Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807030607/tk2166sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807030607/tk2166Isup2.hkl |
CCDC reference: 655592
The raw diffraction measurements of the original study by Niu et al. (2006) were kindly provided by the senior author. In the rerefinement, the raw data were processed by using a multi-scan absorption correction program (Sheldrick, 1996) in which a model with heavy atoms was assumed.
The DMSO is disordered about a mirror plane; the two S—C distances were restrained to be within 0.01 Å of each other.
All H atoms were generated geometrically (O—H 0.82 and C—H 0.93 to 0.97 Å), and were included in the refinement in the riding model approximation, with U(H) set to 1.2–1.5Ueq(C,O).
The final difference Fourier map had only one peak larger than 1 eA-3, at 3.5 Å from H1, but was otherwise featureless. This peak at (0.482, 0.167, 0.145) is 2.2 Å from its symmetry-related peak.
There is no solvent in the solvent-accessible voids other than the disordered DMSO. The original paper by Niu et al. (2006) had formulated the compound (C14H16N2O2)CuI.DMSO.CH3OH.H2O0.25 although the authors did not mention the use of methanol in the synthesis. The present methanol- and water-free formulation is supported by the calculated CH&N percentages (compared with found percentages given in the study) of C 37.26 (37.47), H 4.44 (4.19) and N 5.5 (5.30).
Furthermore, the authors probably used racemic 2,3-di(4-pyridyl)-2,3-butanediol instead of the meso compound in their synthesis as the ligand lies about a center-of-inversion instead of a mirror plane in the crystal structure.
The crystal structure of (C14H16N2O2)CuI.DMSO was originally refined as a monohydrate; the water molecule is disordered over two positions, and each was refined with quarter site occupacy (Niu et al., 2006). Further, the (C14H16N2O2)CuI.DMSO.H2O formula, as given in the CIF, differs from the (C14H16N2O2)CuI.DMSO.CH3OH.(H2O)0.25 given in the publication. Moreover, the study did not mention the use of methanol in the synthesis (Niu et al., 2006). The discrepancy between the formula given in the cif and that presented in the communication promted the present rerefinement. When the structure was refined without water and methanol, the formula corresponded with the formula expected from the reported CH&N elemental percentages (Niu et al., 2006).
The crystal structure has a void of 29% as calculated by PLATON (Spek, 2003). With the exclusion of the DMSO molecules from the calcuation, the void is increased to 53%, so that the compound can be described as being somewhat porous. The layer itself exhibits a flat honeycomb motif. Figure 2 depicts the motif for which the copper atoms are represented as nodes. The DMSO molecules occupy the spaces inside the layer as they interact through H atoms bonds [O···O 2.77 (1) Å].
[CuI(C14H16N2O2)].DMSO was originally incorrectly refined as [CuI(C14H16N2O2)].DMSO.H2O; see the CIF deposited by Niu et al. (2006). Their communication misrepresented the compound as [CuI(C14H16N2O2)].DMSO.CH3OH.0.25H2O.
