Diaqua­bis[2-(2-pyridylmeth­oxy)pyrazine-κN4]bis­(thio­cyanato-κN)cobalt(II)

Yang, Z.N.

doi:10.1107/S1600536808030882

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 10| October 2008| Page m1350

doi:10.1107/S1600536808030882

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Diaquabis[2-(2-pyridylmethoxy)pyrazine-κN⁴]bis(thiocyanato-κN)cobalt(II)

Zhong Nian Yang ^a ^*

^aDepartment of Chemistry and Chemical Engineering, Binzhou University, Binzhou 256603, People's Republic of China
^*Correspondence e-mail: yangzhongnian1978@yahoo.com.cn

(Received 20 September 2008; accepted 24 September 2008; online 30 September 2008)

In the title complex, [Co(NCS)₂(C₁₀H₉N₃O)₂(H₂O)₂], the Co^II ion is located on a crystallographic twofold rotation axis and is in a slightly distorted octahedral CoN₄O₂ coordination environment. The dihedral angle between the pyridine and pyrazine rings is 85.86 (10)°. In the crystal structure, intermolecular O—H⋯N and O—H⋯S hydrogen bonds link complex molecules into a three-dimensional network.

Related literature

For the isostructural Mn complex, see: Li (2007 ). For a related structure, see: Zhao et al. (2007 ).

Experimental

Crystal data

[Co(NCS)₂(C₁₀H₉N₃O)₂(H₂O)₂]
M_r = 585.53
Monoclinic, C 2/c
a = 19.954 (4) Å
b = 10.044 (2) Å
c = 13.650 (3) Å
β = 110.749 (3)°
V = 2558.2 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.88 mm⁻¹
T = 298 (2) K
0.41 × 0.31 × 0.16 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan SADABS (Sheldrick, 1996 ) T_min = 0.714, T_max = 0.872
7123 measured reflections
2768 independent reflections
2361 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.108
S = 1.09
2768 reflections
168 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.75 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Co1—N4	2.0597 (19)
Co1—O2	2.1394 (13)
Co1—N3	2.1856 (15)

N4—Co1—N4ⁱ	175.43 (9)
N4—Co1—O2	91.49 (6)
N4ⁱ—Co1—O2	85.34 (6)
O2—Co1—O2ⁱ	92.24 (8)
N4—Co1—N3ⁱ	92.63 (6)
O2—Co1—N3ⁱ	173.74 (6)
N4—Co1—N3	90.81 (6)
O2—Co1—N3	92.79 (6)
N3ⁱ—Co1—N3	82.45 (8)
Symmetry code: (i) $[-x, y, -z+{\script{3\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H5⋯S1ⁱⁱ	0.86	2.58	3.4123 (17)	164
O2—H8⋯N1ⁱⁱⁱ	0.83	1.98	2.803 (2)	172
Symmetry codes: (ii) $[x, -y+1, z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+2]$ .

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808030882/lh2698sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808030882/lh2698Isup2.hkl

checkCIF report

Comment top

Molecules containing both pyridyl and pyrazinyl groups are useful multi-dentate ligands and a number of complexes have been published dealing with these ligands (e.g. Zhao et al., 2007; Li, 2007). Herein the crystal structure of the title complex, (I), with 2-((pyridin-2-yl)methoxy)pyrazine as ligand, is reported.

The molecular structure of (I) is shown in Fig. 1. In the mono-nuclear complex, atom Co1 lies on a twofold rotation axis and its coordination geometry is slightly distorted octahedral (Table 1). In the crystal structure, complex molecules are linked via intermolecular O—H···S and O—H···N hydrogen bonds as shown in Fig. 2 and Table 2, to form a three-dimensional network. The diheral angle between pyridine and pyrazine rings is 85.86 (10)°. The title compound is isostructural with the Mn^II complex (Li, 2007).

Related literature top

For the isostructural Mn complex, see: Li (2007). For a related structure, see: Zhao et al. (2007).

