Aqua­(azido)(di­methyl­glyoximato)(di­methyl­glyoxime)­cobalt(III) monohydrate

A new mononuclear Co^III complex, [Co(N₃)(dmg)(H₂dmg)(H₂O)]·H₂O or [Co(N₃)(C₂H₆N₂O₂)(C₂H₈N₂O₂)(H₂O)]·H₂O, has been synthesized and characterized by single-crystal X-ray diffraction analysis. In the complex, the Co^III ion is six-coordinated in a distorted octahedral configuration. The compound was also studied by means of room-temperature magnetic susceptibility measurements and IR spectroscopy.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.042
• wR factor = 0.100
• Data-to-parameter ratio = 13.2

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes



ABSTM_02  When printed, the submitted absorption T values will be replaced
          by the scaled T values. Since the ratio of scaled T's is
          identical to the ratio of reported T values, the scaling does
          not imply a change to the absorption corrections used in the
          study.
          Ratio of Tmax expected/reported      3.547
          Tmax scaled      0.954 Tmin scaled      0.798

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S1. Comment

Supramolecular polymer chemistry is an important developing branch of modern chemical science (Lehn, 1995, 1999; Kholbystov et al., 2001). The first and essential problem of supramolecular polymer chemistry is to ensure that the polymer structure is controllable and predictable. According to the basic principles of the engineering of supramolecular polymers (Desiraju, 1995), it is very important for supramolecular polymer researchers to start from simple systems and do further research on more complicated systems through modeling and investigation of simple systems. It is well known that the oximate group (═N—O–) can function as a bridge in binding one metal atom, through the imine N atom, to generate bi- or trinuclear complexes (Zhan & Dai, 1999; Zhan et al., 1999; Xu & Gu, 1998; Chaudhuri & Winter, 1991). At the same time, the deprotonated O atom can also coordinate in diverse ways with metal ions (Cervera et al., 1997; Ruiz, Sanz & Cervera, 1993; Ruiz, Sanz & Lloret, 1993; Ruiz et al., 1998; Kubiak et al., 1995). Dimethylglyoxime, H₂dmg, is a potentially tetradentate ligand and can also act as a mono-, bi- or tridentate ligand. Framework molecular models show that it is more likely to bond to different metal ions and thus act as a bridging ligand rather than as a terminal ligand. Earlier, we have synthesized some one-dimensional chain-like complex polymers, but in this study we have found a new polymer which is not linked through H₂dmg but by intermolecular hydrogen bonding.

A perspective view of the complex, with the atom-numbering scheme, is depicted in Fig. 1 and a packing view along the a direction is shown in Fig. 2. The title compound consists of a mononuclear complex [Co(H₂O)(dmg)(H₂dmg)(N₃)] and a solvate water molecule. The cobalt(III) ion is coordinated by five N atoms and one O atom to form a distorted octahedral configuration. The four N atoms (N1, N2, N3 and N4) and Co1 are approximately coplanar. Atom N5 of the azido group and O5 of the coordinated water molecule occupy the axial positions. The Co1—N1 and Co1—N2 bond lengths are longer than those of Co1—N3 and Co1—N4. The angles C2—N1—O1 and C3—N2—O2 are smaller than C6—N3—O3 and C7—N4—O4.

The H₂dmg and dmg²⁻ groups are linked by two hydrogen bonds (Table 2). An intermolecular hydrogen-bond network is also present, involving atoms O3 and O4 of the dmg group, atom N5 of the azido group, and O1W of the water of crystallization; via this network, the molecules of the complex are stacked to form a one-dimensional structure, with the Co atoms arranged in a zigzag fashion.

The magnetic susceptibility measurement performed at room temperature clearly confirms the cobalt ion to be trivalent and low spin. This means that the Co^II ion was oxidized to Co^III by oxygen in the solution. The IR spectrum shows the characteristic C═N stretching vibration of dmg²⁻ at 1570 cm⁻¹, N—O at 1237 cm⁻¹, and the characteristic N═N stretching vibration of (N₃)⁻ at 2036 cm⁻¹.

