Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807031984/bt2423sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807031984/bt2423Isup2.hkl |
CCDC reference: 657536
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.004 Å
- R factor = 0.034
- wR factor = 0.087
- Data-to-parameter ratio = 22.0
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 21 PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 2 C10 H15 O4 S
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 28.75 From the CIF: _reflns_number_total 7364 Count of symmetry unique reflns 3985 Completeness (_total/calc) 184.79% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 3379 Fraction of Friedel pairs measured 0.848 Are heavy atom types Z>Si present yes PLAT791_ALERT_1_G Confirm the Absolute Configuration of C1 = . S PLAT791_ALERT_1_G Confirm the Absolute Configuration of C1' = . S PLAT791_ALERT_1_G Confirm the Absolute Configuration of C4 = . R PLAT791_ALERT_1_G Confirm the Absolute Configuration of C4' = . R PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn (2) 2.27 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 7 ALERT level G = General alerts; check 5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
For related literature, see: Couldwell et al. (1978); Henderson & Nicholson (1995); Sheldrick (1990).
The title compound was prepared by saturating a hot aqueous solution of D-camphor-10-sulfonic acid with zinc oxide, followed by filtration and slow evaporation at ambient temperature.
All H atoms were refined with a riding model with O—H = 0.84 Å, C—H ranging from 0.98–1.00Å and U(H) = 1.2 Ueq(C,O) or U(H) = 1.5 Ueq(Cmethyl). It is probable that X-ray data alone cannot provide unambiguous positions for all H.
The title compound was prepared as part of an ongoing research project to develop new materials for the zinc-catalyzed production of polycarbonates from CO2 and epoxides (ethylene oxide, propylene oxide etc.). Two analogous metal salts of D-camphor-10-sulfonic acid have been structurally characterized previously (copper: Couldwell et al., 1978; nickel: Henderson & Nicholson, 1995). Here we present the crystal structure of [Zn(H2O)6].
The three metal salts of D-camphor-10 sulfonic acid are isomorphous. The lattice of the title compound consists of [Zn(H2O)6] cations and two crystallographically independent D-camphor-sulfonate anions. The cation is essentially octahedral, with Zn—O distances ranging from 2.048 (2) to 2.099 (2) Å and O—Zn—O angles between 82.99 (11) and 96.47 (6)°. No coordination of either the sulfonate or the ketone O atoms of the anions is observed.