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) and PLATON (Spek, 2003); molecular graphics: X-SEED (Barbour, 2001) and OLEX (Dolomanov et al., 2003); software used to prepare material for publication: publCIF (Westrip, 2007).
[CuI(C14H16N2O2)]·C2H6OS | F(000) = 1016 |
Mr = 512.86 | Dx = 1.328 Mg m−3 |
Monoclinic, C2/m | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2y | Cell parameters from 4414 reflections |
a = 19.122 (1) Å | θ = 2.6–28.4° |
b = 18.499 (1) Å | µ = 2.15 mm−1 |
c = 7.2538 (4) Å | T = 291 K |
β = 91.424 (1)° | Block, light yellow |
V = 2565.1 (2) Å3 | 0.37 × 0.25 × 0.22 mm |
Z = 4 |
Bruker APEX2 diffractometer | 3012 independent reflections |
Radiation source: fine-focus sealed tube | 2601 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.014 |
φ and ω scans | θmax = 27.5°, θmin = 2.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −24→22 |
Tmin = 0.501, Tmax = 0.649 | k = −23→16 |
7562 measured reflections | l = −9→8 |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.184 | H-atom parameters constrained |
S = 1.10 | w = 1/[σ2(Fo2) + (0.1259P)2 + 4.989P] where P = (Fo2 + 2Fc2)/3 |
3012 reflections | (Δ/σ)max = 0.001 |
130 parameters | Δρmax = 1.27 e Å−3 |
1 restraint | Δρmin = −0.52 e Å−3 |
[CuI(C14H16N2O2)]·C2H6OS | V = 2565.1 (2) Å3 |
Mr = 512.86 | Z = 4 |
Monoclinic, C2/m | Mo Kα radiation |
a = 19.122 (1) Å | µ = 2.15 mm−1 |
b = 18.499 (1) Å | T = 291 K |
c = 7.2538 (4) Å | 0.37 × 0.25 × 0.22 mm |
β = 91.424 (1)° |
Bruker APEX2 diffractometer | 3012 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2601 reflections with I > 2σ(I) |
Tmin = 0.501, Tmax = 0.649 | Rint = 0.014 |
7562 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 1 restraint |
wR(F2) = 0.184 | H-atom parameters constrained |
S = 1.10 | Δρmax = 1.27 e Å−3 |
3012 reflections | Δρmin = −0.52 e Å−3 |
130 parameters |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
I1 | 0.42163 (2) | 0.5000 | 1.23186 (6) | 0.0491 (2) | |
Cu1 | 0.5000 | 0.42451 (5) | 1.0000 | 0.0501 (3) | |
S1 | 0.2536 (3) | 0.0590 (2) | 0.0681 (8) | 0.104 (1) | 0.50 |
O1 | 0.3145 (3) | 0.2268 (3) | 0.3303 (6) | 0.079 (1) | |
O2 | 0.3108 (7) | 0.0914 (8) | 0.167 (2) | 0.132 (5) | 0.50 |
N1 | 0.4296 (2) | 0.3634 (2) | 0.8486 (5) | 0.051 (1) | |
C1 | 0.3357 (3) | 0.2772 (4) | 0.6314 (8) | 0.064 (1) | |
C2 | 0.3343 (4) | 0.2783 (4) | 0.8263 (8) | 0.075 (2) | |
C3 | 0.3819 (3) | 0.3202 (4) | 0.9252 (7) | 0.064 (2) | |
C4 | 0.4282 (3) | 0.3658 (4) | 0.6656 (8) | 0.067 (2) | |
C5 | 0.3825 (4) | 0.3243 (5) | 0.5539 (8) | 0.082 (2) | |
C6 | 0.2850 (3) | 0.2308 (4) | 0.5105 (8) | 0.066 (2) | |
C7 | 0.2775 (4) | 0.1568 (4) | 0.5977 (11) | 0.079 (2) | |
C8 | 0.2060 (8) | 0.001 (2) | 0.218 (2) | 0.110 (6) | |
C9 | 0.290 (1) | −0.011 (2) | −0.071 (4) | 0.16 (1) | 0.50 |
H1 | 0.3021 | 0.1890 | 0.2800 | 0.119* | |
H2 | 0.3014 | 0.2509 | 0.8878 | 0.091* | |
H3 | 0.3807 | 0.3185 | 1.0532 | 0.077* | |
H4 | 0.4592 | 0.3967 | 0.6082 | 0.080* | |
H5 | 0.3839 | 0.3287 | 0.4263 | 0.098* | |
H7a | 0.3226 | 0.1341 | 0.6081 | 0.119* | |
H7b | 0.2469 | 0.1275 | 0.5220 | 0.119* | |
H7c | 0.2583 | 0.1618 | 0.7180 | 0.119* | |
H8a | 0.1824 | 0.0302 | 0.3075 | 0.165* | 0.50 |
H8b | 0.2378 | −0.0312 | 0.2802 | 0.165* | 0.50 |
H8c | 0.1721 | −0.0259 | 0.1471 | 0.165* | 0.50 |
