Poly[[μ4-bis­(4-pyridyl­carbon­yl)piperazine-κ4N:N′:O:O′]bis­(thio­cyanato-κN)cobalt(II)]

Wilseck, Z.M.; LaDuca, R.L.

doi:10.1107/S160053681001915X

metal-organic compounds

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Volume 66| Part 6| June 2010| Page m713

https://doi.org/10.1107/S160053681001915X

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Poly[[μ₄-bis(4-pyridylcarbonyl)piperazine-κ⁴N:N′:O:O′]bis(thiocyanato-κN)cobalt(II)]

Zachary M. Wilseck ^a and Robert L. LaDuca ^a ^*

^aLyman Briggs College, Department of Chemistry, Michigan State University, East Lansing, MI 48825, USA
^*Correspondence e-mail: laduca@msu.edu

(Received 12 May 2010; accepted 21 May 2010; online 29 May 2010)

In the title compound, [Co(NCS)₂(C₁₆H₁₆N₄O₂)]_n, the octahedrally coordinated Co^II ion lies on a crystallographic inversion center, with trans isothiocyanate ligands. Pyridyl N-donor atoms and formyl O-donor atoms from exotetradentate bis(4-pyridylcarbonyl)piperazine (4-bpfp) ligands link the Co(NCS)₂ units into a [Co(NCS)₂(4-bpfp)]_n coordination polymer layer that is oriented parallel to (101). The layers stack along [010] to construct the pseudo-three-dimensional structure.

Related literature

For divalent metal isophthalate coordination polymers containing bis(4-pyridylmethyl)piperazine ligands, see: Martin et al. (2007 ). For a cobalt isothiocyanate coordination polymer containing bis(4-pyridylmethyl)piperazine ligands, see: Martin et al. (2009 ). For the preparation of 4-bpfp, see: Hou et al. (2003 ).

Experimental

Crystal data

[Co(NCS)₂(C₁₆H₁₆N₄O₂)]
M_r = 471.44
Triclinic, $[P \overline 1]$
a = 7.7410 (14) Å
b = 7.8943 (15) Å
c = 9.801 (3) Å
α = 101.080 (2)°
β = 102.264 (2)°
γ = 119.136 (2)°
V = 479.58 (18) Å³
Z = 1
Mo Kα radiation
μ = 1.14 mm⁻¹
T = 173 K
0.42 × 0.19 × 0.07 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.643, T_max = 0.928
6955 measured reflections
1753 independent reflections
1646 reflections with I > 2σ(I)
R_int = 0.052

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.105
S = 1.18
1753 reflections
133 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Table 1
Selected bond lengths (Å)

Co1—N1	2.1739 (19)
Co1—N3	2.026 (2)
Co1—O1ⁱ	2.2034 (16)
Symmetry code: (i) -x, -y+1, -z.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalMaker (Palmer, 2007 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S160053681001915X/hy2308sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681001915X/hy2308Isup2.hkl

checkCIF report

Comment top

Recently our group has been investigating the synthesis of divalent metal coordination polymers containing aromatic dicarboxylate and bis(4-pyridyl-methyl)piperazine ligands (Martin et al., 2007). To probe the structural effect of the presence of hydrogen-bond accepting formyl oxygen atoms in a similar ligand, we attempted to prepare a cobalt phthalate coordination polymer containing bis(4-pyridylcarbonyl)piperazine (4-bpfp). Use of cobalt(II) thiocyanate as the metal precursor afforded pink plates of the title compound.

The title compound crystallizes in the centrosymmetric triclinic space group with an asymmetric unit consisting of a Co^II ion on a crystallographic inversion center, one isothiocyanate ligand bound via its N atom, and one-half of a 4-bpfp molecule. The coordination environment at Co is a slightly distorted [CoN₄O₂] octahedron (Fig. 1), with trans isothiocyanate ligands, trans pyridyl N atom donors from two 4-bpfp ligands, and trans formyl O atom donors from two other 4-bpfp ligands.

