Crystal structure of catena-poly[[[trans-bis(aceto­nitrile-κN)diaquacobalt(II)]-μ-pyrazine-κ2N:N′] dinitrate]

Liu, C.; Felts, A.C.; Thuijs, A.E.; Useche, A.; Abboud, K.A.

doi:10.1107/S2056989016000220

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ISSN: 2056-9890

Volume 72| Part 2| February 2016| Pages 151-154

doi:10.1107/S2056989016000220

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Crystal structure of catena-poly[[[trans-bis(acetonitrile-κN)diaquacobalt(II)]-μ-pyrazine-κ²N:N′] dinitrate]

Chen Liu,^a ^* Ashley C. Felts,^b Annaliese E. Thuijs,^b Aaron Useche ^a and Khalil A. Abboud ^b

^aDepartment of Chemistry and Environmental Science, Grenfell Campus, Memorial University of Newfoundland, Corner Brook, NL, A2H 5G4, Canada, and ^bDepartment of Chemistry, University of Florida, Gainesville, FL, 32611-7200, USA
^*Correspondence e-mail: cliu@grenfell.mun.ca

Edited by M. Weil, Vienna University of Technology, Austria (Received 31 December 2015; accepted 5 January 2016; online 13 January 2016)

The central structural motif of the title coordination polymer, [Co(NO₃)₂(C₄H₄N₂)(CH₃CN)₂(H₂O)₂]_n, is a chain composed of Co^II ions linked by bis-monodentate bridging pyrazine ligands through their N atoms. The Co^II ion is located on an inversion center and is additionally coordinated by two O atoms of water molecules and two N atoms of acetonitrile molecules. The resultant N₄O₂ coordination sphere is distorted octahedral. The linear cationic chains extend parallel to the a axis and are aligned into layers parallel to the ac plane. Nitrate anions are situated in the space between the Co^II chains and form O—H⋯O hydrogen bonds with the coordinating water molecules, leading to a three-dimensional network structure. Weak C—H⋯O hydrogen bonds are also present between pyrazine or acetonitrile molecules and the nitrate anions.

Keywords: crystal structure; one dimensional coordination polymer; cobalt(II) complex; pyrazine ligand; acetonitrile ligand.

CCDC reference: 1445438

1. Chemical context

In the design of coordination polymers, the choice of bridging ligands between metal atoms plays an important role in the formation of the final structure and the resulting properties. During our investigations of the preparation conditions and magnetic properties of compounds with ladder-like structures, we have used pyrazine as a bis-monodentate bridging ligand to link paramagnetic metal cations. From the point of view of mediating magnetic interactions, the pyrazine molecule offers some advantages compared to other bidentate bridging ligands such as 4,4′-bipyridine. In some of the structures with the latter ligand, the two pyridine rings are not co-planar and therefore can magnetically isolate metal atoms (Losier & Zaworotko, 1996 ; Ruan et al., 2009 ; Seidel et al., 2011 ; Lehleh et al., 2013 ).

We herein report the preparation and structure of a pyrazine-bridged chain structure obtained by reacting pyrazine and cobalt(II) nitrate hexahydrate using acetonitrile as the solvent.