Experimental top

A 5 ml methanol solution of 2-[(pyridin-2-yl)methoxy]pyrazine (0.0526 g, 0.281 mmol) was added into 10 ml H₂O solution containing Co(ClO₄)₂.6H₂O (0.1032 g, 0.282 mmol) and NaSCN (0.0457 g, 0.564 mmol), and the mixture was stirred for a few minutes. Red single crystals were obtained after the solution had been allowed to stand at room temperature for two weeks.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. View of complex (I), showing the the asymmetric atom numbering scheme with thermal ellipsoids drawn at the 30% probability level. (symmetry code: (i) -x, y, -z + 3/2)
	Fig. 2. Part of the crystal structure of (I). Hydrogen bonds are shown as dashed lines.

Diaquabis[2-(2-pyridylmethoxy)pyrazine-κN⁴]bis(thiocyanato-κN)cobalt(II) top

Crystal data top

[Co(NCS)₂(C₁₀H₉N₃O)₂(H₂O)₂]	F(000) = 1204
M_r = 585.53	D_x = 1.520 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3335 reflections
a = 19.954 (4) Å	θ = 2.3–27.5°
b = 10.044 (2) Å	µ = 0.88 mm⁻¹
c = 13.650 (3) Å	T = 298 K
β = 110.749 (3)°	Block, red
V = 2558.2 (10) Å³	0.41 × 0.31 × 0.16 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	2768 independent reflections
Radiation source: fine-focus sealed tube	2361 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ϕ and ω scans	θ_max = 27.0°, θ_min = 2.2°
Absorption correction: multi-scan SADABS (Sheldrick, 1996)	h = −25→21
T_min = 0.714, T_max = 0.872	k = −11→12
7123 measured reflections	l = −9→17

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0638P)² + 0.3122P] where P = (F_o² + 2F_c²)/3
2768 reflections	(Δ/σ)_max = 0.008
168 parameters	Δρ_max = 0.75 e Å⁻³
1 restraint	Δρ_min = −0.37 e Å⁻³

Crystal data top

[Co(NCS)₂(C₁₀H₉N₃O)₂(H₂O)₂]	V = 2558.2 (10) Å³
M_r = 585.53	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 19.954 (4) Å	µ = 0.88 mm⁻¹
b = 10.044 (2) Å	T = 298 K
c = 13.650 (3) Å	0.41 × 0.31 × 0.16 mm
β = 110.749 (3)°

Data collection top

Bruker SMART APEX CCD diffractometer	2768 independent reflections
Absorption correction: multi-scan SADABS (Sheldrick, 1996)	2361 reflections with I > 2σ(I)
T_min = 0.714, T_max = 0.872	R_int = 0.032
7123 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	1 restraint
wR(F²) = 0.108	H-atom parameters constrained
S = 1.09	Δρ_max = 0.75 e Å⁻³
2768 reflections	Δρ_min = −0.37 e Å⁻³
168 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