The two independent D-camphor-10 sulfonate anions show only small differences in bond parameters. As in the lattices of the related nickel and copper compounds, the water sphere and the O atoms of the sulfonate groups are involved in a complex hydrogen bonding network. In contrast to the structure of the nickel complex, in which all H atoms were reported to take part in hydrogen bonds, we find that two water H atoms (H01 & H03) of the title compound do not form hydrogen bonds. This may be associated with the difficulty in localizing H atoms in pseudosymmetric structures, a problem that surprisingly was not mentioned in the earlier reports (see X-ray details).
For related literature, see: Couldwell et al. (1978); Henderson & Nicholson (1995); Sheldrick (1990).
Data collection: XSCANS (Fait, 1991); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Siemens, 1995); software used to prepare material for publication: SHELXTL-Plus.
Fig. 1. The molecule of the title compound in the crystal. Thermal ellipsoids represent 50% probability levels. H-Atom radii are arbitrary. |
[Zn(H2O)6](C10H15O4S)2 | F(000) = 672 |
Mr = 636.03 | Dx = 1.484 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P2yb | Cell parameters from 66 reflections |
a = 11.7293 (14) Å | θ = 3–12.5° |
b = 7.0854 (8) Å | µ = 1.07 mm−1 |
c = 17.169 (2) Å | T = 173 K |
β = 93.841 (10)° | Plate, colourless |
V = 1423.7 (3) Å3 | 0.60 × 0.60 × 0.20 mm |
Z = 2 |
Siemens P4 diffractometer | 5903 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.023 |
Graphite monochromator | θmax = 28.8°, θmin = 3.0° |
ω scans | h = −15→15 |
Absorption correction: empirical (using intensity measurements) (Siemens, 1994) | k = −9→9 |
Tmin = 0.565, Tmax = 0.814 | l = 0→22 |
7590 measured reflections | 3 standard reflections every 247 reflections |
7364 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)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.087 | w = 1/[σ2(Fo2) + (0.0537P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.97 | (Δ/σ)max = 0.005 |
7364 reflections | Δρmax = 0.51 e Å−3 |
334 parameters | Δρmin = −0.48 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 3392 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.005 (10) |
[Zn(H2O)6](C10H15O4S)2 | V = 1423.7 (3) Å3 |
Mr = 636.03 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 11.7293 (14) Å | µ = 1.07 mm−1 |
b = 7.0854 (8) Å | T = 173 K |
c = 17.169 (2) Å | 0.60 × 0.60 × 0.20 mm |
β = 93.841 (10)° |
Siemens P4 diffractometer | 5903 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) (Siemens, 1994) | Rint = 0.023 |
Tmin = 0.565, Tmax = 0.814 | 3 standard reflections every 247 reflections |
7590 measured reflections | intensity decay: none |
7364 independent reflections |
R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.087 | Δρmax = 0.51 e Å−3 |
S = 0.97 | Δρmin = −0.48 e Å−3 |
7364 reflections | Absolute structure: Flack (1983), 3392 Friedel pairs |
334 parameters | Absolute structure parameter: −0.005 (10) |
1 restraint |
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 | ||
Zn | 0.24152 (2) | 0.23602 (6) | 0.494431 (14) | 0.01905 (7) | |
O11 | 0.35940 (15) | 0.2373 (4) | 0.58803 (11) | 0.0380 (4) | |
