Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807029583/fj2036sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807029583/fj2036Isup2.hkl |
CCDC reference: 654809
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (C-C) = 0.005 Å
- R factor = 0.050
- wR factor = 0.110
- Data-to-parameter ratio = 12.7
checkCIF/PLATON results
No syntax errors found
Alert level A PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low ....... 0.92
Author Response: Due to a cryostat malfunction, the crystal was lost, and some of the data had to be discarded. We have no more sample, and were fortunate to find even the one small usable crystal. The completeness (92.4%) is only slightly short of Acta standards, and the refined model appears otherwise completely acceptable. |
Alert level C REFLT03_ALERT_3_C Reflection count < 95% complete From the CIF: _diffrn_reflns_theta_max 25.00 From the CIF: _diffrn_reflns_theta_full 25.00 From the CIF: _reflns_number_total 3491 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 3788 Completeness (_total/calc) 92.16% PLAT022_ALERT_3_C Ratio Unique / Expected Reflections too Low .... 0.92 PLAT230_ALERT_2_C Hirshfeld Test Diff for O4 - C10 .. 5.42 su PLAT230_ALERT_2_C Hirshfeld Test Diff for C9 - C10 .. 5.43 su PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C11
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1 (2) 2.25
1 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
Cu2(NBA)2 forms a crystalline solvate with two CHCl3 molecules, in which the Cu···Cu distance is 7.349 (1) Å at room temperature (Maverick et al., 1986) and 7.298 (1) Å at 100 K (Burton et al., 2002). With µ-Dabco (define Dabco?), the Cu···Cu distance is 7.403 (4) Å (Maverick et al., 1986), with µ-2,5-dimethylpyrazine it is 7.559 (2) and 7.596 (2) Å (Maverick et al., 1990), and with µ-2-methylpyrazine it is 7.4801 (8) Å (Maverick et al., 2001). For related literature, see: Martin et al. (1959).
The NBAH2, (2,7-naphthalenediylbis(methylene)bis(acetylacetone)) ligand was prepared previously by the general nucleophilic substitution method outlined by Martin et al. (1959). The Cu2(NBA)2 was also prepared by previously published procedures, see Related Literature section. Bis(3,3'-(naphthalene-2,7-diylbis(methylene)bis(2,4-pentanedionato)))δicopper(µ-1,4-dithiane) was prepared by combining a 5.05 mMolar chloroform solution of Cu2(NBA)2 with a 1.02 Molar chloroform solution of 1,4-dithiane. The resulting mixture was layered with acetonitrile and afforded light blue (turquoise) crystals of Cu2(NBA)2(µ-1,4-dithiane) after standing for 5 days.
H atoms were placed in idealized positions with C—H distances 0.95 - 0.99 Å and thereafter treated as riding. Uiso for H was assigned as 1.2 times Ueq of the attached C atoms (1.5 for methyl). A torsional parameter was refined for each methyl group.
Our group has previously prepared binuclear metal complexes derived from polydentate liands, which have been shown to intramolecularly bind bridging substrate molecules, similar to those produced by several other flexible binucleating macrocycles. This work was undertaken in an attempt to associate and quantify the binding between di-sulfur bases and their previously studied nitrogen analogues, see Related Literature section.
The molecule is centrosymmetric, and inclusion of the 1,4-dithiane molecule organizes the host such that the Cu···Cu distance, 8.130 (1) Å, is longer than in complexes with other guests, see Related Literature section. Several distortions take place in this organization. The Cu2(NBA)2 unit is not rectangular, but slipped such that the four CH2 groups (C6, C17 and their inversion equivalents) form a parallelogram with sides 7.578 (5) and 9.570 (5) Å, and interior angles differing from orthogonality by 2.8 (3)°. This involves a slippage of the coordination planes horizontally by 1.865 (1) Å.
