Specific short contacts are important in crystal engineering. Hydrogen bonds have been particularly successful and together with halogen bonds can be useful for assembling small molecules or ions into crystals. The ionic constituents in the isomorphous 3,5-dichloropyridinium (3,5-diClPy) tetrahalometallates 3,5-dichloropyridinium tetrachloridozincate(II), (C
5H
4Cl
2N)
2[ZnCl
4] or (3,5-diClPy)
2ZnCl
4, 3,5-dichloropyridinium tetrabromidozincate(II), (C
5H
4Cl
2N)
2[ZnBr
4] or (3,5-diClPy)
2ZnBr
4, and 3,5-dichloropyridinium tetrabromidocobaltate(II), (C
5H
4Cl
2N)
2[CoBr
4] or (3,5-diClPy)
2CoBr
4, arrange according to favourable electrostatic interactions. Cations are preferably surrounded by anions and
vice versa; rare cation–cation contacts are associated with an antiparallel dipole orientation. N—H
X (
X = Cl and Br) hydrogen bonds and
XX halogen bonds compete as closest contacts between neighbouring residues. The former dominate in the title compounds; the four symmetrically independent pyridinium N—H groups in each compound act as donors in charge-assisted hydrogen bonds, with halogen ligands and the tetrahedral metallate anions as acceptors. The
M—
X coordinative bonds in the latter are significantly longer if the halide ligand is engaged in a classical
XH—N hydrogen bond. In all three solids, triangular halogen-bond interactions are observed. They might contribute to the stabilization of the structures, but even the shortest interhalogen contacts are only slightly shorter than the sum of the van der Waals radii.
Supporting information
CCDC references: 1544665; 1544664; 1544663
For all structures, data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2009); data reduction: SAINT-Plus (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015).
3,5-Dichloropyridinium tetrachloridozincate(II) (a)
top
Crystal data top
(C5H4Cl2N)2[ZnCl4] | Z = 4 |
Mr = 505.15 | F(000) = 992 |
Triclinic, P1 | Dx = 1.877 Mg m−3 |
a = 8.6181 (6) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.8068 (9) Å | Cell parameters from 9898 reflections |
c = 16.7622 (12) Å | θ = 2.5–30.6° |
α = 85.5267 (9)° | µ = 2.56 mm−1 |
β = 79.0539 (10)° | T = 100 K |
γ = 80.1701 (10)° | Block, colourless |
V = 1787.7 (2) Å3 | 0.22 × 0.17 × 0.15 mm |
Data collection top
Bruker D8 goniometer with APEX CCD detector diffractometer | 10232 independent reflections |
Radiation source: Incoatec microsource | 8944 reflections with I > 2σ(I) |
Multilayer optics monochromator | Rint = 0.030 |
ω scans | θmax = 30.8°, θmin = 1.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −12→12 |
Tmin = 0.550, Tmax = 0.746 | k = −18→17 |
27232 measured reflections | l = −23→22 |
Refinement top
Refinement on F2 | 4 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.029 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.075 | w = 1/[σ2(Fo2) + (0.0375P)2 + 0.486P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.001 |
10232 reflections | Δρmax = 0.66 e Å−3 |
391 parameters | Δρmin = −0.81 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Zn1 | 0.04124 (2) | 0.78927 (2) | 0.39906 (2) | 0.01146 (5) | |
Cl9 | 0.26668 (5) | 0.86528 (4) | 0.39903 (3) | 0.01472 (9) | |
Cl10 | −0.14829 (5) | 0.85629 (3) | 0.50523 (3) | 0.01354 (8) | |
Cl11 | 0.09664 (5) | 0.61035 (3) | 0.41480 (3) | 0.01247 (8) | |
Cl12 | −0.03922 (5) | 0.84000 (3) | 0.27916 (2) | 0.01314 (8) | |
Zn2 | 0.36013 (2) | 0.29703 (2) | 0.14760 (2) | 0.01090 (5) | |
Cl13 | 0.59505 (5) | 0.36103 (3) | 0.14726 (2) | 0.01451 (9) | |
Cl14 | 0.17331 (5) | 0.35504 (3) | 0.25770 (2) | 0.01274 (8) | |
Cl15 | 0.41474 (5) | 0.11842 (3) | 0.15994 (3) | 0.01330 (8) | |
Cl16 | 0.27101 (5) | 0.35377 (3) | 0.03059 (2) | 0.01191 (8) | |
Cl1 | 0.26683 (5) | 0.88582 (4) | 0.02446 (3) | 0.01907 (9) | |
Cl2 | 0.86632 (5) | 0.86925 (4) | 0.08192 (3) | 0.01723 (9) | |
N1 | 0.44948 (19) | 0.86663 (12) | 0.22309 (9) | 0.0150 (3) | |
H1 | 0.412 (3) | 0.8646 (17) | 0.2745 (10) | 0.018* | |
C1 | 0.3442 (2) | 0.87317 (14) | 0.17271 (11) | 0.0152 (3) | |
H1A | 0.2333 | 0.8754 | 0.1935 | 0.018* | |
C2 | 0.4009 (2) | 0.87664 (13) | 0.08998 (11) | 0.0137 (3) | |
C3 | 0.5630 (2) | 0.87447 (13) | 0.05965 (11) | 0.0125 (3) | |
H3A | 0.6026 | 0.8764 | 0.0028 | 0.015* | |
C4 | 0.6650 (2) | 0.86933 (14) | 0.11513 (11) | 0.0126 (3) | |
C5 | 0.6072 (2) | 0.86510 (14) | 0.19792 (11) | 0.0151 (3) | |
H5 | 0.6771 | 0.8612 | 0.2359 | 0.018* | |
Cl3 | 0.48206 (6) | 0.91805 (5) | 0.62077 (3) | 0.03215 (13) | |
Cl4 | 0.01348 (6) | 0.85565 (4) | 0.87638 (3) | 0.02460 (11) | |
N2 | 0.02787 (19) | 0.90136 (12) | 0.64179 (10) | 0.0156 (3) | |
H2 | −0.035 (2) | 0.9035 (18) | 0.6090 (12) | 0.019* | |
C6 | 0.1787 (2) | 0.91230 (14) | 0.61020 (11) | 0.0164 (4) | |
