trans-Diaqua­bis[(E)-3-(dimethyl­amino)-1-(2-pyrid­yl)prop-2-en-1-one-κ² N ¹,O]cobalt(II) dinitrate dihydrate

Abstract

In the title compound, [Co(C₁₀H₁₂N₂O)₂(H₂O)₂](NO₃)₂·2H₂O, the Co^II ion, located on an inversion center, is trans-coordinated by two N,O-bidentate chelating (E)-3-(dimethyl­amino)-1-(2-pyrid­yl)prop-2-en-1-one ligands and by two water mol­ecules in a slightly distorted octa­hedral geometry. Inter­molecular O—H⋯O hydrogen bonds link the cations, anions and water mol­ecules into layers parallel to the ac plane. The crystal packing also exhibits weak inter­molecular C—H⋯O hydrogen bonds.

Related literature

For the crystal structures of related complexes, see: Hu & Tian (2007 ▶); Li et al. (2005 ▶); Yan et al. (2004 ▶).

Experimental

Crystal data

• [Co(C₁₀H₁₂N₂O)₂(H₂O)₂](NO₃)₂·2H₂O

• M _r = 607.45

• Triclinic,

• a = 7.8220 (19) Å

• b = 8.646 (2) Å

• c = 11.088 (3) Å

• α = 98.439 (4)°

• β = 101.239 (4)°

• γ = 108.467 (4)°

• V = 679.9 (3) ų

• Z = 1

• Mo Kα radiation

• μ = 0.70 mm⁻¹

• T = 291 K

• 0.30 × 0.20 × 0.20 mm

Data collection

• SMART CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.802, T _max = 0.876

• 3375 measured reflections

• 2342 independent reflections

• 2109 reflections with I > 2σ(I)

• R _int = 0.024

Refinement

• R[F ² > 2σ(F ²)] = 0.052

• wR(F ²) = 0.148

• S = 1.08

• 2342 reflections

• 180 parameters

• H-atom parameters constrained

• Δρ_max = 0.50 e Å⁻³

• Δρ_min = −0.41 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); 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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4B⋯O6	0.85	2.22	2.764 (4)	121
O4—H4C⋯O1i	0.85	2.11	2.909 (6)	156
O4—H4C⋯O2i	0.85	2.42	3.173 (5)	149
O6—H6A⋯O3ii	0.85	2.44	3.011 (5)	125
O6—H6C⋯O3	0.85	2.23	2.987 (6)	148
C1—H1⋯O1iii	0.93	2.40	3.161 (5)	138
C4—H4A⋯O6iv	0.93	2.59	3.508 (4)	168
C9—H9C⋯O3v	0.96	2.53	3.351 (7)	144

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .

supplementary crystallographic information

Comment

The rational design and synthesis of coordinated complexes derived from 2-[3-(dimethylamino)prop-2-enoyl] pyridine have been of increasing interest recently in chemical research (Hu & Tian, 2007; Li et al., 2005; Yan et al., 2004). Here we report a new monomeric cobalt(II) complex, viz.the title compound, [Co(C₁₀H₁₂N₂O)₂(H₂O)₂](NO₃)₂(H₂O)₂.

The coordination geometry of the Co(II) center is shown in Fig.1. The Co(II) center adopts an octahedral coordination geomtry, where two N atoms and two O atoms from two ligands are in the equatorial plane while the apical positions are occupied by two water molecules. The asymmetric unit of the title compound contains a half of the complex, one crystalline water molecule and one nitrate counter-anion. The coordinated water molecules, crystalline water molecules and nitrate anions are involved in the hydrogen bonding interactions (Table 1).

Experimental

All solvents and chemicals were of analytical grade and were used without further purification. For the synthesis of title compoud, a solution of ligand (0.2 mmol) and Co(NO₃)₂(0.1 mmol) in 50 ml me thanol was refluxed for 2 h, and then cooled to room temperature and filtered. Single crystals suitable for X-ray analysis were grown from the methanol solution by slow evaporation at room temperature in air. Anal. Calcd.for C₂₀H₃₂CoN₆O₁₂: C, 39.54; H, 5.31; N, 13.84. Found: C, 39.58; H,5.33; N, 13.79.