2. Structural commentary

The asymmetric unit of the title compound, [Co(C₄H₄N₂)(CH₃CN)₂(H₂O)₂(NO₃)₂]_n, contains one Co^II cation located on an inversion center, one water molecule, one acetonitrile molecule, one nitrate anion, and one half of a pyrazine molecule, the latter being completed by inversion symmetry. The Co^II cation exhibits an N₄O₂ coordination set defined by two O atoms [O1, O1ⁱⁱ; symmetry code: (ii) −3 − x, 1 − y, −z] of two coordinating water molecules, two N atoms (N2, N2ⁱⁱ) of two coordinating acetonitrile molecules, and two nitrogen atoms (N1, N1ⁱⁱ) of two bridging pyrazine molecules (Fig. 1). The two Co—O_water bonds have a length of 2.0315 (8) Å, considerably shorter than the two Co—N_acetonitrile bonds of 2.1263 (9) Å, and the two Co—N_pyrazine bonds of 2.1493 (10) Å. The resulting coordination sphere is compressed octahedral with all bond lengths in good agreement with similar structures (Choudhury et al., 2002 ; Holman et al., 2005 ; Aşkin et al., 2015 ). In contrast to the N₂O₄ coordination spheres observed more frequently in the structures of other Co-containing compounds (Choudhury et al., 2002; Holman et al., 2005; Hyun et al., 2011 ; Aşkin et al., 2015), the title structure exhibits an N₄O₂ coordination sphere due to the inclusion of the solvent acetonitrile molecules in the coordination sphere of Co^II. The bridging bis-monodentate pyrazine molecules link the Co^II ions, forming linear chains extending parallel to the a axis. The distance between two symmetry-related Co^II ions within a chain (symmetry code: 1 + x, y, z) is 7.0798 (3) Å, in good agreement with those reported for similar structures (Choudhury et al., 2002; Holman et al., 2005; Aşkin et al., 2015).

Figure 1
A fragment of the one-dimensional chain structure of the title compound with displacement ellipsoids drawn at the 50% probability level. [Symmetry codes: (i) 1 + x, y, z; (ii) −3 − x, 1 − y, −z; (iii) −4 − x, 1 − y, −z.]

3. Supramolecular features

In the crystal, the cationic chains are arranged to form sheets parallel to the ac plane, and neighboring sheets are related by a glide plane. Nitrate ions are sandwiched in the space between the sheets and form columns parallel to the a axis. Each Co^II chain is surrounded by six columns of nitrate ions that are related by the inversion centers located along the cationic chains. Each cationic chain is further surrounded by six other chains. This structural motif with alternating layers has been observed in similar structures (Choudhury et al., 2002; Yang et al., 2003 ; Holman et al., 2005; Aşkin et al., 2015). Co^II chains in neighboring sheets interact through nitrate ions by forming O—H⋯O hydrogen bonds where the donor O—H groups are provided by the coordinating water molecules and the acceptor oxygen provided by the nitrate ions. One of those hydrogen bonds is bifurcated. For numerical values and symmetry operators, see Table 1. Weak C—H⋯O hydrogen bonds are also present between the C—H groups of bridging pyrazine and coordinating acetonitrile molecules, and the oxygen atoms of nitrate ions, linking Co^II chains both within the same sheet and to adjacent sheets (Table 1, Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1Y⋯O13ⁱ	0.83 (2)	1.85 (2)	2.6819 (12)	173.5 (18)
O1—H1X⋯O12ⁱⁱ	0.80 (2)	1.99 (2)	2.7869 (12)	174.1 (19)
O1—H1X⋯O13ⁱⁱ	0.80 (2)	2.562 (19)	3.0912 (12)	125.3 (17)
C1—H1A⋯O11ⁱⁱⁱ	0.95	2.54	3.1572 (14)	123
C2—H2A⋯O13^iv	0.95	2.59	3.4644 (14)	153
C4—H4A⋯O13^v	0.98	2.49	3.2785 (17)	138
C4—H4B⋯O11^vi	0.98	2.49	3.2823 (17)	138
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) x, y, z-1; (iii) -x, -y+1, -z; (iv) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) -x+1, -y+1, -z; (vi) $[-x, y+{\script{1\over 2}}, -z-{\script{1\over 2}}]$ .

Figure 2
Crystal packing of the title compound, showing hydrogen bonds as dashed lines.

