Aqua­{6,6′-dimeth­oxy-2,2′-[ethane-1,2-diylbis(nitrilo­methyl­idyne)]diphenolato-κ⁴O,N,N′,O′}cobalt(II)

In the title compound, [Co(C₁₈H₁₈N₂O₄)(H₂O)], the Co^II atom is coordinated in a distorted square-pyramidal geometry defined by two O atoms and two N atoms in the basal positions, and one water mol­ecule in the apical position. The Co^II atom and water O atom lie on a symmetry plane defining C_s mol­ecular symmetry. In the crystal structure, the ethyl­enediamine group is disordered over two positions with equal occupancy. Mol­ecules are linked into chains via O—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.005 Å
• Disorder in main residue
• R factor = 0.037
• wR factor = 0.101
• Data-to-parameter ratio = 12.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         N1
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        N1'
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C9
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C9'
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.71
PLAT301_ALERT_3_C Main Residue  Disorder .........................      12.00 Perc.

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          4

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

Using H₂L [where H₂L is N,N'-ethylene-bis(3-methoxysalicylaldiminato)], we have hydrothermally prepared the title compound, (I), namely Co(L)(H₂O). As an example of penta coordinated Co(II) complexes there are series of complexes with 1,4-diazacycloheptane (DACH) functionalized by additional imidazole or pyridine donor pendants [CoL1Cl](ClO4).H2O, [CoL2Cl](ClO4) and [CoL3Cl](ClO4).CH3OH, where L1=1,4-bis(imidazole-4-ylmethyl)-DACH, L2=1,4-bis(N-1-methylimidazol-2-ylmethyl)-DACH and L3=1,4-bis(pyridyl-2-ylmethyl)-DACH that were synthesized and characterized (Guo et al., 2002). In the present structure Co(II) atom is coordinated by two phenolato oxygen atoms and two imine nitrogen atoms from L^2- ligand, and one water molecule to furnish a distorted square pyramidal coordination geometry (Fig. 1, Table 1). The O atom of water molecule is at the apical position of square pyramid and the other two O atoms and two N atoms are at the base of square pyramid. The Co^II and O atom of water molecule lie on a symmetry plane. The two C atoms of ethylenediamine moiety are disordered over two positions with equal occupancy. The complex generates 1-D chain through hydrogen bonds between water molecule and phenolato oxygen (Table 2 and Fig. 2).

Related literature

For related literature, see: Guo et al. (2002).

S2. Experimental

2-Hydroxy-3-methoxy-benzaldehyde (0.152 g, 1 mmol), ethane-1,2-diamine (0.120 g, 2 mmol) and Co(NO₃)₂.6H₂O (0.290 g, 1 mmol) were dissolved in a mixture solution (8 ml of methanol: acetonitrile = 1:1(v / v)). The solution was sealed in a 15 ml Teflon-lined stainless steel bomb and held at 353 K for 5 d. Then, a bomb was cooled to room temperature and red block crystals were filtered off, washed with methanol and dried at room temperature. Elemental analysis, calcd (%) for C₁₈H₂₀CoN₂O₅: C 62.78, H 5.85, N 8.13; found (%): C 62.56, H 5.92, N 8.11.

S3. Refinement

There is positional disorder of C9 and C9'ⁱ over two equally occupied sites. It was assumed that the ethylenediamine moiety has two possible conformations, namely N1–C9(H9A/H9B)–C9'ⁱ(H9Cⁱ/H9Dⁱ)–N1'ⁱ and N1'–C9'(H9C/H9D)–C9ⁱ(H9Aⁱ/H9Bⁱ)–N1ⁱ[symmetry code: (i) x, 1/2 - y, z]. H atoms of the water molecule were located in a difference Fourier map, but their distances and angles were restrained to literature values with U(H) = 1.5 times U_eq(O). All other H atoms were positioned geometrically and refined as riding atoms, with C–H distances of 0.95–0.98 Å and U(H) = 1.2–1.5 times U_eq(C).

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2005); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of (I) with atom labels and the 50% probability displacement ellipsoids for non-H atoms. One of the disorder part is shown by a dashed line. The molecular symmetry Cs is generated by symmetry code: (i) x, 1/2 - y, z.
	Fig. 2. The packing of (I), showing two chains of molecules connected by O—H···O hydrogen bonds (dashed lines). H atoms not involved in hydrogen bonding have been omitted.