Refinement

All hydrogen atoms were geomemetrically positioned (C—H 0.93–0.97 Å, O–H 0.85 Å) and refined as riding, with U_iso(H)=1.2–1.5 U_eq of the parent atom.

Figures

Fig. 1.

Molecular structure of the cation of the title compound, the anions and the free water molecules are omitted for clarity, showing 30% probability displacement ellipsoids and the atom-numbering [symmetry code: (A) -x, 1 - y, -z.

Crystal data

[Co(C10H12N2O)2(H2O)2](NO3)2·2H2O	Z = 1
Mr = 607.45	F(000) = 317
Triclinic, P1	Dx = 1.483 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8220 (19) Å	Cell parameters from 2398 reflections
b = 8.646 (2) Å	θ = 2.6–27.1°
c = 11.088 (3) Å	µ = 0.70 mm−1
α = 98.439 (4)°	T = 291 K
β = 101.239 (4)°	Block, purple
γ = 108.467 (4)°	0.30 × 0.20 × 0.20 mm
V = 679.9 (3) Å3

Data collection

SMART CCD area-detector diffractometer	2342 independent reflections
Radiation source: fine-focus sealed tube	2109 reflections with I > 2σ(I)
graphite	Rint = 0.024
φ and ω scan	θmax = 25.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −9→9
Tmin = 0.802, Tmax = 0.876	k = −6→10
3375 measured reflections	l = −13→11

Refinement

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.148	H-atom parameters constrained
S = 1.08	w = 1/[σ2(Fo2) + (0.1051P)2] where P = (Fo2 + 2Fc2)/3
2342 reflections	(Δ/σ)max = 0.008
180 parameters	Δρmax = 0.50 e Å−3
0 restraints	Δρmin = −0.41 e Å−3

Special details

Experimental. The structure was solved by direct methods (Bruker, 2000) and successive difference Fourier syntheses.

