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
CCDC reference: 182986
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.
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).
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.
catena-Poly[[bis(nicotinamide-
κN1)copper(I)]-µ-thiocyanato-
κ2N:
S]
top
Crystal data top
[Cu(C6H6N2O)2(CNS)] | Dx = 1.679 Mg m−3 |
Mr = 365.88 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pnma | Cell parameters from 8000 reflections |
a = 8.9304 (4) Å | θ = 3–26° |
b = 21.3533 (12) Å | µ = 1.67 mm−1 |
c = 7.5895 (3) Å | T = 293 K |
V = 1447.27 (12) Å3 | Block, yellow |
Z = 4 | 0.12 × 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 tube | Rint = 0.044 |
Graphite monochromator | θmax = 26.0°, θmin = 1.9° |
ϕ scans | h = −10→10 |
11282 measured reflections | k = −26→26 |
1446 independent reflections | l = −9→9 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.030 | H-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 reflections | Δρmax = 0.30 e Å−3 |
107 parameters | Δρmin = −0.43 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0084 (9) |
Crystal data top
[Cu(C6H6N2O)2(CNS)] | V = 1447.27 (12) Å3 |
Mr = 365.88 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 8.9304 (4) Å | µ = 1.67 mm−1 |
b = 21.3533 (12) Å | T = 293 K |
c = 7.5895 (3) Å | 0.12 × 0.09 × 0.05 mm |
Data collection top
Stoe IPDS diffractometer | 1172 reflections with I > 2σ(I) |
11282 measured reflections | Rint = 0.044 |
1446 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.078 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.30 e Å−3 |
1446 reflections | Δρmin = −0.43 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
Cu1 | 0.75590 (4) | 0.2500 | 0.62891 (6) | 0.03028 (17) | |
S1 | 0.76638 (9) | 0.2500 | 0.93515 (13) | 0.0400 (3) | |
C1 | 0.5462 (2) | 0.36175 (10) | 0.6268 (3) | 0.0243 (5) | |
H1 | 0.5456 | 0.3559 | 0.7482 | 0.029* | |
C2 | 0.4521 (2) | 0.40667 (10) | 0.5560 (3) | 0.0236 (5) | |
C3 | 0.4507 (3) | 0.41488 (11) | 0.3753 (3) | 0.0361 (6) | |
H3 | 0.3860 | 0.4435 | 0.3229 | 0.043* | |
C4 | 0.5480 (4) | 0.37949 (13) | 0.2744 (4) | 0.0477 (7) | |
H4 | 0.5517 | 0.3848 | 0.1529 | 0.057* | |
C5 | 0.6390 (3) | 0.33648 (12) | 0.3552 (3) | 0.0392 (6) | |
H5 | 0.7045 | 0.3132 | 0.2860 | 0.047* | |
C6 | 0.3485 (2) | 0.44396 (10) | 0.6696 (3) | 0.0263 (5) | |
N1 | 0.6378 (2) | 0.32644 (8) | 0.5295 (3) | 0.0276 (4) | |
N2 | 0.3939 (2) | 0.45502 (10) | 0.8325 (3) | 0.0350 (5) | |
H1N2 | 0.4850 | 0.4483 | 0.8643 | 0.053* | |
H2N2 | 0.3416 | 0.4779 | 0.9023 | 0.053* | |
O1 | 0.22639 (18) | 0.46248 (9) | 0.6120 (2) | 0.0380 (4) | |
C7 | 0.5838 (3) | 0.2500 | 0.9612 (4) | 0.0254 (7) | |
N3 | 0.4560 (3) | 0.2500 | 0.9782 (4) | 0.0385 (7) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0233 (2) | 0.0290 (2) | 0.0385 (3) | 0.000 | 0.00260 (17) | 0.000 |
S1 | 0.0241 (4) | 0.0657 (6) | 0.0302 (5) | 0.000 | 0.0001 (3) | 0.000 |
C1 | 0.0258 (10) | 0.0245 (10) | 0.0226 (12) | 0.0013 (9) | −0.0003 (9) | 0.0012 (9) |
C2 | 0.0219 (10) | 0.0220 (10) | 0.0268 (12) | −0.0014 (8) | 0.0000 (9) | 0.0016 (9) |
C3 | 0.0447 (13) | 0.0328 (12) | 0.0306 (14) | 0.0103 (11) | −0.0037 (11) | 0.0069 (11) |
C4 | 0.076 (2) | 0.0462 (16) | 0.0209 (14) | 0.0174 (15) | 0.0056 (13) | 0.0042 (11) |
C5 | 0.0530 (15) | 0.0335 (13) | 0.0310 (16) | 0.0112 (12) | 0.0120 (11) | −0.0025 (11) |
C6 | 0.0225 (10) | 0.0248 (10) | 0.0315 (13) | 0.0015 (8) | 0.0022 (9) | 0.0065 (9) |
N1 | 0.0307 (10) | 0.0224 (9) | 0.0298 (12) | 0.0028 (7) | 0.0018 (8) | −0.0011 (8) |
