A crystal engineering approach is used to stabilize a radical anion in the crystalline state and to modulate the separation distance within π-stacks of anion radicals. Alkali metal salts of 2,3-dicyano-5,6-dichlorosemiquinone (C
8Cl
2N
2O
2, DDQ
) radical anions were prepared and their crystal structures determined: LiDDQ·2H
2O·(CH
3)
2CO, RbDDQ·2H
2O and CsDDQ·2H
2O. In these structures, stacked dimers of radical anions are formed within π-stacked columns. Within the stacked dimers, interplanar separation distances are significantly shorter than the sum of the van der Waals radii for two C atoms; the shortest is 2.812 Å for the Li salt and the longest is 2.925 Å for the Cs salt. Diamagnetic character, observed by electron paramagnetic resonance spectroscopy, indicates spin-coupling of the unpaired electrons within the radical anion dimer. The electron-rich cyano substituents on DDQ
influence the electron redistribution within the ring skeleton. The crystalline compounds are also characterized by IR spectroscopy, complemented by quantum-chemical calculations based on both isolated and periodic models.
Supporting information
CCDC references: 964468; 964469; 964470; 964471; 964472
For all compounds, data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008). Molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) & Mercury (Macrae et al., 2006) for LiDDQx2H2OxMe2O, RbDDQx2H2O_293K, RbDDQx2H2O_120K, CsDDQx2H2O_293K. Software used to prepare material for publication: WinGX (Farrugia, 2012) & PLATON (Spek, 2003) for LiDDQx2H2OxMe2O, RbDDQx2H2O_293K, RbDDQx2H2O_120K, CsDDQx2H2O_293K; SHELXL97 for CsDDQx2H2O_120K.
Crystal data top
C11H10Cl2LiN2O5 | Z = 2 |
Mr = 328.06 | F(000) = 334 |
Triclinic, P1 | Dx = 1.461 Mg m−3 |
Hall symbol: -P 1 | Cu Kα radiation, λ = 1.5418 Å |
a = 6.667 (5) Å | Cell parameters from 2953 reflections |
b = 10.495 (5) Å | θ = 4.1–76.7° |
c = 11.977 (5) Å | µ = 4.11 mm−1 |
α = 110.773 (5)° | T = 120 K |
β = 99.693 (5)° | Prism, dark green |
γ = 100.335 (5)° | 0.18 × 0.07 × 0.06 mm |
V = 745.9 (7) Å3 | |
Data collection top
Oxford Diffraction Xcalibur CCD, Ruby, Nova diffractometer | 2981 independent reflections |
Radiation source: fine-focus sealed tube | 2204 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.071 |
ω scans | θmax = 76.9°, θmin = 4.1° |
Absorption correction: multi-scan CrysAlis PRO (Agilent, 2012) | h = −6→8 |
Tmin = 0.621, Tmax = 1.000 | k = −10→13 |
5368 measured reflections | l = −15→14 |
Refinement top
Refinement on F2 | 91 restraints |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.1 | w = 1/[σ2(Fo2) + (0.1271P)2 + 4.0961P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.310 | (Δ/σ)max = 0.001 |
S = 1.08 | Δρmax = 0.63 e Å−3 |
2981 reflections | Δρmin = −0.88 e Å−3 |
257 parameters | |
Crystal data top
C11H10Cl2LiN2O5 | γ = 100.335 (5)° |
Mr = 328.06 | V = 745.9 (7) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.667 (5) Å | Cu Kα radiation |
b = 10.495 (5) Å | µ = 4.11 mm−1 |
c = 11.977 (5) Å | T = 120 K |
α = 110.773 (5)° | 0.18 × 0.07 × 0.06 mm |
β = 99.693 (5)° | |
Data collection top
Oxford Diffraction Xcalibur CCD, Ruby, Nova diffractometer | 2981 independent reflections |
Absorption correction: multi-scan CrysAlis PRO (Agilent, 2012) | 2204 reflections with I > 2σ(I) |
Tmin = 0.621, Tmax = 1.000 | Rint = 0.071 |
5368 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.1 | 91 restraints |
wR(F2) = 0.310 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.63 e Å−3 |
2981 reflections | Δρmin = −0.88 e Å−3 |
257 parameters | |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Li1 | 0.3160 (18) | 0.5055 (10) | 0.4330 (10) | 0.036 (2) | |
O1 | 0.2407 (8) | 0.6714 (5) | 0.4572 (6) | 0.0506 (14) | |
O2 | 0.1574 (7) | 1.1817 (4) | 0.4743 (4) | 0.0354 (11) | |
C1 | 0.2200 (10) | 0.7887 (6) | 0.4601 (7) | 0.0383 (16) | |
C2 | 0.3097 (9) | 0.9166 (7) | 0.5719 (6) | 0.0358 (15) | |
C3 | 0.2919 (9) | 1.0460 (6) | 0.5758 (6) | 0.0337 (14) | |
C4 | 0.1828 (9) | 1.0649 (6) | 0.4698 (6) | 0.0311 (13) | |
C5 | 0.1042 (10) | 0.9372 (6) | 0.3558 (6) | 0.0354 (14) | |
C6 | 0.1266 (9) | 0.8076 (6) | 0.3521 (6) | 0.0360 (14) | |
Cl1B | 0.4113 (9) | 1.2027 (4) | 0.7133 (3) | 0.0369 (9) | 0.658 (6) |
Cl2B | 0.4507 (9) | 0.9014 (7) | 0.7054 (4) | 0.0453 (10) | 0.658 (6) |
N2B | −0.0562 (19) | 0.9755 (12) | 0.1665 (11) | 0.046 (2) | 0.658 (6) |
N1B | −0.006 (2) | 0.5903 (15) | 0.1503 (13) | 0.061 (3) | 0.658 (6) |
C7B | 0.039 (5) | 0.678 (2) | 0.2418 (17) | 0.047 (4) | 0.658 (6) |
C8B | 0.009 (4) | 0.959 (3) | 0.2501 (16) | 0.044 (3) | 0.658 (6) |
Cl1A | 0.0042 (15) | 0.9544 (10) | 0.2118 (7) | 0.0422 (19) | 0.342 (6) |
Cl2A | 0.0395 (18) | 0.6581 (11) | 0.2036 (8) | 0.046 (2) | 0.342 (6) |
C7A | 0.419 (9) | 0.890 (7) | 0.674 (4) | 0.048 (3) | 0.342 (6) |
C8A | 0.395 (8) | 1.174 (3) | 0.682 (3) | 0.036 (3) | 0.342 (6) |
N1A | 0.510 (3) | 0.879 (2) | 0.7566 (16) | 0.049 (2) | 0.342 (6) |
N2A | 0.444 (3) | 1.278 (2) | 0.7637 (18) | 0.043 (3) | 0.342 (6) |
O4 | 0.1132 (8) | 0.3356 (5) | 0.3135 (5) | 0.0438 (12) | |
H4A | −0.012 (6) | 0.365 (6) | 0.302 (6) | 0.03* | |
H4B | 0.072 (9) | 0.252 (4) | 0.328 (6) | 0.03* | |
O5 | 0.3900 (7) | 0.4638 (4) | 0.5826 (4) | 0.0327 (10) | |
H5A | 0.325 (10) | 0.370 (3) | 0.569 (5) | 0.03* | |
H5B | 0.395 (10) | 0.519 (5) | 0.665 (3) | 0.03* | |
O3 | 0.7187 (8) | 0.3656 (5) | 0.2188 (4) | 0.0405 (11) | |
C9 | 0.6198 (13) | 0.3127 (7) | 0.1136 (7) | 0.0449 (17) | |
C10 | 0.6981 (19) | 0.2124 (12) | 0.0172 (8) | 0.082 (3) | |
H10A | 0.8297 | 0.2021 | 0.0551 | 0.123* | |
H10B | 0.7181 | 0.2487 | −0.0440 | 0.123* | |
H10C | 0.5967 | 0.1222 | −0.0200 | 0.123* | |
C11 | 0.4134 (19) | 0.3420 (13) | 0.0739 (10) | 0.089 (4) | |
H11A | 0.3818 | 0.4067 | 0.1443 | 0.133* | |
H11B | 0.3041 | 0.2554 | 0.0381 | 0.133* | |
H11C | 0.4224 | 0.3826 | 0.014 | 0.133* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Li1 | 0.049 (6) | 0.024 (5) | 0.046 (6) | 0.017 (4) | 0.021 (5) | 0.021 (4) |
O1 | 0.055 (3) | 0.035 (2) | 0.096 (4) | 0.030 (2) | 0.045 (3) | 0.046 (3) |
O2 | 0.042 (2) | 0.0254 (19) | 0.062 (3) | 0.0181 (18) | 0.030 (2) | 0.031 (2) |
C1 | 0.036 (3) | 0.031 (3) | 0.080 (5) | 0.026 (3) | 0.040 (3) | 0.038 (3) |
C2 | 0.034 (3) | 0.041 (3) | 0.065 (4) | 0.025 (3) | 0.032 (3) | 0.042 (3) |
C3 | 0.034 (3) | 0.027 (3) | 0.059 (4) | 0.015 (2) | 0.029 (3) | 0.028 (3) |
C4 | 0.030 (3) | 0.023 (3) | 0.059 (4) | 0.016 (2) | 0.028 (3) | 0.026 (3) |
C5 | 0.038 (3) | 0.027 (3) | 0.064 (4) | 0.019 (2) | 0.031 (3) | 0.030 (3) |
C6 | 0.031 (3) | 0.024 (3) | 0.065 (4) | 0.013 (2) | 0.025 (3) | 0.022 (3) |
Cl1B | 0.0443 (17) | 0.035 (2) | 0.051 (3) | 0.0192 (18) | 0.029 (2) | 0.0279 (16) |
Cl2B | 0.048 (3) | 0.0472 (17) | 0.072 (3) | 0.0258 (18) | 0.034 (2) | 0.044 (2) |
N2B | 0.047 (4) | 0.037 (3) | 0.066 (6) | 0.015 (3) | 0.035 (4) | 0.023 (4) |
N1B | 0.064 (6) | 0.054 (6) | 0.076 (8) | 0.018 (6) | 0.036 (6) | 0.027 (5) |
C8B | 0.045 (4) | 0.033 (3) | 0.068 (7) | 0.011 (3) | 0.043 (5) | 0.023 (5) |
C7B | 0.051 (5) | 0.053 (7) | 0.071 (10) | 0.024 (5) | 0.048 (7) | 0.044 (6) |
Cl1A | 0.048 (3) | 0.034 (2) | 0.062 (6) | 0.0202 (18) | 0.035 (4) | 0.025 (4) |
Cl2A | 0.047 (3) | 0.046 (4) | 0.070 (7) | 0.027 (3) | 0.037 (5) | 0.033 (4) |
C8A | 0.041 (4) | 0.035 (5) | 0.055 (5) | 0.023 (4) | 0.032 (5) | 0.029 (4) |
C7A | 0.044 (5) | 0.049 (4) | 0.076 (5) | 0.019 (4) | 0.034 (5) | 0.043 (5) |
N2A | 0.047 (4) | 0.038 (5) | 0.057 (5) | 0.019 (4) | 0.027 (4) | 0.024 (4) |
N1A | 0.045 (5) | 0.051 (4) | 0.076 (5) | 0.020 (4) | 0.027 (4) | 0.044 (4) |
O3 | 0.054 (3) | 0.039 (2) | 0.041 (3) | 0.022 (2) | 0.024 (2) | 0.020 (2) |
C9 | 0.071 (5) | 0.039 (3) | 0.038 (4) | 0.024 (3) | 0.025 (4) | 0.019 (3) |
C10 | 0.107 (8) | 0.102 (8) | 0.034 (4) | 0.063 (7) | 0.013 (5) | 0.009 (5) |
C11 | 0.088 (8) | 0.110 (9) | 0.062 (6) | 0.062 (7) | 0.006 (6) | 0.016 (6) |
