trans-Diaqua­bis[(E)-3-(dimethyl­amino)-1-(2-pyrid­yl)prop-2-en-1-one-κ2N1,O]cobalt(II) dinitrate dihydrate

Bi, J.-H.

doi:10.1107/S1600536809016845

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page m633

doi:10.1107/S1600536809016845

Open

access

trans-Diaquabis[(E)-3-(dimethylamino)-1-(2-pyridyl)prop-2-en-1-one-κ²N¹,O]cobalt(II) dinitrate dihydrate

Jian-Hong Bi ^a ^*

^aDeparment of Chemistry and Chemical Engineering, Hefei Teachers College, Hefei, 230061, People's Republic of China
^*Correspondence e-mail: bi010101@126.com

(Received 2 May 2009; accepted 5 May 2009; online 14 May 2009)

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, $[P \overline 1]$
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) Å³
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[F² > 2σ(F²)] = 0.052
wR(F²) = 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

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⋯O6^iv	0.93	2.59	3.508 (4)	168
C9—H9C⋯O3^v	0.96	2.53	3.351 (7)	144
Symmetry codes: (i) x-1, y, z; (ii) -x+1, -y+1, -z+1; (iii) -x, -y+1, -z; (iv) x, y+1, z; (v) -x+1, -y+2, -z+1.

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.

Supporting information

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536809016845/cv2560sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809016845/cv2560Isup2.hkl

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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.

Computing details top

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

trans-Diaquabis[(E)-3-(dimethylamino)-1-(2-pyridyl)prop-2- en-1-one-κ²N¹,O]cobalt(II) dinitrate dihydrate top

Crystal data top

[Co(C₁₀H₁₂N₂O)₂(H₂O)₂](NO₃)₂·2H₂O	Z = 1
M_r = 607.45	F(000) = 317
Triclinic, P1	D_x = 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 top

SMART CCD area-detector diffractometer	2342 independent reflections
Radiation source: fine-focus sealed tube	2109 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ϕ and ω scan	θ_max = 25.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −9→9
T_min = 0.802, T_max = 0.876	k = −6→10
3375 measured reflections	l = −13→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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.148	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.1051P)²] where P = (F_o² + 2F_c²)/3
2342 reflections	(Δ/σ)_max = 0.008
180 parameters	Δρ_max = 0.50 e Å⁻³
0 restraints	Δρ_min = −0.41 e Å⁻³

Crystal data top

[Co(C₁₀H₁₂N₂O)₂(H₂O)₂](NO₃)₂·2H₂O	γ = 108.467 (4)°
M_r = 607.45	V = 679.9 (3) Å³
Triclinic, P1	Z = 1
a = 7.8220 (19) Å	Mo Kα radiation
b = 8.646 (2) Å	µ = 0.70 mm⁻¹
c = 11.088 (3) Å	T = 291 K
α = 98.439 (4)°	0.30 × 0.20 × 0.20 mm
β = 101.239 (4)°

Data collection top

SMART CCD area-detector diffractometer	2342 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	2109 reflections with I > 2σ(I)
T_min = 0.802, T_max = 0.876	R_int = 0.024
3375 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.148	H-atom parameters constrained
S = 1.08	Δρ_max = 0.50 e Å⁻³
2342 reflections	Δρ_min = −0.41 e Å⁻³
180 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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 code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

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···O6^iv	0.93	2.59	3.508 (4)	168
C9—H9C···O3^v	0.96	2.53	3.351 (7)	144

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

Experimental details

Crystal data
Chemical formula	[Co(C₁₀H₁₂N₂O)₂(H₂O)₂](NO₃)₂·2H₂O
M_r	607.45
Crystal system, space group	Triclinic, P1
Temperature (K)	291
a, b, c (Å)	7.8220 (19), 8.646 (2), 11.088 (3)
α, β, γ (°)	98.439 (4), 101.239 (4), 108.467 (4)
V (Å³)	679.9 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.70
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.802, 0.876
No. of measured, independent and observed [I > 2σ(I)] reflections	3375, 2342, 2109
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.148, 1.08
No. of reflections	2342
No. of parameters	180
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.41

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT (Bruker, 2000, SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4B···O6	0.85	2.22	2.764 (4)	121.0
O4—H4C···O1ⁱ	0.85	2.11	2.909 (6)	156.0
O4—H4C···O2ⁱ	0.85	2.42	3.173 (5)	149.0
O6—H6A···O3ⁱⁱ	0.85	2.44	3.011 (5)	125.0
O6—H6C···O3	0.85	2.23	2.987 (6)	148.0
C1—H1···O1ⁱⁱⁱ	0.93	2.40	3.161 (5)	138.0
C4—H4A···O6^iv	0.93	2.59	3.508 (4)	168.0
C9—H9C···O3^v	0.96	2.53	3.351 (7)	144.0

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

Acknowledgements

The author is indebted to the National Natural Science Foundation of China for financial support (grant No. 20871039).

References

Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Hu, T.-L. & Tian, J.-L. (2007). Acta Cryst. E63, m1092–m1093. Web of Science CSD CrossRef IUCr Journals Google Scholar
Li, G.-X., Li, J.-Q. & Kang, X.-Z. (2005). Acta Cryst. E61, m410–m411. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yan, Z.-Q. (2004). Acta Cryst. E60, m1957–m1958. Web of Science CSD CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.