metal-organic compounds
Aquabis(nicotinamide-κN)(thiocyanato-κN)copper(II)
aDepartment of Applied Chemistry, College of Science, South China Agricultural University, Guangzhou 510642, People's Republic of China, and bSchool of Medicine and Pharmacy, Ocean University of China, Qingdao 266003, People's Republic of China
*Correspondence e-mail: chunyuan-li@163.com
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 the molecules are connected into sheets by N—H⋯O and O—H⋯O hydrogen bonds.
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 1997); cell SAINT (Bruker, 1997); data reduction: SAINT; 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.
Supporting information
10.1107/S1600536807068511/hb2684sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536807068511/hb2684Isup2.hkl
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
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).[Cu(NCS)2(C6H6N2O)2(H2O)] | F(000) = 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 = 12–18° |
b = 8.950 (4) Å | µ = 1.43 mm−1 |
c = 18.702 (9) Å | T = 293 K |
β = 90.333 (8)° | 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) |
Graphite monochromator | Rint = 0.019 |
ω scans | θmax = 27.2°, θmin = 2.5° |
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 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difmap and geom |
R[F2 > 2σ(F2)] = 0.031 | H-atom parameters constrained |
wR(F2) = 0.090 | w = 1/[σ2(Fo2) + (0.045P)2 + 0.9888P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
4041 reflections | Δρmax = 0.35 e Å−3 |
236 parameters | Δρmin = −0.36 e Å−3 |
0 restraints | 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) |
[Cu(NCS)2(C6H6N2O)2(H2O)] | V = 1854.3 (15) Å3 |
Mr = 441.97 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.078 (5) Å | µ = 1.43 mm−1 |
b = 8.950 (4) Å | T = 293 K |
c = 18.702 (9) Å | 0.42 × 0.35 × 0.30 mm |
β = 90.333 (8)° |
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 | 0 restraints |
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 |
236 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 | ||
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. |
Experimental details
Crystal data | |
Chemical formula | [Cu(NCS)2(C6H6N2O)2(H2O)] |
Mr | 441.97 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 11.078 (5), 8.950 (4), 18.702 (9) |
β (°) | 90.333 (8) |
V (Å3) | 1854.3 (15) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.43 |
Crystal size (mm) | 0.42 × 0.35 × 0.30 |
Data collection | |
Diffractometer | Bruker SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1997) |
Tmin, Tmax | 0.542, 0.663 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10592, 4041, 3292 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.643 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.090, 1.07 |
No. of reflections | 4041 |
No. of parameters | 236 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.35, −0.36 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Bruker, 1997).
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. |
Acknowledgements
The authors thank the President's Foundation of South China Agricultural University (grant Nos. 2006X013, 2007Y006 and 2007 K031) for financial support.
References
Aakeröy, C. B., Desper, J. & Valdés-Martínez, J. (2004). CrystEngComm, 6, 413–418. Web of Science CSD CrossRef CAS Google Scholar
Beatty, A. M. (2001). CrystEngComm, 3, 1–13. Web of Science CrossRef Google Scholar
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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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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.