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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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S205322961801015X/ly3068sup1.cif
Contains datablocks 1, 2, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S205322961801015X/ly30681sup2.hkl
Contains datablock 1

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S205322961801015X/ly30682sup3.hkl
Contains datablock 2

CCDC references: 1855669; 1855668

Computing details top

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]·2H2OF(000) = 1552
Mr = 802.52Dx = 2.087 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 7.9226 (9) ÅCell parameters from 9877 reflections
b = 19.1965 (18) Åθ = 2.4–27.4°
c = 17.2011 (16) ŵ = 5.60 mm1
β = 102.460 (3)°T = 298 K
V = 2554.4 (4) Å3Block, orange
Z = 40.31 × 0.27 × 0.25 mm
Data collection top
Bruker APEXII area-detector
diffractometer
4767 reflections with I > 2σ(I)
phi and ω scansRint = 0.040
Absorption correction: empirical (using intensity measurements)
sadabs
θmax = 27.5°, θmin = 2.1°
Tmin = 0.192, Tmax = 0.246h = 1010
37897 measured reflectionsk = 2423
5860 independent reflectionsl = 2222
Refinement top
Refinement on F215 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.028H 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 reflectionsΔρmax = 1.19 e Å3
335 parametersΔρmin = 1.18 e Å3
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
xyzUiso*/Ueq
Br10.93119 (5)0.87547 (2)0.54970 (2)0.04577 (10)
Br20.77918 (5)0.72459 (2)0.25771 (2)0.03916 (9)
Br31.09988 (4)0.59075 (2)0.54485 (2)0.03967 (9)
C10.8670 (3)0.79187 (13)0.40855 (15)0.0242 (6)
C20.8685 (3)0.72880 (13)0.36937 (15)0.0231 (6)
C30.9356 (3)0.66839 (13)0.40864 (15)0.0219 (5)
C41.0017 (4)0.67194 (14)0.48995 (16)0.0252 (6)
C50.9974 (4)0.73296 (15)0.53366 (16)0.0281 (6)
C60.9293 (4)0.79214 (14)0.49059 (16)0.0270 (6)
C70.8186 (4)0.85930 (14)0.36141 (16)0.0280 (6)
C80.9470 (4)0.60220 (14)0.36183 (16)0.0271 (6)
C90.5542 (4)0.86412 (15)0.15364 (18)0.0332 (7)
H90.5211150.8420970.1961480.040*
C100.6513 (4)0.96150 (16)0.10035 (18)0.0364 (7)
H100.6866001.0077760.1055870.044*
C110.6505 (4)0.92750 (17)0.02914 (19)0.0387 (7)
H110.6836390.9505450.0127330.046*
C120.5994 (4)0.85844 (17)0.02191 (19)0.0387 (7)
H120.5981340.8339650.0248720.046*
C130.5504 (4)0.82677 (15)0.08516 (18)0.0323 (7)
C140.4095 (4)0.65520 (15)0.02981 (19)0.0346 (7)
C150.4281 (4)0.61872 (15)0.10139 (18)0.0341 (7)
H150.4719770.6417510.1490370.041*
H180.333 (4)0.6492 (17)0.089 (2)0.041*
H170.253 (4)0.5301 (17)0.085 (2)0.041*
C160.3201 (5)0.52060 (17)0.03290 (19)0.0404 (8)
C170.2996 (5)0.55360 (18)0.0388 (2)0.0488 (9)
C180.3459 (5)0.62155 (18)0.04075 (19)0.0443 (8)
Cd10.61080 (3)0.98664 (2)0.28330 (2)0.02765 (6)
H160.289 (4)0.4688 (19)0.036 (2)0.050 (10)*
N11.0606 (4)0.73580 (15)0.61389 (15)0.0519 (8)
H1A1.1049790.6992310.6391840.062*
H1B1.0561440.7741640.6391830.062*
N20.6034 (3)0.93059 (12)0.16170 (14)0.0305 (5)
N30.5011 (4)0.75417 (14)0.08932 (15)0.0378 (6)
N40.4529 (4)0.72724 (14)0.02370 (15)0.0384 (6)
