Single crystals of tetra(isopropylammonium) decachlorotricadmate(II) as a rare example of a two-dimensional cadmium(II) halide network of [Cd
3Cl
10]
have been synthesized and characterized by means of calorimetry and X-ray diffraction. The crystals exhibit polymorphism in a relatively narrow temperature range (three phase transitions at 353, 294 and 259 K). Our main focus was to establish the mechanism of these successive transformations. The crystal structure was solved and refined in the space group
Cmce at 375 K (Phase I),
Pbca at 320 K (Phase II) and
P2
12
12
1 (Phase III) at 275 K in the same unit-cell metric. The structure is composed of face-sharing polyanionic [Cd
3Cl
10]
4− units which are interconnected at the bridging Cl atom into four-membered rings forming a unique two-dimensional network of [Cd
3Cl
10]
. The interstitial voids within the network are large enough to accommodate isopropylammonium cations and permit thermally activated rotations. While in Phase I isopropylammonium tetrahedra rotate almost freely about the C—N bond, the low-temperature phases are the playground of competition between the thermally activated disorder of isopropylammonium cations and stabilizing N—H
Cl hydrogen-bond interactions. The transition from Phase I to II is dominated by a displacive mechanism that leads to significant rearrangement of the polyanionic units. Cation order–disorder phenomena become prominent at lower temperatures.
Supporting information
CCDC references: 822632; 822633; 822634
For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).
Crystal data top
C12H40Cd3Cl10N4 | Dx = 1.918 Mg m−3 |
Mr = 932.18 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Cmce | Cell parameters from 2337 reflections |
a = 7.4634 (2) Å | θ = 2.8–29.8° |
b = 22.0476 (10) Å | µ = 2.79 mm−1 |
c = 19.6139 (9) Å | T = 375 K |
V = 3227.5 (2) Å3 | , colorles |
Z = 4 | 0.25 × 0.2 × 0.08 mm |
F(000) = 1816 | |
Data collection top
KUMA KM4-CCD diffractometer | 1659 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.031 |
Graphite monochromator | θmax = 29.8°, θmin = 2.8° |
Absorption correction: multi-scan CrysAlis RED, Oxford Diffraction Ltd.,
Version 1.171.32.6 (release 21-05-2007 CrysAlis171 .NET)
(compiled May 21 2007,16:32:00)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm. | h = −10→4 |
Tmin = 0.49, Tmax = 0.79 | k = −29→27 |
14304 measured reflections | l = −26→25 |
2333 independent reflections | |
Refinement top
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)] = 0.025 | w = 1/[σ2(Fo2) + (0.0302P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.054 | (Δ/σ)max = 0.041 |
S = 0.90 | Δρmax = 0.35 e Å−3 |
2333 reflections | Δρmin = −0.41 e Å−3 |
101 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.00042 (3) |
Primary atom site location: structure-invariant direct methods | |
Crystal data top
C12H40Cd3Cl10N4 | V = 3227.5 (2) Å3 |
Mr = 932.18 | Z = 4 |
Orthorhombic, Cmce | Mo Kα radiation |
a = 7.4634 (2) Å | µ = 2.79 mm−1 |
b = 22.0476 (10) Å | T = 375 K |
c = 19.6139 (9) Å | 0.25 × 0.2 × 0.08 mm |
Data collection top
KUMA KM4-CCD diffractometer | 2333 independent reflections |
Absorption correction: multi-scan CrysAlis RED, Oxford Diffraction Ltd.,
Version 1.171.32.6 (release 21-05-2007 CrysAlis171 .NET)
(compiled May 21 2007,16:32:00)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm. | 1659 reflections with I > 2σ(I) |
Tmin = 0.49, Tmax = 0.79 | Rint = 0.031 |
14304 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.025 | 101 parameters |
wR(F2) = 0.054 | 0 restraints |
S = 0.90 | Δρmax = 0.35 e Å−3 |
2333 reflections | Δρmin = −0.41 e Å−3 |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Cd1 | 0.5000 | 0.431045 (6) | 0.158375 (5) | 0.05344 (3) | |
Cd2 | 0.5000 | 0.5000 | 0.0000 | 0.05485 (5) | |
Cl1 | 0.5000 | 0.31990 (2) | 0.17909 (3) | 0.0993 (2) | |
Cl2 | 0.2500 | 0.45344 (3) | 0.2500 | 0.09614 (16) | |
Cl3 | 0.25720 (4) | 0.427020 (15) | 0.055561 (16) | 0.07037 (9) | |
Cl4 | 0.5000 | 0.54794 (2) | 0.12048 (2) | 0.06233 (12) | |
C1B | 0.0000 | 0.60000 (10) | 0.13936 (15) | 0.1253 (11) | |
H1B | −0.1194 | 0.6073 | 0.1482 | 0.150* | 0.50 |
N2B | 0.0000 | 0.53801 (8) | 0.11713 (14) | 0.1337 (9) | |
H2B1 | 0.0478 | 0.5359 | 0.0756 | 0.201* | 0.50 |
H2B2 | −0.1120 | 0.5244 | 0.1159 | 0.201* | 0.50 |
H2B3 | 0.0643 | 0.5158 | 0.1459 | 0.201* | 0.50 |
C3B | −0.0704 (5) | 0.60897 (18) | 0.20523 (15) | 0.1257 (17) | 0.50 |
H3B1 | 0.0216 | 0.6227 | 0.2343 | 0.189* | 0.50 |
H3B2 | −0.1196 | 0.5714 | 0.2206 | 0.189* | 0.50 |
H3B3 | −0.1643 | 0.6389 | 0.2019 | 0.189* | 0.50 |
C4B | −0.0399 (10) | 0.64305 (14) | 0.09523 (16) | 0.1932 (19) | 0.50 |
H4B1 | 0.0280 | 0.6774 | 0.1014 | 0.290* | 0.50 |
H4B2 | −0.1709 | 0.6551 | 0.1070 | 0.290* | 0.50 |
H4B3 | −0.0441 | 0.6279 | 0.0511 | 0.290* | 0.50 |
C1A | 0.4578 (3) | 0.27109 (10) | 0.37415 (15) | 0.0855 (11) | 0.50 |
H1A | 0.3302 | 0.2613 | 0.3787 | 0.103* | 0.50 |
N2A | 0.5000 | 0.33199 (7) | 0.34705 (8) | 0.0819 (5) | |
H2A1 | 0.3877 | 0.3451 | 0.3438 | 0.123* | 0.50 |
H2A2 | 0.5507 | 0.3316 | 0.3062 | 0.123* | 0.50 |
H2A3 | 0.5616 | 0.3562 | 0.3748 | 0.123* | 0.50 |
C3A | 0.5748 (6) | 0.26615 (14) | 0.44216 (18) | 0.139 (2) | 0.50 |
H3A1 | 0.5211 | 0.2331 | 0.4651 | 0.209* | 0.50 |
H3A2 | 0.5550 | 0.3033 | 0.4662 | 0.209* | 0.50 |
H3A3 | 0.7025 | 0.2595 | 0.4377 | 0.209* | 0.50 |
C4A | 0.5689 (7) | 0.22649 (14) | 0.33495 (18) | 0.153 (2) | 0.50 |
H4A1 | 0.5000 | 0.1898 | 0.3458 | 0.229* | 0.50 |
H4A2 | 0.6939 | 0.2220 | 0.3477 | 0.229* | 0.50 |
H4A3 | 0.5575 | 0.2371 | 0.2893 | 0.229* | 0.50 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cd1 | 0.05283 (6) | 0.06686 (7) | 0.04061 (6) | 0.000 | 0.000 | 0.00278 (5) |