The coordination sphere is square pyramidal, with distances given in the Abstract and geometric details table. The two chelate rings tilt differently from the coordination plane, with Cu1 lying only 0.0131 (5) Å out of the best plane O1/O2/C2/C3/C4, but 0.4416 (5) Å out of the best plane O3/O4/C19/C20/C21. Those two planes form a dihedral angle of 11.2 (4)°. The Cu—S bond is tilted away from O1 and O2 (O—Cu—S angles 98.91 (8) and 96.32 (7)°) and toward O3 and O4 (angles 86.77 (7) and 87.66 (7)°), and forms an angle of 20.15 (5)° with the Cu···Cu vector.
Cu2(NBA)2 forms a crystalline solvate with two CHCl3 molecules, in which the Cu···Cu distance is 7.349 (1) Å at room temperature (Maverick et al., 1986) and 7.298 (1) Å at 100 K (Burton et al., 2002). With µ-Dabco (define Dabco?), the Cu···Cu distance is 7.403 (4) Å (Maverick et al., 1986), with µ-2,5-dimethylpyrazine it is 7.559 (2) and 7.596 (2) Å (Maverick et al., 1990), and with µ-2-methylpyrazine it is 7.4801 (8) Å (Maverick et al., 2001). For related literature, see: Martin et al. (1959).
Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
Fig. 1. Numbering scheme and ellipsoids at the 50% level. H atoms are represented with arbitrary radius. |
[Cu2(C22H22O4)(C4H8S2)] | F(000) = 988 |
Mr = 948.10 | Dx = 1.466 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 6304 reflections |
a = 7.758 (2) Å | θ = 2.5–25.0° |
b = 28.981 (7) Å | µ = 1.14 mm−1 |
c = 9.640 (3) Å | T = 120 K |
β = 97.840 (15)° | Prism, light blue |
V = 2147.1 (10) Å3 | 0.15 × 0.08 × 0.07 mm |
Z = 2 |
Nonius KappaCCD diffractometer with an Oxford Cryosystems Cryostream cooler | 3491 independent reflections |
Radiation source: fine-focus sealed tube | 2598 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
ω scans with κ offsets | θmax = 25.0°, θmin = 2.5° |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | h = −9→9 |
Tmin = 0.878, Tmax = 0.924 | k = −33→34 |
10982 measured reflections | l = −11→11 |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0425P)2 + 2.9798P] where P = (Fo2 + 2Fc2)/3 |
3491 reflections | (Δ/σ)max < 0.001 |
275 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.44 e Å−3 |
[Cu2(C22H22O4)(C4H8S2)] | V = 2147.1 (10) Å3 |
Mr = 948.10 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.758 (2) Å | µ = 1.14 mm−1 |
b = 28.981 (7) Å | T = 120 K |
c = 9.640 (3) Å | 0.15 × 0.08 × 0.07 mm |
β = 97.840 (15)° |
