Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807054918/ci2499sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807054918/ci2499Isup2.hkl |
CCDC reference: 672674
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.003 Å
- R factor = 0.024
- wR factor = 0.057
- Data-to-parameter ratio = 15.7
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT230_ALERT_2_C Hirshfeld Test Diff for N3 - C8 .. 5.45 su PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for N4 PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 2 PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 2 N O3
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT794_ALERT_5_G Check Predicted Bond Valency for Cd1 (2) 2.17
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 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: Bell et al. (2003); Hu et al. (2006); Liu et al. (2006, 2007); Paul et al. (2004); Steel (2005); Ward et al. (2001); Zou et al. (2004, 2005, 2006). For hydrogen-bond details, see: Desiraju & Steiner (1999).
3-(2-Pyridyl)-1H-pyrazole) (0.1 mmol) and Cd(NO3)2 (0.1 mmol) were added to methanol (15 ml) containing water (5 ml). In few minutes, a white solid appeared which then was filtered. The resulting solution was kept at room temperature. Colourless single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of the solvent after several days (yield: 30%). Analysis calculated for (C16H18CdN8O8): C 34.15, H 3.22, N 19.91%; found: C 34.26, H 3.14, N 18.77%.
H atoms of the water molecule were located in a difference map and were allowed to ride on the parent atom, with Uiso = 1.2Ueq(O). The remaining H atoms were included in calculated positions and treated in the subsequent refinement as riding atoms, with C-H = 0.93 Å, N-H = 0.86 Å and i>Uiso(H) = 1.2Ueq(C,N).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL (Bruker, 1998) and PLATON (Spek, 2003).
[Cd(C8H7N3)2(H2O)2](NO3)2 | F(000) = 564 |
Mr = 562.78 | Dx = 1.790 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 666 reflections |
a = 8.1283 (16) Å | θ = 2.3–22.5° |
b = 10.461 (2) Å | µ = 1.11 mm−1 |
c = 12.309 (3) Å | T = 293 K |
β = 94.04 (3)° | Block, colourless |
V = 1044.0 (4) Å3 | 0.22 × 0.18 × 0.16 mm |
Z = 2 |
Bruker SMART CCD area-detector diffractometer | 2377 independent reflections |
Radiation source: fine-focus sealed tube | 1810 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
ϕ and ω scans | θmax = 27.5°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | h = −10→10 |
Tmin = 0.795, Tmax = 0.845 | k = −14→13 |
6639 measured reflections | l = −15→15 |
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)] = 0.025 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.057 | H-atom parameters constrained |