Cd2 | 0.04654 (7) | 0.08378 (12) | 0.03422 (7) | 0.000 | 0.000 | 0.00565 (8) |
Cl1 | 0.1522 (5) | 0.0612 (3) | 0.0843 (3) | 0.000 | 0.000 | −0.0041 (3) |
Cl2 | 0.1045 (3) | 0.1032 (4) | 0.0807 (3) | 0.000 | 0.0542 (2) | 0.000 |
Cl3 | 0.05409 (13) | 0.0940 (2) | 0.06299 (17) | −0.02035 (14) | −0.00125 (14) | 0.00214 (16) |
Cl4 | 0.0789 (2) | 0.0647 (2) | 0.0433 (2) | 0.000 | 0.000 | −0.00422 (18) |
C1B | 0.183 (3) | 0.0660 (13) | 0.126 (2) | 0.000 | 0.000 | −0.0262 (14) |
N2B | 0.1233 (15) | 0.0710 (11) | 0.207 (2) | 0.000 | 0.000 | −0.0508 (13) |
C3B | 0.146 (4) | 0.169 (3) | 0.0622 (17) | 0.005 (2) | 0.0146 (17) | 0.005 (2) |
C4B | 0.346 (5) | 0.106 (2) | 0.128 (2) | −0.037 (4) | −0.134 (3) | 0.0345 (18) |
C1A | 0.067 (2) | 0.0747 (15) | 0.1152 (19) | 0.0055 (12) | 0.0045 (14) | 0.0144 (15) |
N2A | 0.1107 (11) | 0.0589 (9) | 0.0759 (11) | 0.000 | 0.000 | −0.0053 (8) |
C3A | 0.225 (7) | 0.099 (2) | 0.094 (2) | −0.007 (2) | −0.017 (3) | 0.0194 (19) |
C4A | 0.233 (6) | 0.0659 (17) | 0.159 (3) | 0.034 (2) | 0.058 (3) | −0.0015 (19) |
Geometric parameters (Å, º) top
Cd1—Cl1 | 2.4839 (5) | N2B—H2B3 | 0.8879 |
Cd1—Cl2i | 2.6372 (2) | C3B—H3B1 | 0.9425 |
Cd1—Cl2 | 2.6372 (2) | C3B—H3B2 | 0.9541 |
Cd1—Cl4 | 2.6823 (5) | C3B—H3B3 | 0.9646 |
Cd1—Cl3 | 2.7126 (3) | C4B—H4B1 | 0.9187 |
Cd1—Cl3ii | 2.7126 (3) | C4B—H4B2 | 1.0387 |
Cd1—Cd2 | 3.4584 (2) | C4B—H4B3 | 0.9295 |
Cd2—Cl4 | 2.5888 (4) | C1A—C4A | 1.499 (4) |
Cd2—Cl4iii | 2.5888 (4) | C1A—N2A | 1.478 (3) |
Cd2—Cl3iii | 2.6571 (3) | C1A—C3A | 1.598 (5) |
Cd2—Cl3iv | 2.6571 (3) | C1A—H1A | 0.9800 |
Cd2—Cl3 | 2.6571 (3) | N2A—C1Aii | 1.478 (3) |
Cd2—Cl3ii | 2.6571 (3) | N2A—H2A1 | 0.8887 |
Cd2—Cd1iii | 3.4584 (2) | N2A—H2A2 | 0.8862 |
Cl2—Cd1v | 2.6372 (2) | N2A—H2A3 | 0.8907 |
C1B—C4Bvi | 1.319 (4) | C3A—C1Aii | 1.360 (4) |
C1B—C4B | 1.319 (4) | C3A—H3A1 | 0.9444 |
C1B—C3Bvi | 1.409 (4) | C3A—H3A2 | 0.9562 |
C1B—C3B | 1.409 (4) | C3A—H3A3 | 0.9684 |
C1B—N2B | 1.435 (3) | C4A—C1Aii | 1.264 (4) |
C1B—H1B | 0.9223 | C4A—H4A1 | 0.9817 |
N2B—H2B1 | 0.8897 | C4A—H4A2 | 0.9709 |
N2B—H2B2 | 0.8887 | C4A—H4A3 | 0.9288 |
| | | |
Cl1—Cd1—Cl2i | 94.199 (16) | C3B—C1B—N2B | 114.4 (3) |
Cl1—Cd1—Cl2 | 94.199 (16) | C4Bvi—C1B—H1B | 102.5 |
Cl2i—Cd1—Cl2 | 90.066 (7) | N2B—C1B—H1B | 103.0 |
Cl1—Cd1—Cl4 | 173.327 (17) | C1B—N2B—H2B1 | 109.1 |
Cl2i—Cd1—Cl4 | 90.513 (15) | C1B—N2B—H2B2 | 109.3 |
Cl2—Cd1—Cl4 | 90.513 (15) | H2B1—N2B—H2B2 | 109.6 |
Cl1—Cd1—Cl3 | 95.124 (13) | C1B—N2B—H2B3 | 109.4 |
Cl2i—Cd1—Cl3 | 170.188 (15) | H2B1—N2B—H2B3 | 109.7 |
Cl2—Cd1—Cl3 | 92.297 (7) | H2B2—N2B—H2B3 | 109.8 |
Cl4—Cd1—Cl3 | 79.948 (10) | C1B—C3B—H3B1 | 109.2 |
Cl1—Cd1—Cl3ii | 95.124 (13) | H1B—C3B—H3B1 | 144.3 |
Cl2i—Cd1—Cl3ii | 92.297 (7) | C1B—C3B—H3B2 | 108.1 |
Cl2—Cd1—Cl3ii | 170.188 (15) | H1B—C3B—H3B2 | 98.9 |
Cl4—Cd1—Cl3ii | 79.948 (10) | H3B1—C3B—H3B2 | 111.5 |
Cl3—Cd1—Cl3ii | 83.832 (13) | C1B—C3B—H3B3 | 107.7 |
Cl1—Cd1—Cd2 | 125.491 (14) | H3B1—C3B—H3B3 | 110.6 |
Cl2i—Cd1—Cd2 | 121.992 (9) | H3B2—C3B—H3B3 | 109.6 |
Cl2—Cd1—Cd2 | 121.992 (9) | C1B—C4B—H4B1 | 112.4 |
Cl4—Cd1—Cd2 | 47.836 (9) | H1B—C4B—H4B1 | 125.8 |
Cl3—Cd1—Cd2 | 49.206 (7) | C1B—C4B—H4B2 | 104.5 |
Cl3ii—Cd1—Cd2 | 49.206 (7) | H1B—C4B—H4B2 | 65.7 |
Cl4—Cd2—Cl4iii | 180.000 (19) | H4B1—C4B—H4B2 | 106.3 |
Cl4—Cd2—Cl3iii | 97.304 (10) | C1B—C4B—H4B3 | 111.1 |
Cl4iii—Cd2—Cl3iii | 82.696 (10) | H1B—C4B—H4B3 | 117.7 |
Cl4—Cd2—Cl3iv | 97.305 (10) | H4B1—C4B—H4B3 | 116.0 |
Cl4iii—Cd2—Cl3iv | 82.696 (10) | H4B2—C4B—H4B3 | 105.5 |
Cl3iii—Cd2—Cl3iv | 85.998 (14) | C4A—C1A—N2A | 107.1 (2) |
Cl4—Cd2—Cl3 | 82.696 (10) | C4A—C1A—C3A | 94.6 (2) |
Cl4iii—Cd2—Cl3 | 97.304 (10) | N2A—C1A—C3A | 104.2 (2) |
Cl3iii—Cd2—Cl3 | 180.0 | C4A—C1A—H1A | 116.1 |
Cl3iv—Cd2—Cl3 | 94.002 (14) | N2A—C1A—H1A | 116.1 |
Cl4—Cd2—Cl3ii | 82.696 (10) | C3A—C1A—H1A | 116.1 |
Cl4iii—Cd2—Cl3ii | 97.304 (10) | C1A—N2A—H2A1 | 96.9 |
Cl3iii—Cd2—Cl3ii | 94.002 (14) | C1Aii—N2A—H2A1 | 121.5 |
Cl3iv—Cd2—Cl3ii | 180.000 (11) | C1A—N2A—H2A2 | 114.1 |
Cl3—Cd2—Cl3ii | 85.998 (14) | C1Aii—N2A—H2A2 | 103.1 |
Cl4—Cd2—Cd1 | 50.175 (10) | H2A1—N2A—H2A2 | 109.9 |
Cl4iii—Cd2—Cd1 | 129.825 (10) | C1A—N2A—H2A3 | 115.8 |
Cl3iii—Cd2—Cd1 | 129.388 (7) | C1Aii—N2A—H2A3 | 102.4 |
Cl3iv—Cd2—Cd1 | 129.388 (7) | H2A1—N2A—H2A3 | 109.5 |
Cl3—Cd2—Cd1 | 50.612 (7) | H2A2—N2A—H2A3 | 109.7 |
Cl3ii—Cd2—Cd1 | 50.612 (7) | C1Aii—C3A—H3A1 | 116.9 |
Cl4—Cd2—Cd1iii | 129.825 (10) | C1A—C3A—H3A1 | 102.6 |
Cl4iii—Cd2—Cd1iii | 50.175 (10) | C1Aii—C3A—H3A2 | 112.7 |
Cl3iii—Cd2—Cd1iii | 50.612 (7) | C1A—C3A—H3A2 | 105.5 |
Cl3iv—Cd2—Cd1iii | 50.612 (7) | H3A1—C3A—H3A2 | 111.1 |
Cl3—Cd2—Cd1iii | 129.388 (7) | C1Aii—C3A—H3A3 | 95.7 |
Cl3ii—Cd2—Cd1iii | 129.388 (7) | C1A—C3A—H3A3 | 118.2 |
Cd1—Cd2—Cd1iii | 180.000 (4) | H3A1—C3A—H3A3 | 110.1 |
Cd1—Cl2—Cd1v | 158.42 (3) | H3A2—C3A—H3A3 | 109.1 |
Cd2—Cl3—Cd1 | 80.182 (9) | C1Aii—C4A—H4A1 | 115.2 |
Cd2—Cl4—Cd1 | 81.988 (13) | C1A—C4A—H4A1 | 98.0 |
C4Bvi—C1B—C3Bvi | 114.6 (3) | C1Aii—C4A—H4A2 | 94.2 |
C4B—C1B—C3Bvi | 125.8 (3) | C1A—C4A—H4A2 | 117.8 |
C4Bvi—C1B—C3B | 125.8 (3) | H4A1—C4A—H4A2 | 111.3 |
C4B—C1B—C3B | 114.6 (3) | C1Aii—C4A—H4A3 | 112.1 |
C4Bvi—C1B—N2B | 119.1 (3) | C1A—C4A—H4A3 | 106.2 |
C4B—C1B—N2B | 119.1 (3) | H4A1—C4A—H4A3 | 111.6 |
C3Bvi—C1B—N2B | 114.4 (3) | H4A2—C4A—H4A3 | 111.2 |
Symmetry codes: (i) x+1/2, y, −z+1/2; (ii) −x+1, y, z; (iii) −x+1, −y+1, −z; (iv) x, −y+1, −z; (v) x−1/2, y, −z+1/2; (vi) −x, y, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2B—H2B2···Cl3vi | 0.89 | 2.68 | 3.3363 (16) | 131.5 |
N2A—H2A2···Cl1 | 0.89 | 2.53 | 3.3052 (16) | 145.8 |
N2A—H2A3···Cl3i | 0.89 | 2.54 | 3.4240 (13) | 174.6 |
Symmetry codes: (i) x+1/2, y, −z+1/2; (vi) −x, y, z. |