	x	y	z	U_iso*/U_eq
C1	0.23226 (11)	−0.20768 (19)	1.25209 (19)	0.0415 (5)
H1	0.1927	−0.2583	1.2136	0.050*
C2	0.25719 (13)	−0.2109 (2)	1.3601 (2)	0.0473 (5)
H2	0.2351	−0.2643	1.3955	0.057*
C3	0.31522 (12)	−0.1337 (2)	1.41439 (17)	0.0471 (5)
H3	0.3328	−0.1326	1.4872	0.057*
C4	0.34682 (12)	−0.0580 (2)	1.35887 (17)	0.0474 (5)
H4	0.3863	−0.0062	1.3961	0.057*
C5	0.26655 (10)	−0.12879 (17)	1.20171 (15)	0.0336 (4)
C6	0.24197 (11)	−0.1258 (2)	1.08505 (16)	0.0431 (5)
H6A	0.2825	−0.1138	1.0625	0.052*
H6B	0.2184	−0.2089	1.0562	0.052*
N2	0.17307 (9)	−0.09050 (15)	0.88100 (13)	0.0385 (4)
C8	0.15889 (10)	−0.00579 (18)	0.94509 (15)	0.0349 (4)
C9	0.13592 (11)	−0.0711 (2)	0.77904 (16)	0.0425 (5)
H9	0.1426	−0.1301	0.7308	0.051*
C10	0.08838 (10)	0.0321 (2)	0.74250 (16)	0.0398 (5)
H10	0.0646	0.0421	0.6708	0.048*
C11	0.10991 (10)	0.09863 (18)	0.91016 (15)	0.0341 (4)
H11	0.1012	0.1545	0.9587	0.041*
C12	0.02714 (11)	0.28829 (18)	0.53206 (17)	0.0365 (4)
Co1	0.0000	0.28266 (3)	0.7500	0.02902 (14)
N4	0.02348 (10)	0.29084 (16)	0.61484 (15)	0.0394 (4)
N3	0.07579 (8)	0.11899 (15)	0.80922 (13)	0.0330 (3)
N1	0.32395 (9)	−0.05466 (17)	1.25423 (13)	0.0402 (4)
O1	0.19253 (8)	−0.01598 (14)	1.04945 (11)	0.0455 (4)
O2	0.07922 (7)	0.43031 (14)	0.82323 (11)	0.0425 (3)
H5	0.0637	0.4916	0.8532	0.064*
H8	0.1079	0.4599	0.7969	0.064*
S1	0.03352 (5)	0.28165 (7)	0.41650 (6)	0.0722 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0319 (10)	0.0342 (10)	0.0538 (13)	0.0006 (7)	0.0096 (10)	0.0005 (9)
C2	0.0484 (13)	0.0442 (11)	0.0552 (14)	0.0083 (9)	0.0257 (11)	0.0133 (10)
C3	0.0505 (13)	0.0511 (12)	0.0351 (11)	0.0126 (10)	0.0096 (10)	0.0053 (10)
C4	0.0409 (11)	0.0471 (12)	0.0439 (12)	−0.0040 (9)	0.0022 (10)	−0.0025 (10)
C5	0.0296 (9)	0.0283 (9)	0.0380 (10)	0.0092 (7)	0.0059 (8)	0.0013 (7)
C6	0.0425 (11)	0.0390 (10)	0.0387 (11)	0.0150 (9)	0.0032 (9)	0.0006 (9)
N2	0.0362 (9)	0.0342 (8)	0.0403 (9)	0.0070 (7)	0.0075 (7)	−0.0012 (7)
C8	0.0310 (9)	0.0330 (9)	0.0339 (10)	0.0013 (7)	0.0032 (8)	−0.0014 (8)
C9	0.0439 (11)	0.0420 (11)	0.0367 (11)	0.0094 (9)	0.0082 (9)	−0.0046 (9)
C10	0.0362 (10)	0.0425 (10)	0.0347 (10)	0.0066 (8)	0.0051 (9)	−0.0033 (9)
C11	0.0294 (9)	0.0315 (9)	0.0354 (10)	0.0028 (7)	0.0040 (8)	−0.0028 (8)
C12	0.0364 (10)	0.0331 (9)	0.0404 (9)	0.0018 (7)	0.0140 (9)	0.0011 (8)
Co1	0.0249 (2)	0.0302 (2)	0.0284 (2)	0.000	0.00494 (15)	0.000
N4	0.0405 (10)	0.0391 (9)	0.0397 (9)	−0.0016 (7)	0.0152 (8)	0.0003 (7)
N3	0.0257 (7)	0.0328 (8)	0.0354 (8)	0.0009 (6)	0.0045 (6)	−0.0013 (6)
N1	0.0346 (9)	0.0398 (9)	0.0419 (9)	−0.0016 (7)	0.0083 (8)	0.0039 (8)
O1	0.0514 (9)	0.0385 (7)	0.0343 (8)	0.0187 (6)	−0.0002 (7)	−0.0015 (6)
O2	0.0415 (8)	0.0437 (8)	0.0417 (8)	−0.0125 (6)	0.0137 (7)	−0.0072 (6)
S1	0.1124 (7)	0.0671 (5)	0.0530 (4)	0.0083 (4)	0.0491 (4)	0.0012 (3)

