

Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810013024/bt5223sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536810013024/bt5223Isup2.hkl |
CCDC reference: 777877
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean
(C-C) = 0.002 Å
- Disorder in main residue
- R factor = 0.029
- wR factor = 0.070
- Data-to-parameter ratio = 19.8
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 3.21 Ratio PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.67 Ratio PLAT230_ALERT_2_C Hirshfeld Test Diff for S2 -- C13 .. 5.65 su PLAT230_ALERT_2_C Hirshfeld Test Diff for C12 -- C18 .. 6.64 su PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C12 - C18 ... 1.43 Ang. PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) ..... 3 PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 2 C4 H10 O PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 10
Alert level G PLAT301_ALERT_3_G Note: Main Residue Disorder ................... 7.00 Perc. PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 18 PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 1 O1 -CA -O1 -C11 71.00 6.00 2.567 1.555 1.555 1.555 PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 54 C13 -C12 -C18 -N2 162.00 14.00 1.555 1.555 1.555 1.555 PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 55 C11 -C12 -C18 -N2 -17.00 14.00 1.555 1.555 1.555 1.555 PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels .......... 1 PLAT779_ALERT_4_G Suspect or Irrelevant (Bond) Angle in CIF ...... 19.70 Deg. C16' -O2 -C16 1.555 1.555 1.555
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 9 ALERT level C = Check and explain 7 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 4 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 ALERT type 3 Indicator that the structure quality may be low 8 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The IR spectrum revealed the presence of cyano group at 2190 cm-1. The 1H NMR spectrum revealed signals at δ 1.06–1.24 ppm (t, CH3), 2.51 (s, SCH2), 4.08–4.15 (qua, ester CH2) 7.43–8.37 (m, aromatic protons) and 8.40 (br s, NH).
NH and OH hydrogens were identified in difference syntheses. The NH hydrogen was refined freely, water H freely but with distance restraints (SADI) to O—H and H···H. Methyl protons were identified in difference syntheses, idealised and allowed to refine as rigid groups (C—H 0.98 Å, H—C—H 109.5°) allowed to rotate but not tip. Other H were included starting from calculated, idealised positions using a riding model with C—H 0.99 Å for methylene groups and 0.95 Å for sp2 carbons. The ethyl group C16/17 is disordered over two positions with occupancies 0.738, 0.262 (4). Similarity restraints to this group were used to improve stability of refinement.
During the course of our studies directed toward exploring the synthetic potential of ketene dithioacetals for synthesizing new classes of novel antimetabolic agents (Elgemeie & Sood, 2006; Elgemeie et al., 2008, 2009), we have recently reported various successful approaches for synthesis of mercaptopurine and pyrimidine analogues by the reaction of ketene dithioacetals with active methylene functions (Elgemeie, 2003; Elgemeie et al., 2004, 2007). In conjunction of this work, we report here a novel calcium salt (I) of a ketene dithioacetal. The structure of (I) was established on the basis of its elemental analysis and spectral data (see Experimental). In order to establish unambiguously the structure of the product, the crystal structure was determined. The X-ray analysis confirms the exclusive presence of the form (I) in the solid state (Figure 1).
The structure consists of a calcium ion on an inversion centre, coordinated octahedrally by four water molecules and two anions of the ketene dithioacetal; the latter coordinate via the amidic carbonyl oxygen O1, with Ca—O1 2.2696 (9) Å. The asymmetric unit also contains one molecule of diethyl ether.
Within the ligand, there is presumably extensive delocalization of the negative charge from its formal position at the "thiolate" sulfur S2 through the ligand backbone (see dimensions in Table 1), in which the ten atoms C1, C11–14, C18, N1, O1, S1 and S2 are approximately coplanar (r.m.s. deviation 0.035 Å). The backbone angles C11—C12—C13 and C12—C13—S2 are noticeably wide at 126.43 (9) and 129.48 (11)° respectively. The Ca atom lies 0.862 (1) Å out of the backbone plane,and the naphthalene plane subtends an interplanar angle to this plane of 29.03 (2)°.
Intramolecular hydrogen bonds (Table 2) are observed from the NH function to the formally thiolate sulfur and from a hydrogen of the coordinated water O1W to the nitrile N. Additionally, the ether molecules are connected by a hydrogen bond from the same water to the ether oxygen. Intramolecular H bonds from the second water to the thiolate sulfur and the 2-oxo function connect the molecules to form chains parallel to the a axis (Fig. 2).
For related literature, see: Elgemeie (2003); Elgemeie & Sood (2006); Elgemeie et al. (2004, 2007, 2008, 2009).
Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
[Ca(C18H15N2O3S2)(H2O)4]·2C4H10O | F(000) = 530 |
Mr = 1003.26 | Dx = 1.333 Mg m−3 |
Triclinic, P1 | Melting point = 479–481 K |
a = 7.8665 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.4361 (5) Å | Cell parameters from 11577 reflections |
c = 13.8045 (6) Å | θ = 2.6–30.8° |
α = 103.692 (4)° | µ = 0.35 mm−1 |
β = 99.963 (4)° | T = 100 K |
γ = 101.609 (3)° | Irregular tablet, pale yellow |
V = 1250.24 (9) Å3 | 0.4 × 0.3 × 0.1 mm |
Z = 1 |
Oxford Diffraction Xcalibur Eos diffractometer | 6443 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 4941 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
Detector resolution: 16.1419 pixels mm-1 | θmax = 28.7°, θmin = 2.7° |
ω–scan | h = −10→10 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | k = −16→16 |
Tmin = 0.970, Tmax = 1.000 | l = −18→18 |
26853 measured reflections |
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) = 0.070 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.96 | w = 1/[σ2(Fo2) + (0.0363P)2] where P = (Fo2 + 2Fc2)/3 |
6443 reflections | (Δ/σ)max = 0.001 |
326 parameters | Δρmax = 0.30 e Å−3 |
18 restraints | Δρmin = −0.28 e Å−3 |
[Ca(C18H15N2O3S2)(H2O)4]·2C4H10O | γ = 101.609 (3)° |
Mr = 1003.26 | V = 1250.24 (9) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.8665 (3) Å | Mo Kα radiation |
b = 12.4361 (5) Å | µ = 0.35 mm−1 |
c = 13.8045 (6) Å | T = 100 K |
α = 103.692 (4)° | 0.4 × 0.3 × 0.1 mm |
β = 99.963 (4)° |
Oxford Diffraction Xcalibur Eos diffractometer | 6443 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | 4941 reflections with I > 2σ(I) |
Tmin = 0.970, Tmax = 1.000 | Rint = 0.031 |
26853 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 18 restraints |
wR(F2) = 0.070 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.96 | Δρmax = 0.30 e Å−3 |
6443 reflections | Δρmin = −0.28 e Å−3 |
326 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 5.7234 (0.0013) x - 5.6563 (0.0020) y + 7.4193 (0.0030) z = 5.4532 (0.0027) * 0.0098 (0.0008) C1 * 0.0042 (0.0011) C11 * 0.0033 (0.0011) C12 * -0.0107 (0.0010) C13 * 0.0215 (0.0007) C14 * 0.0075 (0.0008) C18 * 0.0664 (0.0009) N1 * -0.0508 (0.0008) O1 * 0.0150 (0.0006) S1 * -0.0662 (0.0006) S2 -0.8620 (0.0010) Ca Rms deviation of fitted atoms = 0.0351 7.5293 (0.0008) x - 5.2398 (0.0041) y + 0.8431 (0.0033) z = 1.0859 (0.0024) Angle to previous plane (with approximate esd) = 29.03 ( 0.02 ) * -0.0015 (0.0010) C1 * 0.0157 (0.0010) C2 * 0.0006 (0.0010) C3 * -0.0152 (0.0011) C4 * 0.0063 (0.0011) C5 * 0.0109 (0.0011) C6 * -0.0015 (0.0011) C7 * -0.0092 (0.0010) C8 * -0.0036 (0.0011) C9 * -0.0025 (0.0011) C10 Rms deviation of fitted atoms = 0.0086 |
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 | Occ. (<1) | |
Ca | 0.0000 | 0.5000 | 1.0000 | 0.01453 (8) | |
