (10) |
O171 | 0.095 (10) | 0.041 (6) | 0.034 (6) | 0.012 (7) | −0.004 (6) | −0.006 (5) |
N21 | 0.0200 (13) | 0.0267 (13) | 0.0169 (12) | −0.0010 (11) | −0.0007 (9) | −0.0019 (10) |
C22 | 0.0228 (15) | 0.0262 (16) | 0.0195 (15) | −0.0045 (12) | −0.0037 (12) | −0.0011 (12) |
C23 | 0.0236 (15) | 0.0291 (16) | 0.0195 (15) | −0.0033 (13) | −0.0035 (12) | 0.0019 (12) |
C24 | 0.0331 (18) | 0.0384 (19) | 0.0133 (14) | 0.0014 (15) | −0.0030 (13) | 0.0014 (13) |
C25 | 0.0339 (18) | 0.0347 (17) | 0.0175 (15) | 0.0015 (15) | −0.0037 (13) | −0.0071 (13) |
C26 | 0.0242 (15) | 0.0230 (15) | 0.0218 (15) | 0.0008 (13) | −0.0033 (13) | −0.0045 (12) |
O27 | 0.0534 (16) | 0.0312 (11) | 0.0238 (11) | −0.0108 (12) | −0.0112 (11) | 0.0084 (10) |
N1 | 0.0246 (15) | 0.061 (2) | 0.0249 (15) | −0.0105 (15) | 0.0025 (12) | −0.0157 (14) |
C1 | 0.0225 (16) | 0.0254 (15) | 0.0166 (14) | −0.0005 (13) | 0.0042 (12) | −0.0006 (12) |
N2 | 0.0255 (14) | 0.0334 (14) | 0.0176 (12) | −0.0042 (12) | −0.0002 (11) | 0.0010 (11) |
C2 | 0.0289 (18) | 0.0206 (14) | 0.0168 (14) | −0.0018 (12) | −0.0058 (12) | −0.0044 (11) |
N3 | 0.0242 (16) | 0.0343 (15) | 0.0281 (14) | 0.0002 (12) | 0.0004 (12) | −0.0050 (12) |
N4 | 0.0245 (14) | 0.0304 (14) | 0.0229 (13) | −0.0072 (12) | −0.0023 (11) | 0.0050 (11) |
C3 | 0.0307 (17) | 0.0214 (15) | 0.0123 (13) | −0.0010 (14) | −0.0032 (12) | −0.0016 (11) |
N5 | 0.0301 (15) | 0.0310 (14) | 0.0216 (13) | −0.0089 (13) | −0.0040 (12) | 0.0009 (11) |
C4 | 0.0277 (17) | 0.0232 (14) | 0.0162 (13) | −0.0041 (13) | 0.0032 (14) | −0.0024 (12) |
N6 | 0.0332 (17) | 0.0409 (17) | 0.0260 (14) | −0.0061 (13) | −0.0055 (13) | 0.0007 (13) |
Cu1—N2 | 1.983 (3) | N21—C22 | 1.341 (4) |
Cu1—N5 | 1.988 (3) | N21—C26 | 1.340 (4) |
Cu1—N21 | 2.008 (3) | C22—C23 | 1.385 (4) |
Cu1—N11 | 2.023 (3) | C22—H22A | 0.9500 |
Cu1—N3i | 2.313 (3) | C23—O27 | 1.351 (4) |
N11—C16 | 1.340 (4) | C23—C24 | 1.393 (4) |
N11—C12 | 1.343 (4) | C24—C25 | 1.370 (5) |
C12—C13 | 1.386 (4) | C24—H24A | 0.9500 |
C12—H12A | 0.9500 | C25—C26 | 1.380 (5) |
C13—O17 | 1.351 (4) | C25—H25A | 0.9500 |
C13—C14 | 1.384 (5) | C26—H26A | 0.9500 |
C13—H13A | 0.9622 | O27—H27A | 0.8400 |
C14—C15 | 1.382 (5) | N1—C1 | 1.302 (4) |
C14—H14A | 0.9500 | N1—C2 | 1.305 (4) |
C15—O171 | 1.369 (12) | C1—N2 | 1.144 (4) |
C15—C16 | 1.382 (4) | C2—N3 | 1.151 (4) |
C15—H15A | 0.9653 | N3—Cu1ii | 2.313 (3) |
C16—H16A | 0.9500 | N4—C3 | 1.300 (4) |
O17—H13A | 0.4001 | N4—C4 | 1.325 (4) |
O17—H17A | 0.8400 | C3—N5 | 1.153 (4) |
O171—H15A | 0.4357 | C4—N6 | 1.156 (4) |
O171—H171 | 0.8400 | ||
