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Seven crystal structures of five first-row (Fe, Co, Ni, Cu, and Zn) and one second-row (Cd) transition metal–4-picoline (pic)–sulfate complexes of the form [M(pic)x]SO4 are reported. These complexes are catena-poly[[tetrakis(4-methylpyridine-κN)metal(II)]-μ-sulfato-κ2O:O′], [M(SO4)(C6H7N)4]n, where the metal/M is iron, cobalt, nickel, and cadmium, di-μ-sulfato-κ4O:O-bis[tris(4-methylpyridine-κN)copper(II)], [Cu2(SO4)2(C6H7N)6], catena-poly[[bis(4-methylpyridine-κN)zinc(II)]-μ-sulfato-κ2O:O′], [Zn(SO4)(C6H7N)2]n, and catena-poly[[tris(4-methylpyridine-κN)zinc(II)]-μ-sulfato-κ2O:O′], [Zn(SO4)(C6H7N)3]n. The Fe, Co, Ni, and Cd compounds are isomorphous, displaying polymeric crystal structures with infinite chains of MII ions adopting an octahedral N4O2 coordination environment that involves four picoline ligands and two bridging sulfate anions. The Cu compound features a dimeric crystal structure, with the CuII ions possessing square-pyramidal N3O2 coordination environments that contain three picoline ligands and two bridging sulfate anions. Zinc crystallizes in two forms, one exhibiting a polymeric crystal structure with infinite chains of ZnII ions adopting a tetrahedral N2O2 coordination containing two picoline ligands and two bridging sulfate anions, and the other exhibiting a polymeric crystal structure with infinite chains of ZnII ions adopting a trigonal bipyramidal N3O2 coordination containing three picoline ligands and two bridging sulfate anions. The structures are compared with the analogous pyridine complexes, and the observed coordination environments are examined in relation to crystal field theory.
Supporting information
CCDC references: 1908116; 1908115; 1908114; 1908113; 1908112; 1908111; 1908110
Data collection: APEX3 (Bruker, 2016) for umd1308_a, umd1358_a, umd1307, umd1301_a, UMD1448_a, umd1375_a; APEX2 (Bruker, 2015) for umd1540c_a. Cell refinement: SAINT (Bruker, 2016) for umd1308_a, umd1358_a, umd1307, umd1301_a, UMD1448_a, umd1375_a; SAINT (Bruker, 2015) for umd1540c_a. Data reduction: SAINT (Bruker, 2016) for umd1308_a, umd1358_a, umd1307, umd1301_a, UMD1448_a, umd1375_a; SAINT (Bruker, 2015) for umd1540c_a. For all structures, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).
catena-Poly[[tetrakis(4-methylpyridine-
κN)iron(II)]-sulfato-
κ2O:
O'] (umd1308_a)
top
Crystal data top
[Fe(SO4)(C6H7N)4] | F(000) = 2192 |
Mr = 524.41 | Dx = 1.364 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.4472 (13) Å | Cell parameters from 9601 reflections |
b = 18.822 (2) Å | θ = 3.1–25.8° |
c = 24.010 (3) Å | µ = 0.71 mm−1 |
β = 99.112 (3)° | T = 297 K |
V = 5108.0 (11) Å3 | Block, yellow-brown |
Z = 8 | 0.22 × 0.2 × 0.2 mm |
Data collection top
Bruker D8 Venture CMOS diffractometer | 4320 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.037 |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | θmax = 25.8°, θmin = 2.9° |
Tmin = 0.306, Tmax = 0.332 | h = −13→14 |
80351 measured reflections | k = −22→22 |
4895 independent reflections | l = −29→29 |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.030 | w = 1/[σ2(Fo2) + (0.0378P)2 + 5.7613P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.083 | (Δ/σ)max = 0.002 |
S = 1.10 | Δρmax = 0.40 e Å−3 |
4895 reflections | Δρmin = −0.30 e Å−3 |
314 parameters | Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
6 restraints | Extinction coefficient: 0.00300 (16) |
Primary atom site location: structure-invariant direct methods | |
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 | |
Fe1 | 0.5000 | 0.5000 | 0.5000 | 0.02613 (11) | |
Fe2 | 0.5000 | 0.47022 (2) | 0.7500 | 0.02408 (11) | |
S1 | 0.34329 (4) | 0.47876 (3) | 0.61286 (2) | 0.02862 (12) | |
O1 | 0.42874 (11) | 0.48685 (8) | 0.57272 (5) | 0.0355 (3) | |
O2 | 0.41429 (12) | 0.46837 (8) | 0.66946 (5) | 0.0397 (3) | |
O3 | 0.27471 (15) | 0.54311 (10) | 0.61302 (7) | 0.0601 (5) | |
O4 | 0.27080 (14) | 0.41670 (10) | 0.59876 (6) | 0.0541 (4) | |
N1 | 0.51167 (14) | 0.38214 (9) | 0.49376 (6) | 0.0368 (4) | |
N2 | 0.31868 (13) | 0.50168 (8) | 0.44867 (6) | 0.0317 (3) | |
N3 | 0.61876 (13) | 0.55408 (8) | 0.72335 (6) | 0.0309 (3) | |
N4 | 0.38082 (13) | 0.38122 (8) | 0.76966 (6) | 0.0319 (3) | |
C1 | 0.4357 (2) | 0.33786 (12) | 0.51286 (10) | 0.0503 (5) | |
H1 | 0.3763 | 0.3570 | 0.5305 | 0.060* | |
C2 | 0.4416 (3) | 0.26555 (14) | 0.50761 (13) | 0.0735 (8) | |
H2 | 0.3860 | 0.2370 | 0.5211 | 0.088* | |
C3 | 0.5296 (3) | 0.23473 (14) | 0.48236 (13) | 0.0762 (9) | |
C4 | 0.6085 (3) | 0.28022 (14) | 0.46382 (11) | 0.0614 (7) | |
H4 | 0.6704 | 0.2622 | 0.4472 | 0.074* | |
C5 | 0.59684 (19) | 0.35242 (12) | 0.46958 (9) | 0.0448 (5) | |
H5 | 0.6510 | 0.3820 | 0.4560 | 0.054* | |
C6 | 0.5398 (5) | 0.15502 (19) | 0.4760 (2) | 0.142 (2) | |
H6A | 0.4628 | 0.1353 | 0.4633 | 0.213* | |
H6B | 0.5723 | 0.1345 | 0.5116 | 0.213* | |
H6C | 0.5907 | 0.1447 | 0.4488 | 0.213* | |
C7 | 0.21927 (18) | 0.47721 (12) | 0.46451 (8) | 0.0423 (5) | |
H7 | 0.2243 | 0.4555 | 0.4996 | 0.051* | |
C8 | 0.11013 (18) | 0.48259 (14) | 0.43148 (9) | 0.0480 (6) | |
H8 | 0.0438 | 0.4643 | 0.4444 | 0.058* | |
C9 | 0.09827 (17) | 0.51482 (12) | 0.37941 (9) | 0.0405 (5) | |
C10 | 0.20008 (17) | 0.54053 (12) | 0.36336 (8) | 0.0421 (5) | |
H10 | 0.1968 | 0.5632 | 0.3287 | 0.051* | |
C11 | 0.30687 (17) | 0.53292 (11) | 0.39820 (8) | 0.0381 (5) | |
H11 | 0.3744 | 0.5505 | 0.3860 | 0.046* | |
C12 | −0.0192 (2) | 0.52174 (19) | 0.34214 (12) | 0.0723 (9) | |
H12A | −0.0736 | 0.4879 | 0.3535 | 0.108* | |
H12B | −0.0099 | 0.5128 | 0.3037 | 0.108* | |
H12C | −0.0494 | 0.5689 | 0.3453 | 0.108* | |
C13 | 0.58588 (18) | 0.59392 (11) | 0.67754 (8) | 0.0392 (4) | |
H13 | 0.5089 | 0.5894 | 0.6586 | 0.047* | |
C14 | 0.6601 (2) | 0.64131 (12) | 0.65696 (9) | 0.0486 (5) | |
H14 | 0.6325 | 0.6679 | 0.6249 | 0.058* | |
C15 | 0.7746 (2) | 0.64959 (12) | 0.68349 (10) | 0.0492 (5) | |
C16 | 0.80798 (19) | 0.60973 (14) | 0.73155 (10) | 0.0524 (6) | |
H16 | 0.8840 | 0.6143 | 0.7517 | 0.063* | |
C17 | 0.72941 (17) | 0.56319 (12) | 0.74991 (9) | 0.0418 (5) | |
H17 | 0.7546 | 0.5368 | 0.7824 | 0.050* | |
C18 | 0.8597 (3) | 0.69965 (17) | 0.66174 (15) | 0.0827 (9) | |
H18A | 0.9071 | 0.7231 | 0.6929 | 0.124* | |
H18B | 0.8162 | 0.7344 | 0.6375 | 0.124* | |
H18C | 0.9102 | 0.6733 | 0.6409 | 0.124* | |
C19 | 0.40919 (17) | 0.34134 (11) | 0.81595 (8) | 0.0376 (4) | |
H19 | 0.4811 | 0.3497 | 0.8390 | 0.045* | |
C20 | 0.33698 (19) | 0.28836 (12) | 0.83116 (9) | 0.0444 (5) | |
H20 | 0.3609 | 0.2622 | 0.8638 | 0.053* | |
C21 | 0.22959 (19) | 0.27409 (11) | 0.79815 (9) | 0.0432 (5) | |
C22 | 0.20183 (19) | 0.31401 (12) | 0.74954 (9) | 0.0461 (5) | |
H22 | 0.1313 | 0.3058 | 0.7253 | 0.055* | |
C23 | 0.27806 (17) | 0.36581 (11) | 0.73682 (8) | 0.0388 (4) | |
H23 | 0.2572 | 0.3915 | 0.7037 | 0.047* | |
C24 | 0.1458 (2) | 0.21870 (14) | 0.81395 (11) | 0.0631 (7) | |
H24A | 0.1063 | 0.1958 | 0.7804 | 0.095* | |
H24B | 0.0883 | 0.2409 | 0.8333 | 0.095* | |
H24C | 0.1894 | 0.1840 | 0.8382 | 0.095* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Fe1 | 0.02428 (18) | 0.0346 (2) | 0.02019 (18) | −0.00324 (14) | 0.00571 (13) | 0.00115 (14) |
Fe2 | 0.02236 (18) | 0.0318 (2) | 0.01830 (17) | 0.000 | 0.00385 (12) | 0.000 |
S1 | 0.0230 (2) | 0.0449 (3) | 0.0184 (2) | −0.00246 (17) | 0.00465 (16) | 0.00322 (17) |
O1 | 0.0312 (7) | 0.0534 (8) | 0.0241 (6) | −0.0044 (6) | 0.0112 (5) | 0.0018 (6) |
O2 | 0.0411 (8) | 0.0563 (9) | 0.0203 (6) | −0.0082 (6) | 0.0000 (5) | 0.0051 (6) |
O3 | 0.0550 (10) | 0.0692 (11) | 0.0627 (10) | 0.0278 (8) | 0.0291 (8) | 0.0227 (9) |
O4 | 0.0518 (9) | 0.0755 (11) | 0.0356 (8) | −0.0345 (8) | 0.0090 (7) | −0.0054 (7) |
N1 | 0.0399 (9) | 0.0386 (9) | 0.0325 (8) | −0.0024 (7) | 0.0074 (7) | 0.0014 (7) |
N2 | 0.0285 (8) | 0.0402 (9) | 0.0262 (8) | −0.0036 (7) | 0.0039 (6) | 0.0017 (6) |
N3 | 0.0283 (8) | 0.0359 (8) | 0.0291 (8) | −0.0020 (6) | 0.0060 (6) | −0.0011 (6) |
N4 | 0.0309 (8) | 0.0348 (8) | 0.0314 (8) | 0.0005 (6) | 0.0093 (6) | 0.0015 (6) |
C1 | 0.0578 (14) | 0.0454 (13) | 0.0527 (13) | −0.0091 (10) | 0.0240 (11) | −0.0024 (10) |
C2 | 0.100 (2) | 0.0436 (14) | 0.088 (2) | −0.0173 (14) | 0.0481 (18) | 0.0003 (13) |
C3 | 0.118 (3) | 0.0377 (13) | 0.082 (2) | 0.0009 (15) | 0.0445 (19) | 0.0022 (13) |
C4 | 0.0807 (18) | 0.0494 (14) | 0.0609 (15) | 0.0148 (13) | 0.0320 (13) | 0.0041 (12) |
C5 | 0.0498 (12) | 0.0427 (12) | 0.0450 (12) | 0.0048 (10) | 0.0167 (10) | 0.0062 (9) |
C6 | 0.212 (5) | 0.0458 (19) | 0.192 (5) | −0.003 (2) | 0.110 (4) | −0.009 (2) |
C7 | 0.0389 (11) | 0.0592 (13) | 0.0282 (10) | −0.0125 (10) | 0.0040 (8) | 0.0066 (9) |
C8 | 0.0306 (10) | 0.0749 (16) | 0.0388 (11) | −0.0155 (10) | 0.0067 (8) | 0.0047 (10) |
C9 | 0.0291 (10) | 0.0568 (13) | 0.0350 (10) | −0.0006 (9) | 0.0035 (8) | −0.0030 (9) |
C10 | 0.0343 (10) | 0.0602 (14) | 0.0314 (10) | 0.0031 (9) | 0.0042 (8) | 0.0112 (9) |
C11 | 0.0280 (9) | 0.0521 (12) | 0.0343 (10) | −0.0022 (8) | 0.0055 (8) | 0.0113 (9) |
C12 | 0.0339 (12) | 0.125 (3) | 0.0539 (15) | 0.0001 (14) | −0.0042 (11) | 0.0076 (16) |
C13 | 0.0411 (11) | 0.0383 (11) | 0.0360 (10) | −0.0047 (9) | −0.0002 (8) | 0.0016 (8) |
C14 | 0.0655 (15) | 0.0410 (12) | 0.0401 (11) | −0.0060 (10) | 0.0105 (10) | 0.0084 (9) |
C15 | 0.0484 (12) | 0.0482 (13) | 0.0561 (13) | −0.0122 (10) | 0.0237 (11) | −0.0008 (10) |
C16 | 0.0318 (11) | 0.0664 (16) | 0.0595 (14) | −0.0100 (10) | 0.0087 (10) | 0.0042 (12) |
C17 | 0.0312 (10) | 0.0545 (13) | 0.0396 (11) | −0.0036 (9) | 0.0049 (8) | 0.0061 (9) |
C18 | 0.081 (2) | 0.078 (2) | 0.099 (2) | −0.0275 (17) | 0.0440 (18) | 0.0116 (17) |
C19 | 0.0362 (10) | 0.0396 (11) | 0.0376 (10) | 0.0031 (8) | 0.0080 (8) | 0.0047 (8) |
C20 | 0.0533 (12) | 0.0388 (11) | 0.0431 (11) | 0.0012 (10) | 0.0139 (10) | 0.0108 (9) |
C21 | 0.0513 (12) | 0.0384 (11) | 0.0438 (11) | −0.0078 (9) | 0.0196 (10) | −0.0032 (9) |
C22 | 0.0439 (11) | 0.0547 (13) | 0.0400 (11) | −0.0143 (10) | 0.0074 (9) | −0.0012 (10) |
C23 | 0.0390 (11) | 0.0455 (12) | 0.0320 (10) | −0.0068 (9) | 0.0061 (8) | 0.0042 (8) |
C24 | 0.0746 (17) | 0.0559 (15) | 0.0639 (16) | −0.0226 (13) | 0.0269 (13) | 0.0025 (12) |
Geometric parameters (Å, º) top
Fe1—O1i | 2.0558 (12) | C7—H7 | 0.9300 |
Fe1—O1 | 2.0558 (12) | C7—C8 | 1.373 (3) |
Fe1—N1 | 2.2289 (17) | C8—H8 | 0.9300 |
Fe1—N1i | 2.2289 (17) | C8—C9 | 1.377 (3) |
Fe1—N2i | 2.2400 (15) | C9—C10 | 1.372 (3) |
Fe1—N2 | 2.2400 (15) | C9—C12 | 1.498 (3) |
Fe2—O2ii | 2.0254 (13) | C10—H10 | 0.9300 |
Fe2—O2 | 2.0254 (12) | C10—C11 | 1.375 (3) |
Fe2—N3 | 2.2415 (15) | C11—H11 | 0.9300 |
Fe2—N3ii | 2.2415 (15) | C12—H12A | 0.9600 |
Fe2—N4 | 2.2570 (16) | C12—H12B | 0.9600 |
Fe2—N4ii | 2.2570 (15) | C12—H12C | 0.9600 |
S1—O1 | 1.4856 (12) | C13—H13 | 0.9300 |
S1—O2 | 1.4819 (13) | C13—C14 | 1.376 (3) |
S1—O3 | 1.4437 (17) | C14—H14 | 0.9300 |
S1—O4 | 1.4418 (16) | C14—C15 | 1.373 (3) |
N1—C1 | 1.337 (3) | C15—C16 | 1.379 (3) |
N1—C5 | 1.334 (3) | C15—C18 | 1.508 (3) |
N2—C7 | 1.337 (2) | C16—H16 | 0.9300 |
N2—C11 | 1.334 (2) | C16—C17 | 1.377 (3) |
N3—C13 | 1.335 (2) | C17—H17 | 0.9300 |
N3—C17 | 1.336 (2) | C18—H18A | 0.9600 |
N4—C19 | 1.338 (2) | C18—H18B | 0.9600 |
N4—C23 | 1.340 (2) | C18—H18C | 0.9600 |
C1—H1 | 0.9300 | C19—H19 | 0.9300 |
C1—C2 | 1.370 (4) | C19—C20 | 1.381 (3) |
C2—H2 | 0.9300 | C20—H20 | 0.9300 |
C2—C3 | 1.384 (4) | C20—C21 | 1.379 (3) |
C3—C4 | 1.369 (4) | C21—C22 | 1.382 (3) |
C3—C6 | 1.515 (4) | C21—C24 | 1.505 (3) |
C4—H4 | 0.9300 | C22—H22 | 0.9300 |
C4—C5 | 1.375 (3) | C22—C23 | 1.375 (3) |
C5—H5 | 0.9300 | C23—H23 | 0.9300 |
C6—H6A | 0.9600 | C24—H24A | 0.9600 |
C6—H6B | 0.9600 | C24—H24B | 0.9600 |