4. Synthesis and crystallization

The title compound was obtained by a slow diffusion method in an U-shaped glass tube. The tube was first partially filled with acetonitrile. An acetonitrile solution of 0.333 mmol (97.0 mg) of Co(NO₃)₂·6H₂O was then placed in one arm of the tube. Another acetonitrile solution of 0.500 mmol (40.0 mg) of pyrazine was placed in the other arm of the tube. The slow diffusion of the two solutions in the tube produced pink needle–shaped crystals within one day. The crystals were collected by filtration and washed with fresh acetonitrile and kept under inert atmosphere (yield 31.5%). Selected IR bands (KBr, cm⁻¹): 3273 (O—H), 2283 (C≡N), 1633, 1413, 1384 (N=O), 479 (bridging pyrazine).

5. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 2. C-bound H atoms were calculated in geometrically idealized positions and refined riding on their parent atoms, with U_iso(H) = 1.2U_eq(C) (aromatic) and 1.5U_eq(C) (methyl), and with C—H = 0.95 Å (aromatic) and 0.98 Å (methyl). The methyl H atoms were allowed to rotate around the corresponding C—C bond. H atoms bound to water molecules were found in a difference map and were freely refined.

Table 2
Experimental details

Crystal data
Chemical formula	[Co(NO₃)₂(C₄H₄N₂)(C₂H₃N)₂(H₂O)₂]
M_r	381.18
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	7.0798 (3), 15.0376 (6), 7.9329 (3)
β (°)	110.8803 (6)
V (Å³)	789.10 (5)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.14
Crystal size (mm)	0.29 × 0.11 × 0.08

Data collection
Diffractometer	Bruker APEXII DUO CCD
Absorption correction	Analytical based on measured indexed crystal faces using SHELXTL2014 (Sheldrick, 2015b )
T_min, T_max	0.735, 0.904
No. of measured, independent and observed [I > 2σ(I)] reflections	21292, 1811, 1687
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.019, 0.055, 1.07
No. of reflections	1811
No. of parameters	115
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.31
Computer programs: APEX2 and SAINT (Bruker, 2014 ), SHELXLT (Sheldrick, 2015a ), SHELXL2014/7 (Sheldrick, 2015b), XP in SHELXTL-Plus (Sheldrick, 2008 ), ORTEP-3 for Windows (Farrugia, 2012 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1445438

Crystal structure: contains datablock I. DOI: 10.1107/S2056989016000220/wm5260sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989016000220/wm5260Isup2.hkl

checkCIF report

Chemical context top

In the design of coordination polymers, the choice of bridging ligands between metal atoms plays an important role in the formation of the final structure and the resulting properties. During our investigations of the preparation conditions and magnetic properties of compounds with ladder-like structures, we have used pyrazine as a bis-monodentate bridging ligand to link paramagnetic metal cations. From the point of view of mediating magnetic interactions, the pyrazine molecule offers some advantages compared to other bidentate bridging ligands such as 4,4'-bipyridine. In some of the structures with the latter ligand, the two pyridine rings are not co-planar and therefore can magnetically isolate metal atoms (Losier & Zaworotko, 1996; Ruan et al., 2009; Seidel et al., 2011; Lehleh et al., 2013).

We herein report the preparation and structure of a pyrazine-bridged chain structure obtained by reacting pyrazine and cobalt(II) nitrate hexahydrate using acetonitrile as the solvent.

