The bromo-substituted aromatic dicarboxylic acid 5-amino-2,4,6-tribromoisophthalic acid (H2ATBIP) was used to assemble with CdII ions in the presence of the N-donor flexible bipyridyl ligands 3,3′-(diazene-1,2-diyl)dipyridine (mzpy) and 1,3-bis(pyridin-3-ylmethyl)urea (3bpmu), leading to the formation of two chain coordination polymers by adopting solution methods, namely, catena-poly[[[triaqua(5-amino-2,4,6-tribromoisophthalato-κO)cadmium(II)]-μ-3,3′-(diazene-1,2-diyl)dipyridine-κ2N1:N1′] dihydrate], {[Cd(C8H2Br3NO4)(C10H8N4)(H2O)3]·2H2O}n or {[Cd(ATBIP)(mzpy)(H2O)3]·2H2O}n, (1), and catena-poly[[[tetraaquacadmium(II)]-μ-1,3-bis(pyridin-3-ylmethyl)urea-κ2N1:N1′-[diaquabis(5-amino-2,4,6-tribromoisophthalato-κO)cadmium(II)]-μ-1,3-bis(pyridin-3-ylmethyl)urea-κ2N1:N1′] octahydrate], {[Cd(C8H2Br3NO4)(C12H12N4O)(H2O)3]·4H2O}n or {[Cd(ATBIP)(3bpmu)(H2O)3]·4H2O}n, (2). Both complexes were characterized by FT–IR spectroscopic analysis, thermogravimetric analysis (TGA), solid-state diffuse reflectance UV–Vis spectroscopic analysis, and single-crystal and powder X-ray diffraction analysis (PXRD). The mzpy and 3bpmu ligands bridge the CdII metal centres in (1) and (2) into one-dimensional chains, and the ATBIP2− ligands show a monodentate coordination to the CdII centres in both coordination polymers. A discrete water tetramer exists in (1). Within the chains of (1) and (2), there are halogen bonds between adjacent ATBIP2− and mzpy or 3bpmu ligands, as well as hydrogen bonds between the ATBIP2− ligands and the coordinated water molecules. With the aid of weak interactions, the structures of (1) and (2) are further extended into three-dimensional supramolecular networks. An analysis of the solid-state diffuse reflectance UV–Vis spectra of (1) and (2) indicates that a wide indirect band gap exists in both complexes. Complexes (1) and (2) exhibit irreversible and reversible dehydration–rehydration behaviours, respectively, and the solid-state fluorescence properties of both complexes have been studied.
Supporting information
CCDC references: 1855669; 1855668
For both structures, data collection: SMART (Bruker, 2008); cell refinement: SMART (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXT2017 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: Mercury (Macrae et al., 2008).
catena-Poly[[[triaqua(5-amino-2,4,6-tribromoisophthalato-
κO)cadmium(II)]-µ-3,3'-(diazene-1,2-diyl)dipyridine-
κ2N1:
N1'] dihydrate] (1)
top
Crystal data top
[Cd(C8H2Br3NO4)(C10H8N4)(H2O)3]·2H2O | F(000) = 1552 |
Mr = 802.52 | Dx = 2.087 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.9226 (9) Å | Cell parameters from 9877 reflections |
b = 19.1965 (18) Å | θ = 2.4–27.4° |
c = 17.2011 (16) Å | µ = 5.60 mm−1 |
β = 102.460 (3)° | T = 298 K |
V = 2554.4 (4) Å3 | Block, orange |
Z = 4 | 0.31 × 0.27 × 0.25 mm |
Data collection top
Bruker APEXII area-detector diffractometer | 4767 reflections with I > 2σ(I) |
phi and ω scans | Rint = 0.040 |
Absorption correction: empirical (using intensity measurements) sadabs | θmax = 27.5°, θmin = 2.1° |
Tmin = 0.192, Tmax = 0.246 | h = −10→10 |
37897 measured reflections | k = −24→23 |
5860 independent reflections | l = −22→22 |
Refinement top
Refinement on F2 | 15 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.028 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.060 | w = 1/[σ2(Fo2) + (0.0206P)2 + 3.1799P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.002 |
5860 reflections | Δρmax = 1.19 e Å−3 |
335 parameters | Δρmin = −1.18 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 | |
Br1 | 0.93119 (5) | 0.87547 (2) | 0.54970 (2) | 0.04577 (10) | |
Br2 | 0.77918 (5) | 0.72459 (2) | 0.25771 (2) | 0.03916 (9) | |
Br3 | 1.09988 (4) | 0.59075 (2) | 0.54485 (2) | 0.03967 (9) | |
C1 | 0.8670 (3) | 0.79187 (13) | 0.40855 (15) | 0.0242 (6) | |
C2 | 0.8685 (3) | 0.72880 (13) | 0.36937 (15) | 0.0231 (6) | |
C3 | 0.9356 (3) | 0.66839 (13) | 0.40864 (15) | 0.0219 (5) | |
C4 | 1.0017 (4) | 0.67194 (14) | 0.48995 (16) | 0.0252 (6) | |
C5 | 0.9974 (4) | 0.73296 (15) | 0.53366 (16) | 0.0281 (6) | |
C6 | 0.9293 (4) | 0.79214 (14) | 0.49059 (16) | 0.0270 (6) | |
C7 | 0.8186 (4) | 0.85930 (14) | 0.36141 (16) | 0.0280 (6) | |