C6—H6C | 0.9600 | C24—H24C | 0.9600 |
| | | |
O1i—Fe1—O1 | 180.0 | C3—C6—H6C | 109.5 |
O1—Fe1—N1 | 88.47 (6) | H6A—C6—H6B | 109.5 |
O1i—Fe1—N1 | 91.53 (6) | H6A—C6—H6C | 109.5 |
O1—Fe1—N1i | 91.53 (6) | H6B—C6—H6C | 109.5 |
O1i—Fe1—N1i | 88.47 (6) | N2—C7—H7 | 118.4 |
O1i—Fe1—N2 | 89.36 (5) | N2—C7—C8 | 123.21 (18) |
O1i—Fe1—N2i | 90.64 (5) | C8—C7—H7 | 118.4 |
O1—Fe1—N2 | 90.64 (5) | C7—C8—H8 | 119.8 |
O1—Fe1—N2i | 89.36 (5) | C7—C8—C9 | 120.44 (19) |
N1i—Fe1—N1 | 180.00 (8) | C9—C8—H8 | 119.8 |
N1—Fe1—N2i | 87.87 (6) | C8—C9—C12 | 122.1 (2) |
N1i—Fe1—N2 | 87.87 (6) | C10—C9—C8 | 116.38 (18) |
N1i—Fe1—N2i | 92.13 (6) | C10—C9—C12 | 121.6 (2) |
N1—Fe1—N2 | 92.13 (6) | C9—C10—H10 | 119.8 |
N2—Fe1—N2i | 180.00 (11) | C9—C10—C11 | 120.33 (18) |
O2ii—Fe2—O2 | 178.03 (9) | C11—C10—H10 | 119.8 |
O2ii—Fe2—N3ii | 87.92 (5) | N2—C11—C10 | 123.43 (18) |
O2—Fe2—N3ii | 93.47 (6) | N2—C11—H11 | 118.3 |
O2ii—Fe2—N3 | 93.47 (6) | C10—C11—H11 | 118.3 |
O2—Fe2—N3 | 87.92 (6) | C9—C12—H12A | 109.5 |
O2—Fe2—N4 | 88.25 (6) | C9—C12—H12B | 109.5 |
O2ii—Fe2—N4ii | 88.25 (6) | C9—C12—H12C | 109.5 |
O2—Fe2—N4ii | 90.29 (6) | H12A—C12—H12B | 109.5 |
O2ii—Fe2—N4 | 90.29 (6) | H12A—C12—H12C | 109.5 |
N3ii—Fe2—N3 | 90.47 (8) | H12B—C12—H12C | 109.5 |
N3—Fe2—N4ii | 92.81 (5) | N3—C13—H13 | 118.3 |
N3ii—Fe2—N4 | 92.81 (6) | N3—C13—C14 | 123.39 (19) |
N3—Fe2—N4 | 175.09 (5) | C14—C13—H13 | 118.3 |
N3ii—Fe2—N4ii | 175.09 (5) | C13—C14—H14 | 119.8 |
N4—Fe2—N4ii | 84.16 (8) | C15—C14—C13 | 120.3 (2) |
O2—S1—O1 | 106.66 (8) | C15—C14—H14 | 119.8 |
O3—S1—O1 | 109.27 (9) | C14—C15—C16 | 116.39 (19) |
O3—S1—O2 | 109.12 (10) | C14—C15—C18 | 122.2 (2) |
O4—S1—O1 | 110.14 (9) | C16—C15—C18 | 121.4 (2) |
O4—S1—O2 | 108.67 (9) | C15—C16—H16 | 119.8 |
O4—S1—O3 | 112.79 (11) | C17—C16—C15 | 120.4 (2) |
S1—O1—Fe1 | 162.52 (9) | C17—C16—H16 | 119.8 |
S1—O2—Fe2 | 170.32 (11) | N3—C17—C16 | 123.2 (2) |
C1—N1—Fe1 | 123.25 (14) | N3—C17—H17 | 118.4 |
C5—N1—Fe1 | 120.15 (14) | C16—C17—H17 | 118.4 |
C5—N1—C1 | 116.59 (19) | C15—C18—H18A | 109.5 |
C7—N2—Fe1 | 126.50 (13) | C15—C18—H18B | 109.5 |
C11—N2—Fe1 | 117.23 (12) | C15—C18—H18C | 109.5 |
C11—N2—C7 | 116.20 (16) | H18A—C18—H18B | 109.5 |
C13—N3—Fe2 | 121.74 (13) | H18A—C18—H18C | 109.5 |
C13—N3—C17 | 116.32 (17) | H18B—C18—H18C | 109.5 |
C17—N3—Fe2 | 121.75 (13) | N4—C19—H19 | 118.4 |
C19—N4—Fe2 | 120.99 (13) | N4—C19—C20 | 123.25 (19) |
C19—N4—C23 | 116.25 (17) | C20—C19—H19 | 118.4 |
C23—N4—Fe2 | 122.75 (13) | C19—C20—H20 | 119.8 |
N1—C1—H1 | 118.5 | C21—C20—C19 | 120.33 (19) |
N1—C1—C2 | 123.0 (2) | C21—C20—H20 | 119.8 |
C2—C1—H1 | 118.5 | C20—C21—C22 | 116.37 (19) |
C1—C2—H2 | 119.8 | C20—C21—C24 | 122.4 (2) |
C1—C2—C3 | 120.4 (2) | C22—C21—C24 | 121.3 (2) |
C3—C2—H2 | 119.8 | C21—C22—H22 | 119.9 |
C2—C3—C6 | 122.2 (3) | C23—C22—C21 | 120.3 (2) |
C4—C3—C2 | 116.4 (2) | C23—C22—H22 | 119.9 |
C4—C3—C6 | 121.4 (3) | N4—C23—C22 | 123.49 (19) |
C3—C4—H4 | 119.8 | N4—C23—H23 | 118.3 |
C3—C4—C5 | 120.4 (2) | C22—C23—H23 | 118.3 |
C5—C4—H4 | 119.8 | C21—C24—H24A | 109.5 |
N1—C5—C4 | 123.2 (2) | C21—C24—H24B | 109.5 |
N1—C5—H5 | 118.4 | C21—C24—H24C | 109.5 |
C4—C5—H5 | 118.4 | H24A—C24—H24B | 109.5 |
C3—C6—H6A | 109.5 | H24A—C24—H24C | 109.5 |
C3—C6—H6B | 109.5 | H24B—C24—H24C | 109.5 |
| | | |
Fe1—N1—C1—C2 | 178.3 (2) | C7—N2—C11—C10 | 0.1 (3) |
Fe1—N1—C5—C4 | −179.33 (19) | C7—C8—C9—C10 | −0.1 (4) |
Fe1—N2—C7—C8 | 177.35 (18) | C7—C8—C9—C12 | −180.0 (2) |
Fe1—N2—C11—C10 | −177.06 (17) | C8—C9—C10—C11 | 0.7 (3) |
Fe2—N3—C13—C14 | −173.88 (16) | C9—C10—C11—N2 | −0.7 (4) |
Fe2—N3—C17—C16 | 173.95 (18) | C11—N2—C7—C8 | 0.5 (3) |
Fe2—N4—C19—C20 | 177.08 (15) | C12—C9—C10—C11 | −179.5 (2) |
Fe2—N4—C23—C22 | −176.84 (16) | C13—N3—C17—C16 | −1.1 (3) |
O2—S1—O1—Fe1 | 178.2 (3) | C13—C14—C15—C16 | −1.6 (3) |
O3—S1—O1—Fe1 | −64.0 (3) | C13—C14—C15—C18 | 178.6 (2) |
O4—S1—O1—Fe1 | 60.4 (3) | C14—C15—C16—C17 | 1.7 (4) |
N1—C1—C2—C3 | 0.9 (5) | C15—C16—C17—N3 | −0.3 (4) |
N2—C7—C8—C9 | −0.5 (4) | C17—N3—C13—C14 | 1.2 (3) |
N3—C13—C14—C15 | 0.2 (3) | C18—C15—C16—C17 | −178.6 (2) |
N4—C19—C20—C21 | 0.1 (3) | C19—N4—C23—C22 | 2.2 (3) |
C1—N1—C5—C4 | 0.1 (3) | C19—C20—C21—C22 | 1.7 (3) |
C1—C2—C3—C4 | 0.3 (5) | C19—C20—C21—C24 | −177.8 (2) |
C1—C2—C3—C6 | 179.7 (4) | C20—C21—C22—C23 | −1.5 (3) |
C2—C3—C4—C5 | −1.3 (5) | C21—C22—C23—N4 | −0.5 (3) |
C3—C4—C5—N1 | 1.1 (4) | C23—N4—C19—C20 | −2.0 (3) |
C5—N1—C1—C2 | −1.1 (4) | C24—C21—C22—C23 | 178.0 (2) |
C6—C3—C4—C5 | 179.3 (3) | | |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y, −z+3/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O4 | 0.93 | 2.46 | 3.355 (3) | 163 |
C5—H5···O3i | 0.93 | 2.43 | 3.299 (3) | 156 |
C7—H7···S1 | 0.93 | 2.88 | 3.620 (2) | 138 |
C7—H7···O4 | 0.93 | 2.47 | 3.381 (3) | 168 |
C11—H11···O1i | 0.93 | 2.42 | 3.019 (2) | 122 |
C13—H13···O2 | 0.93 | 2.55 | 3.059 (2) | 115 |
C17—H17···O3ii | 0.93 | 2.59 | 3.320 (3) | 136 |
C19—H19···O2ii | 0.93 | 2.56 | 3.114 (3) | 119 |
C23—H23···O2 | 0.93 | 2.54 | 3.094 (2) | 118 |
C23—H23···O4 | 0.93 | 2.59 | 3.439 (2) | 152 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y, −z+3/2. |
catena-Poly[[tetrakis(4-methylpyridine-
κN)cobalt(II)]-sulfato-
κ2O:
O'] (umd1358_a)
top
Crystal data top
[Co(SO4)(C6H7N)4] | F(000) = 2200 |
Mr = 527.49 | Dx = 1.380 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.3904 (10) Å | Cell parameters from 9954 reflections |
b = 18.7098 (16) Å | θ = 3.1–25.7° |
c = 24.145 (2) Å | µ = 0.80 mm−1 |
β = 99.324 (3)° | T = 297 K |
V = 5077.6 (8) Å3 | BLOCK, pink |
Z = 8 | 0.36 × 0.3 × 0.24 mm |
Data collection top
Bruker D8 Venture CMOS diffractometer | 3999 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.039 |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | θmax = 25.8°, θmin = 3.1° |
Tmin = 0.518, Tmax = 0.562 | h = −13→13 |
58263 measured reflections | k = −22→22 |
4853 independent reflections | l = −29→29 |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.031 | w = 1/[σ2(Fo2) + (0.0387P)2 + 6.6062P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.084 | (Δ/σ)max = 0.002 |
S = 1.06 | Δρmax = 0.55 e Å−3 |
4853 reflections | Δρmin = −0.29 e Å−3 |
314 parameters | Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
6 restraints | Extinction coefficient: 0.00134 (11) |
Primary atom site location: structure-invariant direct methods | |
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 | 0.5000 | 0.5000 | 0.5000 | 0.02482 (11) | |
Co2 | 0.5000 | 0.46925 (2) | 0.2500 | 0.02267 (11) | |
S1 | 0.65907 (4) | 0.47838 (3) | 0.38723 (2) | 0.02747 (13) | |
O1 | 0.57321 (12) | 0.48643 (8) | 0.42671 (6) | 0.0340 (3) | |
O2 | 0.58914 (14) | 0.46684 (9) | 0.33098 (6) | 0.0402 (4) | |
O3 | 0.72749 (16) | 0.54361 (11) | 0.38679 (8) | 0.0605 (5) | |
O4 | 0.73364 (15) | 0.41659 (11) | 0.40208 (7) | 0.0539 (5) | |
N1 | 0.51127 (16) | 0.61564 (10) | 0.49367 (7) | 0.0345 (4) | |
N2 | 0.32237 (14) | 0.49777 (9) | 0.44950 (7) | 0.0296 (4) | |
N3 | 0.61651 (14) | 0.55148 (9) | 0.22427 (7) | 0.0288 (4) | |
N4 | 0.38306 (14) | 0.38189 (9) | 0.26959 (7) | 0.0294 (4) | |
C1 | 0.5965 (2) | 0.64537 (13) | 0.46927 (10) | 0.0417 (6) | |
H1 | 0.6502 | 0.6156 | 0.4553 | 0.050* | |
C2 | 0.6082 (3) | 0.71812 (14) | 0.46383 (12) | 0.0570 (7) | |
H2 | 0.6698 | 0.7363 | 0.4470 | 0.068* | |
C3 | 0.5299 (3) | 0.76398 (15) | 0.48299 (14) | 0.0728 (9) | |
C4 | 0.4420 (3) | 0.73299 (15) | 0.50832 (14) | 0.0711 (9) | |
H4 | 0.3867 | 0.7617 | 0.5220 | 0.085* | |
C5 | 0.4360 (2) | 0.66030 (14) | 0.51334 (11) | 0.0487 (6) | |
H5 | 0.3769 | 0.6410 | 0.5312 | 0.058* | |
C6 | 0.5409 (5) | 0.8442 (2) | 0.4769 (2) | 0.1310 (19) | |
H6A | 0.5904 | 0.8545 | 0.4493 | 0.197* | |
H6B | 0.5758 | 0.8644 | 0.5123 | 0.197* | |
H6C | 0.4634 | 0.8645 | 0.4653 | 0.197* | |
C7 | 0.2222 (2) | 0.52253 (13) | 0.46490 (9) | 0.0407 (6) | |
H7 | 0.2270 | 0.5445 | 0.4997 | 0.049* | |
C8 | 0.1127 (2) | 0.51696 (15) | 0.43170 (10) | 0.0462 (6) | |
H8 | 0.0458 | 0.5353 | 0.4443 | 0.055* | |
C9 | 0.10114 (19) | 0.48443 (13) | 0.38004 (9) | 0.0386 (5) | |
C10 | 0.20364 (19) | 0.45862 (13) | 0.36442 (9) | 0.0398 (5) | |
H10 | 0.2005 | 0.4357 | 0.3300 | 0.048* | |
C11 | 0.31084 (19) | 0.46640 (12) | 0.39919 (9) | 0.0357 (5) | |
H11 | 0.3789 | 0.4490 | 0.3871 | 0.043* | |
C12 | −0.0170 (2) | 0.4774 (2) | 0.34265 (13) | 0.0703 (9) | |
H12A | −0.0691 | 0.5147 | 0.3512 | 0.105* | |
H12B | −0.0512 | 0.4318 | 0.3487 | 0.105* | |
H12C | −0.0062 | 0.4813 | 0.3041 | 0.105* | |
C13 | 0.72826 (18) | 0.56053 (13) | 0.25047 (10) | 0.0398 (5) | |
H13 | 0.7542 | 0.5340 | 0.2827 | 0.048* | |
C14 | 0.8065 (2) | 0.60716 (15) | 0.23192 (11) | 0.0498 (6) | |
H14 | 0.8834 | 0.6115 | 0.2517 | 0.060* | |
C15 | 0.7721 (2) | 0.64756 (14) | 0.18426 (11) | 0.0473 (6) | |
C16 | 0.6566 (2) | 0.63943 (13) | 0.15825 (10) | 0.0465 (6) | |
H16 | 0.6283 | 0.6663 | 0.1265 | 0.056* | |
C17 | 0.5824 (2) | 0.59176 (12) | 0.17893 (9) | 0.0367 (5) | |
H17 | 0.5046 | 0.5874 | 0.1603 | 0.044* | |
C18 | 0.8571 (3) | 0.69786 (18) | 0.16216 (16) | 0.0785 (10) | |
H18A | 0.9036 | 0.7227 | 0.1929 | 0.118* | |
H18B | 0.8129 | 0.7318 | 0.1372 | 0.118* | |
H18C | 0.9089 | 0.6711 | 0.1423 | 0.118* | |
C19 | 0.27944 (19) | 0.36630 (12) | 0.23693 (9) | 0.0364 (5) | |
H19 | 0.2580 | 0.3921 | 0.2039 | 0.044* | |
C20 | 0.2033 (2) | 0.31420 (13) | 0.24978 (10) | 0.0440 (6) | |
H20 | 0.1322 | 0.3058 | 0.2258 | 0.053* | |
C21 | 0.2319 (2) | 0.27413 (12) | 0.29823 (10) | 0.0410 (5) | |
C22 | 0.3401 (2) | 0.28864 (13) | 0.33079 (10) | 0.0427 (6) | |
H22 | 0.3647 | 0.2624 | 0.3633 | 0.051* | |
C23 | 0.41222 (19) | 0.34187 (12) | 0.31547 (9) | 0.0358 (5) | |
H23 | 0.4849 | 0.3503 | 0.3383 | 0.043* | |
C24 | 0.1476 (3) | 0.21859 (15) | 0.31421 (12) | 0.0604 (8) | |
H24A | 0.1086 | 0.1948 | 0.2810 | 0.091* | |
H24B | 0.0891 | 0.2413 | 0.3328 | 0.091* | |
H24C | 0.1912 | 0.1843 | 0.3390 | 0.091* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.0230 (2) | 0.0323 (2) | 0.01965 (19) | 0.00332 (15) | 0.00493 (14) | −0.00122 (15) |
Co2 | 0.02097 (19) | 0.0293 (2) | 0.01818 (19) | 0.000 | 0.00437 (14) | 0.000 |
S1 | 0.0219 (2) | 0.0430 (3) | 0.0179 (2) | 0.0022 (2) | 0.00470 (18) | −0.0034 (2) |
O1 | 0.0300 (8) | 0.0511 (9) | 0.0232 (7) | 0.0045 (7) | 0.0114 (6) | −0.0013 (6) |
O2 | 0.0418 (9) | 0.0573 (10) | 0.0197 (7) | 0.0091 (7) | −0.0004 (6) | −0.0053 (7) |
O3 | 0.0550 (11) | 0.0675 (13) | 0.0665 (12) | −0.0288 (9) | 0.0323 (10) | −0.0246 (10) |
O4 | 0.0510 (10) | 0.0762 (13) | 0.0357 (9) | 0.0358 (9) | 0.0102 (8) | 0.0066 (9) |
N1 | 0.0375 (10) | 0.0366 (10) | 0.0304 (10) | 0.0040 (8) | 0.0082 (8) | −0.0012 (8) |
N2 | 0.0278 (9) | 0.0376 (10) | 0.0236 (9) | 0.0035 (7) | 0.0043 (7) | −0.0017 (7) |
N3 | 0.0265 (9) | 0.0327 (9) | 0.0274 (9) | −0.0010 (7) | 0.0054 (7) | −0.0014 (7) |
N4 | 0.0299 (9) | 0.0325 (9) | 0.0274 (9) | −0.0006 (7) | 0.0097 (7) | 0.0011 (7) |
C1 | 0.0470 (14) | 0.0417 (14) | 0.0390 (13) | −0.0039 (11) | 0.0151 (11) | −0.0060 (10) |
C2 | 0.0749 (19) | 0.0454 (16) | 0.0568 (17) | −0.0128 (14) | 0.0294 (14) | −0.0019 (13) |
C3 | 0.108 (3) | 0.0367 (15) | 0.083 (2) | −0.0006 (16) | 0.043 (2) | −0.0013 (15) |
C4 | 0.095 (2) | 0.0425 (16) | 0.087 (2) | 0.0183 (16) | 0.0480 (19) | 0.0014 (15) |
C5 | 0.0561 (15) | 0.0430 (14) | 0.0526 (15) | 0.0107 (12) | 0.0254 (13) | 0.0039 (12) |
C6 | 0.189 (5) | 0.047 (2) | 0.178 (5) | 0.003 (3) | 0.094 (4) | 0.010 (2) |
C7 | 0.0359 (12) | 0.0581 (15) | 0.0277 (11) | 0.0127 (11) | 0.0037 (9) | −0.0084 (10) |
C8 | 0.0308 (12) | 0.0720 (18) | 0.0363 (13) | 0.0163 (11) | 0.0072 (10) | −0.0037 (12) |
C9 | 0.0286 (11) | 0.0539 (15) | 0.0327 (12) | 0.0011 (10) | 0.0031 (9) | 0.0033 (10) |
C10 | 0.0333 (12) | 0.0569 (15) | 0.0290 (11) | −0.0043 (10) | 0.0042 (9) | −0.0114 (10) |