Each 4-bpfp ligand is exotetradentate, ligating to Co atoms through both pyridyl N atoms and both formyl O atoms. As a result, [Co(NCS)₂(4-bpfp)]_n coordination polymer layers are formed (Fig. 2), which are oriented parallel to the ac crystal planes. Fourteen-membered [CoOC₄N]₂ circuits, whose centroids rest on crystallographic inversion centers, are evident within the layer motifs. The Co···Co distances across these circuits denote the a lattice parameter. The through-ligand Co···Co distances across the full span of the 4-bpfp ligands measure 16.471 (4) Å.

Adjacent [Co(NCS)₂(4-bpfp)]_n layers stack in an AAA pattern along the b direction (Fig. 3), with the isothiocyanate ligands projecting above and below the layer planes. Crystal packing forces cause aggregation of the layer motifs into pseudo three-dimensional crystal structure of the title compound.

Related literature top

For divalent metal isophthalate coordination polymers containing bis(4-pyridyl-methyl)piperazine ligands, see: Martin et al. (2007). For a cobalt isothiocyanate coordination polymer containing bis(4-pyridyl-methyl)piperazine ligands, see: Martin et al. (2009). For the preparation of 4-bpfp, see: Hou, et al. (2003).

Experimental top

All starting materials were obtained commercially, except for 4-bpfp, which was prepared by a published procedure (Hou et al., 2003). Cobalt(II) thiocyanate (130 mg, 0.74 mmol), phthalic acid (123 mg, 0.74 mmol) and 4-bpfp (110 mg, 0.37 mmol) were placed into 10 ml H₂O in a 23 ml Teflon-lined Parr acid digestion bomb. The bomb was heated at 393 K for 48 h and was then allowed to cool to room temperature. Pink plates of the title compound were obtained along with a white powdery solid.

Structure description top

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalMaker (Palmer, 2007); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The coordination environment of the title compound, showing 50% probability ellipsoids. Hydrogen atom positions are shown as grey sticks. [Color codes: dark blue Co, yellow S, red O, light blue N, black C. Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x, -y+1, -z; (iii) x+1, y, z; (iv) -x-1, -y+1, -z-1.]
	Fig. 2. [Co(NCS)₂(4-bpfp)]_n layer in the title compound.
	Fig. 3. Packing diagram of the title compound.

Poly[[µ₄-bis(4-pyridylcarbonyl)piperazine- κ⁴N:N':O:O']bis(thiocyanato- κN)cobalt(II)] top

Crystal data top

[Co(NCS)₂(C₁₆H₁₆N₄O₂)]	Z = 1
M_r = 471.44	F(000) = 241
Triclinic, P1	D_x = 1.632 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7410 (14) Å	Cell parameters from 6955 reflections
b = 7.8943 (15) Å	θ = 2.3–25.3°
c = 9.801 (3) Å	µ = 1.14 mm⁻¹
α = 101.080 (2)°	T = 173 K
β = 102.264 (2)°	Plate, pink
γ = 119.136 (2)°	0.42 × 0.19 × 0.07 mm
V = 479.58 (18) Å³

Data collection top

Bruker APEXII CCD diffractometer	1753 independent reflections
Radiation source: fine-focus sealed tube	1646 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.052
ω and φ scans	θ_max = 25.3°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.643, T_max = 0.928	k = −9→9
6955 measured reflections	l = −11→11

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.105	H-atom parameters constrained
S = 1.18	w = 1/[σ²(F_o²) + (0.0458P)² + 0.1032P] where P = (F_o² + 2F_c²)/3
1753 reflections	(Δ/σ)_max < 0.001
133 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.55 e Å⁻³

