Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680701879X/hk2232sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680701879X/hk2232Isup2.hkl |
CCDC reference: 1103908
Key indicators
- Single-crystal X-ray study
- T = 273 K
- Mean (C-C) = 0.005 Å
- R factor = 0.041
- wR factor = 0.116
- Data-to-parameter ratio = 17.1
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C4 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N1 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C12
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For general backgroud, see: Allen et al. (1987). For a related structure see: Zhong et al. (2007).
Crystals of the title compound were synthesized using hydrothermal method in a Teflon-lined Parr bomb (23 ml), which was then sealed. Copper dinitrate trihydrate (72.5 mg, 0.3 mmol), potassium thiocyanate (58.3 mg, 0.6 mmol), pyridine (2.5 ml), and distilled water (6 g) were placed into the bomb and sealed. The bomb was then heated under autogenous pressure for 4 d at 393 K and allowed to cool at room temperature for 24 h. Upon opening the bomb, a clear colorless solution was decanted from small green crystals. These crystals were washed with distilled water followed by ethanol, and allowed to air-dry at room temperature.
H atoms were positioned geometrically, with C—H = 0.93 Å for aromatic H and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).
The crystal structure of Tetrakis(pyridine-N)dithiocyanatocobalt(II),(II), has previously been reported (Zhong et al., 2007). The crystal structure determination of the title compound, (I), has been carried out in order to elucidate the molecular conformation and to compare it with that of (II). We herein report the crystal structure of (I).
In the molecule of (I), (Fig. 1), the ligand bond lengths and angles are within normal ranges (Allen et al., 1987). The two N atoms of two SCN- and four N atoms of four pyridine ligands are coordinated to the Cu atom, in a distorted octahedral arrangement (Table 1). A crystallographic twofold rotation axis passes through the Cu atom, and the N and para-C atoms of two trans pyridine rings.The planar pyridine rings A (N1/C1—C5), B (N2/C6A/C7A/C6—C8) and C (N3/C9A/C10A/C9—C11) are nearly perpendicular to each other, with dihedral angles of A/B = 110.72 (5), A/C = 87.11 (7) and B/C = 87.22 (5)°, as in (II).
In the crystal structure, the weak π-π stacking interactions, involving the adjacent pyridine rings with centroid-centroid distance of 3.481 (7) %A [symmetry code: 1 - x, 2 - y, 1 - z], cause the formation of a supramolecular network structure (Fig. 2). The both compounds, (I) and (II), are isostructural.
For general backgroud, see: Allen et al. (1987). For a related structure see: Zhong et al. (2007).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXTL.
[Cu(NCS)2(C5H5N)4] | F(000) = 1020 |
Mr = 496.10 | Dx = 1.398 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 2304 reflections |