H6 | 0.2105 | 0.9249 | 0.5533 | 0.020* | |
C7 | 0.2875 (2) | 0.90490 (15) | 0.66191 (12) | 0.0168 (4) | |
C8 | 0.2407 (2) | 0.88611 (14) | 0.74520 (11) | 0.0155 (3) | |
H8 | 0.3152 | 0.8799 | 0.7811 | 0.019* | |
C9 | 0.0816 (2) | 0.87680 (14) | 0.77386 (11) | 0.0145 (3) | |
C10 | −0.0261 (2) | 0.88468 (14) | 0.72147 (11) | 0.0147 (3) | |
H10 | −0.1351 | 0.8785 | 0.7413 | 0.018* | |
Cl5 | 0.58818 (5) | 0.38973 (4) | −0.23486 (3) | 0.01754 (9) | |
Cl6 | 1.16900 (6) | 0.41530 (4) | −0.16871 (3) | 0.02303 (10) | |
N3 | 0.7563 (2) | 0.38242 (12) | −0.03267 (10) | 0.0157 (3) | |
H3 | 0.719 (3) | 0.3781 (17) | 0.0183 (10) | 0.019* | |
C11 | 0.6548 (2) | 0.38432 (14) | −0.08452 (12) | 0.0156 (4) | |
H11 | 0.5447 | 0.3810 | −0.0651 | 0.019* | |
C12 | 0.7146 (2) | 0.39120 (13) | −0.16679 (11) | 0.0133 (3) | |
C13 | 0.8745 (2) | 0.39961 (14) | −0.19524 (11) | 0.0136 (3) | |
H13 | 0.9160 | 0.4046 | −0.2519 | 0.016* | |
C14 | 0.9714 (2) | 0.40048 (14) | −0.13817 (11) | 0.0146 (3) | |
C15 | 0.9111 (2) | 0.39063 (14) | −0.05576 (11) | 0.0157 (4) | |
H15 | 0.9780 | 0.3897 | −0.0166 | 0.019* | |
Cl7 | 0.81474 (5) | 0.36432 (4) | 0.36786 (3) | 0.02234 (10) | |
Cl8 | 0.34307 (6) | 0.35201 (4) | 0.63139 (3) | 0.02176 (10) | |
N4 | 0.35093 (19) | 0.37563 (13) | 0.39696 (10) | 0.0164 (3) | |
H4 | 0.284 (2) | 0.3783 (17) | 0.3626 (12) | 0.020* | |
C16 | 0.5047 (2) | 0.37287 (15) | 0.36260 (11) | 0.0168 (4) | |
H16 | 0.5360 | 0.3760 | 0.3051 | 0.020* | |
C17 | 0.6175 (2) | 0.36545 (14) | 0.41234 (11) | 0.0151 (3) | |
C18 | 0.5707 (2) | 0.35942 (14) | 0.49646 (11) | 0.0149 (3) | |
H18 | 0.6470 | 0.3544 | 0.5313 | 0.018* | |
C19 | 0.4098 (2) | 0.36094 (14) | 0.52803 (11) | 0.0131 (3) | |
C20 | 0.2979 (2) | 0.37024 (14) | 0.47730 (11) | 0.0141 (3) | |
H20 | 0.1872 | 0.3727 | 0.4989 | 0.017* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn1 | 0.01202 (10) | 0.01198 (10) | 0.00960 (10) | −0.00156 (7) | −0.00063 (7) | 0.00023 (7) |
Cl9 | 0.01479 (19) | 0.0199 (2) | 0.00991 (19) | −0.00718 (16) | 0.00090 (15) | −0.00166 (15) |
Cl10 | 0.01211 (19) | 0.0162 (2) | 0.01127 (19) | −0.00156 (15) | 0.00111 (14) | −0.00354 (15) |
Cl11 | 0.01197 (18) | 0.01097 (18) | 0.01310 (19) | −0.00017 (14) | −0.00071 (14) | 0.00035 (14) |
Cl12 | 0.01343 (19) | 0.01568 (19) | 0.01026 (19) | −0.00194 (15) | −0.00345 (14) | 0.00205 (15) |
Zn2 | 0.01249 (10) | 0.01006 (10) | 0.00948 (10) | −0.00175 (7) | −0.00050 (7) | −0.00001 (7) |
Cl13 | 0.0154 (2) | 0.0198 (2) | 0.00902 (19) | −0.00795 (16) | 0.00117 (15) | −0.00195 (15) |
Cl14 | 0.01179 (18) | 0.01463 (19) | 0.01057 (19) | −0.00144 (14) | 0.00104 (14) | −0.00206 (15) |
Cl15 | 0.01467 (19) | 0.00950 (18) | 0.0150 (2) | −0.00072 (14) | −0.00224 (15) | 0.00025 (14) |
Cl16 | 0.01421 (19) | 0.01203 (18) | 0.00923 (18) | −0.00133 (14) | −0.00293 (14) | 0.00136 (14) |
Cl1 | 0.0155 (2) | 0.0210 (2) | 0.0219 (2) | −0.00470 (16) | −0.00650 (17) | 0.00312 (17) |
Cl2 | 0.01146 (19) | 0.0251 (2) | 0.0139 (2) | −0.00222 (16) | −0.00096 (15) | 0.00228 (17) |
N1 | 0.0198 (8) | 0.0122 (7) | 0.0105 (7) | −0.0024 (6) | 0.0028 (6) | 0.0011 (6) |
C1 | 0.0138 (8) | 0.0105 (8) | 0.0190 (9) | −0.0025 (6) | 0.0023 (7) | 0.0015 (7) |
C2 | 0.0157 (8) | 0.0077 (7) | 0.0176 (9) | −0.0013 (6) | −0.0033 (7) | 0.0000 (6) |
C3 | 0.0155 (8) | 0.0097 (8) | 0.0110 (8) | −0.0015 (6) | 0.0004 (6) | −0.0002 (6) |
C4 | 0.0126 (8) | 0.0116 (8) | 0.0122 (8) | −0.0018 (6) | 0.0011 (6) | −0.0005 (6) |
C5 | 0.0190 (9) | 0.0126 (8) | 0.0135 (9) | −0.0021 (7) | −0.0029 (7) | 0.0008 (6) |
Cl3 | 0.0155 (2) | 0.0511 (3) | 0.0268 (3) | −0.0098 (2) | 0.00344 (19) | 0.0089 (2) |
Cl4 | 0.0206 (2) | 0.0403 (3) | 0.0112 (2) | −0.0064 (2) | 0.00051 (17) | 0.00352 (19) |
N2 | 0.0190 (8) | 0.0153 (7) | 0.0140 (8) | −0.0025 (6) | −0.0068 (6) | −0.0002 (6) |
C6 | 0.0208 (9) | 0.0140 (8) | 0.0115 (8) | −0.0006 (7) | 0.0011 (7) | 0.0012 (6) |
C7 | 0.0129 (8) | 0.0185 (9) | 0.0168 (9) | −0.0029 (7) | 0.0019 (7) | 0.0022 (7) |
C8 | 0.0151 (8) | 0.0167 (9) | 0.0146 (9) | −0.0027 (7) | −0.0031 (7) | 0.0012 (7) |
C9 | 0.0169 (9) | 0.0147 (8) | 0.0109 (8) | −0.0031 (7) | 0.0003 (6) | 0.0008 (6) |
C10 | 0.0139 (8) | 0.0142 (8) | 0.0152 (9) | −0.0024 (6) | −0.0005 (7) | −0.0003 (7) |
Cl5 | 0.0165 (2) | 0.0171 (2) | 0.0200 (2) | −0.00340 (16) | −0.00535 (17) | −0.00050 (17) |
Cl6 | 0.0148 (2) | 0.0381 (3) | 0.0162 (2) | −0.00791 (19) | −0.00123 (17) | 0.00305 (19) |
N3 | 0.0218 (8) | 0.0134 (7) | 0.0101 (7) | −0.0040 (6) | 0.0023 (6) | −0.0001 (6) |
C11 | 0.0172 (9) | 0.0097 (8) | 0.0183 (9) | −0.0025 (6) | 0.0016 (7) | −0.0015 (7) |
C12 | 0.0146 (8) | 0.0088 (8) | 0.0167 (9) | −0.0017 (6) | −0.0032 (7) | −0.0004 (6) |
