Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803003520/wn6128sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803003520/wn6128Isup2.hkl |
CCDC reference: 214569
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (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
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.
All H atoms were treated as riding on their parent atoms in the final refinement.
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.
[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) Å3 | Plate, brown |
Z = 4 | 0.4 × 0.2 × 0.04 mm |
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 on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.100 | w = 1/[σ2(Fo2) + (0.001P)2 + 2P] where P = (Fo2 + 2Fc2)/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+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0018 (2) |
[Co(N3)(H2O)(C2H6N2O2)(C2H8N2O2)]·H2O | V = 1513.2 (6) Å3 |
Mr = 367.22 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.6739 (18) Å | µ = 1.18 mm−1 |
b = 17.515 (4) Å | T = 293 K |
c = 11.261 (2) Å | 0.4 × 0.2 × 0.04 mm |
β = 91.243 (14)° |
Bruker P4 diffractometer | 1853 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.038 |
Tmin = 0.225, Tmax = 0.269 | 3 standard reflections every 100 reflections |
3523 measured reflections | intensity decay: none |
2635 independent reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.100 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.30 e Å−3 |
2635 reflections | Δρmin = −0.26 e Å−3 |
200 parameters |
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. |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
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···O3i | 0.99 | 1.81 | 2.769 (4) | 161 |
O5—H5A···O4ii | 1.08 | 1.57 | 2.631 (3) | 167 |
O5—H5B···O1Wiii | 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. |
Experimental details
Crystal data | |
Chemical formula | [Co(N3)(H2O)(C2H6N2O2)(C2H8N2O2)]·H2O |
Mr | 367.22 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 7.6739 (18), 17.515 (4), 11.261 (2) |
β (°) | 91.243 (14) |
V (Å3) | 1513.2 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.18 |
Crystal size (mm) | 0.4 × 0.2 × 0.04 |
Data collection | |
Diffractometer | Bruker P4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.225, 0.269 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3523, 2635, 1853 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.100, 1.02 |
No. of reflections | 2635 |
No. of parameters | 200 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.30, −0.26 |
Computer programs: XSCANS (Bruker, 1997), XSCANS, SHELXTL (Sheldrick, 1995), SHELXTL.
Co1—N4 | 1.883 (3) | O3—N3 | 1.328 (4) |
Co1—N3 | 1.891 (3) | O4—N4 | 1.342 (4) |
Co1—N1 | 1.911 (3) | N1—C2 | 1.290 (5) |
Co1—N5 | 1.919 (3) | N2—C3 | 1.288 (5) |
Co1—N2 | 1.924 (3) | N3—C6 | 1.298 (5) |
Co1—O5 | 1.945 (2) | N4—C7 | 1.309 (5) |
O1—N1 | 1.354 (4) | N5—N6 | 1.210 (4) |
O2—N2 | 1.362 (4) | N6—N7 | 1.139 (5) |
N4—Co1—N3 | 82.49 (14) | C2—N1—O1 | 119.0 (3) |
N4—Co1—N1 | 178.59 (14) | C2—N1—Co1 | 117.6 (3) |
N3—Co1—N1 | 98.64 (14) | O1—N1—Co1 | 123.4 (3) |
N4—Co1—N5 | 93.36 (13) | C3—N2—O2 | 119.0 (3) |
N3—Co1—N5 | 91.10 (14) | C3—N2—Co1 | 117.3 (3) |
N1—Co1—N5 | 87.47 (14) | O2—N2—Co1 | 123.7 (2) |
N4—Co1—N2 | 98.91 (14) | C6—N3—O3 | 122.9 (3) |
N3—Co1—N2 | 178.48 (14) | C6—N3—Co1 | 115.6 (3) |
N1—Co1—N2 | 79.97 (14) | O3—N3—Co1 | 121.5 (2) |
N5—Co1—N2 | 88.24 (14) | C7—N4—O4 | 122.4 (3) |
N4—Co1—O5 | 90.13 (12) | C7—N4—Co1 | 115.7 (3) |
N3—Co1—O5 | 88.39 (12) | O4—N4—Co1 | 121.9 (2) |
N1—Co1—O5 | 89.06 (12) | N6—N5—Co1 | 122.1 (3) |
N5—Co1—O5 | 176.37 (12) | N7—N6—N5 | 175.3 (5) |
N2—Co1—O5 | 92.19 (12) |
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···O3i | 0.99 | 1.81 | 2.769 (4) | 161 |
O5—H5A···O4ii | 1.08 | 1.57 | 2.631 (3) | 167 |
O5—H5B···O1Wiii | 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. |
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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 CoII ion was oxidized to CoIII 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.