a = 10.890 (4) Å | θ = 2.3–23.8° |
b = 14.737 (5) Å | µ = 1.12 mm−1 |
c = 14.692 (4) Å | T = 273 K |
β = 90.517 (6)° | Block, green |
V = 2357.9 (13) Å3 | 0.25 × 0.16 × 0.07 mm |
Z = 4 |
Bruker APEXII area-detector diffractometer | 2465 independent reflections |
Radiation source: fine-focus sealed tube | 1680 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
φ and ω scans | θmax = 26.7°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→13 |
Tmin = 0.763, Tmax = 0.925 | k = −18→18 |
7961 measured reflections | l = −18→18 |
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)] = 0.041 | H-atom parameters constrained |
wR(F2) = 0.116 | w = 1/[σ2(Fo2) + (0.0437P)2 + 1.9905P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
2465 reflections | Δρmax = 0.29 e Å−3 |
144 parameters | Δρmin = −0.39 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0010 (3) |
[Cu(NCS)2(C5H5N)4] | V = 2357.9 (13) Å3 |
Mr = 496.10 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 10.890 (4) Å | µ = 1.12 mm−1 |
b = 14.737 (5) Å | T = 273 K |
c = 14.692 (4) Å | 0.25 × 0.16 × 0.07 mm |
β = 90.517 (6)° |
Bruker APEXII area-detector diffractometer | 2465 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1680 reflections with I > 2σ(I) |
Tmin = 0.763, Tmax = 0.925 | Rint = 0.033 |
7961 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.29 e Å−3 |
2465 reflections | Δρmin = −0.39 e Å−3 |
144 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 | 1.0000 | 0.64045 (3) | 0.2500 | 0.0502 (2) | |
S1 | 1.36255 (10) | 0.63311 (8) | 0.06607 (9) | 0.1004 (4) | |
N1 | 0.8932 (2) | 0.63964 (15) | 0.12550 (16) | 0.0510 (6) | |
N2 | 1.0000 | 0.4940 (2) | 0.2500 | 0.0511 (8) | |
N3 | 1.0000 | 0.7842 (2) | 0.2500 | 0.0503 (8) | |
N4 | 1.1577 (2) | 0.63721 (17) | 0.17641 (17) | 0.0578 (6) | |
C1 | 0.7736 (3) | 0.6587 (2) | 0.1248 (2) | 0.0699 (9) | |
H1 | 0.7389 | 0.6816 | 0.1776 | 0.084* | |
C2 | 0.6990 (3) | 0.6459 (3) | 0.0496 (3) | 0.0875 (12) | |
H2 | 0.6161 | 0.6608 | 0.0520 | 0.105* | |
C3 | 0.7470 (5) | 0.6116 (3) | −0.0275 (3) | 0.0940 (13) | |
H3 | 0.6981 | 0.6007 | −0.0786 | 0.113* | |
C4 | 0.8669 (4) | 0.5941 (4) | −0.0278 (3) | 0.1117 (17) | |
H4 | 0.9030 | 0.5713 | −0.0801 | 0.134* | |
C5 | 0.9372 (3) | 0.6093 (3) | 0.0476 (2) | 0.0875 (12) | |
H5 | 1.0210 | 0.5976 | 0.0442 | 0.105* | |
C6 | 0.9018 (3) | 0.4462 (2) | 0.2236 (2) | 0.0640 (8) | |
H6 | 0.8313 | 0.4777 | 0.2064 | 0.077* | |
C7 | 0.8990 (4) | 0.3538 (3) | 0.2204 (3) | 0.0889 (12) | |
H7 | 0.8297 | 0.3238 | 0.1985 | 0.107* | |
C8 | 1.0000 | 0.3054 (4) | 0.2500 | 0.0995 (19) | |
H8 | 1.0000 | 0.2423 | 0.2500 | 0.119* | |
C9 | 1.0416 (3) | 0.8318 (2) | 0.1787 (2) | 0.0584 (8) | |
H9 | 1.0711 | 0.8003 | 0.1286 | 0.070* | |
C10 | 1.0425 (3) | 0.9244 (2) | 0.1763 (2) | 0.0740 (9) | |
H10 | 1.0716 | 0.9547 | 0.1253 | 0.089* | |
C11 | 1.0000 | 0.9729 (4) | 0.2500 | 0.0814 (15) | |
H11 | 1.0000 | 1.0360 | 0.2500 | 0.098* | |