C13 | 0.0163 (8) | 0.0109 (8) | 0.0125 (8) | −0.0011 (6) | −0.0012 (6) | 0.0000 (6) |
C14 | 0.0128 (8) | 0.0142 (8) | 0.0153 (9) | −0.0016 (6) | 0.0004 (7) | 0.0000 (7) |
C15 | 0.0186 (9) | 0.0137 (8) | 0.0142 (9) | −0.0020 (7) | −0.0021 (7) | −0.0003 (7) |
Cl7 | 0.0132 (2) | 0.0240 (2) | 0.0256 (2) | −0.00157 (17) | 0.00490 (17) | 0.00111 (19) |
Cl8 | 0.0210 (2) | 0.0317 (3) | 0.0108 (2) | −0.00418 (19) | 0.00029 (17) | 0.00184 (18) |
N4 | 0.0171 (8) | 0.0184 (8) | 0.0141 (8) | −0.0019 (6) | −0.0058 (6) | 0.0013 (6) |
C16 | 0.0182 (9) | 0.0160 (9) | 0.0132 (9) | 0.0009 (7) | 0.0012 (7) | −0.0006 (7) |
C17 | 0.0123 (8) | 0.0141 (8) | 0.0166 (9) | −0.0010 (6) | 0.0010 (7) | 0.0016 (7) |
C18 | 0.0137 (8) | 0.0154 (8) | 0.0154 (9) | −0.0020 (7) | −0.0036 (7) | 0.0022 (7) |
C19 | 0.0147 (8) | 0.0131 (8) | 0.0106 (8) | −0.0018 (6) | −0.0007 (6) | 0.0007 (6) |
C20 | 0.0133 (8) | 0.0129 (8) | 0.0152 (9) | −0.0025 (6) | −0.0002 (7) | 0.0005 (6) |
Geometric parameters (Å, º) top
Zn1—Cl12 | 2.2615 (5) | C8—C9 | 1.386 (2) |
Zn1—Cl11 | 2.2646 (5) | C8—H8 | 0.9500 |
Zn1—Cl10 | 2.2863 (5) | C9—C10 | 1.381 (3) |
Zn1—Cl9 | 2.3168 (5) | C10—H10 | 0.9500 |
Zn2—Cl15 | 2.2566 (5) | Cl5—C12 | 1.7236 (19) |
Zn2—Cl16 | 2.2636 (5) | Cl6—C14 | 1.7211 (18) |
Zn2—Cl14 | 2.2863 (5) | N3—C15 | 1.336 (2) |
Zn2—Cl13 | 2.3091 (5) | N3—C11 | 1.341 (2) |
Cl1—C2 | 1.7237 (19) | N3—H3 | 0.854 (15) |
Cl2—C4 | 1.7181 (18) | C11—C12 | 1.379 (3) |
N1—C1 | 1.340 (2) | C11—H11 | 0.9500 |
N1—C5 | 1.341 (2) | C12—C13 | 1.390 (2) |
N1—H1 | 0.860 (15) | C13—C14 | 1.386 (3) |
C1—C2 | 1.380 (3) | C13—H13 | 0.9500 |
C1—H1A | 0.9500 | C14—C15 | 1.385 (2) |
C2—C3 | 1.389 (2) | C15—H15 | 0.9500 |
C3—C4 | 1.387 (2) | Cl7—C17 | 1.7199 (18) |
C3—H3A | 0.9500 | Cl8—C19 | 1.7201 (18) |
C4—C5 | 1.383 (2) | N4—C16 | 1.337 (2) |
C5—H5 | 0.9500 | N4—C20 | 1.338 (2) |
Cl3—C7 | 1.7186 (19) | N4—H4 | 0.886 (15) |
Cl4—C9 | 1.7234 (18) | C16—C17 | 1.383 (3) |
N2—C6 | 1.333 (2) | C16—H16 | 0.9500 |
N2—C10 | 1.341 (2) | C17—C18 | 1.391 (3) |
N2—H2 | 0.841 (15) | C18—C19 | 1.385 (2) |
C6—C7 | 1.381 (3) | C18—H18 | 0.9500 |
C6—H6 | 0.9500 | C19—C20 | 1.387 (2) |
C7—C8 | 1.392 (3) | C20—H20 | 0.9500 |
| | | |
Cl12—Zn1—Cl11 | 111.420 (17) | C10—C9—C8 | 121.15 (17) |
Cl12—Zn1—Cl10 | 110.664 (18) | C10—C9—Cl4 | 118.38 (14) |
Cl11—Zn1—Cl10 | 110.214 (17) | C8—C9—Cl4 | 120.47 (14) |
Cl12—Zn1—Cl9 | 106.721 (17) | N2—C10—C9 | 118.01 (17) |
Cl11—Zn1—Cl9 | 110.837 (17) | N2—C10—H10 | 121.0 |
Cl10—Zn1—Cl9 | 106.835 (17) | C9—C10—H10 | 121.0 |
Cl15—Zn2—Cl16 | 112.014 (17) | C15—N3—C11 | 123.98 (16) |
Cl15—Zn2—Cl14 | 108.093 (17) | C15—N3—H3 | 118.0 (15) |
Cl16—Zn2—Cl14 | 110.582 (17) | C11—N3—H3 | 118.0 (15) |
Cl15—Zn2—Cl13 | 107.358 (17) | N3—C11—C12 | 118.21 (17) |
Cl16—Zn2—Cl13 | 108.789 (17) | N3—C11—H11 | 120.9 |
Cl14—Zn2—Cl13 | 109.945 (17) | C12—C11—H11 | 120.9 |
C1—N1—C5 | 123.88 (16) | C11—C12—C13 | 120.92 (17) |
C1—N1—H1 | 117.2 (15) | C11—C12—Cl5 | 119.22 (14) |
C5—N1—H1 | 118.9 (15) | C13—C12—Cl5 | 119.86 (14) |
N1—C1—C2 | 118.41 (16) | C14—C13—C12 | 117.74 (16) |
N1—C1—H1A | 120.8 | C14—C13—H13 | 121.1 |
C2—C1—H1A | 120.8 | C12—C13—H13 | 121.1 |
C1—C2—C3 | 120.78 (17) | C15—C14—C13 | 120.82 (17) |
C1—C2—Cl1 | 118.93 (14) | C15—C14—Cl6 | 118.79 (14) |
C3—C2—Cl1 | 120.29 (14) | C13—C14—Cl6 | 120.39 (14) |
C4—C3—C2 | 117.85 (16) | N3—C15—C14 | 118.28 (17) |
C4—C3—H3A | 121.1 | N3—C15—H15 | 120.9 |
C2—C3—H3A | 121.1 | C14—C15—H15 | 120.9 |
C5—C4—C3 | 120.92 (16) | C16—N4—C20 | 124.11 (17) |
C5—C4—Cl2 | 118.72 (14) | C16—N4—H4 | 115.3 (15) |
C3—C4—Cl2 | 120.36 (13) | C20—N4—H4 | 120.5 (15) |
N1—C5—C4 | 118.16 (17) | N4—C16—C17 | 118.76 (17) |
N1—C5—H5 | 120.9 | N4—C16—H16 | 120.6 |
C4—C5—H5 | 120.9 | C17—C16—H16 | 120.6 |
C6—N2—C10 | 123.99 (17) | C16—C17—C18 | 120.15 (16) |
C6—N2—H2 | 117.0 (16) | C16—C17—Cl7 | 118.59 (14) |
C10—N2—H2 | 119.0 (16) | C18—C17—Cl7 | 121.27 (14) |
N2—C6—C7 | 118.61 (17) | C19—C18—C17 | 118.11 (17) |
N2—C6—H6 | 120.7 | C19—C18—H18 | 120.9 |
C7—C6—H6 | 120.7 | C17—C18—H18 | 120.9 |
C6—C7—C8 | 120.61 (17) | C18—C19—C20 | 120.99 (17) |
C6—C7—Cl3 | 118.40 (14) | C18—C19—Cl8 | 120.83 (14) |
C8—C7—Cl3 | 120.98 (15) | C20—C19—Cl8 | 118.18 (14) |
C9—C8—C7 | 117.63 (17) | N4—C20—C19 | 117.86 (16) |
C9—C8—H8 | 121.2 | N4—C20—H20 | 121.1 |
C7—C8—H8 | 121.2 | C19—C20—H20 | 121.1 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl9 | 0.86 (2) | 2.22 (2) | 3.0686 (16) | 168 (2) |
N2—H2···Cl10 | 0.84 (2) | 2.31 (2) | 3.1150 (16) | 160 (2) |
N3—H3···Cl13 | 0.85 (2) | 2.23 (2) | 3.0842 (16) | 173 (2) |
N4—H4···Cl14 | 0.89 (2) | 2.21 (2) | 3.0744 (17) | 164 (2) |
3,5-Dichloropyridinium tetrabromidozincate(II) (b)
top
Crystal data top
(C5H4Cl2N)2[ZnBr4] | Z = 4 |
Mr = 682.99 | F(000) = 1280 |
