Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807038706/kp2121sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807038706/kp2121Isup2.hkl |
CCDC reference: 660076
N,N'-(1,1-methyl)bis(imidazole) was synthesized using a reported procedure (Diez-Barra et al., 1992) and sublimated for purification at 453 K under high vacuum. A mixture of LiCl (15 mg, 0.357 mmol) and N,N'–(1,1'–methyl)bis(imidazole) (50 mg, 0.338 mmol) was placed in a 10 ml glass flask in CH3CN/H2O solution. The reaction mixture was heated at 333 K and then cooled to room temperature at a rate of 3 K/h. Colourless cubic single crystals were obtained in excellent yield.
H atoms on N,N'–(1,1'–methyl)bis(imidazole) were positioned geometrically, with C—H = 0.93 Å and 0.97 Å, and refined using a riding model, with Uiso(H) = 1.2Ueq(C). H atoms on water molecules were localized from Fourier difference maps, but their atomic coordinates were not refined.
The design and synthesis of superfunctional coordination polymers have been increased due to their intriguing architectures and flexible bridging ligands in supramolecular chemistry (Kitagawa et al., 2004). The metal coordination architectures with the various heterocyclic aromatic compounds containing S–, N–, and O–donors are of diverse structural types. Significant progress has been achieved by Duncan et al. (1996), Cui et al. (2005) and others in this area. The formation of lithium coordination frameworks constructed from flexible N,N'–(1,1'–methyl)bis(imidazole) ligands and the exploitation of new synthetic methods are still less investigated. The selected N,N'–(1,1'–methyl)bis(imidazole) organic ligand with the N–hetero aromatic ring system could be a metal atom linker forming polymeric structure. The title compound (I) (Fig. 1) reveals tetrahedrally coordinated Li + cations interlinked by (imidazol–1–yl)methane into polymer structure connected by O—H···Cl- hydrogen bonds (Fig. 2, Table 1).
For related literature, see: Diez-Barra et al. (1992); Cui et al. (2005); Duncan et al. (1996); Kitagawa et al. (2004).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
[Li(C7H8N4)(H2O)2]Cl | F(000) = 944 |
Mr = 226.60 | Dx = 1.338 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 3763 reflections |
a = 15.3208 (13) Å | θ = 2.4–26.4° |
b = 10.6729 (9) Å | µ = 0.32 mm−1 |
c = 14.8266 (12) Å | T = 295 K |
β = 111.887 (2)° | Cubic, colourless |
V = 2249.7 (3) Å3 | 0.35 × 0.25 × 0.25 mm |
Z = 8 |
Bruker SMART CCD area-detector diffractometer | 2310 independent reflections |
Radiation source: fine-focus sealed tube | 2005 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
φ and ω scans | θmax = 26.4°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −19→17 |
Tmin = 0.837, Tmax = 0.922 | k = −13→13 |
6383 measured reflections | l = −18→16 |
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 atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.126 | w = 1/[σ2(Fo2) + (0.0746P)2 + 0.5534P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
2310 reflections | Δρmax = 0.30 e Å−3 |
