metal-organic compounds
In the title compound, [Cu(C9H5N4O)Cl(C12H8N2)]n or [Cu(tcnoet)Cl(phen)]n, where phen is 1,10-phenanthroline and tcnoet is 1,1,3,3-tetracyano-2-ethoxypropenide, the axially elongated (4 + 2) coordination polyhedron around the CuII centre contains N atoms from three different tcnoet ligands. The resulting coordination polymer takes the form of sheets which are linked in pairs by a single C-HN hydrogen bond to form bilayers. The bond lengths provide evidence for significant bond fixation in the phen ligand and extensive electronic delocalization in the tcnoet ligand, where the two -C(CN)2 units are rotated, in conrotatory fashion, out of the plane of the central C3O fragment.
Keywords: crystal structure; coordination polymer; hydrogen bonding; anionic polynitrile ligands; tcnoet ligands; 1,1,3,3-tetracyano-2-ethoxypropenide; (4+2) coordination polyhedron; copper complex.
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229613032804/sk3522sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229613032804/sk3522Isup2.hkl |
CCDC reference: 975003
Computing details top
Data collection: APEX2 (Bruker, 2009); cell refinement: APEX2 and SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
Poly[[chlorido(1,10-phenanthroline-κ2N,N')copper(II)]-µ3-1,1,3,3-tetracyano-2-ethoxypropenido-κ3N:N':N''] top
Crystal data top
[Cu(C9H5N4O)Cl(C12H8N2)] | F(000) = 1880 |
Mr = 464.37 | Dx = 1.544 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 6366 reflections |
a = 31.79 (3) Å | θ = 2.6–31.0° |
b = 7.925 (6) Å | µ = 1.25 mm−1 |
c = 16.005 (13) Å | T = 296 K |
β = 97.69 (3)° | Plate, green |
V = 3996 (6) Å3 | 0.27 × 0.23 × 0.14 mm |
Z = 8 |
Data collection top
Bruker X8 APEXII area-detector diffractometer | 4596 independent reflections |
Radiation source: fine-focus sealed tube | 3188 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.058 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.6° |
φ and ω scans | h = −41→41 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −10→10 |
Tmin = 0.722, Tmax = 0.804 | l = −20→20 |
34518 measured reflections |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0551P)2 + 0.7334P] where P = (Fo2 + 2Fc2)/3 |
4596 reflections | (Δ/σ)max = 0.001 |
272 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.109132 (10) | 0.30029 (4) | 0.695410 (18) | 0.03960 (12) | |
Cl1 | 0.05105 (2) | 0.44903 (10) | 0.64741 (5) | 0.0578 (2) | |
N1 | 0.16459 (7) | 0.1941 (2) | 0.75086 (13) | 0.0384 (5) | |