H01 | 0.4241 | 0.2623 | 0.5725 | 0.046* | |
H02 | 0.3635 | 0.1211 | 0.5973 | 0.046* | |
O12 | 0.12659 (17) | 0.2322 (4) | 0.39833 (12) | 0.0437 (5) | |
H03 | 0.0773 | 0.1569 | 0.4132 | 0.052* | |
H04 | 0.0907 | 0.3348 | 0.3941 | 0.052* | |
O13 | 0.1539 (2) | 0.4604 (3) | 0.54210 (15) | 0.0260 (5) | |
H05 | 0.0868 | 0.4420 | 0.5548 | 0.031* | |
H06 | 0.1535 | 0.5749 | 0.5296 | 0.031* | |
O14 | 0.32956 (19) | 0.0144 (3) | 0.44599 (15) | 0.0263 (6) | |
H07 | 0.3961 | 0.0090 | 0.4308 | 0.032* | |
H08 | 0.3149 | −0.0984 | 0.4564 | 0.032* | |
O15 | 0.1528 (2) | 0.0204 (3) | 0.54855 (15) | 0.0265 (5) | |
H09 | 0.1738 | −0.0927 | 0.5527 | 0.032* | |
H10 | 0.0843 | 0.0168 | 0.5597 | 0.032* | |
O16 | 0.3304 (2) | 0.4525 (3) | 0.44272 (16) | 0.0316 (6) | |
H11 | 0.3119 | 0.5651 | 0.4333 | 0.038* | |
H12 | 0.3971 | 0.4458 | 0.4281 | 0.038* | |
S | −0.08148 (4) | 0.23795 (13) | 0.66721 (3) | 0.01718 (10) | |
O1 | −0.0216 (2) | 0.0609 (3) | 0.65366 (14) | 0.0227 (5) | |
O2 | −0.01836 (19) | 0.4015 (3) | 0.64225 (14) | 0.0237 (5) | |
O3 | −0.19981 (12) | 0.2363 (4) | 0.63493 (9) | 0.0248 (3) | |
C1 | 0.00787 (17) | 0.2248 (5) | 0.82661 (12) | 0.0186 (4) | |
C2 | −0.0241 (2) | 0.2782 (4) | 0.90868 (15) | 0.0279 (7) | |
C3 | 0.0859 (2) | 0.2888 (5) | 0.96047 (16) | 0.0353 (8) | |
H3A | 0.0855 | 0.1982 | 1.0044 | 0.042* | |
H3B | 0.0994 | 0.4177 | 0.9814 | 0.042* | |
C4 | 0.17475 (19) | 0.2344 (6) | 0.90275 (13) | 0.0268 (5) | |
H4 | 0.2548 | 0.2727 | 0.9193 | 0.032* | |
C5 | 0.1589 (2) | 0.0215 (4) | 0.88764 (16) | 0.0280 (6) | |
H5A | 0.1549 | −0.0490 | 0.9372 | 0.034* | |
H5B | 0.2219 | −0.0302 | 0.8585 | 0.034* | |
C6 | 0.0428 (2) | 0.0126 (4) | 0.83773 (16) | 0.0226 (5) | |
H6A | −0.0152 | −0.0576 | 0.8655 | 0.027* | |
H6B | 0.0522 | −0.0489 | 0.7868 | 0.027* | |
C7 | 0.1269 (2) | 0.3230 (4) | 0.82407 (15) | 0.0203 (5) | |
C8 | 0.1166 (3) | 0.5399 (4) | 0.8263 (2) | 0.0358 (7) | |
H8A | 0.1923 | 0.5953 | 0.8383 | 0.043* | |
H8B | 0.0655 | 0.5766 | 0.8665 | 0.043* | |
H8C | 0.0855 | 0.5857 | 0.7753 | 0.043* | |
C9 | 0.1999 (2) | 0.2681 (4) | 0.75685 (14) | 0.0260 (7) | |
H9A | 0.2798 | 0.3017 | 0.7704 | 0.031* | |
H9B | 0.1725 | 0.3356 | 0.7094 | 0.031* | |
H9C | 0.1940 | 0.1318 | 0.7478 | 0.031* | |
O4 | −0.11982 (18) | 0.3062 (4) | 0.92834 (12) | 0.0454 (6) | |
C10 | −0.09305 (19) | 0.2637 (4) | 0.76947 (13) | 0.0199 (6) | |
H11A | −0.1178 | 0.3950 | 0.7786 | 0.024* | |
H11B | −0.1561 | 0.1804 | 0.7839 | 0.024* | |
S' | 0.40990 (4) | −0.26391 (13) | 0.65060 (3) | 0.01825 (10) | |
O1' | 0.4675 (2) | −0.4357 (3) | 0.62698 (15) | 0.0253 (5) | |
O2' | 0.46865 (19) | −0.0944 (3) | 0.62639 (15) | 0.0234 (5) | |
O3' | 0.28824 (12) | −0.2646 (4) | 0.62623 (9) | 0.0255 (3) | |
C1' | 0.53121 (17) | −0.2603 (5) | 0.79946 (12) | 0.0202 (4) | |
C2' | 0.5312 (3) | −0.3858 (4) | 0.87247 (17) | 0.0281 (6) | |
C3' | 0.6312 (3) | −0.3214 (4) | 0.92760 (18) | 0.0368 (8) | |
H3'1 | 0.6872 | −0.4244 | 0.9381 | 0.044* | |
