Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807027626/lh2414sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807027626/lh2414Isup2.hkl |
CCDC reference: 654736
3,3',5,5'-Tetramethyl-4,4'-bipyrazolyl was synthesized by using a reported procedure (Mosby, 1957). The ligand (0.02 g, 0.1 mmol), cadmium iodide (0.07 g, 0.2 mmol), potassium iodide (0.03 g, 0.2 mmol), methanol (5 ml) and water (5 ml) were mixed in a 15-ml Telfon-lined, stainless-steel Parr bomb. The bomb was heated at 423 K for 72 h and then cooled to room temperature at a rate of 5 K h-1. The resulting solution was left for two days to give colorless block-shaped crystals in about 70% yield.
All H atoms were generated geometrically (O—H 0.82, N—H 0.86 Å and C—H 0.96 Å), and were included in the refinement in the riding model approximation, with U(H) set to 1.2 or 1.5Ueq(C,N,O).
3,3',5,5'-Tetramethyl-4,4'-bipyrazolyl in its doubly-deprotonated form is capable of connecting to four metal sites (Boldog et al., 2001; Boldog, Rusanov et al., 2003; Boldog, Sieler et al., 2003; He et al., 2006; Ponomarova et al., 2002). The disilver(I) derivative exemplifies such a feature; the framework is porous (Zhang et al., 2007). The attempted synthesis of the cadmium derivative yielded an adduct, the neutral heterocycle binding to cadmium diiodide in a 1:1 molar stoichoimetry. The compound crystallizes with a molecule of methanol. The title compound exists as helical chain that runs along the b-axis of the unit cell; the methanol molecules are linked to the chain by hydrogen bonds, with the –NH group serving as donor.
For the synthesis of 3,3',5,5'-tetramethyl-4,4'-bipyrazole, see: Mosby (1957). For literature on other metal derivatives of 3,3',5,5'-tetramethyl-4,4'-bipyrazole, see: Boldog et al. (2001); Boldog, Rusanov et al. (2003); Boldog, Sieler et al. (2003); He et al. (2006); Ponomarova et al. (2002); Zhang et al. (2007).
Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).
[CdI2(C10H12N4)]·CH4O | F(000) = 1096 |
Mr = 588.49 | Dx = 2.204 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 4773 reflections |
a = 11.1294 (6) Å | θ = 2.2–27.2° |
b = 12.2109 (7) Å | µ = 4.71 mm−1 |
c = 13.2924 (7) Å | T = 293 K |
β = 101.008 (1)° | Block, colourless |
V = 1773.2 (2) Å3 | 0.35 × 0.30 × 0.11 mm |
Z = 4 |
Bruker APEX area-detector diffractometer | 3077 independent reflections |
Radiation source: fine-focus sealed tube | 2813 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