N2—Cu1—N5 | 168.50 (12) | C13—O17—H13A | 11.6 |
N2—Cu1—N21 | 91.54 (11) | C13—O17—H17A | 109.5 |
N5—Cu1—N21 | 91.83 (10) | H13A—O17—H17A | 97.9 |
N2—Cu1—N11 | 87.64 (11) | C15—O171—H15A | 18.5 |
N5—Cu1—N11 | 88.71 (11) | C15—O171—H171 | 109.5 |
N21—Cu1—N11 | 178.38 (11) | H15A—O171—H171 | 108.8 |
N2—Cu1—N3i | 96.10 (11) | C22—N21—C26 | 119.3 (3) |
N5—Cu1—N3i | 94.96 (11) | C22—N21—Cu1 | 118.3 (2) |
N21—Cu1—N3i | 88.91 (10) | C26—N21—Cu1 | 122.4 (2) |
N11—Cu1—N3i | 92.56 (10) | N21—C22—C23 | 122.5 (3) |
C16—N11—C12 | 119.3 (3) | N21—C22—H22A | 118.8 |
C16—N11—Cu1 | 121.1 (2) | C23—C22—H22A | 118.8 |
C12—N11—Cu1 | 119.6 (2) | O27—C23—C22 | 117.5 (3) |
N11—C12—C13 | 121.4 (3) | O27—C23—C24 | 124.4 (3) |
N11—C12—H12A | 119.3 | C22—C23—C24 | 118.1 (3) |
C13—C12—H12A | 119.3 | C25—C24—C23 | 118.8 (3) |
O17—C13—C14 | 124.4 (3) | C25—C24—H24A | 120.6 |
O17—C13—C12 | 115.9 (3) | C23—C24—H24A | 120.6 |
C14—C13—C12 | 119.7 (3) | C24—C25—C26 | 120.4 (3) |
O17—C13—H13A | 4.8 | C24—C25—H25A | 119.8 |
C14—C13—H13A | 119.9 | C26—C25—H25A | 119.8 |
C12—C13—H13A | 120.4 | N21—C26—C25 | 120.9 (3) |
C15—C14—C13 | 118.3 (3) | N21—C26—H26A | 119.5 |
C15—C14—H14A | 120.9 | C25—C26—H26A | 119.5 |
C13—C14—H14A | 120.9 | C23—O27—H27A | 109.5 |
O171—C15—C14 | 120.1 (5) | C1—N1—C2 | 121.4 (3) |
O171—C15—C16 | 119.6 (5) | N2—C1—N1 | 173.4 (3) |
C14—C15—C16 | 119.6 (3) | C1—N2—Cu1 | 164.6 (2) |
O171—C15—H15A | 8.2 | N3—C2—N1 | 173.4 (3) |
C14—C15—H15A | 120.0 | C2—N3—Cu1ii | 121.6 (2) |
C16—C15—H15A | 120.4 | C3—N4—C4 | 120.8 (3) |
N11—C16—C15 | 121.7 (3) | N5—C3—N4 | 172.2 (3) |
N11—C16—H16A | 119.1 | C3—N5—Cu1 | 162.4 (2) |
C15—C16—H16A | 119.1 | N6—C4—N4 | 174.4 (3) |
Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C2N3)2(C5H5NO)2] |
Mr | 385.84 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 193 |
a, b, c (Å) | 7.266 (2), 13.925 (3), 30.327 (6) |
V (Å3) | 3068.5 (12) |
Z | 8 |
Radiation type | Cu Kα |
µ (mm−1) | 2.28 |
Crystal size (mm) | 0.50 × 0.20 × 0.08 |
Data collection | |
Diffractometer | Enraf-nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.755, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2780, 2723, 2241 |
Rint | 0.100 |
(sin θ/λ)max (Å−1) | 0.597 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.120, 0.81 |
No. of reflections | 2723 |
No. of parameters | 235 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.96 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1985), CAD-4 Software, XCAD4 (Harms, 1996), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL/PC (Sheldrick, 1994), SHELXL97.