Crystal data top

[Co(NCS)₂(C₁₆H₁₆N₄O₂)]	γ = 119.136 (2)°
M_r = 471.44	V = 479.58 (18) Å³
Triclinic, P1	Z = 1
a = 7.7410 (14) Å	Mo Kα radiation
b = 7.8943 (15) Å	µ = 1.14 mm⁻¹
c = 9.801 (3) Å	T = 173 K
α = 101.080 (2)°	0.42 × 0.19 × 0.07 mm
β = 102.264 (2)°

Data collection top

Bruker APEXII CCD diffractometer	1753 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1646 reflections with I > 2σ(I)
T_min = 0.643, T_max = 0.928	R_int = 0.052
6955 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.105	H-atom parameters constrained
S = 1.18	Δρ_max = 0.37 e Å⁻³
1753 reflections	Δρ_min = −0.55 e Å⁻³
133 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Co1	0.5000	0.5000	0.0000	0.03453 (19)
S1	0.75373 (12)	1.06782 (11)	0.44195 (8)	0.0504 (2)
N1	0.2531 (3)	0.5500 (3)	−0.0887 (2)	0.0359 (4)
N2	−0.3493 (3)	0.6090 (3)	−0.3539 (2)	0.0384 (5)
N3	0.6324 (3)	0.7503 (3)	0.1850 (2)	0.0409 (5)
C1	0.0560 (4)	0.3911 (4)	−0.1764 (3)	0.0391 (5)
H1	0.0304	0.2594	−0.2075	0.047*
C2	−0.1098 (4)	0.4140 (4)	−0.2225 (3)	0.0389 (5)
H2	−0.2440	0.2996	−0.2828	0.047*
C3	−0.0749 (4)	0.6093 (4)	−0.1781 (2)	0.0364 (5)
C4	0.1289 (4)	0.7751 (4)	−0.0883 (3)	0.0402 (5)
H4	0.1589	0.9085	−0.0564	0.048*
C5	0.2849 (4)	0.7384 (4)	−0.0476 (3)	0.0402 (5)
H5	0.4208	0.8506	0.0119	0.048*
C6	−0.2526 (4)	0.6408 (3)	−0.2131 (3)	0.0366 (5)
C7	−0.5284 (4)	0.6312 (4)	−0.3955 (3)	0.0418 (6)
H7A	−0.4879	0.7492	−0.4281	0.050*
H7B	−0.5682	0.6550	−0.3099	0.050*
C8	−0.2853 (4)	0.5629 (4)	−0.4802 (3)	0.0407 (6)
H8A	−0.1706	0.5438	−0.4478	0.049*
H8B	−0.2349	0.6781	−0.5163	0.049*
C9	0.6850 (4)	0.8842 (4)	0.2928 (3)	0.0368 (5)
O1	−0.3046 (2)	0.6962 (2)	−0.10853 (17)	0.0385 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0345 (3)	0.0389 (3)	0.0305 (3)	0.0226 (2)	0.0083 (2)	0.0097 (2)
S1	0.0535 (4)	0.0462 (4)	0.0441 (4)	0.0265 (4)	0.0163 (3)	0.0048 (3)
N1	0.0353 (10)	0.0408 (11)	0.0334 (10)	0.0222 (9)	0.0114 (8)	0.0142 (8)
N2	0.0369 (11)	0.0495 (12)	0.0346 (10)	0.0276 (10)	0.0121 (8)	0.0157 (9)
N3	0.0404 (11)	0.0456 (11)	0.0369 (11)	0.0262 (10)	0.0100 (9)	0.0114 (10)
C1	0.0401 (13)	0.0394 (12)	0.0372 (12)	0.0234 (11)	0.0121 (10)	0.0102 (10)
C2	0.0365 (12)	0.0426 (13)	0.0315 (12)	0.0212 (11)	0.0071 (10)	0.0082 (10)
C3	0.0384 (12)	0.0459 (13)	0.0300 (12)	0.0250 (11)	0.0141 (10)	0.0158 (10)
C4	0.0393 (13)	0.0399 (13)	0.0408 (13)	0.0225 (11)	0.0105 (10)	0.0149 (10)
C5	0.0352 (12)	0.0393 (13)	0.0403 (13)	0.0185 (11)	0.0083 (10)	0.0139 (10)
C6	0.0344 (12)	0.0361 (12)	0.0363 (12)	0.0186 (10)	0.0092 (10)	0.0124 (10)
C7	0.0438 (14)	0.0579 (15)	0.0361 (13)	0.0358 (13)	0.0143 (11)	0.0181 (11)
C8	0.0368 (12)	0.0589 (15)	0.0363 (13)	0.0308 (12)	0.0153 (10)	0.0207 (11)
C9	0.0322 (12)	0.0415 (13)	0.0374 (13)	0.0210 (11)	0.0109 (10)	0.0147 (11)
O1	0.0394 (9)	0.0435 (9)	0.0352 (9)	0.0253 (8)	0.0122 (7)	0.0124 (7)