S = 0.93 | w = 1/[σ2(Fo2) + (0.0278P)2] where P = (Fo2 + 2Fc2)/3 |
2377 reflections | (Δ/σ)max = 0.001 |
151 parameters | Δρmax = 0.43 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
[Cd(C8H7N3)2(H2O)2](NO3)2 | V = 1044.0 (4) Å3 |
Mr = 562.78 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.1283 (16) Å | µ = 1.11 mm−1 |
b = 10.461 (2) Å | T = 293 K |
c = 12.309 (3) Å | 0.22 × 0.18 × 0.16 mm |
β = 94.04 (3)° |
Bruker SMART CCD area-detector diffractometer | 2377 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | 1810 reflections with I > 2σ(I) |
Tmin = 0.795, Tmax = 0.845 | Rint = 0.032 |
6639 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.057 | H-atom parameters constrained |
S = 0.93 | Δρmax = 0.43 e Å−3 |
2377 reflections | Δρmin = −0.25 e Å−3 |
151 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 | ||
Cd1 | 0.5000 | 1.0000 | 0.5000 | 0.03912 (8) | |
C1 | 0.7329 (3) | 0.6068 (2) | 0.5375 (2) | 0.0564 (6) | |
H1A | 0.8148 | 0.5450 | 0.5353 | 0.068* | |
C2 | 0.5940 (3) | 0.5968 (2) | 0.5903 (2) | 0.0559 (6) | |
H2A | 0.5605 | 0.5283 | 0.6315 | 0.067* | |
C3 | 0.5102 (3) | 0.7142 (2) | 0.56918 (17) | 0.0423 (5) | |
C4 | 0.3529 (3) | 0.7578 (2) | 0.60517 (17) | 0.0419 (5) | |
C5 | 0.2468 (3) | 0.6775 (2) | 0.6560 (2) | 0.0593 (7) | |
H5A | 0.2746 | 0.5923 | 0.6686 | 0.071* | |
C6 | 0.1009 (3) | 0.7249 (3) | 0.6875 (2) | 0.0669 (8) | |
H6A | 0.0294 | 0.6719 | 0.7224 | 0.080* | |
C7 | 0.0596 (3) | 0.8489 (3) | 0.6681 (2) | 0.0610 (7) | |
H7A | −0.0398 | 0.8816 | 0.6890 | 0.073* | |
C8 | 0.1675 (3) | 0.9247 (2) | 0.6172 (2) | 0.0536 (6) | |
H8A | 0.1393 | 1.0095 | 0.6030 | 0.064* | |
N1 | 0.7326 (2) | 0.72088 (19) | 0.48873 (18) | 0.0529 (5) | |
H1B | 0.8102 | 0.7479 | 0.4506 | 0.064* | |
N2 | 0.5972 (2) | 0.78798 (17) | 0.50643 (15) | 0.0444 (4) | |
N3 | 0.3126 (2) | 0.88119 (17) | 0.58709 (14) | 0.0416 (4) | |
N4 | −0.4146 (2) | 0.79729 (19) | 0.84554 (14) | 0.0449 (4) | |
O1 | −0.4736 (2) | 0.69650 (17) | 0.87871 (16) | 0.0685 (5) | |
O2 | −0.2770 (2) | 0.7968 (2) | 0.81080 (17) | 0.0818 (6) | |
O3 | −0.4952 (3) | 0.89658 (17) | 0.84575 (19) | 0.0767 (6) | |
O1W | 0.3392 (2) | 0.96843 (16) | 0.33963 (14) | 0.0583 (5) | |
H1WA | 0.3421 | 1.0117 | 0.2814 | 0.070* | |
H1WB | 0.2902 | 0.8984 | 0.3236 | 0.070* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.03983 (12) | 0.03118 (11) | 0.04703 (13) | −0.00183 (10) | 0.00790 (8) | 0.00727 (10) |
C1 | 0.0514 (14) | 0.0395 (13) | 0.0765 (18) | 0.0158 (11) | −0.0076 (13) | −0.0038 (12) |
C2 | 0.0613 (15) | 0.0411 (12) | 0.0636 (16) | 0.0000 (12) | −0.0068 (12) | 0.0072 (12) |
C3 | 0.0481 (12) | 0.0337 (10) | 0.0436 (12) | −0.0016 (10) | −0.0064 (9) | 0.0007 (9) |