N50.3848 (3)0.55186 (12)0.10320 (14)0.0305 (5)
O11.0804 (3)0.59567 (11)0.33534 (14)0.0414 (5)
O20.8237 (3)0.56067 (10)0.35386 (13)0.0374 (5)
O30.9360 (3)0.88371 (12)0.33132 (15)0.0497 (6)
O40.6726 (3)0.88430 (10)0.35646 (12)0.0364 (5)
O1W0.1950 (3)0.83248 (12)0.26467 (12)0.0434 (5)
H1WA0.1075410.8437750.2831500.065*
H1WB0.2359950.7940080.2844570.065*
O2W0.3124 (3)0.70455 (13)0.34658 (15)0.0532 (6)
H2WA0.2294180.6756620.3422370.080*
H2WB0.3661660.7070320.3948760.080*
O3W0.5174 (3)1.08607 (11)0.20541 (13)0.0410 (5)
H3WA0.5664121.1234020.1965500.062*
H3WB0.4113261.0870650.1829060.062*
O4W0.3165 (3)0.96630 (11)0.26486 (13)0.0393 (5)
H4WA0.2567650.9917740.2292550.059*
H4WB0.2797710.9248690.2604980.059*
O5W0.8933 (3)1.02058 (11)0.29335 (13)0.0384 (5)
H5WA0.9356760.9800730.2984430.058*
H5WB0.9194291.0408460.2535520.058*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0712 (3)0.02838 (17)0.03275 (17)0.01262 (15)0.00021 (16)0.01036 (13)
Br20.0622 (2)0.02873 (16)0.02070 (14)0.00200 (14)0.00399 (13)0.00037 (12)
Br30.0499 (2)0.02596 (16)0.03663 (17)0.01038 (13)0.00516 (14)0.00753 (13)
C10.0293 (15)0.0194 (13)0.0228 (13)0.0031 (11)0.0032 (11)0.0017 (11)
C20.0297 (15)0.0199 (13)0.0180 (12)0.0028 (11)0.0014 (10)0.0006 (10)
C30.0218 (14)0.0182 (13)0.0248 (13)0.0009 (10)0.0029 (10)0.0005 (11)
C40.0302 (15)0.0178 (13)0.0255 (14)0.0041 (11)0.0012 (11)0.0044 (11)
C50.0353 (16)0.0273 (15)0.0198 (13)0.0047 (12)0.0018 (11)0.0024 (11)
C60.0374 (16)0.0188 (13)0.0239 (14)0.0037 (12)0.0048 (12)0.0052 (11)
C70.0405 (18)0.0183 (13)0.0231 (14)0.0049 (12)0.0024 (12)0.0014 (11)
C80.0325 (16)0.0189 (14)0.0266 (14)0.0047 (12)0.0009 (12)0.0015 (11)
C90.0434 (18)0.0220 (15)0.0331 (16)0.0005 (13)0.0058 (13)0.0022 (13)
C100.0464 (19)0.0253 (15)0.0372 (17)0.0061 (13)0.0087 (14)0.0014 (13)
C110.046 (2)0.0401 (18)0.0326 (16)0.0058 (15)0.0139 (14)0.0008 (14)
C120.0435 (19)0.0382 (18)0.0325 (16)0.0017 (15)0.0037 (14)0.0123 (14)
C130.0346 (17)0.0246 (15)0.0358 (16)0.0006 (12)0.0036 (13)0.0028 (13)
C140.0415 (18)0.0220 (15)0.0399 (17)0.0034 (13)0.0077 (14)0.0062 (13)
C150.0424 (18)0.0283 (16)0.0288 (15)0.0058 (13)0.0015 (13)0.0010 (13)
C160.058 (2)0.0260 (17)0.0326 (17)0.0094 (15)0.0000 (15)0.0013 (13)
C170.077 (3)0.0375 (19)0.0261 (16)0.0097 (18)0.0017 (16)0.0003 (15)
C180.065 (2)0.0376 (19)0.0276 (16)0.0029 (16)0.0037 (15)0.0090 (14)
Cd10.03572 (12)0.02188 (11)0.02415 (11)0.00108 (9)0.00378 (8)0.00192 (8)
N10.092 (2)0.0359 (16)0.0202 (13)0.0191 (15)0.0036 (14)0.0005 (12)
N20.0387 (14)0.0239 (12)0.0272 (12)0.0002 (10)0.0037 (10)0.0008 (10)
N30.0514 (17)0.0321 (14)0.0269 (13)0.0010 (12)0.0021 (12)0.0007 (11)
N40.0505 (17)0.0333 (14)0.0300 (14)0.0033 (12)0.0053 (12)0.0021 (11)
N50.0390 (15)0.0234 (12)0.0267 (12)0.0038 (10)0.0019 (10)0.0024 (10)
O10.0424 (13)0.0333 (12)0.0511 (14)0.0042 (10)0.0159 (11)0.0127 (10)
O20.0391 (13)0.0221 (10)0.0469 (13)0.0039 (9)0.0001 (10)0.0075 (10)
O30.0544 (15)0.0329 (13)0.0653 (16)0.0057 (11)0.0206 (13)0.0194 (12)
O40.0451 (13)0.0278 (11)0.0345 (11)0.0133 (10)0.0043 (10)0.0041 (9)