Geometric parameters (Å, º) top

C1—C5	1.379 (3)	C8—C11	1.397 (2)
C1—C2	1.380 (3)	C9—C10	1.373 (3)
C1—H1	0.9300	C9—H9	0.9300
C2—C3	1.372 (3)	C10—N3	1.348 (2)
C2—H2	0.9300	C10—H10	0.9300
C3—C4	1.374 (3)	C11—N3	1.319 (2)
C3—H3	0.9300	C11—H11	0.9300
C4—N1	1.337 (3)	C12—N4	1.158 (3)
C4—H4	0.9300	C12—S1	1.628 (2)
C5—N1	1.341 (2)	Co1—N4	2.0597 (19)
C5—C6	1.491 (3)	Co1—N4ⁱ	2.0597 (19)
C6—O1	1.445 (2)	Co1—O2	2.1394 (13)
C6—H6A	0.9700	Co1—O2ⁱ	2.1394 (13)
C6—H6B	0.9700	Co1—N3ⁱ	2.1856 (15)
N2—C8	1.321 (2)	Co1—N3	2.1856 (15)
N2—C9	1.339 (3)	O2—H5	0.8552
C8—O1	1.346 (2)	O2—H8	0.8316

C5—C1—C2	119.44 (19)	C9—C10—H10	119.6
C5—C1—H1	120.3	N3—C11—C8	120.83 (17)
C2—C1—H1	120.3	N3—C11—H11	119.6
C3—C2—C1	118.7 (2)	C8—C11—H11	119.6
C3—C2—H2	120.7	N4—C12—S1	178.7 (2)
C1—C2—H2	120.7	N4—Co1—N4ⁱ	175.43 (9)
C2—C3—C4	118.6 (2)	N4—Co1—O2	91.49 (6)
C2—C3—H3	120.7	N4ⁱ—Co1—O2	85.34 (6)
C4—C3—H3	120.7	N4—Co1—O2ⁱ	85.34 (6)
N1—C4—C3	123.60 (19)	N4ⁱ—Co1—O2ⁱ	91.49 (6)
N1—C4—H4	118.2	O2—Co1—O2ⁱ	92.24 (8)
C3—C4—H4	118.2	N4—Co1—N3ⁱ	92.63 (6)
N1—C5—C1	122.21 (19)	N4ⁱ—Co1—N3ⁱ	90.81 (6)
N1—C5—C6	117.08 (18)	O2—Co1—N3ⁱ	173.74 (6)
C1—C5—C6	120.69 (18)	O2ⁱ—Co1—N3ⁱ	92.79 (6)
O1—C6—C5	107.55 (16)	N4—Co1—N3	90.81 (6)
O1—C6—H6A	110.2	N4ⁱ—Co1—N3	92.63 (6)
C5—C6—H6A	110.2	O2—Co1—N3	92.79 (6)
O1—C6—H6B	110.2	O2ⁱ—Co1—N3	173.74 (6)
C5—C6—H6B	110.2	N3ⁱ—Co1—N3	82.45 (8)
H6A—C6—H6B	108.5	C12—N4—Co1	170.41 (18)
C8—N2—C9	115.14 (16)	C11—N3—C10	117.06 (16)
N2—C8—O1	120.55 (16)	C11—N3—Co1	122.44 (12)
N2—C8—C11	123.07 (17)	C10—N3—Co1	120.49 (13)
O1—C8—C11	116.38 (17)	C4—N1—C5	117.44 (17)
N2—C9—C10	122.97 (19)	C8—O1—C6	116.04 (15)
N2—C9—H9	118.5	Co1—O2—H5	113.0
C10—C9—H9	118.5	Co1—O2—H8	123.6
N3—C10—C9	120.87 (19)	H5—O2—H8	111.7
N3—C10—H10	119.6