φ and ω scans | θmax = 25.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→13 |
Tmin = 0.255, Tmax = 0.625 | k = −13→14 |
8299 measured reflections | l = −14→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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.090 | H-atom parameters constrained |
S = 1.11 | w = 1/[σ2(Fo2) + (0.048P)2 + 2.2498P] where P = (Fo2 + 2Fc2)/3 |
3077 reflections | (Δ/σ)max = 0.001 |
178 parameters | Δρmax = 0.93 e Å−3 |
0 restraints | Δρmin = −0.90 e Å−3 |
[CdI2(C10H12N4)]·CH4O | V = 1773.2 (2) Å3 |
Mr = 588.49 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.1294 (6) Å | µ = 4.71 mm−1 |
b = 12.2109 (7) Å | T = 293 K |
c = 13.2924 (7) Å | 0.35 × 0.30 × 0.11 mm |
β = 101.008 (1)° |
Bruker APEX area-detector diffractometer | 3077 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2813 reflections with I > 2σ(I) |
Tmin = 0.255, Tmax = 0.625 | Rint = 0.023 |
8299 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.090 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.93 e Å−3 |
3077 reflections | Δρmin = −0.90 e Å−3 |
178 parameters |
Experimental. High-angle reflections were omitted as their inclusion led to somewhat large peaks and deep holes near the iodine atoms. |
x | y | z | Uiso*/Ueq | ||
I1 | 0.70846 (4) | 0.50859 (4) | 0.42967 (3) | 0.06227 (15) | |
I2 | 0.72925 (4) | 0.63673 (4) | 0.10377 (3) | 0.06328 (16) | |
Cd1 | 0.59541 (3) | 0.59870 (3) | 0.24959 (3) | 0.03701 (13) | |
O1 | 0.1126 (6) | 1.2458 (4) | 0.5060 (4) | 0.0839 (15) | |
H1 | 0.1723 | 1.2865 | 0.5149 | 0.126* | |
N1 | 0.5170 (3) | 0.7677 (3) | 0.2704 (3) | 0.0374 (9) | |
N2 | 0.5426 (4) | 0.8568 (3) | 0.2178 (3) | 0.0406 (10) | |
H2 | 0.6002 | 0.8594 | 0.1830 | 0.049* | |
N3 | 0.0920 (3) | 1.0264 (3) | 0.3095 (3) | 0.0373 (9) | |
N4 | 0.1727 (4) | 1.0898 (3) | 0.3735 (3) | 0.0384 (9) | |
H4 | 0.1519 | 1.1447 | 0.4069 | 0.046* | |
C1 | 0.3664 (5) | 0.7180 (4) | 0.3772 (4) | 0.0488 (13) | |
H1A | 0.3066 | 0.6737 | 0.3338 | 0.073* | |
H1B | 0.3277 | 0.7579 | 0.4245 | 0.073* | |
H1C | 0.4293 | 0.6718 | 0.4145 | 0.073* | |
C2 | 0.4215 (4) | 0.7964 (4) | 0.3133 (4) | 0.0354 (10) | |
C3 | 0.3872 (4) | 0.9052 (4) | 0.2869 (4) | 0.0352 (10) | |
C4 | 0.4669 (4) | 0.9408 (4) | 0.2266 (4) | 0.0368 (10) | |
C5 | 0.4749 (5) | 1.0490 (4) | 0.1743 (5) | 0.0514 (14) | |
H5A | 0.5112 | 1.1024 | 0.2240 | 0.077* | |
H5B | 0.3943 | 1.0726 | 0.1427 | 0.077* | |
H5C | 0.5244 | 1.0412 | 0.1230 | 0.077* | |
C6 | 0.1046 (5) | 0.8661 (4) | 0.1984 (5) | 0.0523 (14) | |
H6A | 0.0299 | 0.8405 | 0.2164 | 0.078* | |
