Download citation
Download citation
link to html
The CuI cations in the title compound, [Cu(NCS)(C6H6N2O)2]n, are coordinated by N atoms from each of two mirror-related nicotin­amide ligands, as well as by one N atom of one thio­cyanate ligand and one S atom of a symmetry-related thio­cyanate ligand, within a slightly distorted tetrahedron. The CuI cations and the thio­cyanate anions are located on a crystallographic mirror plane and the nicotin­amide ligands occupy general positions. The CuI cations are connected by the thio­cyanate anions to form chains in the direction of the crystallographic a axis. These chains are connected by hydrogen bonds between the amide H atoms and the O atoms of adjacent nicotin­amide ligands, to give a three-dimensional structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102001592/ln1135sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102001592/ln1135Isup2.hkl
Contains datablock I

CCDC reference: 182986

Comment top

Coordination polymers based on copper(I) halides or pseudohalides and aromatic amine ligands show great structural diversity. The copper(I) halides and pseudohalides form typical inorganic substructures, such as dimers, single and double chains, or helical structures, which are linked by amine ligands to give multidimensional coordination polymers (Blake et al., 1999; Kromp & Sheldrick, 1999; Teichert & Sheldrick, 1999, 2000; Graham et al., 2000; Ro\&senbeck & Sheldrick, 2000; Näther & Greve, 2001; Näther & Je\&s, 2001; Persky et al., 2001).

The dimensionality of such coordination polymers depends predominantly on the coordination behaviour of the organic ligands. If the amine ligand contains two N atoms that are bound to two different CuI cations, mostly two- and three-dimensional structures are observed. A different strategy to connect the CuX substructures (X is Cl, Br, I, SCN or CN) is hydrogen bonding between the organic amine ligands, which are linked to the CuX substructures by N coordination. In this case, the amine ligands must contain hydrogen-bond donor and/or acceptor groups, such as nicotinamide or isonicotinamide. These compounds were used, for example, for the preparation of some coordination polymers based on chromium-arene compounds (Brammer et al., 2000). Starting from these results, we have prepared crystals of the title compound, (I), by the reaction of CuISCN with nicotinamide in acetonitrile. According to a search in the Cambridge Structural Database (CSD; Conquest Version 1.3, 2001; Allen & Kennard, 1993), the only previously known copper complexes with nicotinamide are those involving CuII. \sch

In the crystal structure of (I), the CuI atoms are coordinated by the N atom from one thiocyanate ligand, the S atom from a symmetry-related thiocyanate ligand and an N atom from each of two nicotinamide ligands, which are related by a crystallographic mirror plane that passes through the CuI atoms and the thiocyanate ligands (Fig. 1).

The Cu—N and Cu—S bond lengths in (I) are in the range of comparable CuI complexes retrieved from the CSD. The X—Cu—X angles are between 108.10 (8) and 112.46 (6)°, and the coordination polyhedron around the CuI cation can therefore be described as a slightly distorted tetrahedron. The CuI cations are connected by the thiocyanate ligands via µ-N,S coordination to form single ribbon-like chains which run in the direction of the crystallographic a axis. A similar CuSCN substructure is found in the crystal structure of poly[CuSCN(µ2-2-methylpyrazine)] (Teichert & Sheldrick, 1999).

The CuSCN chains are connected by the nicotinamide ligands, via N—H···O hydrogen bonds between the O atoms and the amide H atoms of adjacent nicotinamide ligands. The O atom acts as an acceptor for two different hydrogen bonds and both amide N atoms are involved as donors. Two O atoms and two amide –NH2 groups of four different nicotinamide ligands form nearly planar eight-membered rings, which are located around centres of inversion. Because the nicotinamide ligand is hydrogen bonded to two further nicotinamide ligands from two neighbouring CuSCN chains, a three-dimensional `loop structure' is formed.