Geometric parameters (Å, º) top

Co1—N1	2.1739 (19)	C2—H2	0.9300
Co1—N3	2.026 (2)	C3—C4	1.391 (3)
Co1—O1ⁱ	2.2034 (16)	C3—C6	1.496 (3)
S1—C9	1.620 (3)	C4—C5	1.372 (4)
N1—C1	1.343 (3)	C4—H4	0.9300
N1—C5	1.344 (3)	C5—H5	0.9300
N2—C6	1.331 (3)	C6—O1	1.256 (3)
N2—C7	1.464 (3)	C7—C8ⁱⁱ	1.515 (3)
N2—C8	1.475 (3)	C7—H7A	0.9700
N3—C9	1.170 (3)	C7—H7B	0.9700
C1—C2	1.377 (3)	C8—C7ⁱⁱ	1.515 (3)
C1—H1	0.9300	C8—H8A	0.9700
C2—C3	1.388 (3)	C8—H8B	0.9700

N3ⁱⁱⁱ—Co1—N3	180.0	C3—C2—H2	120.3
N3ⁱⁱⁱ—Co1—N1	90.06 (8)	C2—C3—C4	118.0 (2)
N3—Co1—N1	89.94 (8)	C2—C3—C6	121.7 (2)
N3ⁱⁱⁱ—Co1—N1ⁱⁱⁱ	89.94 (8)	C4—C3—C6	120.1 (2)
N3—Co1—N1ⁱⁱⁱ	90.06 (8)	C5—C4—C3	118.8 (2)
N1—Co1—N1ⁱⁱⁱ	180.00 (9)	C5—C4—H4	120.6
N3ⁱⁱⁱ—Co1—O1ⁱ	90.43 (7)	C3—C4—H4	120.6
N3—Co1—O1ⁱ	89.57 (7)	N1—C5—C4	123.9 (2)
N1—Co1—O1ⁱ	89.79 (7)	N1—C5—H5	118.0
N1ⁱⁱⁱ—Co1—O1ⁱ	90.21 (7)	C4—C5—H5	118.0
N3ⁱⁱⁱ—Co1—O1^iv	89.57 (7)	O1—C6—N2	122.7 (2)
N3—Co1—O1^iv	90.43 (7)	O1—C6—C3	118.7 (2)
N1—Co1—O1^iv	90.21 (7)	N2—C6—C3	118.7 (2)
N1ⁱⁱⁱ—Co1—O1^iv	89.79 (7)	N2—C7—C8ⁱⁱ	109.9 (2)
O1ⁱ—Co1—O1^iv	180.00 (9)	N2—C7—H7A	109.7
C1—N1—C5	116.8 (2)	C8ⁱⁱ—C7—H7A	109.7
C1—N1—Co1	121.35 (15)	N2—C7—H7B	109.7
C5—N1—Co1	121.59 (15)	C8ⁱⁱ—C7—H7B	109.7
C6—N2—C7	121.13 (19)	H7A—C7—H7B	108.2
C6—N2—C8	125.8 (2)	N2—C8—C7ⁱⁱ	109.98 (19)
C7—N2—C8	112.94 (18)	N2—C8—H8A	109.7
C9—N3—Co1	171.96 (19)	C7ⁱⁱ—C8—H8A	109.7
N1—C1—C2	123.1 (2)	N2—C8—H8B	109.7
N1—C1—H1	118.4	C7ⁱⁱ—C8—H8B	109.7
C2—C1—H1	118.4	H8A—C8—H8B	108.2
C1—C2—C3	119.4 (2)	N3—C9—S1	179.0 (2)
C1—C2—H2	120.3	C6—O1—Co1^v	127.28 (15)