C12 | 1.2431 (2) | 0.63577 (19) | 0.13021 (19) | 0.0502 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0419 (3) | 0.0570 (3) | 0.0519 (3) | 0.000 | 0.01060 (19) | 0.000 |
S1 | 0.0726 (7) | 0.1203 (9) | 0.1094 (9) | 0.0010 (6) | 0.0537 (6) | 0.0005 (7) |
N1 | 0.0466 (13) | 0.0534 (14) | 0.0531 (14) | 0.0006 (11) | 0.0031 (10) | −0.0012 (11) |
N2 | 0.0443 (18) | 0.0478 (19) | 0.061 (2) | 0.000 | 0.0023 (15) | 0.000 |
N3 | 0.0452 (18) | 0.054 (2) | 0.0521 (19) | 0.000 | 0.0015 (14) | 0.000 |
N4 | 0.0434 (13) | 0.0701 (17) | 0.0600 (15) | 0.0017 (11) | 0.0138 (11) | −0.0002 (12) |
C1 | 0.0517 (19) | 0.088 (3) | 0.070 (2) | 0.0120 (16) | 0.0027 (15) | 0.0121 (17) |
C2 | 0.052 (2) | 0.106 (3) | 0.104 (3) | −0.004 (2) | −0.0178 (19) | 0.026 (3) |
C3 | 0.101 (3) | 0.095 (3) | 0.085 (3) | −0.002 (2) | −0.039 (2) | −0.014 (2) |
C4 | 0.098 (3) | 0.163 (5) | 0.074 (3) | 0.035 (3) | −0.021 (2) | −0.042 (3) |
C5 | 0.066 (2) | 0.133 (4) | 0.064 (2) | 0.027 (2) | −0.0068 (17) | −0.029 (2) |
C6 | 0.0515 (18) | 0.058 (2) | 0.082 (2) | −0.0034 (15) | −0.0025 (15) | 0.0017 (17) |
C7 | 0.070 (2) | 0.061 (2) | 0.135 (4) | −0.0104 (19) | −0.017 (2) | 0.000 (2) |
C8 | 0.094 (4) | 0.049 (3) | 0.155 (6) | 0.000 | −0.014 (4) | 0.000 |
C9 | 0.0595 (19) | 0.0592 (19) | 0.0566 (18) | −0.0025 (15) | 0.0032 (14) | 0.0063 (15) |
C10 | 0.086 (2) | 0.064 (2) | 0.071 (2) | −0.0089 (19) | −0.0028 (18) | 0.0155 (18) |
C11 | 0.097 (4) | 0.053 (3) | 0.093 (4) | 0.000 | −0.010 (3) | 0.000 |
C12 | 0.0442 (16) | 0.0526 (17) | 0.0538 (16) | 0.0050 (12) | 0.0063 (12) | −0.0005 (13) |
Cu1—N1 | 2.159 (2) | C3—C4 | 1.331 (6) |
Cu1—N2 | 2.158 (3) | C3—H3 | 0.9300 |
Cu1—N3 | 2.119 (3) | C4—C5 | 1.359 (5) |
Cu1—N4 | 2.038 (2) | C4—H4 | 0.9300 |
Cu1—N4i | 2.038 (2) | C5—H5 | 0.9300 |
Cu1—N1i | 2.159 (2) | C6—C7 | 1.362 (5) |
S1—C12 | 1.613 (3) | C6—H6 | 0.9300 |
N1—C5 | 1.323 (4) | C7—C8 | 1.378 (5) |
N1—C1 | 1.332 (4) | C7—H7 | 0.9300 |
N2—C6 | 1.336 (3) | C8—C7i | 1.378 (5) |
N2—C6i | 1.336 (3) | C8—H8 | 0.9300 |
N3—C9i | 1.343 (3) | C9—C10 | 1.365 (5) |
N3—C9 | 1.343 (3) | C9—H9 | 0.9300 |
N4—C12 | 1.157 (4) | C10—C11 | 1.381 (4) |
C1—C2 | 1.379 (5) | C10—H10 | 0.9300 |
C1—H1 | 0.9300 | C11—C10i | 1.381 (4) |
C2—C3 | 1.351 (6) | C11—H11 | 0.9300 |
C2—H2 | 0.9300 | ||
N1—Cu1—N2 | 89.68 (6) | C1—C2—H2 | 120.2 |
N1—Cu1—N3 | 90.32 (6) | C4—C3—C2 | 117.5 (4) |
N1—Cu1—N4 | 90.02 (10) | C4—C3—H3 | 121.2 |
N2—Cu1—N3 | 180.000 (1) | C2—C3—H3 | 121.2 |
N2—Cu1—N4 | 88.66 (7) | C3—C4—C5 | 120.7 (4) |
N3—Cu1—N4 | 91.34 (7) | C3—C4—H4 | 119.6 |
N4i—Cu1—N4 | 177.31 (14) | C5—C4—H4 | 119.6 |
N4i—Cu1—N3 | 91.34 (7) | N1—C5—C4 | 123.7 (4) |
N4i—Cu1—N2 | 88.66 (7) | N1—C5—H5 | 118.1 |
N4i—Cu1—N1i | 90.02 (10) | C4—C5—H5 | 118.1 |
N4—Cu1—N1i | 89.97 (10) | N2—C6—C7 | 123.7 (3) |
N3—Cu1—N1i | 90.32 (6) | N2—C6—H6 | 118.1 |
N2—Cu1—N1i | 89.68 (6) | C7—C6—H6 | 118.1 |
N4i—Cu1—N1 | 89.97 (10) | C6—C7—C8 | 119.3 (4) |
N1i—Cu1—N1 | 179.37 (12) | C6—C7—H7 | 120.4 |
C5—N1—C1 | 115.2 (3) | C8—C7—H7 | 120.4 |
C5—N1—Cu1 | 122.6 (2) | C7i—C8—C7 | 117.6 (5) |
