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In the crystal structure of the title compound, [CuII{N(CN)2}2(C5H5NO)2], the geometry around the copper(II) ion is distorted square pyramidal, with the basal plane formed by the N atoms of two 3-hydroxy­pyridine mol­ecules, one N atom of a bidentate dicyan­amide anion and one N atom of a monodentate dicyan­amide anion. The apical position is occupied by an N atom of a bidentate dicyan­amide anion, forming a one-dimensional polymeric chain.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680101460X/cv6054sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680101460X/cv6054Isup2.hkl
Contains datablock I

CCDC reference: 175321

Key indicators

  • Single-crystal X-ray study
  • T = 193 K
  • Mean [sigma](C-C) = 0.005 Å
  • Disorder in main residue
  • R factor = 0.041
  • wR factor = 0.120
  • Data-to-parameter ratio = 11.6

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
WEIGH_01 Alert C Extra text has been found in the _refine_ls_weighting_scheme field. This should be in the _refine_ls_weighting_details field. Weighting scheme given as calc w = 1/[\s^2^(Fo^2^)+(0.0878P)^2^+8.761 Weighting scheme identified as calc PLAT_301 Alert C Main Residue Disorder ........................ 4.00 Perc. General Notes
ABSTM_02 When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.834 Tmax scaled 0.834 Tmin scaled 0.629
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check

Comment top

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.

Experimental top

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.

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. ORTEP plot of the title compound with the atom-labelling scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level. H atoms have been omitted for clarity. Atoms marked with an `A' are generated by an inversion centre.
catena-Poly[[dicyanamidobis(3-hydroxypyridine-N)copper(II)]-µ-dicyanamido] top
Crystal data top
[Cu(C2N3)2(C5H5NO)2]Dx = 1.670 Mg m3
Mr = 385.84Cu Kα radiation, λ = 1.54180 Å
Orthorhombic, PbcaCell parameters from 25 reflections
a = 7.266 (2) Åθ = 12–27°
b = 13.925 (3) ŵ = 2.28 mm1
c = 30.327 (6) ÅT = 193 K
V = 3068.5 (12) Å3Prismatic, green
Z = 80.50 × 0.20 × 0.08 mm
F(000) = 1560
Data collection top
Enraf-nonius CAD-4
diffractometer
2241 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.100
Graphite monochromatorθmax = 66.9°, θmin = 2.9°
ω–2θ scansh = 80
Absorption correction: ψ scan
(North et al., 1968)
k = 160
Tmin = 0.755, Tmax = 1.000l = 3611
2780 measured reflections3 standard reflections every 200 reflections
2723 independent reflections intensity decay: 0.0%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.120H-atom parameters constrained
S = 0.81Calculated w = 1/[σ2(Fo2) + (0.0878P)2 + 8.7618P]
where P = (Fo2 + 2Fc2)/3
2723 reflections(Δ/σ)max = 0.001
235 parametersΔρmax = 0.32 e Å3
0 restraintsΔρmin = 0.96 e Å3
Crystal data top
[Cu(C2N3)2(C5H5NO)2]V = 3068.5 (12) Å3
Mr = 385.84Z = 8
Orthorhombic, PbcaCu Kα radiation
a = 7.266 (2) ŵ = 2.28 mm1
b = 13.925 (3) ÅT = 193 K
c = 30.327 (6) Å0.50 × 0.20 × 0.08 mm
Data collection top
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 = 1.0003 standard reflections every 200 reflections
2780 measured reflections intensity decay: 0.0%
2723 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.120H-atom parameters constrained
S = 0.81Δρmax = 0.32 e Å3
2723 reflectionsΔρmin = 0.96 e Å3
235 parameters
Special details top

