Acta Cryst. (2008). E64, m314 [ doi:10.1107/S1600536807068511 ]
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N)(thiocyanato-N)copper(II)In the title compound, [Cu(NCS)2(C6H6N2O)2(H2O)], the Cu atom adopts a square-based pyramidal CuN4O coordination, with the water O atom in the apical position. The pairs of N-bonded nicotinamide ligands and thiocyanate anions in the basal plane are in a trans configuration. In the crystal structure, the molecules are connected into sheets by N-H
O and O-HO hydrogen bonds.
CuCl2.6H2O (1 mmol), nicotinamide (2 mmol) and NaNCS (1 mmol) were dissolved in water and blue blocks of (I) were obtained by slow evaporation at room temperature about 5 days in 82% yield.
The H atoms attached to C or N atoms were placed in idealized positions (C—H = 0.93 Å, N–H = 0.86 Å), and refined as riding with Uiso(H) = 1.2Ueq(C or N).
The O-bound H atoms were located in difference maps and refined as riding in their as-found relative positions with Uiso(H) = 1.2Ueq(O).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).
![[Figure 1]](./hb2684fig1thm.gif)
| Fig. 1. The molecular structure of (I) with displacement ellipsoids drawn at the 40% probability level (arbitrary spheres for the H atoms). |
![[Figure 2]](./hb2684fig2thm.gif)
| Fig. 2. The layered hydrogen-bonded network in (I) viewed down the b axis direction. Hydrogen bonds are shown as dashed lines. |
| [Cu(NCS)2(C6H6N2O)2(H2O)] | F000 = 900 |
| Mr = 441.97 | Dx = 1.583 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 10592 reflections |
| a = 11.078 (5) Å | θ = 12–18º |
| b = 8.950 (4) Å | µ = 1.43 mm−1 |
| c = 18.702 (9) Å | T = 293 (2) K |
| β = 90.333 (8)º | Block, blue |
| V = 1854.3 (15) Å3 | 0.42 × 0.35 × 0.30 mm |
| Z = 4 |
| Bruker SMART CCD diffractometer | 4041 independent reflections |
| Radiation source: fine-focus sealed tube | 3292 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.019 |
| T = 293(2) K | θmax = 27.2º |
| ω scans | θmin = 2.5º |
| Absorption correction: Multi-Scan (SADABS; Bruker, 1997) | h = −14→14 |
| Tmin = 0.542, Tmax = 0.663 | k = −11→8 |
| 10592 measured reflections | l = −23→23 |
| Refinement on F2 | Hydrogen site location: difmap and geom |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.031 | w = 1/[σ2(Fo2) + (0.045P)2 + 0.9888P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.090 | (Δ/σ)max < 0.001 |
| S = 1.07 | Δρmax = 0.35 e Å−3 |
| 4041 reflections | Δρmin = −0.36 e Å−3 |
| 236 parameters | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0017 (5) |
| Secondary atom site location: difference Fourier map |