C1—N1—Cu1 | 121.6 (2) | C7i—C8—H8 | 121.2 |
C6—N2—C6i | 116.2 (4) | C7—C8—H8 | 121.2 |
C6—N2—Cu1 | 121.88 (18) | N3—C9—C10 | 123.0 (3) |
C6i—N2—Cu1 | 121.88 (18) | N3—C9—H9 | 118.5 |
C9i—N3—C9 | 117.0 (4) | C10—C9—H9 | 118.5 |
C9i—N3—Cu1 | 121.49 (19) | C9—C10—C11 | 119.6 (3) |
C9—N3—Cu1 | 121.49 (19) | C9—C10—H10 | 120.2 |
C12—N4—Cu1 | 176.1 (3) | C11—C10—H10 | 120.2 |
N1—C1—C2 | 123.2 (3) | C10i—C11—C10 | 117.7 (5) |
N1—C1—H1 | 118.4 | C10i—C11—H11 | 121.1 |
C2—C1—H1 | 118.4 | C10—C11—H11 | 121.1 |
C3—C2—C1 | 119.6 (4) | N4—C12—S1 | 179.6 (3) |
C3—C2—H2 | 120.2 |
Symmetry code: (i) −x+2, y, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu(NCS)2(C5H5N)4] |
Mr | 496.10 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 273 |
a, b, c (Å) | 10.890 (4), 14.737 (5), 14.692 (4) |
β (°) | 90.517 (6) |
V (Å3) | 2357.9 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.12 |
Crystal size (mm) | 0.25 × 0.16 × 0.07 |
Data collection | |
Diffractometer | Bruker APEXII area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.763, 0.925 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7961, 2465, 1680 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.632 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.116, 1.03 |
No. of reflections | 2465 |
No. of parameters | 144 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.29, −0.39 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Siemens, 1996), SHELXTL.
Cu1—N1 | 2.159 (2) | Cu1—N3 | 2.119 (3) |
Cu1—N2 | 2.158 (3) | Cu1—N4 | 2.038 (2) |
N1—Cu1—N2 | 89.68 (6) | N2—Cu1—N3 | 180.000 (1) |
N1—Cu1—N3 | 90.32 (6) | N2—Cu1—N4 | 88.66 (7) |
N1—Cu1—N4 | 90.02 (10) | N3—Cu1—N4 | 91.34 (7) |
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The crystal structure of Tetrakis(pyridine-N)dithiocyanatocobalt(II),(II), has previously been reported (Zhong et al., 2007). The crystal structure determination of the title compound, (I), has been carried out in order to elucidate the molecular conformation and to compare it with that of (II). We herein report the crystal structure of (I).
In the molecule of (I), (Fig. 1), the ligand bond lengths and angles are within normal ranges (Allen et al., 1987). The two N atoms of two SCN- and four N atoms of four pyridine ligands are coordinated to the Cu atom, in a distorted octahedral arrangement (Table 1). A crystallographic twofold rotation axis passes through the Cu atom, and the N and para-C atoms of two trans pyridine rings.The planar pyridine rings A (N1/C1—C5), B (N2/C6A/C7A/C6—C8) and C (N3/C9A/C10A/C9—C11) are nearly perpendicular to each other, with dihedral angles of A/B = 110.72 (5), A/C = 87.11 (7) and B/C = 87.22 (5)°, as in (II).
In the crystal structure, the weak π-π stacking interactions, involving the adjacent pyridine rings with centroid-centroid distance of 3.481 (7) %A [symmetry code: 1 - x, 2 - y, 1 - z], cause the formation of a supramolecular network structure (Fig. 2). The both compounds, (I) and (II), are isostructural.