O1W0.0539 (15)0.0389 (13)0.0367 (12)0.0055 (11)0.0085 (11)0.0025 (10)
O2W0.0496 (15)0.0466 (15)0.0626 (16)0.0024 (12)0.0106 (12)0.0017 (13)
O3W0.0379 (13)0.0314 (12)0.0515 (14)0.0013 (10)0.0047 (10)0.0142 (10)
O4W0.0388 (13)0.0355 (12)0.0412 (12)0.0061 (10)0.0034 (10)0.0080 (10)
O5W0.0408 (13)0.0304 (12)0.0450 (13)0.0023 (9)0.0117 (10)0.0033 (10)
Geometric parameters (Å, º) top
Br1—C61.894 (3)C14—N41.435 (4)
Br2—C21.900 (3)C15—N51.331 (4)
Br3—C41.900 (3)C15—H150.9300
C1—C21.387 (4)C16—N51.348 (4)
C1—C61.391 (4)C16—C171.365 (4)
C1—C71.532 (4)C16—H161.03 (4)
C2—C31.389 (4)C17—C181.357 (5)
C3—C41.385 (4)C17—H170.92 (3)
C3—C81.517 (4)C18—H180.97 (3)
C4—C51.396 (4)Cd1—O5W2.302 (2)
C5—N11.364 (4)Cd1—N5i2.313 (2)
C5—C61.400 (4)Cd1—O4W2.317 (2)
C7—O41.239 (3)Cd1—O42.327 (2)
C7—O31.249 (4)Cd1—N22.342 (2)
C8—O11.245 (4)Cd1—O3W2.358 (2)
C8—O21.245 (3)N1—H1A0.8600
C9—N21.333 (4)N1—H1B0.8600
C9—C131.374 (4)N3—N41.225 (3)
C9—H90.9300O1W—H1WA0.8504
C10—N21.335 (4)O1W—H1WB0.8479
C10—C111.387 (4)O2W—H2WA0.8511
C10—H100.9300O2W—H2WB0.8492
C11—C121.384 (4)O3W—H3WA0.8443
C11—H110.9300O3W—H3WB0.8464
C12—C131.373 (4)O4W—H4WA0.8445
C12—H120.9300O4W—H4WB0.8447
C13—N31.453 (4)O5W—H5WA0.8439
C14—C181.371 (4)O5W—H5WB0.8508
C14—C151.396 (4)
C2—C1—C6117.3 (2)N5—C16—H16115.5 (19)
C2—C1—C7120.5 (2)C17—C16—H16121 (2)
C6—C1—C7121.8 (2)C18—C17—C16119.2 (3)
C1—C2—C3122.3 (2)C18—C17—H17121 (2)
C1—C2—Br2119.20 (19)C16—C17—H17120 (2)
C3—C2—Br2118.44 (19)C17—C18—C14118.7 (3)
C4—C3—C2118.1 (2)C17—C18—H18125 (2)
C4—C3—C8121.6 (2)C14—C18—H18116.5 (19)
C2—C3—C8120.1 (2)O5W—Cd1—N5i86.91 (8)
C3—C4—C5122.5 (2)O5W—Cd1—O4W172.48 (7)
C3—C4—Br3119.1 (2)N5i—Cd1—O4W92.19 (8)
C5—C4—Br3118.39 (19)O5W—Cd1—O496.36 (8)
N1—C5—C4122.2 (3)N5i—Cd1—O492.14 (8)
N1—C5—C6121.2 (3)O4W—Cd1—O491.13 (8)
C4—C5—C6116.6 (2)O5W—Cd1—N291.93 (8)
C1—C6—C5123.1 (2)N5i—Cd1—N2174.56 (8)
C1—C6—Br1120.5 (2)O4W—Cd1—N288.26 (8)
C5—C6—Br1116.4 (2)O4—Cd1—N293.27 (8)
O4—C7—O3126.4 (3)O5W—Cd1—O3W89.67 (8)
O4—C7—C1119.2 (3)N5i—Cd1—O3W89.26 (8)
O3—C7—C1114.4 (3)O4W—Cd1—O3W82.85 (7)
O1—C8—O2127.1 (3)O4—Cd1—O3W173.87 (8)
O1—C8—C3115.5 (3)N2—Cd1—O3W85.42 (8)
O2—C8—C3117.4 (3)C5—N1—H1A120.0
N2—C9—C13122.7 (3)C5—N1—H1B120.0
N2—C9—H9118.6H1A—N1—H1B120.0
C13—C9—H9118.6C9—N2—C10118.0 (3)
N2—C10—C11122.8 (3)C9—N2—Cd1118.90 (19)
N2—C10—H10118.6C10—N2—Cd1123.04 (19)
C11—C10—H10118.6N4—N3—C13113.1 (3)
C12—C11—C10118.4 (3)N3—N4—C14111.8 (3)
C12—C11—H11120.8C15—N5—C16117.3 (3)
C10—C11—H11120.8C15—N5—Cd1ii125.79 (19)
C13—C12—C11118.7 (3)C16—N5—Cd1ii116.72 (19)
C13—C12—H12120.7C7—O4—Cd1116.66 (19)
C11—C12—H12120.7H1WA—O1W—H1WB110.2
C12—C13—C9119.4 (3)H2WA—O2W—H2WB109.7
C12—C13—N3126.0 (3)Cd1—O3W—H3WA133.6
C9—C13—N3114.5 (3)Cd1—O3W—H3WB115.9
C18—C14—C15119.5 (3)H3WA—O3W—H3WB110.4
C18—C14—N4115.9 (3)Cd1—O4W—H4WA113.1
C15—C14—N4124.5 (3)Cd1—O4W—H4WB119.2
N5—C15—C14121.7 (3)H4WA—O4W—H4WB110.6
N5—C15—H15119.1Cd1—O5W—H5WA96.1
C14—C15—H15119.1Cd1—O5W—H5WB118.1
N5—C16—C17123.5 (3)H5WA—O5W—H5WB110.2
C6—C1—C2—C32.7 (4)C4—C3—C8—O291.4 (3)
C7—C1—C2—C3170.3 (3)C2—C3—C8—O293.1 (3)