H3'2 | 0.6048 | −0.2750 | 0.9777 | 0.044* | |
C4' | 0.6823 (2) | −0.1597 (4) | 0.88023 (16) | 0.0271 (6) | |
H4' | 0.7314 | −0.0691 | 0.9121 | 0.033* | |
C5' | 0.74126 (19) | −0.2540 (6) | 0.81366 (15) | 0.0301 (5) | |
H5'1 | 0.7911 | −0.3587 | 0.8333 | 0.036* | |
H5'2 | 0.7876 | −0.1618 | 0.7861 | 0.036* | |
C6' | 0.6400 (2) | −0.3285 (4) | 0.75948 (16) | 0.0245 (6) | |
H6'1 | 0.6419 | −0.4679 | 0.7560 | 0.029* | |
H6'2 | 0.6421 | −0.2750 | 0.7063 | 0.029* | |
C7' | 0.5732 (2) | −0.0704 (4) | 0.83839 (15) | 0.0218 (5) | |
C8' | 0.4922 (3) | 0.0105 (5) | 0.8950 (2) | 0.0334 (8) | |
H8'1 | 0.4646 | −0.0911 | 0.9276 | 0.040* | |
H8'2 | 0.4271 | 0.0699 | 0.8658 | 0.040* | |
H8'3 | 0.5324 | 0.1049 | 0.9283 | 0.040* | |
C9' | 0.6006 (2) | 0.0861 (4) | 0.78097 (17) | 0.0288 (6) | |
H9'1 | 0.5295 | 0.1317 | 0.7541 | 0.035* | |
H9'2 | 0.6509 | 0.0361 | 0.7425 | 0.035* | |
H9'3 | 0.6389 | 0.1905 | 0.8095 | 0.035* | |
O4' | 0.4641 (2) | −0.5084 (3) | 0.88454 (15) | 0.0405 (6) | |
C10' | 0.41553 (17) | −0.2650 (6) | 0.75433 (12) | 0.0228 (4) | |
H11C | 0.3713 | −0.1549 | 0.7711 | 0.027* | |
H11D | 0.3751 | −0.3795 | 0.7707 | 0.027* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn | 0.01953 (12) | 0.01708 (11) | 0.02041 (12) | −0.00012 (19) | 0.00036 (9) | 0.0005 (2) |
O11 | 0.0426 (10) | 0.0213 (8) | 0.0473 (11) | 0.0010 (15) | −0.0189 (8) | 0.0040 (15) |
O12 | 0.0539 (11) | 0.0211 (9) | 0.0518 (11) | −0.0047 (15) | −0.0287 (9) | 0.0055 (16) |
O13 | 0.0290 (13) | 0.0186 (12) | 0.0311 (13) | −0.0012 (10) | 0.0072 (11) | −0.0011 (10) |
O14 | 0.0218 (13) | 0.0234 (12) | 0.0346 (15) | 0.0021 (10) | 0.0082 (11) | −0.0007 (11) |
O15 | 0.0228 (12) | 0.0240 (13) | 0.0340 (14) | −0.0006 (10) | 0.0104 (10) | 0.0037 (10) |
O16 | 0.0298 (14) | 0.0245 (13) | 0.0416 (17) | 0.0063 (11) | 0.0107 (12) | 0.0131 (12) |
S | 0.0163 (2) | 0.0165 (2) | 0.0185 (2) | 0.0004 (4) | −0.00026 (17) | −0.0013 (4) |
O1 | 0.0243 (12) | 0.0192 (11) | 0.0241 (11) | 0.0017 (9) | −0.0010 (9) | −0.0046 (8) |
O2 | 0.0225 (12) | 0.0206 (11) | 0.0281 (12) | −0.0026 (9) | 0.0027 (9) | 0.0058 (9) |
O3 | 0.0186 (7) | 0.0275 (8) | 0.0273 (8) | −0.0018 (13) | −0.0051 (6) | 0.0003 (13) |
C1 | 0.0178 (9) | 0.0216 (12) | 0.0163 (9) | 0.0030 (14) | 0.0007 (7) | 0.0024 (14) |
C2 | 0.0317 (13) | 0.0301 (18) | 0.0220 (12) | 0.0004 (10) | 0.0032 (10) | −0.0047 (10) |
C3 | 0.0382 (16) | 0.047 (2) | 0.0205 (13) | −0.0005 (12) | −0.0004 (11) | −0.0061 (11) |
C4 | 0.0231 (10) | 0.0327 (12) | 0.0238 (10) | −0.0050 (19) | −0.0048 (8) | 0.0032 (19) |
C5 | 0.0281 (14) | 0.0294 (15) | 0.0258 (14) | 0.0030 (11) | −0.0045 (11) | 0.0048 (11) |
C6 | 0.0255 (13) | 0.0179 (12) | 0.0244 (13) | −0.0023 (10) | 0.0007 (10) | 0.0045 (10) |
C7 | 0.0160 (11) | 0.0205 (12) | 0.0240 (13) | −0.0019 (9) | −0.0008 (10) | −0.0005 (10) |
C8 | 0.0377 (17) | 0.0240 (15) | 0.0445 (18) | −0.0064 (13) | −0.0055 (14) | −0.0038 (13) |