Nonius KappaCCD diffractometer with an Oxford Cryosystems Cryostream cooler | 3491 independent reflections |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | 2598 reflections with I > 2σ(I) |
Tmin = 0.878, Tmax = 0.924 | Rint = 0.046 |
10982 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.30 e Å−3 |
3491 reflections | Δρmin = −0.44 e Å−3 |
275 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 | ||
Cu1 | 0.88337 (6) | 0.458966 (15) | 0.80517 (5) | 0.02939 (16) | |
S1 | 0.66505 (12) | 0.46085 (3) | 0.54758 (10) | 0.0331 (3) | |
O1 | 1.0347 (3) | 0.50850 (8) | 0.7737 (2) | 0.0290 (6) | |
O2 | 0.7427 (3) | 0.49798 (8) | 0.9033 (2) | 0.0291 (6) | |
O3 | 0.2550 (3) | 0.59178 (8) | 0.1455 (2) | 0.0300 (6) | |
O4 | −0.0323 (3) | 0.58236 (8) | 0.2801 (2) | 0.0291 (6) | |
C1 | 1.1720 (4) | 0.58089 (13) | 0.7810 (4) | 0.0356 (10) | |
H1A | 1.2465 | 0.5895 | 0.8676 | 0.053* | |
H1B | 1.1232 | 0.6088 | 0.7336 | 0.053* | |
H1C | 1.2411 | 0.5642 | 0.7194 | 0.053* | |
C2 | 1.0269 (5) | 0.55050 (12) | 0.8153 (4) | 0.0289 (9) | |
C3 | 0.8971 (4) | 0.56851 (12) | 0.8897 (4) | 0.0280 (9) | |
C4 | 0.7629 (4) | 0.54102 (13) | 0.9297 (4) | 0.0285 (9) | |
C5 | 0.6320 (4) | 0.56102 (12) | 1.0147 (4) | 0.0340 (10) | |
H5A | 0.5341 | 0.5396 | 1.0141 | 0.051* | |
H5B | 0.5897 | 0.5906 | 0.9740 | 0.051* | |
H5C | 0.6871 | 0.5659 | 1.1112 | 0.051* | |
C6 | 0.9059 (4) | 0.61985 (11) | 0.9282 (4) | 0.0293 (9) | |
H6A | 0.8458 | 0.6243 | 1.0114 | 0.035* | |
H6B | 1.0296 | 0.6282 | 0.9556 | 0.035* | |
C7 | 0.3945 (5) | 0.66348 (12) | 0.1506 (4) | 0.0393 (10) | |
H7A | 0.5020 | 0.6625 | 0.2171 | 0.059* | |
H7B | 0.3499 | 0.6951 | 0.1435 | 0.059* | |
H7C | 0.4187 | 0.6531 | 0.0585 | 0.059* | |
C8 | 0.2612 (4) | 0.63233 (13) | 0.2010 (4) | 0.0296 (9) | |
C9 | 0.1539 (4) | 0.64831 (12) | 0.2977 (4) | 0.0257 (9) | |
C10 | 0.0089 (4) | 0.62301 (13) | 0.3266 (4) | 0.0294 (9) | |
C11 | −0.1178 (5) | 0.64297 (13) | 0.4144 (4) | 0.0398 (10) | |
H11A | −0.2097 | 0.6204 | 0.4234 | 0.060* | |
H11B | −0.1695 | 0.6710 | 0.3699 | 0.060* | |
H11C | −0.0570 | 0.6505 | 0.5076 | 0.060* | |
C12 | 0.1908 (4) | 0.69621 (12) | 0.3596 (4) | 0.0317 (9) | |
H12A | 0.1820 | 0.7187 | 0.2817 | 0.038* | |
H12B | 0.0985 | 0.7039 | 0.4173 | 0.038* | |
C13 | 0.8278 (4) | 0.65323 (12) | 0.8151 (4) | 0.0282 (9) | |
C14 | 0.9166 (5) | 0.69515 (11) | 0.7956 (4) | 0.0317 (9) | |
H14 | 1.0252 | 0.7011 | 0.8511 | 0.038* | |
C15 | 0.8490 (5) | 0.72711 (12) | 0.6989 (4) | 0.0324 (9) | |