Triclinic, P1 | Dx = 2.324 Mg m−3 |
a = 8.8739 (15) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 13.469 (2) Å | Cell parameters from 4319 reflections |
c = 17.284 (3) Å | θ = 2.5–29.4° |
α = 79.539 (3)° | µ = 9.99 mm−1 |
β = 78.468 (2)° | T = 100 K |
γ = 76.968 (2)° | Plate, colourless |
V = 1951.7 (6) Å3 | 0.22 × 0.21 × 0.13 mm |
Data collection top
Bruker D8 goniometer with APEX CCD detector diffractometer | 11250 independent reflections |
Radiation source: Incoatec microsource | 8368 reflections with I > 2σ(I) |
Multilayer optics monochromator | Rint = 0.074 |
ω scans | θmax = 30.9°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −12→12 |
Tmin = 0.395, Tmax = 0.746 | k = −19→19 |
29870 measured reflections | l = −24→24 |
Refinement top
Refinement on F2 | 5 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.046 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.116 | w = 1/[σ2(Fo2) + (0.010P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
11250 reflections | Δρmax = 1.27 e Å−3 |
391 parameters | Δρmin = −1.99 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Zn1 | 0.05958 (6) | 0.79171 (4) | 0.40526 (3) | 0.01201 (12) | |
Br1 | 0.28751 (5) | 0.86665 (4) | 0.40065 (3) | 0.01551 (11) | |
Br2 | −0.13984 (5) | 0.85914 (4) | 0.51055 (3) | 0.01464 (11) | |
Br3 | 0.12069 (5) | 0.60734 (4) | 0.43019 (3) | 0.01329 (10) | |
Br4 | −0.03055 (5) | 0.84370 (4) | 0.27939 (3) | 0.01509 (11) | |
Zn2 | 0.34879 (6) | 0.29571 (4) | 0.13959 (3) | 0.01176 (12) | |
Br5 | 0.58451 (5) | 0.36099 (4) | 0.13805 (3) | 0.01411 (11) | |
Br6 | 0.15329 (5) | 0.34651 (4) | 0.25230 (3) | 0.01369 (10) | |
Br7 | 0.41323 (5) | 0.11121 (4) | 0.15856 (3) | 0.01391 (10) | |
Br8 | 0.25190 (5) | 0.36278 (4) | 0.01706 (3) | 0.01522 (11) | |
Cl1 | 0.27894 (14) | 0.87957 (11) | 0.03017 (8) | 0.0232 (3) | |
Cl2 | 0.86734 (13) | 0.86474 (10) | 0.07772 (7) | 0.0195 (3) | |
N1 | 0.4681 (5) | 0.8560 (3) | 0.2207 (2) | 0.0166 (9) | |
H1 | 0.435 (6) | 0.849 (4) | 0.2719 (13) | 0.020* | |
C1 | 0.3621 (5) | 0.8631 (4) | 0.1735 (3) | 0.0173 (10) | |
H1A | 0.2548 | 0.8640 | 0.1954 | 0.021* | |
C2 | 0.4136 (6) | 0.8693 (4) | 0.0917 (3) | 0.0162 (10) | |
C3 | 0.5702 (5) | 0.8686 (3) | 0.0606 (3) | 0.0137 (9) | |
H3A | 0.6062 | 0.8722 | 0.0048 | 0.016* | |
C4 | 0.6725 (5) | 0.8627 (4) | 0.1123 (3) | 0.0150 (10) | |
C5 | 0.6208 (6) | 0.8550 (4) | 0.1941 (3) | 0.0147 (10) | |
H5 | 0.6915 | 0.8492 | 0.2300 | 0.018* | |
Cl3 | 0.47673 (15) | 0.91479 (12) | 0.61979 (9) | 0.0309 (3) | |
Cl4 | 0.02785 (16) | 0.86516 (13) | 0.87811 (8) | 0.0313 (3) | |
N2 | 0.0356 (5) | 0.8988 (3) | 0.6483 (2) | 0.0178 (9) | |
H2 | −0.035 (4) | 0.899 (4) | 0.621 (3) | 0.021* | |
C6 | 0.1816 (6) | 0.9077 (4) | 0.6145 (3) | 0.0174 (10) | |
H6 | 0.2111 | 0.9175 | 0.5581 | 0.021* | |
C7 | 0.2886 (5) | 0.9022 (4) | 0.6637 (3) | 0.0153 (10) | |
C8 | 0.2455 (6) | 0.8881 (4) | 0.7453 (3) | 0.0178 (10) | |
H8 | 0.3190 | 0.8843 | 0.7794 | 0.021* | |
C9 | 0.0920 (6) | 0.8794 (4) | 0.7764 (3) | 0.0170 (10) | |
C10 | −0.0152 (6) | 0.8857 (4) | 0.7275 (3) | 0.0161 (10) | |
H10 | −0.1211 | 0.8810 | 0.7487 | 0.019* | |
Cl5 | 0.56835 (14) | 0.39666 (10) | −0.24218 (7) | 0.0203 (3) | |
Cl6 | 1.14594 (14) | 0.40033 (11) | −0.18870 (7) | 0.0212 (3) | |
N3 | 0.7436 (5) | 0.3859 (3) | −0.0496 (2) | 0.0148 (8) | |
H3 | 0.699 (5) | 0.381 (4) | −0.0001 (14) | 0.018* | |
C11 | 0.6414 (6) | 0.3890 (4) | −0.0981 (3) | 0.0166 (10) | |
H11 | 0.5338 | 0.3892 | −0.0775 | 0.020* | |
C12 | 0.6969 (5) | 0.3921 (4) | −0.1785 (3) | 0.0135 (9) | |
C13 | 0.8534 (5) | 0.3952 (4) | −0.2087 (3) | 0.0140 (9) | |
H13 | 0.8917 | 0.3983 | −0.2643 | 0.017* | |
C14 | 0.9526 (5) | 0.3935 (4) | −0.1552 (3) | 0.0128 (9) | |
C15 | 0.8960 (6) | 0.3888 (4) | −0.0750 (3) | 0.0150 (10) | |
H15 | 0.9632 | 0.3877 | −0.0382 | 0.018* | |
Cl7 | 0.78049 (14) | 0.36013 (11) | 0.35036 (8) | 0.0255 (3) | |
Cl8 | 0.34137 (16) | 0.37027 (12) | 0.61751 (7) | 0.0266 (3) | |
N4 | 0.3329 (5) | 0.3542 (3) | 0.3957 (2) | 0.0164 (9) | |
H4 | 0.262 (5) | 0.347 (4) | 0.370 (3) | 0.020* | |
C16 | 0.4796 (6) | 0.3541 (4) | 0.3566 (3) | 0.0170 (10) | |
H16 | 0.5054 | 0.3501 | 0.3011 | 0.020* | |
C17 | 0.5923 (5) | 0.3599 (4) | 0.3999 (3) | 0.0160 (10) | |
C18 | 0.5531 (5) | 0.3653 (4) | 0.4810 (3) | 0.0143 (10) | |
H18 | 0.6293 | 0.3701 | 0.5110 | 0.017* | |
C19 | 0.3989 (5) | 0.3634 (4) | 0.5171 (3) | 0.0142 (10) | |
C20 | 0.2872 (5) | 0.3596 (4) | 0.4739 (3) | 0.0148 (10) | |
H20 | 0.1811 | 0.3607 | 0.4985 | 0.018* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn1 | 0.0136 (3) | 0.0098 (3) | 0.0128 (3) | −0.0051 (2) | −0.0011 (2) | 0.0003 (2) |
Br1 | 0.0174 (2) | 0.0188 (3) | 0.0130 (2) | −0.0118 (2) | 0.00054 (17) | −0.00235 (19) |