S1 | 0.64002 (4) | 0.90145 (3) | 0.93054 (2) | 0.01677 (8) | |
S2 | 0.63380 (4) | 0.69288 (3) | 0.76538 (2) | 0.01590 (8) | |
O1 | 0.25364 (11) | 0.53927 (7) | 0.94360 (7) | 0.0198 (2) | |
O3 | 1.01513 (11) | 0.87570 (7) | 0.93853 (7) | 0.0201 (2) | |
N1 | 0.39935 (14) | 0.49923 (9) | 0.81647 (8) | 0.0156 (2) | |
H01 | 0.471 (2) | 0.5286 (13) | 0.7844 (11) | 0.032 (4)* | |
N2 | 0.36142 (15) | 0.81149 (9) | 1.07579 (8) | 0.0225 (2) | |
C1 | 0.32121 (15) | 0.37980 (10) | 0.77809 (9) | 0.0152 (3) | |
C2 | 0.27106 (16) | 0.31450 (10) | 0.84051 (10) | 0.0173 (3) | |
H2 | 0.2901 | 0.3491 | 0.9120 | 0.021* | |
C3 | 0.19158 (17) | 0.19658 (11) | 0.79947 (10) | 0.0211 (3) | |
H3 | 0.1560 | 0.1523 | 0.8433 | 0.025* | |
C4 | 0.16515 (17) | 0.14516 (11) | 0.69724 (10) | 0.0210 (3) | |
H4 | 0.1102 | 0.0656 | 0.6706 | 0.025* | |
C5 | 0.19573 (17) | 0.15718 (11) | 0.52430 (10) | 0.0236 (3) | |
H5 | 0.1437 | 0.0773 | 0.4969 | 0.028* | |
C6 | 0.24685 (18) | 0.21949 (12) | 0.46050 (10) | 0.0256 (3) | |
H6 | 0.2309 | 0.1830 | 0.3897 | 0.031* | |
C7 | 0.32322 (17) | 0.33790 (12) | 0.49968 (10) | 0.0240 (3) | |
H7 | 0.3580 | 0.3813 | 0.4550 | 0.029* | |
C8 | 0.34779 (17) | 0.39113 (11) | 0.60195 (9) | 0.0193 (3) | |
H8 | 0.3994 | 0.4712 | 0.6272 | 0.023* | |
C9 | 0.21843 (16) | 0.20880 (10) | 0.63064 (10) | 0.0178 (3) | |
C10 | 0.29770 (15) | 0.32891 (10) | 0.67054 (9) | 0.0153 (3) | |
C11 | 0.36103 (16) | 0.57231 (10) | 0.89338 (9) | 0.0143 (2) | |
C12 | 0.44847 (15) | 0.69477 (10) | 0.91915 (9) | 0.0139 (2) | |
C13 | 0.56499 (15) | 0.75240 (10) | 0.87132 (9) | 0.0137 (2) | |
C14 | 0.78632 (16) | 0.94911 (10) | 0.85488 (9) | 0.0147 (2) | |
H14A | 0.7223 | 0.9213 | 0.7818 | 0.018* | |
H14B | 0.8187 | 1.0338 | 0.8744 | 0.018* | |
C15 | 0.95496 (16) | 0.90825 (10) | 0.86744 (9) | 0.0152 (3) | |
O2 | 1.03244 (11) | 0.91600 (8) | 0.78997 (7) | 0.0246 (2) | |
C16 | 1.1903 (3) | 0.8657 (3) | 0.7942 (2) | 0.0354 (7) | 0.738 (4) |
H16A | 1.2878 | 0.9141 | 0.8533 | 0.042* | 0.738 (4) |
H16B | 1.1571 | 0.7883 | 0.8036 | 0.042* | 0.738 (4) |
C17 | 1.2505 (3) | 0.8589 (2) | 0.69962 (17) | 0.0436 (8) | 0.738 (4) |
H17A | 1.3527 | 0.8250 | 0.7021 | 0.065* | 0.738 (4) |
H17B | 1.2859 | 0.9359 | 0.6916 | 0.065* | 0.738 (4) |
H17C | 1.1533 | 0.8113 | 0.6414 | 0.065* | 0.738 (4) |
C16' | 1.2112 (11) | 0.9059 (6) | 0.7918 (7) | 0.029 (2)* | 0.262 (4) |
H16C | 1.2780 | 0.9128 | 0.8616 | 0.034* | 0.262 (4) |
H16D | 1.2780 | 0.9625 | 0.7633 | 0.034* | 0.262 (4) |
C17' | 1.1676 (9) | 0.7828 (6) | 0.7206 (5) | 0.044 (2)* | 0.262 (4) |
H17D | 1.2788 | 0.7609 | 0.7139 | 0.066* | 0.262 (4) |
H17E | 1.0996 | 0.7794 | 0.6529 | 0.066* | 0.262 (4) |
H17F | 1.0967 | 0.7301 | 0.7499 | 0.066* | 0.262 (4) |
C18 | 0.40096 (16) | 0.75993 (10) | 1.00605 (9) | 0.0152 (2) | |
C91 | −0.0616 (2) | 0.49289 (14) | 0.64737 (12) | 0.0380 (4) | |
H91A | 0.0392 | 0.4925 | 0.7000 | 0.057* | |