C2 | 0.19716 (9) | 0.1342 (4) | 0.71602 (18) | 0.0504 (7) | |
H2 | 0.1960 | 0.1372 | 0.6577 | 0.061* | |
C3 | 0.23308 (9) | 0.0670 (4) | 0.7640 (2) | 0.0601 (8) | |
H3 | 0.2552 | 0.0249 | 0.7374 | 0.072* | |
C4 | 0.23586 (9) | 0.0630 (4) | 0.8496 (2) | 0.0586 (8) | |
H4 | 0.2600 | 0.0195 | 0.8818 | 0.070* | |
C4A | 0.20220 (8) | 0.1247 (3) | 0.88875 (17) | 0.0442 (6) | |
C4B | 0.16713 (8) | 0.1896 (3) | 0.83635 (15) | 0.0365 (5) | |
C5 | 0.20146 (10) | 0.1260 (4) | 0.97815 (18) | 0.0565 (8) | |
H5 | 0.2248 | 0.0849 | 1.0136 | 0.068* | |
C6 | 0.16767 (10) | 0.1857 (3) | 1.01196 (17) | 0.0526 (7) | |
H6 | 0.1681 | 0.1853 | 1.0702 | 0.063* | |
C6A | 0.13105 (9) | 0.2496 (3) | 0.95917 (15) | 0.0428 (6) | |
C6B | 0.13112 (8) | 0.2516 (3) | 0.87180 (15) | 0.0355 (5) | |
C7 | 0.09436 (10) | 0.3073 (3) | 0.98932 (17) | 0.0507 (7) | |
H7 | 0.0929 | 0.3090 | 1.0470 | 0.061* | |
C8 | 0.06066 (10) | 0.3611 (4) | 0.93366 (19) | 0.0558 (7) | |
H8 | 0.0359 | 0.3976 | 0.9531 | 0.067* | |
C9 | 0.06358 (9) | 0.3610 (3) | 0.84764 (18) | 0.0483 (7) | |
H9 | 0.0405 | 0.3988 | 0.8105 | 0.058* | |
N10 | 0.09806 (6) | 0.3090 (2) | 0.81664 (13) | 0.0370 (5) | |
C11 | 0.14488 (9) | 0.2787 (3) | 0.43121 (16) | 0.0421 (6) | |
C12 | 0.11597 (8) | 0.2046 (3) | 0.36808 (16) | 0.0411 (6) | |
C13 | 0.11784 (9) | 0.2112 (3) | 0.28176 (15) | 0.0423 (6) | |
C111 | 0.13474 (9) | 0.2791 (3) | 0.51440 (17) | 0.0448 (6) | |
N111 | 0.12696 (8) | 0.2807 (3) | 0.58229 (15) | 0.0523 (6) | |
C112 | 0.18515 (11) | 0.3424 (4) | 0.41863 (17) | 0.0564 (8) | |
N112 | 0.21808 (10) | 0.3930 (5) | 0.41061 (18) | 0.0888 (10) | |
O121 | 0.08607 (6) | 0.1140 (3) | 0.39883 (12) | 0.0552 (5) | |
C121 | 0.04102 (10) | 0.1324 (5) | 0.3638 (2) | 0.0801 (11) | |
H21A | 0.0377 | 0.2240 | 0.3233 | 0.096* | |
H21B | 0.0309 | 0.0294 | 0.3352 | 0.096* | |
C122 | 0.01714 (14) | 0.1667 (7) | 0.4313 (4) | 0.130 (2) | |
H22A | −0.0118 | 0.1891 | 0.4088 | 0.196* | |
H22B | 0.0289 | 0.2634 | 0.4622 | 0.196* | |
H22C | 0.0183 | 0.0709 | 0.4682 | 0.196* | |
C131 | 0.09473 (10) | 0.0948 (3) | 0.22534 (17) | 0.0503 (7) | |
N131 | 0.07748 (10) | −0.0037 (3) | 0.18067 (17) | 0.0710 (8) | |
C132 | 0.14346 (9) | 0.3290 (3) | 0.24406 (17) | 0.0450 (6) | |
N132 | 0.16247 (9) | 0.4237 (3) | 0.21067 (16) | 0.0617 (7) |
Atomic displacement parameters (Å2) top
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0404 (2) | 0.0556 (2) | 0.02246 (18) | 0.00481 (14) | 0.00309 (13) | 0.00303 (12) |
Cl1 | 0.0434 (4) | 0.0846 (5) | 0.0444 (4) | 0.0096 (3) | 0.0016 (3) | 0.0217 (3) |
