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In the crystal structure of the title compound, [Co(H2O)4(NCS)2]·2C6H12N4, the six-coordinated CoII atom lies on a special position of mmm site symmetry and the hexa­methyl­ene­tetra­mine mol­ecule about a special position of \overline{4} site symmetry. The two entities inter­act through an O—H...N hydrogen bond to form a three-dimensional network.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807043024/ng2324sup1.cif
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807043024/ng2324Isup2.hkl
Contains datablock I

CCDC reference: 223965

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](N-C) = 0.004 Å
  • R factor = 0.034
  • wR factor = 0.100
  • Data-to-parameter ratio = 10.8

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT242_ALERT_2_B Check Low Ueq as Compared to Neighbors for Co
Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT164_ALERT_4_C Nr. of Refined C-H H-Atoms in Heavy-At Struct... 3 PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Co - N1 .. 6.53 su PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C1 PLAT742_ALERT_1_C Angle Calc 90.00(10), Rep 90.00 ...... Missing su O1W -CO -N1 1.555 1.555 1.555 PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.18 Ratio
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT794_ALERT_5_G Check Predicted Bond Valency for Co (2) 2.03
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 7 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 5 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 2 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

Comment top

Thiocyanate ion has played an important role in constructing heteronuclear complexes in our systems. (Li, Tong et al.,2004; Li, Zhao et al., 2004). Herein is described a crystal structure of thiocyanate complex, [Co(NCS)2(H2O)4].2(C6H12N4). The cell contains two same units of the title compound. A perspective drawing of the complex with atomic numbering scheme is depicted in Fig. 1 and selected bonding parameters are presented in Table 1.

The cobalt atom locates in a slightly disordered CoN2O4 octahedral coordination geometry. Each hmt connects with four [Co(NCS)2(H2O)4] units and each [Co(NCS)2(H2O)4] unit connects with eight hmt molecules through O—H···N hydrogen bonds leading to 3-D network.

Related literature top

For related compounds, see Li, Tong et al. (2004); Li, Zhao et al. (2004).

Experimental top

AgNO3 (0.68 g, 4.0 mmol), NH4SCN (0.61 g, 4.0 mmol) and hmt (1.4 g, 10 mmol) were added to a stired CoCl2.6H2O (0.47 g, 2.0 mmol) solution in acetonitrile, respectively. The mixture was stirred in r.t. for 12 h. After filtration, the filtrate was disposed to stand in the air. A few days later, purple-red single crystals suitable for X-ray diffraction were obtained.

Refinement top

The positions of hydrogen atoms were generated geometrically (C—H bond fixed at 0.96 Å) expect those connected to O1w atoms which are generated according to the fourier map, assigned isotropic thermal parameters and allowed to ride on their respective parent C atoms before the final cycle of least-squares refinement.

Structure description top

Thiocyanate ion has played an important role in constructing heteronuclear complexes in our systems. (Li, Tong et al.,2004; Li, Zhao et al., 2004). Herein is described a crystal structure of thiocyanate complex, [Co(NCS)2(H2O)4].2(C6H12N4). The cell contains two same units of the title compound. A perspective drawing of the complex with atomic numbering scheme is depicted in Fig. 1 and selected bonding parameters are presented in Table 1.

The cobalt atom locates in a slightly disordered CoN2O4 octahedral coordination geometry. Each hmt connects with four [Co(NCS)2(H2O)4] units and each [Co(NCS)2(H2O)4] unit connects with eight hmt molecules through O—H···N hydrogen bonds leading to 3-D network.

For related compounds, see Li, Tong et al. (2004); Li, Zhao et al. (2004).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1996); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL (Bruker, 1999).