Aqua{6,6'-dimethoxy-2,2'-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolato- κ⁴O,N,N',O'}cobalt(II)

Crystal data

[Co(C18H18N2O4)(H2O)]	F(000) = 836
Mr = 403.29	Dx = 1.583 Mg m^−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 3183 reflections
a = 8.9827 (6) Å	θ = 2.8–28.1°
b = 24.8632 (16) Å	µ = 1.05 mm^−1
c = 7.5784 (5) Å	T = 173 K
V = 1692.55 (19) Å^3	Block, red
Z = 4	0.49 × 0.46 × 0.19 mm

Data collection

Bruker SMART 1000 CCD diffractometer	1694 independent reflections
Radiation source: fine-focus sealed tube	1389 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
ω scans	θmax = 26.0°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→11
Tmin = 0.628, Tmax = 0.826	k = −30→20
6807 measured reflections	l = −9→7

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0463P)^2 + 2.1284P] where P = (Fo^2 + 2Fc^2)/3
1694 reflections	(Δ/σ)max = 0.001
134 parameters	Δρmax = 0.76 e Å^−3
4 restraints	Δρmin = −0.39 e Å^−3

Special details

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	Occ. (<1)
Co1	0.05985 (6)	0.2500	1.06224 (7)	0.0225 (2)
C1	0.2009 (3)	0.35745 (12)	1.0129 (4)	0.0270 (6)
C2	0.3278 (4)	0.39125 (13)	1.0321 (4)	0.0330 (7)
C3	0.3227 (4)	0.44530 (14)	0.9907 (6)	0.0467 (9)
H3	0.4080	0.4672	1.0091	0.056*
C4	0.1929 (5)	0.46784 (15)	0.9220 (6)	0.0554 (11)
H4	0.1895	0.5050	0.8934	0.066*
C5	0.0714 (4)	0.43626 (15)	0.8964 (6)	0.0500 (10)
H5	−0.0162	0.4517	0.8478	0.060*
C6	0.0718 (3)	0.38107 (13)	0.9399 (4)	0.0344 (7)
C7	0.5866 (4)	0.39539 (17)	1.1006 (6)	0.0544 (11)
H7A	0.6086	0.4095	0.9827	0.082*
H7B	0.6679	0.3719	1.1390	0.082*
H7C	0.5763	0.4254	1.1837	0.082*
C8	−0.0616 (4)	0.35127 (16)	0.9037 (5)	0.0502 (11)
H8	−0.1407	0.3701	0.8480	0.060*
C9	−0.2007 (7)	0.2696 (3)	0.8386 (10)	0.0364 (16)	0.50
H9A	−0.1631	0.2612	0.7233	0.044*	0.50
H9B	−0.2889	0.2910	0.8247	0.044*	0.50
C9'	−0.2370 (6)	0.2830 (3)	0.9378 (10)	0.0315 (14)	0.50
H9C	−0.3015	0.3063	0.8717	0.038*	0.50
H9D	−0.2767	0.2768	1.0537	0.038*	0.50
N1	−0.0838 (3)	0.30121 (14)	0.9399 (5)	0.0623 (11)	0.50
N1'	−0.0838 (3)	0.30121 (14)	0.9399 (5)	0.0623 (11)	0.50
O1	0.2129 (2)	0.30725 (8)	1.0632 (3)	0.0276 (5)
O2	0.4510 (2)	0.36547 (10)	1.0954 (3)	0.0431 (6)
O1W	−0.0369 (3)	0.2500	1.3095 (4)	0.0244 (6)
H1W	−0.082 (3)	0.2221 (2)	1.346 (4)	0.037*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0178 (3)	0.0214 (3)	0.0284 (3)	0.000	−0.0003 (2)	0.000
C1	0.0252 (15)	0.0241 (15)	0.0317 (15)	−0.0012 (12)	0.0006 (12)	0.0019 (12)
C2	0.0308 (17)	0.0279 (16)	0.0402 (18)	−0.0021 (14)	−0.0052 (14)	0.0066 (14)
C3	0.044 (2)	0.0273 (18)	0.069 (2)	−0.0093 (16)	−0.0113 (19)	0.0082 (17)
C4	0.054 (2)	0.0252 (18)	0.087 (3)	−0.0007 (17)	−0.008 (2)	0.020 (2)
C5	0.039 (2)	0.0367 (19)	0.074 (3)	0.0063 (16)	−0.0083 (19)	0.0234 (19)
C6	0.0291 (16)	0.0326 (17)	0.0416 (18)	0.0003 (14)	−0.0011 (15)	0.0117 (14)
C7	0.036 (2)	0.058 (2)	0.070 (3)	−0.0231 (18)	−0.0205 (18)	0.030 (2)
C8	0.0273 (17)	0.052 (2)	0.072 (3)	−0.0039 (16)	−0.0160 (17)	0.037 (2)
C9	0.024 (3)	0.040 (4)	0.045 (4)	0.006 (3)	−0.008 (3)	0.010 (3)
C9'	0.016 (3)	0.038 (4)	0.040 (4)	0.006 (3)	0.003 (3)	0.006 (3)
N1	0.0272 (16)	0.060 (2)	0.100 (3)	−0.0151 (15)	−0.0277 (17)	0.051 (2)
N1'	0.0272 (16)	0.060 (2)	0.100 (3)	−0.0151 (15)	−0.0277 (17)	0.051 (2)
O1	0.0208 (10)	0.0209 (10)	0.0412 (12)	−0.0009 (8)	−0.0020 (9)	0.0054 (9)
O2	0.0276 (12)	0.0335 (12)	0.0682 (17)	−0.0103 (10)	−0.0141 (11)	0.0174 (12)
O1W	0.0225 (14)	0.0217 (14)	0.0291 (15)	0.000	0.0029 (12)	0.000