H91B | −0.1516 | 0.5204 | 0.6803 | 0.057* | |
H91C | −0.0198 | 0.5436 | 0.6071 | 0.057* | |
C92 | −0.1421 (2) | 0.37394 (14) | 0.57815 (11) | 0.0314 (3) | |
H92A | −0.2440 | 0.3737 | 0.5247 | 0.038* | |
H92B | −0.0523 | 0.3460 | 0.5439 | 0.038* | |
O93 | −0.20128 (13) | 0.30117 (9) | 0.63788 (7) | 0.0283 (2) | |
C94 | −0.2807 (2) | 0.18547 (13) | 0.57820 (11) | 0.0332 (4) | |
H94A | −0.1931 | 0.1539 | 0.5444 | 0.040* | |
H94B | −0.3842 | 0.1823 | 0.5244 | 0.040* | |
C95 | −0.3405 (2) | 0.11591 (14) | 0.64723 (12) | 0.0375 (4) | |
H95A | −0.4274 | 0.1474 | 0.6803 | 0.056* | |
H95B | −0.2373 | 0.1185 | 0.6997 | 0.056* | |
H95C | −0.3959 | 0.0364 | 0.6067 | 0.056* | |
O1W | −0.17859 (14) | 0.37346 (9) | 0.84531 (8) | 0.0318 (3) | |
H1W | −0.173 (2) | 0.3536 (15) | 0.7848 (10) | 0.051 (6)* | |
H2W | −0.252 (2) | 0.3209 (14) | 0.8526 (14) | 0.064 (7)* | |
O2W | −0.07611 (14) | 0.64913 (9) | 0.94233 (8) | 0.0277 (2) | |
H3W | −0.023 (2) | 0.7169 (11) | 0.9595 (12) | 0.044 (5)* | |
H4W | −0.155 (2) | 0.6389 (15) | 0.8925 (11) | 0.048 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ca | 0.01563 (18) | 0.01361 (17) | 0.01734 (18) | 0.00374 (13) | 0.00750 (14) | 0.00726 (13) |
S1 | 0.01826 (16) | 0.01288 (15) | 0.01747 (16) | 0.00078 (12) | 0.00818 (12) | 0.00085 (12) |
S2 | 0.01890 (16) | 0.01387 (15) | 0.01454 (15) | 0.00153 (12) | 0.00815 (12) | 0.00241 (11) |
O1 | 0.0199 (5) | 0.0174 (4) | 0.0240 (5) | 0.0023 (4) | 0.0127 (4) | 0.0061 (4) |
O3 | 0.0200 (5) | 0.0161 (4) | 0.0215 (5) | 0.0033 (4) | −0.0013 (4) | 0.0058 (4) |
N1 | 0.0165 (5) | 0.0134 (5) | 0.0162 (5) | 0.0004 (4) | 0.0076 (4) | 0.0032 (4) |
N2 | 0.0280 (6) | 0.0196 (6) | 0.0241 (6) | 0.0076 (5) | 0.0136 (5) | 0.0074 (5) |
C1 | 0.0118 (6) | 0.0143 (6) | 0.0184 (6) | 0.0025 (5) | 0.0029 (5) | 0.0036 (5) |
C2 | 0.0182 (6) | 0.0168 (6) | 0.0167 (6) | 0.0039 (5) | 0.0037 (5) | 0.0050 (5) |
C3 | 0.0216 (7) | 0.0176 (6) | 0.0262 (7) | 0.0036 (5) | 0.0064 (6) | 0.0107 (5) |
C4 | 0.0184 (7) | 0.0131 (6) | 0.0277 (7) | 0.0004 (5) | 0.0020 (5) | 0.0038 (5) |
C5 | 0.0192 (7) | 0.0198 (7) | 0.0242 (7) | 0.0025 (5) | 0.0018 (6) | −0.0037 (5) |
C6 | 0.0244 (7) | 0.0304 (8) | 0.0165 (7) | 0.0049 (6) | 0.0045 (6) | −0.0017 (6) |
C7 | 0.0243 (7) | 0.0288 (7) | 0.0189 (7) | 0.0048 (6) | 0.0079 (6) | 0.0063 (6) |
C8 | 0.0201 (7) | 0.0181 (6) | 0.0179 (6) | 0.0017 (5) | 0.0056 (5) | 0.0032 (5) |
C9 | 0.0133 (6) | 0.0166 (6) | 0.0211 (7) | 0.0035 (5) | 0.0022 (5) | 0.0022 (5) |
C10 | 0.0111 (6) | 0.0168 (6) | 0.0166 (6) | 0.0032 (5) | 0.0024 (5) | 0.0031 (5) |
C11 | 0.0129 (6) | 0.0166 (6) | 0.0142 (6) | 0.0043 (5) | 0.0035 (5) | 0.0050 (5) |
C12 | 0.0128 (6) | 0.0154 (6) | 0.0135 (6) | 0.0036 (5) | 0.0041 (5) | 0.0030 (5) |
C13 | 0.0121 (6) | 0.0143 (6) | 0.0135 (6) | 0.0034 (5) | 0.0013 (5) | 0.0029 (5) |
C14 | 0.0165 (6) | 0.0130 (6) | 0.0155 (6) | 0.0029 (5) | 0.0051 (5) | 0.0050 (5) |
