Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104004706/fg1736sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104004706/fg1736Isup2.hkl |
CCDC reference: 187385
The starting material, Cu(L)(ClO4)2 [L is 1,8-bis(2-hydroxyethyl)-1,3,6,8,10,13-hexaazacyclotetradecane] was prepared according to the literature method of Shen (2002). To an aqueous solution (15 ml) of Cu(L)(ClO4)2 (0.48 g, 1 mmol), an aqueous solution (15 ml) containing Na2[Fe(CN)5(NO)]·2H2O (0.29 g, 1 mmol) was added dropwise. After stirring for 30 min at room temperature, the resulting precipitate was collected by suction filtration. Dark-purple single crystals of (I) were obtained by recrystallizing from water in a dark place.
The H atoms were geometrically located and allowed to ride on their parent atoms, with C—H distances of 0.97 Å, N—H distances of 0.91 Å and O—H distances of 0.82 Å, and with Uiso(H) = 1.2Ueq(parent). Please check added text. There is some disorder of the terminal O1—H11 and O2—H12 hydroxy groups, over two orientations in each case. This was allowed for by appropriate occupancy refinement, and resulted in occupancies of 0.724 (5)/0.276 (5) and 0.636 (4)/0.364 (4) for the O1/O1' and O2/O2' sites, respectively.
Data collection: XSCANS (Siemens, 1991); cell refinement: XSCANS; data reduction: SHELXTL (Sheldrick, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[CuFe(CN)5(C12H30N6O2)(NO)] | F(000) = 1180 |
Mr = 569.92 | Dx = 1.545 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 28 reflections |
a = 12.885 (2) Å | θ = 2.7–15.1° |
b = 14.089 (2) Å | µ = 1.51 mm−1 |
c = 13.519 (3) Å | T = 296 K |
β = 93.35 (1)° | Prism, purple |
V = 2450.0 (7) Å3 | 0.40 × 0.36 × 0.36 mm |
Z = 4 |
Siemens P4 diffractometer | 3303 reflections with I > 2σ(I) |
Radiation source: normal-focus sealed tube | Rint = 0.015 |
Graphite monochromator | θmax = 25.0°, θmin = 2.1° |
ω scans | h = 0→15 |
Absorption correction: empirical (using intensity measurements) (North et al., 1968) | k = 0→16 |
Tmin = 0.549, Tmax = 0.582 | l = −16→16 |
4892 measured reflections | 3 standard reflections every 97 reflections |
4324 independent reflections | intensity decay: 5.2% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.032 | H-atom parameters constrained |
wR(F2) = 0.076 | w = 1/[σ2(Fo2) + (0.0405P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.97 | (Δ/σ)max = 0.001 |
4324 reflections | Δρmax = 0.42 e Å−3 |
332 parameters | Δρmin = −0.31 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0010 (3) |
[CuFe(CN)5(C12H30N6O2)(NO)] | V = 2450.0 (7) Å3 |
Mr = 569.92 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.885 (2) Å | µ = 1.51 mm−1 |
b = 14.089 (2) Å | T = 296 K |
c = 13.519 (3) Å | 0.40 × 0.36 × 0.36 mm |
β = 93.35 (1)° |