Geometric parameters (Å, º)

Co1—O1^i	1.979 (2)	C5—H5	0.9500
Co1—O1	1.979 (2)	C6—C8	1.435 (5)
Co1—N1^i	2.036 (3)	C7—O2	1.427 (4)
Co1—N1	2.036 (3)	C7—H7A	0.9800
Co1—O1W	2.066 (3)	C7—H7B	0.9800
C1—O1	1.309 (3)	C7—H7C	0.9800
C1—C6	1.413 (4)	C8—N1	1.290 (5)
C1—C2	1.424 (4)	C8—H8	0.9500
C2—O2	1.366 (4)	C9—N1	1.519 (6)
C2—C3	1.381 (4)	C9—H9A	0.9601
C3—C4	1.394 (5)	C9—H9B	0.9600
C3—H3	0.9500	C9'—H9C	0.9599
C4—C5	1.359 (6)	C9'—H9D	0.9600
C4—H4	0.9500	O1W—H1W	0.848 (10)
C5—C6	1.411 (5)
O1^i—Co1—O1	91.99 (12)	C3—C4—H4	120.2
O1^i—Co1—N1^i	89.55 (10)	C4—C5—C6	121.8 (3)
O1—Co1—N1^i	153.09 (15)	C4—C5—H5	119.1
O1^i—Co1—N1	153.09 (15)	C6—C5—H5	119.1
O1—Co1—N1	89.55 (10)	C5—C6—C1	119.9 (3)
N1^i—Co1—N1	77.4 (2)	C5—C6—C8	117.1 (3)
O1^i—Co1—O1W	106.80 (8)	C1—C6—C8	123.1 (3)
O1—Co1—O1W	106.80 (8)	N1—C8—C6	125.9 (3)
N1^i—Co1—O1W	98.41 (13)	N1—C8—H8	117.0
N1—Co1—O1W	98.41 (13)	C6—C8—H8	117.0
O1—C1—C6	125.3 (3)	N1—C9—H9A	109.3
O1—C1—C2	117.8 (3)	N1—C9—H9B	109.8
C6—C1—C2	116.9 (3)	H9A—C9—H9B	108.1
O2—C2—C3	124.3 (3)	H9C—C9'—H9D	110.5
O2—C2—C1	114.1 (3)	C8—N1—C9	119.9 (4)
C3—C2—C1	121.7 (3)	C8—N1—Co1	127.0 (2)
C2—C3—C4	120.2 (3)	C9—N1—Co1	110.2 (3)
C2—C3—H3	119.9	C1—O1—Co1	128.85 (18)
C4—C3—H3	119.9	C2—O2—C7	117.2 (3)
C5—C4—C3	119.5 (3)	Co1—O1W—H1W	119.5 (17)
C5—C4—H4	120.2

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O1^ii	0.85 (1)	2.10 (2)	2.830 (3)	144 (2)
O1W—H1W···O2^ii	0.85 (1)	2.24 (1)	2.962 (2)	143 (2)

Symmetry code: (ii) x−1/2, −y+1/2, −z+5/2.