C4 | 0.0517 (12) | 0.0379 (11) | 0.0353 (11) | −0.0125 (10) | −0.0017 (9) | 0.0024 (9) |
C5 | 0.0677 (17) | 0.0509 (14) | 0.0596 (15) | −0.0166 (13) | 0.0075 (13) | 0.0097 (12) |
C6 | 0.0603 (16) | 0.075 (2) | 0.0674 (17) | −0.0231 (15) | 0.0199 (14) | 0.0018 (15) |
C7 | 0.0428 (13) | 0.0773 (19) | 0.0655 (16) | −0.0073 (13) | 0.0222 (12) | −0.0123 (15) |
C8 | 0.0530 (13) | 0.0493 (14) | 0.0594 (15) | −0.0037 (12) | 0.0100 (12) | −0.0038 (12) |
N1 | 0.0448 (10) | 0.0454 (11) | 0.0690 (13) | 0.0079 (9) | 0.0072 (9) | −0.0014 (10) |
N2 | 0.0426 (10) | 0.0353 (9) | 0.0553 (11) | 0.0040 (8) | 0.0036 (8) | 0.0031 (9) |
N3 | 0.0402 (9) | 0.0412 (10) | 0.0440 (10) | −0.0051 (8) | 0.0069 (8) | 0.0009 (8) |
N4 | 0.0498 (11) | 0.0432 (10) | 0.0414 (10) | −0.0084 (9) | 0.0017 (8) | −0.0012 (8) |
O1 | 0.0753 (12) | 0.0446 (10) | 0.0860 (13) | −0.0143 (9) | 0.0072 (10) | 0.0178 (10) |
O2 | 0.0574 (11) | 0.1002 (16) | 0.0920 (15) | −0.0163 (11) | 0.0359 (10) | −0.0100 (13) |
O3 | 0.0805 (13) | 0.0438 (10) | 0.1049 (16) | 0.0108 (10) | −0.0012 (11) | −0.0007 (11) |
O1W | 0.0690 (11) | 0.0541 (10) | 0.0504 (9) | −0.0187 (8) | −0.0056 (8) | 0.0104 (8) |
Cd1—N3 | 2.2900 (17) | C5—C6 | 1.367 (4) |
Cd1—N3i | 2.2900 (17) | C5—H5A | 0.93 |
Cd1—O1Wi | 2.3133 (18) | C6—C7 | 1.357 (4) |
Cd1—O1W | 2.3133 (18) | C6—H6A | 0.93 |
Cd1—N2 | 2.3539 (18) | C7—C8 | 1.366 (3) |
Cd1—N2i | 2.3539 (18) | C7—H7A | 0.93 |
C1—N1 | 1.336 (3) | C8—N3 | 1.341 (3) |
C1—C2 | 1.346 (4) | C8—H8A | 0.93 |
C1—H1A | 0.93 | N1—N2 | 1.337 (2) |
C2—C3 | 1.420 (3) | N1—H1B | 0.86 |
C2—H2A | 0.93 | N4—O2 | 1.226 (2) |
C3—N2 | 1.330 (3) | N4—O3 | 1.228 (2) |
C3—C4 | 1.456 (3) | N4—O1 | 1.239 (2) |
C4—N3 | 1.346 (3) | O1W—H1WA | 0.85 |
C4—C5 | 1.384 (3) | O1W—H1WB | 0.85 |
N3—Cd1—N3i | 180 | C6—C5—C4 | 119.3 (3) |
N3—Cd1—O1Wi | 91.87 (6) | C6—C5—H5A | 120.4 |
N3i—Cd1—O1Wi | 88.13 (6) | C4—C5—H5A | 120.4 |
N3—Cd1—O1W | 88.13 (6) | C7—C6—C5 | 120.4 (2) |
N3i—Cd1—O1W | 91.87 (6) | C7—C6—H6A | 119.8 |
O1Wi—Cd1—O1W | 180 | C5—C6—H6A | 119.8 |
N3—Cd1—N2 | 72.87 (6) | C6—C7—C8 | 118.4 (2) |
N3i—Cd1—N2 | 107.13 (6) | C6—C7—H7A | 120.8 |
O1Wi—Cd1—N2 | 86.43 (7) | C8—C7—H7A | 120.8 |
O1W—Cd1—N2 | 93.57 (7) | N3—C8—C7 | 122.4 (2) |
N3—Cd1—N2i | 107.13 (6) | N3—C8—H8A | 118.8 |
N3i—Cd1—N2i | 72.87 (6) | C7—C8—H8A | 118.8 |
O1Wi—Cd1—N2i | 93.57 (7) | C1—N1—N2 | 111.8 (2) |
O1W—Cd1—N2i | 86.43 (7) | C1—N1—H1B | 124.1 |
N2—Cd1—N2i | 180 | N2—N1—H1B | 124.1 |
N1—C1—C2 | 108.2 (2) | C3—N2—N1 | 105.52 (17) |
N1—C1—H1A | 125.9 | C3—N2—Cd1 | 112.07 (13) |
C2—C1—H1A | 125.9 | N1—N2—Cd1 | 140.14 (14) |
C1—C2—C3 | 104.6 (2) | C8—N3—C4 | 119.2 (2) |
C1—C2—H2A | 127.7 | C8—N3—Cd1 | 124.93 (16) |
C3—C2—H2A | 127.7 | C4—N3—Cd1 | 115.83 (14) |