Crystal data top
C12H40Cd3Cl10N4 | Dx = 1.941 Mg m−3 |
Mr = 932.18 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 3010 reflections |
a = 7.4298 (5) Å | θ = 2.8–25.7° |
b = 22.0791 (5) Å | µ = 2.83 mm−1 |
c = 19.4442 (6) Å | T = 320 K |
V = 3189.7 (2) Å3 | , colorles |
Z = 4 | 0.25 × 0.2 × 0.08 mm |
F(000) = 1816 | |
Data collection top
KUMA KM4-CCD diffractometer | 2449 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.030 |
Graphite monochromator | θmax = 25.7°, θmin = 2.8° |
Absorption correction: multi-scan CrysAlis RED, Oxford Diffraction Ltd.,
Version 1.171.32.6 (release 21-05-2007 CrysAlis171 .NET)
(compiled May 21 2007,16:32:00)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm. | h = −9→7 |
Tmin = 0.49, Tmax = 0.79 | k = −26→26 |
26736 measured reflections | l = −23→23 |
3010 independent reflections | |
Refinement top
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)] = 0.024 | w = 1/[σ2(Fo2) + (0.0381P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.062 | (Δ/σ)max = 0.019 |
S = 1.01 | Δρmax = 0.36 e Å−3 |
3010 reflections | Δρmin = −0.50 e Å−3 |
146 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
6 restraints | Extinction coefficient: 0.00290 (9) |
Primary atom site location: structure-invariant direct methods | |
Crystal data top
C12H40Cd3Cl10N4 | V = 3189.7 (2) Å3 |
Mr = 932.18 | Z = 4 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 7.4298 (5) Å | µ = 2.83 mm−1 |
b = 22.0791 (5) Å | T = 320 K |
c = 19.4442 (6) Å | 0.25 × 0.2 × 0.08 mm |
Data collection top
KUMA KM4-CCD diffractometer | 3010 independent reflections |
Absorption correction: multi-scan CrysAlis RED, Oxford Diffraction Ltd.,
Version 1.171.32.6 (release 21-05-2007 CrysAlis171 .NET)
(compiled May 21 2007,16:32:00)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm. | 2449 reflections with I > 2σ(I) |
Tmin = 0.49, Tmax = 0.79 | Rint = 0.030 |
26736 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.024 | 146 parameters |
wR(F2) = 0.062 | 6 restraints |
S = 1.01 | Δρmax = 0.36 e Å−3 |
3010 reflections | Δρmin = −0.50 e Å−3 |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Cd1 | 0.52017 (2) | 0.430197 (8) | 0.158516 (8) | 0.04030 (5) | |
Cd2 | 0.5000 | 0.5000 | 0.0000 | 0.04401 (7) | |
Cl3 | 0.26055 (7) | 0.42592 (3) | 0.06079 (3) | 0.05479 (17) | |
Cl5 | 0.74789 (7) | 0.42648 (3) | 0.04773 (3) | 0.05430 (17) | |
Cl4 | 0.51532 (7) | 0.54646 (3) | 0.12158 (3) | 0.04751 (15) | |
Cl2 | 0.80024 (9) | 0.45142 (3) | 0.23883 (3) | 0.06418 (19) | |
Cl1 | 0.52907 (11) | 0.31885 (3) | 0.17788 (4) | 0.0748 (2) | |
N1B | 1.0235 (7) | 0.5343 (3) | 0.1286 (3) | 0.0682 (16)* | 0.448 (3) |
H1A | 1.1308 | 0.5355 | 0.1084 | 0.102* | 0.45 |
H1B | 0.9420 | 0.5197 | 0.1004 | 0.102* | 0.45 |
H1C | 1.0311 | 0.5105 | 0.1661 | 0.102* | 0.45 |
C2B | 1.0753 (13) | 0.6158 (4) | 0.2077 (5) | 0.094 (3)* | 0.448 (3) |
H22A | 1.0495 | 0.5902 | 0.2464 | 0.140* | 0.448 (3) |
H22B | 1.0449 | 0.6569 | 0.2188 | 0.140* | 0.448 (3) |
H22C | 1.2010 | 0.6133 | 0.1968 | 0.140* | 0.448 (3) |
C1B | 0.9736 (8) | 0.5968 (3) | 0.1510 (4) | 0.0592 (16)* | 0.448 (3) |
H1 | 0.8546 | 0.5942 | 0.1687 | 0.071* | 0.45 |
C3C | 0.8975 (9) | 0.6484 (3) | 0.1159 (3) | 0.0635 (17)* | 0.448 (3) |
H31A | 0.7710 | 0.6507 | 0.1256 | 0.095* | 0.448 (3) |
H31B | 0.9154 | 0.6441 | 0.0673 | 0.095* | 0.448 (3) |
H31C | 0.9556 | 0.6847 | 0.1316 | 0.095* | 0.448 (3) |
C2C | 1.0983 (8) | 0.5948 (3) | 0.2009 (3) | 0.0693 (17)* | 0.552 (3) |
H21A | 1.1680 | 0.6289 | 0.2158 | 0.104* | 0.552 (3) |
H21B | 1.1676 | 0.5584 | 0.2066 | 0.104* | 0.552 (3) |
H21C | 0.9904 | 0.5921 | 0.2278 | 0.104* | 0.552 (3) |
C3B | 0.9773 (9) | 0.6415 (4) | 0.0939 (4) | 0.102 (2)* | 0.552 (3) |
H32A | 0.8742 | 0.6356 | 0.0650 | 0.153* | 0.552 (3) |
H32B | 1.0851 | 0.6361 | 0.0674 | 0.153* | 0.552 (3) |
H32C | 0.9751 | 0.6818 | 0.1126 | 0.153* | 0.552 (3) |
N1C | 0.9824 (5) | 0.5438 (2) | 0.0978 (2) | 0.0533 (11)* | 0.552 (3) |
H2A | 0.8850 | 0.5324 | 0.1211 | 0.080* | 0.55 |
H2B | 1.0673 | 0.5156 | 0.1019 | 0.080* | 0.55 |
H2C | 0.9554 | 0.5492 | 0.0540 | 0.080* | 0.55 |
C1C | 1.0507 (6) | 0.60221 (19) | 0.1275 (2) | 0.0401 (10)* | 0.552 (3) |
H1C1 | 1.1692 | 0.6060 | 0.1058 | 0.048* | 0.552 (3) |
N1AD | 1.0060 (3) | 0.33058 (12) | 0.15318 (13) | 0.0679 (7) | |
H1D | 0.8944 (9) | 0.3411 (10) | 0.1465 (8) | 0.102* | |
H1E | 1.0797 (14) | 0.3531 (8) | 0.1289 (7) | 0.102* | |
H1F | 1.035 (2) | 0.3311 (12) | 0.1968 (4) | 0.102* | |
C1A | 0.9725 (8) | 0.2675 (3) | 0.1267 (3) | 0.0687 (17)* | 0.50 |
H1A1 | 0.8474 | 0.2544 | 0.1324 | 0.082* | 0.50 |
C2A | 1.0321 (11) | 0.2656 (5) | 0.0568 (6) | 0.147 (4)* | 0.50 |
H21D | 0.9765 | 0.2978 | 0.0314 | 0.221* | 0.50 |
H21E | 0.9993 | 0.2274 | 0.0368 | 0.221* | 0.50 |
H21F | 1.1605 | 0.2702 | 0.0553 | 0.221* | 0.50 |
C3A | 1.0981 (11) | 0.2266 (4) | 0.1554 (4) | 0.103 (2)* | 0.50 |
H31D | 1.2151 | 0.2341 | 0.1363 | 0.154* | 0.50 |
H31E | 1.0621 | 0.1858 | 0.1451 | 0.154* | 0.50 |
H31F | 1.1023 | 0.2319 | 0.2044 | 0.154* | 0.50 |
C1D | 1.0586 (10) | 0.2741 (3) | 0.1208 (4) | 0.083 (2)* | 0.50 |
H1D1 | 1.1864 | 0.2705 | 0.1078 | 0.099* | 0.50 |
C2D | 0.9272 (9) | 0.2664 (3) | 0.0540 (3) | 0.0754 (18)* | 0.50 |
H22D | 0.9300 | 0.2251 | 0.0386 | 0.113* | 0.50 |
H22E | 0.9682 | 0.2925 | 0.0177 | 0.113* | 0.50 |
H22F | 0.8063 | 0.2772 | 0.0664 | 0.113* | 0.50 |
C3D | 0.9956 (9) | 0.2217 (4) | 0.1721 (4) | 0.095 (3)* | 0.50 |
H3D1 | 1.0685 | 0.2226 | 0.2129 | 0.142* | 0.50 |
H3D2 | 1.0086 | 0.1831 | 0.1499 | 0.142* | 0.50 |
H3D3 | 0.8717 | 0.2278 | 0.1843 | 0.142* | 0.50 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cd1 | 0.03529 (8) | 0.05048 (11) | 0.03514 (9) | −0.00050 (7) | 0.00044 (6) | 0.00162 (7) |