C11 | 0.0264 (11) | 0.0491 (14) | 0.0319 (12) | 0.0022 (9) | 0.0058 (9) | −0.0104 (10) |
C12 | 0.0318 (14) | 0.126 (3) | 0.0502 (17) | −0.0003 (15) | −0.0022 (12) | −0.0057 (17) |
C13 | 0.0277 (11) | 0.0537 (15) | 0.0377 (12) | −0.0029 (10) | 0.0044 (9) | 0.0065 (11) |
C14 | 0.0298 (12) | 0.0625 (17) | 0.0574 (16) | −0.0097 (11) | 0.0082 (11) | 0.0049 (13) |
C15 | 0.0483 (15) | 0.0452 (14) | 0.0537 (15) | −0.0120 (11) | 0.0245 (12) | −0.0028 (12) |
C16 | 0.0638 (16) | 0.0392 (14) | 0.0372 (13) | −0.0069 (12) | 0.0101 (12) | 0.0081 (11) |
C17 | 0.0389 (12) | 0.0351 (12) | 0.0346 (12) | −0.0032 (10) | 0.0013 (10) | 0.0010 (10) |
C18 | 0.077 (2) | 0.073 (2) | 0.095 (3) | −0.0234 (18) | 0.0439 (19) | 0.0115 (19) |
C19 | 0.0365 (12) | 0.0437 (13) | 0.0290 (11) | −0.0068 (10) | 0.0049 (9) | 0.0040 (9) |
C20 | 0.0419 (13) | 0.0519 (15) | 0.0383 (13) | −0.0137 (11) | 0.0069 (10) | −0.0015 (11) |
C21 | 0.0500 (14) | 0.0356 (13) | 0.0413 (13) | −0.0071 (10) | 0.0186 (11) | −0.0031 (10) |
C22 | 0.0527 (15) | 0.0371 (13) | 0.0407 (13) | 0.0027 (11) | 0.0151 (11) | 0.0107 (10) |
C23 | 0.0361 (12) | 0.0379 (12) | 0.0340 (12) | 0.0034 (10) | 0.0073 (9) | 0.0043 (10) |
C24 | 0.0732 (19) | 0.0528 (17) | 0.0601 (17) | −0.0211 (14) | 0.0253 (15) | 0.0035 (14) |
Geometric parameters (Å, º) top
Co1—O1i | 2.0903 (13) | C7—H7 | 0.9300 |
Co1—O1 | 2.0903 (13) | C7—C8 | 1.373 (3) |
Co1—N1 | 2.1743 (19) | C8—H8 | 0.9300 |
Co1—N1i | 2.1743 (19) | C8—C9 | 1.375 (3) |
Co1—N2 | 2.1869 (17) | C9—C10 | 1.372 (3) |
Co1—N2i | 2.1869 (17) | C9—C12 | 1.500 (3) |
Co2—O2ii | 2.0525 (14) | C10—H10 | 0.9300 |
Co2—O2 | 2.0525 (14) | C10—C11 | 1.373 (3) |
Co2—N3 | 2.1866 (17) | C11—H11 | 0.9300 |
Co2—N3ii | 2.1866 (17) | C12—H12A | 0.9600 |
Co2—N4 | 2.2077 (17) | C12—H12B | 0.9600 |
Co2—N4ii | 2.2078 (17) | C12—H12C | 0.9600 |
S1—O1 | 1.4799 (14) | C13—H13 | 0.9300 |
S1—O2 | 1.4748 (15) | C13—C14 | 1.373 (3) |
S1—O3 | 1.4490 (18) | C14—H14 | 0.9300 |
S1—O4 | 1.4449 (17) | C14—C15 | 1.380 (4) |
N1—C1 | 1.335 (3) | C15—C16 | 1.371 (4) |
N1—C5 | 1.338 (3) | C15—C18 | 1.508 (3) |
N2—C7 | 1.339 (3) | C16—H16 | 0.9300 |
N2—C11 | 1.336 (3) | C16—C17 | 1.377 (3) |
N3—C13 | 1.337 (3) | C17—H17 | 0.9300 |
N3—C17 | 1.334 (3) | C18—H18A | 0.9600 |
N4—C19 | 1.341 (3) | C18—H18B | 0.9600 |
N4—C23 | 1.334 (3) | C18—H18C | 0.9600 |
C1—H1 | 0.9300 | C19—H19 | 0.9300 |
C1—C2 | 1.376 (4) | C19—C20 | 1.373 (3) |
C2—H2 | 0.9300 | C20—H20 | 0.9300 |
C2—C3 | 1.371 (4) | C20—C21 | 1.383 (3) |
C3—C4 | 1.382 (4) | C21—C22 | 1.377 (3) |
C3—C6 | 1.515 (5) | C21—C24 | 1.507 (3) |
C4—H4 | 0.9300 | C22—H22 | 0.9300 |
C4—C5 | 1.368 (4) | C22—C23 | 1.379 (3) |
C5—H5 | 0.9300 | C23—H23 | 0.9300 |
C6—H6A | 0.9600 | C24—H24A | 0.9600 |
C6—H6B | 0.9600 | C24—H24B | 0.9600 |
C6—H6C | 0.9600 | C24—H24C | 0.9600 |
| | | |
O1i—Co1—O1 | 180.00 (3) | C3—C6—H6C | 109.5 |
O1i—Co1—N1 | 88.56 (6) | H6A—C6—H6B | 109.5 |
O1i—Co1—N1i | 91.44 (6) | H6A—C6—H6C | 109.5 |
O1—Co1—N1 | 91.44 (6) | H6B—C6—H6C | 109.5 |
O1—Co1—N1i | 88.56 (6) | N2—C7—H7 | 118.4 |
O1i—Co1—N2i | 89.18 (6) | N2—C7—C8 | 123.1 (2) |
O1—Co1—N2 | 89.18 (6) | C8—C7—H7 | 118.4 |
O1i—Co1—N2 | 90.82 (6) | C7—C8—H8 | 119.8 |
O1—Co1—N2i | 90.82 (6) | C7—C8—C9 | 120.5 (2) |
N1i—Co1—N1 | 180.0 | C9—C8—H8 | 119.8 |
N1i—Co1—N2 | 87.73 (7) | C8—C9—C12 | 122.0 (2) |
N1—Co1—N2i | 87.73 (7) | C10—C9—C8 | 116.4 (2) |
N1—Co1—N2 | 92.27 (7) | C10—C9—C12 | 121.6 (2) |
N1i—Co1—N2i | 92.27 (7) | C9—C10—H10 | 119.8 |
N2i—Co1—N2 | 180.0 | C9—C10—C11 | 120.5 (2) |
O2ii—Co2—O2 | 177.48 (10) | C11—C10—H10 | 119.8 |
O2ii—Co2—N3ii | 93.26 (6) | N2—C11—C10 | 123.3 (2) |
O2ii—Co2—N3 | 88.52 (6) | N2—C11—H11 | 118.3 |
O2—Co2—N3ii | 88.52 (6) | C10—C11—H11 | 118.3 |
O2—Co2—N3 | 93.26 (6) | C9—C12—H12A | 109.5 |
O2—Co2—N4 | 90.12 (7) | C9—C12—H12B | 109.5 |
O2—Co2—N4ii | 88.01 (6) | C9—C12—H12C | 109.5 |
O2ii—Co2—N4ii | 90.12 (7) | H12A—C12—H12B | 109.5 |
O2ii—Co2—N4 | 88.01 (6) | H12A—C12—H12C | 109.5 |
N3ii—Co2—N3 | 90.57 (9) | H12B—C12—H12C | 109.5 |
N3ii—Co2—N4 | 92.58 (6) | N3—C13—H13 | 118.5 |
N3ii—Co2—N4ii | 175.44 (6) | N3—C13—C14 | 123.0 (2) |
N3—Co2—N4ii | 92.58 (6) | C14—C13—H13 | 118.5 |
N3—Co2—N4 | 175.43 (6) | C13—C14—H14 | 119.7 |
N4—Co2—N4ii | 84.47 (9) | C13—C14—C15 | 120.5 (2) |
O2—S1—O1 | 107.06 (9) | C15—C14—H14 | 119.7 |
O3—S1—O1 | 109.36 (10) | C14—C15—C18 | 121.7 (3) |
O3—S1—O2 | 109.11 (11) | C16—C15—C14 | 116.3 (2) |
O4—S1—O1 | 110.17 (9) | C16—C15—C18 | 122.0 (3) |
O4—S1—O2 | 108.63 (10) | C15—C16—H16 | 119.8 |
O4—S1—O3 | 112.36 (12) | C15—C16—C17 | 120.4 (2) |
S1—O1—Co1 | 162.48 (10) | C17—C16—H16 | 119.8 |
S1—O2—Co2 | 169.75 (12) | N3—C17—C16 | 123.3 (2) |
C1—N1—Co1 | 120.06 (15) | N3—C17—H17 | 118.3 |
C1—N1—C5 | 116.7 (2) | C16—C17—H17 | 118.3 |
C5—N1—Co1 | 123.22 (16) | C15—C18—H18A | 109.5 |
C7—N2—Co1 | 126.28 (14) | C15—C18—H18B | 109.5 |
C11—N2—Co1 | 117.45 (13) | C15—C18—H18C | 109.5 |
C11—N2—C7 | 116.22 (18) | H18A—C18—H18B | 109.5 |
C13—N3—Co2 | 121.99 (15) | H18A—C18—H18C | 109.5 |
C17—N3—Co2 | 121.42 (14) | H18B—C18—H18C | 109.5 |
C17—N3—C13 | 116.42 (19) | N4—C19—H19 | 118.3 |
C19—N4—Co2 | 122.63 (14) | N4—C19—C20 | 123.3 (2) |
C23—N4—Co2 | 121.05 (14) | C20—C19—H19 | 118.3 |
C23—N4—C19 | 116.32 (18) | C19—C20—H20 | 119.8 |
N1—C1—H1 | 118.6 | C19—C20—C21 | 120.3 (2) |
N1—C1—C2 | 122.9 (2) | C21—C20—H20 | 119.8 |
C2—C1—H1 | 118.6 | C20—C21—C24 | 121.2 (2) |
C1—C2—H2 | 119.7 | C22—C21—C20 | 116.3 (2) |
C3—C2—C1 | 120.5 (3) | C22—C21—C24 | 122.6 (2) |
C3—C2—H2 | 119.7 | C21—C22—H22 | 119.8 |
C2—C3—C4 | 116.4 (3) | C21—C22—C23 | 120.4 (2) |
C2—C3—C6 | 121.2 (3) | C23—C22—H22 | 119.8 |
C4—C3—C6 | 122.4 (3) | N4—C23—C22 | 123.3 (2) |
C3—C4—H4 | 119.8 | N4—C23—H23 | 118.3 |
C5—C4—C3 | 120.4 (3) | C22—C23—H23 | 118.3 |
C5—C4—H4 | 119.8 | C21—C24—H24A | 109.5 |
N1—C5—C4 | 123.0 (2) | C21—C24—H24B | 109.5 |
N1—C5—H5 | 118.5 | C21—C24—H24C | 109.5 |
C4—C5—H5 | 118.5 | H24A—C24—H24B | 109.5 |
C3—C6—H6A | 109.5 | H24A—C24—H24C | 109.5 |
C3—C6—H6B | 109.5 | H24B—C24—H24C | 109.5 |
| | | |
Co1—N1—C1—C2 | 179.9 (2) | C5—N1—C1—C2 | −0.2 (4) |
Co1—N1—C5—C4 | −178.7 (2) | C6—C3—C4—C5 | −179.4 (4) |
Co1—N2—C7—C8 | −177.52 (19) | C7—N2—C11—C10 | −0.5 (3) |
Co1—N2—C11—C10 | 177.07 (19) | C7—C8—C9—C10 | 0.0 (4) |
Co2—N3—C13—C14 | 173.74 (19) | C7—C8—C9—C12 | −180.0 (3) |
Co2—N3—C17—C16 | −173.79 (18) | C8—C9—C10—C11 | −0.7 (4) |
Co2—N4—C19—C20 | −177.09 (18) | C9—C10—C11—N2 | 1.0 (4) |
Co2—N4—C23—C22 | 177.27 (17) | C11—N2—C7—C8 | −0.2 (4) |
O1—S1—O2—Co2 | 105.8 (6) | C12—C9—C10—C11 | 179.3 (3) |
O2—S1—O1—Co1 | 177.7 (3) | C13—N3—C17—C16 | 1.5 (3) |
O3—S1—O1—Co1 | −64.3 (4) | C13—C14—C15—C16 | 1.5 (4) |
O3—S1—O2—Co2 | −12.5 (6) | C13—C14—C15—C18 | −178.5 (3) |
O4—S1—O1—Co1 | 59.7 (4) | C14—C15—C16—C17 | −1.5 (4) |
O4—S1—O2—Co2 | −135.3 (6) | C15—C16—C17—N3 | 0.0 (4) |
N1—C1—C2—C3 | −1.0 (4) | C17—N3—C13—C14 | −1.5 (3) |
N2—C7—C8—C9 | 0.4 (4) | C18—C15—C16—C17 | 178.5 (3) |
N3—C13—C14—C15 | 0.0 (4) | C19—N4—C23—C22 | −2.2 (3) |
N4—C19—C20—C21 | −0.5 (4) | C19—C20—C21—C22 | −1.5 (3) |
C1—N1—C5—C4 | 1.4 (4) | C19—C20—C21—C24 | 177.7 (2) |
C1—C2—C3—C4 | 1.1 (5) | C20—C21—C22—C23 | 1.7 (3) |
C1—C2—C3—C6 | −179.5 (4) | C21—C22—C23—N4 | 0.2 (4) |
C2—C3—C4—C5 | 0.0 (5) | C23—N4—C19—C20 | 2.4 (3) |
C3—C4—C5—N1 | −1.3 (5) | C24—C21—C22—C23 | −177.5 (2) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O3 | 0.93 | 2.41 | 3.284 (3) | 157 |
C5—H5···O4i | 0.93 | 2.45 | 3.355 (3) | 165 |
C7—H7···S1i | 0.93 | 2.86 | 3.607 (2) | 138 |
C7—H7···O4i | 0.93 | 2.45 | 3.368 (3) | 169 |
C11—H11···O1 | 0.93 | 2.37 | 2.978 (3) | 123 |
C13—H13···O3 | 0.93 | 2.59 | 3.308 (3) | 135 |
C17—H17···S1ii | 0.93 | 2.87 | 3.632 (2) | 140 |
C17—H17···O2ii | 0.93 | 2.52 | 3.031 (3) | 115 |
C19—H19···O2ii | 0.93 | 2.48 | 3.044 (3) | 119 |
C23—H23···O2 | 0.93 | 2.50 | 3.070 (3) | 120 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y, −z+1/2. |
catena-Poly[[tetrakis(4-methylpyridine-
κN)nickel(II)]-sulfato-
κ2O:
O'] (umd1307)
top
Crystal data top
[Ni(SO4)(C6H7N)4] | F(000) = 2208 |
Mr = 527.27 | Dx = 1.394 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.3610 (17) Å | Cell parameters from 9925 reflections |
b = 18.546 (3) Å | θ = 3.1–25.7° |
c = 24.178 (4) Å | µ = 0.89 mm−1 |
β = 99.459 (5)° | T = 297 K |
V = 5025.1 (13) Å3 | PRISM, green |
Z = 8 | 0.25 × 0.19 × 0.12 mm |
Data collection top
Bruker D8 Venture CMOS diffractometer | 4037 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.044 |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | θmax = 25.7°, θmin = 2.9° |
Tmin = 0.289, Tmax = 0.332 | h = −13→13 |
62062 measured reflections | k = −22→22 |
4798 independent reflections | l = −29→29 |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.029 | w = 1/[σ2(Fo2) + (0.0338P)2 + 6.8591P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.077 | (Δ/σ)max = 0.001 |
S = 1.05 | Δρmax = 0.53 e Å−3 |
4798 reflections | Δρmin = −0.29 e Å−3 |
314 parameters | Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.00116 (10) |
Primary atom site location: structure-invariant direct methods | |
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 | |
Ni1 | 0.5000 | 0.5000 | 0.5000 | 0.02536 (11) | |
Ni2 | 0.5000 | 0.46852 (2) | 0.7500 | 0.02357 (10) | |
S1 | 0.34019 (4) | 0.47765 (3) | 0.61271 (2) | 0.02773 (13) | |
O1 | 0.42614 (12) | 0.48641 (8) | 0.57336 (6) | 0.0335 (3) | |
O2 | 0.40988 (14) | 0.46594 (9) | 0.66890 (6) | 0.0414 (4) | |
O3 | 0.27061 (16) | 0.54326 (10) | 0.61312 (8) | 0.0602 (5) | |
O4 | 0.26541 (15) | 0.41507 (10) | 0.59764 (6) | 0.0519 (5) | |
N1 | 0.48860 (15) | 0.61365 (9) | 0.50649 (7) | 0.0334 (4) | |
N2 | 0.67325 (14) | 0.49832 (9) | 0.54977 (7) | 0.0299 (4) | |
N3 | 0.38519 (14) | 0.38311 (9) | 0.76961 (7) | 0.0300 (4) | |
N4 | 0.61420 (14) | 0.54921 (9) | 0.72508 (7) | 0.0288 (4) | |
C1 | 0.5636 (2) | 0.65898 (13) | 0.48683 (10) | 0.0480 (6) | |
H1 | 0.6231 | 0.6398 | 0.4690 | 0.058* | |
C2 | 0.5565 (3) | 0.73261 (15) | 0.49175 (13) | 0.0664 (8) | |
H2 | 0.6113 | 0.7619 | 0.4778 | 0.080* | |
C3 | 0.4685 (3) | 0.76356 (14) | 0.51732 (13) | 0.0640 (8) | |
C4 | 0.3904 (2) | 0.71672 (14) | 0.53641 (11) | 0.0528 (6) | |
H4 | 0.3285 | 0.7348 | 0.5531 | 0.063* | |
C5 | 0.4031 (2) | 0.64333 (12) | 0.53101 (9) | 0.0401 (5) | |
H5 | 0.3497 | 0.6131 | 0.5450 | 0.048* | |
C6 | 0.4574 (4) | 0.84444 (18) | 0.5235 (2) | 0.1170 (17) | |
H6A | 0.4079 | 0.8547 | 0.5511 | 0.176* | |
H6B | 0.4222 | 0.8649 | 0.4882 | 0.176* | |
H6C | 0.5351 | 0.8649 | 0.5351 | 0.176* | |
C7 | 0.7735 (2) | 0.52382 (14) | 0.53425 (9) | 0.0426 (6) | |
H7 | 0.7683 | 0.5460 | 0.4994 | 0.051* | |
C8 | 0.8838 (2) | 0.51860 (15) | 0.56761 (10) | 0.0482 (6) | |
H8 | 0.9503 | 0.5379 | 0.5552 | 0.058* | |
C9 | 0.89660 (19) | 0.48533 (13) | 0.61890 (9) | 0.0406 (5) | |
C10 | 0.79391 (19) | 0.45863 (13) | 0.63449 (9) | 0.0403 (5) | |
H10 | 0.7975 | 0.4353 | 0.6688 | 0.048* | |
C11 | 0.68613 (18) | 0.46613 (12) | 0.59981 (9) | 0.0351 (5) | |
H11 | 0.6184 | 0.4478 | 0.6118 | 0.042* | |
C12 | 1.0162 (2) | 0.4780 (2) | 0.65665 (13) | 0.0706 (9) | |
H12A | 1.0691 | 0.5150 | 0.6478 | 0.106* | |
H12B | 1.0497 | 0.4316 | 0.6511 | 0.106* | |
H12C | 1.0057 | 0.4827 | 0.6951 | 0.106* | |
C13 | 0.41554 (19) | 0.34230 (12) | 0.81550 (9) | 0.0369 (5) | |
H13 | 0.4887 | 0.3506 | 0.8382 | 0.044* | |
C14 | 0.3429 (2) | 0.28850 (12) | 0.83055 (10) | 0.0436 (5) | |
H14 | 0.3679 | 0.2617 | 0.8628 | 0.052* | |
C15 | 0.2339 (2) | 0.27407 (12) | 0.79831 (10) | 0.0425 (5) | |
C16 | 0.2046 (2) | 0.31492 (13) | 0.75013 (10) | 0.0445 (6) | |
H16 | 0.1329 | 0.3067 | 0.7263 | 0.053* | |
C17 | 0.28103 (19) | 0.36763 (12) | 0.73722 (9) | 0.0372 (5) | |