C5—C1—C2—C3	0.8 (3)	C9—C10—N3—Co1	180.00 (15)
C1—C2—C3—C4	−1.0 (3)	N4—Co1—N3—C11	150.92 (14)
C2—C3—C4—N1	0.3 (3)	N4ⁱ—Co1—N3—C11	−26.06 (15)
C2—C1—C5—N1	0.3 (3)	O2—Co1—N3—C11	59.39 (14)
C2—C1—C5—C6	178.48 (17)	N3ⁱ—Co1—N3—C11	−116.53 (16)
N1—C5—C6—O1	−88.0 (2)	N4—Co1—N3—C10	−30.49 (15)
C1—C5—C6—O1	93.7 (2)	N4ⁱ—Co1—N3—C10	152.53 (15)
C9—N2—C8—O1	179.51 (18)	O2—Co1—N3—C10	−122.02 (14)
C9—N2—C8—C11	−1.2 (3)	N3ⁱ—Co1—N3—C10	62.06 (13)
C8—N2—C9—C10	2.4 (3)	C3—C4—N1—C5	0.7 (3)
N2—C9—C10—N3	−1.2 (3)	C1—C5—N1—C4	−1.0 (3)
N2—C8—C11—N3	−1.2 (3)	C6—C5—N1—C4	−179.25 (17)
O1—C8—C11—N3	178.10 (17)	N2—C8—O1—C6	−1.9 (3)
C8—C11—N3—C10	2.4 (3)	C11—C8—O1—C6	178.76 (17)
C8—C11—N3—Co1	−178.94 (13)	C5—C6—O1—C8	−173.42 (17)
C9—C10—N3—C11	−1.3 (3)

Symmetry code: (i) −x, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H5···S1ⁱⁱ	0.86	2.58	3.4123 (17)	164
O2—H8···N1ⁱⁱⁱ	0.83	1.98	2.803 (2)	172

Symmetry codes: (ii) x, −y+1, z+1/2; (iii) −x+1/2, −y+1/2, −z+2.

Experimental details

Crystal data
Chemical formula	[Co(NCS)₂(C₁₀H₉N₃O)₂(H₂O)₂]
M_r	585.53
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	19.954 (4), 10.044 (2), 13.650 (3)
β (°)	110.749 (3)
V (Å³)	2558.2 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.88
Crystal size (mm)	0.41 × 0.31 × 0.16

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan SADABS (Sheldrick, 1996)
T_min, T_max	0.714, 0.872
No. of measured, independent and observed [I > 2σ(I)] reflections	7123, 2768, 2361
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.638

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.108, 1.09
No. of reflections	2768
No. of parameters	168
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.75, −0.37

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Co1—N4	2.0597 (19)	Co1—N3	2.1856 (15)
Co1—O2	2.1394 (13)

N4—Co1—N4ⁱ	175.43 (9)	O2—Co1—N3ⁱ	173.74 (6)
N4—Co1—O2	91.49 (6)	N4—Co1—N3	90.81 (6)
N4ⁱ—Co1—O2	85.34 (6)	O2—Co1—N3	92.79 (6)
O2—Co1—O2ⁱ	92.24 (8)	N3ⁱ—Co1—N3	82.45 (8)
N4—Co1—N3ⁱ	92.63 (6)

Symmetry code: (i) −x, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H5···S1ⁱⁱ	0.86	2.58	3.4123 (17)	164.1
O2—H8···N1ⁱⁱⁱ	0.83	1.98	2.803 (2)	171.6

Symmetry codes: (ii) x, −y+1, z+1/2; (iii) −x+1/2, −y+1/2, −z+2.

Acknowledgements

This work was supported by the Doctors' Foundation of Binzhou University.

References

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