Br2 | 0.0141 (2) | 0.0144 (2) | 0.0161 (2) | −0.00621 (19) | 0.00062 (17) | −0.00318 (19) |
Br3 | 0.0129 (2) | 0.0095 (2) | 0.0174 (2) | −0.00426 (18) | −0.00251 (17) | 0.00100 (18) |
Br4 | 0.0158 (2) | 0.0151 (2) | 0.0150 (2) | −0.00501 (19) | −0.00526 (18) | 0.00182 (19) |
Zn2 | 0.0141 (3) | 0.0099 (3) | 0.0116 (3) | −0.0055 (2) | −0.0017 (2) | 0.0007 (2) |
Br5 | 0.0154 (2) | 0.0174 (3) | 0.0112 (2) | −0.00964 (19) | −0.00089 (17) | 0.00025 (18) |
Br6 | 0.0123 (2) | 0.0145 (2) | 0.0147 (2) | −0.00533 (18) | −0.00061 (17) | −0.00167 (18) |
Br7 | 0.0151 (2) | 0.0092 (2) | 0.0176 (2) | −0.00415 (18) | −0.00310 (18) | 0.00017 (18) |
Br8 | 0.0173 (2) | 0.0151 (3) | 0.0147 (2) | −0.00643 (19) | −0.00597 (18) | 0.00190 (19) |
Cl1 | 0.0181 (6) | 0.0250 (7) | 0.0284 (7) | −0.0092 (5) | −0.0099 (5) | 0.0036 (6) |
Cl2 | 0.0143 (5) | 0.0265 (7) | 0.0168 (6) | −0.0066 (5) | −0.0019 (4) | 0.0016 (5) |
N1 | 0.021 (2) | 0.013 (2) | 0.0127 (19) | −0.0057 (17) | 0.0034 (17) | 0.0029 (17) |
C1 | 0.011 (2) | 0.007 (2) | 0.030 (3) | 0.0003 (18) | 0.000 (2) | 0.002 (2) |
C2 | 0.019 (2) | 0.009 (2) | 0.022 (2) | −0.0032 (19) | −0.006 (2) | −0.001 (2) |
C3 | 0.021 (2) | 0.004 (2) | 0.015 (2) | −0.0002 (18) | −0.0047 (19) | −0.0002 (18) |
C4 | 0.011 (2) | 0.009 (2) | 0.022 (2) | −0.0047 (18) | 0.0037 (18) | −0.0003 (19) |
C5 | 0.019 (2) | 0.010 (2) | 0.013 (2) | −0.0028 (19) | −0.0018 (18) | 0.0013 (19) |
Cl3 | 0.0155 (6) | 0.0355 (9) | 0.0363 (8) | −0.0108 (6) | 0.0062 (5) | 0.0043 (6) |
Cl4 | 0.0295 (7) | 0.0478 (10) | 0.0141 (6) | −0.0099 (7) | 0.0004 (5) | 0.0006 (6) |
N2 | 0.020 (2) | 0.018 (2) | 0.018 (2) | −0.0066 (18) | −0.0063 (17) | −0.0013 (18) |
C6 | 0.022 (3) | 0.012 (3) | 0.015 (2) | −0.003 (2) | 0.0007 (19) | 0.0007 (19) |
C7 | 0.009 (2) | 0.012 (2) | 0.022 (2) | −0.0050 (18) | 0.0013 (18) | 0.004 (2) |
C8 | 0.016 (2) | 0.017 (3) | 0.023 (3) | −0.008 (2) | −0.007 (2) | 0.001 (2) |
C9 | 0.018 (2) | 0.017 (3) | 0.013 (2) | −0.004 (2) | 0.0017 (18) | 0.002 (2) |
C10 | 0.013 (2) | 0.015 (3) | 0.019 (2) | −0.0085 (19) | 0.0036 (18) | −0.001 (2) |
Cl5 | 0.0219 (6) | 0.0174 (6) | 0.0252 (6) | −0.0088 (5) | −0.0091 (5) | 0.0000 (5) |
Cl6 | 0.0141 (6) | 0.0284 (7) | 0.0190 (6) | −0.0062 (5) | −0.0014 (5) | 0.0027 (5) |
N3 | 0.019 (2) | 0.012 (2) | 0.0119 (19) | −0.0050 (17) | 0.0017 (16) | −0.0003 (17) |
C11 | 0.018 (2) | 0.010 (2) | 0.022 (2) | −0.0060 (19) | −0.001 (2) | 0.001 (2) |
C12 | 0.019 (2) | 0.008 (2) | 0.013 (2) | −0.0051 (19) | −0.0040 (18) | 0.0026 (18) |
C13 | 0.019 (2) | 0.010 (2) | 0.015 (2) | −0.0053 (19) | −0.0037 (18) | 0.0000 (18) |
C14 | 0.016 (2) | 0.007 (2) | 0.015 (2) | −0.0031 (18) | −0.0037 (18) | 0.0026 (18) |
C15 | 0.020 (2) | 0.010 (2) | 0.014 (2) | −0.0022 (19) | −0.0040 (19) | 0.0011 (19) |
Cl7 | 0.0147 (6) | 0.0240 (7) | 0.0338 (7) | −0.0081 (5) | 0.0094 (5) | −0.0031 (6) |
Cl8 | 0.0286 (7) | 0.0360 (8) | 0.0142 (6) | −0.0074 (6) | 0.0009 (5) | −0.0050 (6) |
N4 | 0.017 (2) | 0.014 (2) | 0.022 (2) | −0.0037 (17) | −0.0103 (17) | −0.0026 (18) |
C16 | 0.022 (3) | 0.014 (3) | 0.012 (2) | −0.005 (2) | 0.0008 (19) | 0.0029 (19) |
C17 | 0.013 (2) | 0.013 (2) | 0.021 (2) | −0.0069 (19) | 0.0016 (19) | 0.000 (2) |
C18 | 0.015 (2) | 0.008 (2) | 0.021 (2) | −0.0084 (18) | −0.0056 (19) | 0.0039 (19) |
C19 | 0.016 (2) | 0.014 (2) | 0.011 (2) | −0.0028 (19) | −0.0037 (18) | 0.0043 (19) |
C20 | 0.014 (2) | 0.006 (2) | 0.022 (2) | −0.0039 (18) | 0.0018 (19) | −0.0016 (19) |
Geometric parameters (Å, º) top
Zn1—Br3 | 2.3967 (8) | C8—C9 | 1.384 (6) |
Zn1—Br4 | 2.3986 (8) | C8—H8 | 0.9500 |
Zn1—Br2 | 2.4198 (7) | C9—C10 | 1.374 (7) |
Zn1—Br1 | 2.4379 (7) | C10—H10 | 0.9500 |
Zn2—Br8 | 2.3923 (8) | Cl5—C12 | 1.721 (5) |
Zn2—Br7 | 2.3975 (8) | Cl6—C14 | 1.715 (5) |
Zn2—Br6 | 2.4228 (7) | N3—C11 | 1.342 (6) |
Zn2—Br5 | 2.4389 (7) | N3—C15 | 1.343 (6) |
Cl1—C2 | 1.721 (5) | N3—H3 | 0.866 (19) |
Cl2—C4 | 1.717 (5) | C11—C12 | 1.375 (6) |
N1—C5 | 1.339 (6) | C11—H11 | 0.9500 |
N1—C1 | 1.340 (6) | C12—C13 | 1.389 (6) |
N1—H1 | 0.870 (19) | C13—C14 | 1.392 (6) |
C1—C2 | 1.389 (7) | C13—H13 | 0.9500 |
C1—H1A | 0.9500 | C14—C15 | 1.372 (6) |
C2—C3 | 1.385 (7) | C15—H15 | 0.9500 |
C3—C4 | 1.377 (6) | Cl7—C17 | 1.718 (5) |
C3—H3A | 0.9500 | Cl8—C19 | 1.722 (5) |
C4—C5 | 1.388 (6) | N4—C16 | 1.341 (6) |
C5—H5 | 0.9500 | N4—C20 | 1.343 (6) |
Cl3—C7 | 1.722 (5) | N4—H4 | 0.867 (19) |
Cl4—C9 | 1.725 (5) | C16—C17 | 1.386 (7) |
N2—C6 | 1.333 (6) | C16—H16 | 0.9500 |
N2—C10 | 1.344 (6) | C17—C18 | 1.386 (7) |
N2—H2 | 0.850 (14) | C18—C19 | 1.389 (6) |
C6—C7 | 1.378 (7) | C18—H18 | 0.9500 |
C6—H6 | 0.9500 | C19—C20 | 1.368 (6) |
C7—C8 | 1.375 (7) | C20—H20 | 0.9500 |
| | | |
Br3—Zn1—Br4 | 108.73 (3) | C10—C9—C8 | 121.2 (4) |