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
Co1	0.0000	0.5000	0.0000	0.0453 (2)
O4	−0.0719 (3)	0.4009 (3)	0.1563 (2)	0.0642 (6)
H4B	−0.0433	0.3211	0.1800	0.077*
H4C	−0.1233	0.4574	0.1957	0.077*
O5	0.2210 (3)	0.6910 (2)	0.1225 (2)	0.0543 (5)
N2	−0.1181 (3)	0.6828 (3)	0.0345 (2)	0.0452 (5)
N3	0.6416 (3)	1.0643 (3)	0.3847 (2)	0.0521 (6)
C1	−0.2916 (4)	0.6719 (4)	−0.0148 (3)	0.0552 (7)
H1	−0.3744	0.5719	−0.0684	0.066*
C2	−0.3542 (5)	0.8023 (4)	0.0101 (3)	0.0619 (8)
H2	−0.4774	0.7901	−0.0242	0.074*
C3	−0.2303 (5)	0.9504 (4)	0.0866 (3)	0.0619 (8)
H3	−0.2676	1.0416	0.1031	0.074*
C4	−0.0494 (4)	0.9638 (4)	0.1394 (3)	0.0524 (7)
H4A	0.0356	1.0633	0.1924	0.063*
C5	0.0027 (4)	0.8274 (3)	0.1122 (2)	0.0432 (6)
C6	0.1935 (4)	0.8238 (3)	0.1623 (3)	0.0437 (6)
C7	0.3301 (4)	0.9602 (3)	0.2493 (3)	0.0491 (7)
H7	0.3076	1.0585	0.2715	0.059*
C8	0.4988 (4)	0.9492 (3)	0.3024 (3)	0.0488 (7)
H8	0.5128	0.8477	0.2765	0.059*
C9	0.6421 (6)	1.2306 (4)	0.4325 (4)	0.0769 (11)
H9A	0.6102	1.2793	0.3630	0.115*
H9B	0.7640	1.2996	0.4844	0.115*
H9C	0.5526	1.2224	0.4817	0.115*
C10	0.8112 (5)	1.0349 (5)	0.4342 (4)	0.0717 (10)
H10A	0.8014	0.9257	0.3928	0.108*
H10B	0.8292	1.0415	0.5232	0.108*
H10C	0.9153	1.1179	0.4195	0.108*
O1	0.6534 (6)	0.5229 (6)	0.2379 (3)	0.1422 (16)
O2	0.8756 (5)	0.6226 (4)	0.3910 (4)	0.1396 (16)
O3	0.6145 (7)	0.6168 (4)	0.4090 (4)	0.1368 (17)
N1	0.7140 (4)	0.5912 (3)	0.3458 (3)	0.0624 (7)
O6	0.2256 (4)	0.3681 (3)	0.3177 (3)	0.0876 (8)
H6A	0.1895	0.3279	0.3778	0.131*
H6C	0.3108	0.4638	0.3475	0.131*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Co1	0.0425 (3)	0.0399 (3)	0.0469 (4)	0.0153 (2)	0.0049 (2)	−0.0024 (2)
O4	0.0786 (16)	0.0592 (13)	0.0621 (13)	0.0304 (12)	0.0249 (12)	0.0131 (11)
O5	0.0452 (11)	0.0460 (11)	0.0613 (12)	0.0195 (9)	−0.0002 (9)	−0.0080 (9)
N2	0.0417 (12)	0.0468 (12)	0.0447 (12)	0.0182 (10)	0.0061 (10)	0.0046 (10)
N3	0.0490 (14)	0.0405 (12)	0.0561 (15)	0.0129 (11)	0.0024 (11)	−0.0001 (11)
C1	0.0455 (16)	0.0598 (18)	0.0550 (17)	0.0183 (14)	0.0059 (13)	0.0070 (14)
C2	0.0496 (17)	0.071 (2)	0.067 (2)	0.0300 (16)	0.0088 (15)	0.0117 (17)
C3	0.064 (2)	0.065 (2)	0.070 (2)	0.0393 (17)	0.0205 (17)	0.0140 (16)
C4	0.0554 (17)	0.0525 (17)	0.0516 (17)	0.0249 (14)	0.0138 (14)	0.0053 (13)
C5	0.0461 (15)	0.0428 (14)	0.0396 (14)	0.0164 (12)	0.0111 (12)	0.0045 (11)
C6	0.0444 (15)	0.0428 (14)	0.0432 (14)	0.0166 (12)	0.0101 (12)	0.0063 (11)
C7	0.0504 (16)	0.0414 (14)	0.0525 (16)	0.0187 (12)	0.0079 (13)	0.0033 (12)
C8	0.0504 (16)	0.0395 (14)	0.0503 (16)	0.0127 (12)	0.0089 (13)	0.0043 (12)
C9	0.074 (2)	0.0486 (18)	0.087 (3)	0.0204 (17)	−0.005 (2)	−0.0101 (17)
C10	0.0522 (19)	0.065 (2)	0.081 (2)	0.0204 (16)	−0.0068 (17)	−0.0009 (18)
O1	0.121 (3)	0.212 (5)	0.060 (2)	0.042 (3)	−0.0073 (19)	0.011 (2)
O2	0.076 (2)	0.084 (2)	0.202 (4)	0.0161 (17)	−0.033 (2)	−0.020 (2)
O3	0.198 (4)	0.101 (2)	0.179 (4)	0.083 (3)	0.135 (4)	0.050 (2)
N1	0.0638 (18)	0.0571 (16)	0.0681 (18)	0.0249 (14)	0.0141 (15)	0.0154 (13)
O6	0.094 (2)	0.0814 (17)	0.0736 (17)	0.0298 (15)	0.0022 (15)	0.0041 (14)

Geometric parameters (Å, °)