Structural commentary top

The asymmetric unit of the title compound, [Co(C₄H₄N₂)(CH₃CN)₂(H₂O)₂(NO₃)₂]_n, contains one Co^II cation located on an inversion center, one water molecule, one acetonitrile molecule, one nitrate anion, and one half of a pyrazine molecule, the latter being completed by inversion symmetry. The Co^II cation exhibits an N₄O₂ coordination set defined by two O atoms [O1, O1ⁱⁱ; symmetry code: (ii) –3 – x, 1 – y, –z] of two coordinating water molecules, two N atoms (N2, N2ⁱⁱ) of two coordinating acetonitrile molecules, and two nitrogen atoms (N1, N1ⁱⁱ) of two bridging pyrazine molecules (Fig. 1). The two Co—O_water bonds have a length of 2.0315 (8) Å, considerably shorter than the two Co—N_acetonitrile bonds of 2.1263 (9) Å, and the two Co—N_pyrazine bonds of 2.1493 (10) Å. The resulting coordination sphere is compressed octahedral with all bond lengths in good agreement with similar structures (Choudhury et al., 2002; Holman et al., 2005; Aşkin et al., 2015). In contrast to the N₂O₄ coordination spheres observed more frequently in the structures of other Co-containing compounds (Choudhury et al., 2002; Holman et al., 2005; Hyun et al., 2011; Aşkin et al., 2015), the title structure exhibits an N₄O₂ coordination sphere due to the inclusion of the solvent acetonitrile molecules in the coordination sphere of Co^II. The bridging bis-monodentate pyrazine molecules link the Co^II ions, forming linear chains extending parallel to the a axis. The distance between two symmetry-related Co^II ions within a chain (symmetry code: 1 + x, y, z) is 7.0798 (3) Å, in good agreement with those reported for similar structures (Choudhury et al., 2002; Holman et al., 2005; Aşkin et al., 2015).

Supramolecular features top

In the crystal, the cationic chains are arranged to form sheets parallel to the ac plane, and neighboring sheets are related by a glide plane. Nitrate ions are sandwiched in the space between the sheets and form columns parallel to the a axis. Each Co^II chain is surrounded by six columns of nitrate ions that are related by the inversion centers located along the cationic chains. Each cationic chain is further surrounded by six other chains. This structural motif with alternating layers has been observed in similar structures (Choudhury et al., 2002; Yang et al., 2003; Holman et al., 2005; Aşkin et al., 2015). Co^II chains in neighboring sheets interact through nitrate ions by forming O—H···O hydrogen bonds where the donor O—H groups are provided by the coordinating water molecules and the acceptor oxygen provided by the nitrate ions. One of those hydrogen bonds is bifurcated. For numerical values and symmetry operators, see Table 1. Weak C—H···O hydrogen bonds are also present between the C—H groups of bridging pyrazine and coordinating acetonitrile molecules, and the oxygen atoms of nitrate ions, linking Co^II chains both within the same sheet and to adjacent sheets (Table 1, Fig. 2).

Synthesis and crystallization top

The title compound was obtained by a slow diffusion method in an U-shaped glass tube. The tube was first partially filled with acetonitrile. An acetonitrile solution of 0.333 mmol (97.0 mg) of Co(NO₃)₂·6H₂O was then placed in one arm of the tube. Another acetonitrile solution of 0.500 mmol (40.0 mg) of pyrazine was placed in the other arm of the tube. The slow diffusion of the two solutions in the tube produced pink needle–shaped crystals within one day. The crystals were collected by filtration and washed with fresh acetonitrile and kept under inert atmosphere (yield 31.5%). Selected IR bands (KBr, cm^–1): 3273 (O—H), 2283 (C≡N), 1633, 1413, 1384 (N═O), 479 (bridging pyrazine).

Refinement details top

Structure description top

In the design of coordination polymers, the choice of bridging ligands between metal atoms plays an important role in the formation of the final structure and the resulting properties. During our investigations of the preparation conditions and magnetic properties of compounds with ladder-like structures, we have used pyrazine as a bis-monodentate bridging ligand to link paramagnetic metal cations. From the point of view of mediating magnetic interactions, the pyrazine molecule offers some advantages compared to other bidentate bridging ligands such as 4,4'-bipyridine. In some of the structures with the latter ligand, the two pyridine rings are not co-planar and therefore can magnetically isolate metal atoms (Losier & Zaworotko, 1996; Ruan et al., 2009; Seidel et al., 2011; Lehleh et al., 2013).

We herein report the preparation and structure of a pyrazine-bridged chain structure obtained by reacting pyrazine and cobalt(II) nitrate hexahydrate using acetonitrile as the solvent.