Cd2 | 0.03482 (12) | 0.06790 (18) | 0.02930 (12) | 0.00418 (10) | −0.00130 (9) | 0.00328 (11) |
Cl3 | 0.0396 (3) | 0.0719 (4) | 0.0529 (3) | −0.0140 (3) | −0.0028 (3) | 0.0005 (3) |
Cl5 | 0.0420 (3) | 0.0747 (4) | 0.0462 (3) | 0.0179 (3) | 0.0020 (3) | 0.0019 (3) |
Cl4 | 0.0573 (3) | 0.0495 (3) | 0.0357 (3) | −0.0002 (3) | 0.0012 (2) | −0.0028 (3) |
Cl2 | 0.0584 (3) | 0.0737 (4) | 0.0604 (4) | −0.0020 (3) | −0.0306 (3) | 0.0004 (3) |
Cl1 | 0.1032 (6) | 0.0457 (4) | 0.0754 (5) | −0.0020 (4) | 0.0064 (4) | −0.0057 (4) |
N1AD | 0.0842 (17) | 0.0495 (14) | 0.0699 (17) | 0.0026 (11) | 0.0110 (12) | 0.0027 (12) |
Geometric parameters (Å, º) top
Cd1—Cl1 | 2.4881 (8) | C2C—H21B | 0.9600 |
Cd1—Cl2i | 2.6218 (6) | C2C—H21C | 0.9600 |
Cd1—Cl2 | 2.6435 (6) | C3B—H32A | 0.9600 |
Cd1—Cl4 | 2.6657 (7) | C3B—H32B | 0.9600 |
Cd1—Cl3 | 2.7094 (6) | C3B—H32C | 0.9600 |
Cd1—Cl5 | 2.7403 (6) | N1C—C1C | 1.503 (6) |
Cd1—Cd2 | 3.4493 (2) | N1C—H2A | 0.8900 |
Cd2—Cl4 | 2.5795 (6) | N1C—H2B | 0.8904 |
Cd2—Cl4ii | 2.5795 (6) | N1C—H2C | 0.8827 |
Cd2—Cl5 | 2.6245 (6) | C1C—H1C1 | 0.9800 |
Cd2—Cl5ii | 2.6245 (6) | N1AD—C1D | 1.450 (8) |
Cd2—Cl3 | 2.6902 (6) | N1AD—C1A | 1.504 (7) |
Cd2—Cl3ii | 2.6902 (6) | N1AD—H1D | 0.871 (7) |
Cd2—Cd1ii | 3.4493 (2) | N1AD—H1E | 0.877 (8) |
Cl2—Cd1iii | 2.6218 (6) | N1AD—H1F | 0.874 (8) |
N1B—C1B | 1.495 (9) | C1A—C2A | 1.431 (13) |
N1B—C1C | 1.514 (7) | C1A—C3A | 1.415 (10) |
N1B—H1A | 0.8889 | C1A—H1A1 | 0.9800 |
N1B—H1B | 0.8775 | C2A—H21D | 0.9600 |
N1B—H1C | 0.9005 | C2A—H21E | 0.9600 |
N1B—H2A | 1.0401 | C2A—H21F | 0.9600 |
C2B—C1B | 1.401 (11) | C3A—H31D | 0.9600 |
C2B—H22A | 0.9600 | C3A—H31E | 0.9600 |
C2B—H22B | 0.9600 | C3A—H31F | 0.9600 |
C2B—H22C | 0.9600 | C1D—C3D | 1.598 (11) |
C1B—C3C | 1.443 (9) | C1D—C2D | 1.634 (10) |
C1B—C3B | 1.485 (10) | C1D—H1D1 | 0.9857 |
C1B—N1C | 1.565 (8) | C2D—H22D | 0.9600 |
C1B—H1 | 0.9511 | C2D—H22E | 0.9600 |
C3C—H31A | 0.9600 | C2D—H22F | 0.9600 |
C3C—H31B | 0.9600 | C3D—H3D1 | 0.9600 |
C3C—H31C | 0.9600 | C3D—H3D2 | 0.9600 |
C2C—C1C | 1.478 (7) | C3D—H3D3 | 0.9600 |
C2C—H21A | 0.9600 | | |
| | | |
Cl1—Cd1—Cl2i | 94.47 (3) | C2B—C1B—H1 | 103.5 |
Cl1—Cd1—Cl2 | 93.72 (3) | N1B—C1B—H1 | 106.2 |
Cl2i—Cd1—Cl2 | 90.526 (9) | C3B—C1B—H1 | 109.2 |
Cl1—Cd1—Cl4 | 173.04 (2) | N1C—C1B—H1 | 103.5 |
Cl2i—Cd1—Cl4 | 91.41 (2) | C1B—C3C—H31A | 109.5 |
Cl2—Cd1—Cl4 | 89.95 (2) | C1B—C3C—H31B | 109.5 |
Cl1—Cd1—Cl3 | 95.20 (2) | H31A—C3C—H31B | 109.5 |
Cl2i—Cd1—Cl3 | 95.53 (2) | C1B—C3C—H31C | 109.5 |
Cl2—Cd1—Cl3 | 168.79 (2) | H31A—C3C—H31C | 109.5 |
Cl4—Cd1—Cl3 | 80.499 (19) | H31B—C3C—H31C | 109.5 |
Cl1—Cd1—Cl5 | 94.19 (2) | C1C—C2C—H21A | 109.5 |
Cl2i—Cd1—Cl5 | 171.34 (2) | C1C—C2C—H21B | 109.5 |
Cl2—Cd1—Cl5 | 89.07 (2) | H21A—C2C—H21B | 109.5 |
Cl4—Cd1—Cl5 | 79.944 (19) | C1C—C2C—H21C | 109.5 |
Cl3—Cd1—Cl5 | 83.523 (19) | H21A—C2C—H21C | 109.5 |
Cl1—Cd1—Cd2 | 125.30 (2) | H21B—C2C—H21C | 109.5 |
Cl2i—Cd1—Cd2 | 124.984 (17) | C1B—C3B—H32A | 109.5 |
Cl2—Cd1—Cd2 | 118.873 (17) | C1B—C3B—H32B | 109.5 |
Cl4—Cd1—Cd2 | 47.812 (13) | H32A—C3B—H32B | 109.5 |
Cl3—Cd1—Cd2 | 50.052 (13) | C1B—C3B—H32C | 109.5 |
Cl5—Cd1—Cd2 | 48.530 (13) | H32A—C3B—H32C | 109.5 |
Cl4—Cd2—Cl4ii | 180.00 (3) | H32B—C3B—H32C | 109.5 |
Cl4—Cd2—Cl5 | 83.735 (19) | C1C—N1C—H1B | 151.4 |
Cl4ii—Cd2—Cl5 | 96.265 (19) | C1B—N1C—H1B | 125.0 |
Cl4—Cd2—Cl5ii | 96.265 (19) | H1A—N1C—H1B | 108.7 |
Cl4ii—Cd2—Cl5ii | 83.735 (19) | C1C—N1C—H2A | 108.7 |
Cl5—Cd2—Cl5ii | 180.00 (2) | H1A—N1C—H2A | 130.6 |
Cl4—Cd2—Cl3 | 82.429 (19) | C1C—N1C—H2B | 109.1 |
Cl4ii—Cd2—Cl3 | 97.571 (19) | C1B—N1C—H2B | 119.6 |
Cl5—Cd2—Cl3 | 86.14 (2) | H2A—N1C—H2B | 109.4 |
Cl5ii—Cd2—Cl3 | 93.86 (2) | N1B—N1C—H2C | 163.7 |
Cl4—Cd2—Cl3ii | 97.571 (19) | C1C—N1C—H2C | 109.4 |
Cl4ii—Cd2—Cl3ii | 82.429 (19) | C1B—N1C—H2C | 121.7 |
Cl5—Cd2—Cl3ii | 93.86 (2) | H1A—N1C—H2C | 114.8 |
Cl5ii—Cd2—Cl3ii | 86.14 (2) | H2A—N1C—H2C | 110.1 |
Cl3—Cd2—Cl3ii | 180.00 (3) | H2B—N1C—H2C | 110.1 |
Cl4—Cd2—Cd1ii | 130.031 (15) | C2C—C1C—N1C | 110.9 (4) |
Cl4ii—Cd2—Cd1ii | 49.969 (15) | C2C—C1C—H1C1 | 102.1 |
Cl5—Cd2—Cd1ii | 128.522 (13) | N1C—C1C—H1C1 | 102.1 |
Cl5ii—Cd2—Cd1ii | 51.478 (13) | N1B—C1C—H1C1 | 102.1 |
Cl3—Cd2—Cd1ii | 129.458 (13) | C1D—N1AD—H1D | 115.0 (15) |
Cl3ii—Cd2—Cd1ii | 50.542 (13) | C1A—N1AD—H1E | 116.3 (13) |
Cl4—Cd2—Cd1 | 49.969 (15) | H1D—N1AD—H1E | 111.3 (13) |
Cl4ii—Cd2—Cd1 | 130.031 (15) | C1D—N1AD—H1F | 111.5 (18) |
Cl5—Cd2—Cd1 | 51.478 (13) | C1A—N1AD—H1F | 112.6 (18) |
Cl5ii—Cd2—Cd1 | 128.522 (13) | H1D—N1AD—H1F | 111.9 (12) |
Cl3—Cd2—Cd1 | 50.542 (13) | H1E—N1AD—H1F | 111.2 (13) |
Cl3ii—Cd2—Cd1 | 129.458 (13) | C2A—C1A—N1AD | 107.6 (6) |
Cd1ii—Cd2—Cd1 | 180.000 (6) | C3A—C1A—N1AD | 110.3 (5) |
Cd2—Cl3—Cd1 | 79.406 (16) | C2A—C1A—H1A1 | 113.1 |
Cd2—Cl5—Cd1 | 79.992 (16) | C3A—C1A—H1A1 | 113.1 |
Cd2—Cl4—Cd1 | 82.219 (19) | N1AD—C1A—H1A1 | 113.1 |
Cd1iii—Cl2—Cd1 | 155.32 (3) | C1A—C2A—H21D | 109.5 |
N1C—N1B—C1B | 82.2 (7) | C1A—C2A—H21E | 109.5 |
N1C—N1B—C1C | 75.6 (7) | H21D—C2A—H21E | 109.5 |
N1C—N1B—H1A | 90.2 | C1A—C2A—H21F | 109.5 |
C1B—N1B—H1A | 108.8 | H21D—C2A—H21F | 109.5 |
C1B—N1B—H1B | 110.4 | H21E—C2A—H21F | 109.5 |
C1C—N1B—H1B | 116.4 | H21D—C2A—H1D1 | 127.4 |
H1A—N1B—H1B | 110.7 | H21E—C2A—H1D1 | 121.3 |
N1C—N1B—H1C | 152.9 | C1A—C3A—H31D | 109.5 |
C1B—N1B—H1C | 108.7 | C1A—C3A—H31E | 109.5 |
C1C—N1B—H1C | 125.5 | H31D—C3A—H31E | 109.5 |
H1A—N1B—H1C | 108.6 | C1A—C3A—H31F | 109.5 |
H1B—N1B—H1C | 109.6 | H31D—C3A—H31F | 109.5 |
C1B—N1B—H2A | 80.4 | H31E—C3A—H31F | 109.5 |
C1C—N1B—H2A | 99.7 | H31E—C3A—H1D1 | 127.0 |
H1A—N1B—H2A | 145.7 | H31F—C3A—H1D1 | 121.3 |
C1B—N1B—H2B | 146.0 | N1AD—C1D—C3D | 105.9 (5) |