N1 | 0.0375 (12) | 0.0507 (11) | 0.0273 (11) | 0.0018 (9) | 0.0053 (9) | −0.0002 (9) |
C2 | 0.0427 (16) | 0.0718 (17) | 0.0386 (16) | 0.0057 (13) | 0.0122 (13) | −0.0008 (13) |
C3 | 0.0394 (16) | 0.084 (2) | 0.059 (2) | 0.0145 (14) | 0.0147 (15) | −0.0004 (16) |
C4 | 0.0384 (16) | 0.080 (2) | 0.055 (2) | 0.0130 (14) | −0.0019 (14) | 0.0055 (15) |
C4A | 0.0388 (15) | 0.0538 (14) | 0.0378 (15) | 0.0010 (11) | −0.0030 (12) | 0.0010 (11) |
C4B | 0.0371 (14) | 0.0428 (12) | 0.0293 (14) | −0.0028 (10) | 0.0032 (11) | 0.0001 (9) |
C5 | 0.0547 (19) | 0.0720 (18) | 0.0375 (17) | 0.0061 (15) | −0.0133 (14) | 0.0058 (13) |
C6 | 0.062 (2) | 0.0689 (17) | 0.0241 (14) | 0.0041 (14) | −0.0038 (13) | 0.0008 (12) |
C6A | 0.0544 (17) | 0.0492 (13) | 0.0243 (13) | 0.0007 (12) | 0.0034 (12) | −0.0006 (10) |
C6B | 0.0371 (14) | 0.0436 (12) | 0.0251 (13) | −0.0007 (10) | 0.0023 (11) | 0.0003 (9) |
C7 | 0.0625 (19) | 0.0647 (16) | 0.0267 (14) | 0.0034 (14) | 0.0128 (13) | −0.0029 (12) |
C8 | 0.0533 (18) | 0.0749 (18) | 0.0432 (18) | 0.0107 (15) | 0.0216 (15) | −0.0007 (14) |
C9 | 0.0416 (16) | 0.0652 (16) | 0.0393 (16) | 0.0104 (13) | 0.0097 (13) | 0.0023 (12) |
N10 | 0.0341 (11) | 0.0495 (11) | 0.0275 (11) | 0.0042 (9) | 0.0045 (9) | 0.0012 (8) |
C11 | 0.0451 (15) | 0.0578 (15) | 0.0235 (13) | 0.0059 (12) | 0.0053 (11) | −0.0010 (10) |
C12 | 0.0412 (15) | 0.0497 (14) | 0.0321 (14) | 0.0105 (11) | 0.0036 (12) | 0.0009 (10) |
C13 | 0.0506 (16) | 0.0495 (14) | 0.0255 (14) | 0.0084 (12) | 0.0003 (12) | −0.0033 (10) |
C111 | 0.0448 (16) | 0.0580 (15) | 0.0301 (15) | 0.0084 (12) | −0.0005 (12) | −0.0010 (11) |
N111 | 0.0539 (15) | 0.0763 (16) | 0.0267 (13) | 0.0026 (12) | 0.0051 (11) | −0.0015 (11) |
C112 | 0.061 (2) | 0.083 (2) | 0.0246 (15) | −0.0050 (16) | 0.0019 (14) | −0.0071 (13) |
N112 | 0.068 (2) | 0.153 (3) | 0.0455 (18) | −0.040 (2) | 0.0069 (15) | −0.0122 (18) |
O121 | 0.0469 (12) | 0.0730 (12) | 0.0453 (12) | −0.0016 (10) | 0.0050 (9) | 0.0058 (9) |
C121 | 0.046 (2) | 0.121 (3) | 0.071 (3) | −0.0071 (19) | −0.0003 (18) | −0.016 (2) |
C122 | 0.062 (3) | 0.190 (5) | 0.142 (5) | 0.014 (3) | 0.024 (3) | −0.022 (4) |
C131 | 0.0620 (19) | 0.0557 (15) | 0.0317 (15) | 0.0120 (13) | 0.0003 (14) | 0.0000 (12) |
N131 | 0.089 (2) | 0.0700 (17) | 0.0493 (17) | 0.0026 (15) | −0.0084 (15) | −0.0145 (13) |
C132 | 0.0503 (17) | 0.0567 (15) | 0.0261 (14) | 0.0137 (13) | −0.0022 (12) | −0.0038 (11) |
N132 | 0.0654 (17) | 0.0765 (17) | 0.0425 (15) | 0.0009 (14) | 0.0045 (13) | 0.0103 (13) |