C8 | 0.9470 (4) | 0.60220 (14) | 0.36183 (16) | 0.0271 (6) | |
C9 | 0.5542 (4) | 0.86412 (15) | 0.15364 (18) | 0.0332 (7) | |
H9 | 0.521115 | 0.842097 | 0.196148 | 0.040* | |
C10 | 0.6513 (4) | 0.96150 (16) | 0.10035 (18) | 0.0364 (7) | |
H10 | 0.686600 | 1.007776 | 0.105587 | 0.044* | |
C11 | 0.6505 (4) | 0.92750 (17) | 0.02914 (19) | 0.0387 (7) | |
H11 | 0.683639 | 0.950545 | −0.012733 | 0.046* | |
C12 | 0.5994 (4) | 0.85844 (17) | 0.02191 (19) | 0.0387 (7) | |
H12 | 0.598134 | 0.833965 | −0.024872 | 0.046* | |
C13 | 0.5504 (4) | 0.82677 (15) | 0.08516 (18) | 0.0323 (7) | |
C14 | 0.4095 (4) | 0.65520 (15) | 0.02981 (19) | 0.0346 (7) | |
C15 | 0.4281 (4) | 0.61872 (15) | 0.10139 (18) | 0.0341 (7) | |
H15 | 0.471977 | 0.641751 | 0.149037 | 0.041* | |
H18 | 0.333 (4) | 0.6492 (17) | −0.089 (2) | 0.041* | |
H17 | 0.253 (4) | 0.5301 (17) | −0.085 (2) | 0.041* | |
C16 | 0.3201 (5) | 0.52060 (17) | 0.03290 (19) | 0.0404 (8) | |
C17 | 0.2996 (5) | 0.55360 (18) | −0.0388 (2) | 0.0488 (9) | |
C18 | 0.3459 (5) | 0.62155 (18) | −0.04075 (19) | 0.0443 (8) | |
Cd1 | 0.61080 (3) | 0.98664 (2) | 0.28330 (2) | 0.02765 (6) | |
H16 | 0.289 (4) | 0.4688 (19) | 0.036 (2) | 0.050 (10)* | |
N1 | 1.0606 (4) | 0.73580 (15) | 0.61389 (15) | 0.0519 (8) | |
H1A | 1.104979 | 0.699231 | 0.639184 | 0.062* | |
H1B | 1.056144 | 0.774164 | 0.639183 | 0.062* | |
N2 | 0.6034 (3) | 0.93059 (12) | 0.16170 (14) | 0.0305 (5) | |
N3 | 0.5011 (4) | 0.75417 (14) | 0.08932 (15) | 0.0378 (6) | |
N4 | 0.4529 (4) | 0.72724 (14) | 0.02370 (15) | 0.0384 (6) | |
N5 | 0.3848 (3) | 0.55186 (12) | 0.10320 (14) | 0.0305 (5) | |
O1 | 1.0804 (3) | 0.59567 (11) | 0.33534 (14) | 0.0414 (5) | |
O2 | 0.8237 (3) | 0.56067 (10) | 0.35386 (13) | 0.0374 (5) | |
O3 | 0.9360 (3) | 0.88371 (12) | 0.33132 (15) | 0.0497 (6) | |
O4 | 0.6726 (3) | 0.88430 (10) | 0.35646 (12) | 0.0364 (5) | |
O1W | 0.1950 (3) | 0.83248 (12) | 0.26467 (12) | 0.0434 (5) | |
H1WA | 0.107541 | 0.843775 | 0.283150 | 0.065* | |
H1WB | 0.235995 | 0.794008 | 0.284457 | 0.065* | |
O2W | 0.3124 (3) | 0.70455 (13) | 0.34658 (15) | 0.0532 (6) | |
H2WA | 0.229418 | 0.675662 | 0.342237 | 0.080* | |
H2WB | 0.366166 | 0.707032 | 0.394876 | 0.080* | |
O3W | 0.5174 (3) | 1.08607 (11) | 0.20541 (13) | 0.0410 (5) | |
H3WA | 0.566412 | 1.123402 | 0.196550 | 0.062* | |
H3WB | 0.411326 | 1.087065 | 0.182906 | 0.062* | |
O4W | 0.3165 (3) | 0.96630 (11) | 0.26486 (13) | 0.0393 (5) | |
H4WA | 0.256765 | 0.991774 | 0.229255 | 0.059* | |
H4WB | 0.279771 | 0.924869 | 0.260498 | 0.059* | |
O5W | 0.8933 (3) | 1.02058 (11) | 0.29335 (13) | 0.0384 (5) | |
H5WA | 0.935676 | 0.980073 | 0.298443 | 0.058* | |
H5WB | 0.919429 | 1.040846 | 0.253552 | 0.058* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0712 (3) | 0.02838 (17) | 0.03275 (17) | 0.01262 (15) | 0.00021 (16) | −0.01036 (13) |
Br2 | 0.0622 (2) | 0.02873 (16) | 0.02070 (14) | 0.00200 (14) | −0.00399 (13) | −0.00037 (12) |
Br3 | 0.0499 (2) | 0.02596 (16) | 0.03663 (17) | 0.01038 (13) | −0.00516 (14) | 0.00753 (13) |
C1 | 0.0293 (15) | 0.0194 (13) | 0.0228 (13) | 0.0031 (11) | 0.0032 (11) | 0.0017 (11) |
C2 | 0.0297 (15) | 0.0199 (13) | 0.0180 (12) | 0.0028 (11) | 0.0014 (10) | 0.0006 (10) |
C3 | 0.0218 (14) | 0.0182 (13) | 0.0248 (13) | 0.0009 (10) | 0.0029 (10) | 0.0005 (11) |
C4 | 0.0302 (15) | 0.0178 (13) | 0.0255 (14) | 0.0041 (11) | 0.0012 (11) | 0.0044 (11) |
C5 | 0.0353 (16) | 0.0273 (15) | 0.0198 (13) | 0.0047 (12) | 0.0018 (11) | 0.0024 (11) |
C6 | 0.0374 (16) | 0.0188 (13) | 0.0239 (14) | 0.0037 (12) | 0.0048 (12) | −0.0052 (11) |
C7 | 0.0405 (18) | 0.0183 (13) | 0.0231 (14) | 0.0049 (12) | 0.0024 (12) | −0.0014 (11) |
C8 | 0.0325 (16) | 0.0189 (14) | 0.0266 (14) | 0.0047 (12) | −0.0009 (12) | −0.0015 (11) |
C9 | 0.0434 (18) | 0.0220 (15) | 0.0331 (16) | −0.0005 (13) | 0.0058 (13) | 0.0022 (13) |
C10 | 0.0464 (19) | 0.0253 (15) | 0.0372 (17) | −0.0061 (13) | 0.0087 (14) | −0.0014 (13) |
C11 | 0.046 (2) | 0.0401 (18) | 0.0326 (16) | −0.0058 (15) | 0.0139 (14) | 0.0008 (14) |
C12 | 0.0435 (19) | 0.0382 (18) | 0.0325 (16) | −0.0017 (15) | 0.0037 (14) | −0.0123 (14) |
C13 | 0.0346 (17) | 0.0246 (15) | 0.0358 (16) | −0.0006 (12) | 0.0036 (13) | −0.0028 (13) |
C14 | 0.0415 (18) | 0.0220 (15) | 0.0399 (17) | −0.0034 (13) | 0.0077 (14) | 0.0062 (13) |
