


Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536812040913/bt6838sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536812040913/bt6838Isup2.hkl |
CCDC reference: 909715
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean
(C-C) = 0.004 Å
- R factor = 0.026
- wR factor = 0.061
- Data-to-parameter ratio = 20.1
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT125_ALERT_4_C No '_symmetry_space_group_name_Hall' Given ..... ? PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 3.2 Ratio PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O11 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for N1 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C1 PLAT906_ALERT_3_C Large K value in the Analysis of Variance ...... 5.284 PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 3 PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF .... 1
Alert level G PLAT004_ALERT_5_G Info: Polymeric Structure Found with Dimension . 2 PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF .... ? PLAT007_ALERT_5_G Note: Number of Unrefined D-H Atoms ............ 1 PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature 293 K PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X) Cd1 -- O12 .. 11.5 su PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X) Cd1 -- S1_b .. 6.6 su PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels .......... 1 PLAT764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd) . 1.16 Ratio PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 14
0 ALERT level A = Most likely a serious problem - resolve or explain 0 ALERT level B = A potentially serious problem, consider carefully 8 ALERT level C = Check. Ensure it is not caused by an omission or oversight 10 ALERT level G = General information/check it is not something unexpected 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 6 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 4 ALERT type 4 Improvement, methodology, query or suggestion 3 ALERT type 5 Informative message, check
Potassium thiocyanate and isonicotinic acid were purchased from Alfa Aesar, Cd(SO4)2.4H2O was obtained from Merck. The Cd(NCS)2 was prepared by stirring Ba(NCS)2.3H2O (3.076 g, 10 mmol) and CdSO4.8/3H2O (2.566 g, 10 mmol) in water (100 ml). The white precipitate of BaSO4 was filtered off and the water was removed from the filtrate by heating. The final product was dried at 80°C. The homogeneity of the product was investigated by X-ray powder diffraction. The title compound was prepared by the reaction of 34.3 mg Cd(NCS)2(0.15 mmol) and 36.9 mg isonicotinic acid (0.30 mmol) in 2 ml ethanol at 80°C in a closed 10 ml glass culture tube. After several days colourless needles of the title compound were obtained.
The C—H H atoms were positioned with idealized geometry (methyl H atoms allowed to rotate but not to tip) and were refined isotropically with Uiso(H) = 1.2Ueq(C) for aromatic H atoms (1.5 for methyl H atoms) using a riding model with C—H = 0.93 Å (aromatic H atoms) and with C—H = 0.96 Å (methyl H atoms). The O—H H atom was located in difference map, its bond length set to ideal value of 0.82 Å and finally it was refined using a riding model with Uiso(H) = 1.2Ueq(O).
Data collection: X-AREA (Stoe, 2008); cell refinement: X-AREA (Stoe, 2008); data reduction: X-AREA (Stoe, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011); software used to prepare material for publication: publCIF (Westrip, 2010).