H15 | 0.9119 | 0.7547 | 0.6881 | 0.039* | |
C16 | 0.6881 (4) | 0.71991 (12) | 0.6148 (4) | 0.0285 (9) | |
C17 | 0.6175 (4) | 0.75160 (12) | 0.5128 (4) | 0.0305 (9) | |
H17 | 0.6788 | 0.7793 | 0.4998 | 0.037* | |
C18 | 0.4621 (5) | 0.74330 (12) | 0.4318 (4) | 0.0323 (9) | |
H18 | 0.4176 | 0.7652 | 0.3626 | 0.039* | |
C19 | 0.3664 (4) | 0.70273 (12) | 0.4493 (4) | 0.0288 (9) | |
C20 | 0.4350 (4) | 0.67094 (12) | 0.5462 (4) | 0.0285 (9) | |
H20 | 0.3729 | 0.6432 | 0.5565 | 0.034* | |
C21 | 0.5968 (4) | 0.67833 (12) | 0.6320 (4) | 0.0271 (9) | |
C22 | 0.6716 (4) | 0.64566 (12) | 0.7320 (4) | 0.0303 (9) | |
H22 | 0.6117 | 0.6175 | 0.7420 | 0.036* | |
C23 | 0.4616 (5) | 0.46546 (13) | 0.6187 (4) | 0.0360 (10) | |
H23A | 0.4343 | 0.4351 | 0.6577 | 0.043* | |
H23B | 0.4763 | 0.4879 | 0.6968 | 0.043* | |
C24 | 0.6918 (5) | 0.51949 (12) | 0.4876 (4) | 0.0369 (10) | |
H24A | 0.7030 | 0.5407 | 0.5688 | 0.044* | |
H24B | 0.8002 | 0.5215 | 0.4444 | 0.044* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0288 (3) | 0.0309 (3) | 0.0285 (3) | −0.0002 (2) | 0.00385 (19) | −0.0009 (2) |
S1 | 0.0315 (6) | 0.0372 (6) | 0.0301 (6) | 0.0030 (5) | 0.0023 (4) | 0.0026 (5) |
O1 | 0.0273 (14) | 0.0293 (15) | 0.0310 (16) | −0.0012 (11) | 0.0069 (11) | −0.0013 (12) |
O2 | 0.0309 (15) | 0.0271 (15) | 0.0299 (16) | −0.0005 (11) | 0.0066 (12) | −0.0040 (13) |
O3 | 0.0332 (15) | 0.0310 (15) | 0.0260 (16) | −0.0016 (12) | 0.0053 (12) | −0.0006 (12) |
O4 | 0.0316 (14) | 0.0269 (14) | 0.0281 (15) | 0.0012 (12) | 0.0008 (12) | −0.0017 (13) |
C1 | 0.036 (2) | 0.038 (2) | 0.034 (2) | −0.0012 (19) | 0.0103 (19) | −0.004 (2) |
C2 | 0.026 (2) | 0.036 (2) | 0.022 (2) | 0.0000 (18) | −0.0056 (17) | 0.0004 (19) |
C3 | 0.025 (2) | 0.033 (2) | 0.025 (2) | 0.0034 (18) | 0.0019 (17) | −0.0008 (19) |
C4 | 0.030 (2) | 0.034 (2) | 0.019 (2) | 0.003 (2) | −0.0028 (16) | −0.001 (2) |
C5 | 0.030 (2) | 0.036 (2) | 0.036 (2) | 0.0006 (18) | 0.0068 (19) | −0.001 (2) |
C6 | 0.030 (2) | 0.031 (2) | 0.026 (2) | −0.0019 (17) | 0.0003 (17) | −0.0024 (19) |
C7 | 0.044 (3) | 0.034 (2) | 0.041 (3) | −0.0044 (19) | 0.011 (2) | 0.001 (2) |
C8 | 0.031 (2) | 0.033 (2) | 0.023 (2) | −0.0018 (18) | −0.0048 (18) | 0.0065 (19) |
C9 | 0.022 (2) | 0.026 (2) | 0.027 (2) | 0.0017 (17) | −0.0013 (17) | 0.0027 (18) |
C10 | 0.030 (2) | 0.038 (2) | 0.018 (2) | 0.0090 (19) | −0.0032 (17) | 0.0033 (19) |
C11 | 0.037 (2) | 0.041 (2) | 0.043 (3) | −0.004 (2) | 0.010 (2) | −0.002 (2) |