153 parameters | Δρmin = −0.28 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: 0.0112 (12) |
[Li(C7H8N4)(H2O)2]Cl | V = 2249.7 (3) Å3 |
Mr = 226.60 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 15.3208 (13) Å | µ = 0.32 mm−1 |
b = 10.6729 (9) Å | T = 295 K |
c = 14.8266 (12) Å | 0.35 × 0.25 × 0.25 mm |
β = 111.887 (2)° |
Bruker SMART CCD area-detector diffractometer | 2310 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 2005 reflections with I > 2σ(I) |
Tmin = 0.837, Tmax = 0.922 | Rint = 0.037 |
6383 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.126 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.30 e Å−3 |
2310 reflections | Δρmin = −0.28 e Å−3 |
153 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 | ||
C1 | 0.22713 (11) | 0.84155 (15) | 0.38908 (11) | 0.0445 (4) | |
H1 | 0.2621 | 0.9141 | 0.4118 | 0.053* | |
C2 | 0.17854 (13) | 0.66703 (16) | 0.31882 (14) | 0.0564 (4) | |
H2 | 0.1741 | 0.5946 | 0.2825 | 0.068* | |
C3 | 0.11830 (12) | 0.69897 (16) | 0.36197 (13) | 0.0557 (4) | |
H3 | 0.0662 | 0.6539 | 0.3615 | 0.067* | |
C4 | 0.02217 (10) | 1.07972 (15) | 0.38388 (11) | 0.0460 (4) | |
H4 | 0.0734 | 1.1336 | 0.4074 | 0.055* | |
C5 | −0.06186 (12) | 0.90934 (17) | 0.35524 (15) | 0.0627 (5) | |
H5 | −0.0813 | 0.8266 | 0.3540 | 0.075* | |
C6 | −0.11482 (11) | 1.00761 (17) | 0.31130 (14) | 0.0643 (5) | |
H6 | −0.1787 | 1.0033 | 0.2736 | 0.077* | |
C7 | 0.10813 (13) | 0.88548 (17) | 0.46271 (11) | 0.0570 (5) | |
H7A | 0.0899 | 0.8301 | 0.5046 | 0.068* | |
H7B | 0.1550 | 0.9432 | 0.5039 | 0.068* | |
Cl1 | 0.13680 (3) | 0.63139 (4) | 0.03017 (3) | 0.0632 (2) | |
Li1 | 0.36216 (18) | 0.7809 (3) | 0.29113 (18) | 0.0501 (6) | |
N1 | 0.24754 (9) | 0.75656 (13) | 0.33611 (9) | 0.0487 (3) | |
N2 | 0.14968 (9) | 0.81128 (12) | 0.40654 (9) | 0.0448 (3) | |
N3 | 0.02675 (8) | 0.95582 (12) | 0.40227 (8) | 0.0420 (3) | |
N4 | −0.06257 (10) | 1.11534 (13) | 0.32919 (10) | 0.0507 (4) | |
O1 | 0.30302 (11) | 0.81249 (16) | 0.15348 (10) | 0.0683 (4) | |
H1W | 0.3229 (18) | 0.834 (2) | 0.119 (2) | 0.080 (8)* | |
H2W | 0.254 (2) | 0.768 (2) | 0.119 (2) | 0.093 (8)* | |
O2 | 0.43632 (11) | 0.91675 (16) | 0.36717 (12) | 0.0790 (5) | |
H3W | 0.418 (2) | 0.983 (3) | 0.396 (2) | 0.124 (10)* | |
H4W | 0.490 (2) | 0.899 (3) | 0.409 (2) | 0.097 (8)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0435 (8) | 0.0459 (8) | 0.0414 (8) | 0.0082 (6) | 0.0126 (6) | 0.0043 (6) |
C2 | 0.0577 (10) | 0.0487 (9) | 0.0617 (10) | 0.0109 (8) | 0.0210 (8) | −0.0091 (7) |
C3 | 0.0520 (9) | 0.0495 (9) | 0.0683 (11) | 0.0041 (7) | 0.0255 (8) | 0.0008 (8) |
C4 | 0.0440 (8) | 0.0460 (8) | 0.0539 (8) | 0.0018 (6) | 0.0249 (7) | −0.0027 (7) |
C5 | 0.0501 (9) | 0.0487 (9) | 0.0934 (13) | −0.0034 (8) | 0.0316 (9) | −0.0213 (9) |
C6 | 0.0417 (9) | 0.0680 (11) | 0.0723 (12) | 0.0084 (8) | 0.0086 (8) | −0.0321 (9) |
C7 | 0.0646 (11) | 0.0690 (11) | 0.0401 (8) | 0.0271 (9) | 0.0227 (7) | 0.0052 (7) |
Cl1 | 0.0673 (3) | 0.0568 (3) | 0.0587 (3) | −0.00934 (19) | 0.0158 (2) | 0.00771 (18) |