H17 | 0.2592 | 0.3938 | 0.7043 | 0.045* | |
C18 | 0.1496 (3) | 0.21803 (15) | 0.81438 (12) | 0.0628 (8) | |
H18A | 0.1937 | 0.1832 | 0.8389 | 0.094* | |
H18B | 0.1098 | 0.1943 | 0.7812 | 0.094* | |
H18C | 0.0915 | 0.2409 | 0.8332 | 0.094* | |
C19 | 0.57846 (19) | 0.59043 (12) | 0.68007 (9) | 0.0365 (5) | |
H19 | 0.5000 | 0.5864 | 0.6619 | 0.044* | |
C20 | 0.6525 (2) | 0.63862 (13) | 0.65933 (10) | 0.0450 (6) | |
H20 | 0.6233 | 0.6661 | 0.6279 | 0.054* | |
C21 | 0.7689 (2) | 0.64654 (13) | 0.68459 (10) | 0.0460 (6) | |
C22 | 0.8049 (2) | 0.60531 (14) | 0.73190 (11) | 0.0496 (6) | |
H22 | 0.8825 | 0.6095 | 0.7512 | 0.060* | |
C23 | 0.72652 (18) | 0.55802 (13) | 0.75068 (9) | 0.0393 (5) | |
H23 | 0.7532 | 0.5310 | 0.7827 | 0.047* | |
C24 | 0.8539 (3) | 0.69725 (18) | 0.66225 (15) | 0.0769 (9) | |
H24A | 0.8092 | 0.7329 | 0.6388 | 0.115* | |
H24B | 0.9029 | 0.6705 | 0.6408 | 0.115* | |
H24C | 0.9035 | 0.7207 | 0.6930 | 0.115* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni1 | 0.02605 (19) | 0.0310 (2) | 0.01982 (17) | −0.00419 (14) | 0.00613 (13) | 0.00076 (14) |
Ni2 | 0.02264 (18) | 0.0295 (2) | 0.01939 (17) | 0.000 | 0.00592 (13) | 0.000 |
S1 | 0.0242 (2) | 0.0410 (3) | 0.0189 (2) | −0.0030 (2) | 0.00638 (18) | 0.00281 (19) |
O1 | 0.0305 (7) | 0.0491 (9) | 0.0233 (7) | −0.0041 (6) | 0.0120 (6) | 0.0016 (6) |
O2 | 0.0447 (9) | 0.0575 (10) | 0.0203 (7) | −0.0109 (7) | 0.0003 (6) | 0.0057 (6) |
O3 | 0.0561 (11) | 0.0625 (12) | 0.0703 (12) | 0.0262 (9) | 0.0347 (9) | 0.0239 (10) |
O4 | 0.0513 (10) | 0.0692 (12) | 0.0363 (9) | −0.0343 (9) | 0.0103 (7) | −0.0053 (8) |
N1 | 0.0380 (10) | 0.0358 (10) | 0.0274 (9) | −0.0045 (8) | 0.0080 (7) | 0.0007 (7) |
N2 | 0.0303 (9) | 0.0363 (9) | 0.0237 (8) | −0.0044 (7) | 0.0063 (7) | 0.0000 (7) |
N3 | 0.0312 (9) | 0.0333 (9) | 0.0275 (8) | 0.0010 (7) | 0.0109 (7) | 0.0012 (7) |
N4 | 0.0274 (8) | 0.0322 (9) | 0.0274 (8) | −0.0005 (7) | 0.0066 (7) | −0.0019 (7) |
C1 | 0.0565 (15) | 0.0409 (13) | 0.0527 (14) | −0.0096 (11) | 0.0272 (12) | −0.0030 (11) |
C2 | 0.088 (2) | 0.0405 (14) | 0.081 (2) | −0.0174 (14) | 0.0443 (17) | −0.0010 (14) |
C3 | 0.095 (2) | 0.0347 (14) | 0.0683 (18) | −0.0012 (14) | 0.0320 (17) | −0.0005 (13) |
C4 | 0.0682 (17) | 0.0431 (14) | 0.0522 (15) | 0.0121 (12) | 0.0248 (13) | 0.0024 (11) |
C5 | 0.0431 (12) | 0.0412 (13) | 0.0378 (12) | 0.0015 (10) | 0.0126 (10) | 0.0053 (10) |
C6 | 0.168 (4) | 0.0375 (17) | 0.166 (4) | −0.002 (2) | 0.087 (4) | −0.008 (2) |
C7 | 0.0413 (13) | 0.0602 (15) | 0.0267 (11) | −0.0148 (11) | 0.0064 (9) | 0.0049 (10) |
C8 | 0.0338 (12) | 0.0726 (17) | 0.0394 (13) | −0.0201 (12) | 0.0098 (10) | 0.0004 (12) |
C9 | 0.0299 (11) | 0.0570 (15) | 0.0347 (12) | −0.0019 (10) | 0.0048 (9) | −0.0059 (10) |
C10 | 0.0333 (11) | 0.0581 (15) | 0.0299 (11) | 0.0037 (10) | 0.0060 (9) | 0.0090 (10) |
C11 | 0.0275 (10) | 0.0476 (13) | 0.0308 (11) | −0.0019 (9) | 0.0068 (8) | 0.0084 (9) |
C12 | 0.0308 (13) | 0.121 (3) | 0.0581 (18) | −0.0025 (15) | 0.0028 (12) | −0.0044 (17) |
C13 | 0.0388 (12) | 0.0383 (12) | 0.0350 (11) | 0.0057 (9) | 0.0100 (9) | 0.0056 (9) |
C14 | 0.0571 (15) | 0.0367 (12) | 0.0403 (13) | 0.0051 (11) | 0.0180 (11) | 0.0110 (10) |
C15 | 0.0560 (14) | 0.0352 (12) | 0.0413 (13) | −0.0092 (10) | 0.0225 (11) | −0.0050 (10) |
C16 | 0.0444 (13) | 0.0507 (14) | 0.0393 (12) | −0.0146 (11) | 0.0096 (10) | −0.0013 (11) |
C17 | 0.0389 (12) | 0.0432 (13) | 0.0301 (11) | −0.0060 (10) | 0.0073 (9) | 0.0038 (9) |
C18 | 0.081 (2) | 0.0537 (16) | 0.0601 (17) | −0.0204 (15) | 0.0295 (15) | 0.0030 (13) |
C19 | 0.0380 (12) | 0.0347 (12) | 0.0353 (11) | −0.0024 (9) | 0.0017 (9) | 0.0008 (9) |
C20 | 0.0606 (15) | 0.0385 (13) | 0.0368 (12) | −0.0052 (11) | 0.0106 (11) | 0.0053 (10) |
C21 | 0.0497 (14) | 0.0419 (13) | 0.0522 (14) | −0.0115 (11) | 0.0254 (12) | −0.0024 (11) |
C22 | 0.0311 (12) | 0.0606 (16) | 0.0582 (15) | −0.0091 (11) | 0.0102 (11) | 0.0040 (13) |
C23 | 0.0296 (11) | 0.0516 (14) | 0.0368 (11) | −0.0036 (10) | 0.0058 (9) | 0.0065 (10) |
C24 | 0.078 (2) | 0.072 (2) | 0.090 (2) | −0.0243 (17) | 0.0430 (19) | 0.0097 (17) |
Geometric parameters (Å, º) top
Ni1—O1i | 2.0984 (13) | C7—H7 | 0.9300 |
Ni1—O1 | 2.0984 (13) | C7—C8 | 1.377 (3) |
Ni1—N1 | 2.1191 (18) | C8—H8 | 0.9300 |
Ni1—N1i | 2.1190 (18) | C8—C9 | 1.371 (3) |
Ni1—N2 | 2.1318 (16) | C9—C10 | 1.376 (3) |
Ni1—N2i | 2.1318 (16) | C9—C12 | 1.513 (3) |
Ni2—O2ii | 2.0581 (14) | C10—H10 | 0.9300 |
Ni2—O2 | 2.0581 (14) | C10—C11 | 1.373 (3) |
Ni2—N3 | 2.1537 (17) | C11—H11 | 0.9300 |
Ni2—N3ii | 2.1537 (17) | C12—H12A | 0.9600 |
Ni2—N4ii | 2.1313 (16) | C12—H12B | 0.9600 |
Ni2—N4 | 2.1313 (17) | C12—H12C | 0.9600 |
S1—O1 | 1.4800 (13) | C13—H13 | 0.9300 |
S1—O2 | 1.4719 (15) | C13—C14 | 1.381 (3) |
S1—O3 | 1.4520 (18) | C14—H14 | 0.9300 |
S1—O4 | 1.4491 (16) | C14—C15 | 1.377 (3) |
N1—C1 | 1.338 (3) | C15—C16 | 1.384 (3) |
N1—C5 | 1.337 (3) | C15—C18 | 1.507 (3) |
N2—C7 | 1.342 (3) | C16—H16 | 0.9300 |
N2—C11 | 1.335 (3) | C16—C17 | 1.377 (3) |
N3—C13 | 1.341 (3) | C17—H17 | 0.9300 |
N3—C17 | 1.338 (3) | C18—H18A | 0.9600 |
N4—C19 | 1.337 (3) | C18—H18B | 0.9600 |
N4—C23 | 1.334 (3) | C18—H18C | 0.9600 |
C1—H1 | 0.9300 | C19—H19 | 0.9300 |
C1—C2 | 1.374 (4) | C19—C20 | 1.377 (3) |
C2—H2 | 0.9300 | C20—H20 | 0.9300 |
C2—C3 | 1.384 (4) | C20—C21 | 1.370 (3) |
C3—C4 | 1.374 (4) | C21—C22 | 1.381 (4) |
C3—C6 | 1.515 (4) | C21—C24 | 1.510 (3) |
C4—H4 | 0.9300 | C22—H22 | 0.9300 |
C4—C5 | 1.377 (3) | C22—C23 | 1.379 (3) |
C5—H5 | 0.9300 | C23—H23 | 0.9300 |
C6—H6A | 0.9600 | C24—H24A | 0.9600 |
C6—H6B | 0.9600 | C24—H24B | 0.9600 |
C6—H6C | 0.9600 | C24—H24C | 0.9600 |
| | | |
O1i—Ni1—O1 | 180.0 | C3—C6—H6C | 109.5 |
O1—Ni1—N1 | 91.10 (6) | H6A—C6—H6B | 109.5 |
O1i—Ni1—N1 | 88.90 (6) | H6A—C6—H6C | 109.5 |
O1—Ni1—N1i | 88.90 (6) | H6B—C6—H6C | 109.5 |
O1i—Ni1—N1i | 91.10 (6) | N2—C7—H7 | 118.5 |
O1i—Ni1—N2i | 88.94 (6) | N2—C7—C8 | 122.9 (2) |
O1i—Ni1—N2 | 91.06 (6) | C8—C7—H7 | 118.5 |
O1—Ni1—N2i | 91.06 (6) | C7—C8—H8 | 119.6 |
O1—Ni1—N2 | 88.94 (6) | C9—C8—C7 | 120.8 (2) |
N1i—Ni1—N1 | 180.00 (9) | C9—C8—H8 | 119.6 |
N1—Ni1—N2 | 91.99 (7) | C8—C9—C10 | 116.2 (2) |
N1i—Ni1—N2i | 91.99 (7) | C8—C9—C12 | 122.5 (2) |
N1i—Ni1—N2 | 88.01 (7) | C10—C9—C12 | 121.3 (2) |
N1—Ni1—N2i | 88.01 (7) | C9—C10—H10 | 119.7 |
N2i—Ni1—N2 | 180.0 | C11—C10—C9 | 120.5 (2) |
O2ii—Ni2—O2 | 177.34 (9) | C11—C10—H10 | 119.7 |
O2ii—Ni2—N3ii | 88.18 (6) | N2—C11—C10 | 123.55 (19) |
O2ii—Ni2—N3 | 89.86 (7) | N2—C11—H11 | 118.2 |
O2—Ni2—N3 | 88.18 (6) | C10—C11—H11 | 118.2 |
O2—Ni2—N3ii | 89.86 (7) | C9—C12—H12A | 109.5 |
O2ii—Ni2—N4ii | 88.72 (6) | C9—C12—H12B | 109.5 |
O2—Ni2—N4 | 88.72 (6) | C9—C12—H12C | 109.5 |
O2ii—Ni2—N4 | 93.16 (6) | H12A—C12—H12B | 109.5 |
O2—Ni2—N4ii | 93.15 (6) | H12A—C12—H12C | 109.5 |
N3ii—Ni2—N3 | 85.30 (9) | H12B—C12—H12C | 109.5 |
N4—Ni2—N3ii | 92.02 (6) | N3—C13—H13 | 118.6 |
N4ii—Ni2—N3ii | 175.91 (6) | N3—C13—C14 | 122.8 (2) |
N4—Ni2—N3 | 175.91 (6) | C14—C13—H13 | 118.6 |
N4ii—Ni2—N3 | 92.02 (6) | C13—C14—H14 | 119.6 |
N4ii—Ni2—N4 | 90.81 (9) | C15—C14—C13 | 120.8 (2) |
O2—S1—O1 | 107.33 (9) | C15—C14—H14 | 119.6 |
O3—S1—O1 | 109.26 (9) | C14—C15—C16 | 116.1 (2) |
O3—S1—O2 | 109.15 (11) | C14—C15—C18 | 122.6 (2) |
O4—S1—O1 | 110.35 (9) | C16—C15—C18 | 121.3 (2) |
O4—S1—O2 | 108.55 (10) | C15—C16—H16 | 119.8 |
O4—S1—O3 | 112.06 (12) | C17—C16—C15 | 120.4 (2) |
S1—O1—Ni1 | 162.62 (9) | C17—C16—H16 | 119.8 |
S1—O2—Ni2 | 169.73 (12) | N3—C17—C16 | 123.3 (2) |
C1—N1—Ni1 | 123.25 (15) | N3—C17—H17 | 118.3 |
C5—N1—Ni1 | 119.99 (14) | C16—C17—H17 | 118.3 |
C5—N1—C1 | 116.8 (2) | C15—C18—H18A | 109.5 |
C7—N2—Ni1 | 125.74 (14) | C15—C18—H18B | 109.5 |
C11—N2—Ni1 | 118.13 (13) | C15—C18—H18C | 109.5 |
C11—N2—C7 | 116.04 (18) | H18A—C18—H18B | 109.5 |
C13—N3—Ni2 | 120.98 (14) | H18A—C18—H18C | 109.5 |
C17—N3—Ni2 | 122.56 (14) | H18B—C18—H18C | 109.5 |
C17—N3—C13 | 116.46 (18) | N4—C19—H19 | 118.5 |
C19—N4—Ni2 | 120.92 (14) | N4—C19—C20 | 123.0 (2) |
C23—N4—Ni2 | 122.36 (14) | C20—C19—H19 | 118.5 |
C23—N4—C19 | 116.56 (18) | C19—C20—H20 | 119.7 |
N1—C1—H1 | 118.5 | C21—C20—C19 | 120.7 (2) |
N1—C1—C2 | 123.0 (2) | C21—C20—H20 | 119.7 |
C2—C1—H1 | 118.5 | C20—C21—C22 | 116.2 (2) |
C1—C2—H2 | 119.8 | C20—C21—C24 | 122.3 (2) |
C1—C2—C3 | 120.5 (2) | C22—C21—C24 | 121.5 (2) |
C3—C2—H2 | 119.8 | C21—C22—H22 | 119.8 |
C2—C3—C6 | 122.2 (3) | C23—C22—C21 | 120.4 (2) |
C4—C3—C2 | 116.2 (2) | C23—C22—H22 | 119.8 |
C4—C3—C6 | 121.6 (3) | N4—C23—C22 | 123.1 (2) |
C3—C4—H4 | 119.7 | N4—C23—H23 | 118.5 |
C3—C4—C5 | 120.7 (2) | C22—C23—H23 | 118.5 |
C5—C4—H4 | 119.7 | C21—C24—H24A | 109.5 |
N1—C5—C4 | 122.9 (2) | C21—C24—H24B | 109.5 |
N1—C5—H5 | 118.5 | C21—C24—H24C | 109.5 |
C4—C5—H5 | 118.5 | H24A—C24—H24B | 109.5 |
C3—C6—H6A | 109.5 | H24A—C24—H24C | 109.5 |
C3—C6—H6B | 109.5 | H24B—C24—H24C | 109.5 |
| | | |
Ni1—N1—C1—C2 | −179.2 (2) | C5—N1—C1—C2 | 1.0 (4) |
Ni1—N1—C5—C4 | −179.76 (19) | C6—C3—C4—C5 | −179.2 (3) |
Ni1—N2—C7—C8 | −177.41 (19) | C7—N2—C11—C10 | 0.1 (3) |
Ni1—N2—C11—C10 | 176.88 (18) | C7—C8—C9—C10 | −0.4 (4) |
Ni2—N3—C13—C14 | 177.94 (16) | C7—C8—C9—C12 | 179.6 (3) |
Ni2—N3—C17—C16 | −177.65 (17) | C8—C9—C10—C11 | −0.3 (4) |
Ni2—N4—C19—C20 | −173.89 (17) | C9—C10—C11—N2 | 0.5 (4) |
Ni2—N4—C23—C22 | 173.78 (19) | C11—N2—C7—C8 | −0.9 (3) |
O1—S1—O2—Ni2 | 103.4 (6) | C12—C9—C10—C11 | 179.7 (2) |
O2—S1—O1—Ni1 | 176.0 (3) | C13—N3—C17—C16 | 2.5 (3) |
O3—S1—O1—Ni1 | −65.7 (4) | C13—C14—C15—C16 | 1.7 (3) |
O3—S1—O2—Ni2 | −15.0 (6) | C13—C14—C15—C18 | −177.4 (2) |
O4—S1—O1—Ni1 | 57.9 (4) | C14—C15—C16—C17 | −1.5 (3) |
O4—S1—O2—Ni2 | −137.4 (5) | C15—C16—C17—N3 | −0.7 (4) |
N1—C1—C2—C3 | −0.8 (5) | C17—N3—C13—C14 | −2.2 (3) |
N2—C7—C8—C9 | 1.1 (4) | C18—C15—C16—C17 | 177.7 (2) |
N3—C13—C14—C15 | 0.1 (3) | C19—N4—C23—C22 | −1.7 (3) |
N4—C19—C20—C21 | 0.0 (4) | C19—C20—C21—C22 | −1.6 (4) |
C1—N1—C5—C4 | 0.0 (3) | C19—C20—C21—C24 | 178.3 (2) |
C1—C2—C3—C4 | −0.5 (5) | C20—C21—C22—C23 | 1.6 (4) |
C1—C2—C3—C6 | −179.9 (3) | C21—C22—C23—N4 | 0.1 (4) |
C2—C3—C4—C5 | 1.5 (4) | C23—N4—C19—C20 | 1.7 (3) |
C3—C4—C5—N1 | −1.3 (4) | C24—C21—C22—C23 | −178.4 (3) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y, −z+3/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O1i | 0.93 | 2.58 | 3.075 (3) | 114 |
C1—H1···O4i | 0.93 | 2.43 | 3.337 (3) | 165 |
C5—H5···O1 | 0.93 | 2.56 | 3.082 (3) | 116 |
C5—H5···O3 | 0.93 | 2.38 | 3.261 (3) | 157 |
C7—H7···S1i | 0.93 | 2.82 | 3.576 (2) | 139 |
C7—H7···O4i | 0.93 | 2.43 | 3.345 (3) | 170 |
C11—H11···O1 | 0.93 | 2.34 | 2.942 (2) | 122 |
C13—H13···O2ii | 0.93 | 2.45 | 3.015 (3) | 119 |
C17—H17···O2 | 0.93 | 2.44 | 2.999 (3) | 119 |
C19—H19···S1 | 0.93 | 2.84 | 3.593 (2) | 139 |
C19—H19···O2 | 0.93 | 2.47 | 2.984 (3) | 115 |
C23—H23···O3ii | 0.93 | 2.59 | 3.299 (3) | 134 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y, −z+3/2. |
Di-µ-sulfato-
κ4O:
O-bis[tris(4-methylpyridine-
κN)copper(II)] (umd1301_a)
top
Crystal data top
[Cu2(SO4)2(C6H7N)6] | F(000) = 908 |
Mr = 877.95 | Dx = 1.546 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.1304 (8) Å | Cell parameters from 9831 reflections |
b = 21.2148 (19) Å | θ = 2.9–25.7° |
c = 9.9359 (8) Å | µ = 1.30 mm−1 |
β = 101.544 (3)° | T = 200 K |
V = 1885.6 (3) Å3 | BLOCK, blue |
Z = 2 | 0.28 × 0.14 × 0.11 mm |
Data collection top
Bruker D8 Venture CMOS diffractometer | 3110 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.053 |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | θmax = 25.7°, θmin = 3.4° |
Tmin = 0.380, Tmax = 0.429 | h = −11→11 |
59469 measured reflections | k = −25→25 |
3580 independent reflections | l = −12→12 |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.027 | w = 1/[σ2(Fo2) + (0.0237P)2 + 2.015P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.065 | (Δ/σ)max = 0.003 |