C1C—N1B—H2B | 119.0 | N1AD—C1D—C2D | 105.9 (5) |
H1C—N1B—H2B | 102.4 | C3D—C1D—C2D | 104.2 (5) |
H2A—N1B—H2B | 108.3 | N1AD—C1D—H1D1 | 116.1 |
C1B—C2B—H22A | 109.5 | C3D—C1D—H1D1 | 112.6 |
C1B—C2B—H22B | 109.5 | C2D—C1D—H1D1 | 111.3 |
H22A—C2B—H22B | 109.5 | C1D—C2D—H22D | 109.5 |
C1B—C2B—H22C | 109.5 | C1D—C2D—H22E | 109.5 |
H22A—C2B—H22C | 109.5 | H22D—C2D—H22E | 109.5 |
H22B—C2B—H22C | 109.5 | C1D—C2D—H22F | 109.5 |
C2B—C1B—C3C | 110.3 (6) | H22D—C2D—H22F | 109.5 |
C2B—C1B—N1B | 111.8 (6) | H22E—C2D—H22F | 109.5 |
C3C—C1B—N1B | 133.6 (6) | C1D—C3D—H3D1 | 109.5 |
C2B—C1B—C3B | 112.3 (6) | C1D—C3D—H3D2 | 109.5 |
N1B—C1B—C3B | 113.1 (6) | H3D1—C3D—H3D2 | 109.5 |
C2B—C1B—N1C | 136.2 (6) | C1D—C3D—H3D3 | 109.5 |
C3C—C1B—N1C | 107.2 (5) | H3D1—C3D—H3D3 | 109.5 |
C3B—C1B—N1C | 90.2 (5) | H3D2—C3D—H3D3 | 109.5 |
Symmetry codes: (i) x−1/2, y, −z+1/2; (ii) −x+1, −y+1, −z; (iii) x+1/2, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1B—H1C···Cl2 | 0.90 | 2.58 | 3.269 (6) | 134.2 |
N1C—H2A···Cl4 | 0.89 | 2.76 | 3.502 (4) | 141.1 |
N1AD—H1D···Cl1 | 0.87 (1) | 2.83 (1) | 3.586 (2) | 147 (2) |
N1AD—H1E···Cl3iv | 0.88 (1) | 2.48 (1) | 3.352 (2) | 173 (2) |
N1AD—H1F···Cl1iii | 0.87 (1) | 2.45 (1) | 3.299 (3) | 163 (2) |
Symmetry codes: (iii) x+1/2, y, −z+1/2; (iv) x+1, y, z. |
Crystal data top
C12H40Cd3Cl10N4 | Dx = 1.962 Mg m−3 |
Mr = 932.18 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 8299 reflections |
a = 7.3918 (2) Å | θ = 2.8–29.8° |
b = 22.0135 (7) Å | µ = 2.86 mm−1 |
c = 19.3938 (5) Å | T = 275 K |
V = 3155.75 (15) Å3 | , colorles |
Z = 4 | 0.25 × 0.2 × 0.08 mm |
F(000) = 1816 | |
Data collection top
KUMA KM4-CCD diffractometer | 4686 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.043 |
Graphite monochromator | θmax = 25.7°, θmin = 2.8° |
Absorption correction: multi-scan CrysAlis RED, Oxford Diffraction Ltd.,
Version 1.171.32.6 (release 21-05-2007 CrysAlis171 .NET)
(compiled May 21 2007,16:32:00)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm. | h = −9→6 |
Tmin = 0.49, Tmax = 0.79 | k = −26→26 |
25040 measured reflections | l = −23→23 |
5945 independent reflections | |
Refinement top
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)] = 0.028 | w = 1/[σ2(Fo2) + (0.0183P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.047 | (Δ/σ)max = 0.016 |
S = 0.83 | Δρmax = 0.52 e Å−3 |
5945 reflections | Δρmin = −0.37 e Å−3 |
267 parameters | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
0 restraints | Absolute structure parameter: 0.45 (4) |
Primary atom site location: structure-invariant direct methods | |
Crystal data top
C12H40Cd3Cl10N4 | V = 3155.75 (15) Å3 |
Mr = 932.18 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.3918 (2) Å | µ = 2.86 mm−1 |
b = 22.0135 (7) Å | T = 275 K |
c = 19.3938 (5) Å | 0.25 × 0.2 × 0.08 mm |
Data collection top
KUMA KM4-CCD diffractometer | 5945 independent reflections |
Absorption correction: multi-scan CrysAlis RED, Oxford Diffraction Ltd.,
Version 1.171.32.6 (release 21-05-2007 CrysAlis171 .NET)
(compiled May 21 2007,16:32:00)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm. | 4686 reflections with I > 2σ(I) |
Tmin = 0.49, Tmax = 0.79 | Rint = 0.043 |
25040 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.047 | Δρmax = 0.52 e Å−3 |
S = 0.83 | Δρmin = −0.37 e Å−3 |
5945 reflections | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
267 parameters | Absolute structure parameter: 0.45 (4) |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Cd1 | 0.97951 (7) | 0.072912 (16) | 0.163198 (16) | 0.03076 (10) | |
Cd2 | 1.02144 (7) | −0.067097 (16) | −0.153763 (16) | 0.02966 (10) | |
Cd3 | 1.00412 (10) | 0.005030 (17) | 0.004188 (18) | 0.03294 (9) | |
Cl3 | 1.2449 (2) | 0.07719 (9) | 0.06873 (8) | 0.0412 (4) | |
Cl1 | 0.9662 (3) | 0.18464 (6) | 0.18676 (8) | 0.0553 (4) | |
Cl2 | 1.1922 (2) | 0.04967 (7) | 0.26783 (8) | 0.0461 (4) | |
Cl4 | 0.9810 (3) | −0.04358 (5) | 0.12480 (6) | 0.0355 (3) | |
Cl5 | 0.75902 (19) | 0.07969 (9) | 0.05147 (8) | 0.0394 (4) | |
Cl6 | 0.7637 (2) | −0.07220 (9) | −0.05468 (8) | 0.0409 (4) | |
Cl7 | 1.25552 (19) | −0.06714 (9) | −0.04336 (8) | 0.0413 (4) | |
Cl8 | 1.0095 (3) | 0.04975 (5) | −0.11884 (5) | 0.0369 (3) | |
Cl9 | 0.8027 (2) | −0.04738 (8) | −0.25714 (8) | 0.0477 (4) | |
Cl10 | 1.0323 (3) | −0.17967 (6) | −0.16920 (7) | 0.0551 (4) | |
N1A | 1.5009 (10) | −0.16849 (16) | −0.1459 (2) | 0.0517 (12) | |
H1A1 | 1.4420 | −0.1430 | −0.1182 | 0.078* | |
H1A2 | 1.4634 | −0.1632 | −0.1891 | 0.078* | |
H1A3 | 1.6191 | −0.1612 | −0.1434 | 0.078* | |
C11A | 1.5629 (17) | −0.2217 (6) | −0.1037 (7) | 0.049 (2)* | 0.50 |
H11A | 1.5864 | −0.1838 | −0.1198 | 0.059* | 0.50 |
H1 | 0.3643 | 0.0970 | −0.1632 | 0.059* | 0.50 |
C12A | 1.4635 (19) | −0.2334 (5) | −0.1237 (6) | 0.049 (2)* | 0.50 |
H12A | 1.3456 | −0.2407 | −0.1475 | 0.059* | 0.50 |
C21A | 1.457 (2) | −0.2309 (8) | −0.0435 (9) | 0.062 (3)* | 0.50 |
H21A | 1.3450 | −0.2500 | −0.0559 | 0.094* | 0.50 |
H21B | 1.4332 | −0.1925 | −0.0219 | 0.094* | 0.50 |
H21C | 1.5220 | −0.2566 | −0.0120 | 0.094* | 0.50 |
C22A | 1.401 (2) | −0.2292 (8) | −0.0470 (10) | 0.062 (3)* | 0.50 |
H22A | 1.3985 | −0.2692 | −0.0273 | 0.094* | 0.50 |
H22B | 1.2828 | −0.2116 | −0.0448 | 0.094* | 0.50 |
H22C | 1.4848 | −0.2044 | −0.0216 | 0.094* | 0.50 |
C31A | 1.6291 (18) | −0.2726 (7) | −0.1372 (8) | 0.061 (3)* | 0.50 |
H31A | 1.7549 | −0.2776 | −0.1265 | 0.091* | 0.50 |
H31B | 1.6149 | −0.2676 | −0.1861 | 0.091* | 0.50 |
H31C | 1.5631 | −0.3078 | −0.1224 | 0.091* | 0.50 |
C32A | 1.5628 (19) | −0.2766 (6) | −0.1552 (8) | 0.061 (3)* | 0.50 |
H32A | 1.4938 | −0.2942 | −0.1921 | 0.091* | 0.50 |
H32B | 1.5942 | −0.3076 | −0.1225 | 0.091* | 0.50 |
