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In the mol­ecule of the title complex, [Cu(NCS)2(C5H5N)4], the CuII atom is bonded in a distorted octa­hedral arrangement to two N atoms of two SCN and four N atoms of four pyridine ligands. A crystallographic twofold rotation axis passes through the Cu atom, and the N and para-C atoms of two trans pyridine rings. In the crystal structure, weak π–π stacking inter­actions cause the formation of a supra­molecular network structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680701879X/hk2232sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680701879X/hk2232Isup2.hkl
Contains datablock I

CCDC reference: 1103908

Key indicators

  • Single-crystal X-ray study
  • T = 273 K
  • Mean [sigma](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

Comment top

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.

Related literature top

For general backgroud, see: Allen et al. (1987). For a related structure see: Zhong et al. (2007).

Experimental top

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.

Refinement top

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).

Structure description top

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).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level [symmetry code (A): 2 - x, y, z].
[Figure 2] Fig. 2. A packing diagram for (I). The π-π interactions are shown as dashed lines.
Tetrakis(pyridine-κN)bis(thiocyanato-κN)copper(II) top
Crystal data top
[Cu(NCS)2(C5H5N)4]F(000) = 1020
Mr = 496.10Dx = 1.398 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2304 reflections
a = 10.890 (4) Åθ = 2.3–23.8°
b = 14.737 (5) ŵ = 1.12 mm1
c = 14.692 (4) ÅT = 273 K
β = 90.517 (6)°Block, green
V = 2357.9 (13) Å30.25 × 0.16 × 0.07 mm
Z = 4
Data collection top
Bruker APEXII area-detector
diffractometer
2465 independent reflections
Radiation source: fine-focus sealed tube1680 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
φ and ω scansθmax = 26.7°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1313
Tmin = 0.763, Tmax = 0.925k = 1818
7961 measured reflectionsl = 1818
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)] = 0.041H-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 reflectionsΔρmax = 0.29 e Å3
144 parametersΔρmin = 0.39 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0010 (3)
Crystal data top
[Cu(NCS)2(C5H5N)4]V = 2357.9 (13) Å3
Mr = 496.10Z = 4
Monoclinic, C2/cMo Kα radiation
a = 10.890 (4) ŵ = 1.12 mm1
b = 14.737 (5) ÅT = 273 K
c = 14.692 (4) Å0.25 × 0.16 × 0.07 mm
β = 90.517 (6)°
Data collection top
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 = 0.925Rint = 0.033
7961 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.116H-atom parameters constrained
S = 1.03Δρmax = 0.29 e Å3
2465 reflectionsΔρmin = 0.39 e Å3
144 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
Cu11.00000.64045 (3)0.25000.0502 (2)
S11.36255 (10)0.63311 (8)0.06607 (9)0.1004 (4)
N10.8932 (2)0.63964 (15)0.12550 (16)0.0510 (6)
N21.00000.4940 (2)0.25000.0511 (8)
N31.00000.7842 (2)0.25000.0503 (8)
N41.1577 (2)0.63721 (17)0.17641 (17)0.0578 (6)
C10.7736 (3)0.6587 (2)0.1248 (2)0.0699 (9)
H10.73890.68160.17760.084*
C20.6990 (3)0.6459 (3)0.0496 (3)0.0875 (12)
H20.61610.66080.05200.105*
C30.7470 (5)0.6116 (3)0.0275 (3)0.0940 (13)
H30.69810.60070.07860.113*
C40.8669 (4)0.5941 (4)0.0278 (3)0.1117 (17)
H40.90300.57130.08010.134*
C50.9372 (3)0.6093 (3)0.0476 (2)0.0875 (12)
H51.02100.59760.04420.105*
C60.9018 (3)0.4462 (2)0.2236 (2)0.0640 (8)
H60.83130.47770.20640.077*
C70.8990 (4)0.3538 (3)0.2204 (3)0.0889 (12)
H70.82970.32380.19850.107*
C81.00000.3054 (4)0.25000.0995 (19)
H81.00000.24230.25000.119*
C91.0416 (3)0.8318 (2)0.1787 (2)0.0584 (8)
H91.07110.80030.12860.070*
C101.0425 (3)0.9244 (2)0.1763 (2)0.0740 (9)
H101.07160.95470.12530.089*
C111.00000.9729 (4)0.25000.0814 (15)