C12 | 0.032 (2) | 0.029 (2) | 0.034 (2) | 0.0052 (17) | 0.0032 (18) | 0.0004 (19) |
C13 | 0.030 (2) | 0.030 (2) | 0.025 (2) | −0.0011 (18) | 0.0009 (18) | −0.0041 (19) |
C14 | 0.036 (2) | 0.026 (2) | 0.031 (2) | −0.0062 (19) | −0.0021 (19) | −0.005 (2) |
C15 | 0.038 (2) | 0.027 (2) | 0.032 (2) | −0.0063 (18) | 0.0036 (19) | −0.005 (2) |
C16 | 0.027 (2) | 0.032 (2) | 0.025 (2) | 0.0016 (19) | 0.0014 (18) | 0.0009 (19) |
C17 | 0.031 (2) | 0.027 (2) | 0.034 (2) | −0.0059 (18) | 0.0080 (19) | 0.001 (2) |
C18 | 0.036 (2) | 0.031 (2) | 0.029 (2) | 0.0044 (19) | 0.0024 (19) | 0.0053 (19) |
C19 | 0.030 (2) | 0.030 (2) | 0.026 (2) | 0.0016 (18) | 0.0029 (18) | −0.0034 (19) |
C20 | 0.031 (2) | 0.024 (2) | 0.030 (2) | −0.0033 (17) | 0.0058 (19) | −0.0018 (19) |
C21 | 0.031 (2) | 0.024 (2) | 0.025 (2) | 0.0025 (17) | 0.0016 (18) | −0.0039 (18) |
C22 | 0.038 (2) | 0.024 (2) | 0.029 (2) | −0.0057 (18) | 0.0058 (19) | −0.0019 (19) |
C23 | 0.033 (2) | 0.043 (2) | 0.032 (2) | −0.005 (2) | 0.0045 (18) | 0.008 (2) |
C24 | 0.035 (2) | 0.043 (2) | 0.033 (2) | −0.0076 (19) | 0.0058 (19) | 0.001 (2) |
Cu1—O1 | 1.905 (2) | C9—C10 | 1.402 (5) |
Cu1—O2 | 1.910 (2) | C9—C12 | 1.523 (5) |
Cu1—O3i | 1.918 (2) | C10—C11 | 1.499 (5) |
Cu1—O4i | 1.925 (2) | C11—H11A | 0.9800 |
Cu1—S1 | 2.8088 (10) | C11—H11B | 0.9800 |
S1—C23 | 1.809 (4) | C11—H11C | 0.9800 |
S1—C24 | 1.816 (4) | C12—C19 | 1.522 (5) |
O1—C2 | 1.286 (4) | C12—H12A | 0.9900 |
O2—C4 | 1.278 (4) | C12—H12B | 0.9900 |
O3—C8 | 1.289 (4) | C13—C22 | 1.376 (5) |
O3—Cu1i | 1.918 (2) | C13—C14 | 1.422 (5) |
O4—C10 | 1.285 (4) | C14—C15 | 1.367 (5) |
O4—Cu1i | 1.925 (2) | C14—H14 | 0.9500 |
C1—C2 | 1.502 (5) | C15—C16 | 1.408 (5) |
C1—H1A | 0.9800 | C15—H15 | 0.9500 |
C1—H1B | 0.9800 | C16—C17 | 1.401 (5) |
C1—H1C | 0.9800 | C16—C21 | 1.419 (5) |
C2—C3 | 1.413 (5) | C17—C18 | 1.365 (5) |
C3—C4 | 1.406 (5) | C17—H17 | 0.9500 |
C3—C6 | 1.533 (5) | C18—C19 | 1.413 (5) |
C4—C5 | 1.505 (4) | C18—H18 | 0.9500 |
C5—H5A | 0.9800 | C19—C20 | 1.367 (5) |
C5—H5B | 0.9800 | C20—C21 | 1.422 (5) |
C5—H5C | 0.9800 | C20—H20 | 0.9500 |
C6—C13 | 1.520 (5) | C21—C22 | 1.418 (5) |
C6—H6A | 0.9900 | C22—H22 | 0.9500 |
C6—H6B | 0.9900 | C23—C24i | 1.525 (5) |
C7—C8 | 1.502 (5) | C23—H23A | 0.9900 |
C7—H7A | 0.9800 | C23—H23B | 0.9900 |
C7—H7B | 0.9800 | C24—C23i | 1.525 (5) |
C7—H7C | 0.9800 | C24—H24A | 0.9900 |
C8—C9 | 1.410 (5) | C24—H24B | 0.9900 |