C15 | 0.0152 (6) | 0.0091 (5) | 0.0174 (6) | −0.0010 (5) | 0.0025 (5) | 0.0008 (5) |
O2 | 0.0161 (5) | 0.0383 (6) | 0.0213 (5) | 0.0076 (4) | 0.0079 (4) | 0.0089 (4) |
C16 | 0.0198 (12) | 0.055 (2) | 0.0368 (14) | 0.0198 (14) | 0.0121 (10) | 0.0105 (15) |
C17 | 0.0438 (15) | 0.0669 (19) | 0.0368 (13) | 0.0383 (13) | 0.0182 (11) | 0.0195 (12) |
C18 | 0.0151 (6) | 0.0138 (6) | 0.0184 (6) | 0.0032 (5) | 0.0056 (5) | 0.0072 (5) |
C91 | 0.0465 (10) | 0.0441 (10) | 0.0394 (9) | 0.0246 (8) | 0.0220 (8) | 0.0223 (8) |
C92 | 0.0300 (8) | 0.0499 (10) | 0.0230 (7) | 0.0173 (7) | 0.0103 (6) | 0.0173 (7) |
O93 | 0.0310 (6) | 0.0366 (6) | 0.0186 (5) | 0.0095 (4) | 0.0078 (4) | 0.0078 (4) |
C94 | 0.0259 (8) | 0.0439 (9) | 0.0240 (8) | 0.0094 (7) | 0.0017 (6) | 0.0011 (7) |
C95 | 0.0320 (9) | 0.0389 (9) | 0.0366 (9) | 0.0044 (7) | 0.0073 (7) | 0.0056 (7) |
O1W | 0.0370 (6) | 0.0330 (6) | 0.0181 (5) | −0.0079 (5) | 0.0103 (5) | 0.0050 (5) |
O2W | 0.0291 (6) | 0.0183 (5) | 0.0353 (6) | 0.0044 (4) | 0.0007 (5) | 0.0133 (5) |
Ca—O1 | 2.2696 (9) | N1—H01 | 0.855 (16) |
Ca—O2W | 2.3265 (10) | C2—H2 | 0.9500 |
Ca—O1W | 2.3434 (10) | C3—H3 | 0.9500 |
S1—C13 | 1.7686 (12) | C4—H4 | 0.9500 |
S1—C14 | 1.7891 (12) | C5—H5 | 0.9500 |
S2—C13 | 1.7037 (12) | C6—H6 | 0.9500 |
O1—C11 | 1.2494 (14) | C7—H7 | 0.9500 |
O3—C15 | 1.2064 (15) | C8—H8 | 0.9500 |
N1—C11 | 1.3448 (15) | C14—H14A | 0.9900 |
N1—C1 | 1.4184 (15) | C14—H14B | 0.9900 |
N2—C18 | 1.1518 (16) | C16—H16A | 0.9900 |
C1—C2 | 1.3702 (17) | C16—H16B | 0.9900 |
C1—C10 | 1.4325 (17) | C17—H17A | 0.9800 |
C2—C3 | 1.4063 (17) | C17—H17B | 0.9800 |
C3—C4 | 1.3643 (18) | C17—H17C | 0.9800 |
C4—C9 | 1.4113 (18) | C16'—H16C | 0.9900 |
C5—C6 | 1.3631 (19) | C16'—H16D | 0.9900 |
C5—C9 | 1.4199 (18) | C17'—H17D | 0.9800 |
C6—C7 | 1.4059 (19) | C17'—H17E | 0.9800 |
C7—C8 | 1.3713 (17) | C17'—H17F | 0.9800 |
C8—C10 | 1.4156 (17) | C91—H91A | 0.9800 |
C9—C10 | 1.4284 (16) | C91—H91B | 0.9800 |
C11—C12 | 1.4684 (16) | C91—H91C | 0.9800 |
C12—C13 | 1.3996 (17) | C92—H92A | 0.9900 |
C12—C18 | 1.4325 (17) | C92—H92B | 0.9900 |
C14—C15 | 1.5105 (17) | C94—H94A | 0.9900 |
C15—O2 | 1.3323 (15) | C94—H94B | 0.9900 |
O2—C16' | 1.433 (9) | C95—H95A | 0.9800 |
O2—C16 | 1.497 (3) | C95—H95B | 0.9800 |
C16—C17 | 1.455 (3) | C95—H95C | 0.9800 |
C16'—C17' | 1.545 (8) | O1W—H1W | 0.824 (13) |
C91—C92 | 1.499 (2) | O1W—H2W | 0.820 (13) |
C92—O93 | 1.4255 (17) | O2W—H3W | 0.819 (13) |
O93—C94 | 1.4277 (17) | O2W—H4W | 0.810 (13) |
C94—C95 | 1.503 (2) | ||
O1i—Ca—O1 | 180.0 | C9—C5—H5 | 119.2 |
O1—Ca—O2Wi | 92.96 (4) | C5—C6—H6 | 120.1 |
O1i—Ca—O2W | 92.96 (4) | C7—C6—H6 | 120.1 |
O1—Ca—O2W | 87.04 (4) | C8—C7—H7 | 119.8 |
O2Wi—Ca—O2W | 180.0 | C6—C7—H7 | 119.8 |
O1—Ca—O1Wi | 83.15 (3) | C7—C8—H8 | 119.4 |
O2W—Ca—O1Wi | 91.93 (4) | C10—C8—H8 | 119.4 |