C6—C1—C2—Br2178.3 (2)N2—C10—C11—C120.6 (5)
C7—C1—C2—Br28.7 (4)C10—C11—C12—C130.5 (5)
C1—C2—C3—C40.5 (4)C11—C12—C13—C90.3 (5)
Br2—C2—C3—C4179.5 (2)C11—C12—C13—N3176.9 (3)
C1—C2—C3—C8175.1 (3)N2—C9—C13—C120.2 (5)
Br2—C2—C3—C83.9 (4)N2—C9—C13—N3177.2 (3)
C2—C3—C4—C52.4 (4)C18—C14—C15—N50.4 (5)
C8—C3—C4—C5177.9 (3)N4—C14—C15—N5179.7 (3)
C2—C3—C4—Br3178.4 (2)N5—C16—C17—C180.1 (6)
C8—C3—C4—Br32.8 (4)C16—C17—C18—C141.0 (6)
C3—C4—C5—N1179.1 (3)C15—C14—C18—C171.3 (5)
Br3—C4—C5—N10.2 (4)N4—C14—C18—C17178.9 (3)
C3—C4—C5—C62.8 (4)C13—C9—N2—C100.3 (5)
Br3—C4—C5—C6178.0 (2)C13—C9—N2—Cd1178.3 (2)
C2—C1—C6—C52.3 (4)C11—C10—N2—C90.5 (5)
C7—C1—C6—C5170.6 (3)C11—C10—N2—Cd1178.4 (2)
C2—C1—C6—Br1179.6 (2)C12—C13—N3—N422.1 (5)
C7—C1—C6—Br17.5 (4)C9—C13—N3—N4161.2 (3)
N1—C5—C6—C1178.5 (3)C13—N3—N4—C14178.5 (3)
C4—C5—C6—C10.4 (4)C18—C14—N4—N3176.9 (3)
N1—C5—C6—Br10.3 (4)C15—C14—N4—N33.2 (5)
C4—C5—C6—Br1177.9 (2)C14—C15—N5—C160.7 (5)
C2—C1—C7—O4102.5 (3)C14—C15—N5—Cd1ii175.3 (2)
C6—C1—C7—O484.8 (4)C17—C16—N5—C150.9 (5)
C2—C1—C7—O377.6 (4)C17—C16—N5—Cd1ii176.0 (3)
C6—C1—C7—O395.1 (3)O3—C7—O4—Cd10.3 (4)
C4—C3—C8—O188.7 (3)C1—C7—O4—Cd1179.83 (17)
C2—C3—C8—O186.8 (3)
Symmetry codes: (i) x+1, y+1/2, z+1/2; (ii) x+1, y1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C18—H18···O1Wiii0.97 (3)2.55 (3)3.418 (4)150 (3)
C16—H16···O4ii1.03 (4)2.43 (4)3.229 (4)134 (3)
C16—H16···Br1ii1.03 (4)2.71 (4)3.539 (3)138 (3)
C10—H10···O1iv0.932.543.371 (4)148
O5W—H5WB···O1iv0.851.862.687 (3)165
O4W—H4WA···O2i0.841.952.776 (3)165
O3W—H3WB···O2i0.851.902.719 (3)162
O3W—H3WA···O2Wi0.842.052.883 (3)168
O2W—H2WB···N4v0.852.513.282 (4)151
N1—H1A···O1Wvi0.862.212.896 (3)137
O2W—H2WA···O1vii0.851.922.762 (3)168
O1W—H1WA···O3vii0.851.902.740 (3)170
Symmetry codes: (i) x+1, y+1/2, z+1/2; (ii) x+1, y1/2, z+1/2; (iii) x, y+3/2, z1/2; (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) x1, 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]·4H2OF(000) = 1760
Mr = 896.63Dx = 1.962 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 17.7463 (13) ÅCell parameters from 9975 reflections
b = 8.6866 (7) Åθ = 2.5–27.5°
c = 21.9891 (13) ŵ = 4.73 mm1
β = 116.410 (4)°T = 298 K
V = 3036.0 (4) Å3Block, white
Z = 40.27 × 0.25 × 0.23 mm
Data collection top
Bruker APEXII area-detector
diffractometer
5557 reflections with I > 2σ(I)
phi and ω scansRint = 0.032
Absorption correction: empirical (using intensity measurements)
sadabs
θmax = 27.5°, θmin = 2.5°
Tmin = 0.290, Tmax = 0.337h = 2223
28954 measured reflectionsk = 911
6951 independent reflectionsl = 2828
Refinement top
Refinement on F221 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.030H-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 reflectionsΔρmax = 0.98 e Å3
382 parametersΔρmin = 0.98 e Å3
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
xyzUiso*/Ueq
Br11.50292 (3)0.94090 (5)0.76161 (2)0.06931 (14)
Br21.31575 (2)0.55008 (4)0.54134 (2)0.03851 (9)
Br31.20184 (2)0.67014 (4)0.74060 (2)0.04474 (9)
C11.39859 (16)0.7464 (3)0.65385 (13)0.0285 (6)