H9a | 0.3228 | 0.0105 | −0.1542 | 0.243* | 0.50 |
H9b | 0.2535 | −0.0343 | −0.1406 | 0.243* | 0.50 |
H9c | 0.3140 | −0.0451 | 0.0067 | 0.243* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.0485 (3) | 0.0563 (3) | 0.0423 (3) | 0.000 | −0.00370 (19) | 0.000 |
Cu1 | 0.0469 (5) | 0.0587 (5) | 0.0439 (5) | 0.000 | −0.0162 (3) | 0.000 |
S1 | 0.110 (3) | 0.076 (2) | 0.125 (4) | 0.003 (2) | −0.011 (3) | −0.032 (3) |
O1 | 0.078 (3) | 0.099 (3) | 0.060 (2) | −0.027 (3) | 0.002 (2) | −0.027 (2) |
O2 | 0.11 (1) | 0.12 (1) | 0.17 (1) | −0.025 (8) | 0.005 (9) | −0.07 (1) |
N1 | 0.050 (2) | 0.062 (2) | 0.041 (2) | −0.009 (2) | −0.012 (2) | −0.003 (2) |
C1 | 0.068 (3) | 0.076 (4) | 0.048 (3) | −0.021 (3) | −0.013 (2) | −0.001 (3) |
C2 | 0.079 (4) | 0.103 (5) | 0.044 (3) | −0.046 (4) | −0.015 (3) | 0.015 (3) |
C3 | 0.070 (3) | 0.084 (4) | 0.037 (2) | −0.021 (3) | −0.012 (2) | 0.006 (2) |
C4 | 0.069 (3) | 0.088 (4) | 0.043 (3) | −0.033 (3) | −0.005 (2) | −0.001 (3) |
C5 | 0.089 (4) | 0.118 (6) | 0.037 (2) | −0.056 (4) | −0.010 (3) | 0.001 (3) |
C6 | 0.072 (4) | 0.069 (3) | 0.057 (3) | −0.020 (3) | −0.007 (3) | −0.001 (3) |
C7 | 0.085 (4) | 0.061 (3) | 0.090 (5) | −0.018 (3) | −0.031 (4) | 0.001 (3) |
C8 | 0.12 (1) | 0.11 (1) | 0.10 (1) | 0.01 (5) | −0.037 (9) | −0.02 (5) |
C9 | 0.11 (1) | 0.17 (3) | 0.21 (2) | −0.02 (2) | 0.02 (1) | −0.13 (3) |
Cu1—N1 | 2.055 (4) | S1—C8 | 1.79 (2) |
Cu1—I1 | 2.6739 (6) | S1—C9 | 1.79 (2) |
Cu1—N1i | 2.055 (4) | O1—H1 | 0.82 |
Cu1—I1ii | 2.6738 (6) | C2—H2 | 0.93 |
Cu1—Cu1ii | 2.793 (2) | C3—H3 | 0.93 |
O1—C6 | 1.438 (8) | C4—H4 | 0.93 |
N1—C4 | 1.328 (7) | C5—H5 | 0.93 |
N1—C3 | 1.343 (7) | C7—H7a | 0.96 |
C1—C5 | 1.378 (8) | C7—H7b | 0.96 |
C1—C2 | 1.415 (8) | C7—H7c | 0.96 |
C1—C6 | 1.551 (7) | C8—H8a | 0.96 |
C2—C3 | 1.382 (8) | C8—H8b | 0.96 |
C4—C5 | 1.404 (7) | C8—H8c | 0.96 |
C6—C7 | 1.517 (9) | C9—H9a | 0.96 |
C6—C6iii | 1.52 (1) | C9—H9b | 0.96 |
S1—O2 | 1.43 (1) | C9—H9c | 0.96 |
Cu1—I1—Cu1ii | 62.97 (3) | C6—O1—H1 | 109.5 |
N1—Cu1—N1i | 113.2 (3) | C3—C2—H2 | 120.1 |
N1—Cu1—I1 | 104.7 (1) | C1—C2—H2 | 120.1 |
N1—Cu1—I1ii | 108.7 (1) | N1—C3—H3 | 117.8 |
N1i—Cu1—I1ii | 104.7 (1) | C2—C3—H3 | 117.8 |
N1i—Cu1—I1 | 108.7 (1) | N1—C4—H4 | 118.1 |
I1—Cu1—I1ii | 117.03 (3) | C5—C4—H4 | 118.1 |
N1—Cu1—Cu1ii | 123.4 (1) | C1—C5—H5 | 119.7 |
I1—Cu1—Cu1ii | 58.52 (2) | C4—C5—H5 | 119.7 |
C4—N1—C3 | 115.9 (4) | C6—C7—H7a | 109.5 |
C4—N1—Cu1 | 120.8 (4) | C6—C7—H7b | 109.5 |
C3—N1—Cu1 | 123.3 (3) | H7a—C7—H7b | 109.5 |
C5—C1—C2 | 115.3 (5) | C6—C7—H7c | 109.5 |
C5—C1—C6 | 121.5 (5) | H7a—C7—H7c | 109.5 |
C2—C1—C6 | 123.0 (5) | H7b—C7—H7c | 109.5 |
C3—C2—C1 | 119.8 (5) | S1—C8—H8a | 109.5 |
N1—C3—C2 | 124.3 (5) | S1—C8—H8b | 109.5 |
N1—C4—C5 | 123.7 (5) | H8a—C8—H8b | 109.5 |
C1—C5—C4 | 120.7 (5) | S1—C8—H8c | 109.5 |
O1—C6—C7 | 112.0 (6) | H8a—C8—H8c | 109.5 |
O1—C6—C6iii | 107.3 (6) | H8b—C8—H8c | 109.5 |
C7—C6—C6iii | 111.8 (6) | S1—C9—H9a | 109.5 |
O1—C6—C1 | 106.8 (5) | S1—C9—H9b | 109.5 |
C7—C6—C1 | 109.2 (5) | H9a—C9—H9b | 109.5 |
C6iii—C6—C1 | 109.6 (7) | S1—C9—H9c | 109.5 |
O2—S1—C8 | 110 (1) | H9a—C9—H9c | 109.5 |
O2—S1—C9 | 106.3 (8) | H9b—C9—H9c | 109.5 |
C8—S1—C9 | 97 (2) | ||