C15 | 0.0424 (18) | 0.0283 (16) | 0.0288 (15) | −0.0058 (13) | 0.0015 (13) | −0.0010 (13) |
C16 | 0.058 (2) | 0.0260 (17) | 0.0326 (17) | −0.0094 (15) | 0.0000 (15) | 0.0013 (13) |
C17 | 0.077 (3) | 0.0375 (19) | 0.0261 (16) | −0.0097 (18) | −0.0017 (16) | 0.0003 (15) |
C18 | 0.065 (2) | 0.0376 (19) | 0.0276 (16) | −0.0029 (16) | 0.0037 (15) | 0.0090 (14) |
Cd1 | 0.03572 (12) | 0.02188 (11) | 0.02415 (11) | −0.00108 (9) | 0.00378 (8) | −0.00192 (8) |
N1 | 0.092 (2) | 0.0359 (16) | 0.0202 (13) | 0.0191 (15) | −0.0036 (14) | −0.0005 (12) |
N2 | 0.0387 (14) | 0.0239 (12) | 0.0272 (12) | 0.0002 (10) | 0.0037 (10) | −0.0008 (10) |
N3 | 0.0514 (17) | 0.0321 (14) | 0.0269 (13) | −0.0010 (12) | 0.0021 (12) | −0.0007 (11) |
N4 | 0.0505 (17) | 0.0333 (14) | 0.0300 (14) | −0.0033 (12) | 0.0053 (12) | 0.0021 (11) |
N5 | 0.0390 (15) | 0.0234 (12) | 0.0267 (12) | −0.0038 (10) | 0.0019 (10) | 0.0024 (10) |
O1 | 0.0424 (13) | 0.0333 (12) | 0.0511 (14) | 0.0042 (10) | 0.0159 (11) | −0.0127 (10) |
O2 | 0.0391 (13) | 0.0221 (10) | 0.0469 (13) | −0.0039 (9) | 0.0001 (10) | −0.0075 (10) |
O3 | 0.0544 (15) | 0.0329 (13) | 0.0653 (16) | 0.0057 (11) | 0.0206 (13) | 0.0194 (12) |
O4 | 0.0451 (13) | 0.0278 (11) | 0.0345 (11) | 0.0133 (10) | 0.0043 (10) | 0.0041 (9) |
O1W | 0.0539 (15) | 0.0389 (13) | 0.0367 (12) | −0.0055 (11) | 0.0085 (11) | −0.0025 (10) |
O2W | 0.0496 (15) | 0.0466 (15) | 0.0626 (16) | 0.0024 (12) | 0.0106 (12) | −0.0017 (13) |
O3W | 0.0379 (13) | 0.0314 (12) | 0.0515 (14) | −0.0013 (10) | 0.0047 (10) | 0.0142 (10) |
O4W | 0.0388 (13) | 0.0355 (12) | 0.0412 (12) | −0.0061 (10) | 0.0034 (10) | 0.0080 (10) |
O5W | 0.0408 (13) | 0.0304 (12) | 0.0450 (13) | −0.0023 (9) | 0.0117 (10) | 0.0033 (10) |
Geometric parameters (Å, º) top
Br1—C6 | 1.894 (3) | C14—N4 | 1.435 (4) |
Br2—C2 | 1.900 (3) | C15—N5 | 1.331 (4) |
Br3—C4 | 1.900 (3) | C15—H15 | 0.9300 |
C1—C2 | 1.387 (4) | C16—N5 | 1.348 (4) |
C1—C6 | 1.391 (4) | C16—C17 | 1.365 (4) |
C1—C7 | 1.532 (4) | C16—H16 | 1.03 (4) |
C2—C3 | 1.389 (4) | C17—C18 | 1.357 (5) |
C3—C4 | 1.385 (4) | C17—H17 | 0.92 (3) |
C3—C8 | 1.517 (4) | C18—H18 | 0.97 (3) |
C4—C5 | 1.396 (4) | Cd1—O5W | 2.302 (2) |
C5—N1 | 1.364 (4) | Cd1—N5i | 2.313 (2) |
C5—C6 | 1.400 (4) | Cd1—O4W | 2.317 (2) |
C7—O4 | 1.239 (3) | Cd1—O4 | 2.327 (2) |
C7—O3 | 1.249 (4) | Cd1—N2 | 2.342 (2) |
C8—O1 | 1.245 (4) | Cd1—O3W | 2.358 (2) |
C8—O2 | 1.245 (3) | N1—H1A | 0.8600 |
C9—N2 | 1.333 (4) | N1—H1B | 0.8600 |
C9—C13 | 1.374 (4) | N3—N4 | 1.225 (3) |
C9—H9 | 0.9300 | O1W—H1WA | 0.8504 |
C10—N2 | 1.335 (4) | O1W—H1WB | 0.8479 |
C10—C11 | 1.387 (4) | O2W—H2WA | 0.8511 |
C10—H10 | 0.9300 | O2W—H2WB | 0.8492 |
C11—C12 | 1.384 (4) | O3W—H3WA | 0.8443 |
C11—H11 | 0.9300 | O3W—H3WB | 0.8464 |
C12—C13 | 1.373 (4) | O4W—H4WA | 0.8445 |
C12—H12 | 0.9300 | O4W—H4WB | 0.8447 |
C13—N3 | 1.453 (4) | O5W—H5WA | 0.8439 |
C14—C18 | 1.371 (4) | O5W—H5WB | 0.8508 |
C14—C15 | 1.396 (4) | | |
| | | |
C2—C1—C6 | 117.3 (2) | N5—C16—H16 | 115.5 (19) |
C2—C1—C7 | 120.5 (2) | C17—C16—H16 | 121 (2) |
C6—C1—C7 | 121.8 (2) | C18—C17—C16 | 119.2 (3) |
C1—C2—C3 | 122.3 (2) | C18—C17—H17 | 121 (2) |
C1—C2—Br2 | 119.20 (19) | C16—C17—H17 | 120 (2) |
C3—C2—Br2 | 118.44 (19) | C17—C18—C14 | 118.7 (3) |
C4—C3—C2 | 118.1 (2) | C17—C18—H18 | 125 (2) |
C4—C3—C8 | 121.6 (2) | C14—C18—H18 | 116.5 (19) |
C2—C3—C8 | 120.1 (2) | O5W—Cd1—N5i | 86.91 (8) |
C3—C4—C5 | 122.5 (2) | O5W—Cd1—O4W | 172.48 (7) |
C3—C4—Br3 | 119.1 (2) | N5i—Cd1—O4W | 92.19 (8) |
C5—C4—Br3 | 118.39 (19) | O5W—Cd1—O4 | 96.36 (8) |
N1—C5—C4 | 122.2 (3) | N5i—Cd1—O4 | 92.14 (8) |
N1—C5—C6 | 121.2 (3) | O4W—Cd1—O4 | 91.13 (8) |
C4—C5—C6 | 116.6 (2) | O5W—Cd1—N2 | 91.93 (8) |
C1—C6—C5 | 123.1 (2) | N5i—Cd1—N2 | 174.56 (8) |
C1—C6—Br1 | 120.5 (2) | O4W—Cd1—N2 | 88.26 (8) |
C5—C6—Br1 | 116.4 (2) | O4—Cd1—N2 | 93.27 (8) |
O4—C7—O3 | 126.4 (3) | O5W—Cd1—O3W | 89.67 (8) |
O4—C7—C1 | 119.2 (3) | N5i—Cd1—O3W | 89.26 (8) |
O3—C7—C1 | 114.4 (3) | O4W—Cd1—O3W | 82.85 (7) |
O1—C8—O2 | 127.1 (3) | O4—Cd1—O3W | 173.87 (8) |
O1—C8—C3 | 115.5 (3) | N2—Cd1—O3W | 85.42 (8) |
O2—C8—C3 | 117.4 (3) | C5—N1—H1A | 120.0 |
N2—C9—C13 | 122.7 (3) | C5—N1—H1B | 120.0 |
N2—C9—H9 | 118.6 | H1A—N1—H1B | 120.0 |