Siemens P4 diffractometer | 3303 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) (North et al., 1968) | Rint = 0.015 |
Tmin = 0.549, Tmax = 0.582 | 3 standard reflections every 97 reflections |
4892 measured reflections | intensity decay: 5.2% |
4324 independent reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.076 | H-atom parameters constrained |
S = 0.97 | Δρmax = 0.42 e Å−3 |
4324 reflections | Δρmin = −0.31 e Å−3 |
332 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cu | 0.38418 (2) | 0.25509 (2) | 0.70272 (2) | 0.03287 (11) | |
Fe | 0.20441 (3) | −0.01323 (3) | 0.48800 (3) | 0.03253 (12) | |
O1 | 0.3315 (3) | 0.0383 (2) | 1.0973 (2) | 0.0789 (14) | 0.724 (5) |
H11 | 0.3201 | 0.0387 | 1.1563 | 0.095* | 0.724 (5) |
O2 | 0.2995 (3) | 0.2581 (2) | 0.4000 (3) | 0.0521 (11) | 0.636 (4) |
H12 | 0.2855 | 0.2033 | 0.3836 | 0.063* | 0.636 (4) |
O1' | 0.4084 (10) | 0.1594 (7) | 1.1621 (6) | 0.093 (4) | 0.276 (5) |
H1' | 0.3829 | 0.1303 | 1.2072 | 0.112* | 0.276 (5) |
O2' | 0.3773 (9) | 0.2577 (6) | 0.2877 (5) | 0.105 (3) | 0.364 (4) |
H2' | 0.3634 | 0.2013 | 0.2793 | 0.125* | 0.364 (4) |
O3 | 0.06231 (19) | −0.11195 (18) | 0.36358 (17) | 0.0692 (7) | |
N1 | 0.28276 (18) | 0.32092 (15) | 0.60727 (17) | 0.0394 (6) | |
H1 | 0.2679 | 0.2802 | 0.5562 | 0.047* | |
N2 | 0.26164 (17) | 0.23212 (15) | 0.78535 (16) | 0.0366 (5) | |
H2 | 0.2638 | 0.2771 | 0.8337 | 0.044* | |
N3 | 0.3519 (2) | 0.11880 (16) | 0.89814 (17) | 0.0448 (6) | |
N4 | 0.48410 (18) | 0.19866 (15) | 0.80508 (16) | 0.0368 (5) | |
H4 | 0.4942 | 0.2419 | 0.8547 | 0.044* | |
N5 | 0.51106 (17) | 0.28837 (15) | 0.62940 (16) | 0.0371 (5) | |
H5 | 0.5163 | 0.2448 | 0.5802 | 0.045* | |
N6 | 0.4192 (2) | 0.40059 (17) | 0.51878 (17) | 0.0489 (7) | |
N7 | 0.36072 (19) | 0.10973 (16) | 0.61411 (17) | 0.0422 (6) | |
N8 | 0.11865 (19) | −0.07351 (17) | 0.41689 (17) | 0.0413 (6) | |
N9 | 0.1124 (2) | −0.06859 (19) | 0.68614 (19) | 0.0536 (7) | |
N10 | 0.3177 (3) | 0.0508 (2) | 0.3055 (2) | 0.0687 (9) | |
N11 | 0.0866 (2) | 0.1769 (2) | 0.47318 (19) | 0.0574 (7) | |
N12 | 0.3591 (2) | −0.17890 (19) | 0.52350 (19) | 0.0535 (7) | |
C1 | 0.1860 (2) | 0.3355 (2) | 0.6581 (2) | 0.0529 (8) | |
H1A | 0.1282 | 0.3444 | 0.6097 | 0.063* | |
H1B | 0.1920 | 0.3918 | 0.6993 | 0.063* | |
C2 | 0.1667 (2) | 0.2496 (2) | 0.7213 (2) | 0.0523 (8) | |
H2A | 0.1081 | 0.2610 | 0.7616 | 0.063* | |
H2B | 0.1511 | 0.1948 | 0.6796 | 0.063* | |
C3 | 0.2615 (3) | 0.1379 (2) | 0.8355 (2) | 0.0477 (8) | |
H3A | 0.2010 | 0.1342 | 0.8749 | 0.057* | |
H3B | 0.2546 | 0.0887 | 0.7853 | 0.057* | |
C4 | 0.4472 (3) | 0.10900 (19) | 0.8499 (2) | 0.0472 (8) | |
H4A | 0.4378 | 0.0615 | 0.7982 | 0.057* | |
H4B | 0.5005 | 0.0861 | 0.8977 | 0.057* | |
C5 | 0.5841 (2) | 0.1864 (2) | 0.7584 (2) | 0.0474 (8) | |