N2 | 0.0280 (10) | 0.0438 (12) | 0.0333 (12) | 0.0130 (9) | −0.0011 (8) | −0.0078 (9) |
O1 | 0.0244 (8) | 0.0497 (11) | 0.0399 (11) | 0.0132 (7) | −0.0014 (7) | 0.0074 (8) |
C7 | 0.0290 (17) | 0.0269 (15) | 0.0202 (17) | 0.000 | −0.0043 (13) | 0.000 |
N3 | 0.0243 (15) | 0.0511 (19) | 0.0401 (19) | 0.000 | −0.0056 (13) | 0.000 |
Geometric parameters (Å, º) top
Cu1—N3i | 1.963 (3) | C3—H3 | 0.9300 |
Cu1—N1 | 2.0848 (18) | C4—C5 | 1.371 (4) |
Cu1—S1 | 2.3261 (11) | C4—H4 | 0.9300 |
S1—C7 | 1.642 (3) | C5—N1 | 1.339 (3) |
C1—N1 | 1.336 (3) | C5—H5 | 0.9300 |
C1—C2 | 1.384 (3) | C6—O1 | 1.240 (3) |
C1—H1 | 0.9300 | C6—N2 | 1.322 (3) |
C2—C3 | 1.383 (3) | N2—H1N2 | 0.8600 |
C2—C6 | 1.494 (3) | N2—H2N2 | 0.8600 |
C3—C4 | 1.383 (4) | C7—N3 | 1.149 (4) |
| | | |
N3i—Cu1—N1 | 108.10 (8) | C3—C4—H4 | 120.3 |
N1ii—Cu1—N1 | 103.05 (10) | N1—C5—C4 | 123.0 (2) |
N3i—Cu1—S1 | 112.15 (10) | N1—C5—H5 | 118.5 |
N1—Cu1—S1 | 112.46 (6) | C4—C5—H5 | 118.5 |
C7—S1—Cu1 | 94.61 (12) | O1—C6—N2 | 122.9 (2) |
N1—C1—C2 | 123.3 (2) | O1—C6—C2 | 120.7 (2) |
N1—C1—H1 | 118.4 | N2—C6—C2 | 116.39 (19) |
C2—C1—H1 | 118.4 | C1—N1—C5 | 117.4 (2) |
C3—C2—C1 | 118.6 (2) | C1—N1—Cu1 | 123.47 (16) |
C3—C2—C6 | 120.0 (2) | C5—N1—Cu1 | 118.59 (16) |
C1—C2—C6 | 121.4 (2) | C6—N2—H1N2 | 121.5 |
C4—C3—C2 | 118.3 (2) | C6—N2—H2N2 | 120.8 |
C4—C3—H3 | 120.8 | H1N2—N2—H2N2 | 115.9 |
C2—C3—H3 | 120.8 | N3—C7—S1 | 179.5 (3) |
C5—C4—C3 | 119.4 (2) | C7—N3—Cu1iii | 149.1 (3) |
C5—C4—H4 | 120.3 | | |
| | | |
N3i—Cu1—S1—C7 | 180.0 | C1—C2—C6—N2 | 30.7 (3) |
N1—Cu1—S1—C7 | 57.91 (6) | C2—C1—N1—C5 | 1.2 (3) |
N1—C1—C2—C3 | 1.1 (3) | C2—C1—N1—Cu1 | −170.54 (16) |
N1—C1—C2—C6 | 178.4 (2) | C4—C5—N1—C1 | −2.1 (4) |
C1—C2—C3—C4 | −2.6 (4) | C4—C5—N1—Cu1 | 170.1 (2) |
C6—C2—C3—C4 | −179.9 (2) | N3i—Cu1—N1—C1 | −140.89 (18) |
C2—C3—C4—C5 | 1.8 (4) | N1ii—Cu1—N1—C1 | 104.82 (17) |
C3—C4—C5—N1 | 0.5 (5) | S1—Cu1—N1—C1 | −16.54 (19) |
C3—C2—C6—O1 | 28.7 (3) | N3i—Cu1—N1—C5 | 47.4 (2) |
C1—C2—C6—O1 | −148.6 (2) | N1ii—Cu1—N1—C5 | −66.9 (2) |
C3—C2—C6—N2 | −152.0 (2) | S1—Cu1—N1—C5 | 171.77 (17) |
Symmetry codes: (i) x+1/2, y, −z+3/2; (ii) x, −y+1/2, z; (iii) x−1/2, y, −z+3/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H1N2···O1i | 0.86 | 2.18 | 3.003 (3) | 159 |
N2—H2N2···O1iv | 0.86 | 2.13 | 2.959 (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)] |
Mr | 365.88 |
Crystal system, space group | Orthorhombic, Pnma |
Temperature (K) | 293 |
a, b, c (Å) | 8.9304 (4), 21.3533 (12), 7.5895 (3) |
V (Å3) | 1447.27 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.67 |
Crystal size (mm) | 0.12 × 0.09 × 0.05 |
|
Data collection |
Diffractometer | Stoe IPDS diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11282, 1446, 1172 |
Rint | 0.044 |
(sin θ/λ)max (Å−1) | 0.616 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.078, 1.10 |
No. of reflections | 1446 |
No. of parameters | 107 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.30, −0.43 |
Selected geometric parameters (Å, º) topCu1—N3i | 1.963 (3) | Cu1—S1 | 2.3261 (11) |
Cu1—N1 | 2.0848 (18) | | |
| | | |
N3i—Cu1—N1 | 108.10 (8) | N3i—Cu1—S1 | 112.15 (10) |
N1ii—Cu1—N1 | 103.05 (10) | N1—Cu1—S1 | 112.46 (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···A | D—H | H···A | D···A | D—H···A |
N2—H1N2···O1i | 0.86 | 2.18 | 3.003 (3) | 159 |
N2—H2N2···O1iii | 0.86 | 2.13 | 2.959 (3) | 163 |
Symmetry codes: (i) x+1/2, y, −z+3/2; (iii) −x+1/2, −y+1, z+1/2. |
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.