Geometric parameters (Å, º) top
Cu1—Cl1 | 2.2383 (16) | C9—H9 | 0.9300 |
Cu1—N1 | 2.046 (2) | N10—C6B | 1.358 (3) |
Cu1—N10 | 2.019 (3) | C6B—C4B | 1.431 (4) |
Cu1—N111 | 1.974 (3) | C4B—N1 | 1.360 (3) |
Cu1—N131i | 2.555 (3) | C4A—C4B | 1.400 (4) |
Cu1—N132ii | 2.758 (4) | C6A—C6B | 1.399 (4) |
N1—C2 | 1.328 (3) | C11—C12 | 1.401 (4) |
C2—C3 | 1.394 (4) | C11—C111 | 1.411 (4) |
C2—H2 | 0.9300 | C11—C112 | 1.416 (4) |
C3—C4 | 1.362 (4) | C12—O121 | 1.337 (3) |
C3—H3 | 0.9300 | C12—C13 | 1.392 (4) |
C4—C4A | 1.399 (4) | C13—C131 | 1.424 (4) |
C4—H4 | 0.9300 | C13—C132 | 1.425 (4) |
C4A—C5 | 1.434 (4) | C111—N111 | 1.146 (4) |
C5—C6 | 1.351 (4) | C112—N112 | 1.144 (4) |
C5—H5 | 0.9300 | O121—C121 | 1.474 (4) |
C6—C6A | 1.436 (4) | C121—C122 | 1.426 (5) |
C6—H6 | 0.9300 | C121—H21A | 0.9700 |
C6A—C7 | 1.398 (4) | C121—H21B | 0.9700 |
C7—C8 | 1.367 (4) | C122—H22A | 0.9600 |
C7—H7 | 0.9300 | C122—H22B | 0.9600 |
C8—C9 | 1.392 (4) | C122—H22C | 0.9600 |
C8—H8 | 0.9300 | C131—N131 | 1.147 (4) |
C9—N10 | 1.328 (3) | C132—N132 | 1.140 (4) |
Cl1—Cu1—N1 | 171.50 (6) | N10—C6B—C6A | 123.3 (2) |
Cl1—Cu1—N10 | 94.00 (7) | N10—C6B—C4B | 116.6 (2) |
Cl1—Cu1—N111 | 92.95 (8) | C6A—C6B—C4B | 120.1 (2) |
N1—Cu1—N10 | 81.27 (9) | C8—C7—C6A | 119.7 (3) |
N1—Cu1—N111 | 91.66 (10) | C8—C7—H7 | 120.2 |
N10—Cu1—N111 | 172.91 (9) | C6A—C7—H7 | 120.2 |
N131i—Cu1—Cl1 | 98.99 (8) | C7—C8—C9 | 119.6 (3) |
N131i—Cu1—N1 | 88.14 (9) | C7—C8—H8 | 120.2 |
N131i—Cu1—N10 | 90.17 (8) | C9—C8—H8 | 120.2 |
N131i—Cu1—N111 | 90.05 (10) | N10—C9—C8 | 122.5 (3) |
N132ii—Cu1—Cl1 | 94.70 (7) | N10—C9—H9 | 118.7 |
N132ii—Cu1—N1 | 78.69 (8) | C8—C9—H9 | 118.7 |
N132ii—Cu1—N10 | 94.13 (8) | C9—N10—C6B | 117.8 (2) |
N132ii—Cu1—N111 | 83.98 (10) | C9—N10—Cu1 | 128.95 (18) |
N131i—Cu1—N132ii | 165.34 (10) | C6B—N10—Cu1 | 113.20 (17) |
C2—N1—C4B | 117.9 (2) | C12—C11—C111 | 118.1 (3) |
C2—N1—Cu1 | 129.80 (19) | C12—C11—C112 | 124.5 (2) |
C4B—N1—Cu1 | 112.27 (16) | C111—C11—C112 | 117.3 (2) |
N1—C2—C3 | 122.2 (3) | O121—C12—C13 | 120.8 (2) |
N1—C2—H2 | 118.9 | O121—C12—C11 | 113.0 (2) |
C3—C2—H2 | 118.9 | C13—C12—C11 | 126.1 (3) |
C4—C3—C2 | 120.1 (3) | C12—C13—C131 | 121.2 (3) |
C4—C3—H3 | 120.0 | C12—C13—C132 | 123.2 (2) |
C2—C3—H3 | 120.0 | C131—C13—C132 | 115.6 (2) |
C3—C4—C4A | 119.5 (3) | N111—C111—C11 | 179.1 (3) |
C3—C4—H4 | 120.3 | C111—N111—Cu1 | 174.3 (2) |
C4A—C4—H4 | 120.3 | N112—C112—C11 | 178.2 (3) |
C4—C4A—C4B | 117.1 (3) | C12—O121—C121 | 120.7 (2) |