The observed hydrogen-bonding pattern is different from that in other nicotinamide coordination polymers, such as [Pt(nicotinamide)Cl2] (Brammer et al., 2000). In this latter compound, the nicotinamide ligand is connected only to one further ligand, by two N—H···O hydrogen bonds within a six-membered ring. Another complex in which CuISCN coordination polymers are connected via hydrogen bonds between the ligands is catena-poly[(µ2-thiocyanato)bis(4-hydroxypyrimidine)copper(I)] (Teichert & Sheldrick, 2000). In this compound, `zigzag-like' CuSCN chains are also found. In contrast with (I), only a single O—H···N hydrogen bond is found between the hydroxy H atom and the uncoordinated pyrimidine N atom. In this compound, a loop structure is also found which is very similar to that in (I). However, the results presented here show that hydrogen bonding is a useful tool to expand the dimensionality in such CuI coordination polymers.

Experimental top

The title compound was prepared by the reaction of nicotinamide (ACROS; 122.13 mg, 1 mmol) and copper(I) thiocyanate (Alfa; 121.62 mg, 1 mmol) in acetonitrile (4 ml) at room temperature in a glass container. The reaction mixture was stirred for 1 d, and the resulting light-yellow precipitate of (I) was filtered off and washed with water (yield 90.3%). The compound was shown to be phase pure by X-ray powder diffraction. For the preparation of single crystals of (I), the reaction mixture was not stirred.

Refinement top

All H atoms could be located in a difference Fourier map. Aromatic H atoms were positioned with idealized geometry and refined using a riding model, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). The positions of the amide H atoms were taken from the difference Fourier map and they were then refined as rigid groups, with N—H = 0.86 Å and Uiso(H) = 1.5Ueq(N).

Computing details top

Data collection: IPDS (Stoe & Cie, 1998); cell refinement: IPDS; data reduction: IPDS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Bruker AXS, 1997); software used to prepare material for publication: CIFTAB in SHELXL97.