C13—C9—H9 | 118.6 | C9—N2—C10 | 118.0 (3) |
N2—C10—C11 | 122.8 (3) | C9—N2—Cd1 | 118.90 (19) |
N2—C10—H10 | 118.6 | C10—N2—Cd1 | 123.04 (19) |
C11—C10—H10 | 118.6 | N4—N3—C13 | 113.1 (3) |
C12—C11—C10 | 118.4 (3) | N3—N4—C14 | 111.8 (3) |
C12—C11—H11 | 120.8 | C15—N5—C16 | 117.3 (3) |
C10—C11—H11 | 120.8 | C15—N5—Cd1ii | 125.79 (19) |
C13—C12—C11 | 118.7 (3) | C16—N5—Cd1ii | 116.72 (19) |
C13—C12—H12 | 120.7 | C7—O4—Cd1 | 116.66 (19) |
C11—C12—H12 | 120.7 | H1WA—O1W—H1WB | 110.2 |
C12—C13—C9 | 119.4 (3) | H2WA—O2W—H2WB | 109.7 |
C12—C13—N3 | 126.0 (3) | Cd1—O3W—H3WA | 133.6 |
C9—C13—N3 | 114.5 (3) | Cd1—O3W—H3WB | 115.9 |
C18—C14—C15 | 119.5 (3) | H3WA—O3W—H3WB | 110.4 |
C18—C14—N4 | 115.9 (3) | Cd1—O4W—H4WA | 113.1 |
C15—C14—N4 | 124.5 (3) | Cd1—O4W—H4WB | 119.2 |
N5—C15—C14 | 121.7 (3) | H4WA—O4W—H4WB | 110.6 |
N5—C15—H15 | 119.1 | Cd1—O5W—H5WA | 96.1 |
C14—C15—H15 | 119.1 | Cd1—O5W—H5WB | 118.1 |
N5—C16—C17 | 123.5 (3) | H5WA—O5W—H5WB | 110.2 |
| | | |
C6—C1—C2—C3 | −2.7 (4) | C4—C3—C8—O2 | 91.4 (3) |
C7—C1—C2—C3 | 170.3 (3) | C2—C3—C8—O2 | −93.1 (3) |
C6—C1—C2—Br2 | 178.3 (2) | N2—C10—C11—C12 | −0.6 (5) |
C7—C1—C2—Br2 | −8.7 (4) | C10—C11—C12—C13 | 0.5 (5) |
C1—C2—C3—C4 | 0.5 (4) | C11—C12—C13—C9 | −0.3 (5) |
Br2—C2—C3—C4 | 179.5 (2) | C11—C12—C13—N3 | −176.9 (3) |
C1—C2—C3—C8 | −175.1 (3) | N2—C9—C13—C12 | 0.2 (5) |
Br2—C2—C3—C8 | 3.9 (4) | N2—C9—C13—N3 | 177.2 (3) |
C2—C3—C4—C5 | 2.4 (4) | C18—C14—C15—N5 | −0.4 (5) |
C8—C3—C4—C5 | 177.9 (3) | N4—C14—C15—N5 | 179.7 (3) |
C2—C3—C4—Br3 | −178.4 (2) | N5—C16—C17—C18 | −0.1 (6) |
C8—C3—C4—Br3 | −2.8 (4) | C16—C17—C18—C14 | −1.0 (6) |
C3—C4—C5—N1 | 179.1 (3) | C15—C14—C18—C17 | 1.3 (5) |
Br3—C4—C5—N1 | −0.2 (4) | N4—C14—C18—C17 | −178.9 (3) |
C3—C4—C5—C6 | −2.8 (4) | C13—C9—N2—C10 | −0.3 (5) |
Br3—C4—C5—C6 | 178.0 (2) | C13—C9—N2—Cd1 | −178.3 (2) |
C2—C1—C6—C5 | 2.3 (4) | C11—C10—N2—C9 | 0.5 (5) |
C7—C1—C6—C5 | −170.6 (3) | C11—C10—N2—Cd1 | 178.4 (2) |
C2—C1—C6—Br1 | −179.6 (2) | C12—C13—N3—N4 | −22.1 (5) |
C7—C1—C6—Br1 | 7.5 (4) | C9—C13—N3—N4 | 161.2 (3) |
N1—C5—C6—C1 | 178.5 (3) | C13—N3—N4—C14 | 178.5 (3) |
C4—C5—C6—C1 | 0.4 (4) | C18—C14—N4—N3 | 176.9 (3) |
N1—C5—C6—Br1 | 0.3 (4) | C15—C14—N4—N3 | −3.2 (5) |
C4—C5—C6—Br1 | −177.9 (2) | C14—C15—N5—C16 | −0.7 (5) |
C2—C1—C7—O4 | 102.5 (3) | C14—C15—N5—Cd1ii | −175.3 (2) |
C6—C1—C7—O4 | −84.8 (4) | C17—C16—N5—C15 | 0.9 (5) |
C2—C1—C7—O3 | −77.6 (4) | C17—C16—N5—Cd1ii | 176.0 (3) |
C6—C1—C7—O3 | 95.1 (3) | O3—C7—O4—Cd1 | 0.3 (4) |
C4—C3—C8—O1 | −88.7 (3) | C1—C7—O4—Cd1 | −179.83 (17) |
C2—C3—C8—O1 | 86.8 (3) | | |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, y−1/2, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C18—H18···O1Wiii | 0.97 (3) | 2.55 (3) | 3.418 (4) | 150 (3) |
C16—H16···O4ii | 1.03 (4) | 2.43 (4) | 3.229 (4) | 134 (3) |
C16—H16···Br1ii | 1.03 (4) | 2.71 (4) | 3.539 (3) | 138 (3) |
C10—H10···O1iv | 0.93 | 2.54 | 3.371 (4) | 148 |
O5W—H5WB···O1iv | 0.85 | 1.86 | 2.687 (3) | 165 |
O4W—H4WA···O2i | 0.84 | 1.95 | 2.776 (3) | 165 |
O3W—H3WB···O2i | 0.85 | 1.90 | 2.719 (3) | 162 |
O3W—H3WA···O2Wi | 0.84 | 2.05 | 2.883 (3) | 168 |
O2W—H2WB···N4v | 0.85 | 2.51 | 3.282 (4) | 151 |
N1—H1A···O1Wvi | 0.86 | 2.21 | 2.896 (3) | 137 |
O2W—H2WA···O1vii | 0.85 | 1.92 | 2.762 (3) | 168 |
O1W—H1WA···O3vii | 0.85 | 1.90 | 2.740 (3) | 170 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, y−1/2, −z+1/2; (iii) x, −y+3/2, z−1/2; (iv) −x+2, y+1/2, −z+1/2; (v) x, −y+3/2, z+1/2; (vi) x+1, −y+3/2, z+1/2; (vii) x−1, y, z. |
catena-Poly[[[tetraaquacadmium(II)]-µ-1,3-bis(pyridin-3-ylmethyl)urea-
κ2N1:
N1'-[diaquabis(5-amino-2,4,6-tribromoisophthalato-
κO)cadmium(II)]-µ-1,3-bis(pyridin-3-ylmethyl)urea-
κ2N1:
N1'] octahydrate] (2)
top
Crystal data top
[Cd(C8H2Br3NO4)(C12H12N4O)(H2O)3]·4H2O | F(000) = 1760 |
Mr = 896.63 | Dx = 1.962 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 17.7463 (13) Å | Cell parameters from 9975 reflections |
b = 8.6866 (7) Å | θ = 2.5–27.5° |
c = 21.9891 (13) Å | µ = 4.73 mm−1 |
β = 116.410 (4)° | T = 298 K |
V = 3036.0 (4) Å3 | Block, white |
Z = 4 | 0.27 × 0.25 × 0.23 mm |
Data collection top
Bruker APEXII area-detector diffractometer | 5557 reflections with I > 2σ(I) |
phi and ω scans | Rint = 0.032 |