H32C | 1.6712 | −0.2587 | −0.1735 | 0.091* | 0.50 |
N1B | 0.5213 (10) | 0.0396 (2) | −0.1208 (3) | 0.095 (2) | |
H1B1 | 0.4882 | 0.0129 | −0.1528 | 0.142* | |
H1B2 | 0.4581 | 0.0331 | −0.0824 | 0.142* | |
H1B3 | 0.6388 | 0.0353 | −0.1119 | 0.142* | |
C1B | 0.4864 (13) | 0.1013 (3) | −0.1458 (4) | 0.081 (2) | |
C2B | 0.4636 (14) | 0.1441 (3) | −0.0940 (4) | 0.109 (3) | |
H2B1 | 0.5771 | 0.1509 | −0.0712 | 0.164* | |
H2B2 | 0.3765 | 0.1294 | −0.0612 | 0.164* | |
H2B3 | 0.4214 | 0.1815 | −0.1137 | 0.164* | |
C3B | 0.5851 (9) | 0.1143 (4) | −0.2075 (3) | 0.072 (2) | |
H3B1 | 0.5345 | 0.1495 | −0.2295 | 0.108* | |
H3B2 | 0.5776 | 0.0802 | −0.2382 | 0.108* | |
H3B3 | 0.7095 | 0.1219 | −0.1963 | 0.108* | |
N1C | 1.5224 (9) | −0.04044 (17) | 0.1013 (2) | 0.0549 (13) | |
H1C1 | 1.4394 | −0.0117 | 0.1081 | 0.082* | |
H1C2 | 1.5442 | −0.0440 | 0.0564 | 0.082* | |
H1C3 | 1.6240 | −0.0303 | 0.1231 | 0.082* | |
C1C | 1.4539 (8) | −0.0998 (2) | 0.1289 (3) | 0.0417 (16) | |
H1C | 1.3449 | −0.1104 | 0.1028 | 0.050* | |
C2C | 1.4011 (9) | −0.0939 (3) | 0.2016 (3) | 0.0602 (19) | |
H2C1 | 1.5065 | −0.0862 | 0.2291 | 0.090* | |
H2C2 | 1.3448 | −0.1309 | 0.2167 | 0.090* | |
H2C3 | 1.3173 | −0.0609 | 0.2065 | 0.090* | |
C3C | 1.5915 (9) | −0.1478 (3) | 0.1149 (3) | 0.064 (2) | |
H3C1 | 1.6991 | −0.1395 | 0.1409 | 0.096* | |
H3C2 | 1.6199 | −0.1482 | 0.0666 | 0.096* | |
H3C3 | 1.5440 | −0.1867 | 0.1281 | 0.096* | |
N1D | 0.4930 (9) | 0.17110 (16) | 0.1617 (2) | 0.0487 (12) | |
H1D1 | 0.4414 | 0.1417 | 0.1371 | 0.073* | |
H1D2 | 0.4619 | 0.1672 | 0.2058 | 0.073* | |
H1D3 | 0.6127 | 0.1685 | 0.1577 | 0.073* | |
C11D | 0.507 (2) | 0.2303 (6) | 0.1302 (7) | 0.052 (2)* | 0.50 |
H11D | 0.3732 | 0.2400 | 0.1261 | 0.063* | 0.50 |
C12D | 0.4305 (19) | 0.2320 (7) | 0.1353 (8) | 0.052 (2)* | 0.50 |
H12D | 0.2993 | 0.2284 | 0.1412 | 0.063* | 0.50 |
H1D | 0.2964 | 0.2288 | 0.1413 | 0.063* | 0.50 |
C21D | 0.552 (2) | 0.2384 (9) | 0.0630 (9) | 0.075 (3)* | 0.50 |
H21D | 0.5050 | 0.2767 | 0.0473 | 0.112* | 0.50 |
H21E | 0.5010 | 0.2062 | 0.0359 | 0.112* | 0.50 |
H21F | 0.6811 | 0.2382 | 0.0582 | 0.112* | 0.50 |
C22D | 0.444 (2) | 0.2372 (9) | 0.0630 (9) | 0.075 (3)* | 0.50 |
H22D | 0.4025 | 0.2767 | 0.0491 | 0.112* | 0.50 |
H22E | 0.3699 | 0.2067 | 0.0416 | 0.112* | 0.50 |
H22F | 0.5673 | 0.2319 | 0.0492 | 0.112* | 0.50 |
C31D | 0.554 (2) | 0.2792 (10) | 0.1754 (11) | 0.078 (3)* | 0.50 |
H31D | 0.6781 | 0.2748 | 0.1897 | 0.117* | 0.50 |
H31E | 0.4770 | 0.2784 | 0.2151 | 0.117* | 0.50 |
H31F | 0.5398 | 0.3171 | 0.1517 | 0.117* | 0.50 |
C32D | 0.469 (2) | 0.2796 (9) | 0.1794 (10) | 0.078 (3)* | 0.50 |
H32D | 0.5979 | 0.2846 | 0.1826 | 0.117* | 0.50 |
H32E | 0.4208 | 0.2709 | 0.2243 | 0.117* | 0.50 |
H32F | 0.4156 | 0.3162 | 0.1619 | 0.117* | 0.50 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cd1 | 0.0283 (2) | 0.0381 (2) | 0.02589 (18) | 0.0009 (2) | −0.00002 (18) | −0.00299 (15) |
Cd2 | 0.0275 (2) | 0.0362 (2) | 0.02527 (18) | −0.0011 (2) | −0.00046 (18) | −0.00208 (15) |
Cd3 | 0.02812 (15) | 0.0492 (2) | 0.02151 (15) | 0.00323 (17) | 0.00068 (16) | −0.00343 (14) |
Cl3 | 0.0303 (8) | 0.0518 (11) | 0.0416 (9) | −0.0094 (8) | 0.0030 (6) | −0.0036 (8) |
Cl1 | 0.0765 (12) | 0.0349 (7) | 0.0546 (9) | 0.0012 (9) | −0.0015 (9) | 0.0033 (6) |
Cl2 | 0.0429 (9) | 0.0501 (11) | 0.0454 (9) | 0.0020 (8) | −0.0226 (7) | −0.0040 (8) |
Cl4 | 0.0411 (9) | 0.0371 (7) | 0.0284 (6) | 0.0019 (8) | −0.0020 (7) | 0.0012 (5) |
Cl5 | 0.0317 (8) | 0.0524 (11) | 0.0340 (8) | 0.0122 (7) | −0.0010 (6) | 0.0008 (7) |
Cl6 | 0.0318 (8) | 0.0551 (11) | 0.0357 (8) | −0.0130 (8) | 0.0021 (6) | −0.0008 (8) |
Cl7 | 0.0340 (8) | 0.0571 (12) | 0.0327 (8) | 0.0142 (8) | −0.0028 (6) | −0.0062 (8) |
Cl8 | 0.0486 (8) | 0.0362 (6) | 0.0259 (6) | −0.0016 (9) | 0.0005 (8) | 0.0025 (5) |
Cl9 | 0.0418 (9) | 0.0588 (12) | 0.0425 (9) | −0.0014 (8) | −0.0197 (7) | 0.0006 (7) |
Cl10 | 0.0777 (12) | 0.0344 (7) | 0.0533 (9) | −0.0045 (9) | −0.0096 (10) | 0.0028 (6) |
N1A | 0.073 (3) | 0.038 (2) | 0.045 (3) | −0.003 (4) | 0.001 (4) | 0.004 (2) |
N1B | 0.081 (5) | 0.053 (3) | 0.151 (6) | −0.022 (4) | −0.036 (5) | 0.038 (3) |
C1B | 0.101 (6) | 0.048 (4) | 0.094 (5) | 0.013 (5) | 0.046 (6) | 0.027 (4) |
C2B | 0.170 (9) | 0.091 (5) | 0.066 (5) | −0.016 (7) | 0.040 (6) | −0.017 (4) |
C3B | 0.058 (5) | 0.120 (6) | 0.037 (4) | 0.000 (4) | 0.004 (3) | −0.009 (4) |
N1C | 0.051 (3) | 0.040 (3) | 0.074 (3) | −0.006 (3) | −0.019 (3) | 0.018 (2) |
C1C | 0.042 (4) | 0.037 (3) | 0.045 (3) | 0.002 (3) | 0.003 (3) | 0.006 (3) |
C2C | 0.073 (5) | 0.066 (4) | 0.042 (4) | 0.006 (3) | −0.003 (3) | −0.005 (3) |
C3C | 0.077 (5) | 0.051 (4) | 0.064 (5) | −0.002 (3) | 0.031 (3) | −0.007 (4) |
N1D | 0.065 (3) | 0.031 (2) | 0.050 (3) | 0.005 (3) | −0.015 (4) | −0.0016 (19) |
Geometric parameters (Å, º) top
Cd1—Cl1 | 2.5036 (14) | N1B—H1B2 | 0.8900 |
Cd1—Cl2 | 2.6175 (14) | N1B—H1B3 | 0.8900 |
Cd1—Cl9i | 2.6557 (15) | C1B—C2B | 1.387 (9) |
Cd1—Cl4 | 2.6703 (12) | C1B—C3B | 1.431 (8) |
Cd1—Cl3 | 2.6859 (15) | C1B—H1 | 0.9674 |
Cd1—Cl5 | 2.7155 (16) | C2B—H2B1 | 0.9600 |
Cd1—Cd3 | 3.4316 (5) | C2B—H2B2 | 0.9600 |
Cd2—Cl10 | 2.4975 (14) | C2B—H2B3 | 0.9600 |
Cd2—Cl9 | 2.6121 (14) | C3B—H3B1 | 0.9600 |
Cd2—Cl2ii | 2.6344 (14) | C3B—H3B2 | 0.9600 |
Cd2—Cl8 | 2.6613 (12) | C3B—H3B3 | 0.9600 |
Cd2—Cl6 | 2.7083 (16) | N1C—C1C | 1.501 (6) |
Cd2—Cl7 | 2.7529 (15) | N1C—H1C1 | 0.8900 |
Cd2—Cd3 | 3.4527 (5) | N1C—H1C2 | 0.8900 |
Cd3—Cl4 | 2.5778 (11) | N1C—H1C3 | 0.8900 |
Cd3—Cl8 | 2.5813 (11) | C1C—C2C | 1.468 (8) |
Cd3—Cl5 | 2.6123 (18) | C1C—C3C | 1.491 (8) |
Cd3—Cl7 | 2.6130 (17) | C1C—H1C | 0.9800 |
Cd3—Cl3 | 2.6941 (17) | C2C—H2C1 | 0.9600 |
Cd3—Cl6 | 2.7116 (18) | C2C—H2C2 | 0.9600 |