Br3—Zn1—Br2 | 110.52 (3) | C10—C9—Cl4 | 118.0 (4) |
Br4—Zn1—Br2 | 110.15 (3) | C8—C9—Cl4 | 120.7 (4) |
Br3—Zn1—Br1 | 111.83 (3) | N2—C10—C9 | 117.4 (4) |
Br4—Zn1—Br1 | 108.71 (3) | N2—C10—H10 | 121.3 |
Br2—Zn1—Br1 | 106.87 (3) | C9—C10—H10 | 121.3 |
Br8—Zn2—Br7 | 111.71 (3) | C11—N3—C15 | 124.0 (4) |
Br8—Zn2—Br6 | 110.67 (3) | C11—N3—H3 | 111 (3) |
Br7—Zn2—Br6 | 107.25 (3) | C15—N3—H3 | 125 (3) |
Br8—Zn2—Br5 | 109.17 (3) | N3—C11—C12 | 118.1 (4) |
Br7—Zn2—Br5 | 108.53 (3) | N3—C11—H11 | 121.0 |
Br6—Zn2—Br5 | 109.46 (3) | C12—C11—H11 | 121.0 |
C5—N1—C1 | 124.2 (4) | C11—C12—C13 | 120.7 (4) |
C5—N1—H1 | 119 (3) | C11—C12—Cl5 | 119.1 (4) |
C1—N1—H1 | 117 (3) | C13—C12—Cl5 | 120.1 (4) |
N1—C1—C2 | 118.1 (4) | C12—C13—C14 | 118.2 (4) |
N1—C1—H1A | 120.9 | C12—C13—H13 | 120.9 |
C2—C1—H1A | 120.9 | C14—C13—H13 | 120.9 |
C3—C2—C1 | 120.4 (4) | C15—C14—C13 | 120.4 (4) |
C3—C2—Cl1 | 120.8 (4) | C15—C14—Cl6 | 119.0 (4) |
C1—C2—Cl1 | 118.8 (4) | C13—C14—Cl6 | 120.6 (4) |
C4—C3—C2 | 118.6 (4) | N3—C15—C14 | 118.5 (4) |
C4—C3—H3A | 120.7 | N3—C15—H15 | 120.7 |
C2—C3—H3A | 120.7 | C14—C15—H15 | 120.7 |
C3—C4—C5 | 120.8 (4) | C16—N4—C20 | 124.6 (4) |
C3—C4—Cl2 | 121.1 (4) | C16—N4—H4 | 119 (3) |
C5—C4—Cl2 | 118.1 (4) | C20—N4—H4 | 117 (3) |
N1—C5—C4 | 117.9 (4) | N4—C16—C17 | 117.9 (4) |
N1—C5—H5 | 121.0 | N4—C16—H16 | 121.0 |
C4—C5—H5 | 121.0 | C17—C16—H16 | 121.0 |
C6—N2—C10 | 124.5 (4) | C16—C17—C18 | 120.5 (4) |
C6—N2—H2 | 122 (4) | C16—C17—Cl7 | 118.3 (4) |
C10—N2—H2 | 113 (4) | C18—C17—Cl7 | 121.3 (4) |
N2—C6—C7 | 118.1 (4) | C17—C18—C19 | 118.0 (4) |
N2—C6—H6 | 121.0 | C17—C18—H18 | 121.0 |
C7—C6—H6 | 121.0 | C19—C18—H18 | 121.0 |
C8—C7—C6 | 120.8 (4) | C20—C19—C18 | 121.5 (4) |
C8—C7—Cl3 | 121.3 (4) | C20—C19—Cl8 | 117.9 (4) |
C6—C7—Cl3 | 117.9 (4) | C18—C19—Cl8 | 120.6 (4) |
C7—C8—C9 | 118.1 (4) | N4—C20—C19 | 117.6 (4) |
C7—C8—H8 | 121.0 | N4—C20—H20 | 121.2 |
C9—C8—H8 | 121.0 | C19—C20—H20 | 121.2 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Br1 | 0.87 (2) | 2.37 (2) | 3.214 (4) | 164 (5) |
N2—H2···Br2 | 0.85 (1) | 2.48 (3) | 3.271 (4) | 156 (5) |
N3—H3···Br5 | 0.87 (2) | 2.39 (2) | 3.257 (4) | 177 (5) |
N4—H4···Br6 | 0.87 (2) | 2.42 (3) | 3.231 (4) | 156 (5) |
3,5-Dichloropyridinium tetrabromidocobaltate(II) (c)
top
Crystal data top
(C5H4Cl2N)2[CoBr4] | Z = 4 |
Mr = 676.55 | F(000) = 1268 |
Triclinic, P1 | Dx = 2.302 Mg m−3 |
a = 8.8698 (9) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 13.4808 (13) Å | Cell parameters from 4844 reflections |
c = 17.2853 (17) Å | θ = 2.5–30.2° |
α = 79.5702 (15)° | µ = 9.61 mm−1 |
β = 78.4951 (14)° | T = 100 K |
γ = 76.8616 (14)° | Block, blue |
V = 1952.3 (3) Å3 | 0.22 × 0.17 × 0.15 mm |
Data collection top
Bruker D8 goniometer with APEX CCD detector diffractometer | 8583 reflections with I > 2σ(I) |
Radiation source: Incoatec microsource | Rint = 0.053 |
ω scans | θmax = 30.9°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −12→12 |
Tmin = 0.561, Tmax = 0.746 | k = −19→19 |
29995 measured reflections | l = −24→23 |
11214 independent reflections | |
Refinement top
Refinement on F2 | 4 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.038 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.088 | w = 1/[σ2(Fo2) + (0.0271P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.001 |
11214 reflections | Δρmax = 0.89 e Å−3 |
391 parameters | Δρmin = −1.21 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Co1 | 0.05993 (6) | 0.79167 (4) | 0.40511 (3) | 0.00985 (11) | |
Br1 | 0.28728 (4) | 0.86662 (3) | 0.40029 (2) | 0.01432 (9) | |
Br2 | −0.13994 (4) | 0.85904 (3) | 0.51033 (2) | 0.01341 (8) | |
Br3 | 0.12033 (4) | 0.60719 (3) | 0.42951 (2) | 0.01222 (8) | |
Br4 | −0.03061 (4) | 0.84250 (3) | 0.27921 (2) | 0.01406 (8) | |
Co2 | 0.35003 (6) | 0.29517 (4) | 0.14062 (3) | 0.00984 (11) | |
Br5 | 0.58580 (4) | 0.36028 (3) | 0.13844 (2) | 0.01302 (8) | |
Br6 | 0.15376 (4) | 0.34570 (3) | 0.25291 (2) | 0.01254 (8) | |
Br7 | 0.41366 (4) | 0.11084 (3) | 0.15889 (2) | 0.01296 (8) | |
Br8 | 0.25281 (4) | 0.36245 (3) | 0.01780 (2) | 0.01363 (8) | |
Cl1 | 0.27831 (12) | 0.87963 (8) | 0.02966 (7) | 0.0220 (2) | |
Cl2 | 0.86748 (11) | 0.86404 (8) | 0.07751 (6) | 0.0179 (2) | |
N1 | 0.4671 (4) | 0.8552 (3) | 0.2204 (2) | 0.0159 (7) | |
H1 | 0.435 (5) | 0.851 (3) | 0.2711 (12) | 0.019* | |
C1 | 0.3612 (5) | 0.8635 (3) | 0.1728 (2) | 0.0154 (8) | |
H1A | 0.2535 | 0.8653 | 0.1945 | 0.018* | |
C2 | 0.4116 (4) | 0.8692 (3) | 0.0922 (2) | 0.0136 (8) | |
C3 | 0.5707 (4) | 0.8684 (3) | 0.0596 (2) | 0.0122 (8) | |
H3A | 0.6064 | 0.8722 | 0.0038 | 0.015* | |
C4 | 0.6731 (4) | 0.8617 (3) | 0.1121 (2) | 0.0118 (8) | |
C5 | 0.6209 (4) | 0.8548 (3) | 0.1936 (2) | 0.0139 (8) | |