[Cd(NCS)(C6H4NO2)(C2H6O)] | F(000) = 664 |
Mr = 338.65 | Dx = 1.845 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 5.7778 (2) Å | Cell parameters from 17537 reflections |
b = 16.1804 (6) Å | θ = 2.0–28.0° |
c = 13.0855 (6) Å | µ = 1.96 mm−1 |
β = 94.685 (3)° | T = 293 K |
V = 1219.24 (8) Å3 | Needle, colourless |
Z = 4 | 0.28 × 0.10 × 0.04 mm |
Stoe IPDS-1 diffractometer | 2920 independent reflections |
Radiation source: fine-focus sealed tube | 2545 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
ϕ scans | θmax = 28.0°, θmin = 2.0° |
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe, 2008) | h = −7→7 |
Tmin = 0.803, Tmax = 0.931 | k = −21→21 |
17537 measured reflections | l = −17→17 |
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)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.061 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0288P)2 + 0.6822P] where P = (Fo2 + 2Fc2)/3 |
2920 reflections | (Δ/σ)max = 0.001 |
145 parameters | Δρmax = 0.38 e Å−3 |
0 restraints | Δρmin = −0.44 e Å−3 |
[Cd(NCS)(C6H4NO2)(C2H6O)] | V = 1219.24 (8) Å3 |
Mr = 338.65 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.7778 (2) Å | µ = 1.96 mm−1 |
b = 16.1804 (6) Å | T = 293 K |
c = 13.0855 (6) Å | 0.28 × 0.10 × 0.04 mm |
β = 94.685 (3)° |
Stoe IPDS-1 diffractometer | 2920 independent reflections |
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe, 2008) | 2545 reflections with I > 2σ(I) |
Tmin = 0.803, Tmax = 0.931 | Rint = 0.032 |
17537 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.061 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.38 e Å−3 |
2920 reflections | Δρmin = −0.44 e Å−3 |
145 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. |
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 > 2sigma(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 | ||
Cd1 | 0.14587 (3) | 0.856111 (10) | 0.668028 (15) | 0.04089 (7) | |
N1 | −0.1966 (4) | 0.8771 (2) | 0.5822 (2) | 0.0667 (8) | |
C1 | −0.3839 (5) | 0.87582 (19) | 0.5463 (2) | 0.0492 (6) | |
S1 | −0.65079 (13) | 0.87510 (7) | 0.49397 (6) | 0.0662 (2) | |
N11 | 0.7272 (4) | 0.48256 (13) | 0.77586 (18) | 0.0432 (5) | |
C11 | 0.5200 (6) | 0.49095 (17) | 0.7245 (3) | 0.0578 (8) | |
H11 | 0.4417 | 0.4437 | 0.7005 | 0.069* | |
C12 | 0.4168 (5) | 0.56691 (17) | 0.7052 (2) | 0.0540 (7) | |
H12 | 0.2722 | 0.5702 | 0.6687 | 0.065* | |
C13 | 0.5275 (4) | 0.63720 (15) | 0.7401 (2) | 0.0396 (5) | |
C14 | 0.7445 (5) | 0.62913 (15) | 0.7913 (2) | 0.0480 (6) | |
H14 | 0.8275 | 0.6757 | 0.8145 | 0.058* | |
C15 | 0.8372 (5) | 0.55133 (16) | 0.8077 (2) | 0.0490 (6) | |
H15 | 0.9834 | 0.5466 | 0.8426 | 0.059* | |
C16 | 0.4083 (5) | 0.71974 (15) | 0.7252 (2) | 0.0426 (5) | |
O11 | 0.2091 (4) | 0.71926 (12) | 0.67857 (18) | 0.0592 (5) | |
O12 | 0.5052 (3) | 0.78408 (11) | 0.75867 (17) | 0.0510 (5) | |
O21 | −0.0682 (4) | 0.84635 (14) | 0.81279 (16) | 0.0572 (5) | |
H1O1 | −0.2025 | 0.8310 | 0.7996 | 0.086* | |
C21 | 0.0069 (7) | 0.8386 (3) | 0.9186 (3) | 0.0778 (11) | |
H21A | 0.1454 | 0.8720 | 0.9327 | 0.093* | |
H21B | 0.0497 | 0.7815 | 0.9324 | 0.093* | |
C22 | −0.1619 (11) | 0.8630 (4) | 0.9880 (4) | 0.129 (2) | |
H22A | −0.0982 | 0.8552 | 1.0574 | 0.193* | |
H22B | −0.2990 | 0.8298 | 0.9757 | 0.193* | |