C21.32727 (17)0.6523 (3)0.62132 (12)0.0257 (5)
C31.26741 (16)0.6310 (3)0.64476 (12)0.0253 (5)
C41.27963 (17)0.7049 (3)0.70450 (13)0.0280 (6)
C51.34914 (18)0.7978 (3)0.73994 (13)0.0311 (6)
C61.40691 (18)0.8168 (3)0.71394 (14)0.0339 (6)
C71.18978 (18)0.5350 (3)0.60616 (14)0.0329 (6)
C81.3618 (2)0.8740 (4)0.80564 (16)0.0450 (8)
C91.00908 (18)0.5656 (4)0.35737 (14)0.0361 (6)
H90.9589610.6172970.3470730.043*
C101.04376 (18)0.5770 (3)0.31229 (14)0.0325 (6)
C111.1173 (2)0.4969 (4)0.32780 (17)0.0443 (8)
H111.1428660.5016270.2989580.053*
C121.1525 (2)0.4102 (4)0.38600 (16)0.0461 (8)
H121.2015440.3544750.3965590.055*
C131.11451 (19)0.4065 (4)0.42854 (15)0.0400 (7)
H131.1389580.3480020.4680060.048*
C141.0036 (2)0.6780 (4)0.25032 (15)0.0422 (7)
H14A0.9501050.7148890.2466140.051*
H14B1.0392950.7670150.2565340.051*
C150.91877 (18)0.5208 (3)0.15181 (14)0.0326 (6)
C160.83727 (19)0.3655 (4)0.05119 (17)0.0431 (7)
H16A0.8250400.2977410.0807380.052*
H16B0.8508150.3016350.0212120.052*
C170.75956 (18)0.4598 (3)0.00892 (15)0.0317 (6)
C180.7543 (2)0.5511 (4)0.04441 (17)0.0439 (8)
H180.7992890.5554860.0552330.053*
C190.6827 (2)0.6353 (4)0.08146 (18)0.0464 (8)
H190.6789190.6973230.1171910.056*
C200.61698 (19)0.6261 (3)0.06473 (16)0.0387 (7)
H200.5687140.6834780.0896370.046*
C210.69062 (18)0.4577 (3)0.02215 (14)0.0317 (6)
H210.6931880.3975500.0580240.038*
Cd11.0000000.5000000.5000000.03099 (8)
Cd20.5000000.5000000.0000000.02866 (8)
N11.45581 (16)0.7655 (3)0.62946 (13)0.0413 (6)
H1A1.4992420.8226300.6509740.050*
H1B1.4487400.7206150.5924450.050*
N21.04394 (15)0.4837 (3)0.41534 (12)0.0353 (6)
N30.98932 (16)0.6030 (3)0.18749 (12)0.0412 (6)
H31.0264730.6108660.1725730.049*
N40.91001 (16)0.4597 (3)0.09238 (13)0.0432 (6)
H40.9478450.4767570.0788270.052*
N50.61967 (15)0.5381 (3)0.01416 (12)0.0323 (5)
O11.19404 (15)0.3929 (3)0.61404 (12)0.0526 (6)
O21.12560 (13)0.6106 (3)0.56782 (10)0.0429 (5)
O31.3292 (2)1.0018 (3)0.80136 (14)0.0749 (9)
O41.40317 (18)0.8012 (3)0.85925 (11)0.0616 (7)
O60.86516 (14)0.5013 (3)0.17196 (12)0.0442 (5)
O1W0.95270 (19)0.7515 (3)0.46427 (14)0.0708 (8)
H1WA0.9290730.7678390.4225860.106*
H1WB0.9873270.8195730.4867000.106*
O2W0.52206 (13)0.2373 (2)0.00335 (10)0.0388 (5)
H2WB0.4762270.1865460.0173470.058*
H2WA0.5498750.1985720.0427950.058*
O3W0.58079 (14)0.5027 (3)0.11838 (11)0.0432 (5)
H3WA0.6273240.5525230.1365660.065*
H3WB0.5900210.4097360.1320520.065*
O4W0.37092 (16)0.3906 (3)0.43237 (12)0.0574 (6)
H4WB0.3661160.4554670.4018010.086*
H4WA0.3475150.3063410.4131310.086*
O5W0.72906 (16)0.6697 (3)0.16450 (13)0.0596 (6)
H5WA0.7605410.5939500.1660190.089*
H5WB0.7474350.7102760.2035360.089*
O6W0.1971 (2)0.3725 (4)0.19298 (19)0.0982 (11)
H6WA0.2101430.2947970.1764440.147*
H6WB0.2405780.4112780.2248640.147*
O7W0.08093 (16)0.9233 (3)0.59408 (14)0.0679 (8)
H7WA0.0940510.8287230.5983590.102*
H7WB0.1155340.9730440.6285240.102*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0672 (3)0.0808 (3)0.0520 (2)0.0512 (2)0.0194 (2)0.02352 (19)
Br20.04671 (19)0.04058 (17)0.03350 (16)0.01018 (13)0.02259 (14)0.00970 (12)