H5 | 0.6914 | 0.8500 | 0.2295 | 0.017* | |
Cl3 | 0.47623 (12) | 0.91503 (9) | 0.61965 (7) | 0.0295 (3) | |
Cl4 | 0.02645 (13) | 0.86710 (10) | 0.87785 (6) | 0.0296 (3) | |
N2 | 0.0341 (4) | 0.8987 (3) | 0.6480 (2) | 0.0147 (7) | |
H2 | −0.024 (4) | 0.899 (3) | 0.614 (2) | 0.018* | |
C6 | 0.1809 (5) | 0.9072 (3) | 0.6140 (2) | 0.0163 (8) | |
H6 | 0.2106 | 0.9161 | 0.5576 | 0.020* | |
C7 | 0.2878 (4) | 0.9026 (3) | 0.6633 (2) | 0.0131 (8) | |
C8 | 0.2443 (4) | 0.8890 (3) | 0.7455 (2) | 0.0145 (8) | |
H8 | 0.3178 | 0.8854 | 0.7795 | 0.017* | |
C9 | 0.0912 (5) | 0.8806 (3) | 0.7763 (2) | 0.0153 (8) | |
C10 | −0.0150 (5) | 0.8865 (3) | 0.7267 (2) | 0.0155 (8) | |
H10 | −0.1210 | 0.8821 | 0.7480 | 0.019* | |
Cl5 | 0.56872 (11) | 0.39707 (8) | −0.24192 (6) | 0.0186 (2) | |
Cl6 | 1.14615 (11) | 0.40161 (8) | −0.18838 (6) | 0.0200 (2) | |
N3 | 0.7442 (4) | 0.3856 (3) | −0.04924 (19) | 0.0153 (7) | |
H3 | 0.711 (5) | 0.383 (3) | 0.0022 (12) | 0.018* | |
C11 | 0.6428 (5) | 0.3882 (3) | −0.0976 (2) | 0.0136 (8) | |
H11 | 0.5357 | 0.3868 | −0.0769 | 0.016* | |
C12 | 0.6981 (4) | 0.3932 (3) | −0.1785 (2) | 0.0120 (8) | |
C13 | 0.8544 (4) | 0.3963 (3) | −0.2086 (2) | 0.0115 (7) | |
H13 | 0.8930 | 0.3997 | −0.2642 | 0.014* | |
C14 | 0.9526 (4) | 0.3942 (3) | −0.1546 (2) | 0.0123 (8) | |
C15 | 0.8965 (4) | 0.3887 (3) | −0.0743 (2) | 0.0145 (8) | |
H15 | 0.9638 | 0.3871 | −0.0375 | 0.017* | |
Cl7 | 0.78114 (11) | 0.35993 (8) | 0.35111 (7) | 0.0239 (2) | |
Cl8 | 0.34105 (13) | 0.37022 (9) | 0.61794 (6) | 0.0251 (2) | |
N4 | 0.3330 (4) | 0.3541 (3) | 0.3965 (2) | 0.0146 (7) | |
H4 | 0.268 (4) | 0.341 (3) | 0.370 (2) | 0.018* | |
C16 | 0.4805 (5) | 0.3538 (3) | 0.3576 (2) | 0.0157 (8) | |
H16 | 0.5066 | 0.3491 | 0.3021 | 0.019* | |
C17 | 0.5923 (4) | 0.3603 (3) | 0.4000 (2) | 0.0143 (8) | |
C18 | 0.5532 (4) | 0.3647 (3) | 0.4814 (2) | 0.0148 (8) | |
H18 | 0.6301 | 0.3682 | 0.5115 | 0.018* | |
C19 | 0.3999 (4) | 0.3639 (3) | 0.5174 (2) | 0.0124 (8) | |
C20 | 0.2886 (4) | 0.3592 (3) | 0.4739 (2) | 0.0132 (8) | |
H20 | 0.1828 | 0.3597 | 0.4985 | 0.016* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.0103 (2) | 0.0099 (2) | 0.0088 (2) | −0.00251 (19) | 0.00006 (19) | −0.00106 (19) |
Br1 | 0.01429 (19) | 0.0202 (2) | 0.01028 (19) | −0.00900 (15) | 0.00206 (14) | −0.00438 (15) |
Br2 | 0.01159 (18) | 0.01538 (19) | 0.01270 (19) | −0.00298 (14) | 0.00239 (14) | −0.00505 (15) |
Br3 | 0.01096 (18) | 0.01028 (18) | 0.01436 (19) | −0.00152 (14) | −0.00075 (14) | −0.00125 (14) |
Br4 | 0.01402 (19) | 0.01666 (19) | 0.01139 (19) | −0.00218 (15) | −0.00428 (15) | −0.00039 (15) |
Co2 | 0.0107 (2) | 0.0102 (2) | 0.0082 (2) | −0.00211 (19) | −0.00081 (19) | −0.00109 (19) |
Br5 | 0.01312 (18) | 0.0186 (2) | 0.00827 (18) | −0.00699 (15) | 0.00055 (14) | −0.00195 (14) |
Br6 | 0.00955 (17) | 0.01561 (19) | 0.01191 (19) | −0.00234 (14) | 0.00105 (14) | −0.00383 (14) |
Br7 | 0.01302 (18) | 0.01031 (18) | 0.01472 (19) | −0.00126 (14) | −0.00164 (14) | −0.00168 (14) |
Br8 | 0.01438 (19) | 0.01617 (19) | 0.01072 (19) | −0.00331 (15) | −0.00431 (15) | −0.00007 (15) |
Cl1 | 0.0160 (5) | 0.0267 (6) | 0.0249 (6) | −0.0061 (4) | −0.0083 (4) | 0.0000 (4) |
Cl2 | 0.0107 (4) | 0.0273 (5) | 0.0135 (5) | −0.0030 (4) | −0.0004 (4) | 0.0004 (4) |
N1 | 0.0239 (19) | 0.0124 (17) | 0.0081 (16) | −0.0038 (14) | 0.0053 (14) | −0.0012 (13) |
C1 | 0.0122 (19) | 0.0130 (19) | 0.019 (2) | −0.0032 (15) | 0.0021 (16) | −0.0006 (16) |
C2 | 0.0141 (19) | 0.0091 (18) | 0.019 (2) | −0.0017 (14) | −0.0056 (16) | −0.0035 (15) |
C3 | 0.0117 (18) | 0.0103 (18) | 0.0132 (19) | −0.0005 (14) | 0.0003 (15) | −0.0027 (15) |
C4 | 0.0133 (18) | 0.0092 (18) | 0.0110 (18) | −0.0009 (14) | 0.0016 (15) | −0.0024 (14) |
C5 | 0.0127 (19) | 0.0145 (19) | 0.013 (2) | −0.0021 (15) | 0.0012 (15) | −0.0027 (15) |
Cl3 | 0.0135 (5) | 0.0364 (7) | 0.0322 (6) | −0.0081 (4) | 0.0083 (4) | 0.0024 (5) |
Cl4 | 0.0258 (6) | 0.0483 (7) | 0.0106 (5) | −0.0053 (5) | 0.0018 (4) | −0.0012 (5) |
N2 | 0.0144 (17) | 0.0158 (17) | 0.0153 (18) | −0.0026 (13) | −0.0054 (14) | −0.0030 (14) |
C6 | 0.019 (2) | 0.0106 (19) | 0.014 (2) | 0.0010 (15) | 0.0039 (16) | −0.0024 (15) |
C7 | 0.0075 (17) | 0.0148 (19) | 0.015 (2) | −0.0013 (14) | 0.0017 (15) | −0.0017 (15) |
C8 | 0.0123 (19) | 0.0130 (19) | 0.018 (2) | 0.0001 (15) | −0.0040 (16) | −0.0039 (16) |
C9 | 0.0143 (19) | 0.017 (2) | 0.013 (2) | −0.0042 (16) | 0.0011 (15) | −0.0005 (16) |
C10 | 0.0116 (18) | 0.019 (2) | 0.016 (2) | −0.0042 (15) | 0.0012 (15) | −0.0032 (16) |
Cl5 | 0.0179 (5) | 0.0188 (5) | 0.0209 (5) | −0.0049 (4) | −0.0074 (4) | −0.0015 (4) |
Cl6 | 0.0120 (5) | 0.0299 (6) | 0.0161 (5) | −0.0042 (4) | −0.0008 (4) | 0.0006 (4) |