N3ⁱⁱⁱ—Co1—N1—C1	32.05 (18)	Co1—N1—C5—C4	−173.16 (18)
N3—Co1—N1—C1	−147.95 (18)	C3—C4—C5—N1	−0.4 (4)
O1ⁱ—Co1—N1—C1	−58.38 (17)	C7—N2—C6—O1	−1.9 (4)
O1^iv—Co1—N1—C1	121.62 (17)	C8—N2—C6—O1	174.0 (2)
N3ⁱⁱⁱ—Co1—N1—C5	−154.13 (18)	C7—N2—C6—C3	178.1 (2)
N3—Co1—N1—C5	25.87 (18)	C8—N2—C6—C3	−6.1 (3)
O1ⁱ—Co1—N1—C5	115.44 (18)	C2—C3—C6—O1	110.4 (3)
O1^iv—Co1—N1—C5	−64.56 (18)	C4—C3—C6—O1	−64.0 (3)
C5—N1—C1—C2	−0.9 (3)	C2—C3—C6—N2	−69.5 (3)
Co1—N1—C1—C2	173.23 (17)	C4—C3—C6—N2	116.0 (3)
N1—C1—C2—C3	0.3 (4)	C6—N2—C7—C8ⁱⁱ	−126.9 (2)
C1—C2—C3—C4	0.2 (3)	C8—N2—C7—C8ⁱⁱ	56.8 (3)
C1—C2—C3—C6	−174.4 (2)	C6—N2—C8—C7ⁱⁱ	127.0 (2)
C2—C3—C4—C5	−0.2 (3)	C7—N2—C8—C7ⁱⁱ	−56.8 (3)
C6—C3—C4—C5	174.5 (2)	N2—C6—O1—Co1^v	100.8 (2)
C1—N1—C5—C4	0.9 (3)	C3—C6—O1—Co1^v	−79.1 (2)

Symmetry codes: (i) −x, −y+1, −z; (ii) −x−1, −y+1, −z−1; (iii) −x+1, −y+1, −z; (iv) x+1, y, z; (v) x−1, y, z.

Experimental details

Crystal data
Chemical formula	[Co(NCS)₂(C₁₆H₁₆N₄O₂)]
M_r	471.44
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	7.7410 (14), 7.8943 (15), 9.801 (3)
α, β, γ (°)	101.080 (2), 102.264 (2), 119.136 (2)
V (Å³)	479.58 (18)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.14
Crystal size (mm)	0.42 × 0.19 × 0.07

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.643, 0.928
No. of measured, independent and observed [I > 2σ(I)] reflections	6955, 1753, 1646
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.105, 1.18
No. of reflections	1753
No. of parameters	133
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.55

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), CrystalMaker (Palmer, 2007).

Selected bond lengths (Å) top

Co1—N1	2.1739 (19)	Co1—O1ⁱ	2.2034 (16)
Co1—N3	2.026 (2)

Symmetry code: (i) −x, −y+1, −z.

Acknowledgements

We gratefully acknowledge the donors of the American Chemical Society Petroleum Research Fund for funding this work. ZMW thanks Dr Richard Staples for instruction in the use of the crystallographic software.

References

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