Absorption correction: empirical (using intensity measurements) sadabs | θmax = 27.5°, θmin = 2.5° |
Tmin = 0.290, Tmax = 0.337 | h = −22→23 |
28954 measured reflections | k = −9→11 |
6951 independent reflections | l = −28→28 |
Refinement top
Refinement on F2 | 21 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.030 | H-atom parameters constrained |
wR(F2) = 0.079 | w = 1/[σ2(Fo2) + (0.0401P)2 + 1.6888P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.002 |
6951 reflections | Δρmax = 0.98 e Å−3 |
382 parameters | Δρmin = −0.98 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 | |
Br1 | 1.50292 (3) | 0.94090 (5) | 0.76161 (2) | 0.06931 (14) | |
Br2 | 1.31575 (2) | 0.55008 (4) | 0.54134 (2) | 0.03851 (9) | |
Br3 | 1.20184 (2) | 0.67014 (4) | 0.74060 (2) | 0.04474 (9) | |
C1 | 1.39859 (16) | 0.7464 (3) | 0.65385 (13) | 0.0285 (6) | |
C2 | 1.32727 (17) | 0.6523 (3) | 0.62132 (12) | 0.0257 (5) | |
C3 | 1.26741 (16) | 0.6310 (3) | 0.64476 (12) | 0.0253 (5) | |
C4 | 1.27963 (17) | 0.7049 (3) | 0.70450 (13) | 0.0280 (6) | |
C5 | 1.34914 (18) | 0.7978 (3) | 0.73994 (13) | 0.0311 (6) | |
C6 | 1.40691 (18) | 0.8168 (3) | 0.71394 (14) | 0.0339 (6) | |
C7 | 1.18978 (18) | 0.5350 (3) | 0.60616 (14) | 0.0329 (6) | |
C8 | 1.3618 (2) | 0.8740 (4) | 0.80564 (16) | 0.0450 (8) | |
C9 | 1.00908 (18) | 0.5656 (4) | 0.35737 (14) | 0.0361 (6) | |
H9 | 0.958961 | 0.617297 | 0.347073 | 0.043* | |
C10 | 1.04376 (18) | 0.5770 (3) | 0.31229 (14) | 0.0325 (6) | |
C11 | 1.1173 (2) | 0.4969 (4) | 0.32780 (17) | 0.0443 (8) | |
H11 | 1.142866 | 0.501627 | 0.298958 | 0.053* | |
C12 | 1.1525 (2) | 0.4102 (4) | 0.38600 (16) | 0.0461 (8) | |
H12 | 1.201544 | 0.354475 | 0.396559 | 0.055* | |
C13 | 1.11451 (19) | 0.4065 (4) | 0.42854 (15) | 0.0400 (7) | |
H13 | 1.138958 | 0.348002 | 0.468006 | 0.048* | |
C14 | 1.0036 (2) | 0.6780 (4) | 0.25032 (15) | 0.0422 (7) | |
H14A | 0.950105 | 0.714889 | 0.246614 | 0.051* | |
H14B | 1.039295 | 0.767015 | 0.256534 | 0.051* | |
C15 | 0.91877 (18) | 0.5208 (3) | 0.15181 (14) | 0.0326 (6) | |
C16 | 0.83727 (19) | 0.3655 (4) | 0.05119 (17) | 0.0431 (7) | |
H16A | 0.825040 | 0.297741 | 0.080738 | 0.052* | |
H16B | 0.850815 | 0.301635 | 0.021212 | 0.052* | |
C17 | 0.75956 (18) | 0.4598 (3) | 0.00892 (15) | 0.0317 (6) | |
C18 | 0.7543 (2) | 0.5511 (4) | −0.04441 (17) | 0.0439 (8) | |
H18 | 0.799289 | 0.555486 | −0.055233 | 0.053* | |
C19 | 0.6827 (2) | 0.6353 (4) | −0.08146 (18) | 0.0464 (8) | |
H19 | 0.678919 | 0.697323 | −0.117191 | 0.056* | |
C20 | 0.61698 (19) | 0.6261 (3) | −0.06473 (16) | 0.0387 (7) | |
H20 | 0.568714 | 0.683478 | −0.089637 | 0.046* | |
C21 | 0.69062 (18) | 0.4577 (3) | 0.02215 (14) | 0.0317 (6) | |
H21 | 0.693188 | 0.397550 | 0.058024 | 0.038* | |
Cd1 | 1.000000 | 0.500000 | 0.500000 | 0.03099 (8) | |
Cd2 | 0.500000 | 0.500000 | 0.000000 | 0.02866 (8) | |
N1 | 1.45581 (16) | 0.7655 (3) | 0.62946 (13) | 0.0413 (6) | |
H1A | 1.499242 | 0.822630 | 0.650974 | 0.050* | |
H1B | 1.448740 | 0.720615 | 0.592445 | 0.050* | |
N2 | 1.04394 (15) | 0.4837 (3) | 0.41534 (12) | 0.0353 (6) | |
N3 | 0.98932 (16) | 0.6030 (3) | 0.18749 (12) | 0.0412 (6) | |
H3 | 1.026473 | 0.610866 | 0.172573 | 0.049* | |
N4 | 0.91001 (16) | 0.4597 (3) | 0.09238 (13) | 0.0432 (6) | |
H4 | 0.947845 | 0.476757 | 0.078827 | 0.052* | |
N5 | 0.61967 (15) | 0.5381 (3) | −0.01416 (12) | 0.0323 (5) | |
O1 | 1.19404 (15) | 0.3929 (3) | 0.61404 (12) | 0.0526 (6) | |
O2 | 1.12560 (13) | 0.6106 (3) | 0.56782 (10) | 0.0429 (5) | |
O3 | 1.3292 (2) | 1.0018 (3) | 0.80136 (14) | 0.0749 (9) | |
O4 | 1.40317 (18) | 0.8012 (3) | 0.85925 (11) | 0.0616 (7) | |
O6 | 0.86516 (14) | 0.5013 (3) | 0.17196 (12) | 0.0442 (5) | |
O1W | 0.95270 (19) | 0.7515 (3) | 0.46427 (14) | 0.0708 (8) | |
H1WA | 0.929073 | 0.767839 | 0.422586 | 0.106* | |
H1WB | 0.987327 | 0.819573 | 0.486700 | 0.106* | |
O2W | 0.52206 (13) | 0.2373 (2) | 0.00335 (10) | 0.0388 (5) | |
H2WB | 0.476227 | 0.186546 | −0.017347 | 0.058* | |
H2WA | 0.549875 | 0.198572 | 0.042795 | 0.058* | |
O3W | 0.58079 (14) | 0.5027 (3) | 0.11838 (11) | 0.0432 (5) | |
H3WA | 0.627324 | 0.552523 | 0.136566 | 0.065* | |
H3WB | 0.590021 | 0.409736 | 0.132052 | 0.065* | |
O4W | 0.37092 (16) | 0.3906 (3) | 0.43237 (12) | 0.0574 (6) | |