Cu1—N2 | 1.983 (3) | Cu1—N11 | 2.023 (3) |
Cu1—N5 | 1.988 (3) | Cu1—N3i | 2.313 (3) |
Cu1—N21 | 2.008 (3) | ||
N2—Cu1—N5 | 168.50 (12) | N2—Cu1—N3i | 96.10 (11) |
N2—Cu1—N21 | 91.54 (11) | N5—Cu1—N3i | 94.96 (11) |
N5—Cu1—N21 | 91.83 (10) | N21—Cu1—N3i | 88.91 (10) |
N5—Cu1—N11 | 88.71 (11) | N11—Cu1—N3i | 92.56 (10) |
N21—Cu1—N11 | 178.38 (11) |
Symmetry code: (i) x+1, y, z. |
Dicyanamide has gained much interest in recent years, especially in the form of MII[N(CN)2]2 (M = Ni, Co, Cu, Zn), as a new class of magnetic materials (Batten et al., 1998; Jensen, Batten, Fallon, Moubaraki et al., 1999; Kohout et al., 2000; Manson et al., 1998, 1999). The X-ray structures of a number of compounds of copper(II) containing the dicyanamide anion have been reported (Potočňák et al., 2001; Riggio et al., 2001, Martín et al., 2001). Dicyanamide itself is a most interesting anionic bridging ligand and can act as a monodentate, bidentate (two types of binding) or even tridentate ligand (Mroziński et al., 1997; Escuer et al., 2000).
With the ligand used in this study, 3-hydroxypyridine, so far only five structures with CuII are known, i.e. two polymeric structures (Castillo et al., 2000; Kawata et al., 1997) and three structures in which this ligand is used as a coligand (Breeze & Wang 1993; Castillo et al., 2001).
X-ray structures of polymeric compounds with CuII and dicyanamide having the general formula [CuII{N(CN)2}2(L)y]n (y = 1 or 2, L = coordinating organic molecule) are, however, very rare. Up to now, six compounds with different polymeric networks are known. The compound [CuII{N(CN)2}2(2-aminopyrimidine)2]n forms a one-dimensional network of two bridging dicyanamide anions to the same Cu atom (van Albada et al., 2000); β-[CuII{N(CN)2}2(pyrazine)2]n forms a two-dimensional network of which the one-dimensional structure is obtained by bridging of the two dicyanamide anions to the same Cu atom and the two-dimensional structure by bridging of the pyrazine ligand to a different Cu atom (Jensen, Batten, Fallon, Hockless et al., 1999). Compounds α-[CuII{N(CN)2}2(pyrazine)2]n, [CuII{N(CN)2}2(pyrimidine)2]n and [CuII{N(CN)2}2(bipyrimidine)]n forms a two-dimensional network of dicyanamide anions which are bridging to different Cu atoms to form [Cu(dicyanamide)]n sheets and the third dimension is obtained by bridging of the ligand (Jensen, Batten, Fallon, Hockless et al., 1999; Riggio et al., 2001; Martín et al.,2001). The last type are compounds of type [CuII{N(CN)2}2(1,10-phenantroline)2]n (Wang et al., 2000) and [CuII{N(CN)2}2(5,5'-dimethyl-2,2'-bipyridine)]n (Kooijman et al., 2001), these types form a one-dimensional polymeric network of only one bridging dicyanamide anion, while the second dicyanamide is monodenate. The title compound, (I), belongs to this last class of these polymeric compounds.
The geometry around the CuII ion is distorted square pyrimidal, with the basal plane formed by two N atoms of two different 3-hydroxypyridine molecules (N11 and N21), one N atom of the monodentate dicyanamide anion (N5) and one N atom of the bridging dicyanamide anion (N2). The Cu—N distances vary from 1.983 (3) to 2.023 (3) Å. The apical position is occupied by an N atom of the bridging dicyanamide anion (N3) at a distance of 2.313 (3) Å. The N atom at the other apical site (N6A) is at a very long distance [2.967 (3) Å]. The distortion from square pyrimidal can be best described by the structural parameter τ (τ describes the relative amount of trigonality; τ = 0 for a square pyramid and τ = 1 for a trigonal bipyramid), which is, in this case, 0.16 (Addison et al., 1984). The lattice is stabilized by stacking of the pyridine rings, with a distance of 3.743 Å, and by hydrogen bonding between the pyridine OH group and the N4 and N6 atoms of neighbouring dicyanamide anions, with distances of 2.867 and 2.846 Å, respectively. All these structural parameters can be best compared with the compound [CuII{N(CN)2}2(5,5'-dimethyl-2,2'-bipyridine)]n (Kooijman et al., 2001), which has a similar type of structure.
The ligand field spectrum of the copper(II) compound shows a broad d-d transition band centered around 15.5 × 103 cm-1, with a shoulder at the low-energy side. The characteristic IR vibrations for the dicyanamide anion are the νs + ν as(CN) vibration. These vibrations are found as a split band at 2303 and 2287 cm-1, a medium strong band at 2243 cm-1 and a broad very strong band at 2169 cm-1, with a shoulder at 2158 cm-1.