C9 | 0.0216 (11) | 0.033 (2) | 0.0238 (11) | −0.0013 (11) | 0.0026 (9) | 0.0045 (11) |
O4 | 0.0312 (11) | 0.0763 (18) | 0.0298 (11) | 0.0040 (11) | 0.0112 (9) | −0.0116 (10) |
C10 | 0.0163 (9) | 0.0250 (17) | 0.0184 (10) | 0.0023 (10) | 0.0013 (8) | −0.0009 (10) |
S' | 0.0153 (2) | 0.0172 (2) | 0.0220 (2) | −0.0003 (4) | −0.00066 (18) | 0.0007 (4) |
O1' | 0.0248 (13) | 0.0203 (12) | 0.0303 (13) | −0.0014 (10) | −0.0029 (11) | −0.0057 (10) |
O2' | 0.0178 (12) | 0.0217 (11) | 0.0310 (13) | −0.0031 (9) | 0.0034 (10) | 0.0036 (10) |
O3' | 0.0167 (7) | 0.0271 (8) | 0.0319 (8) | −0.0018 (12) | −0.0040 (6) | −0.0023 (14) |
C1' | 0.0187 (9) | 0.0208 (10) | 0.0211 (9) | −0.0035 (16) | 0.0008 (8) | 0.0005 (17) |
C2' | 0.0327 (15) | 0.0248 (14) | 0.0263 (14) | −0.0019 (12) | −0.0011 (12) | 0.0016 (11) |
C3' | 0.0413 (17) | 0.0409 (18) | 0.0265 (14) | −0.0017 (13) | −0.0091 (13) | 0.0050 (11) |
C4' | 0.0248 (13) | 0.0277 (15) | 0.0278 (14) | −0.0003 (11) | −0.0062 (11) | −0.0025 (11) |
C5' | 0.0202 (10) | 0.0333 (14) | 0.0360 (12) | 0.0044 (17) | −0.0044 (9) | −0.0015 (19) |
C6' | 0.0180 (12) | 0.0269 (13) | 0.0284 (13) | 0.0027 (9) | −0.0003 (11) | −0.0052 (10) |
C7' | 0.0182 (12) | 0.0244 (14) | 0.0231 (13) | −0.0024 (10) | 0.0029 (10) | −0.0052 (10) |
C8' | 0.0277 (15) | 0.0366 (17) | 0.0367 (18) | −0.0037 (13) | 0.0086 (14) | −0.0138 (14) |
C9' | 0.0255 (14) | 0.0249 (14) | 0.0358 (16) | −0.0052 (11) | 0.0012 (12) | −0.0010 (12) |
O4' | 0.0471 (15) | 0.0360 (13) | 0.0381 (14) | −0.0126 (11) | −0.0002 (11) | 0.0105 (10) |
C10' | 0.0178 (9) | 0.0294 (11) | 0.0215 (10) | −0.0022 (17) | 0.0032 (8) | −0.0002 (18) |
Zn—O11 | 2.0485 (17) | C7—C8 | 1.543 (4) |
Zn—O12 | 2.0597 (17) | C8—H8A | 0.9800 |
Zn—O14 | 2.083 (2) | C8—H8B | 0.9800 |
Zn—O16 | 2.086 (2) | C8—H8C | 0.9800 |
Zn—O13 | 2.090 (2) | C9—H9A | 0.9800 |
Zn—O15 | 2.100 (2) | C9—H9B | 0.9800 |
O11—H01 | 0.8405 | C9—H9C | 0.9800 |
O11—H02 | 0.8387 | C10—H11A | 0.9900 |
O12—H03 | 0.8394 | C10—H11B | 0.9900 |
O12—H04 | 0.8407 | S'—O2' | 1.459 (2) |
O13—H05 | 0.8401 | S'—O3' | 1.4600 (14) |
O13—H06 | 0.8394 | S'—O1' | 1.462 (2) |
O14—H07 | 0.8404 | S'—C10' | 1.778 (2) |
O14—H08 | 0.8397 | C1'—C10' | 1.517 (3) |
O15—H09 | 0.8403 | C1'—C2' | 1.537 (4) |
O15—H10 | 0.8391 | C1'—C6' | 1.566 (3) |
O16—H11 | 0.8392 | C1'—C7' | 1.567 (4) |
O16—H12 | 0.8396 | C2'—O4' | 1.200 (4) |
S—O2 | 1.455 (2) | C2'—C3' | 1.527 (4) |
S—O3 | 1.4596 (14) | C3'—C4' | 1.549 (4) |
S—O1 | 1.464 (2) | C3'—H3'1 | 0.9900 |
S—C10 | 1.779 (2) | C3'—H3'2 | 0.9900 |
C1—C10 | 1.511 (3) | C4'—C5' | 1.529 (4) |
C1—C2 | 1.530 (3) | C4'—C7' | 1.559 (4) |
C1—C7 | 1.563 (3) | C4'—H4' | 1.0000 |
C1—C6 | 1.566 (4) | C5'—C6' | 1.551 (3) |
C2—O4 | 1.210 (3) | C5'—H5'1 | 0.9900 |
C2—C3 | 1.519 (4) | C5'—H5'2 | 0.9900 |
C3—C4 | 1.535 (4) | C6'—H6'1 | 0.9900 |
C3—H3A | 0.9900 | C6'—H6'2 | 0.9900 |
C3—H3B | 0.9900 | C7'—C8' | 1.517 (4) |
C4—C5 | 1.540 (5) | C7'—C9' | 1.532 (4) |