The asymmetric unit of the title compound, [Co(C₄H₄N₂)(CH₃CN)₂(H₂O)₂(NO₃)₂]_n, contains one Co^II cation located on an inversion center, one water molecule, one acetonitrile molecule, one nitrate anion, and one half of a pyrazine molecule, the latter being completed by inversion symmetry. The Co^II cation exhibits an N₄O₂ coordination set defined by two O atoms [O1, O1ⁱⁱ; symmetry code: (ii) –3 – x, 1 – y, –z] of two coordinating water molecules, two N atoms (N2, N2ⁱⁱ) of two coordinating acetonitrile molecules, and two nitrogen atoms (N1, N1ⁱⁱ) of two bridging pyrazine molecules (Fig. 1). The two Co—O_water bonds have a length of 2.0315 (8) Å, considerably shorter than the two Co—N_acetonitrile bonds of 2.1263 (9) Å, and the two Co—N_pyrazine bonds of 2.1493 (10) Å. The resulting coordination sphere is compressed octahedral with all bond lengths in good agreement with similar structures (Choudhury et al., 2002; Holman et al., 2005; Aşkin et al., 2015). In contrast to the N₂O₄ coordination spheres observed more frequently in the structures of other Co-containing compounds (Choudhury et al., 2002; Holman et al., 2005; Hyun et al., 2011; Aşkin et al., 2015), the title structure exhibits an N₄O₂ coordination sphere due to the inclusion of the solvent acetonitrile molecules in the coordination sphere of Co^II. The bridging bis-monodentate pyrazine molecules link the Co^II ions, forming linear chains extending parallel to the a axis. The distance between two symmetry-related Co^II ions within a chain (symmetry code: 1 + x, y, z) is 7.0798 (3) Å, in good agreement with those reported for similar structures (Choudhury et al., 2002; Holman et al., 2005; Aşkin et al., 2015).

In the crystal, the cationic chains are arranged to form sheets parallel to the ac plane, and neighboring sheets are related by a glide plane. Nitrate ions are sandwiched in the space between the sheets and form columns parallel to the a axis. Each Co^II chain is surrounded by six columns of nitrate ions that are related by the inversion centers located along the cationic chains. Each cationic chain is further surrounded by six other chains. This structural motif with alternating layers has been observed in similar structures (Choudhury et al., 2002; Yang et al., 2003; Holman et al., 2005; Aşkin et al., 2015). Co^II chains in neighboring sheets interact through nitrate ions by forming O—H···O hydrogen bonds where the donor O—H groups are provided by the coordinating water molecules and the acceptor oxygen provided by the nitrate ions. One of those hydrogen bonds is bifurcated. For numerical values and symmetry operators, see Table 1. Weak C—H···O hydrogen bonds are also present between the C—H groups of bridging pyrazine and coordinating acetonitrile molecules, and the oxygen atoms of nitrate ions, linking Co^II chains both within the same sheet and to adjacent sheets (Table 1, Fig. 2).

Synthesis and crystallization top

The title compound was obtained by a slow diffusion method in an U-shaped glass tube. The tube was first partially filled with acetonitrile. An acetonitrile solution of 0.333 mmol (97.0 mg) of Co(NO₃)₂·6H₂O was then placed in one arm of the tube. Another acetonitrile solution of 0.500 mmol (40.0 mg) of pyrazine was placed in the other arm of the tube. The slow diffusion of the two solutions in the tube produced pink needle–shaped crystals within one day. The crystals were collected by filtration and washed with fresh acetonitrile and kept under inert atmosphere (yield 31.5%). Selected IR bands (KBr, cm^–1): 3273 (O—H), 2283 (C≡N), 1633, 1413, 1384 (N═O), 479 (bridging pyrazine).