O4 | 0.052 (3) | 0.030 (2) | 0.061 (3) | 0.016 (2) | 0.018 (2) | 0.026 (2) |
O5 | 0.044 (2) | 0.0241 (19) | 0.042 (2) | 0.0146 (18) | 0.022 (2) | 0.0189 (18) |
Geometric parameters (Å, º) top
Li1—O1 | 1.837 (10) | C6—C7B | 1.457 (16) |
Li1—O4 | 1.931 (12) | C6—Cl2A | 1.819 (10) |
Li1—O5i | 1.980 (12) | N2B—C8B | 1.108 (15) |
Li1—O5 | 1.994 (11) | N1B—C7B | 1.100 (16) |
Li1—Li1i | 2.74 (2) | C8A—N2A | 1.125 (17) |
Li1—H4A | 2.34 (5) | C7A—N1A | 1.128 (16) |
O1—C1 | 1.251 (7) | O3—C9 | 1.194 (9) |
O2—C4 | 1.252 (6) | C9—C11 | 1.499 (12) |
C1—C6 | 1.435 (10) | C9—C10 | 1.500 (10) |
C1—C2 | 1.456 (10) | C10—H10A | 0.96 |
C2—C3 | 1.369 (8) | C10—H10B | 0.96 |
C2—C7A | 1.453 (16) | C10—H10C | 0.96 |
C2—Cl2B | 1.788 (7) | C11—H11A | 0.96 |
C3—C8A | 1.435 (18) | C11—H11B | 0.96 |
C3—C4 | 1.449 (9) | C11—H11C | 0.96 |
C3—Cl1B | 1.793 (7) | O4—H4A | 0.94 (2) |
C4—C5 | 1.464 (9) | O4—H4B | 0.95 (2) |
C5—C6 | 1.381 (7) | O5—Li1i | 1.980 (12) |
C5—C8B | 1.429 (15) | O5—H5A | 0.95 (2) |
C5—Cl1A | 1.824 (10) | O5—H5B | 0.95 (2) |
| | | |
O1—Li1—O4 | 116.2 (6) | C6—C5—Cl1A | 119.1 (6) |
O1—Li1—O5i | 107.4 (5) | C4—C5—Cl1A | 118.7 (5) |
O4—Li1—O5i | 117.7 (5) | C5—C6—C1 | 122.2 (6) |
O1—Li1—O5 | 116.2 (6) | C5—C6—C7B | 122.8 (14) |
O4—Li1—O5 | 104.5 (5) | C1—C6—C7B | 114.7 (13) |
O5i—Li1—O5 | 92.8 (5) | C5—C6—Cl2A | 118.1 (7) |
O1—Li1—Li1i | 122.5 (7) | C1—C6—Cl2A | 119.6 (6) |
O4—Li1—Li1i | 121.2 (6) | N2B—C8B—C5 | 177 (2) |
O5i—Li1—Li1i | 46.6 (4) | N1B—C7B—C6 | 168 (2) |
O5—Li1—Li1i | 46.2 (3) | N2A—C8A—C3 | 169 (5) |
O1—Li1—H4A | 93.8 (11) | N1A—C7A—C2 | 176 (6) |
O4—Li1—H4A | 23.1 (10) | O3—C9—C11 | 121.4 (7) |
O5i—Li1—H4A | 135.2 (15) | O3—C9—C10 | 120.4 (8) |
O5—Li1—H4A | 112.8 (15) | C11—C9—C10 | 118.1 (8) |
Li1i—Li1—H4A | 142.6 (11) | C9—C10—H10A | 109.5 |
C1—O1—Li1 | 166.9 (5) | C9—C10—H10B | 109.5 |
O1—C1—C6 | 122.4 (7) | H10A—C10—H10B | 109.5 |
O1—C1—C2 | 121.3 (7) | C9—C10—H10C | 109.5 |
C6—C1—C2 | 116.0 (5) | H10A—C10—H10C | 109.5 |
C3—C2—C7A | 125 (3) | H10B—C10—H10C | 109.5 |
C3—C2—C1 | 121.9 (6) | C9—C11—H11A | 109.5 |
C7A—C2—C1 | 113 (3) | C9—C11—H11B | 109.5 |
C3—C2—Cl2B | 120.1 (6) | H11A—C11—H11B | 109.5 |
C1—C2—Cl2B | 118.0 (4) | C9—C11—H11C | 109.5 |
C2—C3—C8A | 122 (2) | H11A—C11—H11C | 109.5 |
C2—C3—C4 | 122.5 (6) | H11B—C11—H11C | 109.5 |
C8A—C3—C4 | 115 (2) | Li1—O4—H4A | 103 (4) |
C2—C3—Cl1B | 120.9 (6) | Li1—O4—H4B | 124 (4) |
C4—C3—Cl1B | 116.6 (4) | H4A—O4—H4B | 104 (4) |
O2—C4—C3 | 122.8 (6) | Li1i—O5—Li1 | 87.2 (5) |
O2—C4—C5 | 121.8 (6) | Li1i—O5—H5A | 114 (4) |
C3—C4—C5 | 115.3 (5) | Li1—O5—H5A | 112 (4) |
C6—C5—C8B | 123.4 (12) | Li1i—O5—H5B | 107 (4) |
C6—C5—C4 | 121.7 (6) | Li1—O5—H5B | 129 (4) |
C8B—C5—C4 | 114.8 (11) | H5A—O5—H5B | 106 (4) |
| | | |
O4—Li1—O1—C1 | −107 (3) | C8A—C3—C4—C5 | 171 (2) |
O5i—Li1—O1—C1 | 27 (3) | Cl1B—C3—C4—C5 | 174.4 (4) |
O5—Li1—O1—C1 | 130 (3) | O2—C4—C5—C6 | −177.9 (5) |
Li1i—Li1—O1—C1 | 77 (3) | C3—C4—C5—C6 | 2.4 (8) |
Li1—O1—C1—C6 | 69 (3) | O2—C4—C5—C8B | 3.5 (12) |
Li1—O1—C1—C2 | −104 (3) | C3—C4—C5—C8B | −176.2 (10) |
O1—C1—C2—C3 | 178.7 (5) | O2—C4—C5—Cl1A | 9.8 (8) |
C6—C1—C2—C3 | 4.7 (8) | C3—C4—C5—Cl1A | −169.9 (5) |
O1—C1—C2—C7A | 0 (3) | C8B—C5—C6—C1 | −179.0 (11) |
C6—C1—C2—C7A | −174 (3) | C4—C5—C6—C1 | 2.6 (9) |
O1—C1—C2—Cl2B | −0.1 (8) | Cl1A—C5—C6—C1 | 174.8 (5) |
C6—C1—C2—Cl2B | −174.0 (5) | C8B—C5—C6—C7B | −5.3 (18) |
C7A—C2—C3—C8A | 4 (4) | C4—C5—C6—C7B | 176.2 (13) |
C1—C2—C3—C8A | −175 (2) | C4—C5—C6—Cl2A | −175.9 (6) |
Cl2B—C2—C3—C8A | 4 (3) | Cl1A—C5—C6—Cl2A | −3.6 (8) |
C7A—C2—C3—C4 | 179 (3) | O1—C1—C6—C5 | −179.9 (6) |
C1—C2—C3—C4 | 0.1 (8) | C2—C1—C6—C5 | −6.0 (8) |
Cl2B—C2—C3—C4 | 178.9 (5) | O1—C1—C6—C7B | 5.9 (14) |
C1—C2—C3—Cl1B | −177.9 (4) | C2—C1—C6—C7B | 179.8 (12) |
Cl2B—C2—C3—Cl1B | 0.8 (7) | O1—C1—C6—Cl2A | −1.5 (9) |
C2—C3—C4—O2 | 176.6 (5) | C2—C1—C6—Cl2A | 172.4 (5) |
C8A—C3—C4—O2 | −8 (2) | O1—Li1—O5—Li1i | −111.0 (8) |
Cl1B—C3—C4—O2 | −5.3 (7) | O4—Li1—O5—Li1i | 119.6 (6) |
C2—C3—C4—C5 | −3.7 (8) | | |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Crystal data top
C8H4Cl2N2O4Rb | F(000) = 676 |
Mr = 348.50 | Dx = 2.034 Mg m−3 |
Orthorhombic, P21212 | Cu Kα radiation, λ = 1.5418 Å |
Hall symbol: P 2 2ab | Cell parameters from 2206 reflections |
a = 6.5088 (2) Å | θ = 4.6–75.7° |
b = 18.1788 (6) Å | µ = 10.39 mm−1 |
c = 9.6194 (2) Å | T = 293 K |
V = 1138.19 (6) Å3 | Prism, dark red |
Z = 4 | 0.36 × 0.04 × 0.02 mm |
Data collection top
Oxford Diffraction Xcalibur CCD diffractometer | 2060 independent reflections |
Radiation source: fine-focus sealed tube | 1948 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
ω scans | θmax = 75.9°, θmin = 4.6° |
Absorption correction: multi-scan CrysAlis PRO (Agilent, 2012) | h = −8→5 |
Tmin = 0.182, Tmax = 1.000 | k = −18→22 |
3524 measured reflections | l = −11→12 |
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)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.119 | w = 1/[σ2(Fo2) + (0.0671P)2 + 0.9965P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
2060 reflections | Δρmax = 0.61 e Å−3 |
155 parameters | Δρmin = −0.82 e Å−3 |
0 restraints | Absolute structure: Refined as an inversion twin (TWIN + BASF) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.46 (4) |
Crystal data top
C8H4Cl2N2O4Rb | V = 1138.19 (6) Å3 |
Mr = 348.50 | Z = 4 |
Orthorhombic, P21212 | Cu Kα radiation |
a = 6.5088 (2) Å | µ = 10.39 mm−1 |
b = 18.1788 (6) Å | T = 293 K |
c = 9.6194 (2) Å | 0.36 × 0.04 × 0.02 mm |
Data collection top
Oxford Diffraction Xcalibur CCD diffractometer | 2060 independent reflections |
Absorption correction: multi-scan CrysAlis PRO (Agilent, 2012) | 1948 reflections with I > 2σ(I) |
Tmin = 0.182, Tmax = 1.000 | Rint = 0.031 |
3524 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.119 | Δρmax = 0.61 e Å−3 |
S = 1.03 | Δρmin = −0.82 e Å−3 |
2060 reflections | Absolute structure: Refined as an inversion twin (TWIN + BASF) |
155 parameters | Absolute structure parameter: 0.46 (4) |
0 restraints | |
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 | |
Rb1 | 0.39937 (8) | 0.64811 (3) | 0.51784 (6) | 0.04939 (19) | |
Cl1 | 0.1652 (3) | 0.70121 (8) | −0.13979 (17) | 0.0498 (4) | |
Cl2 | 0.1622 (3) | 0.69914 (8) | 0.18398 (17) | 0.0491 (4) | |
O1 | 0.2032 (7) | 0.5514 (2) | 0.3006 (4) | 0.0435 (9) | |
O2 | 0.2005 (7) | 0.5540 (2) | −0.2614 (4) | 0.0421 (9) | |
O3 | 0.7605 (9) | 0.5530 (3) | 0.5164 (5) | 0.0641 (13) | |
H3A | 0.8039 | 0.5200 | 0.5872 | 0.096* | |
H3B | 0.7979 | 0.5299 | 0.4315 | 0.096* | |
O4 | 0.4394 (9) | 0.8067 (3) | 0.4727 (8) | 0.0864 (18) | |
H4A | 0.3784 | 0.8541 | 0.4772 | 0.130* | |
H4B | 0.4789 | 0.8015 | 0.3782 | 0.130* | |
N1 | 0.3281 (9) | 0.3700 (3) | 0.2316 (5) | 0.0481 (13) | |
N2 | 0.3264 (10) | 0.3730 (3) | −0.2019 (6) | 0.0492 (13) | |
C1 | 0.2031 (8) | 0.5511 (3) | 0.1718 (5) | 0.0317 (11) | |
C2 | 0.2332 (8) | 0.4851 (3) | 0.0894 (5) | 0.0300 (10) | |
C3 | 0.2338 (7) | 0.4864 (3) | −0.0541 (5) | 0.0298 (10) | |
C4 | 0.2017 (9) | 0.5533 (3) | −0.1344 (6) | 0.0349 (11) | |
C5 | 0.1805 (8) | 0.6207 (3) | −0.0492 (6) | 0.0358 (11) | |
C6 | 0.1815 (9) | 0.6198 (3) | 0.0900 (6) | 0.0359 (11) | |
C7 | 0.2843 (9) | 0.4192 (3) | 0.1671 (5) | 0.0342 (11) | |
C8 | 0.2821 (9) | 0.4215 (3) | −0.1343 (5) | 0.0355 (12) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Rb1 | 0.0537 (3) | 0.0511 (3) | 0.0433 (3) | 0.0016 (2) | −0.0018 (3) | 0.0026 (2) |
Cl1 | 0.0606 (9) | 0.0349 (7) | 0.0537 (8) | −0.0018 (7) | −0.0011 (7) | 0.0115 (6) |
Cl2 | 0.0578 (9) | 0.0355 (7) | 0.0540 (8) | −0.0002 (7) | −0.0040 (7) | −0.0105 (6) |
O1 | 0.055 (2) | 0.044 (2) | 0.0321 (18) | −0.004 (2) | −0.0067 (18) | −0.0050 (17) |
O2 | 0.055 (2) | 0.046 (2) | 0.0254 (17) | −0.007 (2) | 0.0021 (17) | 0.0077 (16) |
O3 | 0.108 (4) | 0.051 (2) | 0.0330 (19) | 0.016 (2) | 0.000 (3) | −0.004 (2) |