Br30.04461 (19)0.0597 (2)0.04058 (18)0.00181 (15)0.02854 (15)0.00068 (14)
C10.0247 (14)0.0286 (13)0.0265 (13)0.0047 (11)0.0063 (11)0.0034 (10)
C20.0291 (14)0.0257 (13)0.0214 (12)0.0015 (10)0.0104 (11)0.0012 (10)
C30.0222 (13)0.0262 (13)0.0238 (12)0.0006 (10)0.0068 (11)0.0004 (10)
C40.0285 (14)0.0314 (14)0.0257 (13)0.0001 (11)0.0134 (12)0.0016 (10)
C50.0367 (16)0.0294 (14)0.0215 (13)0.0008 (12)0.0078 (12)0.0012 (10)
C60.0326 (16)0.0316 (14)0.0285 (14)0.0140 (12)0.0055 (12)0.0005 (11)
C70.0291 (16)0.0451 (17)0.0275 (14)0.0073 (13)0.0152 (13)0.0039 (12)
C80.060 (2)0.0391 (18)0.0324 (17)0.0130 (16)0.0178 (16)0.0102 (13)
C90.0291 (16)0.0447 (17)0.0325 (15)0.0012 (13)0.0118 (13)0.0042 (13)
C100.0321 (16)0.0386 (16)0.0285 (14)0.0087 (12)0.0151 (13)0.0100 (12)
C110.0406 (19)0.061 (2)0.0379 (17)0.0080 (15)0.0240 (16)0.0122 (15)
C120.0306 (17)0.066 (2)0.0394 (18)0.0087 (15)0.0134 (14)0.0089 (15)
C130.0333 (17)0.0498 (18)0.0337 (16)0.0002 (14)0.0119 (14)0.0039 (13)
C140.051 (2)0.0424 (17)0.0367 (16)0.0057 (14)0.0230 (15)0.0012 (13)
C150.0271 (15)0.0419 (16)0.0320 (15)0.0039 (12)0.0160 (13)0.0072 (12)
C160.0328 (17)0.0480 (19)0.0462 (18)0.0036 (14)0.0154 (15)0.0088 (14)
C170.0255 (15)0.0338 (15)0.0349 (15)0.0017 (11)0.0126 (12)0.0097 (12)
C180.0380 (18)0.0504 (18)0.056 (2)0.0042 (15)0.0323 (17)0.0005 (16)
C190.049 (2)0.0483 (19)0.0520 (19)0.0006 (15)0.0314 (17)0.0110 (15)
C200.0358 (17)0.0379 (16)0.0455 (17)0.0015 (13)0.0210 (15)0.0049 (13)
C210.0292 (15)0.0367 (15)0.0315 (15)0.0006 (12)0.0156 (13)0.0008 (12)
Cd10.02508 (16)0.03903 (16)0.02994 (16)0.00448 (12)0.01320 (13)0.00137 (11)
Cd20.02405 (15)0.03401 (15)0.03125 (15)0.00392 (11)0.01529 (13)0.00396 (11)
N10.0347 (14)0.0519 (16)0.0410 (14)0.0168 (12)0.0200 (12)0.0025 (12)
N20.0276 (13)0.0477 (15)0.0309 (13)0.0033 (11)0.0133 (11)0.0046 (10)
N30.0347 (14)0.0607 (16)0.0346 (13)0.0080 (12)0.0212 (12)0.0018 (12)
N40.0275 (14)0.0673 (18)0.0400 (15)0.0063 (12)0.0196 (12)0.0098 (13)
N50.0300 (13)0.0343 (12)0.0366 (13)0.0001 (10)0.0184 (11)0.0008 (10)
O10.0596 (15)0.0369 (12)0.0621 (15)0.0192 (11)0.0278 (13)0.0074 (11)
O20.0263 (11)0.0595 (14)0.0359 (11)0.0077 (10)0.0075 (9)0.0028 (10)
O30.124 (3)0.0475 (15)0.0541 (17)0.0074 (15)0.0400 (18)0.0128 (12)
O40.0827 (19)0.0636 (16)0.0230 (11)0.0143 (14)0.0094 (12)0.0013 (10)
O60.0387 (13)0.0556 (13)0.0505 (13)0.0032 (10)0.0309 (12)0.0014 (10)
O1W0.096 (2)0.0454 (15)0.0586 (16)0.0102 (14)0.0236 (16)0.0136 (12)
O2W0.0437 (12)0.0363 (11)0.0355 (11)0.0069 (9)0.0168 (10)0.0026 (9)
O3W0.0376 (12)0.0544 (13)0.0355 (12)0.0021 (10)0.0144 (10)0.0028 (10)
O4W0.0636 (16)0.0595 (15)0.0486 (14)0.0074 (13)0.0244 (13)0.0112 (12)
O5W0.0630 (16)0.0533 (15)0.0652 (16)0.0024 (12)0.0311 (14)0.0039 (12)
O6W0.110 (3)0.079 (2)0.125 (3)0.027 (2)0.070 (2)0.036 (2)
O7W0.0588 (17)0.0726 (18)0.082 (2)0.0145 (14)0.0405 (16)0.0172 (15)
Geometric parameters (Å, º) top
Br1—C61.891 (3)C18—C191.375 (5)
Br2—C21.898 (2)C18—H180.9300
Br3—C41.898 (3)C19—C201.373 (4)
C1—N11.353 (3)C19—H190.9300
C1—C61.403 (4)C20—N51.333 (4)