H6B | 0.1606 | 0.8060 | 0.2003 | 0.078* | |
H6C | 0.0873 | 0.8965 | 0.1306 | 0.078* | |
C7 | 0.1599 (4) | 0.9514 (4) | 0.2722 (4) | 0.0353 (10) | |
C8 | 0.2850 (4) | 0.9679 (4) | 0.3138 (4) | 0.0334 (10) | |
C9 | 0.2887 (4) | 1.0570 (4) | 0.3788 (4) | 0.0362 (10) | |
C10 | 0.3915 (5) | 1.1113 (4) | 0.4491 (5) | 0.0499 (13) | |
H10A | 0.3749 | 1.1882 | 0.4526 | 0.075* | |
H10B | 0.4660 | 1.1009 | 0.4240 | 0.075* | |
H10C | 0.3999 | 1.0798 | 0.5163 | 0.075* | |
C11 | 0.1035 (11) | 1.1962 (7) | 0.5970 (7) | 0.110 (3) | |
H11A | 0.1789 | 1.1593 | 0.6243 | 0.165* | |
H11B | 0.0378 | 1.1440 | 0.5855 | 0.165* | |
H11C | 0.0876 | 1.2506 | 0.6450 | 0.165* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.0510 (2) | 0.0729 (3) | 0.0595 (3) | −0.00489 (18) | 0.00184 (19) | 0.0232 (2) |
I2 | 0.0582 (3) | 0.0767 (3) | 0.0645 (3) | −0.00017 (19) | 0.0359 (2) | 0.0071 (2) |
Cd1 | 0.02859 (19) | 0.0373 (2) | 0.0473 (2) | 0.00236 (13) | 0.01280 (16) | 0.00152 (15) |
O1 | 0.108 (4) | 0.060 (3) | 0.090 (4) | −0.007 (3) | 0.036 (3) | −0.023 (3) |
N1 | 0.034 (2) | 0.033 (2) | 0.047 (2) | 0.0043 (16) | 0.0137 (18) | −0.0008 (17) |
N2 | 0.034 (2) | 0.041 (2) | 0.051 (3) | −0.0006 (17) | 0.0182 (19) | 0.0022 (19) |
N3 | 0.0305 (19) | 0.040 (2) | 0.043 (2) | 0.0010 (17) | 0.0102 (18) | −0.0054 (18) |
N4 | 0.036 (2) | 0.038 (2) | 0.041 (2) | 0.0054 (17) | 0.0073 (18) | −0.0076 (17) |
C1 | 0.053 (3) | 0.041 (3) | 0.058 (3) | 0.004 (2) | 0.025 (3) | 0.006 (2) |
C2 | 0.036 (2) | 0.035 (2) | 0.037 (3) | 0.0016 (19) | 0.011 (2) | −0.0009 (19) |
C3 | 0.029 (2) | 0.036 (2) | 0.041 (3) | −0.0002 (19) | 0.006 (2) | −0.001 (2) |
C4 | 0.030 (2) | 0.035 (2) | 0.045 (3) | 0.0005 (19) | 0.008 (2) | −0.001 (2) |
C5 | 0.044 (3) | 0.048 (3) | 0.065 (4) | 0.004 (2) | 0.017 (3) | 0.013 (3) |
C6 | 0.042 (3) | 0.050 (3) | 0.065 (4) | 0.004 (2) | 0.010 (3) | −0.020 (3) |
C7 | 0.035 (2) | 0.033 (2) | 0.040 (3) | 0.0041 (19) | 0.013 (2) | −0.001 (2) |
C8 | 0.033 (2) | 0.032 (2) | 0.036 (3) | 0.0047 (19) | 0.0096 (19) | 0.0036 (19) |
C9 | 0.034 (2) | 0.033 (2) | 0.041 (3) | 0.0053 (19) | 0.006 (2) | 0.004 (2) |
C10 | 0.047 (3) | 0.042 (3) | 0.056 (4) | 0.005 (2) | −0.003 (3) | −0.005 (2) |
C11 | 0.190 (11) | 0.061 (4) | 0.091 (6) | 0.000 (5) | 0.058 (7) | −0.010 (4) |
I1—Cd1 | 2.7154 (5) | C3—C4 | 1.375 (7) |
I2—Cd1 | 2.7008 (5) | C3—C8 | 1.470 (6) |
Cd1—N1 | 2.277 (4) | C4—C5 | 1.503 (7) |
Cd1—N3i | 2.263 (4) | C5—H5A | 0.9600 |
O1—C11 | 1.374 (10) | C5—H5B | 0.9600 |
O1—H1 | 0.8200 | C5—H5C | 0.9600 |