O1—Cu1—O2 | 92.23 (10) | O4—C10—C11 | 113.5 (3) |
O1—Cu1—O3i | 174.31 (10) | C9—C10—C11 | 121.1 (3) |
O2—Cu1—O3i | 87.38 (10) | C10—C11—H11A | 109.5 |
O1—Cu1—O4i | 88.97 (10) | C10—C11—H11B | 109.5 |
O2—Cu1—O4i | 175.62 (10) | H11A—C11—H11B | 109.5 |
O3i—Cu1—O4i | 91.01 (10) | C10—C11—H11C | 109.5 |
O1—Cu1—S1 | 98.91 (8) | H11A—C11—H11C | 109.5 |
O2—Cu1—S1 | 96.32 (7) | H11B—C11—H11C | 109.5 |
O3i—Cu1—S1 | 86.77 (7) | C19—C12—C9 | 116.2 (3) |
O4i—Cu1—S1 | 87.66 (7) | C19—C12—H12A | 108.2 |
C23—S1—C24 | 101.26 (17) | C9—C12—H12A | 108.2 |
C23—S1—Cu1 | 96.79 (13) | C19—C12—H12B | 108.2 |
C24—S1—Cu1 | 102.62 (13) | C9—C12—H12B | 108.2 |
C2—O1—Cu1 | 127.4 (2) | H12A—C12—H12B | 107.4 |
C4—O2—Cu1 | 127.8 (2) | C22—C13—C14 | 117.6 (3) |
C8—O3—Cu1i | 126.0 (2) | C22—C13—C6 | 123.3 (3) |
C10—O4—Cu1i | 125.7 (2) | C14—C13—C6 | 119.1 (3) |
C2—C1—H1A | 109.5 | C15—C14—C13 | 121.4 (3) |
C2—C1—H1B | 109.5 | C15—C14—H14 | 119.3 |
H1A—C1—H1B | 109.5 | C13—C14—H14 | 119.3 |
C2—C1—H1C | 109.5 | C14—C15—C16 | 121.3 (3) |
H1A—C1—H1C | 109.5 | C14—C15—H15 | 119.4 |
H1B—C1—H1C | 109.5 | C16—C15—H15 | 119.4 |
O1—C2—C3 | 125.1 (3) | C17—C16—C15 | 122.5 (3) |
O1—C2—C1 | 114.7 (3) | C17—C16—C21 | 119.0 (3) |
C3—C2—C1 | 120.2 (3) | C15—C16—C21 | 118.4 (3) |
C4—C3—C2 | 122.4 (3) | C18—C17—C16 | 121.0 (3) |
C4—C3—C6 | 119.6 (3) | C18—C17—H17 | 119.5 |
C2—C3—C6 | 118.0 (3) | C16—C17—H17 | 119.5 |
O2—C4—C3 | 125.0 (3) | C17—C18—C19 | 121.1 (3) |
O2—C4—C5 | 114.2 (3) | C17—C18—H18 | 119.5 |
C3—C4—C5 | 120.7 (3) | C19—C18—H18 | 119.5 |
C4—C5—H5A | 109.5 | C20—C19—C18 | 118.7 (3) |
C4—C5—H5B | 109.5 | C20—C19—C12 | 122.6 (3) |
H5A—C5—H5B | 109.5 | C18—C19—C12 | 118.7 (3) |
C4—C5—H5C | 109.5 | C19—C20—C21 | 121.8 (3) |
H5A—C5—H5C | 109.5 | C19—C20—H20 | 119.1 |
H5B—C5—H5C | 109.5 | C21—C20—H20 | 119.1 |
C13—C6—C3 | 116.3 (3) | C22—C21—C16 | 118.8 (3) |
C13—C6—H6A | 108.2 | C22—C21—C20 | 122.8 (3) |
C3—C6—H6A | 108.2 | C16—C21—C20 | 118.4 (3) |
C13—C6—H6B | 108.2 | C13—C22—C21 | 122.4 (3) |
C3—C6—H6B | 108.2 | C13—C22—H22 | 118.8 |
H6A—C6—H6B | 107.4 | C21—C22—H22 | 118.8 |
C8—C7—H7A | 109.5 | C24i—C23—S1 | 114.1 (3) |
C8—C7—H7B | 109.5 | C24i—C23—H23A | 108.7 |
H7A—C7—H7B | 109.5 | S1—C23—H23A | 108.7 |
C8—C7—H7C | 109.5 | C24i—C23—H23B | 108.7 |
H7A—C7—H7C | 109.5 | S1—C23—H23B | 108.7 |
H7B—C7—H7C | 109.5 | H23A—C23—H23B | 107.6 |
O3—C8—C9 | 125.5 (3) | C23i—C24—S1 | 111.7 (3) |
O3—C8—C7 | 113.7 (3) | C23i—C24—H24A | 109.3 |