C1—C21.406 (4)C20—H200.9300
C2—C31.384 (4)C21—N51.348 (4)
C3—C41.390 (4)C21—H210.9300
C3—C71.508 (4)Cd1—O22.271 (2)
C4—C51.388 (4)Cd1—O2i2.271 (2)
C5—C61.388 (4)Cd1—N22.321 (2)
C5—C81.512 (4)Cd1—N2i2.321 (2)
C7—O11.243 (4)Cd1—O1W2.347 (2)
C7—O21.259 (4)Cd1—O1Wi2.347 (2)
C8—O31.236 (4)Cd2—N5ii2.303 (2)
C8—O41.248 (4)Cd2—N52.303 (2)
C9—N21.346 (4)Cd2—O2Wii2.311 (2)
C9—C101.383 (4)Cd2—O2W2.311 (2)
C9—H90.9300Cd2—O3W2.348 (2)
C10—C111.382 (5)Cd2—O3Wii2.348 (2)
C10—C141.507 (4)N1—H1A0.8600
C11—C121.373 (5)N1—H1B0.8600
C11—H110.9300N3—H30.8600
C12—C131.376 (4)N4—H40.8600
C12—H120.9300O1W—H1WA0.8331
C13—N21.334 (4)O1W—H1WB0.8369
C13—H130.9300O2W—H2WB0.8564
C14—N31.444 (4)O2W—H2WA0.8533
C14—H14A0.9700O3W—H3WA0.8578
C14—H14B0.9700O3W—H3WB0.8513
C15—O61.227 (3)O4W—H4WB0.8517
C15—N31.349 (4)O4W—H4WA0.8550
C15—N41.354 (4)O5W—H5WA0.8539
C16—N41.455 (4)O5W—H5WB0.8477
C16—C171.516 (4)O6W—H6WA0.8461
C16—H16A0.9700O6W—H6WB0.8483
C16—H16B0.9700O7W—H7WA0.8475
C17—C211.378 (4)O7W—H7WB0.8508
C17—C181.384 (4)
N1—C1—C6122.4 (2)N5—C20—H20118.7
N1—C1—C2122.3 (2)C19—C20—H20118.7
C6—C1—C2115.2 (2)N5—C21—C17123.4 (3)
C3—C2—C1123.7 (2)N5—C21—H21118.3
C3—C2—Br2119.91 (19)C17—C21—H21118.3
C1—C2—Br2116.42 (19)O2—Cd1—O2i180.0
C2—C3—C4117.9 (2)O2—Cd1—N288.32 (8)
C2—C3—C7121.6 (2)O2i—Cd1—N291.68 (8)
C4—C3—C7120.5 (2)O2—Cd1—N2i91.68 (8)
C5—C4—C3121.7 (2)O2i—Cd1—N2i88.32 (8)
C5—C4—Br3119.21 (19)N2—Cd1—N2i180.0
C3—C4—Br3119.0 (2)O2—Cd1—O1W85.79 (9)
C4—C5—C6118.2 (2)O2i—Cd1—O1W94.21 (9)
C4—C5—C8120.5 (3)N2—Cd1—O1W89.20 (9)
C6—C5—C8121.3 (3)N2i—Cd1—O1W90.80 (9)
C5—C6—C1123.3 (2)O2—Cd1—O1Wi94.21 (9)
C5—C6—Br1119.2 (2)O2i—Cd1—O1Wi85.79 (9)
C1—C6—Br1117.5 (2)N2—Cd1—O1Wi90.80 (9)
O1—C7—O2126.3 (3)N2i—Cd1—O1Wi89.20 (9)
O1—C7—C3119.1 (3)O1W—Cd1—O1Wi180.0
O2—C7—C3114.6 (3)N5ii—Cd2—N5180.0
O3—C8—O4125.8 (3)N5ii—Cd2—O2Wii89.58 (8)
O3—C8—C5117.0 (3)N5—Cd2—O2Wii90.42 (8)
O4—C8—C5117.1 (3)N5ii—Cd2—O2W90.42 (8)
N2—C9—C10123.6 (3)N5—Cd2—O2W89.58 (8)
N2—C9—H9118.2O2Wii—Cd2—O2W180.0
C10—C9—H9118.2N5ii—Cd2—O3W89.80 (8)
C11—C10—C9117.4 (3)N5—Cd2—O3W90.20 (8)
C11—C10—C14122.1 (3)O2Wii—Cd2—O3W92.11 (7)
C9—C10—C14120.5 (3)O2W—Cd2—O3W87.89 (7)
C12—C11—C10119.6 (3)N5ii—Cd2—O3Wii90.20 (8)
C12—C11—H11120.2N5—Cd2—O3Wii89.80 (8)
C10—C11—H11120.2O2Wii—Cd2—O3Wii87.89 (7)
C11—C12—C13119.3 (3)O2W—Cd2—O3Wii92.11 (7)
C11—C12—H12120.4O3W—Cd2—O3Wii180.0
C13—C12—H12120.4C1—N1—H1A120.0
N2—C13—C12122.5 (3)C1—N1—H1B120.0
N2—C13—H13118.7H1A—N1—H1B120.0
C12—C13—H13118.7C13—N2—C9117.6 (3)
N3—C14—C10114.4 (3)C13—N2—Cd1118.3 (2)
N3—C14—H14A108.7C9—N2—Cd1123.39 (19)
C10—C14—H14A108.7C15—N3—C14121.2 (2)
N3—C14—H14B108.7C15—N3—H3119.4
C10—C14—H14B108.7C14—N3—H3119.4
H14A—C14—H14B107.6C15—N4—C16120.7 (3)
O6—C15—N3122.1 (3)C15—N4—H4119.7
O6—C15—N4121.3 (3)C16—N4—H4119.7
N3—C15—N4116.6 (2)C20—N5—C21118.0 (2)
N4—C16—C17113.0 (3)C20—N5—Cd2120.14 (19)
N4—C16—H16A109.0C21—N5—Cd2121.34 (18)
C17—C16—H16A109.0C7—O2—Cd1123.40 (19)
N4—C16—H16B109.0Cd1—O1W—H1WA117.2
C17—C16—H16B109.0Cd1—O1W—H1WB113.6
H16A—C16—H16B107.8H1WA—O1W—H1WB114.0
C21—C17—C18117.1 (3)Cd2—O2W—H2WB112.6