H22C | −0.2010 | 0.9201 | 0.9771 | 0.193* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.03291 (10) | 0.03170 (10) | 0.05680 (12) | −0.00051 (7) | −0.00408 (7) | 0.00070 (8) |
N1 | 0.0336 (12) | 0.098 (2) | 0.0675 (16) | 0.0051 (13) | −0.0028 (11) | 0.0164 (15) |
C1 | 0.0382 (14) | 0.0617 (17) | 0.0476 (14) | 0.0037 (12) | 0.0028 (11) | 0.0077 (12) |
S1 | 0.0357 (3) | 0.1101 (7) | 0.0514 (4) | −0.0010 (4) | −0.0046 (3) | 0.0062 (4) |
N11 | 0.0401 (11) | 0.0317 (10) | 0.0569 (13) | 0.0011 (8) | −0.0020 (10) | −0.0014 (9) |
C11 | 0.0541 (17) | 0.0349 (13) | 0.080 (2) | −0.0018 (12) | −0.0226 (16) | −0.0042 (13) |
C12 | 0.0452 (15) | 0.0390 (13) | 0.0739 (19) | 0.0016 (12) | −0.0192 (14) | 0.0019 (13) |
C13 | 0.0386 (12) | 0.0341 (11) | 0.0466 (13) | 0.0009 (10) | 0.0053 (10) | 0.0031 (10) |
C14 | 0.0381 (13) | 0.0320 (12) | 0.0724 (18) | −0.0039 (10) | −0.0043 (12) | −0.0003 (11) |
C15 | 0.0381 (13) | 0.0376 (13) | 0.0692 (18) | 0.0013 (10) | −0.0074 (13) | −0.0007 (12) |
C16 | 0.0408 (13) | 0.0357 (12) | 0.0517 (14) | 0.0007 (10) | 0.0052 (11) | 0.0057 (11) |
O11 | 0.0486 (11) | 0.0379 (10) | 0.0880 (15) | 0.0055 (9) | −0.0130 (11) | 0.0024 (10) |
O12 | 0.0483 (11) | 0.0317 (9) | 0.0721 (13) | 0.0001 (8) | −0.0004 (9) | 0.0024 (8) |
O21 | 0.0479 (11) | 0.0665 (14) | 0.0564 (12) | −0.0085 (10) | −0.0011 (9) | 0.0004 (10) |
C21 | 0.072 (2) | 0.092 (3) | 0.066 (2) | 0.011 (2) | −0.0128 (18) | 0.0078 (19) |
C22 | 0.125 (5) | 0.201 (7) | 0.059 (2) | 0.049 (4) | −0.002 (3) | 0.000 (3) |
Cd1—N1 | 2.220 (3) | C12—H12 | 0.9300 |
Cd1—O11 | 2.247 (2) | C13—C14 | 1.379 (4) |
Cd1—N11i | 2.275 (2) | C13—C16 | 1.508 (3) |
Cd1—O21 | 2.351 (2) | C14—C15 | 1.378 (4) |
Cd1—O12 | 2.583 (2) | C14—H14 | 0.9300 |
Cd1—S1ii | 2.6644 (9) | C15—H15 | 0.9300 |
Cd1—C16 | 2.746 (3) | C16—O12 | 1.245 (3) |
N1—C1 | 1.144 (4) | C16—O11 | 1.258 (3) |
C1—S1 | 1.635 (3) | O21—C21 | 1.422 (4) |
S1—Cd1iii | 2.6644 (9) | O21—H1O1 | 0.8199 |
N11—C11 | 1.331 (4) | C21—C22 | 1.441 (7) |
N11—C15 | 1.331 (3) | C21—H21A | 0.9700 |
N11—Cd1iv | 2.275 (2) | C21—H21B | 0.9700 |
C11—C12 | 1.380 (4) | C22—H22A | 0.9600 |
C11—H11 | 0.9300 | C22—H22B | 0.9600 |
C12—C13 | 1.365 (4) | C22—H22C | 0.9600 |
N1—Cd1—O11 | 108.39 (10) | C12—C13—C14 | 117.8 (2) |
N1—Cd1—N11i | 106.05 (11) | C12—C13—C16 | 119.9 (2) |
O11—Cd1—N11i | 145.09 (8) | C14—C13—C16 | 122.3 (2) |
N1—Cd1—O21 | 84.95 (9) | C15—C14—C13 | 119.2 (2) |
O11—Cd1—O21 | 88.73 (8) | C15—C14—H14 | 120.4 |
N11i—Cd1—O21 | 88.70 (8) | C13—C14—H14 | 120.4 |
N1—Cd1—O12 | 161.97 (10) | N11—C15—C14 | 123.0 (2) |
O11—Cd1—O12 | 53.60 (7) | N11—C15—H15 | 118.5 |
N11i—Cd1—O12 | 91.82 (7) | C14—C15—H15 | 118.5 |
O21—Cd1—O12 | 93.19 (7) | O12—C16—O11 | 122.9 (2) |
N1—Cd1—S1ii | 89.26 (8) | O12—C16—C13 | 120.5 (2) |
O11—Cd1—S1ii | 94.89 (7) | O11—C16—C13 | 116.6 (2) |
N11i—Cd1—S1ii | 91.09 (6) | O12—C16—Cd1 | 69.29 (14) |
O21—Cd1—S1ii | 173.91 (6) | O11—C16—Cd1 | 53.83 (13) |
O12—Cd1—S1ii | 92.90 (5) | C13—C16—Cd1 | 169.39 (19) |
N1—Cd1—C16 | 135.24 (11) | C16—O11—Cd1 | 99.30 (16) |
O11—Cd1—C16 | 26.87 (8) | C16—O12—Cd1 | 83.93 (15) |
N11i—Cd1—C16 | 118.58 (8) | C21—O21—Cd1 | 130.7 (2) |
O21—Cd1—C16 | 92.37 (8) | C21—O21—H1O1 | 112.8 |
O12—Cd1—C16 | 26.78 (7) | Cd1—O21—H1O1 | 113.7 |
S1ii—Cd1—C16 | 93.06 (6) | O21—C21—C22 | 114.9 (3) |
C1—N1—Cd1 | 168.3 (3) | O21—C21—H21A | 108.5 |
N1—C1—S1 | 179.2 (3) | C22—C21—H21A | 108.5 |
C1—S1—Cd1iii | 96.29 (10) | O21—C21—H21B | 108.5 |