| [Cu(NCS)2(C6H6N2O)2(H2O)] | V = 1854.3 (15) Å3 |
| Mr = 441.97 | Z = 4 |
| Monoclinic, P21/c | Mo Kα |
| a = 11.078 (5) Å | µ = 1.43 mm−1 |
| b = 8.950 (4) Å | T = 293 (2) K |
| c = 18.702 (9) Å | 0.42 × 0.35 × 0.30 mm |
| β = 90.333 (8)º |
| Bruker SMART CCD diffractometer | 4041 independent reflections |
| Absorption correction: Multi-Scan (SADABS; Bruker, 1997) | 3292 reflections with I > 2σ(I) |
| Tmin = 0.542, Tmax = 0.663 | Rint = 0.019 |
| 10592 measured reflections |
| R[F2 > 2σ(F2)] = 0.031 | 236 parameters |
| wR(F2) = 0.090 | H-atom parameters constrained |
| S = 1.07 | Δρmax = 0.35 e Å−3 |
| 4041 reflections | Δρmin = −0.36 e Å−3 |
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 | 0.70192 (3) | 0.10898 (3) | 0.092940 (14) | 0.03511 (11) | |
| S1 | 0.56142 (6) | −0.14977 (7) | −0.11161 (3) | 0.04101 (16) | |
| S2 | 0.72370 (6) | 0.27895 (8) | 0.33102 (3) | 0.04644 (17) | |
| O1 | 0.96149 (19) | −0.1681 (2) | 0.29467 (12) | 0.0631 (6) | |
| O2 | 0.96200 (17) | 0.76310 (19) | 0.03689 (11) | 0.0528 (5) | |
| O3 | 0.91522 (15) | 0.06510 (18) | 0.06824 (9) | 0.0398 (4) | |
| H3A | 0.9289 | −0.0271 | 0.0537 | 0.048* | |
| H3B | 0.9461 | 0.1164 | 0.0342 | 0.048* | |
| N1 | 0.70065 (17) | −0.0949 (2) | 0.14278 (10) | 0.0354 (4) | |
| N2 | 0.8973 (2) | −0.3974 (3) | 0.32101 (14) | 0.0633 (7) | |
| H2A | 0.9542 | −0.4107 | 0.3519 | 0.076* | |
| H2B | 0.8453 | −0.4670 | 0.3133 | 0.076* | |
| N3 | 0.72932 (17) | 0.3169 (2) | 0.04894 (10) | 0.0349 (4) | |
| N4 | 1.0166 (2) | 0.5956 (2) | 0.12020 (13) | 0.0503 (6) | |
| H4A | 1.0755 | 0.6508 | 0.1346 | 0.060* | |
| H4B | 1.0036 | 0.5107 | 0.1402 | 0.060* | |
| N5 | 0.65964 (18) | 0.0179 (2) | 0.00029 (10) | 0.0391 (4) | |
| N6 | 0.7224 (2) | 0.2002 (2) | 0.18720 (11) | 0.0467 (5) | |
| C1 | 0.7870 (2) | −0.1250 (3) | 0.19112 (12) | 0.0351 (5) | |
| H1A | 0.8483 | −0.0554 | 0.1981 | 0.042* | |
| C2 | 0.7894 (2) | −0.2552 (3) | 0.23123 (12) | 0.0345 (5) | |
| C3 | 0.6977 (2) | −0.3586 (3) | 0.22028 (13) | 0.0394 (5) | |
| H3C | 0.6965 | −0.4475 | 0.2460 | 0.047* | |
| C4 | 0.6086 (2) | −0.3276 (3) | 0.17083 (15) | 0.0451 (6) | |
| H4C | 0.5462 | −0.3952 | 0.1629 | 0.054* | |
| C5 | 0.6128 (2) | −0.1952 (3) | 0.13314 (13) | 0.0394 (5) | |
| H5A | 0.5523 | −0.1751 | 0.0998 | 0.047* | |
| C6 | 0.8898 (2) | −0.2704 (3) | 0.28559 (13) | 0.0404 (5) | |
| C7 | 0.6561 (2) | 0.3698 (3) | −0.00225 (14) | 0.0429 (6) | |
| H7A | 0.5926 | 0.3104 | −0.0182 | 0.052* | |
| C8 | 0.6714 (3) | 0.5085 (3) | −0.03205 (15) | 0.0508 (7) | |
| H8A | 0.6180 | 0.5431 | −0.0668 | 0.061* | |