C9—C8—C7 | 120.7 (3) | S1—C24—H24A | 109.3 |
C10—C9—C8 | 121.4 (3) | C23i—C24—H24B | 109.3 |
C10—C9—C12 | 120.8 (3) | S1—C24—H24B | 109.3 |
C8—C9—C12 | 117.5 (3) | H24A—C24—H24B | 107.9 |
O4—C10—C9 | 125.4 (3) | ||
O1—Cu1—S1—C23 | −125.86 (14) | C12—C9—C10—O4 | −179.5 (3) |
O2—Cu1—S1—C23 | −32.59 (14) | C8—C9—C10—C11 | −171.8 (3) |
O3i—Cu1—S1—C23 | 54.41 (14) | C12—C9—C10—C11 | 2.4 (5) |
O4i—Cu1—S1—C23 | 145.55 (14) | C10—C9—C12—C19 | 121.8 (4) |
O1—Cu1—S1—C24 | −22.68 (15) | C8—C9—C12—C19 | −63.8 (4) |
O2—Cu1—S1—C24 | 70.59 (14) | C3—C6—C13—C22 | 43.2 (5) |
O3i—Cu1—S1—C24 | 157.59 (15) | C3—C6—C13—C14 | −138.7 (3) |
O4i—Cu1—S1—C24 | −111.27 (15) | C22—C13—C14—C15 | 0.5 (5) |
O2—Cu1—O1—C2 | 1.7 (3) | C6—C13—C14—C15 | −177.6 (3) |
O4i—Cu1—O1—C2 | −174.1 (3) | C13—C14—C15—C16 | 0.3 (5) |
S1—Cu1—O1—C2 | 98.4 (3) | C14—C15—C16—C17 | −178.6 (3) |
O1—Cu1—O2—C4 | −0.5 (3) | C14—C15—C16—C21 | −0.3 (5) |
O3i—Cu1—O2—C4 | 173.8 (3) | C15—C16—C17—C18 | 179.2 (3) |
S1—Cu1—O2—C4 | −99.7 (3) | C21—C16—C17—C18 | 0.9 (5) |
Cu1—O1—C2—C3 | −2.6 (5) | C16—C17—C18—C19 | 0.7 (5) |
Cu1—O1—C2—C1 | 176.5 (2) | C17—C18—C19—C20 | −2.1 (5) |
O1—C2—C3—C4 | 1.9 (5) | C17—C18—C19—C12 | 177.8 (3) |
C1—C2—C3—C4 | −177.1 (3) | C9—C12—C19—C20 | −43.3 (5) |
O1—C2—C3—C6 | −178.6 (3) | C9—C12—C19—C18 | 136.8 (3) |
C1—C2—C3—C6 | 2.4 (5) | C18—C19—C20—C21 | 1.9 (5) |
Cu1—O2—C4—C3 | 0.1 (5) | C12—C19—C20—C21 | −178.0 (3) |
Cu1—O2—C4—C5 | −177.7 (2) | C17—C16—C21—C22 | 177.9 (3) |
C2—C3—C4—O2 | −0.6 (6) | C15—C16—C21—C22 | −0.5 (5) |
C6—C3—C4—O2 | 179.9 (3) | C17—C16—C21—C20 | −1.1 (5) |
C2—C3—C4—C5 | 177.1 (3) | C15—C16—C21—C20 | −179.5 (3) |
C6—C3—C4—C5 | −2.4 (5) | C19—C20—C21—C22 | −179.2 (3) |
C4—C3—C6—C13 | −97.4 (4) | C19—C20—C21—C16 | −0.3 (5) |
C2—C3—C6—C13 | 83.1 (4) | C14—C13—C22—C21 | −1.4 (5) |
Cu1i—O3—C8—C9 | −7.1 (5) | C6—C13—C22—C21 | 176.7 (3) |
Cu1i—O3—C8—C7 | 174.3 (2) | C16—C21—C22—C13 | 1.4 (5) |
O3—C8—C9—C10 | −10.2 (6) | C20—C21—C22—C13 | −179.7 (3) |
C7—C8—C9—C10 | 168.3 (3) | C24—S1—C23—C24i | 59.9 (3) |
O3—C8—C9—C12 | 175.4 (3) | Cu1—S1—C23—C24i | 164.3 (2) |
C7—C8—C9—C12 | −6.1 (5) | C23—S1—C24—C23i | −58.2 (3) |
Cu1i—O4—C10—C9 | 14.3 (5) | Cu1—S1—C24—C23i | −157.9 (2) |
Cu1i—O4—C10—C11 | −167.5 (2) | S1—C24—C23i—S1i | 66.0 (3) |
C8—C9—C10—O4 | 6.3 (5) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu2(C22H22O4)(C4H8S2)] |
Mr | 948.10 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 120 |
a, b, c (Å) | 7.758 (2), 28.981 (7), 9.640 (3) |