O1i—Ca—O1W | 83.15 (4) | C15—C14—H14A | 109.0 |
O1—Ca—O1W | 96.85 (3) | S1—C14—H14A | 109.0 |
O2Wi—Ca—O1W | 91.93 (4) | C15—C14—H14B | 109.0 |
O2W—Ca—O1W | 88.07 (4) | S1—C14—H14B | 109.0 |
O1Wi—Ca—O1W | 180.0 | H14A—C14—H14B | 107.8 |
C13—S1—C14 | 103.00 (6) | C17—C16—H16A | 109.8 |
C11—O1—Ca | 161.36 (9) | O2—C16—H16A | 109.8 |
C11—N1—C1 | 126.41 (11) | C17—C16—H16B | 109.8 |
C2—C1—N1 | 122.01 (11) | O2—C16—H16B | 109.8 |
C2—C1—C10 | 120.73 (11) | H16A—C16—H16B | 108.2 |
N1—C1—C10 | 117.26 (11) | C16—C17—H17A | 109.5 |
C1—C2—C3 | 120.42 (12) | C16—C17—H17B | 109.5 |
C4—C3—C2 | 120.61 (12) | H17A—C17—H17B | 109.5 |
C3—C4—C9 | 120.80 (12) | C16—C17—H17C | 109.5 |
C6—C5—C9 | 121.59 (12) | H17A—C17—H17C | 109.5 |
C5—C6—C7 | 119.90 (12) | H17B—C17—H17C | 109.5 |
C8—C7—C6 | 120.40 (13) | O2—C16'—H16C | 112.1 |
C7—C8—C10 | 121.21 (12) | C17'—C16'—H16C | 112.1 |
C4—C9—C5 | 122.03 (12) | O2—C16'—H16D | 112.1 |
C4—C9—C10 | 119.51 (11) | C17'—C16'—H16D | 112.1 |
C5—C9—C10 | 118.46 (12) | H16C—C16'—H16D | 109.7 |
C8—C10—C9 | 118.44 (11) | C16'—C17'—H17D | 109.5 |
C8—C10—C1 | 123.63 (11) | C16'—C17'—H17E | 109.5 |
C9—C10—C1 | 117.93 (11) | H17D—C17'—H17E | 109.5 |
O1—C11—N1 | 122.08 (11) | C16'—C17'—H17F | 109.5 |
O1—C11—C12 | 119.03 (11) | H17D—C17'—H17F | 109.5 |
N1—C11—C12 | 118.89 (11) | H17E—C17'—H17F | 109.5 |
C13—C12—C18 | 118.58 (11) | C92—C91—H91A | 109.5 |
C13—C12—C11 | 129.48 (11) | C92—C91—H91B | 109.5 |
C18—C12—C11 | 111.94 (10) | H91A—C91—H91B | 109.5 |
C12—C13—S2 | 126.43 (9) | C92—C91—H91C | 109.5 |
C12—C13—S1 | 113.61 (9) | H91A—C91—H91C | 109.5 |
S2—C13—S1 | 119.95 (7) | H91B—C91—H91C | 109.5 |
C15—C14—S1 | 113.08 (9) | O93—C92—H92A | 109.9 |
O3—C15—O2 | 124.07 (12) | C91—C92—H92A | 109.9 |
O3—C15—C14 | 125.39 (12) | O93—C92—H92B | 109.9 |
O2—C15—C14 | 110.52 (10) | C91—C92—H92B | 109.9 |
C15—O2—C16' | 122.7 (4) | H92A—C92—H92B | 108.3 |
C15—O2—C16 | 112.09 (14) | O93—C94—H94A | 109.9 |
C16'—O2—C16 | 19.7 (3) | C95—C94—H94A | 109.9 |
C17—C16—O2 | 109.5 (2) | O93—C94—H94B | 109.9 |
O2—C16'—C17' | 98.6 (5) | C95—C94—H94B | 109.9 |
N2—C18—C12 | 179.36 (14) | H94A—C94—H94B | 108.3 |
O93—C92—C91 | 108.82 (12) | C94—C95—H95A | 109.5 |
C92—O93—C94 | 112.91 (11) | C94—C95—H95B | 109.5 |
O93—C94—C95 | 109.05 (12) | H95A—C95—H95B | 109.5 |
C11—N1—H01 | 116.6 (10) | C94—C95—H95C | 109.5 |
C1—N1—H01 | 116.8 (10) | H95A—C95—H95C | 109.5 |
C1—C2—H2 | 119.8 | H95B—C95—H95C | 109.5 |
C3—C2—H2 | 119.8 | Ca—O1W—H1W | 138.0 (12) |
C4—C3—H3 | 119.7 | Ca—O1W—H2W | 113.9 (13) |
C2—C3—H3 | 119.7 | H1W—O1W—H2W | 105.2 (16) |
C3—C4—H4 | 119.6 | Ca—O2W—H3W | 129.2 (12) |
C9—C4—H4 | 119.6 | Ca—O2W—H4W | 122.9 (13) |
C6—C5—H5 | 119.2 | H3W—O2W—H4W | 107.1 (16) |
O1i—Ca—O1—C11 | 71 (6) | Ca—O1—C11—C12 | 79.9 (3) |
O2Wi—Ca—O1—C11 | 153.0 (3) | C1—N1—C11—O1 | 3.5 (2) |
O2W—Ca—O1—C11 | −27.0 (3) | C1—N1—C11—C12 | −176.62 (11) |