Co1—O5	2.0443 (19)	C3—H3	0.9300
Co1—O5i	2.0443 (19)	C4—C5	1.377 (4)
Co1—N2i	2.093 (2)	C4—H4A	0.9300
Co1—N2	2.093 (2)	C5—C6	1.499 (4)
Co1—O4i	2.136 (2)	C6—C7	1.389 (4)
Co1—O4	2.136 (2)	C7—C8	1.374 (4)
O4—H4B	0.8499	C7—H7	0.9300
O4—H4C	0.8500	C8—H8	0.9300
O5—C6	1.266 (3)	C9—H9A	0.9600
N2—C1	1.328 (4)	C9—H9B	0.9600
N2—C5	1.348 (3)	C9—H9C	0.9600
N3—C8	1.305 (4)	C10—H10A	0.9600
N3—C10	1.448 (4)	C10—H10B	0.9600
N3—C9	1.456 (4)	C10—H10C	0.9600
C1—C2	1.378 (5)	O1—N1	1.183 (4)
C1—H1	0.9300	O2—N1	1.191 (4)
C2—C3	1.369 (5)	O3—N1	1.192 (4)
C2—H2	0.9300	O6—H6A	0.8500
C3—C4	1.382 (4)	O6—H6C	0.8500
O5—Co1—O5i	180.0	C4—C3—H3	120.1
O5—Co1—N2i	101.59 (8)	C5—C4—C3	118.9 (3)
O5i—Co1—N2i	78.41 (8)	C5—C4—H4A	120.5
O5—Co1—N2	78.41 (8)	C3—C4—H4A	120.5
O5i—Co1—N2	101.59 (8)	N2—C5—C4	121.4 (3)
N2i—Co1—N2	180.00 (13)	N2—C5—C6	113.8 (2)
O5—Co1—O4i	90.60 (9)	C4—C5—C6	124.8 (2)
O5i—Co1—O4i	89.40 (9)	O5—C6—C7	122.7 (3)
N2i—Co1—O4i	91.84 (9)	O5—C6—C5	116.7 (2)
N2—Co1—O4i	88.16 (9)	C7—C6—C5	120.6 (2)
O5—Co1—O4	89.40 (9)	C8—C7—C6	119.7 (2)
O5i—Co1—O4	90.60 (9)	C8—C7—H7	120.1
N2i—Co1—O4	88.16 (9)	C6—C7—H7	120.1
N2—Co1—O4	91.84 (9)	N3—C8—C7	127.8 (3)
O4i—Co1—O4	180.0	N3—C8—H8	116.1
Co1—O4—H4B	124.2	C7—C8—H8	116.1
Co1—O4—H4C	111.2	N3—C9—H9A	109.5
H4B—O4—H4C	124.4	N3—C9—H9B	109.5
C6—O5—Co1	117.12 (18)	H9A—C9—H9B	109.5
C1—N2—C5	118.9 (2)	N3—C9—H9C	109.5
C1—N2—Co1	127.2 (2)	H9A—C9—H9C	109.5
C5—N2—Co1	113.84 (17)	H9B—C9—H9C	109.5
C8—N3—C10	122.0 (3)	N3—C10—H10A	109.5
C8—N3—C9	122.6 (3)	N3—C10—H10B	109.5
C10—N3—C9	115.5 (3)	H10A—C10—H10B	109.5
N2—C1—C2	122.9 (3)	N3—C10—H10C	109.5
N2—C1—H1	118.6	H10A—C10—H10C	109.5
C2—C1—H1	118.6	H10B—C10—H10C	109.5
C3—C2—C1	118.2 (3)	O1—N1—O2	117.4 (4)
C3—C2—H2	120.9	O1—N1—O3	121.2 (4)
C1—C2—H2	120.9	O2—N1—O3	121.2 (4)
C2—C3—C4	119.7 (3)	H6A—O6—H6C	109.5
C2—C3—H3	120.1

Symmetry codes: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4B···O6	0.85	2.22	2.764 (4)	121
O4—H4C···O1ii	0.85	2.11	2.909 (6)	156
O4—H4C···O2ii	0.85	2.42	3.173 (5)	149
O6—H6A···O3iii	0.85	2.44	3.011 (5)	125
O6—H6C···O3	0.85	2.23	2.987 (6)	148
C1—H1···O1i	0.93	2.40	3.161 (5)	138
C4—H4A···O6iv	0.93	2.59	3.508 (4)	168
C9—H9C···O3v	0.96	2.53	3.351 (7)	144

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