S = 1.06 | Δρmax = 0.27 e Å−3 |
3580 reflections | Δρmin = −0.31 e Å−3 |
248 parameters | Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0044 (5) |
Primary atom site location: structure-invariant direct methods | |
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 | |
Cu1 | 0.34858 (3) | 0.54221 (2) | 0.48079 (2) | 0.01881 (10) | |
S1 | 0.30849 (6) | 0.42609 (2) | 0.63867 (5) | 0.02033 (13) | |
O1 | 0.42042 (15) | 0.46049 (7) | 0.56673 (14) | 0.0193 (3) | |
O2 | 0.2810 (2) | 0.36429 (8) | 0.57543 (19) | 0.0404 (4) | |
O3 | 0.37729 (18) | 0.42162 (8) | 0.78368 (15) | 0.0336 (4) | |
O4 | 0.17490 (17) | 0.46582 (8) | 0.61602 (16) | 0.0309 (4) | |
N1 | 0.41898 (19) | 0.59060 (8) | 0.65957 (17) | 0.0213 (4) | |
N2 | 0.25128 (19) | 0.62219 (8) | 0.39875 (17) | 0.0220 (4) | |
N3 | 0.25106 (19) | 0.49886 (8) | 0.30406 (17) | 0.0199 (4) | |
C1 | 0.5258 (2) | 0.63458 (10) | 0.6657 (2) | 0.0245 (5) | |
H1 | 0.5709 | 0.6403 | 0.5883 | 0.029* | |
C2 | 0.5725 (3) | 0.67179 (10) | 0.7800 (2) | 0.0261 (5) | |
H2 | 0.6478 | 0.7027 | 0.7795 | 0.031* | |
C3 | 0.5105 (3) | 0.66455 (10) | 0.8957 (2) | 0.0268 (5) | |
C4 | 0.4017 (3) | 0.61830 (11) | 0.8888 (2) | 0.0304 (5) | |
H4 | 0.3564 | 0.6111 | 0.9656 | 0.037* | |
C5 | 0.3590 (2) | 0.58275 (10) | 0.7717 (2) | 0.0257 (5) | |
H5 | 0.2843 | 0.5514 | 0.7699 | 0.031* | |
C6 | 0.5586 (3) | 0.70482 (12) | 1.0209 (2) | 0.0409 (6) | |
H6A | 0.4706 | 0.7244 | 1.0460 | 0.061* | |
H6B | 0.6267 | 0.7377 | 1.0013 | 0.061* | |
H6C | 0.6099 | 0.6786 | 1.0971 | 0.061* | |
C7 | 0.3149 (3) | 0.66404 (11) | 0.3272 (2) | 0.0292 (5) | |
H7 | 0.4151 | 0.6572 | 0.3175 | 0.035* | |
C8 | 0.2403 (3) | 0.71650 (11) | 0.2672 (2) | 0.0319 (5) | |
H8 | 0.2893 | 0.7450 | 0.2172 | 0.038* | |
C9 | 0.0942 (3) | 0.72788 (10) | 0.2794 (2) | 0.0276 (5) | |
C10 | 0.0286 (2) | 0.68434 (11) | 0.3534 (2) | 0.0269 (5) | |
H10 | −0.0713 | 0.6902 | 0.3649 | 0.032* | |
C11 | 0.1090 (2) | 0.63269 (10) | 0.4097 (2) | 0.0256 (5) | |
H11 | 0.0618 | 0.6030 | 0.4587 | 0.031* | |
C12 | 0.0077 (3) | 0.78367 (13) | 0.2126 (3) | 0.0501 (7) | |
H12A | 0.0771 | 0.8149 | 0.1884 | 0.075* | |
H12B | −0.0488 | 0.8025 | 0.2765 | 0.075* | |
H12C | −0.0616 | 0.7700 | 0.1293 | 0.075* | |
C13 | 0.1195 (2) | 0.46930 (10) | 0.2929 (2) | 0.0245 (5) | |
H13 | 0.0717 | 0.4692 | 0.3695 | 0.029* | |
C14 | 0.0515 (2) | 0.43909 (11) | 0.1740 (2) | 0.0270 (5) | |
H14 | −0.0426 | 0.4192 | 0.1694 | 0.032* | |
C15 | 0.1192 (2) | 0.43750 (10) | 0.0612 (2) | 0.0236 (5) | |
C16 | 0.2530 (2) | 0.46990 (10) | 0.0720 (2) | 0.0245 (5) | |
H16 | 0.3020 | 0.4713 | −0.0038 | 0.029* | |
C17 | 0.3146 (2) | 0.50015 (10) | 0.1932 (2) | 0.0225 (4) | |
H17 | 0.4054 | 0.5228 | 0.1984 | 0.027* | |
C18 | 0.0528 (3) | 0.40159 (12) | −0.0668 (2) | 0.0364 (6) | |
H18A | 0.0920 | 0.4184 | −0.1445 | 0.055* | |
H18B | −0.0562 | 0.4061 | −0.0855 | 0.055* | |
H18C | 0.0793 | 0.3569 | −0.0541 | 0.055* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.01960 (14) | 0.02127 (15) | 0.01567 (14) | −0.00091 (10) | 0.00378 (9) | −0.00101 (10) |
S1 | 0.0188 (3) | 0.0233 (3) | 0.0215 (3) | −0.0043 (2) | 0.0102 (2) | 0.0006 (2) |
O1 | 0.0173 (7) | 0.0230 (7) | 0.0193 (7) | −0.0034 (6) | 0.0077 (6) | 0.0030 (6) |
O2 | 0.0462 (10) | 0.0296 (9) | 0.0547 (11) | −0.0177 (8) | 0.0322 (9) | −0.0132 (8) |
O3 | 0.0314 (9) | 0.0492 (11) | 0.0219 (8) | −0.0029 (8) | 0.0091 (7) | 0.0118 (7) |
O4 | 0.0186 (8) | 0.0425 (10) | 0.0329 (9) | 0.0013 (7) | 0.0086 (7) | 0.0002 (7) |
N1 | 0.0229 (9) | 0.0223 (9) | 0.0192 (9) | 0.0017 (7) | 0.0051 (7) | −0.0010 (7) |
N2 | 0.0213 (9) | 0.0234 (9) | 0.0210 (9) | −0.0024 (7) | 0.0034 (7) | −0.0016 (7) |
N3 | 0.0200 (9) | 0.0217 (9) | 0.0178 (8) | −0.0001 (7) | 0.0032 (7) | 0.0005 (7) |
C1 | 0.0272 (11) | 0.0261 (11) | 0.0217 (11) | −0.0009 (9) | 0.0089 (9) | 0.0000 (9) |
C2 | 0.0285 (12) | 0.0236 (11) | 0.0263 (11) | −0.0032 (9) | 0.0058 (9) | −0.0005 (9) |
C3 | 0.0381 (13) | 0.0207 (11) | 0.0206 (11) | 0.0049 (10) | 0.0037 (9) | −0.0013 (9) |
C4 | 0.0429 (14) | 0.0293 (12) | 0.0235 (11) | −0.0005 (11) | 0.0175 (10) | −0.0016 (9) |
C5 | 0.0280 (12) | 0.0258 (12) | 0.0262 (11) | −0.0026 (9) | 0.0121 (9) | −0.0023 (9) |
C6 | 0.0651 (18) | 0.0314 (14) | 0.0252 (12) | −0.0027 (13) | 0.0069 (12) | −0.0064 (11) |
C7 | 0.0233 (11) | 0.0326 (13) | 0.0334 (12) | −0.0029 (10) | 0.0096 (10) | 0.0005 (10) |
C8 | 0.0328 (13) | 0.0282 (12) | 0.0365 (13) | −0.0069 (10) | 0.0109 (10) | 0.0056 (10) |
C9 | 0.0324 (12) | 0.0218 (11) | 0.0282 (12) | −0.0013 (10) | 0.0048 (10) | −0.0036 (9) |
C10 | 0.0220 (11) | 0.0298 (12) | 0.0297 (12) | −0.0013 (9) | 0.0071 (9) | −0.0044 (10) |
C11 | 0.0263 (11) | 0.0254 (11) | 0.0261 (11) | −0.0053 (9) | 0.0077 (9) | −0.0008 (9) |
C12 | 0.0527 (17) | 0.0364 (15) | 0.0621 (19) | 0.0109 (13) | 0.0135 (15) | 0.0147 (14) |
C13 | 0.0227 (11) | 0.0292 (12) | 0.0228 (11) | −0.0013 (9) | 0.0069 (9) | −0.0004 (9) |
C14 | 0.0218 (11) | 0.0277 (12) | 0.0312 (12) | −0.0065 (9) | 0.0043 (9) | −0.0021 (10) |
C15 | 0.0259 (11) | 0.0210 (11) | 0.0217 (11) | 0.0029 (9) | −0.0003 (9) | −0.0012 (9) |
C16 | 0.0257 (11) | 0.0308 (12) | 0.0171 (10) | 0.0020 (9) | 0.0049 (9) | 0.0001 (9) |
C17 | 0.0209 (10) | 0.0260 (11) | 0.0205 (10) | −0.0009 (9) | 0.0041 (8) | 0.0035 (9) |
C18 | 0.0399 (14) | 0.0375 (14) | 0.0287 (13) | −0.0038 (11) | −0.0004 (11) | −0.0097 (11) |
Geometric parameters (Å, º) top
Cu1—O1 | 1.9853 (14) | C6—H6B | 0.9800 |
Cu1—O1i | 2.2525 (14) | C6—H6C | 0.9800 |
Cu1—N1 | 2.0408 (17) | C7—H7 | 0.9500 |
Cu1—N2 | 2.0106 (18) | C7—C8 | 1.377 (3) |
Cu1—N3 | 2.0240 (17) | C8—H8 | 0.9500 |
S1—O1 | 1.5428 (14) | C8—C9 | 1.385 (3) |
S1—O2 | 1.4538 (17) | C9—C10 | 1.388 (3) |
S1—O3 | 1.4551 (16) | C9—C12 | 1.502 (3) |
S1—O4 | 1.4625 (16) | C10—H10 | 0.9500 |
O1—Cu1i | 2.2525 (14) | C10—C11 | 1.374 (3) |
N1—C1 | 1.342 (3) | C11—H11 | 0.9500 |
N1—C5 | 1.346 (3) | C12—H12A | 0.9800 |
N2—C7 | 1.340 (3) | C12—H12B | 0.9800 |
N2—C11 | 1.344 (3) | C12—H12C | 0.9800 |
N3—C13 | 1.340 (3) | C13—H13 | 0.9500 |
N3—C17 | 1.344 (3) | C13—C14 | 1.378 (3) |
C1—H1 | 0.9500 | C14—H14 | 0.9500 |
C1—C2 | 1.378 (3) | C14—C15 | 1.385 (3) |
C2—H2 | 0.9500 | C15—C16 | 1.387 (3) |
C2—C3 | 1.388 (3) | C15—C18 | 1.503 (3) |
C3—C4 | 1.388 (3) | C16—H16 | 0.9500 |
C3—C6 | 1.500 (3) | C16—C17 | 1.381 (3) |
C4—H4 | 0.9500 | C17—H17 | 0.9500 |
C4—C5 | 1.376 (3) | C18—H18A | 0.9800 |
C5—H5 | 0.9500 | C18—H18B | 0.9800 |
C6—H6A | 0.9800 | C18—H18C | 0.9800 |
| | | |
O1—Cu1—O1i | 79.94 (6) | H6A—C6—H6B | 109.5 |
O1—Cu1—N1 | 92.61 (6) | H6A—C6—H6C | 109.5 |
O1—Cu1—N2 | 172.98 (6) | H6B—C6—H6C | 109.5 |
O1—Cu1—N3 | 91.51 (6) | N2—C7—H7 | 118.8 |
N1—Cu1—O1i | 92.88 (6) | N2—C7—C8 | 122.4 (2) |
N2—Cu1—O1i | 107.02 (6) | C8—C7—H7 | 118.8 |
N2—Cu1—N1 | 88.00 (7) | C7—C8—H8 | 119.8 |
N2—Cu1—N3 | 87.12 (7) | C7—C8—C9 | 120.3 (2) |
N3—Cu1—O1i | 94.26 (6) | C9—C8—H8 | 119.8 |
N3—Cu1—N1 | 172.28 (7) | C8—C9—C10 | 117.1 (2) |
O2—S1—O1 | 107.41 (9) | C8—C9—C12 | 121.9 (2) |
O2—S1—O3 | 111.85 (11) | C10—C9—C12 | 120.9 (2) |
O2—S1—O4 | 112.76 (10) | C9—C10—H10 | 120.2 |
O3—S1—O1 | 107.15 (9) | C11—C10—C9 | 119.7 (2) |
O3—S1—O4 | 111.80 (10) | C11—C10—H10 | 120.2 |
O4—S1—O1 | 105.39 (9) | N2—C11—C10 | 123.0 (2) |
Cu1—O1—Cu1i | 100.06 (5) | N2—C11—H11 | 118.5 |
S1—O1—Cu1 | 114.83 (8) | C10—C11—H11 | 118.5 |
S1—O1—Cu1i | 145.08 (9) | C9—C12—H12A | 109.5 |
C1—N1—Cu1 | 119.26 (14) | C9—C12—H12B | 109.5 |
C1—N1—C5 | 117.40 (18) | C9—C12—H12C | 109.5 |
C5—N1—Cu1 | 123.27 (15) | H12A—C12—H12B | 109.5 |
C7—N2—Cu1 | 124.81 (15) | H12A—C12—H12C | 109.5 |
C7—N2—C11 | 117.51 (19) | H12B—C12—H12C | 109.5 |
C11—N2—Cu1 | 117.56 (14) | N3—C13—H13 | 119.0 |
C13—N3—Cu1 | 121.04 (14) | N3—C13—C14 | 122.1 (2) |
C13—N3—C17 | 117.95 (18) | C14—C13—H13 | 119.0 |
C17—N3—Cu1 | 120.98 (14) | C13—C14—H14 | 119.8 |
N1—C1—H1 | 118.7 | C13—C14—C15 | 120.5 (2) |
N1—C1—C2 | 122.6 (2) | C15—C14—H14 | 119.8 |
C2—C1—H1 | 118.7 | C14—C15—C16 | 117.06 (19) |
C1—C2—H2 | 119.7 | C14—C15—C18 | 121.8 (2) |
C1—C2—C3 | 120.6 (2) | C16—C15—C18 | 121.1 (2) |
C3—C2—H2 | 119.7 | C15—C16—H16 | 120.1 |
C2—C3—C4 | 116.4 (2) | C17—C16—C15 | 119.7 (2) |
C2—C3—C6 | 121.6 (2) | C17—C16—H16 | 120.1 |
C4—C3—C6 | 122.1 (2) | N3—C17—C16 | 122.55 (19) |
C3—C4—H4 | 119.7 | N3—C17—H17 | 118.7 |
C5—C4—C3 | 120.5 (2) | C16—C17—H17 | 118.7 |
C5—C4—H4 | 119.7 | C15—C18—H18A | 109.5 |
N1—C5—C4 | 122.6 (2) | C15—C18—H18B | 109.5 |
N1—C5—H5 | 118.7 | C15—C18—H18C | 109.5 |
C4—C5—H5 | 118.7 | H18A—C18—H18B | 109.5 |
C3—C6—H6A | 109.5 | H18A—C18—H18C | 109.5 |
C3—C6—H6B | 109.5 | H18B—C18—H18C | 109.5 |
C3—C6—H6C | 109.5 | | |
| | | |
Cu1—N1—C1—C2 | 175.95 (17) | C2—C3—C4—C5 | −0.6 (3) |
Cu1—N1—C5—C4 | −176.14 (17) | C3—C4—C5—N1 | 0.0 (4) |
Cu1—N2—C7—C8 | 176.59 (17) | C5—N1—C1—C2 | −1.2 (3) |
Cu1—N2—C11—C10 | −177.43 (17) | C6—C3—C4—C5 | 179.2 (2) |
Cu1—N3—C13—C14 | −179.55 (16) | C7—N2—C11—C10 | −1.1 (3) |
Cu1—N3—C17—C16 | 178.49 (16) | C7—C8—C9—C10 | −0.2 (3) |
O2—S1—O1—Cu1i | −60.22 (17) | C7—C8—C9—C12 | −178.5 (2) |
O2—S1—O1—Cu1 | 122.28 (11) | C8—C9—C10—C11 | −0.3 (3) |
O3—S1—O1—Cu1 | −117.39 (10) | C9—C10—C11—N2 | 1.0 (3) |
O3—S1—O1—Cu1i | 60.10 (17) | C11—N2—C7—C8 | 0.6 (3) |
O4—S1—O1—Cu1i | 179.32 (14) | C12—C9—C10—C11 | 178.0 (2) |
O4—S1—O1—Cu1 | 1.82 (11) | C13—N3—C17—C16 | −3.1 (3) |
N1—C1—C2—C3 | 0.6 (3) | C13—C14—C15—C16 | −3.0 (3) |
N2—C7—C8—C9 | 0.1 (4) | C13—C14—C15—C18 | 176.1 (2) |
N3—C13—C14—C15 | 1.0 (3) | C14—C15—C16—C17 | 2.0 (3) |
C1—N1—C5—C4 | 0.9 (3) | C15—C16—C17—N3 | 1.1 (3) |
C1—C2—C3—C4 | 0.3 (3) | C17—N3—C13—C14 | 2.0 (3) |
C1—C2—C3—C6 | −179.5 (2) | C18—C15—C16—C17 | −177.2 (2) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O2i | 0.95 | 2.32 | 3.247 (3) | 166 |
C5—H5···O4 | 0.95 | 2.45 | 3.214 (3) | 137 |
C10—H10···O2ii | 0.95 | 2.41 | 3.218 (3) | 143 |
C11—H11···O4ii | 0.95 | 2.59 | 3.299 (3) | 132 |
C13—H13···O4 | 0.95 | 2.44 | 3.149 (3) | 131 |
C16—H16···O3iii | 0.95 | 2.57 | 3.441 (3) | 152 |
C17—H17···O1i | 0.95 | 2.57 | 3.152 (2) | 120 |
C17—H17···O3i | 0.95 | 2.28 | 3.235 (3) | 178 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1; (iii) x, y, z−1. |
catena-Poly[[bis(4-methylpyridine-
κN)zinc(II)]-sulfato-
κ2O:
O'] (UMD1448_a)
top
Crystal data top
[Zn(SO4)(C6H7N)2] | F(000) = 712 |
Mr = 347.68 | Dx = 1.635 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 14.9703 (10) Å | Cell parameters from 9901 reflections |
b = 9.7229 (7) Å | θ = 3.0–25.4° |
c = 9.8290 (6) Å | µ = 1.90 mm−1 |
β = 99.161 (2)° | T = 295 K |
V = 1412.41 (16) Å3 | BLOCK, colourless |
Z = 4 | 0.33 × 0.18 × 0.17 mm |
Data collection top
Bruker D8 Venture CMOS diffractometer | 2245 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.047 |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | θmax = 25.4°, θmin = 3.0° |
Tmin = 0.368, Tmax = 0.429 | h = −18→18 |
36405 measured reflections | k = −11→11 |
2587 independent reflections | l = −11→11 |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.029 | w = 1/[σ2(Fo2) + (0.0106P)2 + 2.2444P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.063 | (Δ/σ)max = 0.001 |
S = 1.05 | Δρmax = 0.28 e Å−3 |
2587 reflections | Δρmin = −0.26 e Å−3 |
184 parameters | Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0064 (4) |
Primary atom site location: structure-invariant direct methods | |
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 | 0.73426 (2) | 0.67083 (3) | 0.34428 (3) | 0.03279 (12) | |
S1 | 0.77109 (4) | 0.91047 (7) | 0.56007 (6) | 0.03436 (17) | |
O1 | 0.75464 (16) | 0.8521 (2) | 0.41889 (19) | 0.0534 (6) | |
O2 | 0.86570 (14) | 0.9318 (3) | 0.6042 (3) | 0.0683 (7) | |