O4 | 0.085 (3) | 0.056 (3) | 0.118 (5) | 0.007 (3) | −0.002 (4) | 0.006 (4) |
N1 | 0.057 (3) | 0.043 (3) | 0.044 (3) | 0.009 (3) | −0.003 (2) | 0.001 (2) |
N2 | 0.063 (3) | 0.043 (3) | 0.041 (3) | 0.004 (3) | 0.007 (2) | −0.005 (2) |
C1 | 0.032 (3) | 0.033 (3) | 0.031 (2) | −0.001 (2) | 0.000 (2) | −0.002 (2) |
C2 | 0.031 (2) | 0.032 (3) | 0.027 (2) | 0.000 (2) | 0.0003 (17) | 0.0000 (18) |
C3 | 0.027 (2) | 0.026 (3) | 0.035 (2) | −0.0015 (18) | −0.0001 (17) | −0.0014 (18) |
C4 | 0.031 (3) | 0.035 (3) | 0.039 (3) | −0.004 (2) | 0.002 (2) | 0.002 (2) |
C5 | 0.034 (2) | 0.035 (3) | 0.038 (3) | −0.004 (2) | 0.001 (2) | 0.000 (2) |
C6 | 0.033 (2) | 0.030 (2) | 0.044 (3) | −0.001 (2) | −0.003 (2) | 0.000 (2) |
C7 | 0.038 (3) | 0.032 (3) | 0.032 (2) | 0.002 (2) | 0.000 (2) | −0.004 (2) |
C8 | 0.034 (3) | 0.042 (3) | 0.030 (2) | 0.000 (3) | 0.0006 (19) | 0.002 (2) |
Geometric parameters (Å, º) top
Rb1—O3 | 2.919 (5) | O3—H3A | 0.9500 |
Rb1—O4 | 2.926 (6) | O3—H3B | 0.9500 |
Rb1—O1 | 3.015 (4) | O4—Rb1v | 3.106 (6) |
Rb1—O2i | 3.018 (4) | O4—Rb1ii | 3.611 (6) |
Rb1—O4ii | 3.106 (6) | O4—H4A | 0.9500 |
Rb1—N2iii | 3.256 (5) | O4—H4B | 0.9500 |
Rb1—N1iv | 3.292 (5) | N1—C7 | 1.125 (8) |
Rb1—O4v | 3.611 (6) | N1—Rb1iv | 3.292 (5) |
Rb1—Cl2 | 3.6818 (17) | N2—C8 | 1.133 (8) |
Rb1—Cl1i | 3.7551 (18) | N2—Rb1vii | 3.256 (5) |
Rb1—Rb1ii | 4.9427 (9) | C1—C2 | 1.452 (7) |
Rb1—Rb1v | 4.9427 (9) | C1—C6 | 1.482 (7) |
Rb1—H4B | 3.1382 | C2—C3 | 1.381 (6) |
Cl1—C5 | 1.706 (6) | C2—C7 | 1.450 (7) |
Cl1—Rb1vi | 3.7550 (18) | C3—C8 | 1.444 (7) |
Cl2—C6 | 1.707 (6) | C3—C4 | 1.456 (7) |
O1—C1 | 1.239 (7) | C4—C5 | 1.481 (8) |
O2—C4 | 1.221 (7) | C5—C6 | 1.340 (8) |
O2—Rb1vi | 3.018 (4) | | |
| | | |
O3—Rb1—O4 | 120.76 (16) | O4ii—Rb1—Rb1v | 116.00 (11) |
O3—Rb1—O1 | 89.55 (13) | N2iii—Rb1—Rb1v | 77.58 (10) |
O4—Rb1—O1 | 120.63 (17) | N1iv—Rb1—Rb1v | 70.24 (10) |
O3—Rb1—O2i | 90.74 (14) | O4v—Rb1—Rb1v | 35.92 (9) |
O4—Rb1—O2i | 134.47 (17) | Cl2—Rb1—Rb1v | 91.53 (3) |
O1—Rb1—O2i | 88.60 (11) | Cl1i—Rb1—Rb1v | 97.79 (3) |
O3—Rb1—O4ii | 158.96 (15) | Rb1ii—Rb1—Rb1v | 82.359 (18) |
O4—Rb1—O4ii | 80.18 (13) | O3—Rb1—H4B | 113.1 |
O1—Rb1—O4ii | 76.49 (16) | O4—Rb1—H4B | 17.6 |
O2i—Rb1—O4ii | 73.51 (15) | O1—Rb1—H4B | 106.9 |
O3—Rb1—N2iii | 59.50 (14) | O2i—Rb1—H4B | 151.1 |
O4—Rb1—N2iii | 100.96 (17) | O4ii—Rb1—H4B | 86.4 |
O1—Rb1—N2iii | 137.50 (12) | N2iii—Rb1—H4B | 111.6 |
O2i—Rb1—N2iii | 65.52 (14) | N1iv—Rb1—H4B | 69.0 |
O4ii—Rb1—N2iii | 122.37 (19) | O4v—Rb1—H4B | 69.4 |
O3—Rb1—N1iv | 60.19 (13) | Cl2—Rb1—H4B | 58.1 |
O4—Rb1—N1iv | 85.78 (18) | Cl1i—Rb1—H4B | 102.4 |
O1—Rb1—N1iv | 65.81 (14) | Rb1ii—Rb1—H4B | 54.1 |
O2i—Rb1—N1iv | 139.73 (12) | Rb1v—Rb1—H4B | 36.5 |
O4ii—Rb1—N1iv | 124.77 (18) | C5—Cl1—Rb1vi | 101.7 (2) |
N2iii—Rb1—N1iv | 112.67 (13) | C6—Cl2—Rb1 | 102.6 (2) |
O3—Rb1—O4v | 49.54 (14) | C1—O1—Rb1 | 134.1 (4) |
O4—Rb1—O4v | 72.11 (14) | C4—O2—Rb1vi | 135.0 (4) |
O1—Rb1—O4v | 124.22 (15) | Rb1—O3—H3A | 127.6 |
O2i—Rb1—O4v | 121.92 (14) | Rb1—O3—H3B | 118.1 |
O4ii—Rb1—O4v | 151.32 (19) | H3A—O3—H3B | 105.2 |
N2iii—Rb1—O4v | 58.16 (16) | Rb1—O4—Rb1v | 110.00 (18) |
N1iv—Rb1—O4v | 61.26 (16) | Rb1—O4—Rb1ii | 97.70 (16) |
O3—Rb1—Cl2 | 118.87 (9) | Rb1v—O4—Rb1ii | 151.32 (19) |
O4—Rb1—Cl2 | 70.11 (15) | Rb1—O4—H4A | 148.2 |
O1—Rb1—Cl2 | 50.57 (9) | Rb1v—O4—H4A | 99.3 |
O2i—Rb1—Cl2 | 125.22 (9) | Rb1ii—O4—H4A | 52.1 |
O4ii—Rb1—Cl2 | 63.56 (15) | Rb1—O4—H4B | 93.9 |
N2iii—Rb1—Cl2 | 169.03 (11) | Rb1v—O4—H4B | 78.1 |
N1iv—Rb1—Cl2 | 61.41 (10) | Rb1ii—O4—H4B | 108.1 |
O4v—Rb1—Cl2 | 111.87 (12) | H4A—O4—H4B | 104.3 |
O3—Rb1—Cl1i | 118.90 (9) | C7—N1—Rb1iv | 132.6 (4) |
O4—Rb1—Cl1i | 85.01 (15) | C8—N2—Rb1vii | 134.9 (5) |
O1—Rb1—Cl1i | 125.87 (9) | O1—C1—C2 | 123.3 (5) |
O2i—Rb1—Cl1i | 49.79 (9) | O1—C1—C6 | 121.9 (5) |
O4ii—Rb1—Cl1i | 61.00 (15) | C2—C1—C6 | 114.8 (4) |
N2iii—Rb1—Cl1i | 61.74 (12) | C3—C2—C7 | 121.9 (5) |
N1iv—Rb1—Cl1i | 167.95 (11) | C3—C2—C1 | 122.1 (5) |
O4v—Rb1—Cl1i | 108.33 (13) | C7—C2—C1 | 115.7 (4) |
Cl2—Rb1—Cl1i | 122.01 (3) | C2—C3—C8 | 121.4 (5) |
O3—Rb1—Rb1ii | 166.95 (11) | C2—C3—C4 | 123.0 (5) |
O4—Rb1—Rb1ii | 46.38 (12) | C8—C3—C4 | 115.4 (5) |
O1—Rb1—Rb1ii | 96.33 (9) | O2—C4—C3 | 122.8 (6) |
O2i—Rb1—Rb1ii | 101.02 (9) | O2—C4—C5 | 122.9 (6) |
O4ii—Rb1—Rb1ii | 33.80 (10) | C3—C4—C5 | 114.2 (5) |
N2iii—Rb1—Rb1ii | 120.45 (10) | C6—C5—C4 | 122.9 (6) |
N1iv—Rb1—Rb1ii | 111.82 (10) | C6—C5—Cl1 | 121.4 (5) |
O4v—Rb1—Rb1ii | 118.17 (9) | C4—C5—Cl1 | 115.6 (4) |
Cl2—Rb1—Rb1ii | 58.31 (3) | C5—C6—C1 | 122.8 (5) |
Cl1i—Rb1—Rb1ii | 66.49 (3) | C5—C6—Cl2 | 121.2 (5) |
O3—Rb1—Rb1v | 85.04 (11) | C1—C6—Cl2 | 116.0 (4) |
O4—Rb1—Rb1v | 36.19 (12) | N1—C7—C2 | 176.9 (6) |
O1—Rb1—Rb1v | 131.90 (9) | N2—C8—C3 | 176.2 (6) |
O2i—Rb1—Rb1v | 139.09 (8) | | |
| | | |
O3—Rb1—Cl2—C6 | 38.6 (2) | N1iv—Rb1—O4—Rb1ii | 125.80 (19) |
O4—Rb1—Cl2—C6 | 153.5 (3) | O4v—Rb1—O4—Rb1ii | −173.1 (3) |
O1—Rb1—Cl2—C6 | −23.7 (2) | Cl2—Rb1—O4—Rb1ii | 64.72 (13) |
O2i—Rb1—Cl2—C6 | −75.4 (2) | Cl1i—Rb1—O4—Rb1ii | −61.97 (14) |
O4ii—Rb1—Cl2—C6 | −117.8 (2) | Rb1v—Rb1—O4—Rb1ii | −172.4 (4) |
N2iii—Rb1—Cl2—C6 | 117.0 (6) | Rb1—O1—C1—C2 | 134.6 (5) |
N1iv—Rb1—Cl2—C6 | 57.3 (2) | Rb1—O1—C1—C6 | −42.4 (8) |
O4v—Rb1—Cl2—C6 | 93.4 (2) | O1—C1—C2—C3 | −179.5 (6) |
Cl1i—Rb1—Cl2—C6 | −136.1 (2) | C6—C1—C2—C3 | −2.3 (8) |
Rb1ii—Rb1—Cl2—C6 | −156.2 (2) | O1—C1—C2—C7 | −5.9 (8) |
Rb1v—Rb1—Cl2—C6 | 123.8 (2) | C6—C1—C2—C7 | 171.4 (5) |
O3—Rb1—O1—C1 | −89.9 (6) | C7—C2—C3—C8 | 1.2 (9) |
O4—Rb1—O1—C1 | 36.2 (6) | C1—C2—C3—C8 | 174.4 (4) |
O2i—Rb1—O1—C1 | 179.3 (6) | C7—C2—C3—C4 | −174.2 (4) |
O4ii—Rb1—O1—C1 | 105.9 (6) | C1—C2—C3—C4 | −1.0 (9) |
N2iii—Rb1—O1—C1 | −130.5 (5) | Rb1vi—O2—C4—C3 | −132.6 (5) |
N1iv—Rb1—O1—C1 | −32.7 (5) | Rb1vi—O2—C4—C5 | 44.4 (9) |
O4v—Rb1—O1—C1 | −52.1 (6) | C2—C3—C4—O2 | −179.3 (6) |
Cl2—Rb1—O1—C1 | 39.2 (5) | C8—C3—C4—O2 | 5.1 (8) |
Cl1i—Rb1—O1—C1 | 143.9 (5) | C2—C3—C4—C5 | 3.5 (8) |
Rb1ii—Rb1—O1—C1 | 78.4 (5) | C8—C3—C4—C5 | −172.1 (4) |
Rb1v—Rb1—O1—C1 | −7.0 (6) | O2—C4—C5—C6 | 179.9 (6) |
O3—Rb1—O4—Rb1v | −10.4 (3) | C3—C4—C5—C6 | −2.9 (9) |
O1—Rb1—O4—Rb1v | −120.3 (2) | O2—C4—C5—Cl1 | −2.7 (8) |
O2i—Rb1—O4—Rb1v | 116.9 (2) | C3—C4—C5—Cl1 | 174.5 (4) |
O4ii—Rb1—O4—Rb1v | 171.9 (4) | Rb1vi—Cl1—C5—C6 | 156.4 (5) |
N2iii—Rb1—O4—Rb1v | 50.5 (3) | Rb1vi—Cl1—C5—C4 | −21.0 (4) |
N1iv—Rb1—O4—Rb1v | −61.8 (2) | C4—C5—C6—C1 | −0.2 (11) |
O4v—Rb1—O4—Rb1v | −0.6 (2) | Cl1—C5—C6—C1 | −177.5 (4) |
Cl2—Rb1—O4—Rb1v | −122.8 (2) | C4—C5—C6—Cl2 | 178.6 (4) |
Cl1i—Rb1—O4—Rb1v | 110.5 (2) | Cl1—C5—C6—Cl2 | 1.3 (9) |
Rb1ii—Rb1—O4—Rb1v | 172.4 (4) | O1—C1—C6—C5 | −179.9 (6) |
O3—Rb1—O4—Rb1ii | 177.20 (12) | C2—C1—C6—C5 | 2.9 (9) |
O1—Rb1—O4—Rb1ii | 67.2 (2) | O1—C1—C6—Cl2 | 1.3 (8) |
O2i—Rb1—O4—Rb1ii | −55.6 (3) | C2—C1—C6—Cl2 | −176.0 (4) |
O4ii—Rb1—O4—Rb1ii | −0.6 (2) | Rb1—Cl2—C6—C5 | −156.3 (5) |
N2iii—Rb1—O4—Rb1ii | −121.90 (18) | Rb1—Cl2—C6—C1 | 22.6 (5) |
Symmetry codes: (i) x, y, z+1; (ii) x−1/2, −y+3/2, −z+1; (iii) −x+1, −y+1, z+1; (iv) −x+1, −y+1, z; (v) x+1/2, −y+3/2, −z+1; (vi) x, y, z−1; (vii) −x+1, −y+1, z−1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3B···O1iv | 0.95 | 1.94 | 2.822 (6) | 153 |
O3—H3A···O2iii | 0.95 | 1.98 | 2.901 (6) | 162 |
O4—H4A···O3ii | 0.95 | 1.86 | 2.807 (8) | 179 |
O4—H4B···Cl1viii | 0.95 | 2.59 | 3.527 (8) | 167 |
O4—H4B···N2ix | 0.95 | 2.92 | 3.352 (9) | 109 |
Symmetry codes: (ii) x−1/2, −y+3/2, −z+1; (iii) −x+1, −y+1, z+1; (iv) −x+1, −y+1, z; (viii) x+1/2, −y+3/2, −z; (ix) −x+1/2, y+1/2, −z. |
Crystal data top
C8H4Cl2N2O4Rb | F(000) = 676 |
Mr = 348.50 | Dx = 2.088 Mg m−3 |
Orthorhombic, P21212 | Cu Kα radiation, λ = 1.54180 Å |
Hall symbol: P 2 2ab | Cell parameters from 3496 reflections |
a = 6.4217 (2) Å | θ = 4.6–75.9° |
b = 18.0295 (6) Å | µ = 10.67 mm−1 |
c = 9.5740 (2) Å | T = 120 K |
V = 1108.48 (6) Å3 | Prism, dark red |
Z = 4 | 0.28 × 0.04 × 0.02 mm |
Data collection top