Li1 | 0.0513 (14) | 0.0538 (15) | 0.0450 (13) | 0.0108 (12) | 0.0177 (11) | 0.0014 (11) |
N1 | 0.0470 (7) | 0.0540 (8) | 0.0466 (7) | 0.0138 (6) | 0.0190 (6) | 0.0028 (6) |
N2 | 0.0473 (7) | 0.0481 (7) | 0.0406 (6) | 0.0133 (5) | 0.0181 (5) | 0.0036 (5) |
N3 | 0.0435 (7) | 0.0448 (7) | 0.0417 (6) | 0.0063 (5) | 0.0206 (5) | −0.0036 (5) |
N4 | 0.0522 (8) | 0.0560 (8) | 0.0476 (7) | 0.0148 (6) | 0.0229 (6) | 0.0000 (6) |
O1 | 0.0636 (9) | 0.0930 (11) | 0.0448 (7) | −0.0140 (8) | 0.0163 (7) | 0.0036 (7) |
O2 | 0.0591 (8) | 0.0836 (10) | 0.0792 (10) | 0.0102 (7) | 0.0084 (7) | −0.0280 (8) |
C1—N1 | 1.312 (2) | C6—H6 | 0.9300 |
C1—N2 | 1.345 (2) | C7—N3 | 1.4450 (19) |
C1—H1 | 0.9300 | C7—N2 | 1.4564 (19) |
C2—C3 | 1.348 (2) | C7—H7A | 0.9700 |
C2—N1 | 1.376 (2) | C7—H7B | 0.9700 |
C2—H2 | 0.9300 | Li1—O2 | 1.926 (3) |
C3—N2 | 1.367 (2) | Li1—O1 | 1.929 (3) |
C3—H3 | 0.9300 | Li1—N4i | 2.070 (3) |
C4—N4 | 1.305 (2) | Li1—N1 | 2.114 (3) |
C4—N3 | 1.347 (2) | N4—Li1ii | 2.070 (3) |
C4—H4 | 0.9300 | O1—H1W | 0.72 (3) |
C5—C6 | 1.337 (3) | O1—H2W | 0.87 (3) |
C5—N3 | 1.367 (2) | O2—H3W | 0.93 (3) |
C5—H5 | 0.9300 | O2—H4W | 0.85 (3) |
C6—N4 | 1.369 (2) | ||
N1—C1—N2 | 111.94 (14) | O2—Li1—O1 | 115.43 (15) |
N1—C1—H1 | 124.0 | O2—Li1—N4i | 109.63 (14) |
N2—C1—H1 | 124.0 | O1—Li1—N4i | 115.59 (14) |
C3—C2—N1 | 110.51 (15) | O2—Li1—N1 | 106.61 (13) |
C3—C2—H2 | 124.7 | O1—Li1—N1 | 103.73 (13) |
N1—C2—H2 | 124.7 | N4i—Li1—N1 | 104.66 (13) |
C2—C3—N2 | 105.76 (15) | C1—N1—C2 | 104.69 (13) |
C2—C3—H3 | 127.1 | C1—N1—Li1 | 121.03 (14) |
N2—C3—H3 | 127.1 | C2—N1—Li1 | 134.20 (13) |
N4—C4—N3 | 112.12 (14) | C1—N2—C3 | 107.11 (13) |
N4—C4—H4 | 123.9 | C1—N2—C7 | 125.78 (14) |
N3—C4—H4 | 123.9 | C3—N2—C7 | 127.11 (15) |
C6—C5—N3 | 105.70 (15) | C4—N3—C5 | 106.63 (13) |
C6—C5—H5 | 127.2 | C4—N3—C7 | 127.12 (14) |
N3—C5—H5 | 127.2 | C5—N3—C7 | 126.22 (14) |
C5—C6—N4 | 111.07 (14) | C4—N4—C6 | 104.48 (14) |
C5—C6—H6 | 124.5 | C4—N4—Li1ii | 137.92 (14) |
N4—C6—H6 | 124.5 | C6—N4—Li1ii | 115.97 (13) |
N3—C7—N2 | 112.83 (12) | Li1—O1—H1W | 130 (2) |
N3—C7—H7A | 109.0 | Li1—O1—H2W | 118.7 (17) |
N2—C7—H7A | 109.0 | H1W—O1—H2W | 105 (3) |
N3—C7—H7B | 109.0 | Li1—O2—H3W | 129.5 (18) |
N2—C7—H7B | 109.0 | Li1—O2—H4W | 117.5 (19) |
H7A—C7—H7B | 107.8 | H3W—O2—H4W | 102 (2) |
N1—C2—C3—N2 | 0.5 (2) | C2—C3—N2—C1 | −0.41 (18) |
N3—C5—C6—N4 | −0.2 (2) | C2—C3—N2—C7 | 179.65 (15) |
N2—C1—N1—C2 | 0.13 (17) | N3—C7—N2—C1 | 101.44 (18) |
N2—C1—N1—Li1 | 177.35 (12) | N3—C7—N2—C3 | −78.6 (2) |
C3—C2—N1—C1 | −0.39 (19) | N4—C4—N3—C5 | 0.27 (17) |
C3—C2—N1—Li1 | −177.07 (15) | N4—C4—N3—C7 | −177.63 (12) |
O2—Li1—N1—C1 | 13.56 (19) | C6—C5—N3—C4 | −0.06 (19) |
O1—Li1—N1—C1 | −108.73 (15) | C6—C5—N3—C7 | 177.86 (14) |
N4i—Li1—N1—C1 | 129.70 (14) | N2—C7—N3—C4 | −104.58 (18) |
O2—Li1—N1—C2 | −170.19 (16) | N2—C7—N3—C5 | 77.9 (2) |
O1—Li1—N1—C2 | 67.5 (2) | N3—C4—N4—C6 | −0.35 (17) |
N4i—Li1—N1—C2 | −54.1 (2) | N3—C4—N4—Li1ii | 163.57 (15) |
N1—C1—N2—C3 | 0.18 (17) | C5—C6—N4—C4 | 0.3 (2) |
N1—C1—N2—C7 | −179.88 (13) | C5—C6—N4—Li1ii | −167.78 (15) |