O3 | 0.71701 (16) | 1.0322 (2) | 0.5637 (2) | 0.0584 (6) | |
O4 | 0.73861 (14) | 0.8018 (2) | 0.64984 (18) | 0.0452 (5) | |
N1 | 0.60062 (15) | 0.6304 (2) | 0.3468 (2) | 0.0400 (5) | |
N2 | 0.81748 (15) | 0.5253 (2) | 0.4368 (2) | 0.0353 (5) | |
C1 | 0.5570 (2) | 0.6899 (3) | 0.4395 (3) | 0.0506 (8) | |
H1A | 0.5906 | 0.7376 | 0.5123 | 0.061* | |
C2 | 0.4647 (2) | 0.6836 (3) | 0.4320 (3) | 0.0510 (8) | |
H2A | 0.4372 | 0.7274 | 0.4986 | 0.061* | |
C3 | 0.41246 (18) | 0.6127 (3) | 0.3264 (3) | 0.0406 (7) | |
C4 | 0.45827 (19) | 0.5495 (3) | 0.2325 (3) | 0.0490 (8) | |
H4A | 0.4262 | 0.4995 | 0.1601 | 0.059* | |
C5 | 0.5506 (2) | 0.5595 (3) | 0.2445 (3) | 0.0466 (7) | |
H5A | 0.5796 | 0.5157 | 0.1796 | 0.056* | |
C6 | 0.3116 (2) | 0.6041 (4) | 0.3144 (4) | 0.0618 (9) | |
H6A | 0.2909 | 0.6711 | 0.3741 | 0.093* | |
H6B | 0.2948 | 0.5138 | 0.3406 | 0.093* | |
H6C | 0.2844 | 0.6220 | 0.2209 | 0.093* | |
C7 | 0.8198 (2) | 0.3996 (3) | 0.3815 (3) | 0.0465 (7) | |
H7A | 0.7821 | 0.3813 | 0.2987 | 0.056* | |
C8 | 0.8752 (2) | 0.2967 (3) | 0.4412 (3) | 0.0477 (7) | |
H8A | 0.8738 | 0.2107 | 0.3993 | 0.057* | |
C9 | 0.93307 (17) | 0.3198 (3) | 0.5629 (3) | 0.0381 (6) | |
C10 | 0.92991 (19) | 0.4486 (3) | 0.6201 (3) | 0.0449 (7) | |
H10A | 0.9670 | 0.4688 | 0.7028 | 0.054* | |
C11 | 0.87254 (19) | 0.5478 (3) | 0.5561 (3) | 0.0418 (7) | |
H11A | 0.8719 | 0.6338 | 0.5973 | 0.050* | |
C12 | 0.9960 (2) | 0.2102 (3) | 0.6282 (4) | 0.0561 (9) | |
H12A | 1.0340 | 0.1801 | 0.5641 | 0.084* | |
H12B | 0.9615 | 0.1338 | 0.6534 | 0.084* | |
H12C | 1.0329 | 0.2465 | 0.7091 | 0.084* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn1 | 0.03253 (18) | 0.03542 (19) | 0.02896 (17) | −0.00093 (13) | 0.00042 (12) | 0.00190 (13) |
S1 | 0.0396 (4) | 0.0349 (4) | 0.0276 (3) | −0.0059 (3) | 0.0023 (3) | −0.0029 (3) |
O1 | 0.0915 (17) | 0.0413 (12) | 0.0273 (10) | −0.0098 (11) | 0.0094 (10) | −0.0040 (9) |
O2 | 0.0416 (12) | 0.0901 (19) | 0.0710 (16) | −0.0201 (13) | 0.0020 (11) | −0.0040 (14) |
O3 | 0.0808 (16) | 0.0455 (13) | 0.0483 (13) | 0.0172 (12) | 0.0084 (11) | −0.0002 (10) |
O4 | 0.0614 (13) | 0.0453 (12) | 0.0276 (10) | −0.0145 (10) | 0.0038 (9) | 0.0006 (8) |
N1 | 0.0355 (12) | 0.0463 (14) | 0.0371 (13) | −0.0036 (10) | 0.0024 (10) | 0.0001 (11) |
N2 | 0.0371 (12) | 0.0349 (12) | 0.0319 (12) | −0.0033 (10) | −0.0008 (9) | 0.0030 (10) |
C1 | 0.0433 (16) | 0.064 (2) | 0.0440 (17) | −0.0114 (15) | 0.0053 (13) | −0.0160 (15) |
C2 | 0.0433 (17) | 0.060 (2) | 0.0517 (18) | −0.0053 (15) | 0.0147 (14) | −0.0157 (16) |
C3 | 0.0346 (14) | 0.0445 (16) | 0.0415 (16) | −0.0054 (13) | 0.0028 (12) | 0.0045 (13) |
C4 | 0.0399 (16) | 0.062 (2) | 0.0435 (17) | −0.0141 (15) | 0.0021 (13) | −0.0104 (15) |
C5 | 0.0449 (17) | 0.0548 (19) | 0.0411 (16) | −0.0053 (14) | 0.0099 (13) | −0.0113 (14) |
C6 | 0.0374 (17) | 0.077 (2) | 0.071 (2) | −0.0071 (17) | 0.0090 (16) | −0.0064 (19) |
C7 | 0.0587 (19) | 0.0421 (17) | 0.0330 (15) | −0.0027 (14) | −0.0102 (13) | −0.0016 (13) |
C8 | 0.064 (2) | 0.0331 (16) | 0.0420 (17) | 0.0021 (14) | −0.0041 (14) | −0.0022 (13) |
C9 | 0.0328 (14) | 0.0377 (15) | 0.0429 (16) | −0.0051 (12) | 0.0031 (11) | 0.0096 (13) |
C10 | 0.0447 (16) | 0.0421 (17) | 0.0412 (16) | −0.0048 (13) | −0.0135 (13) | 0.0006 (13) |
C11 | 0.0429 (16) | 0.0363 (15) | 0.0426 (16) | −0.0049 (13) | −0.0039 (13) | −0.0015 (13) |
C12 | 0.0490 (18) | 0.0463 (19) | 0.068 (2) | 0.0035 (15) | −0.0045 (16) | 0.0178 (16) |
Geometric parameters (Å, º) top
Zn1—O1 | 1.915 (2) | C4—H4A | 0.9300 |
Zn1—O4i | 1.9410 (18) | C4—C5 | 1.372 (4) |
Zn1—N1 | 2.043 (2) | C5—H5A | 0.9300 |
Zn1—N2 | 2.005 (2) | C6—H6A | 0.9600 |
S1—O1 | 1.483 (2) | C6—H6B | 0.9600 |
S1—O2 | 1.429 (2) | C6—H6C | 0.9600 |
S1—O3 | 1.438 (2) | C7—H7A | 0.9300 |
S1—O4 | 1.506 (2) | C7—C8 | 1.370 (4) |
O4—Zn1ii | 1.9409 (18) | C8—H8A | 0.9300 |
N1—C1 | 1.334 (4) | C8—C9 | 1.379 (4) |
N1—C5 | 1.344 (4) | C9—C10 | 1.377 (4) |
N2—C7 | 1.341 (4) | C9—C12 | 1.498 (4) |
N2—C11 | 1.340 (3) | C10—H10A | 0.9300 |
C1—H1A | 0.9300 | C10—C11 | 1.375 (4) |
C1—C2 | 1.374 (4) | C11—H11A | 0.9300 |
C2—H2A | 0.9300 | C12—H12A | 0.9600 |
C2—C3 | 1.381 (4) | C12—H12B | 0.9600 |
C3—C4 | 1.379 (4) | C12—H12C | 0.9600 |
C3—C6 | 1.498 (4) | | |
| | | |
O1—Zn1—O4i | 102.86 (8) | C5—C4—H4A | 119.6 |
O1—Zn1—N1 | 105.61 (10) | N1—C5—C4 | 122.3 (3) |
O1—Zn1—N2 | 115.24 (9) | N1—C5—H5A | 118.8 |
O4i—Zn1—N1 | 102.98 (9) | C4—C5—H5A | 118.8 |
O4i—Zn1—N2 | 115.32 (9) | C3—C6—H6A | 109.5 |
N2—Zn1—N1 | 113.43 (9) | C3—C6—H6B | 109.5 |
O1—S1—O4 | 105.01 (11) | C3—C6—H6C | 109.5 |
O2—S1—O1 | 110.40 (15) | H6A—C6—H6B | 109.5 |
O2—S1—O3 | 114.06 (16) | H6A—C6—H6C | 109.5 |
O2—S1—O4 | 108.72 (14) | H6B—C6—H6C | 109.5 |
O3—S1—O1 | 109.13 (13) | N2—C7—H7A | 118.5 |
O3—S1—O4 | 109.11 (13) | N2—C7—C8 | 123.0 (3) |
S1—O1—Zn1 | 134.66 (13) | C8—C7—H7A | 118.5 |
S1—O4—Zn1ii | 123.04 (12) | C7—C8—H8A | 119.8 |
C1—N1—Zn1 | 120.74 (19) | C7—C8—C9 | 120.4 (3) |
C1—N1—C5 | 117.3 (2) | C9—C8—H8A | 119.8 |
C5—N1—Zn1 | 121.3 (2) | C8—C9—C12 | 121.4 (3) |
C7—N2—Zn1 | 120.91 (18) | C10—C9—C8 | 116.4 (3) |
C11—N2—Zn1 | 122.21 (19) | C10—C9—C12 | 122.2 (3) |
C11—N2—C7 | 116.9 (2) | C9—C10—H10A | 119.6 |
N1—C1—H1A | 118.6 | C11—C10—C9 | 120.7 (3) |
N1—C1—C2 | 122.8 (3) | C11—C10—H10A | 119.6 |
C2—C1—H1A | 118.6 | N2—C11—C10 | 122.5 (3) |
C1—C2—H2A | 119.8 | N2—C11—H11A | 118.7 |
C1—C2—C3 | 120.5 (3) | C10—C11—H11A | 118.7 |
C3—C2—H2A | 119.8 | C9—C12—H12A | 109.5 |
C2—C3—C6 | 122.0 (3) | C9—C12—H12B | 109.5 |
C4—C3—C2 | 116.3 (3) | C9—C12—H12C | 109.5 |
C4—C3—C6 | 121.7 (3) | H12A—C12—H12B | 109.5 |
C3—C4—H4A | 119.6 | H12A—C12—H12C | 109.5 |
C5—C4—C3 | 120.8 (3) | H12B—C12—H12C | 109.5 |
| | | |
Zn1—N1—C1—C2 | 169.3 (3) | C1—C2—C3—C4 | 0.6 (5) |
Zn1—N1—C5—C4 | −169.5 (2) | C1—C2—C3—C6 | −179.7 (3) |
Zn1—N2—C7—C8 | −179.7 (2) | C2—C3—C4—C5 | −0.8 (5) |
Zn1—N2—C11—C10 | −179.9 (2) | C3—C4—C5—N1 | −0.1 (5) |
O1—S1—O4—Zn1ii | −174.58 (14) | C5—N1—C1—C2 | −1.5 (5) |
O2—S1—O1—Zn1 | 98.2 (2) | C6—C3—C4—C5 | 179.4 (3) |
O2—S1—O4—Zn1ii | 67.26 (19) | C7—N2—C11—C10 | 0.6 (4) |
O3—S1—O1—Zn1 | −135.7 (2) | C7—C8—C9—C10 | 1.4 (5) |
O3—S1—O4—Zn1ii | −57.70 (18) | C7—C8—C9—C12 | −178.4 (3) |
O4—S1—O1—Zn1 | −18.8 (2) | C8—C9—C10—C11 | −1.0 (4) |
N1—C1—C2—C3 | 0.6 (5) | C9—C10—C11—N2 | 0.0 (5) |
N2—C7—C8—C9 | −0.9 (5) | C11—N2—C7—C8 | −0.1 (4) |
C1—N1—C5—C4 | 1.2 (5) | C12—C9—C10—C11 | 178.8 (3) |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) x, −y+3/2, z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···O4 | 0.93 | 2.48 | 3.325 (3) | 150 |
C5—H5A···O3i | 0.93 | 2.55 | 3.401 (4) | 153 |
C7—H7A···O3i | 0.93 | 2.51 | 3.321 (4) | 147 |
Symmetry code: (i) x, −y+3/2, z−1/2. |
catena-Poly[[tris(4-methylpyridine-
κN)zinc(II)]-sulfato-
κ2O:
O'] (umd1540c_a)
top
Crystal data top
[Zn(SO4)(C6H7N)2] | Dx = 1.499 Mg m−3 |
Mr = 440.81 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 8899 reflections |
a = 9.4926 (5) Å | θ = 2.9–25.2° |
b = 11.4128 (7) Å | µ = 1.39 mm−1 |
c = 18.0235 (11) Å | T = 296 K |
V = 1952.6 (2) Å3 | ROD, colourless |
Z = 4 | 0.2 × 0.03 × 0.03 mm |
F(000) = 912 | |
Data collection top
Bruker D8 Venture CMOS diffractometer | 3118 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.060 |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | θmax = 25.4°, θmin = 2.9° |
Tmin = 0.450, Tmax = 0.490 | h = −11→8 |
24507 measured reflections | k = −13→13 |
3561 independent reflections | l = −21→21 |
Refinement top
Refinement on F2 | H-atom parameters constrained |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0216P)2 + 0.4739P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.027 | (Δ/σ)max = 0.001 |
wR(F2) = 0.056 | Δρmax = 0.21 e Å−3 |
S = 1.03 | Δρmin = −0.33 e Å−3 |
3561 reflections | Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
248 parameters | Extinction coefficient: 0.0025 (6) |
0 restraints | Absolute structure: Flack x determined using 1244 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons et al., 2013) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.002 (7) |
Hydrogen site location: inferred from neighbouring sites | |
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 | 0.63333 (4) | 0.71323 (4) | 0.53749 (2) | 0.02618 (13) | |
S1 | 0.32426 (9) | 0.70122 (9) | 0.59603 (5) | 0.0257 (2) | |
O1 | 0.4259 (2) | 0.7098 (3) | 0.53201 (14) | 0.0312 (6) | |
O2 | 0.3635 (3) | 0.7833 (3) | 0.65349 (13) | 0.0458 (7) | |
O3 | 0.3196 (3) | 0.5814 (3) | 0.62307 (16) | 0.0414 (7) | |
O4 | 0.1848 (3) | 0.7333 (2) | 0.56397 (13) | 0.0297 (6) | |
N1 | 0.7391 (3) | 0.6428 (3) | 0.62840 (18) | 0.0294 (8) | |
N2 | 0.6501 (3) | 0.8884 (3) | 0.58363 (17) | 0.0299 (7) | |
N3 | 0.6465 (4) | 0.5285 (3) | 0.49194 (17) | 0.0378 (8) | |
C1 | 0.8793 (4) | 0.6460 (3) | 0.6338 (2) | 0.0358 (9) | |
H1 | 0.9290 | 0.6929 | 0.6007 | 0.043* | |
C2 | 0.9538 (4) | 0.5834 (4) | 0.6859 (2) | 0.0390 (11) | |
H2 | 1.0516 | 0.5886 | 0.6875 | 0.047* | |
C3 | 0.8829 (4) | 0.5126 (3) | 0.7359 (2) | 0.0300 (9) | |
C4 | 0.7381 (4) | 0.5124 (4) | 0.7321 (2) | 0.0326 (10) | |
H4 | 0.6859 | 0.4692 | 0.7661 | 0.039* | |
C5 | 0.6702 (4) | 0.5761 (3) | 0.6778 (2) | 0.0325 (10) | |
H5 | 0.5725 | 0.5727 | 0.6754 | 0.039* | |
C6 | 0.9593 (5) | 0.4383 (4) | 0.7926 (3) | 0.0505 (13) | |
H6A | 1.0235 | 0.4865 | 0.8201 | 0.076* | |
H6B | 1.0108 | 0.3775 | 0.7676 | 0.076* | |
H6C | 0.8922 | 0.4038 | 0.8258 | 0.076* | |
C7 | 0.6571 (4) | 0.9810 (3) | 0.5392 (2) | 0.0391 (10) | |
H7 | 0.6566 | 0.9690 | 0.4882 | 0.047* | |
C8 | 0.6649 (6) | 1.0932 (4) | 0.5655 (3) | 0.0560 (15) | |
H8 | 0.6700 | 1.1553 | 0.5322 | 0.067* | |
C9 | 0.6653 (5) | 1.1157 (4) | 0.6403 (3) | 0.0495 (13) | |
C10 | 0.6562 (5) | 1.0207 (4) | 0.6866 (2) | 0.0420 (11) | |
H10 | 0.6555 | 1.0311 | 0.7378 | 0.050* | |
C11 | 0.6481 (5) | 0.9097 (4) | 0.6566 (2) | 0.0381 (10) | |
H11 | 0.6409 | 0.8463 | 0.6888 | 0.046* | |
C12 | 0.6763 (9) | 1.2407 (5) | 0.6692 (3) | 0.102 (3) | |
H12A | 0.7370 | 1.2424 | 0.7118 | 0.153* | |
H12B | 0.5844 | 1.2683 | 0.6829 | 0.153* | |
H12C | 0.7145 | 1.2903 | 0.6311 | 0.153* | |
C13 | 0.7642 (5) | 0.4938 (4) | 0.4579 (3) | 0.0504 (12) | |
H13 | 0.8426 | 0.5425 | 0.4602 | 0.061* | |
C14 | 0.7758 (6) | 0.3903 (4) | 0.4196 (3) | 0.0558 (14) | |
H14 | 0.8603 | 0.3706 | 0.3966 | 0.067* | |
C15 | 0.6629 (6) | 0.3163 (4) | 0.4152 (3) | 0.0531 (13) | |
C16 | 0.5436 (6) | 0.3499 (4) | 0.4520 (3) | 0.0592 (14) | |
H16 | 0.4652 | 0.3010 | 0.4520 | 0.071* | |
C17 | 0.5381 (5) | 0.4556 (4) | 0.4891 (3) | 0.0467 (12) | |
H17 | 0.4550 | 0.4764 | 0.5130 | 0.056* | |
C18 | 0.6692 (8) | 0.2030 (5) | 0.3704 (3) | 0.092 (2) | |
H18A | 0.7471 | 0.1564 | 0.3871 | 0.138* | |
H18B | 0.6812 | 0.2213 | 0.3188 | 0.138* | |
H18C | 0.5832 | 0.1601 | 0.3771 | 0.138* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn1 | 0.0254 (2) | 0.0290 (2) | 0.0242 (2) | 0.0005 (2) | −0.00078 (19) | 0.0021 (2) |
S1 | 0.0231 (5) | 0.0323 (5) | 0.0216 (4) | 0.0001 (4) | −0.0011 (3) | −0.0004 (4) |
O1 | 0.0250 (12) | 0.0431 (15) | 0.0254 (13) | −0.0037 (12) | 0.0028 (10) | −0.0028 (16) |
O2 | 0.0448 (16) | 0.0613 (18) | 0.0312 (14) | −0.0061 (19) | −0.0037 (13) | −0.0188 (15) |
O3 | 0.0409 (18) | 0.0413 (18) | 0.0421 (18) | 0.0013 (13) | −0.0021 (14) | 0.0162 (14) |
O4 | 0.0230 (13) | 0.0404 (17) | 0.0257 (13) | 0.0063 (12) | −0.0027 (10) | 0.0015 (12) |
N1 | 0.0284 (19) | 0.0284 (19) | 0.0315 (19) | −0.0021 (14) | −0.0045 (14) | 0.0022 (16) |
N2 | 0.0310 (19) | 0.0318 (17) | 0.0269 (17) | −0.0018 (15) | 0.0010 (15) | −0.0010 (14) |
N3 | 0.046 (2) | 0.0337 (18) | 0.0343 (19) | 0.0044 (18) | −0.0013 (18) | −0.0034 (15) |
C1 | 0.032 (2) | 0.040 (2) | 0.035 (2) | −0.004 (2) | 0.004 (2) | 0.0093 (19) |