Refinement details top

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXLT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015b); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008) and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. A fragment of the one-dimensional chain structure of the title compound with displacement ellipsoids drawn at the 50% probability level. [Symmetry codes: (i) 1 + x, y, z; (ii) -3 - x, 1 - y, -z; (iii) -4 - x, 1 - y, -z.]
	Fig. 2. Crystal packing of the title compound, showing hydrogen bonds as dashed lines.

catena-Poly[[[trans-bis(acetonitrile-κN)diaquacobalt(II)]-µ-pyrazine-κ²N:N'] dinitrate] top

Crystal data top

[Co(NO₃)₂(C₄H₄N₂)(C₂H₃N)₂(H₂O)₂]	F(000) = 390
M_r = 381.18	D_x = 1.604 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.0798 (3) Å	Cell parameters from 9896 reflections
b = 15.0376 (6) Å	θ = 2.0–28.0°
c = 7.9329 (3) Å	µ = 1.14 mm⁻¹
β = 110.8803 (6)°	T = 100 K
V = 789.10 (5) Å³	Needle, pink
Z = 2	0.29 × 0.11 × 0.08 mm

Data collection top

Bruker APEXII DUO CCD diffractometer	1687 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.022
φ– and ω–scans	θ_max = 27.5°, θ_min = 2.7°
Absorption correction: analytical based on measured indexed crystal faces using SHELXTL2014 (Sheldrick, 2015b)	h = −9→9
T_min = 0.735, T_max = 0.904	k = −19→19
21292 measured reflections	l = −10→10
1811 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.019	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.055	w = 1/[σ²(F_o²) + (0.0316P)² + 0.2947P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
1811 reflections	Δρ_max = 0.34 e Å⁻³
115 parameters	Δρ_min = −0.31 e Å⁻³

Crystal data top

[Co(NO₃)₂(C₄H₄N₂)(C₂H₃N)₂(H₂O)₂]	V = 789.10 (5) Å³
M_r = 381.18	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.0798 (3) Å	µ = 1.14 mm⁻¹
b = 15.0376 (6) Å	T = 100 K
c = 7.9329 (3) Å	0.29 × 0.11 × 0.08 mm
β = 110.8803 (6)°

