Tetra­aquabis­(thio­cyanato-κN)cobalt(II) hexa­methyl­enetetra­mine (1/2) cocrystal

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

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

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S1. Comment

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

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

S2. Experimental

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.

S3. Refinement

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.

Computing details

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

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

Crystal data

[Co(H2O)4(NCS)2]·2C6H12N4	Dx = 1.418 Mg m^−3
Mr = 527.55	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P42/mnm	Cell parameters from 200 reflections
Hall symbol: -P 4n 2n	θ = 2.6–25.1°
a = 9.4846 (4) Å	µ = 0.90 mm^−1
c = 13.7339 (6) Å	T = 293 K
V = 1235.47 (7) Å^3	Prism, purple-red
Z = 2	0.43 × 0.40 × 0.25 mm
F(000) = 554

Data collection

Siemens SMART diffractometer	625 independent reflections
Radiation source: fine-focus sealed tube	554 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
φ and ω scans	θmax = 25.1°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→11
Tmin = 0.685, Tmax = 0.798	k = −11→11
2871 measured reflections	l = −16→10

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.100	w = 1/[σ^2(Fo^2) + (0.0614P)^2 + 0.8126P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.01
626 reflections	Δρmax = 0.33 e Å^−3
58 parameters	Δρmin = −0.46 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.052 (5)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Co	0.5000	0.5000	0.5000	0.0295 (4)
S1	0.86349 (9)	0.86349 (9)	0.5000	0.0606 (5)
O1W	0.3901 (3)	0.6099 (3)	0.3938 (3)	0.0960 (13)
H1	0.3990	0.7114	0.3810	0.115*
N1	0.6560 (3)	0.6560 (3)	0.5000	0.0413 (9)
C1	0.7427 (3)	0.7427 (3)	0.5000	0.0348 (10)
N2	0.1198 (3)	0.5440 (3)	0.31207 (17)	0.0558 (7)
C2	0.0000	0.5000	0.3713 (3)	0.0637 (13)
H2	−0.023 (4)	0.572 (4)	0.409 (2)	0.081 (11)*
C3	0.1598 (3)	0.4253 (4)	0.2505 (3)	0.0632 (9)
H3A	0.179 (4)	0.350 (4)	0.293 (3)	0.078 (11)*
H3B	0.243 (4)	0.457 (4)	0.212 (3)	0.079 (10)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co	0.0285 (4)	0.0285 (4)	0.0315 (5)	−0.0055 (3)	0.000	0.000
S1	0.0445 (6)	0.0445 (6)	0.0930 (11)	−0.0205 (6)	0.000	0.000
O1W	0.0788 (14)	0.0788 (14)	0.131 (3)	−0.0392 (18)	−0.0664 (18)	0.0664 (18)
N1	0.0391 (14)	0.0391 (14)	0.046 (2)	−0.0050 (18)	0.000	0.000
C1	0.0322 (15)	0.0322 (15)	0.040 (2)	−0.0018 (19)	0.000	0.000
N2	0.0523 (14)	0.0631 (15)	0.0520 (13)	0.0067 (11)	−0.0179 (11)	−0.0131 (11)
C2	0.095 (4)	0.065 (3)	0.0310 (18)	0.031 (2)	0.000	0.000
C3	0.0467 (17)	0.071 (2)	0.072 (2)	0.0158 (15)	0.0021 (14)	−0.0125 (17)

Geometric parameters (Å, º)

Co—O1W^i	2.074 (3)	N2—C2	1.459 (3)
Co—O1W^ii	2.074 (3)	N2—C3^iv	1.459 (4)
Co—O1W	2.074 (3)	N2—C3	1.458 (4)
Co—O1W^iii	2.074 (3)	C2—N2^v	1.459 (3)
Co—N1^ii	2.092 (4)	C2—H2	0.88 (3)
Co—N1	2.092 (4)	C3—N2^vi	1.459 (4)
S1—C1	1.621 (5)	C3—H3A	0.94 (4)
O1W—H1	0.9821	C3—H3B	0.99 (4)
N1—C1	1.163 (6)
O1W^i—Co—O1W^ii	89.4 (3)	Co—O1W—H1	125.1
O1W^i—Co—O1W	90.6 (3)	C1—N1—Co	180.0
O1W^ii—Co—O1W	180.0	N1—C1—S1	179.999 (1)
O1W^i—Co—O1W^iii	180.0	C2—N2—C3^iv	108.4 (2)
O1W^ii—Co—O1W^iii	90.6 (3)	C2—N2—C3	107.8 (2)
O1W—Co—O1W^iii	89.4 (3)	C3^iv—N2—C3	108.44 (18)
O1W^i—Co—N1^ii	90.0	N2—C2—N2^v	112.2 (3)
O1W^ii—Co—N1^ii	90.0	N2—C2—H2	107 (2)
O1W—Co—N1^ii	90.0	N2^v—C2—H2	111 (2)
O1W^iii—Co—N1^ii	90.0	N2^vi—C3—N2	111.8 (3)
O1W^i—Co—N1	90.0	N2^vi—C3—H3A	107 (2)
O1W^ii—Co—N1	90.0	N2—C3—H3A	106 (2)
O1W—Co—N1	90.0	N2^vi—C3—H3B	112 (2)
O1W^iii—Co—N1	90.0	N2—C3—H3B	106 (2)
N1^ii—Co—N1	180.0	H3A—C3—H3B	114 (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) y−1/2, −x+1/2, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1···N2^vii	0.98	1.94	2.867 (3)	157.1

Symmetry code: (vii) −y+1, −x+1, z.