| C9 | 0.7665 (2) | 0.5957 (3) | −0.00991 (14) | 0.0447 (6) | |
| H9A | 0.7792 | 0.6889 | −0.0305 | 0.054* | |
| C10 | 0.8437 (2) | 0.5437 (2) | 0.04359 (12) | 0.0340 (5) | |
| C11 | 0.8209 (2) | 0.4028 (2) | 0.07201 (12) | 0.0335 (5) | |
| H11A | 0.8710 | 0.3669 | 0.1082 | 0.040* | |
| C12 | 0.9465 (2) | 0.6412 (2) | 0.06743 (14) | 0.0379 (5) | |
| C13 | 0.6193 (2) | −0.0526 (2) | −0.04580 (12) | 0.0326 (5) | |
| C14 | 0.7230 (2) | 0.2317 (2) | 0.24690 (13) | 0.0353 (5) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cu1 | 0.04718 (19) | 0.02743 (16) | 0.03065 (17) | −0.00594 (12) | −0.00671 (12) | 0.00229 (10) |
| S1 | 0.0488 (4) | 0.0379 (3) | 0.0363 (3) | −0.0021 (3) | −0.0041 (3) | −0.0064 (2) |
| S2 | 0.0540 (4) | 0.0510 (4) | 0.0343 (3) | 0.0064 (3) | −0.0001 (3) | −0.0033 (3) |
| O1 | 0.0675 (13) | 0.0435 (11) | 0.0777 (15) | −0.0095 (10) | −0.0353 (11) | 0.0047 (10) |
| O2 | 0.0603 (12) | 0.0309 (9) | 0.0673 (13) | −0.0082 (8) | 0.0081 (10) | 0.0094 (8) |
| O3 | 0.0437 (9) | 0.0324 (8) | 0.0432 (9) | −0.0031 (7) | 0.0032 (7) | 0.0007 (7) |
| N1 | 0.0378 (10) | 0.0320 (10) | 0.0364 (10) | −0.0048 (8) | −0.0049 (8) | 0.0045 (8) |
| N2 | 0.0633 (16) | 0.0509 (15) | 0.0754 (18) | −0.0085 (12) | −0.0333 (14) | 0.0199 (12) |
| N3 | 0.0431 (11) | 0.0284 (9) | 0.0331 (10) | −0.0021 (8) | −0.0024 (8) | 0.0022 (8) |
| N4 | 0.0463 (12) | 0.0393 (12) | 0.0653 (15) | −0.0105 (10) | −0.0087 (11) | 0.0048 (10) |
| N5 | 0.0452 (11) | 0.0387 (11) | 0.0333 (10) | −0.0053 (9) | −0.0055 (8) | −0.0001 (8) |
| N6 | 0.0654 (14) | 0.0382 (11) | 0.0364 (12) | −0.0099 (10) | −0.0068 (10) | 0.0004 (9) |
| C1 | 0.0358 (12) | 0.0320 (11) | 0.0376 (12) | −0.0039 (9) | −0.0038 (9) | 0.0025 (9) |
| C2 | 0.0369 (12) | 0.0320 (11) | 0.0346 (12) | 0.0016 (9) | 0.0000 (9) | −0.0008 (9) |
| C3 | 0.0448 (13) | 0.0309 (12) | 0.0423 (13) | −0.0025 (10) | −0.0019 (10) | 0.0066 (10) |
| C4 | 0.0436 (13) | 0.0375 (13) | 0.0541 (15) | −0.0115 (11) | −0.0082 (11) | 0.0054 (11) |
| C5 | 0.0392 (12) | 0.0364 (12) | 0.0425 (13) | −0.0037 (10) | −0.0089 (10) | 0.0043 (10) |
| C6 | 0.0431 (13) | 0.0376 (13) | 0.0405 (13) | 0.0050 (10) | −0.0055 (10) | −0.0007 (10) |
| C7 | 0.0502 (14) | 0.0362 (13) | 0.0423 (14) | −0.0020 (11) | −0.0104 (11) | 0.0031 (10) |
| C8 | 0.0602 (16) | 0.0420 (14) | 0.0498 (15) | 0.0032 (12) | −0.0162 (13) | 0.0090 (12) |
| C9 | 0.0555 (15) | 0.0311 (12) | 0.0475 (15) | 0.0021 (11) | −0.0011 (12) | 0.0092 (10) |
| C10 | 0.0392 (12) | 0.0259 (10) | 0.0368 (12) | 0.0032 (9) | 0.0061 (9) | −0.0006 (9) |