N2—C3—C2 | 109.9 (2) | O2—N4—O3 | 120.3 (2) |
N2—C3—C4 | 120.58 (18) | O2—N4—O1 | 119.7 (2) |
C2—C3—C4 | 129.5 (2) | O3—N4—O1 | 120.0 (2) |
N3—C4—C5 | 120.3 (2) | Cd1—O1W—H1WA | 126.6 |
N3—C4—C3 | 117.32 (18) | Cd1—O1W—H1WB | 123.3 |
C5—C4—C3 | 122.4 (2) | H1WA—O1W—H1WB | 107.7 |
N1—C1—C2—C3 | 0.1 (3) | O1Wi—Cd1—N2—C3 | 83.94 (15) |
C1—C2—C3—N2 | 0.3 (3) | O1W—Cd1—N2—C3 | −96.06 (15) |
C1—C2—C3—C4 | 179.9 (2) | N3—Cd1—N2—N1 | −168.5 (2) |
N2—C3—C4—N3 | −10.1 (3) | N3i—Cd1—N2—N1 | 11.5 (2) |
C2—C3—C4—N3 | 170.3 (2) | O1Wi—Cd1—N2—N1 | −75.4 (2) |
N2—C3—C4—C5 | 169.8 (2) | O1W—Cd1—N2—N1 | 104.6 (2) |
C2—C3—C4—C5 | −9.8 (4) | C7—C8—N3—C4 | 1.5 (4) |
N3—C4—C5—C6 | 0.1 (4) | C7—C8—N3—Cd1 | 179.34 (19) |
C3—C4—C5—C6 | −179.9 (2) | C5—C4—N3—C8 | −1.1 (3) |
C4—C5—C6—C7 | 0.7 (4) | C3—C4—N3—C8 | 178.82 (19) |
C5—C6—C7—C8 | −0.3 (4) | C5—C4—N3—Cd1 | −179.15 (17) |
C6—C7—C8—N3 | −0.8 (4) | C3—C4—N3—Cd1 | 0.8 (2) |
C2—C1—N1—N2 | −0.4 (3) | O1Wi—Cd1—N3—C8 | 100.70 (18) |
C2—C3—N2—N1 | −0.5 (2) | O1W—Cd1—N3—C8 | −79.30 (18) |
C4—C3—N2—N1 | 179.83 (19) | N2—Cd1—N3—C8 | −173.62 (19) |
C2—C3—N2—Cd1 | −166.96 (15) | N2i—Cd1—N3—C8 | 6.38 (19) |
C4—C3—N2—Cd1 | 13.4 (2) | O1Wi—Cd1—N3—C4 | −81.39 (16) |
C1—N1—N2—C3 | 0.6 (3) | O1W—Cd1—N3—C4 | 98.61 (16) |
C1—N1—N2—Cd1 | 160.79 (18) | N2—Cd1—N3—C4 | 4.29 (14) |
N3—Cd1—N2—C3 | −9.12 (14) | N2i—Cd1—N3—C4 | −175.71 (14) |
N3i—Cd1—N2—C3 | 170.88 (14) |
Symmetry code: (i) −x+1, −y+2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O2ii | 0.85 | 2.34 | 3.096 (3) | 148 |
O1W—H1WA···O3ii | 0.85 | 2.28 | 3.036 (3) | 149 |
O1W—H1WB···O2iii | 0.85 | 2.12 | 2.944 (3) | 164 |
N1—H1B···O1iv | 0.86 | 2.10 | 2.956 (3) | 171 |
N1—H1B···O3iv | 0.86 | 2.60 | 3.170 (3) | 125 |
O1W—H1WB···O1iii | 0.85 | 2.50 | 3.138 (2) | 133 |
C1—H1A···O3v | 0.93 | 2.53 | 3.319 (3) | 143 |
C8—H8A···O1vi | 0.93 | 2.39 | 3.253 (3) | 153 |
Symmetry codes: (ii) −x, −y+2, −z+1; (iii) x+1/2, −y+3/2, z−1/2; (iv) x+3/2, −y+3/2, z−1/2; (v) −x+1/2, y−1/2, −z+3/2; (vi) −x−1/2, y+1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Cd(C8H7N3)2(H2O)2](NO3)2 |
Mr | 562.78 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 8.1283 (16), 10.461 (2), 12.309 (3) |
β (°) | 94.04 (3) |
V (Å3) | 1044.0 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.11 |
Crystal size (mm) | 0.22 × 0.18 × 0.16 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1998) |
Tmin, Tmax | 0.795, 0.845 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6639, 2377, 1810 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.057, 0.93 |
No. of reflections | 2377 |
No. of parameters | 151 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.43, −0.25 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998) and PLATON (Spek, 2003).