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) top
xyzUiso*/UeqOcc. (<1)
Cu10.11022 (6)0.14599 (3)0.130442 (13)0.01939 (17)
N110.1003 (4)0.19606 (19)0.06788 (8)0.0229 (6)
C120.0875 (4)0.1339 (2)0.03419 (10)0.0240 (7)
H12A0.08170.06700.04020.029*
C130.0826 (5)0.1652 (2)0.00915 (10)0.0258 (7)
H13A0.07440.11980.03300.031*0.25
C140.0892 (5)0.2626 (2)0.01816 (10)0.0288 (7)
H14A0.08640.28540.04770.035*
C150.0998 (5)0.3258 (2)0.01689 (11)0.0309 (8)
H15A0.10280.39410.01160.037*0.75
C160.1066 (5)0.2905 (2)0.05945 (10)0.0280 (7)
H16A0.11600.33430.08340.034*
O170.0654 (4)0.09604 (19)0.04008 (8)0.0261 (7)0.75
H17A0.08760.11930.06510.039*0.75
O1710.1309 (19)0.4214 (8)0.0094 (4)0.057 (3)0.25
H1710.13920.43120.01780.085*0.25
N210.1136 (3)0.09834 (19)0.19294 (8)0.0212 (5)
C220.0691 (4)0.0064 (2)0.20051 (10)0.0229 (6)
H22A0.04190.03400.17610.027*
C230.0611 (4)0.0321 (2)0.24258 (10)0.0241 (7)
C240.1007 (5)0.0281 (3)0.27804 (10)0.0282 (7)
H24A0.09420.00480.30740.034*
C250.1490 (5)0.1215 (3)0.26978 (11)0.0287 (7)
H25A0.17900.16300.29360.034*
C260.1544 (4)0.1556 (2)0.22707 (10)0.0230 (6)
H26A0.18750.22060.22180.028*
O270.0140 (4)0.12552 (15)0.24642 (8)0.0361 (6)
H27A0.03280.14390.27240.054*
N10.4039 (4)0.0225 (3)0.08212 (9)0.0368 (8)
C10.2654 (4)0.0571 (2)0.10424 (9)0.0215 (6)
N20.1348 (4)0.0875 (2)0.11995 (8)0.0255 (6)
C20.5689 (4)0.0191 (2)0.09899 (9)0.0221 (7)
N30.7200 (4)0.0127 (2)0.11002 (9)0.0289 (6)
N40.6075 (4)0.3220 (2)0.12620 (9)0.0260 (6)
C30.4645 (5)0.2703 (2)0.13617 (9)0.0215 (6)
N50.3280 (4)0.2293 (2)0.14094 (8)0.0276 (6)
C40.7622 (5)0.3143 (2)0.14901 (9)0.0224 (6)
N60.9038 (4)0.3123 (2)0.16638 (10)0.0334 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0201 (3)0.0245 (3)0.0135 (2)0.00362 (18)0.00160 (16)0.00089 (16)
N110.0255 (14)0.0234 (13)0.0197 (12)0.0024 (11)0.0015 (10)0.0005 (10)
C120.0307 (17)0.0210 (15)0.0202 (15)0.0040 (13)0.0007 (13)0.0019 (12)
C130.0329 (18)0.0296 (17)0.0149 (14)0.0036 (14)0.0004 (13)0.0012 (13)
C140.0420 (19)0.0276 (17)0.0170 (15)0.0014 (15)0.0018 (14)0.0034 (13)
C150.048 (2)0.0218 (15)0.0226 (16)0.0003 (15)0.0041 (15)0.0026 (13)
C160.0407 (19)0.0235 (15)0.0198 (16)0.0000 (14)0.0016 (14)0.0009 (13)
O170.0506 (19)0.0192 (13)0.0085 (12)0.0036 (13)0.0039 (12)0.0028 (10)
O1710.095 (10)0.041 (6)0.034 (6)0.012 (7)0.004 (6)0.006 (5)
N210.0200 (13)0.0267 (13)0.0169 (12)0.0010 (11)0.0007 (9)0.0019 (10)
C220.0228 (15)0.0262 (16)0.0195 (15)0.0045 (12)0.0037 (12)0.0011 (12)
C230.0236 (15)0.0291 (16)0.0195 (15)0.0033 (13)0.0035 (12)0.0019 (12)
C240.0331 (18)0.0384 (19)0.0133 (14)0.0014 (15)0.0030 (13)0.0014 (13)
C250.0339 (18)0.0347 (17)0.0175 (15)0.0015 (15)0.0037 (13)0.0071 (13)
C260.0242 (15)0.0230 (15)0.0218 (15)0.0008 (13)0.0033 (13)0.0045 (12)
O270.0534 (16)0.0312 (11)0.0238 (11)0.0108 (12)0.0112 (11)0.0084 (10)
N10.0246 (15)0.061 (2)0.0249 (15)0.0105 (15)0.0025 (12)0.0157 (14)
C10.0225 (16)0.0254 (15)0.0166 (14)0.0005 (13)0.0042 (12)0.0006 (12)
N20.0255 (14)0.0334 (14)0.0176 (12)0.0042 (12)0.0002 (11)0.0010 (11)
C20.0289 (18)0.0206 (14)0.0168 (14)0.0018 (12)0.0058 (12)0.0044 (11)
N30.0242 (16)0.0343 (15)0.0281 (14)0.0002 (12)0.0004 (12)0.0050 (12)
N40.0245 (14)0.0304 (14)0.0229 (13)0.0072 (12)0.0023 (11)0.0050 (11)
C30.0307 (17)0.0214 (15)0.0123 (13)0.0010 (14)0.0032 (12)0.0016 (11)
N50.0301 (15)0.0310 (14)0.0216 (13)0.0089 (13)0.0040 (12)0.0009 (11)
C40.0277 (17)0.0232 (14)0.0162 (13)0.0041 (13)0.0032 (14)0.0024 (12)
N60.0332 (17)0.0409 (17)0.0260 (14)0.0061 (13)0.0055 (13)0.0007 (13)
Geometric parameters (Å, º) top
Cu1—N21.983 (3)N21—C221.341 (4)
Cu1—N51.988 (3)N21—C261.340 (4)
Cu1—N212.008 (3)C22—C231.385 (4)
Cu1—N112.023 (3)C22—H22A0.9500
Cu1—N3i2.313 (3)C23—O271.351 (4)
N11—C161.340 (4)C23—C241.393 (4)
N11—C121.343 (4)C24—C251.370 (5)
C12—C131.386 (4)C24—H24A0.9500
C12—H12A0.9500C25—C261.380 (5)
C13—O171.351 (4)C25—H25A0.9500
C13—C141.384 (5)C26—H26A0.9500
C13—H13A0.9622O27—H27A0.8400
C14—C151.382 (5)N1—C11.302 (4)
C14—H14A0.9500N1—C21.305 (4)
C15—O1711.369 (12)C1—N21.144 (4)
C15—C161.382 (4)C2—N31.151 (4)
C15—H15A0.9653N3—Cu1ii2.313 (3)
C16—H16A0.9500N4—C31.300 (4)
O17—H13A0.4001N4—C41.325 (4)
O17—H17A0.8400C3—N51.153 (4)
O171—H15A0.4357C4—N61.156 (4)
O171—H1710.8400
N2—Cu1—N5168.50 (12)C13—O17—H13A11.6
N2—Cu1—N2191.54 (11)C13—O17—H17A109.5
N5—Cu1—N2191.83 (10)H13A—O17—H17A97.9
N2—Cu1—N1187.64 (11)C15—O171—H15A18.5
N5—Cu1—N1188.71 (11)C15—O171—H171109.5
N21—Cu1—N11178.38 (11)H15A—O171—H171108.8
N2—Cu1—N3i96.10 (11)C22—N21—C26119.3 (3)
N5—Cu1—N3i94.96 (11)C22—N21—Cu1118.3 (2)
N21—Cu1—N3i88.91 (10)C26—N21—Cu1122.4 (2)
N11—Cu1—N3i92.56 (10)N21—C22—C23122.5 (3)
C16—N11—C12119.3 (3)N21—C22—H22A118.8
C16—N11—Cu1121.1 (2)C23—C22—H22A118.8
C12—N11—Cu1119.6 (2)O27—C23—C22117.5 (3)
N11—C12—C13121.4 (3)O27—C23—C24124.4 (3)
N11—C12—H12A119.3C22—C23—C24118.1 (3)
C13—C12—H12A119.3C25—C24—C23118.8 (3)
O17—C13—C14124.4 (3)C25—C24—H24A120.6
O17—C13—C12115.9 (3)C23—C24—H24A120.6
C14—C13—C12119.7 (3)C24—C25—C26120.4 (3)
O17—C13—H13A4.8C24—C25—H25A119.8
C14—C13—H13A119.9C26—C25—H25A119.8
C12—C13—H13A120.4N21—C26—C25120.9 (3)
C15—C14—C13118.3 (3)N21—C26—H26A119.5
C15—C14—H14A120.9C25—C26—H26A119.5
C13—C14—H14A120.9C23—O27—H27A109.5
O171—C15—C14120.1 (5)C1—N1—C2121.4 (3)
O171—C15—C16119.6 (5)N2—C1—N1173.4 (3)
C14—C15—C16119.6 (3)C1—N2—Cu1164.6 (2)
O171—C15—H15A8.2N3—C2—N1173.4 (3)
C14—C15—H15A120.0C2—N3—Cu1ii121.6 (2)
C16—C15—H15A120.4C3—N4—C4120.8 (3)
N11—C16—C15121.7 (3)N5—C3—N4172.2 (3)
N11—C16—H16A119.1C3—N5—Cu1162.4 (2)
C15—C16—H16A119.1N6—C4—N4174.4 (3)
Symmetry codes: (i) x+1, y, z; (ii) x1, y, z.