H4WB | 0.366116 | 0.455467 | 0.401801 | 0.086* | |
H4WA | 0.347515 | 0.306341 | 0.413131 | 0.086* | |
O5W | 0.72906 (16) | 0.6697 (3) | 0.16450 (13) | 0.0596 (6) | |
H5WA | 0.760541 | 0.593950 | 0.166019 | 0.089* | |
H5WB | 0.747435 | 0.710276 | 0.203536 | 0.089* | |
O6W | 0.1971 (2) | 0.3725 (4) | 0.19298 (19) | 0.0982 (11) | |
H6WA | 0.210143 | 0.294797 | 0.176444 | 0.147* | |
H6WB | 0.240578 | 0.411278 | 0.224864 | 0.147* | |
O7W | 0.08093 (16) | 0.9233 (3) | 0.59408 (14) | 0.0679 (8) | |
H7WA | 0.094051 | 0.828723 | 0.598359 | 0.102* | |
H7WB | 0.115534 | 0.973044 | 0.628524 | 0.102* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0672 (3) | 0.0808 (3) | 0.0520 (2) | −0.0512 (2) | 0.0194 (2) | −0.02352 (19) |
Br2 | 0.04671 (19) | 0.04058 (17) | 0.03350 (16) | −0.01018 (13) | 0.02259 (14) | −0.00970 (12) |
Br3 | 0.04461 (19) | 0.0597 (2) | 0.04058 (18) | −0.00181 (15) | 0.02854 (15) | −0.00068 (14) |
C1 | 0.0247 (14) | 0.0286 (13) | 0.0265 (13) | −0.0047 (11) | 0.0063 (11) | 0.0034 (10) |
C2 | 0.0291 (14) | 0.0257 (13) | 0.0214 (12) | −0.0015 (10) | 0.0104 (11) | 0.0012 (10) |
C3 | 0.0222 (13) | 0.0262 (13) | 0.0238 (12) | −0.0006 (10) | 0.0068 (11) | 0.0004 (10) |
C4 | 0.0285 (14) | 0.0314 (14) | 0.0257 (13) | 0.0001 (11) | 0.0134 (12) | 0.0016 (10) |
C5 | 0.0367 (16) | 0.0294 (14) | 0.0215 (13) | −0.0008 (12) | 0.0078 (12) | 0.0012 (10) |
C6 | 0.0326 (16) | 0.0316 (14) | 0.0285 (14) | −0.0140 (12) | 0.0055 (12) | −0.0005 (11) |
C7 | 0.0291 (16) | 0.0451 (17) | 0.0275 (14) | −0.0073 (13) | 0.0152 (13) | −0.0039 (12) |
C8 | 0.060 (2) | 0.0391 (18) | 0.0324 (17) | −0.0130 (16) | 0.0178 (16) | −0.0102 (13) |
C9 | 0.0291 (16) | 0.0447 (17) | 0.0325 (15) | −0.0012 (13) | 0.0118 (13) | −0.0042 (13) |
C10 | 0.0321 (16) | 0.0386 (16) | 0.0285 (14) | −0.0087 (12) | 0.0151 (13) | −0.0100 (12) |
C11 | 0.0406 (19) | 0.061 (2) | 0.0379 (17) | −0.0080 (15) | 0.0240 (16) | −0.0122 (15) |
C12 | 0.0306 (17) | 0.066 (2) | 0.0394 (18) | 0.0087 (15) | 0.0134 (14) | −0.0089 (15) |
C13 | 0.0333 (17) | 0.0498 (18) | 0.0337 (16) | 0.0002 (14) | 0.0119 (14) | −0.0039 (13) |
C14 | 0.051 (2) | 0.0424 (17) | 0.0367 (16) | −0.0057 (14) | 0.0230 (15) | −0.0012 (13) |
C15 | 0.0271 (15) | 0.0419 (16) | 0.0320 (15) | 0.0039 (12) | 0.0160 (13) | 0.0072 (12) |
C16 | 0.0328 (17) | 0.0480 (19) | 0.0462 (18) | 0.0036 (14) | 0.0154 (15) | −0.0088 (14) |
C17 | 0.0255 (15) | 0.0338 (15) | 0.0349 (15) | −0.0017 (11) | 0.0126 (12) | −0.0097 (12) |
C18 | 0.0380 (18) | 0.0504 (18) | 0.056 (2) | −0.0042 (15) | 0.0323 (17) | −0.0005 (16) |
C19 | 0.049 (2) | 0.0483 (19) | 0.0520 (19) | −0.0006 (15) | 0.0314 (17) | 0.0110 (15) |
C20 | 0.0358 (17) | 0.0379 (16) | 0.0455 (17) | 0.0015 (13) | 0.0210 (15) | 0.0049 (13) |
C21 | 0.0292 (15) | 0.0367 (15) | 0.0315 (15) | −0.0006 (12) | 0.0156 (13) | 0.0008 (12) |
Cd1 | 0.02508 (16) | 0.03903 (16) | 0.02994 (16) | −0.00448 (12) | 0.01320 (13) | 0.00137 (11) |
Cd2 | 0.02405 (15) | 0.03401 (15) | 0.03125 (15) | 0.00392 (11) | 0.01529 (13) | 0.00396 (11) |
N1 | 0.0347 (14) | 0.0519 (16) | 0.0410 (14) | −0.0168 (12) | 0.0200 (12) | −0.0025 (12) |
N2 | 0.0276 (13) | 0.0477 (15) | 0.0309 (13) | −0.0033 (11) | 0.0133 (11) | −0.0046 (10) |
N3 | 0.0347 (14) | 0.0607 (16) | 0.0346 (13) | −0.0080 (12) | 0.0212 (12) | −0.0018 (12) |
N4 | 0.0275 (14) | 0.0673 (18) | 0.0400 (15) | −0.0063 (12) | 0.0196 (12) | −0.0098 (13) |
N5 | 0.0300 (13) | 0.0343 (12) | 0.0366 (13) | −0.0001 (10) | 0.0184 (11) | 0.0008 (10) |
O1 | 0.0596 (15) | 0.0369 (12) | 0.0621 (15) | −0.0192 (11) | 0.0278 (13) | −0.0074 (11) |
O2 | 0.0263 (11) | 0.0595 (14) | 0.0359 (11) | −0.0077 (10) | 0.0075 (9) | −0.0028 (10) |
O3 | 0.124 (3) | 0.0475 (15) | 0.0541 (17) | 0.0074 (15) | 0.0400 (18) | −0.0128 (12) |
O4 | 0.0827 (19) | 0.0636 (16) | 0.0230 (11) | −0.0143 (14) | 0.0094 (12) | −0.0013 (10) |
O6 | 0.0387 (13) | 0.0556 (13) | 0.0505 (13) | −0.0032 (10) | 0.0309 (12) | 0.0014 (10) |
O1W | 0.096 (2) | 0.0454 (15) | 0.0586 (16) | 0.0102 (14) | 0.0236 (16) | 0.0136 (12) |
O2W | 0.0437 (12) | 0.0363 (11) | 0.0355 (11) | 0.0069 (9) | 0.0168 (10) | 0.0026 (9) |
O3W | 0.0376 (12) | 0.0544 (13) | 0.0355 (12) | 0.0021 (10) | 0.0144 (10) | 0.0028 (10) |
O4W | 0.0636 (16) | 0.0595 (15) | 0.0486 (14) | 0.0074 (13) | 0.0244 (13) | 0.0112 (12) |