| C11 | 0.0379 (12) | 0.0264 (11) | 0.0362 (12) | −0.0002 (9) | −0.0012 (9) | 0.0028 (9) |
| C12 | 0.0384 (12) | 0.0263 (11) | 0.0492 (14) | −0.0007 (9) | 0.0114 (10) | −0.0009 (10) |
| C13 | 0.0363 (11) | 0.0287 (11) | 0.0329 (11) | 0.0008 (9) | 0.0018 (9) | 0.0049 (9) |
| C14 | 0.0402 (12) | 0.0270 (11) | 0.0386 (13) | −0.0017 (9) | −0.0039 (10) | 0.0040 (9) |
| Cu1—N6 | 1.955 (2) | N5—C13 | 1.156 (3) |
| Cu1—N5 | 1.969 (2) | N6—C14 | 1.151 (3) |
| Cu1—N1 | 2.049 (2) | C1—C2 | 1.386 (3) |
| Cu1—N3 | 2.058 (2) | C1—H1A | 0.9300 |
| Cu1—O3 | 2.442 (4) | C2—C3 | 1.389 (3) |
| S1—C13 | 1.635 (2) | C2—C6 | 1.509 (3) |
| S2—C14 | 1.629 (3) | C3—C4 | 1.377 (3) |
| O1—C6 | 1.223 (3) | C3—H3C | 0.9300 |
| O2—C12 | 1.244 (3) | C4—C5 | 1.380 (3) |
| O3—H3A | 0.8821 | C4—H4C | 0.9300 |
| O3—H3B | 0.8574 | C5—H5A | 0.9300 |
| N1—C5 | 1.336 (3) | C7—C8 | 1.372 (4) |
| N1—C1 | 1.340 (3) | C7—H7A | 0.9300 |
| N2—C6 | 1.318 (3) | C8—C9 | 1.373 (4) |
| N2—H2A | 0.8600 | C8—H8A | 0.9300 |
| N2—H2B | 0.8600 | C9—C10 | 1.393 (3) |
| N3—C7 | 1.337 (3) | C9—H9A | 0.9300 |
| N3—C11 | 1.342 (3) | C10—C11 | 1.392 (3) |
| N4—C12 | 1.317 (3) | C10—C12 | 1.501 (3) |
| N4—H4A | 0.8600 | C11—H11A | 0.9300 |
| N4—H4B | 0.8600 | ||
| N6—Cu1—N5 | 172.90 (9) | C4—C3—H3C | 120.5 |
| N6—Cu1—N1 | 87.87 (9) | C2—C3—H3C | 120.5 |
| N5—Cu1—N1 | 91.70 (9) | C3—C4—C5 | 119.3 (2) |
| N6—Cu1—N3 | 88.06 (9) | C3—C4—H4C | 120.3 |
| N5—Cu1—N3 | 93.28 (8) | C5—C4—H4C | 120.3 |
| N1—Cu1—N3 | 171.32 (8) | N1—C5—C4 | 122.4 (2) |
| O3—Cu1—N1 | 87.25 (7) | N1—C5—H5A | 118.8 |
| O3—Cu1—N3 | 85.68 (7) | C4—C5—H5A | 118.8 |
| O3—Cu1—N5 | 89.57 (7) | O1—C6—N2 | 122.5 (2) |
| O3—Cu1—N6 | 97.49 (8) | O1—C6—C2 | 120.1 (2) |
| H3A—O3—H3B | 101.7 | N2—C6—C2 | 117.4 (2) |
| C5—N1—C1 | 118.2 (2) | N3—C7—C8 | 122.4 (2) |
| C5—N1—Cu1 | 122.97 (16) | N3—C7—H7A | 118.8 |
| C1—N1—Cu1 | 118.66 (15) | C8—C7—H7A | 118.8 |
| C6—N2—H2A | 120.0 | C7—C8—C9 | 119.2 (2) |
| C6—N2—H2B | 120.0 | C7—C8—H8A | 120.4 |
| H2A—N2—H2B | 120.0 | C9—C8—H8A | 120.4 |
| C7—N3—C11 | 118.8 (2) | C8—C9—C10 | 119.6 (2) |
| C7—N3—Cu1 | 121.07 (16) | C8—C9—H9A | 120.2 |
| C11—N3—Cu1 | 120.14 (15) | C10—C9—H9A | 120.2 |
| C12—N4—H4A | 120.0 | C11—C10—C9 | 117.7 (2) |
| C12—N4—H4B | 120.0 | C11—C10—C12 | 123.5 (2) |
| H4A—N4—H4B | 120.0 | C9—C10—C12 | 118.8 (2) |
| C13—N5—Cu1 | 166.17 (19) | N3—C11—C10 | 122.3 (2) |
| C14—N6—Cu1 | 167.6 (2) | N3—C11—H11A | 118.9 |
| N1—C1—C2 | 123.1 (2) | C10—C11—H11A | 118.9 |
| N1—C1—H1A | 118.5 | O2—C12—N4 | 122.2 (2) |
| C2—C1—H1A | 118.5 | O2—C12—C10 | 118.7 (2) |
| C1—C2—C3 | 118.0 (2) | N4—C12—C10 | 119.1 (2) |