N3 | 0.0193 (18) | 0.0165 (17) | 0.0070 (16) | −0.0027 (14) | 0.0031 (13) | −0.0003 (13) |
C11 | 0.0148 (19) | 0.0086 (18) | 0.016 (2) | −0.0042 (14) | 0.0022 (15) | −0.0008 (15) |
C12 | 0.0118 (18) | 0.0082 (18) | 0.016 (2) | −0.0024 (14) | −0.0018 (15) | −0.0024 (15) |
C13 | 0.0104 (18) | 0.0100 (18) | 0.0121 (19) | 0.0003 (14) | 0.0005 (14) | −0.0017 (14) |
C14 | 0.0091 (17) | 0.0119 (18) | 0.0116 (19) | −0.0011 (14) | 0.0042 (14) | 0.0019 (15) |
C15 | 0.016 (2) | 0.0130 (19) | 0.014 (2) | −0.0006 (15) | −0.0047 (16) | −0.0009 (15) |
Cl7 | 0.0124 (5) | 0.0229 (5) | 0.0317 (6) | −0.0053 (4) | 0.0106 (4) | −0.0053 (5) |
Cl8 | 0.0272 (6) | 0.0350 (6) | 0.0117 (5) | −0.0046 (5) | 0.0013 (4) | −0.0064 (4) |
N4 | 0.0140 (17) | 0.0162 (17) | 0.0170 (18) | −0.0037 (13) | −0.0078 (14) | −0.0039 (14) |
C16 | 0.017 (2) | 0.0136 (19) | 0.0112 (19) | 0.0008 (15) | 0.0045 (15) | −0.0001 (15) |
C17 | 0.0119 (18) | 0.0088 (18) | 0.019 (2) | −0.0001 (14) | 0.0011 (16) | 0.0002 (15) |
C18 | 0.0137 (19) | 0.0118 (19) | 0.019 (2) | −0.0018 (15) | −0.0056 (16) | 0.0000 (16) |
C19 | 0.0147 (19) | 0.0090 (18) | 0.0114 (19) | 0.0001 (14) | −0.0009 (15) | −0.0006 (14) |
C20 | 0.0104 (18) | 0.0116 (19) | 0.016 (2) | −0.0017 (14) | 0.0023 (15) | −0.0024 (15) |
Geometric parameters (Å, º) top
Co1—Br3 | 2.3989 (7) | C8—C9 | 1.378 (5) |
Co1—Br4 | 2.3994 (7) | C8—H8 | 0.9500 |
Co1—Br2 | 2.4198 (6) | C9—C10 | 1.376 (6) |
Co1—Br1 | 2.4338 (6) | C10—H10 | 0.9500 |
Co2—Br7 | 2.3964 (7) | Cl5—C12 | 1.725 (4) |
Co2—Br8 | 2.3981 (6) | Cl6—C14 | 1.719 (4) |
Co2—Br6 | 2.4194 (6) | N3—C11 | 1.335 (5) |
Co2—Br5 | 2.4363 (6) | N3—C15 | 1.342 (5) |
Cl1—C2 | 1.721 (4) | N3—H3 | 0.876 (18) |
Cl2—C4 | 1.714 (4) | C11—C12 | 1.381 (5) |
N1—C1 | 1.342 (5) | C11—H11 | 0.9500 |
N1—C5 | 1.350 (5) | C12—C13 | 1.388 (5) |
N1—H1 | 0.861 (18) | C13—C14 | 1.391 (5) |
C1—C2 | 1.370 (5) | C13—H13 | 0.9500 |
C1—H1A | 0.9500 | C14—C15 | 1.371 (5) |
C2—C3 | 1.410 (5) | C15—H15 | 0.9500 |
C3—C4 | 1.386 (5) | Cl7—C17 | 1.718 (4) |
C3—H3A | 0.9500 | Cl8—C19 | 1.724 (4) |
C4—C5 | 1.385 (5) | N4—C20 | 1.327 (5) |
C5—H5 | 0.9500 | N4—C16 | 1.346 (5) |
Cl3—C7 | 1.723 (4) | N4—H4 | 0.861 (18) |
Cl4—C9 | 1.724 (4) | C16—C17 | 1.372 (6) |
N2—C10 | 1.334 (5) | C16—H16 | 0.9500 |
N2—C6 | 1.339 (5) | C17—C18 | 1.390 (6) |
N2—H2 | 0.852 (18) | C18—C19 | 1.379 (5) |
C6—C7 | 1.381 (6) | C18—H18 | 0.9500 |
C6—H6 | 0.9500 | C19—C20 | 1.373 (5) |
C7—C8 | 1.385 (5) | C20—H20 | 0.9500 |
| | | |
Br3—Co1—Br4 | 108.04 (2) | C10—C9—C8 | 120.7 (4) |
Br3—Co1—Br2 | 110.50 (2) | C10—C9—Cl4 | 118.4 (3) |
Br4—Co1—Br2 | 110.23 (2) | C8—C9—Cl4 | 120.8 (3) |
Br3—Co1—Br1 | 112.23 (2) | N2—C10—C9 | 118.6 (4) |
Br4—Co1—Br1 | 108.85 (2) | N2—C10—H10 | 120.7 |
Br2—Co1—Br1 | 106.98 (2) | C9—C10—H10 | 120.7 |
Br7—Co2—Br8 | 111.37 (2) | C11—N3—C15 | 124.1 (3) |
Br7—Co2—Br6 | 107.22 (2) | C11—N3—H3 | 119 (3) |
Br8—Co2—Br6 | 110.52 (2) | C15—N3—H3 | 117 (3) |
Br7—Co2—Br5 | 108.85 (2) | N3—C11—C12 | 118.2 (3) |
Br8—Co2—Br5 | 108.88 (2) | N3—C11—H11 | 120.9 |
Br6—Co2—Br5 | 109.97 (2) | C12—C11—H11 | 120.9 |
C1—N1—C5 | 123.9 (3) | C11—C12—C13 | 120.8 (4) |
C1—N1—H1 | 118 (3) | C11—C12—Cl5 | 118.9 (3) |
C5—N1—H1 | 118 (3) | C13—C12—Cl5 | 120.3 (3) |
N1—C1—C2 | 118.6 (4) | C12—C13—C14 | 117.7 (3) |
N1—C1—H1A | 120.7 | C12—C13—H13 | 121.2 |
C2—C1—H1A | 120.7 | C14—C13—H13 | 121.2 |
C1—C2—C3 | 120.9 (4) | C15—C14—C13 | 121.0 (3) |
C1—C2—Cl1 | 119.6 (3) | C15—C14—Cl6 | 119.1 (3) |
C3—C2—Cl1 | 119.6 (3) | C13—C14—Cl6 | 119.9 (3) |
C4—C3—C2 | 117.5 (4) | N3—C15—C14 | 118.2 (4) |
C4—C3—H3A | 121.2 | N3—C15—H15 | 120.9 |
C2—C3—H3A | 121.2 | C14—C15—H15 | 120.9 |
C3—C4—C5 | 121.0 (4) | C20—N4—C16 | 124.1 (3) |
C3—C4—Cl2 | 120.7 (3) | C20—N4—H4 | 119 (3) |
C5—C4—Cl2 | 118.3 (3) | C16—N4—H4 | 116 (3) |
N1—C5—C4 | 118.1 (4) | N4—C16—C17 | 118.4 (4) |
N1—C5—H5 | 121.0 | N4—C16—H16 | 120.8 |
C4—C5—H5 | 121.0 | C17—C16—H16 | 120.8 |
C10—N2—C6 | 123.9 (4) | C16—C17—C18 | 120.2 (4) |
C10—N2—H2 | 123 (3) | C16—C17—Cl7 | 118.9 (3) |
C6—N2—H2 | 113 (3) | C18—C17—Cl7 | 121.0 (3) |
N2—C6—C7 | 118.0 (4) | C19—C18—C17 | 118.3 (4) |
N2—C6—H6 | 121.0 | C19—C18—H18 | 120.9 |
C7—C6—H6 | 121.0 | C17—C18—H18 | 120.9 |
C6—C7—C8 | 120.8 (4) | C20—C19—C18 | 120.9 (4) |
C6—C7—Cl3 | 118.1 (3) | C20—C19—Cl8 | 117.8 (3) |
C8—C7—Cl3 | 121.1 (3) | C18—C19—Cl8 | 121.3 (3) |
C9—C8—C7 | 118.0 (4) | N4—C20—C19 | 118.2 (3) |
C9—C8—H8 | 121.0 | N4—C20—H20 | 120.9 |
C7—C8—H8 | 121.0 | C19—C20—H20 | 120.9 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Br1 | 0.86 (2) | 2.37 (2) | 3.212 (3) | 165 (4) |
N2—H2···Br2 | 0.85 (2) | 2.43 (2) | 3.261 (3) | 165 (4) |
N3—H3···Br5 | 0.88 (2) | 2.39 (2) | 3.258 (3) | 169 (4) |
N4—H4···Br6 | 0.86 (2) | 2.43 (2) | 3.233 (3) | 156 (4) |