O5W | 0.0630 (16) | 0.0533 (15) | 0.0652 (16) | 0.0024 (12) | 0.0311 (14) | −0.0039 (12) |
O6W | 0.110 (3) | 0.079 (2) | 0.125 (3) | −0.027 (2) | 0.070 (2) | −0.036 (2) |
O7W | 0.0588 (17) | 0.0726 (18) | 0.082 (2) | 0.0145 (14) | 0.0405 (16) | 0.0172 (15) |
Geometric parameters (Å, º) top
Br1—C6 | 1.891 (3) | C18—C19 | 1.375 (5) |
Br2—C2 | 1.898 (2) | C18—H18 | 0.9300 |
Br3—C4 | 1.898 (3) | C19—C20 | 1.373 (4) |
C1—N1 | 1.353 (3) | C19—H19 | 0.9300 |
C1—C6 | 1.403 (4) | C20—N5 | 1.333 (4) |
C1—C2 | 1.406 (4) | C20—H20 | 0.9300 |
C2—C3 | 1.384 (4) | C21—N5 | 1.348 (4) |
C3—C4 | 1.390 (4) | C21—H21 | 0.9300 |
C3—C7 | 1.508 (4) | Cd1—O2 | 2.271 (2) |
C4—C5 | 1.388 (4) | Cd1—O2i | 2.271 (2) |
C5—C6 | 1.388 (4) | Cd1—N2 | 2.321 (2) |
C5—C8 | 1.512 (4) | Cd1—N2i | 2.321 (2) |
C7—O1 | 1.243 (4) | Cd1—O1W | 2.347 (2) |
C7—O2 | 1.259 (4) | Cd1—O1Wi | 2.347 (2) |
C8—O3 | 1.236 (4) | Cd2—N5ii | 2.303 (2) |
C8—O4 | 1.248 (4) | Cd2—N5 | 2.303 (2) |
C9—N2 | 1.346 (4) | Cd2—O2Wii | 2.311 (2) |
C9—C10 | 1.383 (4) | Cd2—O2W | 2.311 (2) |
C9—H9 | 0.9300 | Cd2—O3W | 2.348 (2) |
C10—C11 | 1.382 (5) | Cd2—O3Wii | 2.348 (2) |
C10—C14 | 1.507 (4) | N1—H1A | 0.8600 |
C11—C12 | 1.373 (5) | N1—H1B | 0.8600 |
C11—H11 | 0.9300 | N3—H3 | 0.8600 |
C12—C13 | 1.376 (4) | N4—H4 | 0.8600 |
C12—H12 | 0.9300 | O1W—H1WA | 0.8331 |
C13—N2 | 1.334 (4) | O1W—H1WB | 0.8369 |
C13—H13 | 0.9300 | O2W—H2WB | 0.8564 |
C14—N3 | 1.444 (4) | O2W—H2WA | 0.8533 |
C14—H14A | 0.9700 | O3W—H3WA | 0.8578 |
C14—H14B | 0.9700 | O3W—H3WB | 0.8513 |
C15—O6 | 1.227 (3) | O4W—H4WB | 0.8517 |
C15—N3 | 1.349 (4) | O4W—H4WA | 0.8550 |
C15—N4 | 1.354 (4) | O5W—H5WA | 0.8539 |
C16—N4 | 1.455 (4) | O5W—H5WB | 0.8477 |
C16—C17 | 1.516 (4) | O6W—H6WA | 0.8461 |
C16—H16A | 0.9700 | O6W—H6WB | 0.8483 |
C16—H16B | 0.9700 | O7W—H7WA | 0.8475 |
C17—C21 | 1.378 (4) | O7W—H7WB | 0.8508 |
C17—C18 | 1.384 (4) | | |
| | | |
N1—C1—C6 | 122.4 (2) | N5—C20—H20 | 118.7 |
N1—C1—C2 | 122.3 (2) | C19—C20—H20 | 118.7 |
C6—C1—C2 | 115.2 (2) | N5—C21—C17 | 123.4 (3) |
C3—C2—C1 | 123.7 (2) | N5—C21—H21 | 118.3 |
C3—C2—Br2 | 119.91 (19) | C17—C21—H21 | 118.3 |
C1—C2—Br2 | 116.42 (19) | O2—Cd1—O2i | 180.0 |
C2—C3—C4 | 117.9 (2) | O2—Cd1—N2 | 88.32 (8) |
C2—C3—C7 | 121.6 (2) | O2i—Cd1—N2 | 91.68 (8) |
C4—C3—C7 | 120.5 (2) | O2—Cd1—N2i | 91.68 (8) |
C5—C4—C3 | 121.7 (2) | O2i—Cd1—N2i | 88.32 (8) |
C5—C4—Br3 | 119.21 (19) | N2—Cd1—N2i | 180.0 |
C3—C4—Br3 | 119.0 (2) | O2—Cd1—O1W | 85.79 (9) |
C4—C5—C6 | 118.2 (2) | O2i—Cd1—O1W | 94.21 (9) |
C4—C5—C8 | 120.5 (3) | N2—Cd1—O1W | 89.20 (9) |
C6—C5—C8 | 121.3 (3) | N2i—Cd1—O1W | 90.80 (9) |
C5—C6—C1 | 123.3 (2) | O2—Cd1—O1Wi | 94.21 (9) |
C5—C6—Br1 | 119.2 (2) | O2i—Cd1—O1Wi | 85.79 (9) |
C1—C6—Br1 | 117.5 (2) | N2—Cd1—O1Wi | 90.80 (9) |
O1—C7—O2 | 126.3 (3) | N2i—Cd1—O1Wi | 89.20 (9) |
O1—C7—C3 | 119.1 (3) | O1W—Cd1—O1Wi | 180.0 |
O2—C7—C3 | 114.6 (3) | N5ii—Cd2—N5 | 180.0 |
O3—C8—O4 | 125.8 (3) | N5ii—Cd2—O2Wii | 89.58 (8) |
O3—C8—C5 | 117.0 (3) | N5—Cd2—O2Wii | 90.42 (8) |
O4—C8—C5 | 117.1 (3) | N5ii—Cd2—O2W | 90.42 (8) |
N2—C9—C10 | 123.6 (3) | N5—Cd2—O2W | 89.58 (8) |
N2—C9—H9 | 118.2 | O2Wii—Cd2—O2W | 180.0 |
C10—C9—H9 | 118.2 | N5ii—Cd2—O3W | 89.80 (8) |
C11—C10—C9 | 117.4 (3) | N5—Cd2—O3W | 90.20 (8) |
C11—C10—C14 | 122.1 (3) | O2Wii—Cd2—O3W | 92.11 (7) |
C9—C10—C14 | 120.5 (3) | O2W—Cd2—O3W | 87.89 (7) |
C12—C11—C10 | 119.6 (3) | N5ii—Cd2—O3Wii | 90.20 (8) |
C12—C11—H11 | 120.2 | N5—Cd2—O3Wii | 89.80 (8) |
C10—C11—H11 | 120.2 | O2Wii—Cd2—O3Wii | 87.89 (7) |
C11—C12—C13 | 119.3 (3) | O2W—Cd2—O3Wii | 92.11 (7) |
C11—C12—H12 | 120.4 | O3W—Cd2—O3Wii | 180.0 |
C13—C12—H12 | 120.4 | C1—N1—H1A | 120.0 |
N2—C13—C12 | 122.5 (3) | C1—N1—H1B | 120.0 |
N2—C13—H13 | 118.7 | H1A—N1—H1B | 120.0 |
C12—C13—H13 | 118.7 | C13—N2—C9 | 117.6 (3) |
N3—C14—C10 | 114.4 (3) | C13—N2—Cd1 | 118.3 (2) |
N3—C14—H14A | 108.7 | C9—N2—Cd1 | 123.39 (19) |
C10—C14—H14A | 108.7 | C15—N3—C14 | 121.2 (2) |
N3—C14—H14B | 108.7 | C15—N3—H3 | 119.4 |
C10—C14—H14B | 108.7 | C14—N3—H3 | 119.4 |
H14A—C14—H14B | 107.6 | C15—N4—C16 | 120.7 (3) |
O6—C15—N3 | 122.1 (3) | C15—N4—H4 | 119.7 |
O6—C15—N4 | 121.3 (3) | C16—N4—H4 | 119.7 |
N3—C15—N4 | 116.6 (2) | C20—N5—C21 | 118.0 (2) |
N4—C16—C17 | 113.0 (3) | C20—N5—Cd2 | 120.14 (19) |