Oxford Diffraction Xcalibur CCD diffractometer | 2194 independent reflections |
Radiation source: fine-focus sealed tube | 2103 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
ω scans | θmax = 76.1°, θmin = 4.6° |
Absorption correction: multi-scan CrysAlis PRO (Agilent, 2012) | h = −5→8 |
Tmin = 0.651, Tmax = 1.000 | k = −22→22 |
5137 measured reflections | l = −11→11 |
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)] = 0.041 | H-atom parameters constrained |
wR(F2) = 0.118 | w = 1/[σ2(Fo2) + (0.0777P)2 + 0.3657P] where P = (Fo2 + 2Fc2)/3 |
S = 1.12 | (Δ/σ)max = 0.001 |
2194 reflections | Δρmax = 0.72 e Å−3 |
155 parameters | Δρmin = −0.72 e Å−3 |
0 restraints | Absolute structure: Refined as an inversion twin (TWIN + BASF)
The refined BASF value indicates that this model represents the *minor*
component. However, this model is retained since it has the same handedness
as all other structures in this paper (it can be overlaid directly with the
other structures and the DFT-optimized structures. |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.64 (4) |
Crystal data top
C8H4Cl2N2O4Rb | V = 1108.48 (6) Å3 |
Mr = 348.50 | Z = 4 |
Orthorhombic, P21212 | Cu Kα radiation |
a = 6.4217 (2) Å | µ = 10.67 mm−1 |
b = 18.0295 (6) Å | T = 120 K |
c = 9.5740 (2) Å | 0.28 × 0.04 × 0.02 mm |
Data collection top
Oxford Diffraction Xcalibur CCD diffractometer | 2194 independent reflections |
Absorption correction: multi-scan CrysAlis PRO (Agilent, 2012) | 2103 reflections with I > 2σ(I) |
Tmin = 0.651, Tmax = 1.000 | Rint = 0.043 |
5137 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.041 | H-atom parameters constrained |
wR(F2) = 0.118 | Δρmax = 0.72 e Å−3 |
S = 1.12 | Δρmin = −0.72 e Å−3 |
2194 reflections | Absolute structure: Refined as an inversion twin (TWIN + BASF)
The refined BASF value indicates that this model represents the *minor*
component. However, this model is retained since it has the same handedness
as all other structures in this paper (it can be overlaid directly with the
other structures and the DFT-optimized structures. |
155 parameters | Absolute structure parameter: 0.64 (4) |
0 restraints | |
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 | |
Rb1 | 0.39798 (7) | 0.65151 (3) | 0.53116 (5) | 0.02556 (17) | |
Cl1 | 0.1626 (2) | 0.70374 (7) | −0.12323 (12) | 0.0258 (3) | |
Cl2 | 0.1563 (2) | 0.69946 (7) | 0.20293 (12) | 0.0258 (3) | |
O1 | 0.2022 (6) | 0.5507 (2) | 0.3174 (4) | 0.0251 (8) | |
O2 | 0.2000 (7) | 0.5552 (2) | −0.2499 (4) | 0.0233 (8) | |
O3 | 0.7606 (7) | 0.5536 (2) | 0.5294 (4) | 0.0305 (8) | |
H3A | 0.8043 | 0.5204 | 0.6007 | 0.046* | |
H3B | 0.7982 | 0.5304 | 0.4440 | 0.046* | |
O4 | 0.4395 (7) | 0.8062 (2) | 0.4472 (4) | 0.0324 (9) | |
H4A | 0.3779 | 0.8541 | 0.4517 | 0.049* | |
H4B | 0.4792 | 0.8010 | 0.3521 | 0.049* | |
N1 | 0.3357 (8) | 0.3674 (3) | 0.2436 (4) | 0.0266 (10) | |
N2 | 0.3306 (8) | 0.3726 (3) | −0.1918 (5) | 0.0262 (10) | |
C1 | 0.2011 (9) | 0.5505 (3) | 0.1872 (5) | 0.0210 (10) | |
C2 | 0.2341 (8) | 0.4847 (3) | 0.1046 (5) | 0.0204 (10) | |
C3 | 0.2324 (7) | 0.4857 (3) | −0.0402 (5) | 0.0192 (9) | |
C4 | 0.2015 (8) | 0.5542 (3) | −0.1198 (6) | 0.0207 (10) | |
C5 | 0.1783 (7) | 0.6215 (3) | −0.0341 (6) | 0.0207 (9) | |
C6 | 0.1782 (8) | 0.6201 (3) | 0.1074 (6) | 0.0200 (9) | |
C7 | 0.2875 (8) | 0.4174 (3) | 0.1808 (5) | 0.0221 (10) | |
C8 | 0.2854 (8) | 0.4220 (3) | −0.1216 (5) | 0.0218 (10) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Rb1 | 0.0294 (3) | 0.0238 (3) | 0.0235 (2) | 0.00083 (18) | −0.0010 (2) | 0.00145 (18) |
Cl1 | 0.0344 (6) | 0.0179 (6) | 0.0251 (5) | −0.0016 (5) | −0.0015 (5) | 0.0038 (4) |
Cl2 | 0.0325 (7) | 0.0180 (6) | 0.0268 (5) | 0.0017 (5) | −0.0021 (5) | −0.0036 (4) |
O1 | 0.0334 (19) | 0.026 (2) | 0.0162 (16) | −0.0035 (17) | −0.0052 (14) | −0.0029 (14) |
O2 | 0.0297 (19) | 0.0237 (19) | 0.0167 (16) | −0.0041 (17) | 0.0009 (14) | 0.0016 (14) |
O3 | 0.051 (2) | 0.0204 (18) | 0.0204 (16) | 0.0058 (15) | −0.005 (2) | −0.0019 (15) |
O4 | 0.043 (2) | 0.0225 (19) | 0.0315 (18) | −0.0041 (17) | 0.0005 (17) | 0.0013 (16) |
N1 | 0.035 (2) | 0.025 (3) | 0.020 (2) | 0.002 (2) | 0.0010 (17) | 0.0014 (17) |
N2 | 0.031 (2) | 0.017 (2) | 0.031 (2) | 0.0044 (17) | 0.0011 (19) | −0.0037 (17) |
C1 | 0.026 (3) | 0.021 (3) | 0.016 (2) | −0.003 (2) | −0.0021 (18) | 0.0001 (18) |
C2 | 0.021 (2) | 0.020 (3) | 0.020 (2) | −0.0008 (18) | −0.0010 (19) | 0.0009 (18) |
C3 | 0.020 (2) | 0.017 (2) | 0.021 (2) | −0.0007 (16) | 0.000 (2) | −0.0037 (19) |
C4 | 0.019 (2) | 0.021 (3) | 0.022 (2) | −0.0017 (19) | 0.0006 (18) | −0.0008 (19) |
C5 | 0.023 (2) | 0.016 (2) | 0.023 (2) | −0.0016 (16) | 0.000 (2) | −0.0043 (19) |
C6 | 0.024 (2) | 0.013 (2) | 0.023 (2) | −0.0038 (17) | −0.003 (2) | −0.0027 (18) |
C7 | 0.024 (3) | 0.022 (3) | 0.020 (2) | 0.000 (2) | 0.0019 (19) | −0.005 (2) |
C8 | 0.021 (2) | 0.023 (3) | 0.021 (2) | −0.008 (2) | −0.0021 (19) | 0.006 (2) |
Geometric parameters (Å, º) top
Rb1—O4 | 2.915 (4) | O3—H3A | 0.9500 |
Rb1—O3 | 2.922 (4) | O3—H3B | 0.9501 |
Rb1—O2i | 3.004 (4) | O4—Rb1v | 3.048 (4) |
Rb1—O1 | 3.012 (4) | O4—Rb1ii | 3.566 (4) |
Rb1—O4ii | 3.048 (4) | O4—H4A | 0.9501 |
Rb1—N2iii | 3.204 (5) | O4—H4B | 0.9500 |
Rb1—N1iv | 3.259 (5) | N1—C7 | 1.128 (8) |
Rb1—O4v | 3.566 (4) | N1—Rb1iv | 3.259 (5) |
Rb1—Cl2 | 3.6098 (13) | N2—C8 | 1.153 (7) |
Rb1—Cl1i | 3.7576 (13) | N2—Rb1vii | 3.204 (5) |
Rb1—Rb1v | 4.8247 (7) | C1—C2 | 1.442 (7) |
Rb1—Rb1ii | 4.8247 (7) | C1—C6 | 1.477 (7) |
Rb1—H4B | 3.2373 | C2—C3 | 1.386 (7) |
Cl1—C5 | 1.713 (5) | C2—C7 | 1.456 (7) |
Cl1—Rb1vi | 3.7576 (13) | C3—C8 | 1.429 (7) |
Cl2—C6 | 1.703 (5) | C3—C4 | 1.465 (7) |
O1—C1 | 1.246 (6) | C4—C5 | 1.472 (7) |
O2—C4 | 1.246 (7) | C5—C6 | 1.355 (7) |
O2—Rb1vi | 3.004 (4) | | |
| | | |
O4—Rb1—O3 | 120.23 (12) | O4ii—Rb1—Rb1ii | 35.08 (8) |
O4—Rb1—O2i | 141.65 (11) | N2iii—Rb1—Rb1ii | 124.37 (9) |
O3—Rb1—O2i | 89.54 (12) | N1iv—Rb1—Rb1ii | 108.77 (9) |
O4—Rb1—O1 | 115.35 (11) | O4v—Rb1—Rb1ii | 119.93 (7) |
O3—Rb1—O1 | 87.96 (11) | Cl2—Rb1—Rb1ii | 55.25 (2) |
O2i—Rb1—O1 | 87.06 (10) | Cl1i—Rb1—Rb1ii | 69.92 (2) |
O4—Rb1—O4ii | 82.41 (9) | Rb1v—Rb1—Rb1ii | 83.442 (16) |
O3—Rb1—O4ii | 157.09 (12) | O4—Rb1—H4B | 16.7 |
O2i—Rb1—O4ii | 71.84 (11) | O3—Rb1—H4B | 111.8 |
O1—Rb1—O4ii | 78.11 (12) | O2i—Rb1—H4B | 156.8 |
O4—Rb1—N2iii | 107.97 (12) | O1—Rb1—H4B | 102.1 |
O3—Rb1—N2iii | 59.26 (12) | O4ii—Rb1—H4B | 89.1 |
O2i—Rb1—N2iii | 64.79 (11) | N2iii—Rb1—H4B | 117.6 |
O1—Rb1—N2iii | 135.05 (11) | N1iv—Rb1—H4B | 63.6 |
O4ii—Rb1—N2iii | 120.21 (12) | O4v—Rb1—H4B | 72.3 |
O4—Rb1—N1iv | 79.58 (12) | Cl2—Rb1—H4B | 53.8 |
O3—Rb1—N1iv | 60.91 (12) | Cl1i—Rb1—H4B | 108.8 |
O2i—Rb1—N1iv | 138.67 (11) | Rb1v—Rb1—H4B | 38.2 |
O1—Rb1—N1iv | 65.28 (12) | Rb1ii—Rb1—H4B | 55.2 |
O4ii—Rb1—N1iv | 126.19 (12) | C5—Cl1—Rb1vi | 101.43 (19) |
N2iii—Rb1—N1iv | 113.55 (12) | C6—Cl2—Rb1 | 103.36 (18) |
O4—Rb1—O4v | 73.89 (11) | C1—O1—Rb1 | 133.1 (3) |
O3—Rb1—O4v | 49.62 (11) | C4—O2—Rb1vi | 134.6 (3) |
O2i—Rb1—O4v | 119.71 (10) | Rb1—O3—H3A | 127.7 |
O1—Rb1—O4v | 125.13 (11) | Rb1—O3—H3B | 118.2 |
O4ii—Rb1—O4v | 152.20 (15) | H3A—O3—H3B | 105.4 |
N2iii—Rb1—O4v | 56.65 (11) | Rb1—O4—Rb1v | 107.98 (13) |
N1iv—Rb1—O4v | 63.88 (11) | Rb1—O4—Rb1ii | 95.69 (11) |
O4—Rb1—Cl2 | 64.54 (8) | Rb1v—O4—Rb1ii | 152.20 (15) |
O3—Rb1—Cl2 | 118.84 (8) | Rb1—O4—H4A | 144.9 |
O2i—Rb1—Cl2 | 124.32 (8) | Rb1v—O4—H4A | 99.9 |
O1—Rb1—Cl2 | 51.21 (8) | Rb1ii—O4—H4A | 53.0 |
O4ii—Rb1—Cl2 | 65.43 (8) | Rb1—O4—H4B | 101.2 |
N2iii—Rb1—Cl2 | 170.82 (9) | Rb1v—O4—H4B | 80.2 |
N1iv—Rb1—Cl2 | 61.01 (9) | Rb1ii—O4—H4B | 109.8 |
O4v—Rb1—Cl2 | 114.75 (7) | H4A—O4—H4B | 104.2 |
O4—Rb1—Cl1i | 92.28 (8) | C7—N1—Rb1iv | 132.7 (4) |
O3—Rb1—Cl1i | 118.48 (8) | C8—N2—Rb1vii | 136.4 (4) |
O2i—Rb1—Cl1i | 50.23 (8) | O1—C1—C2 | 123.3 (5) |
O1—Rb1—Cl1i | 125.57 (8) | O1—C1—C6 | 121.1 (5) |
O4ii—Rb1—Cl1i | 59.27 (8) | C2—C1—C6 | 115.5 (4) |