H5A | 0.5811 | 0.1316 | 0.7149 | 0.057* | |
H5B | 0.6400 | 0.1772 | 0.8086 | 0.057* | |
C6 | 0.6019 (2) | 0.2754 (2) | 0.7001 (2) | 0.0503 (8) | |
H6A | 0.6092 | 0.3296 | 0.7443 | 0.060* | |
H6B | 0.6649 | 0.2696 | 0.6647 | 0.060* | |
C7 | 0.5078 (3) | 0.3843 (2) | 0.5822 (2) | 0.0494 (8) | |
H7A | 0.5106 | 0.4321 | 0.6340 | 0.059* | |
H7B | 0.5692 | 0.3920 | 0.5447 | 0.059* | |
C8 | 0.3227 (3) | 0.4109 (2) | 0.5636 (2) | 0.0529 (9) | |
H8A | 0.2712 | 0.4342 | 0.5143 | 0.064* | |
H8B | 0.3306 | 0.4582 | 0.6156 | 0.064* | |
C9 | 0.3594 (3) | 0.1711 (2) | 0.9926 (2) | 0.0538 (9) | |
H9A | 0.2921 | 0.1984 | 1.0043 | 0.065* | |
H9B | 0.4085 | 0.2229 | 0.9876 | 0.065* | |
C10 | 0.3929 (3) | 0.1107 (3) | 1.0775 (2) | 0.0722 (12) | |
H10A | 0.4612 | 0.0857 | 1.0659 | 0.087* | |
H10B | 0.4001 | 0.1506 | 1.1360 | 0.087* | |
C11 | 0.4204 (3) | 0.3753 (2) | 0.4144 (2) | 0.0665 (10) | |
H11A | 0.4883 | 0.3913 | 0.3918 | 0.080* | |
H11B | 0.3699 | 0.4149 | 0.3778 | 0.080* | |
C12 | 0.3981 (4) | 0.2748 (3) | 0.3874 (3) | 0.0738 (12) | |
H12A | 0.4131 | 0.2636 | 0.3189 | 0.089* | |
H12B | 0.4414 | 0.2328 | 0.4291 | 0.089* | |
C13 | 0.3052 (2) | 0.06183 (18) | 0.56653 (19) | 0.0334 (6) | |
C14 | 0.1454 (2) | −0.04565 (19) | 0.6131 (2) | 0.0368 (6) | |
C15 | 0.2786 (3) | 0.0267 (2) | 0.3745 (2) | 0.0451 (7) | |
C16 | 0.1273 (2) | 0.1057 (2) | 0.47955 (19) | 0.0391 (7) | |
C17 | 0.3028 (2) | −0.1169 (2) | 0.50964 (19) | 0.0379 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu | 0.03360 (19) | 0.02835 (18) | 0.03625 (19) | −0.00066 (14) | −0.00141 (14) | 0.00592 (14) |
Fe | 0.0423 (2) | 0.0291 (2) | 0.0258 (2) | −0.00181 (18) | −0.00071 (16) | −0.00139 (16) |
O1 | 0.134 (3) | 0.067 (2) | 0.0356 (18) | −0.044 (2) | 0.000 (2) | 0.0081 (16) |
O2 | 0.051 (2) | 0.048 (2) | 0.056 (2) | −0.0105 (17) | −0.0016 (17) | −0.0048 (18) |
O1' | 0.147 (10) | 0.093 (8) | 0.039 (5) | −0.057 (7) | 0.005 (6) | 0.001 (5) |
O2' | 0.152 (8) | 0.113 (7) | 0.051 (5) | −0.029 (7) | 0.020 (5) | −0.032 (4) |
O3 | 0.0733 (17) | 0.0764 (17) | 0.0559 (15) | −0.0188 (14) | −0.0142 (13) | −0.0197 (13) |
N1 | 0.0433 (14) | 0.0340 (13) | 0.0402 (13) | 0.0080 (11) | −0.0025 (11) | 0.0010 (10) |
N2 | 0.0416 (13) | 0.0312 (12) | 0.0373 (13) | −0.0043 (10) | 0.0055 (10) | −0.0050 (10) |
N3 | 0.0717 (18) | 0.0305 (12) | 0.0324 (13) | −0.0010 (12) | 0.0035 (13) | 0.0033 (10) |
N4 | 0.0466 (14) | 0.0314 (12) | 0.0316 (12) | 0.0047 (11) | −0.0041 (11) | −0.0052 (10) |
N5 | 0.0423 (14) | 0.0319 (12) | 0.0373 (13) | −0.0051 (11) | 0.0023 (11) | −0.0040 (10) |
N6 | 0.075 (2) | 0.0351 (14) | 0.0375 (14) | −0.0018 (13) | 0.0090 (14) | 0.0069 (11) |
N7 | 0.0495 (15) | 0.0347 (13) | 0.0419 (14) | −0.0034 (12) | −0.0011 (12) | −0.0045 (11) |