C4—C4A—C5 | 124.4 (3) | C122—C121—O121 | 108.7 (3) |
C4B—C4A—C5 | 118.5 (2) | C122—C121—H21A | 110.0 |
N1—C4B—C4A | 123.2 (2) | O121—C121—H21A | 110.0 |
N1—C4B—C6B | 116.5 (2) | C122—C121—H21B | 110.0 |
C4A—C4B—C6B | 120.3 (2) | O121—C121—H21B | 110.0 |
C6—C5—C4A | 121.5 (3) | H21A—C121—H21B | 108.3 |
C6—C5—H5 | 119.3 | C121—C122—H22A | 109.5 |
C4A—C5—H5 | 119.3 | C121—C122—H22B | 109.5 |
C5—C6—C6A | 120.9 (3) | H22A—C122—H22B | 109.5 |
C5—C6—H6 | 119.6 | C121—C122—H22C | 109.5 |
C6A—C6—H6 | 119.6 | H22A—C122—H22C | 109.5 |
C7—C6A—C6B | 117.0 (2) | H22B—C122—H22C | 109.5 |
C7—C6A—C6 | 124.1 (3) | N131—C131—C13 | 177.1 (3) |
C6B—C6A—C6 | 118.8 (3) | N132—C132—C13 | 176.7 (3) |
N111—Cu1—N1—C2 | −2.0 (2) | C4A—C4B—C6B—N10 | −178.6 (2) |
N10—Cu1—N1—C2 | 178.4 (2) | N1—C4B—C6B—C6A | 179.3 (2) |
N111—Cu1—N1—C4B | 176.87 (17) | C4A—C4B—C6B—C6A | 0.8 (4) |
N10—Cu1—N1—C4B | −2.66 (16) | C6B—C6A—C7—C8 | 0.4 (4) |
C4B—N1—C2—C3 | 0.4 (4) | C6—C6A—C7—C8 | −178.0 (3) |
Cu1—N1—C2—C3 | 179.3 (2) | C6A—C7—C8—C9 | −1.2 (4) |
N1—C2—C3—C4 | −0.8 (5) | C7—C8—C9—N10 | 0.5 (5) |
C2—C3—C4—C4A | 0.8 (5) | C8—C9—N10—C6B | 1.1 (4) |
C3—C4—C4A—C4B | −0.6 (4) | C8—C9—N10—Cu1 | −179.4 (2) |
C3—C4—C4A—C5 | 179.6 (3) | C6A—C6B—N10—C9 | −2.1 (4) |
C2—N1—C4B—C4A | −0.2 (4) | C4B—C6B—N10—C9 | 177.4 (2) |
Cu1—N1—C4B—C4A | −179.24 (19) | C6A—C6B—N10—Cu1 | 178.4 (2) |
C2—N1—C4B—C6B | −178.6 (2) | C4B—C6B—N10—Cu1 | −2.2 (3) |
Cu1—N1—C4B—C6B | 2.3 (3) | N1—Cu1—N10—C9 | −176.9 (2) |
C4—C4A—C4B—N1 | 0.2 (4) | Cl1—Cu1—N10—C9 | 10.2 (2) |
C5—C4A—C4B—N1 | −179.9 (2) | N1—Cu1—N10—C6B | 2.62 (16) |
C4—C4A—C4B—C6B | 178.6 (2) | Cl1—Cu1—N10—C6B | −170.27 (16) |
C5—C4A—C4B—C6B | −1.5 (4) | C111—C11—C12—O121 | −12.4 (3) |
C4—C4A—C5—C6 | −179.2 (3) | C112—C11—C12—O121 | 162.7 (3) |
C4B—C4A—C5—C6 | 1.0 (4) | C111—C11—C12—C13 | 171.3 (2) |
C4A—C5—C6—C6A | 0.2 (4) | C112—C11—C12—C13 | −13.6 (4) |
C5—C6—C6A—C7 | 177.5 (3) | O121—C12—C13—C131 | −14.2 (4) |
C5—C6—C6A—C6B | −0.9 (4) | C11—C12—C13—C131 | 161.8 (3) |
C7—C6A—C6B—N10 | 1.3 (4) | O121—C12—C13—C132 | 167.7 (2) |
C6—C6A—C6B—N10 | 179.8 (2) | C11—C12—C13—C132 | −16.2 (4) |
C7—C6A—C6B—C4B | −178.1 (2) | C13—C12—O121—C121 | −50.1 (4) |
C6—C6A—C6B—C4B | 0.4 (4) | C11—C12—O121—C121 | 133.4 (3) |
N1—C4B—C6B—N10 | −0.1 (3) | C12—O121—C121—C122 | −126.9 (4) |
Symmetry codes: (i) x, −y, z+1/2; (ii) x, −y+1, z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···N112iii | 0.93 | 2.55 | 3.450 (6) | 163 |
Symmetry code: (iii) −x+1/2, y−1/2, −z+3/2. |