Figures top
[Figure 1] Fig. 1. A view of (I) showing the coordination of the CuI atom and the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii [symmetry codes: (i) 1/2 + x, y, 3/2 - z; (ii) x, 1/2 - y, z].
[Figure 2] Fig. 2. The crystal structure of (I) viewed down (010). Hydrogen bonds are shown as dashed lines and the H atoms bonded to C atoms have been omitted for clarity.
catena-Poly[[bis(nicotinamide-κN1)copper(I)]-µ-thiocyanato-κ2N:S] top
Crystal data top
[Cu(C6H6N2O)2(CNS)]Dx = 1.679 Mg m3
Mr = 365.88Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PnmaCell parameters from 8000 reflections
a = 8.9304 (4) Åθ = 3–26°
b = 21.3533 (12) ŵ = 1.67 mm1
c = 7.5895 (3) ÅT = 293 K
V = 1447.27 (12) Å3Block, yellow
Z = 40.12 × 0.09 × 0.05 mm
F(000) = 744
Data collection top
Stoe IPDS
diffractometer
1172 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.044
Graphite monochromatorθmax = 26.0°, θmin = 1.9°
ϕ scansh = 1010
11282 measured reflectionsk = 2626
1446 independent reflectionsl = 99
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030H-atom parameters constrained
wR(F2) = 0.078 w = 1/[σ2(Fo2) + (0.0398P)2 + 0.7777P]
where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max = 0.001
1446 reflectionsΔρmax = 0.30 e Å3
107 parametersΔρmin = 0.43 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0084 (9)
Crystal data top
[Cu(C6H6N2O)2(CNS)]V = 1447.27 (12) Å3
Mr = 365.88Z = 4
Orthorhombic, PnmaMo Kα radiation
a = 8.9304 (4) ŵ = 1.67 mm1
b = 21.3533 (12) ÅT = 293 K
c = 7.5895 (3) Å0.12 × 0.09 × 0.05 mm
Data collection top
Stoe IPDS
diffractometer
1172 reflections with I > 2σ(I)
11282 measured reflectionsRint = 0.044
1446 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.078H-atom parameters constrained
S = 1.10Δρmax = 0.30 e Å3
1446 reflectionsΔρmin = 0.43 e Å3
107 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*/Ueq
Cu10.75590 (4)0.25000.62891 (6)0.03028 (17)
S10.76638 (9)0.25000.93515 (13)0.0400 (3)
C10.5462 (2)0.36175 (10)0.6268 (3)0.0243 (5)
H10.54560.35590.74820.029*
C20.4521 (2)0.40667 (10)0.5560 (3)0.0236 (5)
C30.4507 (3)0.41488 (11)0.3753 (3)0.0361 (6)
H30.38600.44350.32290.043*
C40.5480 (4)0.37949 (13)0.2744 (4)0.0477 (7)
H40.55170.38480.15290.057*
C50.6390 (3)0.33648 (12)0.3552 (3)0.0392 (6)
H50.70450.31320.28600.047*
C60.3485 (2)0.44396 (10)0.6696 (3)0.0263 (5)
N10.6378 (2)0.32644 (8)0.5295 (3)0.0276 (4)
N20.3939 (2)0.45502 (10)0.8325 (3)0.0350 (5)
H1N20.48500.44830.86430.053*
H2N20.34160.47790.90230.053*
O10.22639 (18)0.46248 (9)0.6120 (2)0.0380 (4)
C70.5838 (3)0.25000.9612 (4)0.0254 (7)
N30.4560 (3)0.25000.9782 (4)0.0385 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0233 (2)0.0290 (2)0.0385 (3)0.0000.00260 (17)0.000
S10.0241 (4)0.0657 (6)0.0302 (5)0.0000.0001 (3)0.000
C10.0258 (10)0.0245 (10)0.0226 (12)0.0013 (9)0.0003 (9)0.0012 (9)
C20.0219 (10)0.0220 (10)0.0268 (12)0.0014 (8)0.0000 (9)0.0016 (9)
C30.0447 (13)0.0328 (12)0.0306 (14)0.0103 (11)0.0037 (11)0.0069 (11)
C40.076 (2)0.0462 (16)0.0209 (14)0.0174 (15)0.0056 (13)0.0042 (11)
C50.0530 (15)0.0335 (13)0.0310 (16)0.0112 (12)0.0120 (11)0.0025 (11)
C60.0225 (10)0.0248 (10)0.0315 (13)0.0015 (8)0.0022 (9)0.0065 (9)
N10.0307 (10)0.0224 (9)0.0298 (12)0.0028 (7)0.0018 (8)0.0011 (8)
N20.0280 (10)0.0438 (12)0.0333 (12)0.0130 (9)0.0011 (8)0.0078 (9)
O10.0244 (8)0.0497 (11)0.0399 (11)0.0132 (7)0.0014 (7)0.0074 (8)
C70.0290 (17)0.0269 (15)0.0202 (17)0.0000.0043 (13)0.000
N30.0243 (15)0.0511 (19)0.0401 (19)0.0000.0056 (13)0.000
Geometric parameters (Å, º) top
Cu1—N3i1.963 (3)C3—H30.9300
Cu1—N12.0848 (18)C4—C51.371 (4)
Cu1—S12.3261 (11)C4—H40.9300
S1—C71.642 (3)C5—N11.339 (3)
C1—N11.336 (3)C5—H50.9300
C1—C21.384 (3)C6—O11.240 (3)
C1—H10.9300C6—N21.322 (3)
C2—C31.383 (3)N2—H1N20.8600
C2—C61.494 (3)N2—H2N20.8600
C3—C41.383 (4)C7—N31.149 (4)
N3i—Cu1—N1108.10 (8)C3—C4—H4120.3
N1ii—Cu1—N1103.05 (10)N1—C5—C4123.0 (2)
N3i—Cu1—S1112.15 (10)N1—C5—H5118.5
N1—Cu1—S1112.46 (6)C4—C5—H5118.5
C7—S1—Cu194.61 (12)O1—C6—N2122.9 (2)
N1—C1—C2123.3 (2)O1—C6—C2120.7 (2)
N1—C1—H1118.4N2—C6—C2116.39 (19)
C2—C1—H1118.4C1—N1—C5117.4 (2)
C3—C2—C1118.6 (2)C1—N1—Cu1123.47 (16)
C3—C2—C6120.0 (2)C5—N1—Cu1118.59 (16)
C1—C2—C6121.4 (2)C6—N2—H1N2121.5
C4—C3—C2118.3 (2)C6—N2—H2N2120.8
C4—C3—H3120.8H1N2—N2—H2N2115.9
C2—C3—H3120.8N3—C7—S1179.5 (3)
C5—C4—C3119.4 (2)C7—N3—Cu1iii149.1 (3)
C5—C4—H4120.3
N3i—Cu1—S1—C7180.0C1—C2—C6—N230.7 (3)
N1—Cu1—S1—C757.91 (6)C2—C1—N1—C51.2 (3)
N1—C1—C2—C31.1 (3)C2—C1—N1—Cu1170.54 (16)
N1—C1—C2—C6178.4 (2)C4—C5—N1—C12.1 (4)
C1—C2—C3—C42.6 (4)C4—C5—N1—Cu1170.1 (2)
C6—C2—C3—C4179.9 (2)N3i—Cu1—N1—C1140.89 (18)
C2—C3—C4—C51.8 (4)N1ii—Cu1—N1—C1104.82 (17)
C3—C4—C5—N10.5 (5)S1—Cu1—N1—C116.54 (19)
C3—C2—C6—O128.7 (3)N3i—Cu1—N1—C547.4 (2)
C1—C2—C6—O1148.6 (2)N1ii—Cu1—N1—C566.9 (2)
C3—C2—C6—N2152.0 (2)S1—Cu1—N1—C5171.77 (17)
Symmetry codes: (i) x+1/2, y, z+3/2; (ii) x, y+1/2, z; (iii) x1/2, y, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H1N2···O1i0.862.183.003 (3)159
N2—H2N2···O1iv0.862.132.959 (3)163
Symmetry codes: (i) x+1/2, y, z+3/2; (iv) x+1/2, y+1, z+1/2.