C2 | 0.026 (2) | 0.052 (3) | 0.038 (3) | 0.003 (2) | −0.0035 (19) | 0.009 (2) |
C3 | 0.033 (2) | 0.032 (2) | 0.024 (2) | 0.0062 (19) | −0.0027 (18) | −0.0011 (16) |
C4 | 0.037 (2) | 0.030 (2) | 0.030 (2) | −0.0056 (18) | 0.0040 (19) | 0.0067 (19) |
C5 | 0.027 (2) | 0.037 (2) | 0.034 (2) | −0.0069 (18) | −0.0008 (18) | 0.0049 (19) |
C6 | 0.051 (3) | 0.060 (3) | 0.041 (3) | 0.016 (2) | −0.005 (2) | 0.012 (2) |
C7 | 0.057 (3) | 0.032 (2) | 0.028 (2) | 0.0040 (19) | 0.008 (2) | −0.003 (2) |
C8 | 0.093 (4) | 0.036 (3) | 0.039 (3) | 0.001 (3) | 0.014 (3) | 0.000 (2) |
C9 | 0.068 (4) | 0.034 (2) | 0.047 (3) | −0.003 (2) | 0.010 (2) | −0.015 (2) |
C10 | 0.047 (3) | 0.048 (3) | 0.031 (2) | −0.004 (2) | 0.001 (2) | −0.014 (2) |
C11 | 0.040 (3) | 0.045 (2) | 0.029 (2) | −0.002 (2) | −0.003 (2) | −0.0006 (19) |
C12 | 0.192 (8) | 0.046 (4) | 0.069 (4) | −0.009 (4) | 0.022 (5) | −0.029 (3) |
C13 | 0.048 (3) | 0.043 (3) | 0.060 (3) | 0.009 (2) | 0.007 (3) | −0.001 (3) |
C14 | 0.068 (4) | 0.047 (3) | 0.052 (3) | 0.023 (3) | 0.011 (3) | −0.006 (3) |
C15 | 0.084 (4) | 0.037 (3) | 0.038 (3) | 0.018 (3) | −0.010 (3) | −0.004 (2) |
C16 | 0.066 (3) | 0.039 (3) | 0.072 (4) | −0.008 (2) | −0.015 (3) | −0.007 (3) |
C17 | 0.048 (3) | 0.036 (3) | 0.055 (3) | 0.002 (2) | 0.000 (2) | −0.003 (2) |
C18 | 0.157 (7) | 0.048 (3) | 0.072 (4) | 0.018 (5) | −0.020 (4) | −0.029 (3) |
Geometric parameters (Å, º) top
Zn1—O1 | 1.972 (2) | C6—H6B | 0.9600 |
Zn1—O4i | 1.989 (2) | C6—H6C | 0.9600 |
Zn1—N1 | 2.083 (3) | C7—H7 | 0.9300 |
Zn1—N2 | 2.172 (3) | C7—C8 | 1.368 (6) |
Zn1—N3 | 2.265 (3) | C8—H8 | 0.9300 |
S1—O1 | 1.507 (2) | C8—C9 | 1.372 (6) |
S1—O2 | 1.445 (3) | C9—C10 | 1.371 (6) |
S1—O3 | 1.452 (3) | C9—C12 | 1.523 (6) |
S1—O4 | 1.490 (3) | C10—H10 | 0.9300 |
O4—Zn1ii | 1.989 (2) | C10—C11 | 1.380 (5) |
N1—C1 | 1.334 (5) | C11—H11 | 0.9300 |
N1—C5 | 1.342 (5) | C12—H12A | 0.9600 |
N2—C7 | 1.327 (5) | C12—H12B | 0.9600 |
N2—C11 | 1.338 (5) | C12—H12C | 0.9600 |
N3—C13 | 1.335 (5) | C13—H13 | 0.9300 |
N3—C17 | 1.325 (6) | C13—C14 | 1.373 (7) |
C1—H1 | 0.9300 | C14—H14 | 0.9300 |
C1—C2 | 1.376 (6) | C14—C15 | 1.367 (7) |
C2—H2 | 0.9300 | C15—C16 | 1.368 (7) |
C2—C3 | 1.386 (6) | C15—C18 | 1.525 (6) |
C3—C4 | 1.376 (6) | C16—H16 | 0.9300 |
C3—C6 | 1.512 (5) | C16—C17 | 1.380 (7) |
C4—H4 | 0.9300 | C17—H17 | 0.9300 |
C4—C5 | 1.378 (6) | C18—H18A | 0.9600 |
C5—H5 | 0.9300 | C18—H18B | 0.9600 |
C6—H6A | 0.9600 | C18—H18C | 0.9600 |
| | | |
O1—Zn1—O4i | 101.86 (10) | H6A—C6—H6B | 109.5 |
O1—Zn1—N1 | 120.88 (12) | H6A—C6—H6C | 109.5 |
O1—Zn1—N2 | 96.34 (12) | H6B—C6—H6C | 109.5 |
O1—Zn1—N3 | 91.06 (13) | N2—C7—H7 | 118.7 |
O4i—Zn1—N1 | 136.31 (12) | N2—C7—C8 | 122.6 (4) |
O4i—Zn1—N2 | 92.97 (11) | C8—C7—H7 | 118.7 |
O4i—Zn1—N3 | 86.48 (11) | C7—C8—H8 | 119.5 |
N1—Zn1—N2 | 91.08 (12) | C7—C8—C9 | 121.0 (4) |
N1—Zn1—N3 | 84.23 (13) | C9—C8—H8 | 119.5 |
N2—Zn1—N3 | 172.53 (14) | C8—C9—C12 | 120.7 (5) |
O2—S1—O1 | 109.97 (16) | C10—C9—C8 | 116.8 (4) |
O2—S1—O3 | 112.19 (18) | C10—C9—C12 | 122.5 (4) |
O2—S1—O4 | 110.32 (17) | C9—C10—H10 | 120.3 |
O3—S1—O1 | 109.74 (17) | C9—C10—C11 | 119.4 (4) |
O3—S1—O4 | 109.55 (16) | C11—C10—H10 | 120.3 |
O4—S1—O1 | 104.81 (14) | N2—C11—C10 | 123.4 (4) |
S1—O1—Zn1 | 127.02 (15) | N2—C11—H11 | 118.3 |
S1—O4—Zn1ii | 130.57 (15) | C10—C11—H11 | 118.3 |
C1—N1—Zn1 | 121.8 (3) | C9—C12—H12A | 109.5 |
C1—N1—C5 | 117.0 (4) | C9—C12—H12B | 109.5 |
C5—N1—Zn1 | 120.4 (3) | C9—C12—H12C | 109.5 |
C7—N2—Zn1 | 120.4 (3) | H12A—C12—H12B | 109.5 |
C7—N2—C11 | 116.7 (3) | H12A—C12—H12C | 109.5 |
C11—N2—Zn1 | 122.8 (3) | H12B—C12—H12C | 109.5 |
C13—N3—Zn1 | 119.3 (3) | N3—C13—H13 | 118.2 |
C17—N3—Zn1 | 123.8 (3) | N3—C13—C14 | 123.6 (5) |
C17—N3—C13 | 116.4 (4) | C14—C13—H13 | 118.2 |
N1—C1—H1 | 118.4 | C13—C14—H14 | 120.1 |
N1—C1—C2 | 123.2 (4) | C15—C14—C13 | 119.8 (5) |
C2—C1—H1 | 118.4 | C15—C14—H14 | 120.1 |
C1—C2—H2 | 120.1 | C14—C15—C16 | 116.7 (4) |
C1—C2—C3 | 119.8 (4) | C14—C15—C18 | 121.6 (5) |
C3—C2—H2 | 120.1 | C16—C15—C18 | 121.8 (5) |
C2—C3—C6 | 122.2 (4) | C15—C16—H16 | 119.6 |
C4—C3—C2 | 117.0 (4) | C15—C16—C17 | 120.7 (5) |
C4—C3—C6 | 120.8 (4) | C17—C16—H16 | 119.6 |
C3—C4—H4 | 119.9 | N3—C17—C16 | 122.6 (5) |
C3—C4—C5 | 120.1 (4) | N3—C17—H17 | 118.7 |
C5—C4—H4 | 119.9 | C16—C17—H17 | 118.7 |
N1—C5—C4 | 122.8 (4) | C15—C18—H18A | 109.5 |
N1—C5—H5 | 118.6 | C15—C18—H18B | 109.5 |
C4—C5—H5 | 118.6 | C15—C18—H18C | 109.5 |
C3—C6—H6A | 109.5 | H18A—C18—H18B | 109.5 |
C3—C6—H6B | 109.5 | H18A—C18—H18C | 109.5 |
C3—C6—H6C | 109.5 | H18B—C18—H18C | 109.5 |
| | | |
Zn1—N1—C1—C2 | −168.4 (3) | C2—C3—C4—C5 | 3.2 (6) |
Zn1—N1—C5—C4 | 169.5 (3) | C3—C4—C5—N1 | −2.0 (7) |
Zn1—N2—C7—C8 | 178.7 (4) | C5—N1—C1—C2 | 1.2 (6) |
Zn1—N2—C11—C10 | −178.8 (3) | C6—C3—C4—C5 | −176.8 (4) |
Zn1—N3—C13—C14 | −170.6 (4) | C7—N2—C11—C10 | −1.6 (6) |
Zn1—N3—C17—C16 | 170.8 (4) | C7—C8—C9—C10 | −0.6 (8) |
O1—S1—O4—Zn1ii | −3.6 (3) | C7—C8—C9—C12 | 179.1 (5) |
O2—S1—O1—Zn1 | 47.0 (3) | C8—C9—C10—C11 | 0.4 (7) |
O2—S1—O4—Zn1ii | 114.7 (2) | C9—C10—C11—N2 | 0.7 (7) |
O3—S1—O1—Zn1 | −76.8 (2) | C11—N2—C7—C8 | 1.3 (6) |
O3—S1—O4—Zn1ii | −121.3 (2) | C12—C9—C10—C11 | −179.3 (5) |
O4—S1—O1—Zn1 | 165.61 (19) | C13—N3—C17—C16 | −1.2 (7) |
N1—C1—C2—C3 | 0.1 (7) | C13—C14—C15—C16 | −1.7 (8) |
N2—C7—C8—C9 | −0.2 (8) | C13—C14—C15—C18 | 177.2 (5) |
N3—C13—C14—C15 | −0.3 (8) | C14—C15—C16—C17 | 2.2 (8) |
C1—N1—C5—C4 | −0.3 (6) | C15—C16—C17—N3 | −0.8 (8) |
C1—C2—C3—C4 | −2.3 (6) | C17—N3—C13—C14 | 1.7 (7) |
C1—C2—C3—C6 | 177.7 (4) | C18—C15—C16—C17 | −176.7 (5) |
Symmetry codes: (i) x+1/2, −y+3/2, −z+1; (ii) x−1/2, −y+3/2, −z+1. |
catena-Poly[[tetrakis(4-methylpyridine-
κN)cadmium(II)]-sulfato-
κ2O:
O'] (umd1375_a)
top
Crystal data top
[Cd(SO4)(C6H7N)4] | F(000) = 2368 |
Mr = 580.96 | Dx = 1.487 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.4545 (12) Å | Cell parameters from 9677 reflections |
b = 18.657 (2) Å | θ = 3.0–25.7° |
c = 24.714 (3) Å | µ = 0.96 mm−1 |
β = 100.691 (3)° | T = 297 K |
V = 5190.0 (10) Å3 | BLOCK, colourless |
Z = 8 | 0.34 × 0.2 × 0.18 mm |
Data collection top
Bruker D8 Venture CMOS diffractometer | 4336 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.038 |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | θmax = 25.8°, θmin = 3.0° |
Tmin = 0.224, Tmax = 0.259 | h = −13→13 |
89835 measured reflections | k = −22→22 |
4957 independent reflections | l = −30→30 |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.026 | w = 1/[σ2(Fo2) + (0.0313P)2 + 8.6618P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.071 | (Δ/σ)max = 0.001 |
S = 1.09 | Δρmax = 0.74 e Å−3 |
4957 reflections | Δρmin = −0.34 e Å−3 |
314 parameters | Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
18 restraints | Extinction coefficient: 0.00105 (7) |
Primary atom site location: structure-invariant direct methods | |
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 | |
Cd1 | 0.5000 | 0.5000 | 0.5000 | 0.03761 (9) | |
Cd2 | 0.5000 | 0.47768 (2) | 0.2500 | 0.03604 (9) | |
S1 | 0.67059 (5) | 0.47963 (4) | 0.39044 (2) | 0.03846 (15) | |
O1 | 0.57078 (17) | 0.48567 (12) | 0.42023 (8) | 0.0565 (5) | |
O2 | 0.6224 (2) | 0.47972 (15) | 0.33195 (8) | 0.0767 (7) | |
O3 | 0.7461 (3) | 0.54068 (17) | 0.40324 (14) | 0.1038 (10) | |
O4 | 0.7339 (2) | 0.41422 (16) | 0.40457 (10) | 0.0870 (8) | |
N1 | 0.69302 (19) | 0.49835 (12) | 0.55385 (9) | 0.0416 (5) | |
N2 | 0.48552 (19) | 0.37501 (13) | 0.50421 (9) | 0.0475 (5) | |
N3 | 0.62050 (18) | 0.56493 (12) | 0.21844 (8) | 0.0411 (5) | |
N4 | 0.37958 (19) | 0.38282 (12) | 0.27345 (9) | 0.0447 (5) | |
C1 | 0.7931 (2) | 0.47415 (17) | 0.53984 (11) | 0.0522 (7) | |
H1 | 0.7889 | 0.4536 | 0.5053 | 0.063* | |
C2 | 0.9015 (3) | 0.47826 (19) | 0.57395 (12) | 0.0606 (8) | |
H2 | 0.9686 | 0.4606 | 0.5623 | 0.073* | |
C3 | 0.9119 (2) | 0.50853 (17) | 0.62568 (12) | 0.0508 (7) | |
C4 | 0.8090 (2) | 0.53346 (17) | 0.63967 (11) | 0.0521 (7) | |
H4 | 0.8109 | 0.5549 | 0.6738 | 0.062* | |
C5 | 0.7035 (2) | 0.52700 (16) | 0.60374 (11) | 0.0477 (7) | |
H5 | 0.6351 | 0.5436 | 0.6148 | 0.057* | |
C6 | 1.0286 (3) | 0.5145 (3) | 0.66412 (16) | 0.0960 (15) | |
H6A | 1.0913 | 0.5169 | 0.6433 | 0.144* | |
H6B | 1.0401 | 0.4733 | 0.6878 | 0.144* | |
H6C | 1.0293 | 0.5571 | 0.6860 | 0.144* | |
C7 | 0.5607 (3) | 0.33064 (17) | 0.48611 (13) | 0.0577 (8) | |
H7 | 0.6182 | 0.3498 | 0.4683 | 0.069* | |
C8 | 0.5566 (4) | 0.25743 (19) | 0.49280 (15) | 0.0755 (10) | |
H8 | 0.6115 | 0.2284 | 0.4800 | 0.091* | |
C9 | 0.4720 (4) | 0.22718 (19) | 0.51828 (16) | 0.0754 (10) | |
C10 | 0.3928 (3) | 0.27309 (18) | 0.53557 (14) | 0.0640 (8) | |
H10 | 0.3323 | 0.2550 | 0.5520 | 0.077* | |
C11 | 0.4028 (3) | 0.34583 (16) | 0.52866 (12) | 0.0524 (7) | |
H11 | 0.3494 | 0.3759 | 0.5416 | 0.063* | |
C12 | 0.4641 (6) | 0.1468 (2) | 0.5266 (3) | 0.132 (2) | |
H12A | 0.4193 | 0.1374 | 0.5550 | 0.198* | |
H12B | 0.5427 | 0.1274 | 0.5372 | 0.198* | |
H12C | 0.4255 | 0.1248 | 0.4929 | 0.198* | |
C13 | 0.5875 (3) | 0.59980 (15) | 0.17102 (11) | 0.0484 (6) | |
H13 | 0.5120 | 0.5914 | 0.1507 | 0.058* | |
C14 | 0.6599 (3) | 0.64749 (17) | 0.15084 (13) | 0.0608 (8) | |
H14 | 0.6327 | 0.6708 | 0.1176 | 0.073* | |
C15 | 0.7720 (3) | 0.66099 (18) | 0.17936 (15) | 0.0626 (8) | |
C16 | 0.8052 (3) | 0.6257 (2) | 0.22835 (16) | 0.0692 (9) | |
H16 | 0.8803 | 0.6335 | 0.2494 | 0.083* | |
C17 | 0.7286 (2) | 0.57882 (18) | 0.24682 (13) | 0.0563 (7) | |
H17 | 0.7533 | 0.5560 | 0.2804 | 0.068* | |
C18 | 0.8554 (4) | 0.7123 (2) | 0.1581 (2) | 0.1022 (15) | |
H18A | 0.8101 | 0.7462 | 0.1336 | 0.153* | |
H18B | 0.9068 | 0.6859 | 0.1388 | 0.153* | |
H18C | 0.9024 | 0.7373 | 0.1885 | 0.153* | |
C19 | 0.4080 (3) | 0.34684 (16) | 0.32063 (12) | 0.0514 (7) | |
H19 | 0.4793 | 0.3575 | 0.3439 | 0.062* | |
C20 | 0.3363 (3) | 0.29446 (17) | 0.33643 (14) | 0.0597 (8) | |
H20 | 0.3598 | 0.2707 | 0.3697 | 0.072* | |
C21 | 0.2299 (3) | 0.27737 (17) | 0.30290 (14) | 0.0609 (8) | |
C22 | 0.2021 (3) | 0.31364 (19) | 0.25367 (14) | 0.0638 (8) | |
H22 | 0.1319 | 0.3034 | 0.2294 | 0.077* | |
C23 | 0.2781 (3) | 0.36497 (17) | 0.24042 (12) | 0.0542 (7) | |
H23 | 0.2578 | 0.3884 | 0.2068 | 0.065* | |
C24 | 0.1456 (4) | 0.2226 (2) | 0.31918 (17) | 0.0899 (13) | |
H24A | 0.1899 | 0.1877 | 0.3432 | 0.135* | |
H24B | 0.1034 | 0.1992 | 0.2868 | 0.135* | |
H24C | 0.0901 | 0.2462 | 0.3379 | 0.135* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cd1 | 0.03155 (14) | 0.04792 (17) | 0.03387 (14) | 0.00385 (10) | 0.00739 (10) | 0.00098 (10) |
Cd2 | 0.03247 (14) | 0.04608 (17) | 0.03132 (14) | 0.000 | 0.01050 (10) | 0.000 |
S1 | 0.0296 (3) | 0.0605 (4) | 0.0262 (3) | 0.0049 (3) | 0.0075 (2) | −0.0016 (2) |
O1 | 0.0434 (11) | 0.0866 (15) | 0.0451 (11) | 0.0059 (10) | 0.0227 (9) | 0.0010 (10) |
O2 | 0.0671 (14) | 0.130 (2) | 0.0306 (10) | 0.0288 (13) | 0.0030 (10) | −0.0046 (11) |
O3 | 0.0834 (18) | 0.113 (2) | 0.131 (2) | −0.0468 (17) | 0.0617 (18) | −0.0550 (19) |
O4 | 0.0931 (18) | 0.104 (2) | 0.0715 (15) | 0.0555 (16) | 0.0351 (13) | 0.0270 (14) |
N1 | 0.0368 (11) | 0.0494 (13) | 0.0384 (12) | 0.0039 (9) | 0.0062 (9) | −0.0011 (9) |
N2 | 0.0480 (13) | 0.0514 (14) | 0.0446 (13) | 0.0025 (10) | 0.0122 (10) | −0.0014 (10) |
N3 | 0.0355 (11) | 0.0474 (13) | 0.0411 (12) | −0.0035 (9) | 0.0092 (9) | −0.0011 (9) |
N4 | 0.0413 (12) | 0.0460 (13) | 0.0501 (13) | 0.0009 (10) | 0.0171 (10) | −0.0014 (10) |
C1 | 0.0470 (16) | 0.074 (2) | 0.0370 (14) | 0.0145 (14) | 0.0102 (12) | −0.0046 (13) |
C2 | 0.0435 (16) | 0.096 (2) | 0.0444 (16) | 0.0218 (15) | 0.0140 (13) | 0.0004 (15) |
C3 | 0.0346 (14) | 0.076 (2) | 0.0414 (15) | 0.0014 (13) | 0.0056 (11) | 0.0057 (13) |
C4 | 0.0451 (15) | 0.072 (2) | 0.0393 (14) | −0.0031 (14) | 0.0083 (12) | −0.0132 (13) |