| C1—C2—C6 | 116.9 (2) | N5—C13—S1 | 179.0 (2) |
| C3—C2—C6 | 125.1 (2) | N6—C14—S2 | 179.1 (2) |
| C4—C3—C2 | 119.1 (2) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O3—H3A···O2i | 0.88 | 1.94 | 2.815 (3) | 171 |
| O3—H3B···O2ii | 0.86 | 2.00 | 2.848 (3) | 172 |
| N2—H2A···O3iii | 0.86 | 2.09 | 2.944 (3) | 176 |
| N4—H4B···O1iv | 0.86 | 2.05 | 2.857 (3) | 157 |
| Symmetry codes: (i) x, y−1, z; (ii) −x+2, −y+1, −z; (iii) −x+2, y−1/2, −z+1/2; (iv) −x+2, y+1/2, −z+1/2. |
| Cu1—N6 | 1.955 (2) | Cu1—N3 | 2.058 (2) |
| Cu1—N5 | 1.969 (2) | Cu1—O3 | 2.442 (4) |
| Cu1—N1 | 2.049 (2) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O3—H3A···O2i | 0.88 | 1.94 | 2.815 (3) | 171 |
| O3—H3B···O2ii | 0.86 | 2.00 | 2.848 (3) | 172 |
| N2—H2A···O3iii | 0.86 | 2.09 | 2.944 (3) | 176 |
| N4—H4B···O1iv | 0.86 | 2.05 | 2.857 (3) | 157 |
| Symmetry codes: (i) x, y−1, z; (ii) −x+2, −y+1, −z; (iii) −x+2, y−1/2, −z+1/2; (iv) −x+2, y+1/2, −z+1/2. |
The authors thank the President's Foundation of South China Agricultural University (grants No. 2006X013, No. 2007Y006 and No. 2007 K031) for financial support.
Beatty, A. M. (2001). CrystEngComm, 51, 1–13.
Bruker (1997). SMART (Version 5.6), SAINT (Version 5.06A), SADABS (Version ??) and SHELXTL (Version 6.12). Bruker AXS Inc., Madison, Wisconsin, USA.
Christer, B. A., John, P. & Jesús, V. M. (2004). CrystEngComm, 6, 413–418.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Due to their inherent coordination and hydrogen bonding donor/acceptor functionalities, nicotinamide ligands have been used in crystal engineering to construct extended frameworks sustained both by hydrogen bonds and coordination bonds (Beatty 2001; Christer et al., 2004). In this paper, we report the synthesis and crystal structure of the title compound, (I).
In compound (I), the metal center occupies a general position, and is coordinated with four nitrogen atoms from two trans-nicotinamide ligands and two trans-NCS anions in a square-planar geometry, as shown in Fig 1. The amide moieties are oriented in same directions. The two pyridine rings coordinated to the Cu centre are twisted by 3.63 (2)°. The distance between Cu center and the O atom of the aqua ligand is 2.442 (4) Å, which suggests a weak non-covalent interaction (Table 1). The Cu complex units are connected via N—H···O hydrogen bonds in a head-to-head fashion, resulting in chains in the crystal. The chains are further linked via O—H···O hydrogen bonds between the coordinated water molecules and amide groups to lead to infinite sheets, as shown in Fig 2.