Experimental details

Crystal data
Chemical formula[Cu(C2N3)2(C5H5NO)2]
Mr385.84
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)193
a, b, c (Å)7.266 (2), 13.925 (3), 30.327 (6)
V3)3068.5 (12)
Z8
Radiation typeCu Kα
µ (mm1)2.28
Crystal size (mm)0.50 × 0.20 × 0.08
Data collection
DiffractometerEnraf-nonius CAD-4
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.755, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
2780, 2723, 2241
Rint0.100
(sin θ/λ)max1)0.597
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.120, 0.81
No. of reflections2723
No. of parameters235
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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.

Selected geometric parameters (Å, º) top
Cu1—N21.983 (3)Cu1—N112.023 (3)
Cu1—N51.988 (3)Cu1—N3i2.313 (3)
Cu1—N212.008 (3)
N2—Cu1—N5168.50 (12)N2—Cu1—N3i96.10 (11)
N2—Cu1—N2191.54 (11)N5—Cu1—N3i94.96 (11)
N5—Cu1—N2191.83 (10)N21—Cu1—N3i88.91 (10)
N5—Cu1—N1188.71 (11)N11—Cu1—N3i92.56 (10)
N21—Cu1—N11178.38 (11)
Symmetry code: (i) x+1, y, z.
 

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