C5 | 0.0340 (13) | 0.0639 (18) | 0.0467 (15) | 0.0031 (12) | 0.0113 (11) | −0.0137 (13) |
C6 | 0.0418 (19) | 0.183 (5) | 0.059 (2) | 0.005 (2) | −0.0025 (16) | −0.007 (2) |
C7 | 0.0604 (18) | 0.0611 (19) | 0.0569 (18) | 0.0072 (15) | 0.0251 (15) | −0.0006 (14) |
C8 | 0.099 (3) | 0.055 (2) | 0.081 (2) | 0.0172 (19) | 0.040 (2) | −0.0067 (17) |
C9 | 0.105 (3) | 0.0510 (19) | 0.076 (2) | −0.0013 (19) | 0.033 (2) | −0.0039 (17) |
C10 | 0.075 (2) | 0.058 (2) | 0.064 (2) | −0.0127 (16) | 0.0251 (17) | −0.0039 (15) |
C11 | 0.0526 (17) | 0.0557 (18) | 0.0509 (17) | −0.0011 (13) | 0.0153 (13) | −0.0062 (13) |
C12 | 0.190 (6) | 0.053 (2) | 0.175 (5) | 0.005 (3) | 0.091 (5) | 0.005 (3) |
C13 | 0.0498 (15) | 0.0516 (16) | 0.0426 (15) | −0.0060 (12) | 0.0053 (12) | 0.0001 (12) |
C14 | 0.077 (2) | 0.0550 (18) | 0.0525 (18) | −0.0102 (16) | 0.0177 (16) | 0.0036 (14) |
C15 | 0.0604 (19) | 0.0580 (19) | 0.077 (2) | −0.0128 (15) | 0.0322 (17) | −0.0038 (16) |
C16 | 0.0366 (16) | 0.081 (2) | 0.088 (3) | −0.0143 (15) | 0.0079 (15) | −0.001 (2) |
C17 | 0.0380 (15) | 0.070 (2) | 0.0585 (18) | −0.0054 (13) | 0.0019 (13) | 0.0089 (15) |
C18 | 0.101 (3) | 0.089 (3) | 0.132 (4) | −0.036 (3) | 0.062 (3) | 0.000 (3) |
C19 | 0.0501 (16) | 0.0513 (17) | 0.0556 (17) | 0.0051 (13) | 0.0173 (13) | 0.0028 (13) |
C20 | 0.071 (2) | 0.0539 (18) | 0.0591 (18) | 0.0036 (15) | 0.0254 (16) | 0.0075 (14) |
C21 | 0.072 (2) | 0.0558 (18) | 0.0632 (19) | −0.0140 (15) | 0.0328 (17) | −0.0090 (15) |
C22 | 0.0589 (19) | 0.074 (2) | 0.061 (2) | −0.0203 (16) | 0.0163 (15) | −0.0097 (16) |
C23 | 0.0531 (17) | 0.0617 (19) | 0.0496 (16) | −0.0073 (14) | 0.0142 (13) | −0.0017 (14) |
C24 | 0.106 (3) | 0.085 (3) | 0.089 (3) | −0.037 (2) | 0.044 (2) | −0.005 (2) |
Geometric parameters (Å, º) top
Cd1—O1i | 2.2822 (19) | C7—H7 | 0.9300 |
Cd1—O1 | 2.2822 (19) | C7—C8 | 1.378 (5) |
Cd1—N1i | 2.360 (2) | C8—H8 | 0.9300 |
Cd1—N1 | 2.360 (2) | C8—C9 | 1.371 (5) |
Cd1—N2 | 2.342 (2) | C9—C10 | 1.372 (5) |
Cd1—N2i | 2.342 (2) | C9—C12 | 1.518 (6) |
Cd2—O2ii | 2.240 (2) | C10—H10 | 0.9300 |
Cd2—O2 | 2.240 (2) | C10—C11 | 1.375 (4) |
Cd2—N3ii | 2.358 (2) | C11—H11 | 0.9300 |
Cd2—N3 | 2.358 (2) | C12—H12A | 0.9600 |
Cd2—N4 | 2.381 (2) | C12—H12B | 0.9600 |
Cd2—N4ii | 2.381 (2) | C12—H12C | 0.9600 |
S1—O1 | 1.4745 (19) | C13—H13 | 0.9300 |
S1—O2 | 1.448 (2) | C13—C14 | 1.372 (4) |
S1—O3 | 1.430 (3) | C14—H14 | 0.9300 |
S1—O4 | 1.429 (2) | C14—C15 | 1.368 (5) |
N1—C1 | 1.336 (3) | C15—C16 | 1.369 (5) |
N1—C5 | 1.329 (3) | C15—C18 | 1.514 (4) |
N2—C7 | 1.330 (4) | C16—H16 | 0.9300 |
N2—C11 | 1.332 (4) | C16—C17 | 1.375 (4) |
N3—C13 | 1.332 (3) | C17—H17 | 0.9300 |
N3—C17 | 1.330 (3) | C18—H18A | 0.9600 |
N4—C19 | 1.332 (4) | C18—H18B | 0.9600 |
N4—C23 | 1.332 (4) | C18—H18C | 0.9600 |
C1—H1 | 0.9300 | C19—H19 | 0.9300 |
C1—C2 | 1.367 (4) | C19—C20 | 1.378 (4) |
C2—H2 | 0.9300 | C20—H20 | 0.9300 |
C2—C3 | 1.382 (4) | C20—C21 | 1.378 (5) |
C3—C4 | 1.370 (4) | C21—C22 | 1.377 (5) |
C3—C6 | 1.493 (4) | C21—C24 | 1.510 (4) |
C4—H4 | 0.9300 | C22—H22 | 0.9300 |
C4—C5 | 1.365 (4) | C22—C23 | 1.374 (4) |
C5—H5 | 0.9300 | C23—H23 | 0.9300 |
C6—H6A | 0.9600 | C24—H24A | 0.9600 |
C6—H6B | 0.9600 | C24—H24B | 0.9600 |
C6—H6C | 0.9600 | C24—H24C | 0.9600 |
| | | |
O1i—Cd1—O1 | 180.0 | C3—C6—H6C | 109.5 |
O1—Cd1—N1 | 92.28 (7) | H6A—C6—H6B | 109.5 |
O1i—Cd1—N1 | 87.72 (7) | H6A—C6—H6C | 109.5 |
O1—Cd1—N1i | 87.72 (7) | H6B—C6—H6C | 109.5 |
O1i—Cd1—N1i | 92.28 (7) | N2—C7—H7 | 118.7 |
O1i—Cd1—N2 | 92.23 (8) | N2—C7—C8 | 122.6 (3) |
O1i—Cd1—N2i | 87.77 (8) | C8—C7—H7 | 118.7 |
O1—Cd1—N2 | 87.77 (8) | C7—C8—H8 | 119.8 |
O1—Cd1—N2i | 92.23 (8) | C9—C8—C7 | 120.4 (3) |
N1—Cd1—N1i | 180.0 | C9—C8—H8 | 119.8 |
N2—Cd1—N1i | 88.36 (8) | C8—C9—C10 | 116.8 (3) |
N2i—Cd1—N1i | 91.64 (8) | C8—C9—C12 | 122.2 (4) |
N2—Cd1—N1 | 91.64 (8) | C10—C9—C12 | 121.0 (4) |
N2i—Cd1—N1 | 88.36 (8) | C9—C10—H10 | 119.9 |
N2—Cd1—N2i | 180.0 | C9—C10—C11 | 120.2 (3) |
O2ii—Cd2—O2 | 178.05 (15) | C11—C10—H10 | 119.9 |
O2ii—Cd2—N3ii | 88.89 (9) | N2—C11—C10 | 122.8 (3) |
O2ii—Cd2—N3 | 89.77 (8) | N2—C11—H11 | 118.6 |
O2—Cd2—N3ii | 89.77 (8) | C10—C11—H11 | 118.6 |
O2—Cd2—N3 | 88.89 (9) | C9—C12—H12A | 109.5 |
O2—Cd2—N4 | 94.95 (9) | C9—C12—H12B | 109.5 |
O2—Cd2—N4ii | 86.50 (8) | C9—C12—H12C | 109.5 |
O2ii—Cd2—N4ii | 94.95 (9) | H12A—C12—H12B | 109.5 |
O2ii—Cd2—N4 | 86.50 (8) | H12A—C12—H12C | 109.5 |
N3ii—Cd2—N3 | 92.71 (10) | H12B—C12—H12C | 109.5 |
N3ii—Cd2—N4 | 91.81 (7) | N3—C13—H13 | 118.5 |
N3ii—Cd2—N4ii | 174.08 (7) | N3—C13—C14 | 123.0 (3) |
N3—Cd2—N4ii | 91.81 (7) | C14—C13—H13 | 118.5 |
N3—Cd2—N4 | 174.08 (7) | C13—C14—H14 | 119.8 |
N4—Cd2—N4ii | 83.95 (10) | C15—C14—C13 | 120.3 (3) |
O2—S1—O1 | 108.14 (13) | C15—C14—H14 | 119.8 |
O3—S1—O1 | 108.78 (14) | C14—C15—C16 | 116.6 (3) |
O3—S1—O2 | 108.82 (19) | C14—C15—C18 | 122.0 (4) |
O4—S1—O1 | 110.40 (14) | C16—C15—C18 | 121.4 (3) |
O4—S1—O2 | 109.08 (15) | C15—C16—H16 | 119.7 |
O4—S1—O3 | 111.6 (2) | C15—C16—C17 | 120.7 (3) |
S1—O1—Cd1 | 150.80 (13) | C17—C16—H16 | 119.7 |
S1—O2—Cd2 | 163.96 (16) | N3—C17—C16 | 122.5 (3) |
C1—N1—Cd1 | 128.14 (18) | N3—C17—H17 | 118.7 |
C5—N1—Cd1 | 115.61 (17) | C16—C17—H17 | 118.7 |
C5—N1—C1 | 116.2 (2) | C15—C18—H18A | 109.5 |
C7—N2—Cd1 | 123.3 (2) | C15—C18—H18B | 109.5 |
C7—N2—C11 | 117.2 (3) | C15—C18—H18C | 109.5 |
C11—N2—Cd1 | 119.31 (18) | H18A—C18—H18B | 109.5 |
C13—N3—Cd2 | 122.70 (17) | H18A—C18—H18C | 109.5 |
C17—N3—Cd2 | 120.31 (18) | H18B—C18—H18C | 109.5 |
C17—N3—C13 | 116.9 (2) | N4—C19—H19 | 118.5 |
C19—N4—Cd2 | 121.96 (19) | N4—C19—C20 | 122.9 (3) |
C23—N4—Cd2 | 121.02 (19) | C20—C19—H19 | 118.5 |
C23—N4—C19 | 117.0 (2) | C19—C20—H20 | 120.0 |
N1—C1—H1 | 118.5 | C21—C20—C19 | 120.0 (3) |
N1—C1—C2 | 123.1 (3) | C21—C20—H20 | 120.0 |
C2—C1—H1 | 118.5 | C20—C21—C24 | 122.3 (3) |
C1—C2—H2 | 119.8 | C22—C21—C20 | 116.8 (3) |
C1—C2—C3 | 120.4 (3) | C22—C21—C24 | 120.9 (3) |
C3—C2—H2 | 119.8 | C21—C22—H22 | 120.0 |
C2—C3—C6 | 122.1 (3) | C23—C22—C21 | 120.0 (3) |
C4—C3—C2 | 116.2 (3) | C23—C22—H22 | 120.0 |
C4—C3—C6 | 121.7 (3) | N4—C23—C22 | 123.2 (3) |
C3—C4—H4 | 119.8 | N4—C23—H23 | 118.4 |
C5—C4—C3 | 120.3 (3) | C22—C23—H23 | 118.4 |
C5—C4—H4 | 119.8 | C21—C24—H24A | 109.5 |
N1—C5—C4 | 123.8 (2) | C21—C24—H24B | 109.5 |
N1—C5—H5 | 118.1 | C21—C24—H24C | 109.5 |
C4—C5—H5 | 118.1 | H24A—C24—H24B | 109.5 |
C3—C6—H6A | 109.5 | H24A—C24—H24C | 109.5 |
C3—C6—H6B | 109.5 | H24B—C24—H24C | 109.5 |
| | | |
Cd1—N1—C1—C2 | 177.6 (2) | C5—N1—C1—C2 | −0.3 (5) |
Cd1—N1—C5—C4 | −177.2 (2) | C6—C3—C4—C5 | −179.7 (3) |
Cd1—N2—C7—C8 | 174.8 (3) | C7—N2—C11—C10 | 0.0 (4) |
Cd1—N2—C11—C10 | −176.2 (2) | C7—C8—C9—C10 | 0.8 (6) |
Cd2—N3—C13—C14 | −176.0 (2) | C7—C8—C9—C12 | −180.0 (4) |
Cd2—N3—C17—C16 | 175.6 (3) | C8—C9—C10—C11 | −2.1 (6) |
Cd2—N4—C19—C20 | 176.3 (2) | C9—C10—C11—N2 | 1.7 (5) |
Cd2—N4—C23—C22 | −175.9 (2) | C11—N2—C7—C8 | −1.2 (5) |
O1—S1—O2—Cd2 | −8.4 (7) | C12—C9—C10—C11 | 178.7 (4) |
O2—S1—O1—Cd1 | −172.5 (3) | C13—N3—C17—C16 | −1.3 (5) |
O3—S1—O1—Cd1 | −54.5 (3) | C13—C14—C15—C16 | −1.1 (5) |
O3—S1—O2—Cd2 | −126.4 (7) | C13—C14—C15—C18 | 179.0 (3) |
O4—S1—O1—Cd1 | 68.2 (3) | C14—C15—C16—C17 | 0.6 (5) |
O4—S1—O2—Cd2 | 111.7 (7) | C15—C16—C17—N3 | 0.6 (5) |
N1—C1—C2—C3 | −0.1 (5) | C17—N3—C13—C14 | 0.8 (4) |
N2—C7—C8—C9 | 0.9 (6) | C18—C15—C16—C17 | −179.5 (4) |
N3—C13—C14—C15 | 0.4 (5) | C19—N4—C23—C22 | 1.9 (4) |
N4—C19—C20—C21 | −0.1 (5) | C19—C20—C21—C22 | 1.4 (5) |
C1—N1—C5—C4 | 1.0 (4) | C19—C20—C21—C24 | −177.4 (3) |
C1—C2—C3—C4 | −0.2 (5) | C20—C21—C22—C23 | −1.1 (5) |
C1—C2—C3—C6 | −179.6 (4) | C21—C22—C23—N4 | −0.6 (5) |
C2—C3—C4—C5 | 0.8 (5) | C23—N4—C19—C20 | −1.6 (4) |
C3—C4—C5—N1 | −1.3 (5) | C24—C21—C22—C23 | 177.8 (3) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O4 | 0.93 | 2.56 | 3.471 (4) | 167 |
C5—H5···O1i | 0.93 | 2.42 | 3.097 (3) | 130 |
C7—H7···O4 | 0.93 | 2.54 | 3.452 (4) | 167 |
C11—H11···O3i | 0.93 | 2.45 | 3.360 (4) | 164 |
C17—H17···O2 | 0.93 | 2.57 | 3.205 (4) | 126 |
C23—H23···O2ii | 0.93 | 2.49 | 3.136 (4) | 127 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y, −z+1/2. |
Synthetic conditions for the isolation of crystals of compounds
(1)–(7) topCompound | Salt | mg of Salt | H2O (ml) | 4-Picoline (ml) | T (°C) |
(1) | Fe(SO4)·7H2O | 8.8 | 0.0 | 2.0 | 90 |
(2) | Co(SO4)·7H2O | 4.8 | 0.2 | 2.0 | 85 |
(3) | Ni(SO4)·6H2O | 3.7 | 0.2 | 2.0 | 90 |
(4) | Cu(SO4) anhydrous | 11.6 | 0.2 | 3.0 | 90 |
(5) | Zn(SO4)·7H2O | 9.8 | 0.1 | 2.0 | 50 |
(6) | Zn(SO4)·7H2O | 23.0 | 0.0 | 2.0 | 60 |
(7) | Cd(SO4)·8/3H2O | 9.8 | 0.0 | 1.5 | 80 |
Geometric parameters (Å, °) for the reported complexes top | M = Fe, (1) | | M = Co, (2) | | M = Ni, (3) | | M = Cd, (7) | | | | |
M—O | Fe1—O1 | 2.056 (1) | | Co1—O1 | 2.090 (1) | | Ni1—O1 | 2.098 (1) | | Cd1—O1 | 2.282 (2) |
| Fe2—O2 | 2.025 (1) | | Co2—O2 | 2.053 (1) | | Ni2—O2 | 2.058 (1) | | Cd2—O2 | 2.240 (2) |
M—N | Fe1—N1 | 2.229 (2) | | Co1—N1 | 2.174 (2) | | Ni1—N1 | 2.119 (2) | | Cd1—N1 | 2.360 (2) |
| Fe1—N2 | 2.240 (2) | | Co1—N2 | 2.187 (2) | | Ni1—N2 | 2.132 (2) | | Cd1—N2 | 2.343 (2) |
| Fe2—N3 | 2.242 (2) | | Co2—N3 | 2.187 (2) | | Ni2—N3 | 2.154 (2) | | Cd2—N3 | 2.358 (2) |
| Fe2—N4 | 2.257 (2) | | Co2—N4 | 2.208 (2) | | Ni2—N4 | 2.131 (2) | | Cd2—N4 | 2.381 (2) |
O—M—O | O1—Fe1—O1i | 180.0 | | O1—Co1—O1i | 180.0 | | O1—Ni1—O1i | 180.0 | | O1—Cd1—O1i | 180.0 |
| O2—Fe2—O2ii | 178.03 (9) | | O2—Co2—O2iii | 177.5 (1) | | O2—Ni2—O2ii | 180.0 | | O2—Cd2—O2iii | 178.1 (2) |
N—M—N | N1—Fe1—N2 | 92.13 (6) | | N1—Co1—N2 | 92.27 (7) | | N1—Ni1—N2 | 91.99 (7) | | N1—Cd1—N2 | 91.64 (8) |
| N1—Fe1—N2i | 87.87 (6) | | N1—Co1—N2i | 87.73 (7) | | N1—Ni1—N2i | 88.01 (7) | | N1—Cd1—N2i | 88.36 (8) |
| N1—Fe1—N1i | 180.0 | | N1—Co1—N1i | 180.0 | | N1—Ni1—N1i | 180.00 (9) | | N1—Cd1—N1i | 180.0 |
| N2—Fe1—N2i | 180.0 | | N2—Co1—N2i | 180.0 | | N2—Ni1—N2i | 180.0 | | N2—Cd1—N2i | 180.0 |
| N3—Fe2—N3ii | 92.81 (5) | | N3—Co2—N3iii | 90.57 (9) | | N3—Ni2—N3ii | 85.30 (9) | | N3—Cd2—N3iii | 92.7 (1) |
| N3—Fe2—N4ii | 90.47 (8) | | N3—Co2—N4iii | 92.58 (6) | | N3—Ni2—N4ii | 92.02 (6) | | N3—Cd2—N4iii | 91.81 (7) |
| N4—Fe2—N4ii | 84.16 (8) | | N4—Co2—N4iii | 84.47 (9) | | N4—Ni2—N4ii | 90.81 (9) | | N4—Cd2—N4iii | 84.0 (1) |
| N3—Fe2—N4 | 175.09 (5) | | N3—Co2—N4 | 175.43 (6) | | N3—Ni2—N4 | 175.91 (6) | | N3—Cd2—N4 | 174.08 (7) |
| M = Cu, (4) | | M = Zn, (5) | | M = Zn, (6) | | | | | | |
M—O | Cu1—O1 | 1.985 (1) | | Zn1—O1 | 1.915 (2) | | Zn1—O1 | 1.972 (2) | | | |
| Cu1—O1i | 2.253 (1) | | Zn1—O4iv | 1.941 (2) | | Zn1—O4v | 1.989 (2) | | | |
M—N | Cu1—N1 | 2.041 (2) | | Zn1—N1 | 2.043 (2) | | Zn1—N1 | 2.083 (3) | | | |
| Cu1—N2 | 2.011 (2) | | Zn1—N2 | 2.005 (2) | | Zn1—N2 | 2.172 (3) | | | |
| Cu1—N3 | 2.024 (2) | | | | | Zn1—N3 | 2.265 (3) | | | |
O—M—O | O1—Cu1—O1i | 79.94 (6) | | O1—Zn1—O4iv | 102.86 (8) | | O1—Zn1—O4v | 101.9 (1) | | | |
N—M—N | N1—Cu1—N2 | 88.00 (7) | | N1—Zn1—N2 | 113.43 (9) | | N1—Zn1—N2 | 91.1 (1) | | | |
| N1—Cu1—N3 | 172.28 (7) | | | | | N1—Zn1—N3 | 84.2 (1) | | | |
| N2—Cu1—N3 | 87.12 (7) | | | | | N2—Zn1—N3 | 172.5 (1) | | | |
Symmetry codes: (i) -x+1, -y+1, -z+1;
(ii) -x+1, y, -z+3/2;
(iii) -x+1, y, -z+1/2;
(iv) x, -y+3/2, z-1/2;
(v) x+1/2, -y+3/2, -z+1. |
Crystal field stabilization energy [units are Dq (Oh)] topObserved geometries are highlighted in bold. |
| Tetrahedral | Trigonal bipyramidal | Square pyramidal | Octahedral |
Iron (d6) | 2.67 | 2.73 | 4.57 | 4 |
Cobalt (d7) | 5.34 | 5.45 | 9.14 | 8 |
Nickel (d8) | 3.56 | 6.27 | 10 | 12 |
Copper (d9) | 1.78 | 7.09 | 9.14 | 6 |
Zinc (d10) | 0 | 0 | 0 | 0 |
Cadmium (d10) | 0 | 0 | 0 | 0 |
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