Cl2—Cd2iii | 2.6344 (14) | C2C—H2C3 | 0.9600 |
Cl9—Cd1iv | 2.6557 (15) | C3C—H3C1 | 0.9600 |
N1A—C12A | 1.517 (12) | C3C—H3C2 | 0.9600 |
N1A—H1A1 | 0.8900 | C3C—H3C3 | 0.9600 |
N1A—H1A2 | 0.8900 | N1D—C12D | 1.507 (15) |
N1A—H1A3 | 0.8900 | N1D—H1D1 | 0.8900 |
C11A—C31A | 1.386 (18) | N1D—H1D2 | 0.8900 |
C11A—H11A | 0.9300 | N1D—H1D3 | 0.8900 |
C11A—C21A | 1.42 (2) | C11D—C21D | 1.36 (2) |
C12A—C32A | 1.348 (17) | C11D—C31D | 1.43 (2) |
C12A—C22A | 1.56 (2) | C12D—C32D | 1.38 (2) |
C12A—H12A | 0.9997 | C12D—C22D | 1.41 (2) |
C21A—H21A | 0.9600 | C12D—H12D | 0.9800 |
C21A—H21B | 0.9600 | C21D—H21D | 0.9600 |
C21A—H21C | 0.9600 | C21D—H21E | 0.9600 |
C22A—H22A | 0.9600 | C21D—H21F | 0.9600 |
C22A—H22B | 0.9600 | C22D—H22D | 0.9600 |
C22A—H22C | 0.9600 | C22D—H22E | 0.9600 |
C31A—H31A | 0.9600 | C22D—H22F | 0.9600 |
C31A—H31B | 0.9600 | C31D—H31D | 0.9600 |
C31A—H31C | 0.9600 | C31D—H31E | 0.9600 |
C32A—H32A | 0.9600 | C31D—H31F | 0.9600 |
C32A—H32B | 0.9600 | C32D—H32D | 0.9600 |
C32A—H32C | 0.9600 | C32D—H32E | 0.9600 |
N1B—C1B | 1.466 (7) | C32D—H32F | 0.9600 |
N1B—H1B1 | 0.8900 | | |
| | | |
Cl1—Cd1—Cl2 | 94.25 (6) | H31A—C31A—H31B | 109.5 |
Cl1—Cd1—Cl9i | 94.07 (6) | C11A—C31A—H31C | 109.5 |
Cl2—Cd1—Cl9i | 88.81 (7) | H31A—C31A—H31C | 109.5 |
Cl1—Cd1—Cl4 | 173.98 (5) | H31B—C31A—H31C | 109.5 |
Cl2—Cd1—Cl4 | 91.49 (5) | C12A—C32A—H32A | 109.5 |
Cl9i—Cd1—Cl4 | 87.83 (5) | C12A—C32A—H32B | 109.5 |
Cl1—Cd1—Cl3 | 96.82 (6) | H32A—C32A—H32B | 109.5 |
Cl2—Cd1—Cl3 | 95.57 (6) | C12A—C32A—H32C | 109.5 |
Cl9i—Cd1—Cl3 | 167.92 (6) | H32A—C32A—H32C | 109.5 |
Cl4—Cd1—Cl3 | 80.82 (5) | H32B—C32A—H32C | 109.5 |
Cl1—Cd1—Cl5 | 93.91 (6) | C1B—N1B—H1B1 | 109.5 |
Cl2—Cd1—Cl5 | 171.83 (6) | C1B—N1B—H1B2 | 109.5 |
Cl9i—Cd1—Cl5 | 90.26 (5) | H1B1—N1B—H1B2 | 109.5 |
Cl4—Cd1—Cl5 | 80.36 (5) | C1B—N1B—H1B3 | 109.5 |
Cl3—Cd1—Cl5 | 83.81 (4) | H1B1—N1B—H1B3 | 109.5 |
Cl1—Cd1—Cd3 | 126.43 (4) | H1B2—N1B—H1B3 | 109.5 |
Cl2—Cd1—Cd3 | 125.43 (4) | C2B—C1B—C3B | 122.2 (7) |
Cl9i—Cd1—Cd3 | 118.18 (4) | C2B—C1B—N1B | 114.2 (7) |
Cl4—Cd1—Cd3 | 48.01 (2) | C3B—C1B—N1B | 111.8 (7) |
Cl3—Cd1—Cd3 | 50.47 (4) | C2B—C1B—H1 | 101.9 |
Cl5—Cd1—Cd3 | 48.60 (4) | C3B—C1B—H1 | 101.8 |
Cl10—Cd2—Cl9 | 95.32 (6) | N1B—C1B—H1 | 100.8 |
Cl10—Cd2—Cl2ii | 92.84 (6) | C1B—C2B—H2B1 | 109.5 |
Cl9—Cd2—Cl2ii | 91.74 (7) | C1B—C2B—H2B2 | 109.5 |
Cl10—Cd2—Cl8 | 172.14 (4) | H2B1—C2B—H2B2 | 109.5 |
Cl9—Cd2—Cl8 | 90.81 (5) | C1B—C2B—H2B3 | 109.5 |
Cl2ii—Cd2—Cl8 | 91.88 (5) | H2B1—C2B—H2B3 | 109.5 |
Cl10—Cd2—Cl6 | 93.81 (6) | H2B2—C2B—H2B3 | 109.5 |
Cl9—Cd2—Cl6 | 96.66 (5) | C1B—C3B—H3B1 | 109.5 |
Cl2ii—Cd2—Cl6 | 168.76 (6) | C1B—C3B—H3B2 | 109.5 |
Cl8—Cd2—Cl6 | 80.57 (6) | H3B1—C3B—H3B2 | 109.5 |
Cl10—Cd2—Cl7 | 94.17 (6) | C1B—C3B—H3B3 | 109.5 |
Cl9—Cd2—Cl7 | 170.46 (6) | H3B1—C3B—H3B3 | 109.5 |
Cl2ii—Cd2—Cl7 | 86.79 (6) | H3B2—C3B—H3B3 | 109.5 |
Cl8—Cd2—Cl7 | 79.82 (6) | C1C—N1C—H1C1 | 109.5 |
Cl6—Cd2—Cl7 | 83.70 (4) | C1C—N1C—H1C2 | 109.5 |
Cl10—Cd2—Cd3 | 124.32 (4) | H1C1—N1C—H1C2 | 109.5 |
Cl9—Cd2—Cd3 | 125.56 (4) | C1C—N1C—H1C3 | 109.5 |
Cl2ii—Cd2—Cd3 | 118.35 (4) | H1C1—N1C—H1C3 | 109.5 |
Cl8—Cd2—Cd3 | 47.82 (2) | H1C2—N1C—H1C3 | 109.5 |
Cl6—Cd2—Cd3 | 50.47 (4) | C2C—C1C—C3C | 114.8 (5) |
Cl7—Cd2—Cd3 | 48.20 (4) | C2C—C1C—N1C | 110.8 (5) |
Cl4—Cd3—Cl8 | 176.36 (8) | C3C—C1C—N1C | 108.8 (5) |
Cl4—Cd3—Cl5 | 84.07 (5) | C2C—C1C—H1C | 107.4 |
Cl8—Cd3—Cl5 | 95.46 (5) | C3C—C1C—H1C | 107.4 |
Cl4—Cd3—Cl7 | 96.61 (5) | N1C—C1C—H1C | 107.4 |
Cl8—Cd3—Cl7 | 83.96 (6) | C1C—C2C—H2C1 | 109.5 |
Cl5—Cd3—Cl7 | 178.42 (8) | C1C—C2C—H2C2 | 109.5 |
Cl4—Cd3—Cl3 | 82.36 (5) | H2C1—C2C—H2C2 | 109.5 |
Cl8—Cd3—Cl3 | 101.21 (5) | C1C—C2C—H2C3 | 109.5 |
Cl5—Cd3—Cl3 | 85.65 (4) | H2C1—C2C—H2C3 | 109.5 |
Cl7—Cd3—Cl3 | 93.02 (6) | H2C2—C2C—H2C3 | 109.5 |
Cl4—Cd3—Cl6 | 94.49 (5) | C1C—C3C—H3C1 | 109.5 |
Cl8—Cd3—Cl6 | 81.95 (5) | C1C—C3C—H3C2 | 109.5 |
Cl5—Cd3—Cl6 | 95.03 (7) | H3C1—C3C—H3C2 | 109.5 |
Cl7—Cd3—Cl6 | 86.35 (4) | C1C—C3C—H3C3 | 109.5 |
Cl3—Cd3—Cl6 | 176.70 (7) | H3C1—C3C—H3C3 | 109.5 |
Cl4—Cd3—Cd1 | 50.34 (3) | H3C2—C3C—H3C3 | 109.5 |
Cl8—Cd3—Cd1 | 131.71 (3) | C12D—N1D—H1D1 | 109.5 |
Cl5—Cd3—Cd1 | 51.23 (4) | C12D—N1D—H1D2 | 109.5 |
Cl7—Cd3—Cd1 | 128.29 (4) | H1D1—N1D—H1D2 | 109.5 |
Cl3—Cd3—Cd1 | 50.26 (3) | C12D—N1D—H1D3 | 109.5 |
Cl6—Cd3—Cd1 | 128.07 (4) | H1D1—N1D—H1D3 | 109.5 |
Cl4—Cd3—Cd2 | 128.07 (3) | H1D2—N1D—H1D3 | 109.5 |
Cl8—Cd3—Cd2 | 49.81 (3) | C21D—C11D—C31D | 115.5 (17) |
Cl5—Cd3—Cd2 | 128.79 (4) | C21D—C11D—H1D | 112.0 |
Cl7—Cd3—Cd2 | 51.75 (3) | C32D—C12D—C22D | 122.6 (17) |
Cl3—Cd3—Cd2 | 131.21 (4) | C32D—C12D—N1D | 113.6 (13) |
Cl6—Cd3—Cd2 | 50.39 (3) | C22D—C12D—N1D | 112.9 (13) |
Cd1—Cd3—Cd2 | 178.21 (2) | N1D—C12D—H11D | 134.9 |
Cd1—Cl3—Cd3 | 79.26 (4) | C32D—C12D—H12D | 101.1 |
Cd1—Cl2—Cd2iii | 154.37 (8) | C22D—C12D—H12D | 101.1 |
Cd3—Cl4—Cd1 | 81.65 (3) | N1D—C12D—H12D | 101.1 |
Cd3—Cl5—Cd1 | 80.17 (4) | C32D—C12D—H1D | 100.7 |
Cd2—Cl6—Cd3 | 79.14 (4) | C22D—C12D—H1D | 100.9 |
Cd3—Cl7—Cd2 | 80.05 (4) | N1D—C12D—H1D | 101.6 |
Cd3—Cl8—Cd2 | 82.37 (3) | C11D—C21D—H21D | 109.5 |
Cd2—Cl9—Cd1iv | 153.84 (8) | C11D—C21D—H21E | 109.5 |
C12A—N1A—H1A1 | 109.5 | H21D—C21D—H21E | 109.5 |
C12A—N1A—H1A2 | 109.5 | C11D—C21D—H21F | 109.5 |
H1A1—N1A—H1A2 | 109.5 | H21D—C21D—H21F | 109.5 |
C12A—N1A—H1A3 | 109.5 | H21E—C21D—H21F | 109.5 |
H1A1—N1A—H1A3 | 109.5 | C12D—C22D—H22D | 109.5 |
H1A2—N1A—H1A3 | 109.5 | C12D—C22D—H22E | 109.5 |
C31A—C11A—C21A | 117.7 (13) | H11D—C22D—H22E | 102.0 |
C32A—C12A—N1A | 115.9 (11) | H22D—C22D—H22E | 109.5 |
C32A—C12A—C22A | 129.4 (13) | C12D—C22D—H22F | 109.5 |
N1A—C12A—C22A | 105.6 (10) | H11D—C22D—H22F | 129.4 |
C32A—C12A—H12A | 98.7 | H22D—C22D—H22F | 109.5 |