C4—C7 | 1.560 (3) | C8'—H8'1 | 0.9800 |
C4—H4 | 1.0000 | C8'—H8'2 | 0.9800 |
C5—C6 | 1.561 (3) | C8'—H8'3 | 0.9800 |
C5—H5A | 0.9900 | C9'—H9'1 | 0.9800 |
C5—H5B | 0.9900 | C9'—H9'2 | 0.9800 |
C6—H6A | 0.9900 | C9'—H9'3 | 0.9800 |
C6—H6B | 0.9900 | C10'—H11C | 0.9900 |
C7—C9 | 1.533 (3) | C10'—H11D | 0.9900 |
O11—Zn—O12 | 178.36 (9) | H8A—C8—H8B | 109.5 |
O11—Zn—O14 | 89.42 (10) | C7—C8—H8C | 109.5 |
O12—Zn—O14 | 89.18 (11) | H8A—C8—H8C | 109.5 |
O11—Zn—O16 | 90.03 (11) | H8B—C8—H8C | 109.5 |
O12—Zn—O16 | 89.28 (11) | C7—C9—H9A | 109.5 |
O14—Zn—O16 | 96.27 (6) | C7—C9—H9B | 109.5 |
O11—Zn—O13 | 90.77 (11) | H9A—C9—H9B | 109.5 |
O12—Zn—O13 | 90.62 (11) | C7—C9—H9C | 109.5 |
O14—Zn—O13 | 179.36 (12) | H9A—C9—H9C | 109.5 |
O16—Zn—O13 | 83.13 (11) | H9B—C9—H9C | 109.5 |
O11—Zn—O15 | 89.10 (11) | C1—C10—S | 120.91 (16) |
O12—Zn—O15 | 91.61 (11) | C1—C10—H11A | 107.1 |
O14—Zn—O15 | 84.37 (11) | S—C10—H11A | 107.1 |
O16—Zn—O15 | 178.92 (12) | C1—C10—H11B | 107.1 |
O13—Zn—O15 | 96.24 (6) | S—C10—H11B | 107.1 |
Zn—O11—H01 | 109.1 | H11A—C10—H11B | 106.8 |
Zn—O11—H02 | 99.9 | O2'—S'—O3' | 113.11 (15) |
H01—O11—H02 | 103.0 | O2'—S'—O1' | 111.75 (9) |
Zn—O12—H03 | 101.0 | O3'—S'—O1' | 112.23 (15) |
Zn—O12—H04 | 110.8 | O2'—S'—C10' | 107.61 (17) |
H03—O12—H04 | 103.0 | O3'—S'—C10' | 104.89 (9) |
Zn—O13—H05 | 118.5 | O1'—S'—C10' | 106.69 (17) |
Zn—O13—H06 | 128.9 | C10'—C1'—C2' | 110.8 (2) |
H05—O13—H06 | 103.2 | C10'—C1'—C6' | 119.8 (2) |
Zn—O14—H07 | 130.8 | C2'—C1'—C6' | 102.9 (2) |
Zn—O14—H08 | 121.2 | C10'—C1'—C7' | 118.8 (3) |
H07—O14—H08 | 103.3 | C2'—C1'—C7' | 99.55 (19) |
Zn—O15—H09 | 125.5 | C6'—C1'—C7' | 102.11 (19) |
Zn—O15—H10 | 129.3 | O4'—C2'—C3' | 126.5 (3) |
H09—O15—H10 | 103.4 | O4'—C2'—C1' | 126.6 (3) |
Zn—O16—H11 | 130.6 | C3'—C2'—C1' | 106.9 (2) |
Zn—O16—H12 | 126.0 | C2'—C3'—C4' | 101.7 (2) |
H11—O16—H12 | 103.3 | C2'—C3'—H3'1 | 111.4 |
O2—S—O3 | 112.59 (15) | C4'—C3'—H3'1 | 111.4 |
O2—S—O1 | 112.13 (10) | C2'—C3'—H3'2 | 111.4 |
O3—S—O1 | 112.77 (16) | C4'—C3'—H3'2 | 111.4 |
O2—S—C10 | 106.45 (14) | H3'1—C3'—H3'2 | 109.3 |
O3—S—C10 | 104.01 (10) | C5'—C4'—C3' | 106.2 (3) |
O1—S—C10 | 108.28 (14) | C5'—C4'—C7' | 103.4 (2) |
C10—C1—C2 | 108.9 (2) | C3'—C4'—C7' | 102.0 (2) |
C10—C1—C7 | 124.3 (2) | C5'—C4'—H4' | 114.6 |
C2—C1—C7 | 100.9 (2) | C3'—C4'—H4' | 114.6 |
C10—C1—C6 | 116.2 (2) | C7'—C4'—H4' | 114.6 |
C2—C1—C6 | 101.7 (2) | C4'—C5'—C6' | 103.34 (19) |
C7—C1—C6 | 101.77 (19) | C4'—C5'—H5'1 | 111.1 |
O4—C2—C3 | 126.6 (3) | C6'—C5'—H5'1 | 111.1 |
O4—C2—C1 | 125.9 (2) | C4'—C5'—H5'2 | 111.1 |
C3—C2—C1 | 107.5 (2) | C6'—C5'—H5'2 | 111.1 |
C2—C3—C4 | 101.3 (2) | H5'1—C5'—H5'2 | 109.1 |
C2—C3—H3A | 111.5 | C5'—C6'—C1' | 104.2 (2) |
C4—C3—H3A | 111.5 | C5'—C6'—H6'1 | 110.9 |
C2—C3—H3B | 111.5 | C1'—C6'—H6'1 | 110.9 |
C4—C3—H3B | 111.5 | C5'—C6'—H6'2 | 110.9 |
H3A—C3—H3B | 109.3 | C1'—C6'—H6'2 | 110.9 |
C3—C4—C5 | 106.0 (2) | H6'1—C6'—H6'2 | 108.9 |