Cd1—N3 | 2.2900 (17) | Cd1—N2 | 2.3539 (18) |
Cd1—O1W | 2.3133 (18) | ||
N3—Cd1—N3i | 180 | O1W—Cd1—N2 | 93.57 (7) |
N3—Cd1—O1Wi | 91.87 (6) | N3—Cd1—N2i | 107.13 (6) |
N3—Cd1—O1W | 88.13 (6) | O1W—Cd1—N2i | 86.43 (7) |
O1Wi—Cd1—O1W | 180 | N2—Cd1—N2i | 180 |
N3—Cd1—N2 | 72.87 (6) |
Symmetry code: (i) −x+1, −y+2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O2ii | 0.85 | 2.34 | 3.096 (3) | 148 |
O1W—H1WA···O3ii | 0.85 | 2.28 | 3.036 (3) | 149 |
O1W—H1WB···O2iii | 0.85 | 2.12 | 2.944 (3) | 164 |
N1—H1B···O1iv | 0.86 | 2.10 | 2.956 (3) | 171 |
N1—H1B···O3iv | 0.86 | 2.60 | 3.170 (3) | 125 |
O1W—H1WB···O1iii | 0.85 | 2.50 | 3.138 (2) | 133 |
C1—H1A···O3v | 0.93 | 2.53 | 3.319 (3) | 143 |
C8—H8A···O1vi | 0.93 | 2.39 | 3.253 (3) | 153 |
Symmetry codes: (ii) −x, −y+2, −z+1; (iii) x+1/2, −y+3/2, z−1/2; (iv) x+3/2, −y+3/2, z−1/2; (v) −x+1/2, y−1/2, −z+3/2; (vi) −x−1/2, y+1/2, −z+3/2. |
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In recent years, much attention has been focused on the synthetic approach and the structural control of metal-organic coordination architectures with ligands based on pyrazolyl-pyridine chelating units (Steel, 2005; Ward et al., 2001). Many novel functional complexes with 3-(2-pyridyl)-1H-pyrazole (L) and/or 3-(2-pyridyl)pyrazole ligands have been reported (Bell et al., 2003; Paul et al., 2004; Singh et al., 2003; Ward et al., 2001). Recently, we have used 3-(2-pyridyl)-1H-pyrazole and its derivatives to obtain complexes with various structures, including discrete multinuclear molecules, one- and two-dimensional coordination polymers, which exhibit luminescent and magnetic properties (Hu et al., 2006; Liu et al., 2006, 2007; Zou et al., 2004,2005,2006). Now we report here the crystal structure of a cadmium(II) complex of L ligand, [Cd(L)2(H2O)2]2+.2NO32-, the title compound.
In the title centrosymmetric complex, the CdII center is six-coordinated by four N donors from two L ligands and two O atoms from two water molecules (Table 1). The L ligand chelates to the CdII atom, which lies on an inversion center, in a nearly isobidentate manner [Cd1—N2 = 2.3539 (18) Å and Cd1—N3 = 2.2900 (17) Å]. The two other coordination sites are occupied by two water molecules. The coordination geometry around the CdII center can be described as a distorted octahedron (Fig. 1). The distortion from the ideal octahedral geometry is evident from the bond angles given in Table 1.
The CdII mononuclear units are linked to nitrate anions through intermolecular O–H···O, N–H···O and C–H···O (Desiraju & Steiner, 1999) hydrogen-bonding interactions (Table 2) involving the coordinated water molecules and free nitrate anions, forming a three-dimensional framework (Fig. 2).