O1Wi—Ca—O1—C11 | −119.3 (3) | O1—C11—C12—C13 | −176.38 (12) |
O1W—Ca—O1—C11 | 60.7 (3) | N1—C11—C12—C13 | 3.71 (19) |
C11—N1—C1—C2 | −34.63 (18) | O1—C11—C12—C18 | 3.10 (16) |
C11—N1—C1—C10 | 145.94 (12) | N1—C11—C12—C18 | −176.80 (11) |
N1—C1—C2—C3 | 179.07 (11) | C18—C12—C13—S2 | −177.98 (9) |
C10—C1—C2—C3 | −1.52 (19) | C11—C12—C13—S2 | 1.48 (19) |
C1—C2—C3—C4 | 0.79 (19) | C18—C12—C13—S1 | 1.28 (15) |
C2—C3—C4—C9 | 0.62 (19) | C11—C12—C13—S1 | −179.27 (10) |
C9—C5—C6—C7 | −0.3 (2) | C14—S1—C13—C12 | 178.99 (9) |
C5—C6—C7—C8 | 0.4 (2) | C14—S1—C13—S2 | −1.70 (9) |
C6—C7—C8—C10 | 0.1 (2) | C13—S1—C14—C15 | −68.69 (9) |
C3—C4—C9—C5 | 178.77 (13) | S1—C14—C15—O3 | −20.07 (15) |
C3—C4—C9—C10 | −1.27 (19) | S1—C14—C15—O2 | 161.69 (8) |
C6—C5—C9—C4 | 179.68 (13) | O3—C15—O2—C16' | −11.5 (4) |
C6—C5—C9—C10 | −0.29 (19) | C14—C15—O2—C16' | 166.8 (3) |
C7—C8—C10—C9 | −0.74 (19) | O3—C15—O2—C16 | 7.3 (2) |
C7—C8—C10—C1 | 179.59 (12) | C14—C15—O2—C16 | −174.45 (16) |
C4—C9—C10—C8 | −179.15 (12) | C15—O2—C16—C17 | 170.4 (2) |
C5—C9—C10—C8 | 0.82 (17) | C16'—O2—C16—C17 | −63.0 (12) |
C4—C9—C10—C1 | 0.53 (17) | C15—O2—C16'—C17' | 103.4 (5) |
C5—C9—C10—C1 | −179.50 (12) | C16—O2—C16'—C17' | 41.3 (9) |
C2—C1—C10—C8 | −179.49 (12) | C13—C12—C18—N2 | 162 (14) |
N1—C1—C10—C8 | −0.05 (18) | C11—C12—C18—N2 | −17 (14) |
C2—C1—C10—C9 | 0.84 (17) | C91—C92—O93—C94 | 179.86 (11) |
N1—C1—C10—C9 | −179.72 (10) | C92—O93—C94—C95 | −179.38 (12) |
Ca—O1—C11—N1 | −100.2 (3) |
Symmetry code: (i) −x, −y+1, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H01···S2 | 0.855 (16) | 2.279 (16) | 3.0274 (11) | 146.2 (14) |
O1W—H1W···O93 | 0.82 (1) | 1.94 (1) | 2.7531 (14) | 171 (2) |
O1W—H2W···N2i | 0.82 (1) | 2.22 (1) | 2.9902 (15) | 157 (2) |
O2W—H3W···O3ii | 0.82 (1) | 2.03 (1) | 2.7797 (13) | 151 (2) |
O2W—H4W···S2ii | 0.81 (1) | 2.51 (1) | 3.2666 (11) | 157 (2) |
Symmetry codes: (i) −x, −y+1, −z+2; (ii) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Ca(C18H15N2O3S2)(H2O)4]·2C4H10O |
Mr | 1003.26 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 7.8665 (3), 12.4361 (5), 13.8045 (6) |
α, β, γ (°) | 103.692 (4), 99.963 (4), 101.609 (3) |
V (Å3) | 1250.24 (9) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.35 |
Crystal size (mm) | 0.4 × 0.3 × 0.1 |
Data collection | |
Diffractometer | Oxford Diffraction Xcalibur Eos |
Absorption correction | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) |
Tmin, Tmax | 0.970, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 26853, 6443, 4941 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.675 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.070, 0.96 |
No. of reflections | 6443 |
No. of parameters | 326 |
No. of restraints | 18 |
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: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP (Siemens, 1994).