C3—C4—C7 | 103.7 (2) | C8'—C7'—C9' | 107.8 (2) |
C5—C4—C7 | 102.5 (2) | C8'—C7'—C4' | 112.8 (2) |
C3—C4—H4 | 114.4 | C9'—C7'—C4' | 112.9 (2) |
C5—C4—H4 | 114.4 | C8'—C7'—C1' | 113.9 (2) |
C7—C4—H4 | 114.4 | C9'—C7'—C1' | 114.9 (2) |
C4—C5—C6 | 102.9 (2) | C4'—C7'—C1' | 94.2 (2) |
C4—C5—H5A | 111.2 | C7'—C8'—H8'1 | 109.5 |
C6—C5—H5A | 111.2 | C7'—C8'—H8'2 | 109.5 |
C4—C5—H5B | 111.2 | H8'1—C8'—H8'2 | 109.5 |
C6—C5—H5B | 111.2 | C7'—C8'—H8'3 | 109.5 |
H5A—C5—H5B | 109.1 | H8'1—C8'—H8'3 | 109.5 |
C5—C6—C1 | 103.9 (2) | H8'2—C8'—H8'3 | 109.5 |
C5—C6—H6A | 111.0 | C7'—C9'—H9'1 | 109.5 |
C1—C6—H6A | 111.0 | C7'—C9'—H9'2 | 109.5 |
C5—C6—H6B | 111.0 | H9'1—C9'—H9'2 | 109.5 |
C1—C6—H6B | 111.0 | C7'—C9'—H9'3 | 109.5 |
H6A—C6—H6B | 109.0 | H9'1—C9'—H9'3 | 109.5 |
C9—C7—C8 | 108.6 (2) | H9'2—C9'—H9'3 | 109.5 |
C9—C7—C4 | 111.3 (2) | C1'—C10'—S' | 118.91 (14) |
C8—C7—C4 | 113.8 (3) | C1'—C10'—H11C | 107.6 |
C9—C7—C1 | 116.9 (2) | S'—C10'—H11C | 107.6 |
C8—C7—C1 | 111.8 (2) | C1'—C10'—H11D | 107.6 |
C4—C7—C1 | 93.85 (19) | S'—C10'—H11D | 107.6 |
C7—C8—H8A | 109.5 | H11C—C10'—H11D | 107.0 |
C7—C8—H8B | 109.5 | ||
C10—C1—C2—O4 | 15.3 (4) | C10'—C1'—C2'—O4' | 18.1 (5) |
C7—C1—C2—O4 | 147.5 (3) | C6'—C1'—C2'—O4' | −111.2 (3) |
C6—C1—C2—O4 | −107.9 (3) | C7'—C1'—C2'—O4' | 144.0 (3) |
C10—C1—C2—C3 | −164.9 (2) | C10'—C1'—C2'—C3' | −160.6 (3) |
C7—C1—C2—C3 | −32.7 (3) | C6'—C1'—C2'—C3' | 70.2 (3) |
C6—C1—C2—C3 | 71.9 (2) | C7'—C1'—C2'—C3' | −34.7 (3) |
O4—C2—C3—C4 | 178.5 (3) | O4'—C2'—C3'—C4' | −178.8 (3) |
C1—C2—C3—C4 | −1.3 (3) | C1'—C2'—C3'—C4' | −0.2 (3) |
C2—C3—C4—C5 | −72.1 (3) | C2'—C3'—C4'—C5' | −72.4 (3) |
C2—C3—C4—C7 | 35.4 (3) | C2'—C3'—C4'—C7' | 35.5 (3) |
C3—C4—C5—C6 | 71.2 (2) | C3'—C4'—C5'—C6' | 70.7 (3) |
C7—C4—C5—C6 | −37.2 (2) | C7'—C4'—C5'—C6' | −36.3 (3) |
C4—C5—C6—C1 | 2.5 (2) | C4'—C5'—C6'—C1' | 2.4 (3) |
C10—C1—C6—C5 | 170.7 (2) | C10'—C1'—C6'—C5' | 165.4 (3) |
C2—C1—C6—C5 | −71.2 (2) | C2'—C1'—C6'—C5' | −71.2 (3) |
C7—C1—C6—C5 | 32.7 (2) | C7'—C1'—C6'—C5' | 31.7 (3) |
C3—C4—C7—C9 | −175.0 (2) | C5'—C4'—C7'—C8' | 172.5 (3) |
C5—C4—C7—C9 | −64.9 (3) | C3'—C4'—C7'—C8' | 62.3 (3) |
C3—C4—C7—C8 | 61.9 (3) | C5'—C4'—C7'—C9' | −64.9 (3) |
C5—C4—C7—C8 | 172.0 (2) | C3'—C4'—C7'—C9' | −175.1 (2) |
C3—C4—C7—C1 | −54.1 (3) | C5'—C4'—C7'—C1' | 54.3 (2) |
C5—C4—C7—C1 | 56.1 (2) | C3'—C4'—C7'—C1' | −55.8 (2) |
C10—C1—C7—C9 | −70.6 (4) | C10'—C1'—C7'—C8' | 57.0 (3) |
C2—C1—C7—C9 | 167.4 (2) | C2'—C1'—C7'—C8' | −63.2 (3) |
C6—C1—C7—C9 | 62.8 (3) | C6'—C1'—C7'—C8' | −168.8 (2) |
C10—C1—C7—C8 | 55.5 (3) | C10'—C1'—C7'—C9' | −68.1 (3) |
C2—C1—C7—C8 | −66.5 (3) | C2'—C1'—C7'—C9' | 171.7 (2) |
C6—C1—C7—C8 | −171.1 (2) | C6'—C1'—C7'—C9' | 66.1 (3) |
C10—C1—C7—C4 | 173.1 (3) | C10'—C1'—C7'—C4' | 174.2 (2) |
C2—C1—C7—C4 | 51.1 (3) | C2'—C1'—C7'—C4' | 54.0 (2) |
C6—C1—C7—C4 | −53.5 (2) | C6'—C1'—C7'—C4' | −51.5 (2) |
C2—C1—C10—S | 174.2 (2) | C2'—C1'—C10'—S' | −142.1 (3) |