N2iii—Rb1—Cl1i | 61.57 (9) | C3—C2—C1 | 122.4 (5) |
N1iv—Rb1—Cl1i | 168.87 (9) | C3—C2—C7 | 120.9 (5) |
O4v—Rb1—Cl1i | 106.71 (7) | C1—C2—C7 | 116.4 (4) |
Cl2—Rb1—Cl1i | 122.25 (3) | C2—C3—C8 | 122.2 (5) |
O4—Rb1—Rb1v | 36.94 (8) | C2—C3—C4 | 122.2 (5) |
O3—Rb1—Rb1v | 85.04 (8) | C8—C3—C4 | 115.2 (4) |
O2i—Rb1—Rb1v | 142.51 (8) | O2—C4—C3 | 122.2 (5) |
O1—Rb1—Rb1v | 129.63 (8) | O2—C4—C5 | 123.0 (5) |
O4ii—Rb1—Rb1v | 117.86 (8) | C3—C4—C5 | 114.8 (4) |
N2iii—Rb1—Rb1v | 80.81 (9) | C6—C5—C4 | 122.8 (5) |
N1iv—Rb1—Rb1v | 67.87 (9) | C6—C5—Cl1 | 120.9 (4) |
O4v—Rb1—Rb1v | 36.96 (7) | C4—C5—Cl1 | 116.2 (4) |
Cl2—Rb1—Rb1v | 90.13 (3) | C5—C6—C1 | 122.2 (5) |
Cl1i—Rb1—Rb1v | 101.08 (3) | C5—C6—Cl2 | 121.4 (4) |
O4—Rb1—Rb1ii | 47.34 (9) | C1—C6—Cl2 | 116.3 (4) |
O3—Rb1—Rb1ii | 166.98 (9) | N1—C7—C2 | 176.6 (6) |
O2i—Rb1—Rb1ii | 103.31 (8) | N2—C8—C3 | 177.2 (5) |
O1—Rb1—Rb1ii | 94.72 (8) | | |
| | | |
O4—Rb1—Cl2—C6 | 148.3 (2) | O4v—Rb1—O4—Rb1ii | −166.48 (16) |
O3—Rb1—Cl2—C6 | 36.3 (2) | Cl2—Rb1—O4—Rb1ii | 65.18 (7) |
O2i—Rb1—Cl2—C6 | −75.1 (2) | Cl1i—Rb1—O4—Rb1ii | −59.75 (8) |
O1—Rb1—Cl2—C6 | −24.1 (2) | Rb1v—Rb1—O4—Rb1ii | −165.23 (18) |
O4ii—Rb1—Cl2—C6 | −118.5 (2) | Rb1—O1—C1—C2 | 135.2 (5) |
N1iv—Rb1—Cl2—C6 | 56.2 (2) | Rb1—O1—C1—C6 | −41.0 (7) |
O4v—Rb1—Cl2—C6 | 92.2 (2) | O1—C1—C2—C3 | −180.0 (5) |
Cl1i—Rb1—Cl2—C6 | −136.12 (19) | C6—C1—C2—C3 | −3.6 (8) |
Rb1v—Rb1—Cl2—C6 | 120.66 (19) | O1—C1—C2—C7 | −5.1 (8) |
Rb1ii—Rb1—Cl2—C6 | −157.42 (19) | C6—C1—C2—C7 | 171.3 (5) |
O4—Rb1—O1—C1 | 31.0 (5) | C1—C2—C3—C8 | 173.7 (4) |
O3—Rb1—O1—C1 | −91.7 (5) | C7—C2—C3—C8 | −1.0 (8) |
O2i—Rb1—O1—C1 | 178.6 (5) | C1—C2—C3—C4 | 1.4 (9) |
O4ii—Rb1—O1—C1 | 106.6 (5) | C7—C2—C3—C4 | −173.2 (4) |
N2iii—Rb1—O1—C1 | −132.3 (5) | Rb1vi—O2—C4—C3 | −134.1 (4) |
N1iv—Rb1—O1—C1 | −33.0 (5) | Rb1vi—O2—C4—C5 | 44.2 (7) |
O4v—Rb1—O1—C1 | −56.6 (5) | C2—C3—C4—O2 | 180.0 (5) |
Cl2—Rb1—O1—C1 | 38.7 (5) | C8—C3—C4—O2 | 7.2 (7) |
Cl1i—Rb1—O1—C1 | 144.2 (5) | C2—C3—C4—C5 | 1.5 (7) |
Rb1v—Rb1—O1—C1 | −9.9 (5) | C8—C3—C4—C5 | −171.2 (4) |
Rb1ii—Rb1—O1—C1 | 75.5 (5) | O2—C4—C5—C6 | 179.4 (5) |
O3—Rb1—O4—Rb1v | −19.66 (18) | C3—C4—C5—C6 | −2.2 (7) |
O2i—Rb1—O4—Rb1v | 116.54 (16) | O2—C4—C5—Cl1 | −3.4 (7) |
O1—Rb1—O4—Rb1v | −122.98 (13) | C3—C4—C5—Cl1 | 175.0 (3) |
O4ii—Rb1—O4—Rb1v | 164.06 (19) | Rb1vi—Cl1—C5—C6 | 157.1 (4) |
N2iii—Rb1—O4—Rb1v | 44.69 (16) | Rb1vi—Cl1—C5—C4 | −20.2 (4) |
N1iv—Rb1—O4—Rb1v | −66.87 (13) | C4—C5—C6—C1 | −0.1 (9) |
O4v—Rb1—O4—Rb1v | −1.26 (3) | Cl1—C5—C6—C1 | −177.2 (4) |
Cl2—Rb1—O4—Rb1v | −129.59 (14) | C4—C5—C6—Cl2 | 178.6 (3) |
Cl1i—Rb1—O4—Rb1v | 105.48 (11) | Cl1—C5—C6—Cl2 | 1.5 (7) |
Rb1ii—Rb1—O4—Rb1v | 165.23 (18) | O1—C1—C6—C5 | 179.4 (6) |
O3—Rb1—O4—Rb1ii | 175.11 (9) | C2—C1—C6—C5 | 3.0 (8) |
O2i—Rb1—O4—Rb1ii | −48.7 (2) | O1—C1—C6—Cl2 | 0.6 (7) |
O1—Rb1—O4—Rb1ii | 71.79 (13) | C2—C1—C6—Cl2 | −175.8 (4) |
O4ii—Rb1—O4—Rb1ii | −1.16 (9) | Rb1—Cl2—C6—C5 | −155.3 (4) |
N2iii—Rb1—O4—Rb1ii | −120.54 (12) | Rb1—Cl2—C6—C1 | 23.5 (4) |
N1iv—Rb1—O4—Rb1ii | 127.90 (12) | | |
Symmetry codes: (i) x, y, z+1; (ii) x−1/2, −y+3/2, −z+1; (iii) −x+1, −y+1, z+1; (iv) −x+1, −y+1, z; (v) x+1/2, −y+3/2, −z+1; (vi) x, y, z−1; (vii) −x+1, −y+1, z−1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3B···O1iv | 0.95 | 1.90 | 2.778 (6) | 153 |
O3—H3A···O2iii | 0.95 | 1.98 | 2.894 (6) | 162 |
O4—H4A···O3ii | 0.95 | 1.84 | 2.784 (6) | 177 |
O4—H4B···Cl1viii | 0.95 | 2.49 | 3.421 (4) | 167 |
O4—H4B···N2ix | 0.95 | 2.82 | 3.228 (6) | 107 |
Symmetry codes: (ii) x−1/2, −y+3/2, −z+1; (iii) −x+1, −y+1, z+1; (iv) −x+1, −y+1, z; (viii) x+1/2, −y+3/2, −z; (ix) −x+1/2, y+1/2, −z. |
Crystal data top
C8H4Cl2CsN2O4 | F(000) = 748 |
Mr = 395.94 | Dx = 2.221 Mg m−3 |
Orthorhombic, P21212 | Cu Kα radiation, λ = 1.5418 Å |
Hall symbol: P 2 2ab | Cell parameters from 2948 reflections |
a = 6.6462 (1) Å | θ = 4.5–75.5° |
b = 18.2212 (3) Å | µ = 28.64 mm−1 |
c = 9.7758 (2) Å | T = 293 K |
V = 1183.87 (4) Å3 | Prism, dark red |
Z = 4 | 0.12 × 0.04 × 0.03 mm |
Data collection top
Oxford Diffraction Xcalibur CCD diffractometer | 2232 independent reflections |
Radiation source: fine-focus sealed tube | 2176 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
ω scans | θmax = 75.6°, θmin = 4.5° |
Absorption correction: multi-scan CrysAlis PRO (Agilent, 2012) | h = −7→8 |
Tmin = 0.500, Tmax = 1.000 | k = −22→12 |
3678 measured reflections | l = −7→12 |
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)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.093 | w = 1/[σ2(Fo2) + (0.057P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.001 |
2232 reflections | Δρmax = 0.87 e Å−3 |
154 parameters | Δρmin = −0.87 e Å−3 |
0 restraints | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.016 (8) |
Crystal data top
C8H4Cl2CsN2O4 | V = 1183.87 (4) Å3 |
Mr = 395.94 | Z = 4 |
Orthorhombic, P21212 | Cu Kα radiation |
a = 6.6462 (1) Å | µ = 28.64 mm−1 |
b = 18.2212 (3) Å | T = 293 K |
c = 9.7758 (2) Å | 0.12 × 0.04 × 0.03 mm |
Data collection top
Oxford Diffraction Xcalibur CCD diffractometer | 2232 independent reflections |
Absorption correction: multi-scan CrysAlis PRO (Agilent, 2012) | 2176 reflections with I > 2σ(I) |
Tmin = 0.500, Tmax = 1.000 | Rint = 0.036 |
3678 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.093 | Δρmax = 0.87 e Å−3 |
S = 1.07 | Δρmin = −0.87 e Å−3 |
2232 reflections | Absolute structure: Flack (1983) |
154 parameters | Absolute structure parameter: −0.016 (8) |
0 restraints | |
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 | |
Cs1 | 0.40430 (6) | 0.65307 (2) | 0.54107 (3) | 0.04063 (13) | |
Cl1 | 0.1462 (3) | 0.70343 (7) | −0.11081 (15) | 0.0455 (3) | |
Cl2 | 0.1451 (3) | 0.69924 (7) | 0.20835 (14) | 0.0455 (4) | |
O1 | 0.1937 (8) | 0.5520 (2) | 0.3206 (4) | 0.0406 (9) | |
O2 | 0.1891 (8) | 0.5573 (2) | −0.2341 (4) | 0.0398 (9) | |
O3 | 0.7728 (10) | 0.5457 (3) | 0.5409 (4) | 0.0566 (13) | |
H3A | 0.7972 | 0.5137 | 0.6157 | 0.085* | |
H3B | 0.8098 | 0.5183 | 0.4622 | 0.085* | |
O4 | 0.4248 (10) | 0.8126 (3) | 0.4318 (6) | 0.0591 (13) | |
H4A | 0.3857 | 0.8608 | 0.4581 | 0.089* | |
H4B | 0.4673 | 0.8167 | 0.3394 | 0.089* | |
N1 | 0.3368 (11) | 0.3718 (3) | 0.2453 (6) | 0.0490 (13) | |
N2 | 0.3331 (12) | 0.3774 (3) | −0.1748 (6) | 0.0498 (14) | |
C1 | 0.1947 (9) | 0.5528 (3) | 0.1941 (5) | 0.0307 (10) | |
C2 | 0.2313 (8) | 0.4871 (3) | 0.1120 (5) | 0.0283 (10) | |
C3 | 0.2309 (8) | 0.4891 (3) | −0.0302 (4) | 0.0272 (9) | |
C4 | 0.1926 (9) | 0.5556 (3) | −0.1070 (5) | 0.0299 (10) | |
C5 | 0.1666 (9) | 0.6225 (3) | −0.0231 (5) | 0.0312 (10) | |
C6 | 0.1654 (9) | 0.6204 (3) | 0.1136 (5) | 0.0316 (10) | |
C7 | 0.2879 (10) | 0.4224 (3) | 0.1858 (5) | 0.0340 (11) | |
C8 | 0.2838 (9) | 0.4260 (3) | −0.1091 (5) | 0.0339 (11) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cs1 | 0.04436 (19) | 0.04621 (19) | 0.03132 (16) | −0.00106 (15) | −0.00285 (13) | 0.00398 (13) |
Cl1 | 0.0671 (10) | 0.0318 (6) | 0.0376 (6) | −0.0027 (6) | −0.0018 (7) | 0.0095 (5) |
Cl2 | 0.0639 (10) | 0.0334 (6) | 0.0391 (6) | 0.0017 (6) | −0.0045 (7) | −0.0113 (5) |
O1 | 0.060 (3) | 0.0421 (19) | 0.0197 (14) | −0.006 (2) | −0.0007 (16) | −0.0039 (14) |
O2 | 0.056 (3) | 0.0421 (19) | 0.0209 (14) | −0.007 (2) | 0.0045 (17) | 0.0029 (14) |
O3 | 0.093 (4) | 0.046 (2) | 0.0304 (18) | 0.011 (3) | 0.004 (2) | −0.0017 (18) |
O4 | 0.069 (3) | 0.049 (2) | 0.059 (3) | 0.003 (3) | −0.004 (3) | 0.009 (2) |
N1 | 0.062 (4) | 0.046 (3) | 0.039 (2) | 0.005 (3) | −0.010 (2) | 0.007 (2) |
N2 | 0.064 (4) | 0.044 (3) | 0.042 (2) | 0.005 (3) | 0.009 (3) | −0.010 (2) |
C1 | 0.036 (3) | 0.035 (2) | 0.0211 (19) | −0.002 (2) | −0.0044 (19) | −0.0034 (19) |
C2 | 0.033 (2) | 0.030 (2) | 0.0216 (18) | −0.001 (2) | −0.0024 (19) | 0.0006 (18) |
C3 | 0.030 (2) | 0.032 (2) | 0.0198 (17) | −0.0019 (19) | 0.0008 (19) | −0.0010 (18) |