S2. Experimental

0.116 g (1.0 mmol) H₂dmg was dissolved in 20 ml e thanol, and 0.185 g (0.5 mmol) Co(ClO₄)₂·6H₂O was added to yield a dark-brown solution. 0.032 g (0.5 mmol) sodium azide, dissolved in 10 ml water, was then added to the solution. The dark-red mixture was filtered to remove any solid particles and allowed to evaporate slowly at room temperature. After 12 d, brown plates of the title complex, suitable for X-ray analysis, were obtained. They were collected by suction filtration and air dried.

S3. Refinement

All H atoms were treated as riding on their parent atoms in the final refinement.

Computing details

Data collection: XSCANS (Bruker, 1997); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL (Sheldrick, 1995); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The structure of the title complex, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 35% probability level. H atoms attached to non-water O atoms have been omitted.
	Fig. 2. A view of the packing, along the a direction. Hydrogen bonds are indicated by dashed lines.

(aqua)bis(dimethylglyoxime)cobalt(III) azide hydrate

Crystal data

[Co(N3)(H2O)(C2H6N2O2)(C2H8N2O2)]·H2O	F(000) = 760
Mr = 367.22	Dx = 1.612 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.6739 (18) Å	Cell parameters from 31 reflections
b = 17.515 (4) Å	θ = 5.0–12.6°
c = 11.261 (2) Å	µ = 1.18 mm^−1
β = 91.243 (14)°	T = 293 K
V = 1513.2 (6) Å^3	Plate, brown
Z = 4	0.4 × 0.2 × 0.04 mm

Data collection

Bruker P4 diffractometer	1853 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.038
Graphite monochromator	θmax = 25.0°, θmin = 2.2°
ω scans	h = −9→1
Absorption correction: ψ scan (North et al., 1968)	k = −1→20
Tmin = 0.225, Tmax = 0.269	l = −13→13
3523 measured reflections	3 standard reflections every 100 reflections
2635 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.042	H-atom parameters constrained
wR(F^2) = 0.100	w = 1/[σ^2(Fo^2) + (0.001P)^2 + 2P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.004
2635 reflections	Δρmax = 0.30 e Å^−3
200 parameters	Δρmin = −0.26 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0018 (2)