H111.00001.03600.25000.098*
C121.2431 (2)0.63577 (19)0.13021 (19)0.0502 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0419 (3)0.0570 (3)0.0519 (3)0.0000.01060 (19)0.000
S10.0726 (7)0.1203 (9)0.1094 (9)0.0010 (6)0.0537 (6)0.0005 (7)
N10.0466 (13)0.0534 (14)0.0531 (14)0.0006 (11)0.0031 (10)0.0012 (11)
N20.0443 (18)0.0478 (19)0.061 (2)0.0000.0023 (15)0.000
N30.0452 (18)0.054 (2)0.0521 (19)0.0000.0015 (14)0.000
N40.0434 (13)0.0701 (17)0.0600 (15)0.0017 (11)0.0138 (11)0.0002 (12)
C10.0517 (19)0.088 (3)0.070 (2)0.0120 (16)0.0027 (15)0.0121 (17)
C20.052 (2)0.106 (3)0.104 (3)0.004 (2)0.0178 (19)0.026 (3)
C30.101 (3)0.095 (3)0.085 (3)0.002 (2)0.039 (2)0.014 (2)
C40.098 (3)0.163 (5)0.074 (3)0.035 (3)0.021 (2)0.042 (3)
C50.066 (2)0.133 (4)0.064 (2)0.027 (2)0.0068 (17)0.029 (2)
C60.0515 (18)0.058 (2)0.082 (2)0.0034 (15)0.0025 (15)0.0017 (17)
C70.070 (2)0.061 (2)0.135 (4)0.0104 (19)0.017 (2)0.000 (2)
C80.094 (4)0.049 (3)0.155 (6)0.0000.014 (4)0.000
C90.0595 (19)0.0592 (19)0.0566 (18)0.0025 (15)0.0032 (14)0.0063 (15)
C100.086 (2)0.064 (2)0.071 (2)0.0089 (19)0.0028 (18)0.0155 (18)
C110.097 (4)0.053 (3)0.093 (4)0.0000.010 (3)0.000
C120.0442 (16)0.0526 (17)0.0538 (16)0.0050 (12)0.0063 (12)0.0005 (13)
Geometric parameters (Å, º) top
Cu1—N12.159 (2)C3—C41.331 (6)
Cu1—N22.158 (3)C3—H30.9300
Cu1—N32.119 (3)C4—C51.359 (5)
Cu1—N42.038 (2)C4—H40.9300
Cu1—N4i2.038 (2)C5—H50.9300
Cu1—N1i2.159 (2)C6—C71.362 (5)
S1—C121.613 (3)C6—H60.9300
N1—C51.323 (4)C7—C81.378 (5)
N1—C11.332 (4)C7—H70.9300
N2—C61.336 (3)C8—C7i1.378 (5)
N2—C6i1.336 (3)C8—H80.9300
N3—C9i1.343 (3)C9—C101.365 (5)
N3—C91.343 (3)C9—H90.9300
N4—C121.157 (4)C10—C111.381 (4)
C1—C21.379 (5)C10—H100.9300
C1—H10.9300C11—C10i1.381 (4)
C2—C31.351 (6)C11—H110.9300
C2—H20.9300
N1—Cu1—N289.68 (6)C1—C2—H2120.2
N1—Cu1—N390.32 (6)C4—C3—C2117.5 (4)
N1—Cu1—N490.02 (10)C4—C3—H3121.2
N2—Cu1—N3180.000 (1)C2—C3—H3121.2
N2—Cu1—N488.66 (7)C3—C4—C5120.7 (4)
N3—Cu1—N491.34 (7)C3—C4—H4119.6
N4i—Cu1—N4177.31 (14)C5—C4—H4119.6
N4i—Cu1—N391.34 (7)N1—C5—C4123.7 (4)
N4i—Cu1—N288.66 (7)N1—C5—H5118.1
N4i—Cu1—N1i90.02 (10)C4—C5—H5118.1
N4—Cu1—N1i89.97 (10)N2—C6—C7123.7 (3)
N3—Cu1—N1i90.32 (6)N2—C6—H6118.1
N2—Cu1—N1i89.68 (6)C7—C6—H6118.1
N4i—Cu1—N189.97 (10)C6—C7—C8119.3 (4)
N1i—Cu1—N1179.37 (12)C6—C7—H7120.4
C5—N1—C1115.2 (3)C8—C7—H7120.4
C5—N1—Cu1122.6 (2)C7i—C8—C7117.6 (5)
C1—N1—Cu1121.6 (2)C7i—C8—H8121.2
C6—N2—C6i116.2 (4)C7—C8—H8121.2
C6—N2—Cu1121.88 (18)N3—C9—C10123.0 (3)
C6i—N2—Cu1121.88 (18)N3—C9—H9118.5
C9i—N3—C9117.0 (4)C10—C9—H9118.5
C9i—N3—Cu1121.49 (19)C9—C10—C11119.6 (3)
C9—N3—Cu1121.49 (19)C9—C10—H10120.2
C12—N4—Cu1176.1 (3)C11—C10—H10120.2
N1—C1—C2123.2 (3)C10i—C11—C10117.7 (5)
N1—C1—H1118.4C10i—C11—H11121.1
C2—C1—H1118.4C10—C11—H11121.1
C3—C2—C1119.6 (4)N4—C12—S1179.6 (3)
C3—C2—H2120.2
Symmetry code: (i) x+2, y, z+1/2.

Experimental details

Crystal data
Chemical formula[Cu(NCS)2(C5H5N)4]
Mr496.10
Crystal system, space groupMonoclinic, C2/c
Temperature (K)273
a, b, c (Å)10.890 (4), 14.737 (5), 14.692 (4)
β (°) 90.517 (6)
V3)2357.9 (13)
Z4
Radiation typeMo Kα
µ (mm1)1.12
Crystal size (mm)0.25 × 0.16 × 0.07
Data collection
DiffractometerBruker APEXII area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.763, 0.925
No. of measured, independent and
observed [I > 2σ(I)] reflections
7961, 2465, 1680
Rint0.033
(sin θ/λ)max1)0.632
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.116, 1.03
No. of reflections2465
No. of parameters144
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.29, 0.39

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Siemens, 1996), SHELXTL.

Selected geometric parameters (Å, º) top
Cu1—N12.159 (2)Cu1—N32.119 (3)
Cu1—N22.158 (3)Cu1—N42.038 (2)
N1—Cu1—N289.68 (6)N2—Cu1—N3180.000 (1)
N1—Cu1—N390.32 (6)N2—Cu1—N488.66 (7)
N1—Cu1—N490.02 (10)N3—Cu1—N491.34 (7)
 

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