Experimental details

Crystal data
Chemical formula[Cu(C6H6N2O)2(CNS)]
Mr365.88
Crystal system, space groupOrthorhombic, Pnma
Temperature (K)293
a, b, c (Å)8.9304 (4), 21.3533 (12), 7.5895 (3)
V3)1447.27 (12)
Z4
Radiation typeMo Kα
µ (mm1)1.67
Crystal size (mm)0.12 × 0.09 × 0.05
Data collection
DiffractometerStoe IPDS
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
11282, 1446, 1172
Rint0.044
(sin θ/λ)max1)0.616
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.078, 1.10
No. of reflections1446
No. of parameters107
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.30, 0.43

Computer programs: IPDS (Stoe & Cie, 1998), IPDS, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL (Bruker AXS, 1997), CIFTAB in SHELXL97.

Selected geometric parameters (Å, º) top
Cu1—N3i1.963 (3)Cu1—S12.3261 (11)
Cu1—N12.0848 (18)
N3i—Cu1—N1108.10 (8)N3i—Cu1—S1112.15 (10)
N1ii—Cu1—N1103.05 (10)N1—Cu1—S1112.46 (6)
Symmetry codes: (i) x+1/2, y, z+3/2; (ii) x, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H1N2···O1i0.862.183.003 (3)159
N2—H2N2···O1iii0.862.132.959 (3)163
Symmetry codes: (i) x+1/2, y, z+3/2; (iii) x+1/2, y+1, z+1/2.
 

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds