Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107002314/av3059sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107002314/av3059Isup2.hkl |
CCDC reference: 641782
For related literature, see: Bernstein et al. (1995); Graham & Pike (2000); Janiak (2003); Kitagawa et al. (2004); Li et al. (2006); Mitzi et al. (1995); Wang et al. (2005); Yaghi et al. (2003); Yang et al. (2003).
An aqueous solution of Co(NO3)2·6H2O (60 mg, 0.1 mmol) and an ethanol solution of phen (40 mg, 0.1 mmol) were mixed and stirred for 30 min. The resulting solution was then left for aerial evaporation at room temperature. Dark-red crystals of (I), suitable in size for single-crystal X-ray diffraction, appeared after three weeks (yield 38%).
H atoms of the phen ring sysytem were positioned geometrically and refined as riding, with C—H distances of 0.93 Å and Uiso(H) values of 1.2Ueq(C). H atoms of water molecules were located in a difference map and refined with restraints of O—H = 0.85 (2) Å and H···H 1.33 (2) Å, with Uiso(H) set at 1.5Ueq(O).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.
[Co(C12H8N2)(H2O)4](NO3)2 | F(000) = 892 |
Mr = 435.22 | Dx = 1.635 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 2877 reflections |
a = 13.9136 (16) Å | θ = 2.5–25.9° |
b = 10.4852 (12) Å | µ = 1.03 mm−1 |
c = 12.3991 (14) Å | T = 293 K |
β = 102.165 (2)° | Block, dark red |
V = 1768.2 (3) Å3 | 0.30 × 0.25 × 0.12 mm |
Z = 4 |
Bruker SMART APEX CCD area-detector diffractometer | 1752 independent reflections |
Radiation source: fine-focus sealed tube | 1618 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.015 |
ϕ and ω scans | θmax = 26.1°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→17 |
Tmin = 0.746, Tmax = 0.887 | k = −12→12 |
4991 measured reflections | l = −15→14 |
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)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.075 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0413P)2 + 0.9246P] where P = (Fo2 + 2Fc2)/3 |
1752 reflections | (Δ/σ)max < 0.001 |
135 parameters | Δρmax = 0.27 e Å−3 |
6 restraints | Δρmin = −0.30 e Å−3 |
[Co(C12H8N2)(H2O)4](NO3)2 | V = 1768.2 (3) Å3 |
Mr = 435.22 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 13.9136 (16) Å | µ = 1.03 mm−1 |
b = 10.4852 (12) Å | T = 293 K |
c = 12.3991 (14) Å | 0.30 × 0.25 × 0.12 mm |
β = 102.165 (2)° |
Bruker SMART APEX CCD area-detector diffractometer | 1752 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1618 reflections with I > 2σ(I) |
Tmin = 0.746, Tmax = 0.887 | Rint = 0.015 |
4991 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 6 restraints |
wR(F2) = 0.075 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.27 e Å−3 |
1752 reflections | Δρmin = −0.30 e Å−3 |
135 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 | ||
Co | 0.5000 | 0.27515 (3) | 0.2500 | 0.03887 (13) | |
N1 | 0.44785 (11) | 0.43326 (13) | 0.14626 (11) | 0.0395 (3) | |
N2 | 0.17761 (12) | 0.45284 (15) | 0.12111 (14) | 0.0503 (4) | |
O1 | 0.35265 (10) | 0.25288 (14) | 0.26938 (13) | 0.0538 (4) | |
H1A | 0.3061 (16) | 0.291 (2) | 0.228 (2) | 0.081* | |
H1B | 0.3319 (18) | 0.1785 (15) | 0.270 (2) | 0.081* | |
O2 | 0.52925 (12) | 0.14077 (16) | 0.37456 (14) | 0.0688 (5) | |
H2A | 0.4836 (15) | 0.105 (3) | 0.396 (2) | 0.103* | |
H2B | 0.5809 (13) | 0.123 (3) | 0.414 (2) | 0.103* | |
O3 | 0.19687 (12) | 0.34428 (14) | 0.09400 (16) | 0.0748 (5) | |
O4 | 0.21561 (14) | 0.49567 (17) | 0.21250 (13) | 0.0770 (5) | |
O5 | 0.12028 (12) | 0.52086 (16) | 0.05359 (13) | 0.0701 (4) | |
C1 | 0.39318 (14) | 0.43170 (19) | 0.04427 (15) | 0.0476 (4) | |
H1 | 0.3777 | 0.3533 | 0.0098 | 0.057* | |
C2 | 0.35809 (16) | 0.5425 (2) | −0.01330 (17) | 0.0576 (5) | |
H2 | 0.3192 | 0.5375 | −0.0841 | 0.069* | |
C3 | 0.38140 (16) | 0.6581 (2) | 0.03535 (17) | 0.0590 (5) | |
H3 | 0.3586 | 0.7325 | −0.0023 | 0.071* | |
C4 | 0.43995 (15) | 0.66483 (17) | 0.14252 (16) | 0.0493 (4) | |
C5 | 0.47112 (19) | 0.78144 (18) | 0.1990 (2) | 0.0644 (6) | |
H5 | 0.4512 | 0.8587 | 0.1647 | 0.077* | |
C6 | 0.47060 (12) | 0.54846 (16) | 0.19459 (14) | 0.0394 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co | 0.0427 (2) | 0.03023 (19) | 0.0396 (2) | 0.000 | −0.00060 (14) | 0.000 |
N1 | 0.0425 (8) | 0.0361 (7) | 0.0389 (7) | −0.0007 (6) | 0.0061 (6) | 0.0021 (6) |
N2 | 0.0446 (9) | 0.0474 (9) | 0.0553 (9) | 0.0037 (7) | 0.0020 (7) | −0.0059 (7) |
O1 | 0.0450 (8) | 0.0484 (7) | 0.0645 (9) | 0.0004 (6) | 0.0038 (7) | 0.0132 (7) |
O2 | 0.0631 (9) | 0.0619 (9) | 0.0710 (10) | −0.0048 (8) | −0.0096 (8) | 0.0298 (8) |
O3 | 0.0681 (10) | 0.0470 (9) | 0.1079 (13) | 0.0072 (7) | 0.0150 (9) | −0.0215 (8) |
O4 | 0.0844 (11) | 0.0761 (11) | 0.0566 (9) | 0.0113 (9) | −0.0165 (8) | −0.0120 (8) |
O5 | 0.0697 (10) | 0.0692 (10) | 0.0609 (9) | 0.0196 (8) | −0.0098 (7) | −0.0005 (8) |
C1 | 0.0477 (10) | 0.0503 (10) | 0.0424 (9) | −0.0020 (8) | 0.0038 (8) | 0.0019 (8) |
C2 | 0.0557 (12) | 0.0669 (13) | 0.0468 (10) | 0.0023 (10) | 0.0029 (9) | 0.0158 (9) |
C3 | 0.0639 (13) | 0.0534 (12) | 0.0597 (12) | 0.0108 (10) | 0.0132 (10) | 0.0226 (10) |
C4 | 0.0564 (11) | 0.0388 (10) | 0.0559 (11) | 0.0055 (8) | 0.0192 (9) | 0.0109 (8) |
C5 | 0.0861 (17) | 0.0327 (10) | 0.0783 (15) | 0.0058 (9) | 0.0258 (13) | 0.0096 (9) |
C6 | 0.0424 (9) | 0.0340 (8) | 0.0435 (9) | 0.0013 (7) | 0.0128 (7) | 0.0030 (7) |
Co—O2 | 2.0667 (14) | O2—H2A | 0.828 (16) |
Co—O2i | 2.0668 (14) | O2—H2B | 0.804 (16) |
Co—O1 | 2.1268 (15) | C1—C2 | 1.397 (3) |
Co—O1i | 2.1268 (15) | C1—H1 | 0.9300 |
Co—N1 | 2.1298 (14) | C2—C3 | 1.362 (3) |
Co—N1i | 2.1298 (14) | C2—H2 | 0.9300 |
N1—C1 | 1.331 (2) | C3—C4 | 1.406 (3) |
N1—C6 | 1.356 (2) | C3—H3 | 0.9300 |
N2—O4 | 1.230 (2) | C4—C6 | 1.404 (2) |
N2—O3 | 1.232 (2) | C4—C5 | 1.430 (3) |
N2—O5 | 1.251 (2) | C5—C5i | 1.348 (5) |
O1—H1A | 0.839 (16) | C5—H5 | 0.9300 |
O1—H1B | 0.832 (16) | C6—C6i | 1.444 (3) |
O2—Co—O2i | 94.04 (11) | H1A—O1—H1B | 103 (2) |
O2—Co—O1 | 83.30 (6) | Co—O2—H2A | 120 (2) |
O2i—Co—O1 | 88.10 (7) | Co—O2—H2B | 129 (2) |
O2—Co—O1i | 88.10 (7) | H2A—O2—H2B | 110 (2) |
O2i—Co—O1i | 83.31 (6) | N1—C1—C2 | 122.90 (18) |
O1—Co—O1i | 167.39 (8) | N1—C1—H1 | 118.5 |
O2—Co—N1 | 166.02 (7) | C2—C1—H1 | 118.5 |
O2i—Co—N1 | 95.22 (6) | C3—C2—C1 | 119.26 (18) |
O1—Co—N1 | 86.56 (5) | C3—C2—H2 | 120.4 |
O1i—Co—N1 | 103.36 (6) | C1—C2—H2 | 120.4 |
O2—Co—N1i | 95.22 (6) | C2—C3—C4 | 119.97 (18) |
O2i—Co—N1i | 166.02 (7) | C2—C3—H3 | 120.0 |
O1—Co—N1i | 103.36 (6) | C4—C3—H3 | 120.0 |
O1i—Co—N1i | 86.55 (5) | C6—C4—C3 | 116.75 (18) |
N1—Co—N1i | 77.77 (8) | C6—C4—C5 | 119.11 (18) |
C1—N1—C6 | 117.66 (15) | C3—C4—C5 | 124.12 (18) |
C1—N1—Co | 128.15 (12) | C5i—C5—C4 | 121.24 (12) |
C6—N1—Co | 114.11 (11) | C5i—C5—H5 | 119.4 |
O4—N2—O3 | 120.84 (18) | C4—C5—H5 | 119.4 |
O4—N2—O5 | 119.88 (17) | N1—C6—C4 | 123.44 (15) |
O3—N2—O5 | 119.26 (17) | N1—C6—C6i | 116.96 (9) |
Co—O1—H1A | 121.2 (18) | C4—C6—C6i | 119.60 (11) |
Co—O1—H1B | 116.7 (17) |
Symmetry code: (i) −x+1, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O3 | 0.84 (2) | 2.08 (2) | 2.891 (2) | 163 (3) |
O1—H1B···O4ii | 0.83 (2) | 2.05 (2) | 2.884 (2) | 175 (2) |
O2—H2A···O5ii | 0.83 (2) | 1.91 (2) | 2.736 (2) | 179 (3) |
O2—H2B···O5iii | 0.80 (2) | 2.27 (3) | 2.867 (2) | 132 (2) |
Symmetry codes: (ii) −x+1/2, y−1/2, −z+1/2; (iii) x+1/2, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Co(C12H8N2)(H2O)4](NO3)2 |
Mr | 435.22 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 13.9136 (16), 10.4852 (12), 12.3991 (14) |
β (°) | 102.165 (2) |
V (Å3) | 1768.2 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.03 |
Crystal size (mm) | 0.30 × 0.25 × 0.12 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.746, 0.887 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4991, 1752, 1618 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.618 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.075, 1.05 |
No. of reflections | 1752 |
No. of parameters | 135 |
No. of restraints | 6 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.27, −0.30 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O3 | 0.84 (2) | 2.08 (2) | 2.891 (2) | 163 (3) |
O1—H1B···O4i | 0.83 (2) | 2.05 (2) | 2.884 (2) | 175 (2) |
O2—H2A···O5i | 0.83 (2) | 1.91 (2) | 2.736 (2) | 179 (3) |
O2—H2B···O5ii | 0.80 (2) | 2.27 (3) | 2.867 (2) | 132 (2) |
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) x+1/2, −y+1/2, z+1/2. |
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Metal-organic supramolecular complexes with various fascinating topologies have been widely studied for their versatile chemical and physical properties and potential applications as functional materials (Janiak, 2003; Kitagawa et al., 2004; Yaghi et al., 2003). Self-assembly based on molecular building blocks has become an effective approach to construct these functional materials. In the development of supramolecular chemistry, hydrogen-bonding and π–π interactions acting as two main driving forces play an important role in self-assembling multidimensional metal–organic supramolecular frameworks or networks (Graham & Pike, 2000; Mitzi et al., 1995). We report here the structure of [Co(phen)(H2O)4](NO3)2, (I) (phen is 1,10-phenanthroline), in which hydrogen-bonding interactions lead to a three-dimensional supramolecular network.
Compound (I), as shown in Fig.1, consists of [Co(phen)(H2O)4]2+ cations and NO3- anions. The Co atom, lying on a twofold rotation axis, is six-coordinated by two N atoms of a chelating phen ligand and four O atoms of water molecules in a octahedral geometry. The twofold rotation axis passes through the phen ligand. Therefore, the asymmetric unit of (I) contains half of the Co atom and half of the phen ligand accompanied by two water molecules and one NO3- anion. In the complex cation, two water molecules and two N atoms are located in the equatorial plane, and the other two water molecules occupy the axial positions. Bond lengths and angles are in normal ranges (Wang et al., 2005; Yang et al., 2003). Each of the coordinated water molecules donates its two H atoms to two neighboring nitrate anions, while each nitrate ion accepts four hydrogen bonds from four neighboring coordinated water molecules (Table 1). The equatorial water molecule (O2) is hydrogen-bonded to atoms O5 of two centrosymmetrically related nitrates at (1/2 - x, y - 1/2, 1/2 - z) and (1/2 + x, 1/2 - y, 1/2 + z), so generating a centrosymmetric R42(8) motif (Bernstein et al., 1995). The axial water molecule acts as hydrogen-bond donor to atom O3 of the nitrate group at (x, y, z) and atom O4 of another nitrate group at (1/2 - x, y - 1/2, 1/2 - z). In this way, a C44(12) helical chain is formed along the 21 screw axis in the [010] direction (Fig. 2). As a result, each complex cation is hydrogen bonded to six nitrate anions, which in turn link the other eight cations (Fig. 3). The effect of the two hydrogen-bond motifs is to link the complex cations and nitrate anions into a three-dimensional network. The structure is further stabilized by weak π–π stacking interactions between two adjacent phen rings in an offset arrangement. The distance between centroids of the six-membered C1–C4/C6/N1 ring and its equivalent at (1 - x, 1 - y, -z) is 3.73 (1) Å and the average interplanar spacing is 3.431 Å.
The phen ligand has strong chelating ability. CoII–phen complexes can be formed with a CoII to phen ratio of 1:1, 1:2 or 1:3. We have previously reported the structure of a 1:2 complex, [Co(phen)2(NO3)]NO3·4H2O (Li et al., 2006), in which a layer-like structure was observed consisting of hydrogen-bonded water–nitrate anionic sheets and π–π-interaction-linked [Co(phen)2(NO3)]+ cationic sheets. Thus, the hydrogen-bonding interactions between water molecules and nitrates, and π–π-interactions between phen ligands, are crucial to the structural architecture. We intend to examine further how anions influence supramolecular structures in the CoII–phen system by varying the ratio of CoII to phen when the anions have different geometry and hydrogen-bonding ability.