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
Co1	0.03698 (7)	0.13454 (3)	0.16493 (4)	0.04133 (18)
O1	−0.0583 (4)	0.29237 (15)	0.1988 (3)	0.0629 (8)
H1F	−0.1561	0.2553	0.2302	0.076*
O2	0.3519 (4)	0.07993 (16)	0.0533 (2)	0.0569 (7)
H2A	0.2546	0.0301	0.0844	0.068*
O3	−0.2602 (4)	0.19309 (15)	0.2768 (3)	0.0560 (7)
O4	0.1384 (3)	−0.01871 (15)	0.1260 (2)	0.0521 (7)
O5	−0.0936 (3)	0.13720 (14)	0.0150 (2)	0.0465 (6)
H5A	−0.0951	0.0864	−0.0392	0.056*
H5B	−0.0722	0.1807	−0.0452	0.056*
N1	0.0612 (4)	0.24297 (17)	0.1568 (3)	0.0483 (8)
N2	0.2565 (4)	0.14171 (18)	0.0862 (3)	0.0459 (8)
N3	−0.1777 (4)	0.13010 (18)	0.2440 (3)	0.0452 (8)
N4	0.0155 (4)	0.02748 (17)	0.1692 (3)	0.0430 (7)
N5	0.1633 (4)	0.13874 (18)	0.3137 (3)	0.0507 (8)
N6	0.1613 (5)	0.0866 (2)	0.3842 (3)	0.0583 (9)
N7	0.1673 (7)	0.0404 (3)	0.4553 (4)	0.1052 (17)
C1	0.2388 (7)	0.3530 (2)	0.0999 (4)	0.0745 (14)
H1A	0.1449	0.3818	0.1326	0.112*
H1B	0.2507	0.3660	0.0176	0.112*
H1C	0.3452	0.3648	0.1424	0.112*
C2	0.2012 (6)	0.2697 (2)	0.1108 (3)	0.0510 (10)
C3	0.3186 (5)	0.2091 (2)	0.0694 (3)	0.0498 (10)
C4	0.4918 (6)	0.2240 (3)	0.0167 (4)	0.0674 (13)
H4A	0.5451	0.1764	−0.0042	0.101*
H4B	0.5650	0.2503	0.0735	0.101*
H4C	0.4767	0.2550	−0.0531	0.101*
C5	−0.4121 (5)	0.0458 (3)	0.3129 (4)	0.0607 (11)
H5C	−0.4670	0.0929	0.3344	0.091*
H5D	−0.3954	0.0147	0.3825	0.091*
H5E	−0.4848	0.0192	0.2562	0.091*
C6	−0.2405 (5)	0.0621 (2)	0.2599 (3)	0.0472 (9)
C7	−0.1262 (5)	0.0013 (2)	0.2175 (3)	0.0456 (9)
C8	−0.1677 (6)	−0.0815 (2)	0.2305 (4)	0.0607 (11)
H8A	−0.0760	−0.1115	0.1974	0.091*
H8B	−0.2756	−0.0927	0.1894	0.091*
H8C	−0.1782	−0.0937	0.3132	0.091*
O1W	0.4305 (4)	0.24869 (17)	0.3647 (3)	0.0701 (9)
H1D	0.3396	0.2100	0.3667	0.084*
H1E	0.5334	0.2184	0.3410	0.084*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0382 (3)	0.0401 (3)	0.0456 (3)	0.0002 (2)	0.0000 (2)	−0.0012 (2)
O1	0.067 (2)	0.0441 (16)	0.078 (2)	0.0101 (15)	0.0086 (16)	−0.0062 (15)
O2	0.0477 (16)	0.0617 (18)	0.0617 (17)	0.0110 (14)	0.0074 (14)	−0.0011 (14)
O3	0.0479 (16)	0.0512 (16)	0.0694 (18)	0.0106 (14)	0.0118 (14)	−0.0079 (14)
O4	0.0496 (16)	0.0444 (15)	0.0623 (17)	0.0050 (13)	0.0033 (13)	−0.0067 (13)
O5	0.0502 (15)	0.0447 (14)	0.0443 (14)	0.0004 (13)	−0.0057 (12)	0.0005 (12)
N1	0.052 (2)	0.0382 (17)	0.0543 (19)	0.0004 (16)	−0.0014 (16)	−0.0002 (15)
N2	0.0415 (18)	0.0509 (19)	0.0454 (17)	0.0006 (16)	−0.0010 (14)	0.0021 (15)
N3	0.0418 (18)	0.0477 (18)	0.0461 (17)	0.0002 (16)	−0.0006 (14)	0.0000 (15)
N4	0.0411 (18)	0.0423 (17)	0.0453 (17)	0.0001 (15)	−0.0041 (14)	−0.0032 (14)
N5	0.053 (2)	0.0477 (19)	0.0510 (19)	−0.0040 (17)	−0.0077 (16)	0.0004 (16)
N6	0.056 (2)	0.062 (2)	0.057 (2)	−0.0036 (19)	−0.0022 (18)	−0.003 (2)
N7	0.140 (5)	0.100 (4)	0.074 (3)	−0.024 (3)	−0.025 (3)	0.036 (3)
C1	0.089 (4)	0.042 (2)	0.092 (4)	−0.016 (2)	−0.003 (3)	0.010 (2)
C2	0.056 (3)	0.045 (2)	0.052 (2)	−0.008 (2)	−0.010 (2)	0.0029 (18)
C3	0.044 (2)	0.061 (3)	0.044 (2)	−0.008 (2)	−0.0099 (18)	0.0084 (19)
C4	0.048 (3)	0.085 (3)	0.069 (3)	−0.009 (2)	0.005 (2)	0.015 (3)
C5	0.046 (2)	0.070 (3)	0.066 (3)	−0.003 (2)	0.003 (2)	0.003 (2)
C6	0.045 (2)	0.054 (2)	0.043 (2)	−0.002 (2)	−0.0030 (17)	0.0044 (18)
C7	0.047 (2)	0.047 (2)	0.043 (2)	−0.0014 (19)	−0.0061 (18)	0.0004 (18)
C8	0.073 (3)	0.049 (2)	0.061 (3)	−0.010 (2)	0.003 (2)	0.003 (2)
O1W	0.0538 (19)	0.0640 (19)	0.093 (2)	−0.0060 (15)	0.0054 (16)	−0.0280 (17)