Data collection top

Bruker APEXII DUO CCD diffractometer	1811 independent reflections
Absorption correction: analytical based on measured indexed crystal faces using SHELXTL2014 (Sheldrick, 2015b)	1687 reflections with I > 2σ(I)
T_min = 0.735, T_max = 0.904	R_int = 0.022
21292 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.019	0 restraints
wR(F²) = 0.055	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.34 e Å⁻³
1811 reflections	Δρ_min = −0.31 e Å⁻³
115 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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	0.00977 (8)
O1	0.45432 (12)	0.38331 (6)	−0.13782 (12)	0.01522 (17)
H1Y	0.431 (3)	0.3365 (13)	−0.092 (2)	0.035 (5)*
H1X	0.391 (3)	0.3842 (13)	−0.243 (3)	0.036 (5)*
N1	0.19570 (15)	0.49931 (6)	−0.00181 (13)	0.01163 (19)
N2	0.39794 (14)	0.56807 (6)	−0.25144 (13)	0.01470 (19)
C1	0.07744 (16)	0.57128 (7)	−0.05354 (15)	0.0134 (2)
H1A	0.1283	0.6228	−0.0923	0.016*
C2	−0.11795 (16)	0.57209 (7)	−0.05167 (14)	0.0131 (2)
H2A	−0.1981	0.6242	−0.0889	0.016*
C3	0.31802 (17)	0.58923 (8)	−0.39744 (16)	0.0158 (2)
C4	0.2144 (2)	0.61342 (10)	−0.58544 (17)	0.0278 (3)
H4A	0.3122	0.6380	−0.6346	0.042*
H4B	0.1106	0.6580	−0.5939	0.042*
H4C	0.1508	0.5605	−0.6545	0.042*
N11	0.23020 (15)	0.30295 (7)	0.44860 (13)	0.0172 (2)
O11	0.09637 (15)	0.26787 (6)	0.31960 (13)	0.0295 (2)
O12	0.21017 (14)	0.38082 (6)	0.49826 (12)	0.0228 (2)
O13	0.39023 (13)	0.26094 (6)	0.53329 (12)	0.0230 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.00857 (12)	0.01064 (12)	0.01028 (12)	−0.00011 (7)	0.00357 (8)	0.00023 (7)
O1	0.0187 (4)	0.0130 (4)	0.0136 (4)	−0.0023 (3)	0.0053 (3)	−0.0011 (3)
N1	0.0107 (4)	0.0130 (5)	0.0112 (4)	0.0000 (3)	0.0038 (3)	−0.0005 (3)
N2	0.0142 (4)	0.0151 (5)	0.0151 (5)	0.0002 (4)	0.0056 (4)	0.0010 (4)
C1	0.0135 (5)	0.0125 (5)	0.0144 (5)	−0.0006 (4)	0.0051 (4)	0.0011 (4)
C2	0.0128 (5)	0.0127 (5)	0.0138 (5)	0.0012 (4)	0.0045 (4)	0.0013 (4)
C3	0.0144 (5)	0.0164 (5)	0.0178 (6)	−0.0005 (4)	0.0072 (4)	0.0008 (4)
C4	0.0215 (6)	0.0426 (8)	0.0162 (6)	0.0002 (6)	0.0029 (5)	0.0093 (5)
N11	0.0222 (5)	0.0137 (5)	0.0149 (4)	−0.0015 (4)	0.0057 (4)	0.0004 (4)
O11	0.0319 (5)	0.0190 (5)	0.0236 (5)	−0.0026 (4)	−0.0073 (4)	−0.0018 (4)
O12	0.0315 (5)	0.0134 (4)	0.0213 (4)	0.0030 (4)	0.0067 (4)	−0.0024 (3)
O13	0.0207 (4)	0.0198 (4)	0.0232 (5)	0.0041 (3)	0.0012 (3)	−0.0054 (3)

Geometric parameters (Å, º) top

Co1—O1	2.0315 (8)	C1—C2	1.3888 (15)
Co1—O1ⁱ	2.0315 (8)	C1—H1A	0.9500
Co1—N2ⁱ	2.1263 (9)	C2—N1ⁱⁱ	1.3425 (14)
Co1—N2	2.1263 (9)	C2—H2A	0.9500
Co1—N1ⁱ	2.1493 (10)	C3—C4	1.4542 (16)
Co1—N1	2.1493 (10)	C4—H4A	0.9800
O1—H1Y	0.83 (2)	C4—H4B	0.9800
O1—H1X	0.80 (2)	C4—H4C	0.9800
N1—C1	1.3401 (14)	N11—O11	1.2378 (13)
N1—C2ⁱⁱ	1.3425 (14)	N11—O12	1.2595 (13)
N2—C3	1.1383 (15)	N11—O13	1.2616 (13)