C4 | 0.037 (3) | 0.032 (2) | 0.0206 (18) | −0.006 (2) | 0.0012 (19) | −0.0004 (18) |
C5 | 0.035 (2) | 0.031 (2) | 0.028 (2) | −0.005 (2) | −0.002 (2) | 0.0011 (19) |
C6 | 0.037 (3) | 0.030 (2) | 0.028 (2) | −0.003 (2) | −0.002 (2) | −0.0033 (19) |
C7 | 0.041 (3) | 0.036 (3) | 0.025 (2) | 0.001 (2) | −0.004 (2) | −0.001 (2) |
C8 | 0.035 (3) | 0.038 (3) | 0.029 (2) | −0.001 (2) | 0.000 (2) | −0.001 (2) |
Geometric parameters (Å, º) top
Cs1—O4 | 3.100 (5) | O3—Cs1iv | 3.808 (5) |
Cs1—O3 | 3.135 (6) | O3—H3A | 0.9499 |
Cs1—O2i | 3.150 (4) | O3—H3B | 0.9499 |
Cs1—O1 | 3.161 (4) | O4—Cs1v | 3.258 (7) |
Cs1—O4ii | 3.258 (7) | O4—Cs1ii | 3.525 (7) |
Cs1—N2iii | 3.327 (6) | O4—H4A | 0.9500 |
Cs1—N1iv | 3.395 (6) | O4—H4B | 0.9500 |
Cs1—O4v | 3.525 (7) | N1—C7 | 1.138 (9) |
Cs1—Cl2 | 3.7756 (15) | N1—Cs1iv | 3.395 (6) |
Cs1—O3iv | 3.808 (5) | N2—C8 | 1.143 (8) |
Cs1—Cl1i | 3.9198 (16) | N2—Cs1vii | 3.327 (6) |
Cs1—Cl2v | 3.9752 (14) | C1—C2 | 1.462 (7) |
Cl1—C5 | 1.711 (5) | C1—C6 | 1.475 (7) |
Cl1—Cs1vi | 3.9198 (16) | C2—C3 | 1.391 (6) |
Cl2—C6 | 1.714 (5) | C2—C7 | 1.432 (7) |
Cl2—Cs1ii | 3.9752 (14) | C3—C8 | 1.429 (7) |
O1—C1 | 1.237 (6) | C3—C4 | 1.448 (7) |
O2—C4 | 1.243 (6) | C4—C5 | 1.479 (7) |
O2—Cs1vi | 3.150 (4) | C5—C6 | 1.337 (7) |
| | | |
O4—Cs1—O3 | 123.42 (16) | O4—Cs1—Cl2v | 63.88 (11) |
O4—Cs1—O2i | 141.25 (14) | O3—Cs1—Cl2v | 96.22 (10) |
O3—Cs1—O2i | 90.53 (13) | O2i—Cs1—Cl2v | 97.35 (8) |
O4—Cs1—O1 | 109.33 (13) | O1—Cs1—Cl2v | 173.02 (8) |
O3—Cs1—O1 | 88.96 (13) | O4ii—Cs1—Cl2v | 102.34 (11) |
O2i—Cs1—O1 | 87.24 (10) | N2iii—Cs1—Cl2v | 52.20 (11) |
O4—Cs1—O4ii | 83.75 (14) | N1iv—Cs1—Cl2v | 114.28 (12) |
O3—Cs1—O4ii | 152.12 (14) | O4v—Cs1—Cl2v | 55.85 (10) |
O2i—Cs1—O4ii | 66.76 (13) | Cl2—Cs1—Cl2v | 124.313 (19) |
O1—Cs1—O4ii | 74.58 (14) | O3iv—Cs1—Cl2v | 140.22 (7) |
O4—Cs1—N2iii | 114.88 (15) | Cl1i—Cs1—Cl2v | 58.85 (4) |
O3—Cs1—N2iii | 59.11 (14) | C5—Cl1—Cs1vi | 101.47 (19) |
O2i—Cs1—N2iii | 64.11 (15) | C6—Cl2—Cs1 | 104.05 (19) |
O1—Cs1—N2iii | 134.77 (13) | C6—Cl2—Cs1ii | 158.7 (2) |
O4ii—Cs1—N2iii | 118.50 (17) | Cs1—Cl2—Cs1ii | 78.68 (3) |
O4—Cs1—N1iv | 79.03 (15) | C1—O1—Cs1 | 132.3 (4) |
O3—Cs1—N1iv | 61.33 (13) | C4—O2—Cs1vi | 134.6 (4) |
O2i—Cs1—N1iv | 138.62 (12) | Cs1—O3—Cs1iv | 110.62 (18) |
O1—Cs1—N1iv | 64.28 (14) | Cs1—O3—H3A | 121.1 |
O4ii—Cs1—N1iv | 126.20 (16) | Cs1iv—O3—H3A | 57.9 |
N2iii—Cs1—N1iv | 115.02 (16) | Cs1—O3—H3B | 122.1 |
O4—Cs1—O4v | 79.42 (13) | Cs1iv—O3—H3B | 65.2 |
O3—Cs1—O4v | 49.01 (14) | H3A—O3—H3B | 104.8 |
O2i—Cs1—O4v | 119.44 (13) | Cs1—O4—Cs1v | 101.24 (16) |
O1—Cs1—O4v | 126.08 (13) | Cs1—O4—Cs1ii | 95.58 (16) |
O4ii—Cs1—O4v | 156.87 (18) | Cs1v—O4—Cs1ii | 156.87 (18) |
N2iii—Cs1—O4v | 56.78 (15) | Cs1—O4—H4A | 139.5 |
N1iv—Cs1—O4v | 65.81 (15) | Cs1v—O4—H4A | 93.9 |
O4—Cs1—Cl2 | 60.95 (11) | Cs1ii—O4—H4A | 63.1 |
O3—Cs1—Cl2 | 119.68 (8) | Cs1—O4—H4B | 114.5 |
O2i—Cs1—Cl2 | 121.15 (9) | Cs1v—O4—H4B | 76.8 |
O1—Cs1—Cl2 | 48.74 (8) | Cs1ii—O4—H4B | 110.4 |
O4ii—Cs1—Cl2 | 65.22 (10) | H4A—O4—H4B | 105.4 |
N2iii—Cs1—Cl2 | 174.71 (12) | C7—N1—Cs1iv | 133.6 (5) |
N1iv—Cs1—Cl2 | 61.80 (12) | C8—N2—Cs1vii | 138.5 (5) |
O4v—Cs1—Cl2 | 118.23 (9) | O1—C1—C2 | 122.7 (5) |
O4—Cs1—O3iv | 154.87 (14) | O1—C1—C6 | 122.8 (5) |
O3—Cs1—O3iv | 69.37 (18) | C2—C1—C6 | 114.5 (4) |
O2i—Cs1—O3iv | 48.17 (10) | C3—C2—C7 | 121.7 (5) |
O1—Cs1—O3iv | 46.28 (10) | C3—C2—C1 | 121.7 (5) |
O4ii—Cs1—O3iv | 83.12 (13) | C7—C2—C1 | 116.2 (4) |
N2iii—Cs1—O3iv | 90.23 (13) | C2—C3—C8 | 121.2 (5) |
N1iv—Cs1—O3iv | 91.67 (13) | C2—C3—C4 | 122.8 (5) |
O4v—Cs1—O3iv | 118.16 (13) | C8—C3—C4 | 115.9 (4) |
Cl2—Cs1—O3iv | 94.04 (8) | O2—C4—C3 | 122.8 (5) |
O4—Cs1—Cl1i | 95.67 (12) | O2—C4—C5 | 122.1 (5) |
O3—Cs1—Cl1i | 119.23 (8) | C3—C4—C5 | 115.0 (4) |
O2i—Cs1—Cl1i | 47.56 (8) | C6—C5—C4 | 122.1 (5) |
O1—Cs1—Cl1i | 122.31 (9) | C6—C5—Cl1 | 121.7 (4) |
O4ii—Cs1—Cl1i | 57.09 (11) | C4—C5—Cl1 | 116.2 (4) |
N2iii—Cs1—Cl1i | 62.84 (13) | C5—C6—C1 | 123.8 (5) |
N1iv—Cs1—Cl1i | 172.93 (11) | C5—C6—Cl2 | 121.1 (4) |
O4v—Cs1—Cl1i | 108.82 (10) | C1—C6—Cl2 | 115.0 (4) |
Cl2—Cs1—Cl1i | 119.74 (3) | N1—C7—C2 | 178.4 (7) |
O3iv—Cs1—Cl1i | 95.04 (8) | N2—C8—C3 | 176.9 (7) |
| | | |
O4—Cs1—Cl2—C6 | 147.4 (3) | O3iv—Cs1—O4—Cs1v | −137.7 (3) |
O3—Cs1—Cl2—C6 | 33.2 (2) | Cl1i—Cs1—O4—Cs1v | 107.48 (13) |
O2i—Cs1—Cl2—C6 | −77.7 (2) | Cl2v—Cs1—O4—Cs1v | 56.36 (11) |
O1—Cs1—Cl2—C6 | −24.9 (2) | O3—Cs1—O4—Cs1ii | 172.62 (11) |
O4ii—Cs1—Cl2—C6 | −115.8 (2) | O2i—Cs1—O4—Cs1ii | −40.2 (3) |
N1iv—Cs1—Cl2—C6 | 54.4 (2) | O1—Cs1—O4—Cs1ii | 70.59 (16) |
O4v—Cs1—Cl2—C6 | 89.8 (2) | O4ii—Cs1—O4—Cs1ii | −0.64 (14) |
O3iv—Cs1—Cl2—C6 | −35.3 (2) | N2iii—Cs1—O4—Cs1ii | −119.21 (17) |
Cl1i—Cs1—Cl2—C6 | −133.4 (2) | N1iv—Cs1—O4—Cs1ii | 128.15 (17) |
Cl2v—Cs1—Cl2—C6 | 155.9 (2) | O4v—Cs1—O4—Cs1ii | −164.7 (2) |
O4—Cs1—Cl2—Cs1ii | −54.30 (14) | Cl2—Cs1—O4—Cs1ii | 64.44 (11) |
O3—Cs1—Cl2—Cs1ii | −168.42 (12) | O3iv—Cs1—O4—Cs1ii | 58.2 (4) |
O2i—Cs1—Cl2—Cs1ii | 80.66 (10) | Cl1i—Cs1—O4—Cs1ii | −56.57 (11) |
O1—Cs1—Cl2—Cs1ii | 133.43 (13) | Cl2v—Cs1—O4—Cs1ii | −107.69 (14) |
O4ii—Cs1—Cl2—Cs1ii | 42.55 (11) | Cs1—O1—C1—C2 | 131.7 (5) |
N1iv—Cs1—Cl2—Cs1ii | −147.21 (12) | Cs1—O1—C1—C6 | −46.3 (9) |
O4v—Cs1—Cl2—Cs1ii | −111.85 (10) | O1—C1—C2—C3 | 179.7 (6) |
O3iv—Cs1—Cl2—Cs1ii | 123.06 (9) | C6—C1—C2—C3 | −2.0 (8) |
Cl1i—Cs1—Cl2—Cs1ii | 24.91 (4) | O1—C1—C2—C7 | −6.5 (9) |
Cl2v—Cs1—Cl2—Cs1ii | −45.74 (6) | C6—C1—C2—C7 | 171.7 (5) |
O4—Cs1—O1—C1 | 34.1 (6) | C7—C2—C3—C8 | 1.2 (9) |
O3—Cs1—O1—C1 | −91.1 (6) | C1—C2—C3—C8 | 174.5 (5) |
O2i—Cs1—O1—C1 | 178.3 (6) | C7—C2—C3—C4 | −174.1 (5) |
O4ii—Cs1—O1—C1 | 111.6 (6) | C1—C2—C3—C4 | −0.7 (9) |
N2iii—Cs1—O1—C1 | −133.3 (5) | Cs1vi—O2—C4—C3 | −127.6 (5) |
N1iv—Cs1—O1—C1 | −32.7 (6) | Cs1vi—O2—C4—C5 | 49.7 (9) |
O4v—Cs1—O1—C1 | −56.7 (6) | C2—C3—C4—O2 | −178.8 (6) |
Cl2—Cs1—O1—C1 | 41.3 (5) | C8—C3—C4—O2 | 5.7 (8) |
O3iv—Cs1—O1—C1 | −153.1 (6) | C2—C3—C4—C5 | 3.8 (8) |
Cl1i—Cs1—O1—C1 | 144.4 (5) | C8—C3—C4—C5 | −171.7 (5) |
O4—Cs1—O3—Cs1iv | −155.64 (14) | O2—C4—C5—C6 | 178.3 (6) |
O2i—Cs1—O3—Cs1iv | 44.21 (13) | C3—C4—C5—C6 | −4.3 (9) |
O1—Cs1—O3—Cs1iv | −43.02 (12) | O2—C4—C5—Cl1 | −3.7 (8) |
O4ii—Cs1—O3—Cs1iv | 9.9 (3) | C3—C4—C5—Cl1 | 173.7 (4) |
N2iii—Cs1—O3—Cs1iv | 103.25 (18) | Cs1vi—Cl1—C5—C6 | 155.6 (5) |
N1iv—Cs1—O3—Cs1iv | −104.02 (18) | Cs1vi—Cl1—C5—C4 | −22.4 (5) |
O4v—Cs1—O3—Cs1iv | 174.2 (2) | C4—C5—C6—C1 | 1.7 (10) |
Cl2—Cs1—O3—Cs1iv | −82.71 (12) | Cl1—C5—C6—C1 | −176.2 (4) |
O3iv—Cs1—O3—Cs1iv | −0.05 (13) | C4—C5—C6—Cl2 | 177.4 (4) |
Cl1i—Cs1—O3—Cs1iv | 84.03 (12) | Cl1—C5—C6—Cl2 | −0.5 (9) |
Cl2v—Cs1—O3—Cs1iv | 141.66 (9) | O1—C1—C6—C5 | 179.8 (7) |
O3—Cs1—O4—Cs1v | −23.3 (2) | C2—C1—C6—C5 | 1.5 (9) |
O2i—Cs1—O4—Cs1v | 123.8 (2) | O1—C1—C6—Cl2 | 3.8 (8) |
O1—Cs1—O4—Cs1v | −125.36 (15) | C2—C1—C6—Cl2 | −174.4 (4) |
O4ii—Cs1—O4—Cs1v | 163.4 (2) | Cs1—Cl2—C6—C5 | −152.9 (5) |
N2iii—Cs1—O4—Cs1v | 44.8 (2) | Cs1ii—Cl2—C6—C5 | 112.3 (6) |
N1iv—Cs1—O4—Cs1v | −67.80 (17) | Cs1—Cl2—C6—C1 | 23.2 (5) |
O4v—Cs1—O4—Cs1v | −0.66 (14) | Cs1ii—Cl2—C6—C1 | −71.7 (7) |
Cl2—Cs1—O4—Cs1v | −131.51 (18) | | |
Symmetry codes: (i) x, y, z+1; (ii) x−1/2, −y+3/2, −z+1; (iii) −x+1, −y+1, z+1; (iv) −x+1, −y+1, z; (v) x+1/2, −y+3/2, −z+1; (vi) x, y, z−1; (vii) −x+1, −y+1, z−1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3B···O1iv | 0.95 | 1.89 | 2.803 (6) | 162 |
O3—H3A···O2iii | 0.95 | 1.96 | 2.902 (6) | 172 |
O4—H4A···O3ii | 0.95 | 1.86 | 2.785 (8) | 163 |
O4—H4B···Cl1viii | 0.95 | 2.56 | 3.479 (6) | 163 |
O4—H4B···N2ix | 0.95 | 2.79 | 3.263 (9) | 112 |
Symmetry codes: (ii) x−1/2, −y+3/2, −z+1; (iii) −x+1, −y+1, z+1; (iv) −x+1, −y+1, z; (viii) x+1/2, −y+3/2, −z; (ix) −x+1/2, y+1/2, −z. |
Crystal data top
C8H4Cl2CsN2O4 | F(000) = 748 |
Mr = 395.94 | Dx = 2.269 Mg m−3 |
Orthorhombic, P21212 | Cu Kα radiation, λ = 1.5418 Å |
Hall symbol: P 2 2ab | Cell parameters from 1958 reflections |