Figures top
[Figure 1] Fig. 1. A view of the complex with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
Tetraaquabis(thiocyanato-κN)cobalt(II) hexamethylenetetramine (1/2) cocrystal top
Crystal data top
[Co(H2O)4(NCS)2]·2C6H12N4Dx = 1.418 Mg m3
Mr = 527.55Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P42/mnmCell parameters from 200 reflections
Hall symbol: -P 4n 2nθ = 2.6–25.1°
a = 9.4846 (4) ŵ = 0.90 mm1
c = 13.7339 (6) ÅT = 293 K
V = 1235.47 (7) Å3Prism, purple-red
Z = 20.43 × 0.40 × 0.25 mm
F(000) = 554
Data collection top
Siemens SMART
diffractometer
625 independent reflections
Radiation source: fine-focus sealed tube554 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.024
φ and ω scansθmax = 25.1°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 711
Tmin = 0.685, Tmax = 0.798k = 1111
2871 measured reflectionsl = 1610
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)] = 0.034H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.100 w = 1/[σ2(Fo2) + (0.0614P)2 + 0.8126P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.01
626 reflectionsΔρmax = 0.33 e Å3
58 parametersΔρmin = 0.46 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.052 (5)
Crystal data top
[Co(H2O)4(NCS)2]·2C6H12N4Z = 2
Mr = 527.55Mo Kα radiation
Tetragonal, P42/mnmµ = 0.90 mm1
a = 9.4846 (4) ÅT = 293 K
c = 13.7339 (6) Å0.43 × 0.40 × 0.25 mm
V = 1235.47 (7) Å3
Data collection top
Siemens SMART
diffractometer
625 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
554 reflections with I > 2σ(I)
Tmin = 0.685, Tmax = 0.798Rint = 0.024
2871 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.100H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.33 e Å3
626 reflectionsΔρmin = 0.46 e Å3
58 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
Co0.50000.50000.50000.0295 (4)
S10.86349 (9)0.86349 (9)0.50000.0606 (5)
O1W0.3901 (3)0.6099 (3)0.3938 (3)0.0960 (13)
H10.39900.71140.38100.115*
N10.6560 (3)0.6560 (3)0.50000.0413 (9)
C10.7427 (3)0.7427 (3)0.50000.0348 (10)
N20.1198 (3)0.5440 (3)0.31207 (17)0.0558 (7)
C20.00000.50000.3713 (3)0.0637 (13)
H20.023 (4)0.572 (4)0.409 (2)0.081 (11)*
C30.1598 (3)0.4253 (4)0.2505 (3)0.0632 (9)
H3A0.179 (4)0.350 (4)0.293 (3)0.078 (11)*
H3B0.243 (4)0.457 (4)0.212 (3)0.079 (10)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co0.0285 (4)0.0285 (4)0.0315 (5)0.0055 (3)0.0000.000
S10.0445 (6)0.0445 (6)0.0930 (11)0.0205 (6)0.0000.000
O1W0.0788 (14)0.0788 (14)0.131 (3)0.0392 (18)0.0664 (18)0.0664 (18)
N10.0391 (14)0.0391 (14)0.046 (2)0.0050 (18)0.0000.000
C10.0322 (15)0.0322 (15)0.040 (2)0.0018 (19)0.0000.000
N20.0523 (14)0.0631 (15)0.0520 (13)0.0067 (11)0.0179 (11)0.0131 (11)
C20.095 (4)0.065 (3)0.0310 (18)0.031 (2)0.0000.000
C30.0467 (17)0.071 (2)0.072 (2)0.0158 (15)0.0021 (14)0.0125 (17)
Geometric parameters (Å, º) top
Co—O1Wi2.074 (3)N2—C21.459 (3)
Co—O1Wii2.074 (3)N2—C3iv1.459 (4)
Co—O1W2.074 (3)N2—C31.458 (4)
Co—O1Wiii2.074 (3)C2—N2v1.459 (3)
Co—N1ii2.092 (4)C2—H20.88 (3)
Co—N12.092 (4)C3—N2vi1.459 (4)
S1—C11.621 (5)C3—H3A0.94 (4)
O1W—H10.9821C3—H3B0.99 (4)
N1—C11.163 (6)
O1Wi—Co—O1Wii89.4 (3)Co—O1W—H1125.1
O1Wi—Co—O1W90.6 (3)C1—N1—Co180.0
O1Wii—Co—O1W180.0N1—C1—S1179.999 (1)
O1Wi—Co—O1Wiii180.0C2—N2—C3iv108.4 (2)
O1Wii—Co—O1Wiii90.6 (3)C2—N2—C3107.8 (2)
O1W—Co—O1Wiii89.4 (3)C3iv—N2—C3108.44 (18)
O1Wi—Co—N1ii90.0N2—C2—N2v112.2 (3)
O1Wii—Co—N1ii90.0N2—C2—H2107 (2)
O1W—Co—N1ii90.0N2v—C2—H2111 (2)
O1Wiii—Co—N1ii90.0N2vi—C3—N2111.8 (3)
O1Wi—Co—N190.0N2vi—C3—H3A107 (2)
O1Wii—Co—N190.0N2—C3—H3A106 (2)
O1W—Co—N190.0N2vi—C3—H3B112 (2)
O1Wiii—Co—N190.0N2—C3—H3B106 (2)
N1ii—Co—N1180.0H3A—C3—H3B114 (3)
Symmetry codes: (i) x+1, y+1, z; (ii) x+1, y+1, z+1; (iii) x, y, z+1; (iv) y+1/2, x+1/2, z+1/2; (v) x, y+1, z; (vi) y1/2, x+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1···N2vii0.981.942.867 (3)157.1
Symmetry code: (vii) y+1, x+1, z.

Experimental details

Crystal data
Chemical formula[Co(H2O)4(NCS)2]·2C6H12N4
Mr527.55
Crystal system, space groupTetragonal, P42/mnm
Temperature (K)293
a, c (Å)9.4846 (4), 13.7339 (6)
V3)1235.47 (7)
Z2
Radiation typeMo Kα
µ (mm1)0.90
Crystal size (mm)0.43 × 0.40 × 0.25
Data collection
DiffractometerSiemens SMART
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.685, 0.798
No. of measured, independent and
observed [I > 2σ(I)] reflections
2871, 625, 554
Rint0.024
(sin θ/λ)max1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.100, 1.06
No. of reflections626
No. of parameters58
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.33, 0.46

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1996), SHELXTL (Bruker, 1999).

Selected bond angles (º) top
O1Wi—Co—O1W90.6 (3)C1—N1—Co180.0
O1W—Co—O1Wii89.4 (3)N1—C1—S1179.999 (1)
Symmetry codes: (i) x+1, y+1, z; (ii) x, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1···N2iii0.981.942.867 (3)157.1
Symmetry code: (iii) y+1, x+1, z.
 

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