β (°) | 97.840 (15) |
V (Å3) | 2147.1 (10) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.14 |
Crystal size (mm) | 0.15 × 0.08 × 0.07 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer with an Oxford Cryosystems Cryostream cooler |
Absorption correction | Multi-scan (SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.878, 0.924 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10982, 3491, 2598 |
Rint | 0.046 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.110, 1.06 |
No. of reflections | 3491 |
No. of parameters | 275 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.30, −0.44 |
Computer programs: COLLECT (Nonius, 2000), SCALEPACK (Otwinowski & Minor, 1997), SCALEPACK and DENZO (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97.
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Our group has previously prepared binuclear metal complexes derived from polydentate liands, which have been shown to intramolecularly bind bridging substrate molecules, similar to those produced by several other flexible binucleating macrocycles. This work was undertaken in an attempt to associate and quantify the binding between di-sulfur bases and their previously studied nitrogen analogues, see Related Literature section.
The molecule is centrosymmetric, and inclusion of the 1,4-dithiane molecule organizes the host such that the Cu···Cu distance, 8.130 (1) Å, is longer than in complexes with other guests, see Related Literature section. Several distortions take place in this organization. The Cu2(NBA)2 unit is not rectangular, but slipped such that the four CH2 groups (C6, C17 and their inversion equivalents) form a parallelogram with sides 7.578 (5) and 9.570 (5) Å, and interior angles differing from orthogonality by 2.8 (3)°. This involves a slippage of the coordination planes horizontally by 1.865 (1) Å.
The coordination sphere is square pyramidal, with distances given in the Abstract and geometric details table. The two chelate rings tilt differently from the coordination plane, with Cu1 lying only 0.0131 (5) Å out of the best plane O1/O2/C2/C3/C4, but 0.4416 (5) Å out of the best plane O3/O4/C19/C20/C21. Those two planes form a dihedral angle of 11.2 (4)°. The Cu—S bond is tilted away from O1 and O2 (O—Cu—S angles 98.91 (8) and 96.32 (7)°) and toward O3 and O4 (angles 86.77 (7) and 87.66 (7)°), and forms an angle of 20.15 (5)° with the Cu···Cu vector.