C7—C1—C10—S | 55.8 (4) | C6'—C1'—C10'—S' | −22.6 (5) |
C6—C1—C10—S | −71.7 (3) | C7'—C1'—C10'—S' | 103.6 (3) |
O2—S—C10—C1 | −75.9 (3) | O2'—S'—C10'—C1' | −58.0 (3) |
O3—S—C10—C1 | 165.0 (3) | O3'—S'—C10'—C1' | −178.7 (3) |
O1—S—C10—C1 | 44.9 (3) | O1'—S'—C10'—C1' | 62.1 (3) |
Experimental details
Crystal data | |
Chemical formula | [Zn(H2O)6](C10H15O4S)2 |
Mr | 636.03 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 173 |
a, b, c (Å) | 11.7293 (14), 7.0854 (8), 17.169 (2) |
β (°) | 93.841 (10) |
V (Å3) | 1423.7 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.07 |
Crystal size (mm) | 0.60 × 0.60 × 0.20 |
Data collection | |
Diffractometer | Siemens P4 |
Absorption correction | Empirical (using intensity measurements) (Siemens, 1994) |
Tmin, Tmax | 0.565, 0.814 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7590, 7364, 5903 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.677 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.087, 0.97 |
No. of reflections | 7364 |
No. of parameters | 334 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.51, −0.48 |
Absolute structure | Flack (1983), 3392 Friedel pairs |
Absolute structure parameter | −0.005 (10) |
Computer programs: XSCANS (Fait, 1991), XSCANS, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL-Plus (Siemens, 1995), SHELXTL-Plus.
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The title compound was prepared as part of an ongoing research project to develop new materials for the zinc-catalyzed production of polycarbonates from CO2 and epoxides (ethylene oxide, propylene oxide etc.). Two analogous metal salts of D-camphor-10-sulfonic acid have been structurally characterized previously (copper: Couldwell et al., 1978; nickel: Henderson & Nicholson, 1995). Here we present the crystal structure of [Zn(H2O)6].
The three metal salts of D-camphor-10 sulfonic acid are isomorphous. The lattice of the title compound consists of [Zn(H2O)6] cations and two crystallographically independent D-camphor-sulfonate anions. The cation is essentially octahedral, with Zn—O distances ranging from 2.048 (2) to 2.099 (2) Å and O—Zn—O angles between 82.99 (11) and 96.47 (6)°. No coordination of either the sulfonate or the ketone O atoms of the anions is observed.
The two independent D-camphor-10 sulfonate anions show only small differences in bond parameters. As in the lattices of the related nickel and copper compounds, the water sphere and the O atoms of the sulfonate groups are involved in a complex hydrogen bonding network. In contrast to the structure of the nickel complex, in which all H atoms were reported to take part in hydrogen bonds, we find that two water H atoms (H01 & H03) of the title compound do not form hydrogen bonds. This may be associated with the difficulty in localizing H atoms in pseudosymmetric structures, a problem that surprisingly was not mentioned in the earlier reports (see X-ray details).