Geometric parameters (Å, º)

Co1—N4	1.883 (3)	N2—C3	1.288 (5)
Co1—N3	1.891 (3)	N3—C6	1.298 (5)
Co1—N1	1.911 (3)	N4—C7	1.309 (5)
Co1—N5	1.919 (3)	N5—N6	1.210 (4)
Co1—N2	1.924 (3)	N6—N7	1.139 (5)
Co1—O5	1.945 (2)	C1—C2	1.493 (5)
O1—N1	1.354 (4)	C2—C3	1.475 (6)
O2—N2	1.362 (4)	C3—C4	1.490 (6)
O3—N3	1.328 (4)	C5—C6	1.486 (5)
O4—N4	1.342 (4)	C6—C7	1.467 (5)
N1—C2	1.290 (5)	C7—C8	1.493 (5)
N4—Co1—N3	82.49 (14)	C6—N3—O3	122.9 (3)
N4—Co1—N1	178.59 (14)	C6—N3—Co1	115.6 (3)
N3—Co1—N1	98.64 (14)	O3—N3—Co1	121.5 (2)
N4—Co1—N5	93.36 (13)	C7—N4—O4	122.4 (3)
N3—Co1—N5	91.10 (14)	C7—N4—Co1	115.7 (3)
N1—Co1—N5	87.47 (14)	O4—N4—Co1	121.9 (2)
N4—Co1—N2	98.91 (14)	N6—N5—Co1	122.1 (3)
N3—Co1—N2	178.48 (14)	N7—N6—N5	175.3 (5)
N1—Co1—N2	79.97 (14)	N1—C2—C3	112.7 (3)
N5—Co1—N2	88.24 (14)	N1—C2—C1	123.5 (4)
N4—Co1—O5	90.13 (12)	C3—C2—C1	123.8 (4)
N3—Co1—O5	88.39 (12)	N2—C3—C2	112.5 (4)
N1—Co1—O5	89.06 (12)	N2—C3—C4	123.8 (4)
N5—Co1—O5	176.37 (12)	C2—C3—C4	123.7 (4)
N2—Co1—O5	92.19 (12)	N3—C6—C7	113.3 (3)
C2—N1—O1	119.0 (3)	N3—C6—C5	124.5 (4)
C2—N1—Co1	117.6 (3)	C7—C6—C5	122.2 (4)
O1—N1—Co1	123.4 (3)	N4—C7—C6	112.8 (3)
C3—N2—O2	119.0 (3)	N4—C7—C8	124.2 (4)
C3—N2—Co1	117.3 (3)	C6—C7—C8	122.9 (4)
O2—N2—Co1	123.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1F···O3	1.06	1.45	2.501 (4)	168
O2—H2A···O4	1.21	1.33	2.529 (4)	174
O1W—H1D···N5	0.97	1.93	2.862 (4)	161
O1W—H1E···O3^i	0.99	1.81	2.769 (4)	161
O5—H5A···O4^ii	1.08	1.57	2.631 (3)	167
O5—H5B···O1W^iii	1.04	1.60	2.628 (4)	171

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