Ca—O1 | 2.2696 (9) | N1—C11 | 1.3448 (15) |
Ca—O2W | 2.3265 (10) | N1—C1 | 1.4184 (15) |
Ca—O1W | 2.3434 (10) | N2—C18 | 1.1518 (16) |
S1—C13 | 1.7686 (12) | C11—C12 | 1.4684 (16) |
S1—C14 | 1.7891 (12) | C12—C13 | 1.3996 (17) |
S2—C13 | 1.7037 (12) | C12—C18 | 1.4325 (17) |
O1—C11 | 1.2494 (14) | ||
O1—Ca—O2Wi | 92.96 (4) | O1—C11—N1 | 122.08 (11) |
O1—Ca—O2W | 87.04 (4) | O1—C11—C12 | 119.03 (11) |
O1—Ca—O1Wi | 83.15 (3) | N1—C11—C12 | 118.89 (11) |
O2W—Ca—O1Wi | 91.93 (4) | C13—C12—C18 | 118.58 (11) |
O1—Ca—O1W | 96.85 (3) | C13—C12—C11 | 129.48 (11) |
O2W—Ca—O1W | 88.07 (4) | C18—C12—C11 | 111.94 (10) |
C13—S1—C14 | 103.00 (6) | C12—C13—S2 | 126.43 (9) |
C11—O1—Ca | 161.36 (9) | C12—C13—S1 | 113.61 (9) |
C11—N1—C1 | 126.41 (11) | S2—C13—S1 | 119.95 (7) |
C11—N1—C1—C2 | −34.63 (18) | C11—C12—C13—S2 | 1.48 (19) |
C1—N1—C11—C12 | −176.62 (11) | C11—C12—C13—S1 | −179.27 (10) |
N1—C11—C12—C13 | 3.71 (19) | C14—S1—C13—C12 | 178.99 (9) |
Symmetry code: (i) −x, −y+1, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H01···S2 | 0.855 (16) | 2.279 (16) | 3.0274 (11) | 146.2 (14) |
O1W—H1W···O93 | 0.824 (13) | 1.936 (13) | 2.7531 (14) | 171.1 (17) |
O1W—H2W···N2i | 0.820 (13) | 2.218 (14) | 2.9902 (15) | 157.1 (18) |
O2W—H3W···O3ii | 0.819 (13) | 2.034 (14) | 2.7797 (13) | 151.2 (15) |
O2W—H4W···S2ii | 0.810 (13) | 2.506 (14) | 3.2666 (11) | 156.9 (16) |
Symmetry codes: (i) −x, −y+1, −z+2; (ii) x−1, y, z. |
During the course of our studies directed toward exploring the synthetic potential of ketene dithioacetals for synthesizing new classes of novel antimetabolic agents (Elgemeie & Sood, 2006; Elgemeie et al., 2008, 2009), we have recently reported various successful approaches for synthesis of mercaptopurine and pyrimidine analogues by the reaction of ketene dithioacetals with active methylene functions (Elgemeie, 2003; Elgemeie et al., 2004, 2007). In conjunction of this work, we report here a novel calcium salt (I) of a ketene dithioacetal. The structure of (I) was established on the basis of its elemental analysis and spectral data (see Experimental). In order to establish unambiguously the structure of the product, the crystal structure was determined. The X-ray analysis confirms the exclusive presence of the form (I) in the solid state (Figure 1).
The structure consists of a calcium ion on an inversion centre, coordinated octahedrally by four water molecules and two anions of the ketene dithioacetal; the latter coordinate via the amidic carbonyl oxygen O1, with Ca—O1 2.2696 (9) Å. The asymmetric unit also contains one molecule of diethyl ether.
Within the ligand, there is presumably extensive delocalization of the negative charge from its formal position at the "thiolate" sulfur S2 through the ligand backbone (see dimensions in Table 1), in which the ten atoms C1, C11–14, C18, N1, O1, S1 and S2 are approximately coplanar (r.m.s. deviation 0.035 Å). The backbone angles C11—C12—C13 and C12—C13—S2 are noticeably wide at 126.43 (9) and 129.48 (11)° respectively. The Ca atom lies 0.862 (1) Å out of the backbone plane,and the naphthalene plane subtends an interplanar angle to this plane of 29.03 (2)°.
Intramolecular hydrogen bonds (Table 2) are observed from the NH function to the formally thiolate sulfur and from a hydrogen of the coordinated water O1W to the nitrile N. Additionally, the ether molecules are connected by a hydrogen bond from the same water to the ether oxygen. Intramolecular H bonds from the second water to the thiolate sulfur and the 2-oxo function connect the molecules to form chains parallel to the a axis (Fig. 2).