a = 6.5601 (3) Å | θ = 4.5–75.6° |
b = 18.152 (1) Å | µ = 29.25 mm−1 |
c = 9.7345 (4) Å | T = 120 K |
V = 1159.17 (10) Å3 | Prism, dark red |
Z = 4 | 0.37 × 0.05 × 0.03 mm |
Data collection top
Oxford Diffraction Xcalibur CCD diffractometer | 2051 independent reflections |
Radiation source: fine-focus sealed tube | 1953 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.054 |
ω scans | θmax = 75.7°, θmin = 4.5° |
Absorption correction: multi-scan CrysAlis PRO (Agilent, 2012) | h = −7→8 |
Tmin = 0.300, Tmax = 1.000 | k = −18→22 |
3404 measured reflections | l = −7→12 |
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)] = 0.059 | H-atom parameters constrained |
wR(F2) = 0.159 | w = 1/[σ2(Fo2) + (0.1197P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
2051 reflections | Δρmax = 1.58 e Å−3 |
155 parameters | Δρmin = −1.34 e Å−3 |
72 restraints | Absolute structure: Refined as an inversion twin (TWIN + BASF) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.283 (17) |
Crystal data top
C8H4Cl2CsN2O4 | V = 1159.17 (10) Å3 |
Mr = 395.94 | Z = 4 |
Orthorhombic, P21212 | Cu Kα radiation |
a = 6.5601 (3) Å | µ = 29.25 mm−1 |
b = 18.152 (1) Å | T = 120 K |
c = 9.7345 (4) Å | 0.37 × 0.05 × 0.03 mm |
Data collection top
Oxford Diffraction Xcalibur CCD diffractometer | 2051 independent reflections |
Absorption correction: multi-scan CrysAlis PRO (Agilent, 2012) | 1953 reflections with I > 2σ(I) |
Tmin = 0.300, Tmax = 1.000 | Rint = 0.054 |
3404 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.059 | H-atom parameters constrained |
wR(F2) = 0.159 | Δρmax = 1.58 e Å−3 |
S = 1.06 | Δρmin = −1.34 e Å−3 |
2051 reflections | Absolute structure: Refined as an inversion twin (TWIN + BASF) |
155 parameters | Absolute structure parameter: 0.283 (17) |
72 restraints | |
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 | |
Cs1 | 0.39888 (9) | 0.65426 (3) | 0.54302 (6) | 0.0248 (2) | |
Cl1 | 0.1475 (4) | 0.70419 (16) | −0.1083 (3) | 0.0324 (6) | |
Cl2 | 0.1427 (5) | 0.69915 (15) | 0.2119 (3) | 0.0324 (6) | |
O1 | 0.1958 (13) | 0.5506 (4) | 0.3234 (7) | 0.0255 (16) | |
O2 | 0.1895 (14) | 0.5559 (5) | −0.2334 (8) | 0.0286 (17) | |
O3 | 0.7690 (12) | 0.5480 (4) | 0.5436 (8) | 0.0270 (15) | |
H3A | 0.7816 | 0.5050 | 0.5986 | 0.040* | |
H3B | 0.8231 | 0.5343 | 0.4568 | 0.040* | |
O4 | 0.4193 (13) | 0.8121 (4) | 0.4290 (8) | 0.0284 (16) | |
H4A | 0.3327 | 0.8508 | 0.4593 | 0.043* | |
H4B | 0.4454 | 0.8233 | 0.3354 | 0.043* | |
N1 | 0.3384 (17) | 0.3727 (7) | 0.2426 (12) | 0.037 (3) | |
N2 | 0.3367 (18) | 0.3765 (7) | −0.1735 (13) | 0.037 (2) | |
C1 | 0.1949 (17) | 0.5520 (6) | 0.1958 (11) | 0.0206 (19) | |
C2 | 0.2342 (15) | 0.4854 (5) | 0.1142 (9) | 0.0166 (18) | |
C3 | 0.2324 (16) | 0.4875 (6) | −0.0275 (9) | 0.0203 (19) | |
C4 | 0.1931 (18) | 0.5551 (6) | −0.1057 (11) | 0.025 (2) | |
C5 | 0.1679 (16) | 0.6205 (6) | −0.0218 (10) | 0.0213 (19) | |
C6 | 0.1653 (18) | 0.6201 (7) | 0.1178 (12) | 0.028 (2) | |
C7 | 0.2940 (17) | 0.4176 (7) | 0.1914 (10) | 0.022 (2) | |
C8 | 0.2888 (17) | 0.4213 (7) | −0.1100 (10) | 0.025 (2) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cs1 | 0.0270 (3) | 0.0357 (3) | 0.0119 (3) | 0.0002 (2) | −0.0014 (2) | 0.0011 (2) |
Cl1 | 0.0414 (15) | 0.0364 (12) | 0.0194 (11) | −0.0005 (11) | −0.0033 (11) | 0.0025 (9) |
Cl2 | 0.0419 (16) | 0.0360 (13) | 0.0193 (11) | 0.0002 (11) | −0.0040 (11) | −0.0037 (9) |
O1 | 0.031 (3) | 0.038 (3) | 0.007 (2) | −0.004 (3) | −0.003 (3) | 0.003 (2) |
O2 | 0.032 (3) | 0.039 (3) | 0.014 (3) | 0.000 (3) | 0.002 (3) | 0.003 (3) |
O3 | 0.037 (3) | 0.030 (3) | 0.015 (3) | 0.001 (3) | 0.003 (3) | 0.002 (3) |
O4 | 0.035 (3) | 0.025 (3) | 0.025 (3) | −0.004 (3) | 0.005 (3) | −0.001 (3) |
N1 | 0.026 (5) | 0.053 (6) | 0.033 (5) | −0.002 (5) | 0.007 (4) | −0.025 (5) |
N2 | 0.033 (5) | 0.044 (6) | 0.035 (5) | 0.006 (5) | −0.006 (5) | −0.003 (5) |
C1 | 0.019 (3) | 0.026 (4) | 0.017 (3) | −0.001 (3) | 0.003 (3) | −0.005 (3) |
C2 | 0.013 (3) | 0.023 (4) | 0.013 (3) | −0.001 (3) | −0.001 (3) | 0.001 (3) |
C3 | 0.022 (4) | 0.028 (4) | 0.011 (3) | −0.002 (3) | 0.001 (3) | 0.001 (3) |
C4 | 0.028 (4) | 0.030 (4) | 0.016 (4) | −0.005 (3) | −0.003 (3) | 0.005 (3) |
C5 | 0.020 (3) | 0.028 (3) | 0.017 (4) | −0.001 (3) | 0.000 (3) | 0.000 (3) |
C6 | 0.028 (4) | 0.032 (4) | 0.024 (4) | 0.002 (3) | −0.003 (4) | −0.002 (3) |
C7 | 0.025 (4) | 0.032 (4) | 0.009 (3) | −0.001 (4) | 0.001 (3) | −0.006 (3) |
C8 | 0.021 (4) | 0.043 (4) | 0.010 (3) | −0.006 (3) | 0.005 (3) | 0.002 (3) |
Geometric parameters (Å, º) top
Cs1—O4 | 3.075 (7) | O3—H3A | 0.9500 |
Cs1—O3 | 3.101 (8) | O3—H3B | 0.9500 |
Cs1—O2i | 3.133 (8) | O4—Cs1v | 3.217 (9) |
Cs1—O1 | 3.145 (8) | O4—Cs1ii | 3.479 (9) |
Cs1—O4ii | 3.217 (9) | O4—H4A | 0.9501 |
Cs1—N2iii | 3.307 (12) | O4—H4B | 0.9500 |
Cs1—N1iv | 3.430 (13) | N1—C7 | 1.000 (17) |
Cs1—O4v | 3.479 (9) | N1—Cs1iv | 3.430 (13) |
Cs1—Cl2 | 3.725 (3) | N2—C8 | 1.069 (16) |
Cs1—Cl1i | 3.880 (3) | N2—Cs1vii | 3.307 (12) |
Cs1—Cl2v | 3.915 (3) | C1—C6 | 1.463 (15) |
Cs1—Cs1v | 4.8519 (9) | C1—C2 | 1.469 (14) |
Cl1—C5 | 1.742 (11) | C2—C3 | 1.380 (11) |
Cl1—Cs1vi | 3.880 (3) | C2—C7 | 1.494 (15) |
Cl2—C6 | 1.710 (12) | C3—C4 | 1.466 (14) |
Cl2—Cs1ii | 3.915 (3) | C3—C8 | 1.491 (15) |
O1—C1 | 1.243 (13) | C4—C5 | 1.450 (15) |
O2—C4 | 1.243 (14) | C5—C6 | 1.359 (15) |
O2—Cs1vi | 3.133 (8) | | |
| | | |
O4—Cs1—O3 | 123.1 (2) | Cl2—Cs1—Cl2v | 124.25 (3) |
O4—Cs1—O2i | 143.2 (2) | Cl1i—Cs1—Cl2v | 58.80 (6) |
O3—Cs1—O2i | 89.3 (2) | O4—Cs1—Cs1v | 40.62 (16) |
O4—Cs1—O1 | 109.3 (2) | O3—Cs1—Cs1v | 85.21 (14) |
O3—Cs1—O1 | 87.7 (2) | O2i—Cs1—Cs1v | 145.56 (16) |
O2i—Cs1—O1 | 86.87 (19) | O1—Cs1—Cs1v | 126.72 (14) |
O4—Cs1—O4ii | 84.03 (19) | O4ii—Cs1—Cs1v | 122.66 (14) |
O3—Cs1—O4ii | 152.12 (19) | N2iii—Cs1—Cs1v | 84.9 (2) |
O2i—Cs1—O4ii | 67.7 (2) | N1iv—Cs1—Cs1v | 67.4 (2) |
O1—Cs1—O4ii | 75.9 (2) | O4v—Cs1—Cs1v | 39.12 (12) |
O4—Cs1—N2iii | 115.8 (3) | Cl2—Cs1—Cs1v | 89.94 (5) |
O3—Cs1—N2iii | 58.8 (2) | Cl1i—Cs1—Cs1v | 105.72 (5) |
O2i—Cs1—N2iii | 63.5 (3) | Cl2v—Cs1—Cs1v | 48.87 (4) |
O1—Cs1—N2iii | 133.5 (3) | C5—Cl1—Cs1vi | 100.8 (4) |
O4ii—Cs1—N2iii | 118.3 (3) | C6—Cl2—Cs1 | 103.9 (4) |
O4—Cs1—N1iv | 78.6 (3) | C6—Cl2—Cs1ii | 158.9 (4) |
O3—Cs1—N1iv | 61.3 (2) | Cs1—Cl2—Cs1ii | 78.80 (5) |
O2i—Cs1—N1iv | 137.0 (2) | C1—O1—Cs1 | 132.0 (7) |
O1—Cs1—N1iv | 63.1 (2) | C4—O2—Cs1vi | 133.9 (8) |
O4ii—Cs1—N1iv | 126.2 (2) | Cs1—O3—H3A | 125.5 |
N2iii—Cs1—N1iv | 115.1 (2) | Cs1—O3—H3B | 117.0 |
O4—Cs1—O4v | 79.7 (2) | H3A—O3—H3B | 104.7 |
O3—Cs1—O4v | 48.76 (19) | Cs1—O4—Cs1v | 100.9 (2) |
O2i—Cs1—O4v | 118.4 (2) | Cs1—O4—Cs1ii | 95.3 (2) |
O1—Cs1—O4v | 125.0 (2) | Cs1v—O4—Cs1ii | 156.9 (3) |
O4ii—Cs1—O4v | 156.9 (3) | Cs1—O4—H4A | 123.4 |
N2iii—Cs1—O4v | 56.6 (2) | Cs1v—O4—H4A | 114.7 |
N1iv—Cs1—O4v | 66.3 (2) | Cs1—O4—H4B | 123.7 |
O4—Cs1—Cl2 | 60.23 (15) | Cs1v—O4—H4B | 82.2 |
O3—Cs1—Cl2 | 119.40 (15) | Cs1ii—O4—H4B | 102.4 |
O2i—Cs1—Cl2 | 121.88 (17) | H4A—O4—H4B | 104.2 |
O1—Cs1—Cl2 | 49.57 (14) | C7—N1—Cs1iv | 133.4 (9) |
O4ii—Cs1—Cl2 | 65.82 (15) | C8—N2—Cs1vii | 139.9 (10) |
N2iii—Cs1—Cl2 | 174.6 (2) | O1—C1—C6 | 122.5 (10) |
N1iv—Cs1—Cl2 | 61.33 (18) | O1—C1—C2 | 121.5 (10) |
O4v—Cs1—Cl2 | 118.17 (14) | C6—C1—C2 | 116.0 (9) |
O4—Cs1—Cl1i | 96.69 (15) | C3—C2—C1 | 121.1 (10) |
O3—Cs1—Cl1i | 118.45 (15) | C3—C2—C7 | 121.9 (9) |
O2i—Cs1—Cl1i | 48.64 (16) | C1—C2—C7 | 116.9 (8) |
O1—Cs1—Cl1i | 123.67 (16) | C2—C3—C4 | 122.9 (10) |
O4ii—Cs1—Cl1i | 57.72 (15) | C2—C3—C8 | 120.9 (10) |
N2iii—Cs1—Cl1i | 62.1 (2) | C4—C3—C8 | 116.0 (8) |
N1iv—Cs1—Cl1i | 173.0 (2) | O2—C4—C5 | 123.4 (10) |
O4v—Cs1—Cl1i | 107.90 (13) | O2—C4—C3 | 122.1 (10) |
Cl2—Cs1—Cl1i | 120.92 (6) | C5—C4—C3 | 114.4 (9) |
O4—Cs1—Cl2v | 64.47 (15) | C6—C5—C4 | 124.0 (11) |
O3—Cs1—Cl2v | 95.84 (15) | C6—C5—Cl1 | 119.2 (9) |
O2i—Cs1—Cl2v | 98.23 (16) | C4—C5—Cl1 | 116.8 (8) |
O1—Cs1—Cl2v | 173.78 (14) | C5—C6—C1 | 121.5 (11) |