Cu1ii—I1—Cu1—N1 | −120.5 (1) | Cu1—N1—C3—C2 | −179.6 (6) |
Cu1ii—I1—Cu1—N1i | 118.3 (1) | C1—C2—C3—N1 | 2 (1) |
Cu1ii—I1—Cu1—I1ii | 0.0 | C3—N1—C4—C5 | −3 (1) |
N1i—Cu1—N1—C4 | −116.2 (5) | Cu1—N1—C4—C5 | 178.6 (6) |
I1ii—Cu1—N1—C4 | −0.3 (5) | C2—C1—C5—C4 | 4 (1) |
I1—Cu1—N1—C4 | 125.5 (5) | C6—C1—C5—C4 | −179.8 (7) |
Cu1ii—Cu1—N1—C4 | 63.8 (5) | N1—C4—C5—C1 | −0.4 (13) |
N1i—Cu1—N1—C3 | 65.3 (5) | C5—C1—C6—O1 | 21.1 (9) |
I1ii—Cu1—N1—C3 | −178.8 (5) | C2—C1—C6—O1 | −163.4 (7) |
I1—Cu1—N1—C3 | −53.0 (5) | C5—C1—C6—C7 | 142.4 (8) |
Cu1ii—Cu1—N1—C3 | −114.7 (5) | C2—C1—C6—C7 | −42.1 (9) |
C5—C1—C2—C3 | −5 (1) | C5—C1—C6—C6iii | −94.8 (9) |
C6—C1—C2—C3 | 179.0 (7) | C2—C1—C6—C6iii | 80.7 (9) |
C4—N1—C3—C2 | 1.8 (10) |
Symmetry codes: (i) −x+1, y, −z+2; (ii) −x+1, −y+1, −z+2; (iii) −x+1/2, −y+1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [CuI(C14H16N2O2)]·C2H6OS |
Mr | 512.86 |
Crystal system, space group | Monoclinic, C2/m |
Temperature (K) | 291 |
a, b, c (Å) | 19.122 (1), 18.499 (1), 7.2538 (4) |
β (°) | 91.424 (1) |
V (Å3) | 2565.1 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.15 |
Crystal size (mm) | 0.37 × 0.25 × 0.22 |
Data collection | |
Diffractometer | Bruker APEX2 |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.501, 0.649 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7562, 3012, 2601 |
Rint | 0.014 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.184, 1.10 |
No. of reflections | 3012 |
No. of parameters | 130 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.27, −0.52 |
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997) and PLATON (Spek, 2003), X-SEED (Barbour, 2001) and OLEX (Dolomanov et al., 2003), publCIF (Westrip, 2007).
Cu1—N1 | 2.055 (4) | Cu1—I1 | 2.6739 (6) |
Cu1—I1—Cu1i | 62.97 (3) | N1—Cu1—I1i | 108.7 (1) |
N1—Cu1—N1ii | 113.2 (3) | N1ii—Cu1—I1 | 108.7 (1) |
N1—Cu1—I1 | 104.7 (1) |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, y, −z+2. |
The crystal structure of (C14H16N2O2)CuI.DMSO was originally refined as a monohydrate; the water molecule is disordered over two positions, and each was refined with quarter site occupacy (Niu et al., 2006). Further, the (C14H16N2O2)CuI.DMSO.H2O formula, as given in the CIF, differs from the (C14H16N2O2)CuI.DMSO.CH3OH.(H2O)0.25 given in the publication. Moreover, the study did not mention the use of methanol in the synthesis (Niu et al., 2006). The discrepancy between the formula given in the cif and that presented in the communication promted the present rerefinement. When the structure was refined without water and methanol, the formula corresponded with the formula expected from the reported CH&N elemental percentages (Niu et al., 2006).
The crystal structure has a void of 29% as calculated by PLATON (Spek, 2003). With the exclusion of the DMSO molecules from the calcuation, the void is increased to 53%, so that the compound can be described as being somewhat porous. The layer itself exhibits a flat honeycomb motif. Figure 2 depicts the motif for which the copper atoms are represented as nodes. The DMSO molecules occupy the spaces inside the layer as they interact through H atoms bonds [O···O 2.77 (1) Å].