C11—N11—C15 | 117.4 (2) | C22—C21—H21B | 108.5 |
C11—N11—Cd1iv | 120.52 (17) | H21A—C21—H21B | 107.5 |
C15—N11—Cd1iv | 121.17 (18) | C21—C22—H22A | 109.5 |
N11—C11—C12 | 122.7 (3) | C21—C22—H22B | 109.5 |
N11—C11—H11 | 118.7 | H22A—C22—H22B | 109.5 |
C12—C11—H11 | 118.7 | C21—C22—H22C | 109.5 |
C13—C12—C11 | 119.8 (3) | H22A—C22—H22C | 109.5 |
C13—C12—H12 | 120.1 | H22B—C22—H22C | 109.5 |
C11—C12—H12 | 120.1 |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x+1, y, z; (iii) x−1, y, z; (iv) −x+1, y−1/2, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O21—H1O1···O12iii | 0.82 | 1.89 | 2.703 (3) | 172 |
Symmetry code: (iii) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Cd(NCS)(C6H4NO2)(C2H6O)] |
Mr | 338.65 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 5.7778 (2), 16.1804 (6), 13.0855 (6) |
β (°) | 94.685 (3) |
V (Å3) | 1219.24 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.96 |
Crystal size (mm) | 0.28 × 0.10 × 0.04 |
Data collection | |
Diffractometer | Stoe IPDS1 diffractometer |
Absorption correction | Numerical (X-SHAPE and X-RED32; Stoe, 2008) |
Tmin, Tmax | 0.803, 0.931 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17537, 2920, 2545 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.660 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.061, 1.06 |
No. of reflections | 2920 |
No. of parameters | 145 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.38, −0.44 |
Computer programs: X-AREA (Stoe, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011), publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
O21—H1O1···O12i | 0.8200 | 1.8900 | 2.703 (3) | 172.00 |
Symmetry code: (i) x−1, y, z. |
The structure of the title compound was prepared within a project on the synthesis of transition metal thiocyanato coordination polymers in which the metal cations are µ-1,3 bridged by the anionic ligands (Näther & Greve, 2003; Boeckmann & Näther, 2010, 2011; Wöhlert et al., 2011). In the course of our investigations crystals of the title compound were obtained and characterized by single-crystal X-ray diffraction.
In the crystal structure the cadmium(II) cations are coordinated by one N and two O atoms of two µ-1,3,6 bridging isonicotinato anions which are related by symmetry, one N and one S atom of two symmetry-related µ-1,3 bridging thiocyanato anions and one O atom of an ethanol molecule (Fig. 1). The coordination polyhedron of the cadmium cations can be described as a slightly distorted octahedron (Table 1).
The Cd2+ cations are µ-1,3 bridged by thiocyanato anions into chains, which elongate in the direction of the crystallographic a axis. These chains are bridged by µ-1,3,6 bridging isonicotinato anions into layers in the direction of the crystallographic b axis and the layers are stacked along the crystallographic c axis (Fig. 2).
The shortest Cd···Cd distances within the layers amounts to 5.7778 (3) Å and to 9.2393 (4) Å. It must be noted that according to research in the CCDC database (ConQuest Ver.1.14; Allen, 2002) one coordination compound based on Cd(NCS)2, isonicotinato anions and thiocyanato anions is known, in which ethanol is exchanged by water. The overall coordination topology is similar but this compound is not isotypic to the title compound (Yang et al., 2001).
The crystal structure is stabilized by an O—H···O hydrogen bond.