O4ii—Cs1—Cl2v | 102.64 (14) | C5—C6—Cl2 | 122.2 (10) |
N2iii—Cs1—Cl2v | 52.6 (2) | C1—C6—Cl2 | 116.3 (8) |
N1iv—Cs1—Cl2v | 114.3 (2) | N1—C7—C2 | 178.3 (13) |
O4v—Cs1—Cl2v | 55.39 (13) | N2—C8—C3 | 175.7 (12) |
| | | |
O4—Cs1—Cl2—C6 | 146.8 (5) | O4ii—Cs1—O4—Cs1ii | −0.66 (19) |
O3—Cs1—Cl2—C6 | 33.2 (5) | N2iii—Cs1—O4—Cs1ii | −119.3 (3) |
O2i—Cs1—Cl2—C6 | −76.3 (5) | N1iv—Cs1—O4—Cs1ii | 128.2 (2) |
O1—Cs1—Cl2—C6 | −24.2 (5) | O4v—Cs1—O4—Cs1ii | −164.1 (3) |
O4ii—Cs1—Cl2—C6 | −116.0 (5) | Cl2—Cs1—O4—Cs1ii | 64.84 (15) |
N1iv—Cs1—Cl2—C6 | 53.6 (5) | Cl1i—Cs1—O4—Cs1ii | −57.09 (16) |
O4v—Cs1—Cl2—C6 | 89.4 (5) | Cl2v—Cs1—O4—Cs1ii | −107.73 (18) |
Cl1i—Cs1—Cl2—C6 | −134.0 (4) | Cs1v—Cs1—O4—Cs1ii | −163.5 (3) |
Cl2v—Cs1—Cl2—C6 | 154.9 (4) | Cs1—O1—C1—C6 | −43.4 (16) |
Cs1v—Cs1—Cl2—C6 | 117.7 (4) | Cs1—O1—C1—C2 | 133.5 (9) |
O4—Cs1—Cl2—Cs1ii | −54.72 (18) | O1—C1—C2—C3 | 179.8 (11) |
O3—Cs1—Cl2—Cs1ii | −168.28 (16) | C6—C1—C2—C3 | −3.1 (16) |
O2i—Cs1—Cl2—Cs1ii | 82.24 (19) | O1—C1—C2—C7 | −5.4 (16) |
O1—Cs1—Cl2—Cs1ii | 134.4 (2) | C6—C1—C2—C7 | 171.6 (9) |
O4ii—Cs1—Cl2—Cs1ii | 42.49 (15) | C1—C2—C3—C4 | 0.4 (18) |
N1iv—Cs1—Cl2—Cs1ii | −147.8 (2) | C7—C2—C3—C4 | −174.1 (9) |
O4v—Cs1—Cl2—Cs1ii | −112.10 (14) | C1—C2—C3—C8 | 175.0 (8) |
Cl1i—Cs1—Cl2—Cs1ii | 24.56 (7) | C7—C2—C3—C8 | 0.5 (17) |
Cl2v—Cs1—Cl2—Cs1ii | −46.61 (11) | Cs1vi—O2—C4—C5 | 47.4 (17) |
Cs1v—Cs1—Cl2—Cs1ii | −83.81 (4) | Cs1vi—O2—C4—C3 | −129.9 (9) |
O4—Cs1—O1—C1 | 31.0 (10) | C2—C3—C4—O2 | −179.1 (12) |
O3—Cs1—O1—C1 | −93.5 (10) | C8—C3—C4—O2 | 6.0 (17) |
O2i—Cs1—O1—C1 | 177.1 (10) | C2—C3—C4—C5 | 3.4 (16) |
O4ii—Cs1—O1—C1 | 109.4 (10) | C8—C3—C4—C5 | −171.5 (9) |
N2iii—Cs1—O1—C1 | −134.8 (10) | O2—C4—C5—C6 | 177.9 (13) |
N1iv—Cs1—O1—C1 | −34.7 (10) | C3—C4—C5—C6 | −4.6 (17) |
O4v—Cs1—O1—C1 | −59.9 (11) | O2—C4—C5—Cl1 | −4.0 (16) |
Cl2—Cs1—O1—C1 | 39.3 (9) | C3—C4—C5—Cl1 | 173.5 (8) |
Cl1i—Cs1—O1—C1 | 143.4 (9) | Cs1vi—Cl1—C5—C6 | 156.6 (10) |
Cs1v—Cs1—O1—C1 | −11.1 (11) | Cs1vi—Cl1—C5—C4 | −21.5 (9) |
O3—Cs1—O4—Cs1v | −24.1 (3) | C4—C5—C6—C1 | 2 (2) |
O2i—Cs1—O4—Cs1v | 123.8 (3) | Cl1—C5—C6—C1 | −176.0 (8) |
O1—Cs1—O4—Cs1v | −124.4 (2) | C4—C5—C6—Cl2 | 178.0 (8) |
O4ii—Cs1—O4—Cs1v | 162.8 (3) | Cl1—C5—C6—Cl2 | 0.0 (16) |
N2iii—Cs1—O4—Cs1v | 44.2 (3) | O1—C1—C6—C5 | 179.0 (12) |
N1iv—Cs1—O4—Cs1v | −68.4 (2) | C2—C1—C6—C5 | 2.0 (16) |
O4v—Cs1—O4—Cs1v | −0.67 (5) | O1—C1—C6—Cl2 | 2.8 (15) |
Cl2—Cs1—O4—Cs1v | −131.7 (2) | C2—C1—C6—Cl2 | −174.2 (8) |
Cl1i—Cs1—O4—Cs1v | 106.39 (17) | Cs1—Cl2—C6—C5 | −153.1 (10) |
Cl2v—Cs1—O4—Cs1v | 55.74 (15) | Cs1ii—Cl2—C6—C5 | 111.9 (13) |
O3—Cs1—O4—Cs1ii | 172.44 (18) | Cs1—Cl2—C6—C1 | 23.2 (9) |
O2i—Cs1—O4—Cs1ii | −39.7 (4) | Cs1ii—Cl2—C6—C1 | −71.9 (15) |
O1—Cs1—O4—Cs1ii | 72.2 (2) | | |
Symmetry codes: (i) x, y, z+1; (ii) x−1/2, −y+3/2, −z+1; (iii) −x+1, −y+1, z+1; (iv) −x+1, −y+1, z; (v) x+1/2, −y+3/2, −z+1; (vi) x, y, z−1; (vii) −x+1, −y+1, z−1. |
Experimental details
| (LiDDQx2H2OxMe2O) | (RbDDQx2H2O_293K) | (RbDDQx2H2O_120K) | (CsDDQx2H2O_293K) |
Crystal data |
Chemical formula | C11H10Cl2LiN2O5 | C8H4Cl2N2O4Rb | C8H4Cl2N2O4Rb | C8H4Cl2CsN2O4 |
Mr | 328.06 | 348.50 | 348.50 | 395.94 |
Crystal system, space group | Triclinic, P1 | Orthorhombic, P21212 | Orthorhombic, P21212 | Orthorhombic, P21212 |
Temperature (K) | 120 | 293 | 120 | 293 |
a, b, c (Å) | 6.667 (5), 10.495 (5), 11.977 (5) | 6.5088 (2), 18.1788 (6), 9.6194 (2) | 6.4217 (2), 18.0295 (6), 9.5740 (2) | 6.6462 (1), 18.2212 (3), 9.7758 (2) |
α, β, γ (°) | 110.773 (5), 99.693 (5), 100.335 (5) | 90, 90, 90 | 90, 90, 90 | 90, 90, 90 |
V (Å3) | 745.9 (7) | 1138.19 (6) | 1108.48 (6) | 1183.87 (4) |
Z | 2 | 4 | 4 | 4 |
Radiation type | Cu Kα | Cu Kα | Cu Kα | Cu Kα |
µ (mm−1) | 4.11 | 10.39 | 10.67 | 28.64 |
Crystal size (mm) | 0.18 × 0.07 × 0.06 | 0.36 × 0.04 × 0.02 | 0.28 × 0.04 × 0.02 | 0.12 × 0.04 × 0.03 |
|
Data collection |
Diffractometer | Oxford Diffraction Xcalibur CCD, Ruby, Nova diffractometer | Oxford Diffraction Xcalibur CCD diffractometer | Oxford Diffraction Xcalibur CCD diffractometer | Oxford Diffraction Xcalibur CCD diffractometer |
Absorption correction | Multi-scan CrysAlis PRO (Agilent, 2012) | Multi-scan CrysAlis PRO (Agilent, 2012) | Multi-scan CrysAlis PRO (Agilent, 2012) | Multi-scan CrysAlis PRO (Agilent, 2012) |
Tmin, Tmax | 0.621, 1.000 | 0.182, 1.000 | 0.651, 1.000 | 0.500, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5368, 2981, 2204 | 3524, 2060, 1948 | 5137, 2194, 2103 | 3678, 2232, 2176 |
Rint | 0.071 | 0.031 | 0.043 | 0.036 |
(sin θ/λ)max (Å−1) | 0.632 | 0.629 | 0.630 | 0.628 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.1, 0.310, 1.08 | 0.042, 0.119, 1.03 | 0.041, 0.118, 1.12 | 0.037, 0.093, 1.07 |
No. of reflections | 2981 | 2060 | 2194 | 2232 |
No. of parameters | 257 | 155 | 155 | 154 |
No. of restraints | 91 | 0 | 0 | 0 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.63, −0.88 | 0.61, −0.82 | 0.72, −0.72 | 0.87, −0.87 |
Absolute structure | ? | Refined as an inversion twin (TWIN + BASF) | Refined as an inversion twin (TWIN + BASF)
The refined BASF value indicates that this model represents the *minor*
component. However, this model is retained since it has the same handedness
as all other structures in this paper (it can be overlaid directly with the
other structures and the DFT-optimized structures. | Flack (1983) |
Absolute structure parameter | ? | 0.46 (4) | 0.64 (4) | −0.016 (8) |
| (CsDDQx2H2O_120K) |
Crystal data |
Chemical formula | C8H4Cl2CsN2O4 |
Mr | 395.94 |
Crystal system, space group | Orthorhombic, P21212 |
Temperature (K) | 120 |
a, b, c (Å) | 6.5601 (3), 18.152 (1), 9.7345 (4) |
α, β, γ (°) | 90, 90, 90 |
V (Å3) | 1159.17 (10) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 29.25 |
Crystal size (mm) | 0.37 × 0.05 × 0.03 |
|
Data collection |
Diffractometer | Oxford Diffraction Xcalibur CCD diffractometer |
Absorption correction | Multi-scan CrysAlis PRO (Agilent, 2012) |
Tmin, Tmax | 0.300, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3404, 2051, 1953 |
Rint | 0.054 |
(sin θ/λ)max (Å−1) | 0.629 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.159, 1.06 |
No. of reflections | 2051 |
No. of parameters | 155 |
No. of restraints | 72 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.58, −1.34 |
Absolute structure | Refined as an inversion twin (TWIN + BASF) |
Absolute structure parameter | 0.283 (17) |
Hydrogen-bond geometry (Å, º) for (RbDDQx2H2O_293K) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3B···O1i | 0.95 | 1.94 | 2.822 (6) | 153.2 |
O3—H3A···O2ii | 0.95 | 1.98 | 2.901 (6) | 161.8 |
O4—H4A···O3iii | 0.95 | 1.86 | 2.807 (8) | 179.2 |
O4—H4B···Cl1iv | 0.95 | 2.59 | 3.527 (8) | 167.1 |
O4—H4B···N2v | 0.95 | 2.92 | 3.352 (9) | 109.1 |
Symmetry codes: (i) −x+1, −y+1, z; (ii) −x+1, −y+1, z+1; (iii) x−1/2, −y+3/2, −z+1; (iv) x+1/2, −y+3/2, −z; (v) −x+1/2, y+1/2, −z. |
Hydrogen-bond geometry (Å, º) for (RbDDQx2H2O_120K) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3B···O1i | 0.95 | 1.90 | 2.778 (6) | 152.6 |
O3—H3A···O2ii | 0.95 | 1.98 | 2.894 (6) | 161.9 |
O4—H4A···O3iii | 0.95 | 1.84 | 2.784 (6) | 177.0 |
O4—H4B···Cl1iv | 0.95 | 2.49 | 3.421 (4) | 166.9 |
O4—H4B···N2v | 0.95 | 2.82 | 3.228 (6) | 106.6 |
Symmetry codes: (i) −x+1, −y+1, z; (ii) −x+1, −y+1, z+1; (iii) x−1/2, −y+3/2, −z+1; (iv) x+1/2, −y+3/2, −z; (v) −x+1/2, y+1/2, −z. |
Hydrogen-bond geometry (Å, º) for (CsDDQx2H2O_293K) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3B···O1i | 0.95 | 1.89 | 2.803 (6) | 161.5 |
O3—H3A···O2ii | 0.95 | 1.96 | 2.902 (6) | 172.3 |
O4—H4A···O3iii | 0.95 | 1.86 | 2.785 (8) | 163.1 |
O4—H4B···Cl1iv | 0.95 | 2.56 | 3.479 (6) | 163.4 |
O4—H4B···N2v | 0.95 | 2.79 | 3.263 (9) | 111.5 |
Symmetry codes: (i) −x+1, −y+1, z; (ii) −x+1, −y+1, z+1; (iii) x−1/2, −y+3/2, −z+1; (iv) x+1/2, −y+3/2, −z; (v) −x+1/2, y+1/2, −z. |