N1—C2 | 1.345 (6) | C6—C7 | 1.482 (7) |
N1—N2 | 1.353 (5) | C6—H6A | 0.9600 |
N2—C4 | 1.347 (6) | C6—H6B | 0.9600 |
N2—H2 | 0.8600 | C6—H6C | 0.9600 |
N3—C7 | 1.341 (6) | C7—C8 | 1.411 (6) |
N3—N4 | 1.356 (6) | C8—C9 | 1.386 (7) |
N3—Cd1ii | 2.263 (4) | C9—C10 | 1.488 (7) |
N4—C9 | 1.341 (6) | C10—H10A | 0.9600 |
N4—H4 | 0.8600 | C10—H10B | 0.9600 |
C1—C2 | 1.488 (7) | C10—H10C | 0.9600 |
C1—H1A | 0.9600 | C11—H11A | 0.9600 |
C1—H1B | 0.9600 | C11—H11B | 0.9600 |
C1—H1C | 0.9600 | C11—H11C | 0.9600 |
C2—C3 | 1.409 (6) | ||
I1—Cd1—I2 | 118.43 (2) | C4—C5—H5A | 109.5 |
I1—Cd1—N1 | 112.6 (1) | C4—C5—H5B | 109.5 |
I1—Cd1—N3i | 112.9 (1) | H5A—C5—H5B | 109.5 |
I2—Cd1—N1 | 102.0 (1) | C4—C5—H5C | 109.5 |
I2—Cd1—N3i | 114.6 (1) | H5A—C5—H5C | 109.5 |
N1—Cd1—N3i | 92.7 (1) | H5B—C5—H5C | 109.5 |
C11—O1—H1 | 109.5 | C7—C6—H6A | 109.5 |
C2—N1—N2 | 105.7 (4) | C7—C6—H6B | 109.5 |
C2—N1—Cd1 | 129.7 (3) | H6A—C6—H6B | 109.5 |
N2—N1—Cd1 | 122.9 (3) | C7—C6—H6C | 109.5 |
C4—N2—N1 | 111.8 (4) | H6A—C6—H6C | 109.5 |
C4—N2—H2 | 124.1 | H6B—C6—H6C | 109.5 |
N1—N2—H2 | 124.1 | N3—C7—C8 | 110.0 (4) |
C7—N3—N4 | 105.6 (4) | N3—C7—C6 | 122.2 (4) |
C7—N3—Cd1ii | 133.2 (3) | C8—C7—C6 | 127.9 (4) |
N4—N3—Cd1ii | 116.8 (3) | C9—C8—C7 | 105.4 (4) |
C9—N4—N3 | 112.2 (4) | C9—C8—C3 | 128.9 (4) |
C9—N4—H4 | 123.9 | C7—C8—C3 | 125.6 (4) |
N3—N4—H4 | 123.9 | N4—C9—C8 | 106.7 (4) |
C2—C1—H1A | 109.5 | N4—C9—C10 | 121.1 (4) |
C2—C1—H1B | 109.5 | C8—C9—C10 | 132.1 (4) |
H1A—C1—H1B | 109.5 | C9—C10—H10A | 109.5 |
C2—C1—H1C | 109.5 | C9—C10—H10B | 109.5 |
H1A—C1—H1C | 109.5 | H10A—C10—H10B | 109.5 |
H1B—C1—H1C | 109.5 | C9—C10—H10C | 109.5 |
N1—C2—C3 | 109.8 (4) | H10A—C10—H10C | 109.5 |
N1—C2—C1 | 121.3 (4) | H10B—C10—H10C | 109.5 |
C3—C2—C1 | 128.9 (4) | O1—C11—H11A | 109.5 |
C4—C3—C2 | 105.6 (4) | O1—C11—H11B | 109.5 |
C4—C3—C8 | 126.3 (4) | H11A—C11—H11B | 109.5 |
C2—C3—C8 | 128.0 (4) | O1—C11—H11C | 109.5 |
N2—C4—C3 | 107.1 (4) | H11A—C11—H11C | 109.5 |
N2—C4—C5 | 122.4 (4) | H11B—C11—H11C | 109.5 |
C3—C4—C5 | 130.5 (4) | ||
N3i—Cd1—N1—C2 | 46.2 (4) | C8—C3—C4—N2 | −177.3 (5) |
I2—Cd1—N1—C2 | 162.0 (4) | C2—C3—C4—C5 | 179.1 (5) |
I1—Cd1—N1—C2 | −70.0 (4) | C8—C3—C4—C5 | 1.2 (9) |
N3i—Cd1—N1—N2 | −116.9 (4) | N4—N3—C7—C8 | 0.2 (5) |
I2—Cd1—N1—N2 | −1.1 (4) | Cd1ii—N3—C7—C8 | 155.2 (3) |
I1—Cd1—N1—N2 | 126.9 (3) | N4—N3—C7—C6 | −179.9 (5) |
C2—N1—N2—C4 | 0.3 (5) | Cd1ii—N3—C7—C6 | −24.8 (7) |
Cd1—N1—N2—C4 | 166.9 (3) | N3—C7—C8—C9 | 0.2 (5) |
C7—N3—N4—C9 | −0.6 (5) | C6—C7—C8—C9 | −179.7 (5) |