Symmetry codes: (i) x+1/2, y−1/2, z; (ii) x−1/2, y+1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1W···Cl1iii | 0.72 (3) | 2.54 (3) | 3.2394 (17) | 165 (3) |
O1—H2W···Cl1 | 0.87 (3) | 2.31 (3) | 3.1769 (17) | 173 (2) |
O2—H3W···Cl1iv | 0.93 (3) | 2.25 (3) | 3.1766 (16) | 174 (3) |
O2—H4W···Cl1v | 0.85 (3) | 2.31 (3) | 3.1631 (17) | 174 (3) |
C1—H1···Cl1iv | 0.93 | 2.74 | 3.6726 (17) | 177 |
Symmetry codes: (iii) −x+1/2, −y+3/2, −z; (iv) −x+1/2, y+1/2, −z+1/2; (v) x+1/2, −y+3/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Li(C7H8N4)(H2O)2]Cl |
Mr | 226.60 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 295 |
a, b, c (Å) | 15.3208 (13), 10.6729 (9), 14.8266 (12) |
β (°) | 111.887 (2) |
V (Å3) | 2249.7 (3) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.32 |
Crystal size (mm) | 0.35 × 0.25 × 0.25 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.837, 0.922 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6383, 2310, 2005 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.126, 1.07 |
No. of reflections | 2310 |
No. of parameters | 153 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.30, −0.28 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.
C1—N1 | 1.312 (2) | Li1—N4i | 2.070 (3) |
C4—N4 | 1.305 (2) | Li1—N1 | 2.114 (3) |
Li1—O2 | 1.926 (3) | N4—Li1ii | 2.070 (3) |
Li1—O1 | 1.929 (3) | ||
O2—Li1—O1 | 115.43 (15) | O1—Li1—N1 | 103.73 (13) |
O2—Li1—N4i | 109.63 (14) | N4i—Li1—N1 | 104.66 (13) |
O1—Li1—N4i | 115.59 (14) | C4—N4—Li1ii | 137.92 (14) |
O2—Li1—N1 | 106.61 (13) | C6—N4—Li1ii | 115.97 (13) |
Symmetry codes: (i) x+1/2, y−1/2, z; (ii) x−1/2, y+1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1W···Cl1iii | 0.72 (3) | 2.54 (3) | 3.2394 (17) | 165 (3) |
O1—H2W···Cl1 | 0.87 (3) | 2.31 (3) | 3.1769 (17) | 173 (2) |
O2—H3W···Cl1iv | 0.93 (3) | 2.25 (3) | 3.1766 (16) | 174 (3) |
O2—H4W···Cl1v | 0.85 (3) | 2.31 (3) | 3.1631 (17) | 174 (3) |
C1—H1···Cl1iv | 0.93 | 2.74 | 3.6726 (17) | 177.2 |
Symmetry codes: (iii) −x+1/2, −y+3/2, −z; (iv) −x+1/2, y+1/2, −z+1/2; (v) x+1/2, −y+3/2, z+1/2. |
The design and synthesis of superfunctional coordination polymers have been increased due to their intriguing architectures and flexible bridging ligands in supramolecular chemistry (Kitagawa et al., 2004). The metal coordination architectures with the various heterocyclic aromatic compounds containing S–, N–, and O–donors are of diverse structural types. Significant progress has been achieved by Duncan et al. (1996), Cui et al. (2005) and others in this area. The formation of lithium coordination frameworks constructed from flexible N,N'–(1,1'–methyl)bis(imidazole) ligands and the exploitation of new synthetic methods are still less investigated. The selected N,N'–(1,1'–methyl)bis(imidazole) organic ligand with the N–hetero aromatic ring system could be a metal atom linker forming polymeric structure. The title compound (I) (Fig. 1) reveals tetrahedrally coordinated Li + cations interlinked by (imidazol–1–yl)methane into polymer structure connected by O—H···Cl- hydrogen bonds (Fig. 2, Table 1).