C21—C17—C16120.9 (3)Cd2—O2W—H2WA115.8
C18—C17—C16122.0 (3)H2WB—O2W—H2WA108.7
C19—C18—C17120.2 (3)Cd2—O3W—H3WA120.5
C19—C18—H18119.9Cd2—O3W—H3WB108.0
C17—C18—H18119.9H3WA—O3W—H3WB108.7
C20—C19—C18118.8 (3)H4WB—O4W—H4WA108.7
C20—C19—H19120.6H5WA—O5W—H5WB109.3
C18—C19—H19120.6H6WA—O6W—H6WB110.5
N5—C20—C19122.5 (3)H7WA—O7W—H7WB109.9
N1—C1—C2—C3179.6 (3)N2—C9—C10—C111.3 (4)
C6—C1—C2—C31.4 (4)N2—C9—C10—C14176.6 (3)
N1—C1—C2—Br20.8 (3)C9—C10—C11—C120.2 (4)
C6—C1—C2—Br2178.14 (19)C14—C10—C11—C12178.1 (3)
C1—C2—C3—C41.2 (4)C10—C11—C12—C131.0 (5)
Br2—C2—C3—C4178.30 (19)C11—C12—C13—N20.4 (5)
C1—C2—C3—C7177.0 (3)C11—C10—C14—N352.8 (4)
Br2—C2—C3—C73.5 (3)C9—C10—C14—N3129.5 (3)
C2—C3—C4—C50.3 (4)N4—C16—C17—C21112.4 (3)
C7—C3—C4—C5178.0 (3)N4—C16—C17—C1867.8 (4)
C2—C3—C4—Br3176.85 (19)C21—C17—C18—C190.3 (5)
C7—C3—C4—Br34.9 (3)C16—C17—C18—C19179.9 (3)
C3—C4—C5—C60.4 (4)C17—C18—C19—C200.4 (5)
Br3—C4—C5—C6177.5 (2)C18—C19—C20—N50.3 (5)
C3—C4—C5—C8178.6 (3)C18—C17—C21—N50.5 (4)
Br3—C4—C5—C81.5 (4)C16—C17—C21—N5179.4 (3)
C4—C5—C6—C10.2 (4)C12—C13—N2—C91.0 (4)
C8—C5—C6—C1178.9 (3)C12—C13—N2—Cd1169.8 (2)
C4—C5—C6—Br1179.3 (2)C10—C9—N2—C131.9 (4)
C8—C5—C6—Br10.2 (4)C10—C9—N2—Cd1168.4 (2)
N1—C1—C6—C5179.6 (3)O6—C15—N3—C142.6 (4)
C2—C1—C6—C50.7 (4)N4—C15—N3—C14177.7 (3)
N1—C1—C6—Br10.5 (4)C10—C14—N3—C1586.1 (4)
C2—C1—C6—Br1178.44 (19)O6—C15—N4—C161.5 (4)
C2—C3—C7—O183.8 (3)N3—C15—N4—C16178.2 (3)
C4—C3—C7—O198.0 (3)C17—C16—N4—C1580.0 (4)
C2—C3—C7—O295.8 (3)C19—C20—N5—C211.1 (4)
C4—C3—C7—O282.4 (3)C19—C20—N5—Cd2170.5 (2)
C4—C5—C8—O388.6 (4)C17—C21—N5—C201.2 (4)
C6—C5—C8—O392.4 (4)C17—C21—N5—Cd2170.4 (2)
C4—C5—C8—O490.5 (4)O1—C7—O2—Cd11.8 (4)
C6—C5—C8—O488.5 (4)C3—C7—O2—Cd1177.76 (16)
Symmetry codes: (i) x+2, y+1, z+1; (ii) x+1, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O1i0.832.412.708 (4)102
O2W—H2WA···O4i0.851.932.727 (3)154
O3W—H3WB···O4i0.851.842.677 (3)167
N1—H1A···O3Wiii0.862.423.085 (3)135
N1—H1B···O2Wiv0.862.393.125 (3)144
O1W—H1WA···O7Wv0.832.703.050 (4)107
N3—H3···O7Wvi0.862.343.144 (3)155
N4—H4···O7Wvi0.862.403.183 (4)153
O2W—H2WB···O4Wvii0.861.822.672 (3)170
O4W—H4WB···O3viii0.852.042.797 (4)148
O4W—H4WB···O4viii0.852.513.301 (4)154
O6W—H6WB···O3viii0.851.882.720 (5)173
O5W—H5WB···O6Wix0.852.483.315 (5)170
O7W—H7WA···O2x0.852.172.958 (4)156
O7W—H7WB···O6Wxi0.852.022.853 (5)166
O4W—H4WA···O5Wxii0.862.032.830 (4)156
O6W—H6WA···O1xiii0.852.072.872 (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, z1/2; (vii) x, y+1/2, z1/2; (viii) x1, y+3/2, z1/2; (ix) x+1, y+1/2, z+1/2; (x) x1, y, z; (xi) x, y+3/2, z+1/2; (xii) x+1, y1/2, z+1/2; (xiii) x1, y+1/2, z1/2.
Halogen-bond geometry (Å, °) for (1) top
C—Br···NC—BrBr···NC···NC—Br···N
C2—Br2···N31.900 (3)3.288 (3)5.086 (3)156
Halogen-bond geometry (Å, °) for (2) top
C—O···BrC—OO···BrC···BrC—O···Br
C15—O6···Br3xiii1.227 (5)3.060 (3)4.176 (4)151
C—Br···OC—BrBr···OC···OC—Br···O
C2—Br2···O4Wxiv1.898 (3)3.272 (3)5.089 (4)158
Symmetry codes: (xiii) -x+2, -y+1, -z+1; (xiv) x+1, y, z.
 

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