Cd1ii—N3—N4—C9 | −160.4 (3) | N3—C7—C8—C3 | −176.7 (4) |
N2—N1—C2—C3 | 0.0 (5) | C6—C7—C8—C3 | 3.4 (8) |
Cd1—N1—C2—C3 | −165.3 (3) | C4—C3—C8—C9 | −71.1 (7) |
N2—N1—C2—C1 | 179.5 (5) | C2—C3—C8—C9 | 111.5 (6) |
Cd1—N1—C2—C1 | 14.1 (7) | C4—C3—C8—C7 | 105.1 (6) |
N1—C2—C3—C4 | −0.3 (6) | C2—C3—C8—C7 | −72.3 (7) |
C1—C2—C3—C4 | −179.7 (5) | N3—N4—C9—C8 | 0.8 (5) |
N1—C2—C3—C8 | 177.5 (5) | N3—N4—C9—C10 | −176.5 (4) |
C1—C2—C3—C8 | −1.9 (8) | C7—C8—C9—N4 | −0.6 (5) |
N1—N2—C4—C3 | −0.6 (6) | C3—C8—C9—N4 | 176.2 (5) |
N1—N2—C4—C5 | −179.3 (5) | C7—C8—C9—C10 | 176.2 (5) |
C2—C3—C4—N2 | 0.5 (5) | C3—C8—C9—C10 | −7.0 (9) |
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+1/2, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [CdI2(C10H12N4)]·CH4O |
Mr | 588.49 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 11.1294 (6), 12.2109 (7), 13.2924 (7) |
β (°) | 101.008 (1) |
V (Å3) | 1773.2 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 4.71 |
Crystal size (mm) | 0.35 × 0.30 × 0.11 |
Data collection | |
Diffractometer | Bruker APEX area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.255, 0.625 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8299, 3077, 2813 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.090, 1.11 |
No. of reflections | 3077 |
No. of parameters | 178 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.93, −0.90 |
Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), X-SEED (Barbour, 2001), publCIF (Westrip, 2007).
I1—Cd1 | 2.7154 (5) | Cd1—N1 | 2.277 (4) |
I2—Cd1 | 2.7008 (5) | Cd1—N3i | 2.263 (4) |
I1—Cd1—I2 | 118.43 (2) | I2—Cd1—N1 | 102.0 (1) |
I1—Cd1—N1 | 112.6 (1) | I2—Cd1—N3i | 114.6 (1) |
I1—Cd1—N3i | 112.9 (1) | N1—Cd1—N3i | 92.7 (1) |
Symmetry code: (i) −x+1/2, y−1/2, −z+1/2. |
3,3',5,5'-Tetramethyl-4,4'-bipyrazolyl in its doubly-deprotonated form is capable of connecting to four metal sites (Boldog et al., 2001; Boldog, Rusanov et al., 2003; Boldog, Sieler et al., 2003; He et al., 2006; Ponomarova et al., 2002). The disilver(I) derivative exemplifies such a feature; the framework is porous (Zhang et al., 2007). The attempted synthesis of the cadmium derivative yielded an adduct, the neutral heterocycle binding to cadmium diiodide in a 1:1 molar stoichoimetry. The compound crystallizes with a molecule of methanol. The title compound exists as helical chain that runs along the b-axis of the unit cell; the methanol molecules are linked to the chain by hydrogen bonds, with the –NH group serving as donor.