N4—C16—H16A | 109.0 | C21—N5—Cd2 | 121.34 (18) |
C17—C16—H16A | 109.0 | C7—O2—Cd1 | 123.40 (19) |
N4—C16—H16B | 109.0 | Cd1—O1W—H1WA | 117.2 |
C17—C16—H16B | 109.0 | Cd1—O1W—H1WB | 113.6 |
H16A—C16—H16B | 107.8 | H1WA—O1W—H1WB | 114.0 |
C21—C17—C18 | 117.1 (3) | Cd2—O2W—H2WB | 112.6 |
C21—C17—C16 | 120.9 (3) | Cd2—O2W—H2WA | 115.8 |
C18—C17—C16 | 122.0 (3) | H2WB—O2W—H2WA | 108.7 |
C19—C18—C17 | 120.2 (3) | Cd2—O3W—H3WA | 120.5 |
C19—C18—H18 | 119.9 | Cd2—O3W—H3WB | 108.0 |
C17—C18—H18 | 119.9 | H3WA—O3W—H3WB | 108.7 |
C20—C19—C18 | 118.8 (3) | H4WB—O4W—H4WA | 108.7 |
C20—C19—H19 | 120.6 | H5WA—O5W—H5WB | 109.3 |
C18—C19—H19 | 120.6 | H6WA—O6W—H6WB | 110.5 |
N5—C20—C19 | 122.5 (3) | H7WA—O7W—H7WB | 109.9 |
| | | |
N1—C1—C2—C3 | −179.6 (3) | N2—C9—C10—C11 | 1.3 (4) |
C6—C1—C2—C3 | 1.4 (4) | N2—C9—C10—C14 | −176.6 (3) |
N1—C1—C2—Br2 | 0.8 (3) | C9—C10—C11—C12 | 0.2 (4) |
C6—C1—C2—Br2 | −178.14 (19) | C14—C10—C11—C12 | 178.1 (3) |
C1—C2—C3—C4 | −1.2 (4) | C10—C11—C12—C13 | −1.0 (5) |
Br2—C2—C3—C4 | 178.30 (19) | C11—C12—C13—N2 | 0.4 (5) |
C1—C2—C3—C7 | 177.0 (3) | C11—C10—C14—N3 | 52.8 (4) |
Br2—C2—C3—C7 | −3.5 (3) | C9—C10—C14—N3 | −129.5 (3) |
C2—C3—C4—C5 | 0.3 (4) | N4—C16—C17—C21 | −112.4 (3) |
C7—C3—C4—C5 | −178.0 (3) | N4—C16—C17—C18 | 67.8 (4) |
C2—C3—C4—Br3 | −176.85 (19) | C21—C17—C18—C19 | 0.3 (5) |
C7—C3—C4—Br3 | 4.9 (3) | C16—C17—C18—C19 | −179.9 (3) |
C3—C4—C5—C6 | 0.4 (4) | C17—C18—C19—C20 | −0.4 (5) |
Br3—C4—C5—C6 | 177.5 (2) | C18—C19—C20—N5 | −0.3 (5) |
C3—C4—C5—C8 | −178.6 (3) | C18—C17—C21—N5 | 0.5 (4) |
Br3—C4—C5—C8 | −1.5 (4) | C16—C17—C21—N5 | −179.4 (3) |
C4—C5—C6—C1 | −0.2 (4) | C12—C13—N2—C9 | 1.0 (4) |
C8—C5—C6—C1 | 178.9 (3) | C12—C13—N2—Cd1 | −169.8 (2) |
C4—C5—C6—Br1 | −179.3 (2) | C10—C9—N2—C13 | −1.9 (4) |
C8—C5—C6—Br1 | −0.2 (4) | C10—C9—N2—Cd1 | 168.4 (2) |
N1—C1—C6—C5 | −179.6 (3) | O6—C15—N3—C14 | −2.6 (4) |
C2—C1—C6—C5 | −0.7 (4) | N4—C15—N3—C14 | 177.7 (3) |
N1—C1—C6—Br1 | −0.5 (4) | C10—C14—N3—C15 | 86.1 (4) |
C2—C1—C6—Br1 | 178.44 (19) | O6—C15—N4—C16 | −1.5 (4) |
C2—C3—C7—O1 | 83.8 (3) | N3—C15—N4—C16 | 178.2 (3) |
C4—C3—C7—O1 | −98.0 (3) | C17—C16—N4—C15 | 80.0 (4) |
C2—C3—C7—O2 | −95.8 (3) | C19—C20—N5—C21 | 1.1 (4) |
C4—C3—C7—O2 | 82.4 (3) | C19—C20—N5—Cd2 | −170.5 (2) |
C4—C5—C8—O3 | −88.6 (4) | C17—C21—N5—C20 | −1.2 (4) |
C6—C5—C8—O3 | 92.4 (4) | C17—C21—N5—Cd2 | 170.4 (2) |
C4—C5—C8—O4 | 90.5 (4) | O1—C7—O2—Cd1 | −1.8 (4) |
C6—C5—C8—O4 | −88.5 (4) | C3—C7—O2—Cd1 | 177.76 (16) |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+1, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O1i | 0.83 | 2.41 | 2.708 (4) | 102 |
O2W—H2WA···O4i | 0.85 | 1.93 | 2.727 (3) | 154 |
O3W—H3WB···O4i | 0.85 | 1.84 | 2.677 (3) | 167 |
N1—H1A···O3Wiii | 0.86 | 2.42 | 3.085 (3) | 135 |
N1—H1B···O2Wiv | 0.86 | 2.39 | 3.125 (3) | 144 |
O1W—H1WA···O7Wv | 0.83 | 2.70 | 3.050 (4) | 107 |
N3—H3···O7Wvi | 0.86 | 2.34 | 3.144 (3) | 155 |
N4—H4···O7Wvi | 0.86 | 2.40 | 3.183 (4) | 153 |
O2W—H2WB···O4Wvii | 0.86 | 1.82 | 2.672 (3) | 170 |
O4W—H4WB···O3viii | 0.85 | 2.04 | 2.797 (4) | 148 |
O4W—H4WB···O4viii | 0.85 | 2.51 | 3.301 (4) | 154 |
O6W—H6WB···O3viii | 0.85 | 1.88 | 2.720 (5) | 173 |
O5W—H5WB···O6Wix | 0.85 | 2.48 | 3.315 (5) | 170 |
O7W—H7WA···O2x | 0.85 | 2.17 | 2.958 (4) | 156 |
O7W—H7WB···O6Wxi | 0.85 | 2.02 | 2.853 (5) | 166 |
O4W—H4WA···O5Wxii | 0.86 | 2.03 | 2.830 (4) | 156 |
O6W—H6WA···O1xiii | 0.85 | 2.07 | 2.872 (4) | 159 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (iii) x+1, −y+3/2, z+1/2; (iv) −x+2, y+1/2, −z+1/2; (v) −x+1, −y+2, −z+1; (vi) x+1, −y+3/2, z−1/2; (vii) x, −y+1/2, z−1/2; (viii) x−1, −y+3/2, z−1/2; (ix) −x+1, y+1/2, −z+1/2; (x) x−1, y, z; (xi) x, −y+3/2, z+1/2; (xii) −x+1, y−1/2, −z+1/2; (xiii) x−1, −y+1/2, z−1/2. |
Halogen-bond geometry (Å, °) for (1) topC—Br···N | C—Br | Br···N | C···N | C—Br···N |
C2—Br2···N3 | 1.900 (3) | 3.288 (3) | 5.086 (3) | 156 |
Halogen-bond geometry (Å, °) for (2) topC—O···Br | C—O | O···Br | C···Br | C—O···Br |
C15—O6···Br3xiii | 1.227 (5) | 3.060 (3) | 4.176 (4) | 151 |
| | | | |
C—Br···O | C—Br | Br···O | C···O | C—Br···O |
C2—Br2···O4Wxiv | 1.898 (3) | 3.272 (3) | 5.089 (4) | 158 |
Symmetry codes: (xiii) -x+2, -y+1, -z+1;
(xiv) x+1, y, z. |