N1A—C12A—H12A | 100.3 | H22E—C22D—H22F | 109.5 |
C22A—C12A—H12A | 101.2 | C11D—C31D—H31D | 109.5 |
C11A—C21A—H21A | 109.5 | C11D—C31D—H31E | 109.5 |
C11A—C21A—H21B | 109.5 | H31D—C31D—H31E | 109.5 |
H21A—C21A—H21B | 109.5 | C11D—C31D—H31F | 109.5 |
C11A—C21A—H21C | 109.5 | H31D—C31D—H31F | 109.5 |
H21A—C21A—H21C | 109.5 | H31E—C31D—H31F | 109.5 |
H21B—C21A—H21C | 109.5 | C12D—C32D—H32D | 109.5 |
C12A—C22A—H22A | 109.5 | H11D—C32D—H32D | 124.8 |
C12A—C22A—H22B | 109.5 | C12D—C32D—H32E | 109.5 |
H22A—C22A—H22B | 109.5 | H11D—C32D—H32E | 109.1 |
C12A—C22A—H22C | 109.5 | H32D—C32D—H32E | 109.5 |
H22A—C22A—H22C | 109.5 | C12D—C32D—H32F | 109.5 |
H22B—C22A—H22C | 109.5 | H32D—C32D—H32F | 109.5 |
C11A—C31A—H31A | 109.5 | H32E—C32D—H32F | 109.5 |
C11A—C31A—H31B | 109.5 | | |
Symmetry codes: (i) −x+3/2, −y, z+1/2; (ii) −x+5/2, −y, z−1/2; (iii) −x+5/2, −y, z+1/2; (iv) −x+3/2, −y, z−1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A1···Cl7 | 0.89 | 2.61 | 3.496 (5) | 177 |
N1A—H1A2···Cl1ii | 0.89 | 2.51 | 3.274 (4) | 145 |
N1A—H1A2···Cl2ii | 0.89 | 2.88 | 3.418 (5) | 121 |
N1A—H1A3···Cl6v | 0.89 | 2.82 | 3.376 (5) | 122 |
N1B—H1B1···Cl2iv | 0.89 | 2.46 | 3.319 (6) | 163 |
N1B—H1B2···Cl7vi | 0.89 | 2.77 | 3.411 (6) | 130 |
N1B—H1B3···Cl8 | 0.89 | 2.76 | 3.616 (8) | 161 |
N1B—H1B3···Cl6 | 0.89 | 2.77 | 3.303 (6) | 120 |
N1C—H1C1···Cl3 | 0.89 | 2.55 | 3.363 (5) | 153 |
N1C—H1C2···Cl6v | 0.89 | 2.77 | 3.581 (6) | 153 |
N1C—H1C3···Cl4v | 0.89 | 2.66 | 3.421 (7) | 145 |
N1C—H1C3···Cl9iii | 0.89 | 2.94 | 3.598 (5) | 133 |
N1D—H1D1···Cl3vi | 0.89 | 2.43 | 3.300 (5) | 167 |
N1D—H1D2···Cl10i | 0.89 | 2.44 | 3.290 (4) | 160 |
N1D—H1D3···Cl1 | 0.89 | 2.70 | 3.544 (7) | 160 |
Symmetry codes: (i) −x+3/2, −y, z+1/2; (ii) −x+5/2, −y, z−1/2; (iii) −x+5/2, −y, z+1/2; (iv) −x+3/2, −y, z−1/2; (v) x+1, y, z; (vi) x−1, y, z. |
Experimental details
| (Cmce) | (pbca) | (P212121) |
Crystal data |
Chemical formula | C12H40Cd3Cl10N4 | C12H40Cd3Cl10N4 | C12H40Cd3Cl10N4 |
Mr | 932.18 | 932.18 | 932.18 |
Crystal system, space group | Orthorhombic, Cmce | Orthorhombic, Pbca | Orthorhombic, P212121 |
Temperature (K) | 375 | 320 | 275 |
a, b, c (Å) | 7.4634 (2), 22.0476 (10), 19.6139 (9) | 7.4298 (5), 22.0791 (5), 19.4442 (6) | 7.3918 (2), 22.0135 (7), 19.3938 (5) |
V (Å3) | 3227.5 (2) | 3189.7 (2) | 3155.75 (15) |
Z | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 2.79 | 2.83 | 2.86 |
Crystal size (mm) | 0.25 × 0.2 × 0.08 | 0.25 × 0.2 × 0.08 | 0.25 × 0.2 × 0.08 |
|
Data collection |
Diffractometer | KUMA KM4-CCD diffractometer | KUMA KM4-CCD diffractometer | KUMA KM4-CCD diffractometer |
Absorption correction | Multi-scan CrysAlis RED, Oxford Diffraction Ltd.,
Version 1.171.32.6 (release 21-05-2007 CrysAlis171 .NET)
(compiled May 21 2007,16:32:00)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm. | Multi-scan CrysAlis RED, Oxford Diffraction Ltd.,
Version 1.171.32.6 (release 21-05-2007 CrysAlis171 .NET)
(compiled May 21 2007,16:32:00)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm. | Multi-scan CrysAlis RED, Oxford Diffraction Ltd.,
Version 1.171.32.6 (release 21-05-2007 CrysAlis171 .NET)
(compiled May 21 2007,16:32:00)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm. |
Tmin, Tmax | 0.49, 0.79 | 0.49, 0.79 | 0.49, 0.79 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14304, 2333, 1659 | 26736, 3010, 2449 | 25040, 5945, 4686 |
Rint | 0.031 | 0.030 | 0.043 |
(sin θ/λ)max (Å−1) | 0.698 | 0.610 | 0.610 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.054, 0.90 | 0.024, 0.062, 1.01 | 0.028, 0.047, 0.83 |
No. of reflections | 2333 | 3010 | 5945 |
No. of parameters | 101 | 146 | 267 |
No. of restraints | 0 | 6 | 0 |
Δρmax, Δρmin (e Å−3) | 0.35, −0.41 | 0.36, −0.50 | 0.52, −0.37 |
Absolute structure | ? | ? | Flack H D (1983), Acta Cryst. A39, 876-881 |
Absolute structure parameter | ? | ? | 0.45 (4) |
Hydrogen-bond geometry (Å, º) for (Cmce) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2B—H2B2···Cl3i | 0.89 | 2.68 | 3.3363 (16) | 131.5 |
N2A—H2A2···Cl1 | 0.89 | 2.53 | 3.3052 (16) | 145.8 |
N2A—H2A3···Cl3ii | 0.89 | 2.54 | 3.4240 (13) | 174.6 |
Symmetry codes: (i) −x, y, z; (ii) x+1/2, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) for (pbca) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1B—H1C···Cl2 | 0.90 | 2.58 | 3.269 (6) | 134.2 |
N1C—H2A···Cl4 | 0.89 | 2.76 | 3.502 (4) | 141.1 |
N1AD—H1D···Cl1 | 0.871 (7) | 2.825 (8) | 3.586 (2) | 146.7 (15) |
N1AD—H1E···Cl3i | 0.877 (8) | 2.479 (9) | 3.352 (2) | 173.3 (15) |
N1AD—H1F···Cl1ii | 0.874 (8) | 2.453 (8) | 3.299 (3) | 163.3 (15) |
Symmetry codes: (i) x+1, y, z; (ii) x+1/2, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) for (P212121) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A1···Cl7 | 0.89 | 2.61 | 3.496 (5) | 176.5 |
N1A—H1A2···Cl1i | 0.89 | 2.51 | 3.274 (4) | 144.6 |
N1A—H1A2···Cl2i | 0.89 | 2.88 | 3.418 (5) | 120.7 |
N1A—H1A3···Cl6ii | 0.89 | 2.82 | 3.376 (5) | 122.1 |
N1B—H1B1···Cl2iii | 0.89 | 2.46 | 3.319 (6) | 163.0 |
N1B—H1B2···Cl7iv | 0.89 | 2.77 | 3.411 (6) | 129.8 |
N1B—H1B3···Cl8 | 0.89 | 2.76 | 3.616 (8) | 161.2 |
N1B—H1B3···Cl6 | 0.89 | 2.77 | 3.303 (6) | 119.5 |
N1C—H1C1···Cl3 | 0.89 | 2.55 | 3.363 (5) | 152.9 |
N1C—H1C2···Cl6ii | 0.89 | 2.77 | 3.581 (6) | 152.7 |
N1C—H1C3···Cl4ii | 0.89 | 2.66 | 3.421 (7) | 144.8 |
N1C—H1C3···Cl9v | 0.89 | 2.94 | 3.598 (5) | 132.6 |
N1D—H1D1···Cl3iv | 0.89 | 2.43 | 3.300 (5) | 167.3 |
N1D—H1D2···Cl10vi | 0.89 | 2.44 | 3.290 (4) | 160.0 |
N1D—H1D3···Cl1 | 0.89 | 2.70 | 3.544 (7) | 159.5 |
Symmetry codes: (i) −x+5/2, −y, z−1/2; (ii) x+1, y, z; (iii) −x+3/2, −y, z−1/2; (iv) x−1, y, z; (v) −x+5/2, −y, z+1/2; (vi) −x+3/2, −y, z+1/2. |