O1—Co1—O1ⁱ	180.0	C1—N1—Co1	120.89 (7)
O1—Co1—N2ⁱ	91.42 (4)	C2ⁱⁱ—N1—Co1	121.65 (7)
O1ⁱ—Co1—N2ⁱ	88.58 (4)	C3—N2—Co1	165.59 (9)
O1—Co1—N2	88.58 (4)	N1—C1—C2	121.32 (10)
O1ⁱ—Co1—N2	91.42 (4)	N1—C1—H1A	119.3
N2ⁱ—Co1—N2	180.0	C2—C1—H1A	119.3
O1—Co1—N1ⁱ	88.55 (3)	N1ⁱⁱ—C2—C1	121.23 (10)
O1ⁱ—Co1—N1ⁱ	91.45 (3)	N1ⁱⁱ—C2—H2A	119.4
N2ⁱ—Co1—N1ⁱ	89.51 (4)	C1—C2—H2A	119.4
N2—Co1—N1ⁱ	90.49 (4)	N2—C3—C4	178.24 (13)
O1—Co1—N1	91.45 (3)	C3—C4—H4A	109.5
O1ⁱ—Co1—N1	88.55 (3)	C3—C4—H4B	109.5
N2ⁱ—Co1—N1	90.49 (4)	H4A—C4—H4B	109.5
N2—Co1—N1	89.51 (4)	C3—C4—H4C	109.5
N1ⁱ—Co1—N1	180.0	H4A—C4—H4C	109.5
Co1—O1—H1Y	121.0 (12)	H4B—C4—H4C	109.5
Co1—O1—H1X	118.3 (14)	O11—N11—O12	121.09 (10)
H1Y—O1—H1X	110.2 (18)	O11—N11—O13	120.29 (10)
C1—N1—C2ⁱⁱ	117.45 (10)	O12—N11—O13	118.61 (10)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1Y···O13ⁱⁱⁱ	0.83 (2)	1.85 (2)	2.6819 (12)	173.5 (18)
O1—H1X···O12^iv	0.80 (2)	1.99 (2)	2.7869 (12)	174.1 (19)
O1—H1X···O13^iv	0.80 (2)	2.562 (19)	3.0912 (12)	125.3 (17)
C1—H1A···O11ⁱⁱ	0.95	2.54	3.1572 (14)	123
C2—H2A···O13^v	0.95	2.59	3.4644 (14)	153
C4—H4A···O13ⁱ	0.98	2.49	3.2785 (17)	138
C4—H4B···O11^vi	0.98	2.49	3.2823 (17)	138

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1Y···O13ⁱ	0.83 (2)	1.85 (2)	2.6819 (12)	173.5 (18)
O1—H1X···O12ⁱⁱ	0.80 (2)	1.99 (2)	2.7869 (12)	174.1 (19)
O1—H1X···O13ⁱⁱ	0.80 (2)	2.562 (19)	3.0912 (12)	125.3 (17)
C1—H1A···O11ⁱⁱⁱ	0.95	2.54	3.1572 (14)	123.0
C2—H2A···O13^iv	0.95	2.59	3.4644 (14)	153.3
C4—H4A···O13^v	0.98	2.49	3.2785 (17)	137.6
C4—H4B···O11^vi	0.98	2.49	3.2823 (17)	137.5

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

Experimental details

Crystal data
Chemical formula	[Co(NO₃)₂(C₄H₄N₂)(C₂H₃N)₂(H₂O)₂]
M_r	381.18
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	7.0798 (3), 15.0376 (6), 7.9329 (3)
β (°)	110.8803 (6)
V (Å³)	789.10 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.14
Crystal size (mm)	0.29 × 0.11 × 0.08

Data collection
Diffractometer	Bruker APEXII DUO CCD
Absorption correction	Analytical based on measured indexed crystal faces using SHELXTL2014 (Sheldrick, 2015b)
T_min, T_max	0.735, 0.904
No. of measured, independent and observed [I > 2σ(I)] reflections	21292, 1811, 1687
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.019, 0.055, 1.07
No. of reflections	1811
No. of parameters	115
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.31

Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2014), SHELXLT (Sheldrick, 2015a), SHELXL2014/7 (Sheldrick, 2015b), XP in SHELXTL-Plus (Sheldrick, 2008) and ORTEP-3 for Windows (Farrugia, 2012), publCIF (Westrip, 2010).

Acknowledgements

CL wishes to thank the Research & Development Corporation of Newfoundland and Labrador for financial support. KAA wishes to acknowledge the National Science Foundation and the University of Florida for funding the purchase of the X-ray equipment.

References

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Volume 72| Part 2| February 2016| Pages 151-154

doi:10.1107/S2056989016000220

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