N8 | 0.0494 (15) | 0.0406 (14) | 0.0333 (13) | −0.0010 (12) | −0.0015 (12) | −0.0036 (11) |
N9 | 0.0575 (17) | 0.0624 (18) | 0.0411 (15) | −0.0019 (14) | 0.0045 (13) | 0.0075 (13) |
N10 | 0.100 (2) | 0.0612 (18) | 0.0473 (17) | −0.0028 (18) | 0.0261 (17) | 0.0033 (15) |
N11 | 0.070 (2) | 0.0535 (18) | 0.0476 (16) | 0.0178 (15) | −0.0021 (14) | 0.0063 (13) |
N12 | 0.0578 (18) | 0.0449 (16) | 0.0584 (17) | 0.0090 (14) | 0.0081 (14) | −0.0008 (13) |
C1 | 0.0430 (19) | 0.057 (2) | 0.058 (2) | 0.0154 (16) | −0.0028 (16) | 0.0029 (16) |
C2 | 0.0350 (16) | 0.067 (2) | 0.0549 (19) | −0.0011 (16) | 0.0021 (14) | −0.0077 (17) |
C3 | 0.064 (2) | 0.0365 (16) | 0.0433 (17) | −0.0151 (15) | 0.0127 (16) | −0.0017 (13) |
C4 | 0.075 (2) | 0.0265 (15) | 0.0392 (17) | 0.0094 (15) | −0.0057 (16) | 0.0033 (13) |
C5 | 0.0426 (18) | 0.0548 (19) | 0.0434 (17) | 0.0095 (15) | −0.0083 (14) | −0.0054 (15) |
C6 | 0.0343 (17) | 0.066 (2) | 0.0501 (18) | −0.0081 (15) | 0.0002 (14) | −0.0142 (16) |
C7 | 0.064 (2) | 0.0375 (16) | 0.0478 (18) | −0.0143 (15) | 0.0120 (16) | 0.0035 (14) |
C8 | 0.079 (2) | 0.0324 (16) | 0.0468 (19) | 0.0124 (16) | −0.0033 (17) | 0.0069 (14) |
C9 | 0.091 (3) | 0.0365 (17) | 0.0349 (17) | −0.0036 (17) | 0.0073 (17) | 0.0000 (13) |
C10 | 0.104 (3) | 0.074 (3) | 0.038 (2) | −0.025 (2) | 0.004 (2) | −0.0069 (18) |
C11 | 0.087 (3) | 0.060 (2) | 0.054 (2) | −0.007 (2) | 0.0095 (19) | 0.0056 (18) |
C12 | 0.097 (3) | 0.064 (2) | 0.059 (2) | 0.007 (2) | −0.009 (2) | −0.0139 (19) |
C13 | 0.0427 (17) | 0.0273 (14) | 0.0304 (14) | 0.0034 (13) | 0.0046 (13) | 0.0017 (12) |
C14 | 0.0440 (17) | 0.0308 (14) | 0.0352 (16) | 0.0014 (13) | −0.0024 (13) | −0.0002 (12) |
C15 | 0.067 (2) | 0.0376 (16) | 0.0309 (16) | 0.0019 (15) | 0.0048 (15) | −0.0026 (13) |
C16 | 0.0466 (18) | 0.0418 (17) | 0.0282 (15) | 0.0010 (15) | −0.0042 (13) | 0.0039 (12) |
C17 | 0.0475 (18) | 0.0353 (16) | 0.0315 (15) | −0.0046 (15) | 0.0060 (13) | −0.0022 (13) |
Cu—N4 | 1.999 (2) | N4—C4 | 1.491 (3) |
Cu—N1 | 2.009 (2) | N4—H4 | 0.91 |
Cu—N2 | 2.013 (2) | N5—C6 | 1.479 (3) |
Cu—N5 | 2.016 (2) | N5—C7 | 1.494 (3) |
Cu—N7 | 2.383 (2) | N5—H5 | 0.91 |
Cu—N9i | 2.902 (3) | N6—C7 | 1.407 (4) |
Fe—N8 | 1.656 (2) | N6—C8 | 1.423 (4) |
Fe—C15 | 1.938 (3) | N6—C11 | 1.456 (4) |
Fe—C13 | 1.942 (3) | N7—C13 | 1.152 (3) |
Fe—C17 | 1.946 (3) | N9—C14 | 1.145 (3) |
Fe—C16 | 1.947 (3) | N10—C15 | 1.138 (4) |
Fe—C14 | 1.948 (3) | N11—C16 | 1.134 (4) |
O1—C10 | 1.327 (5) | N12—C17 | 1.144 (4) |
O1—H11 | 0.82 | C1—C2 | 1.511 (4) |
O2—C12 | 1.313 (5) | C1—H1A | 0.97 |
O2—H12 | 0.82 | C1—H1B | 0.97 |
C10—C9 | 1.474 (4) | C2—H2A | 0.97 |
C10—H10A | 0.97 | C2—H2B | 0.97 |
C10—H10B | 0.97 | C3—H3A | 0.97 |
C12—C11 | 1.485 (5) | C3—H3B | 0.97 |
C12—H12A | 0.97 | C4—H4A | 0.97 |
C12—H12B | 0.97 | C4—H4B | 0.97 |
O1'—H1' | 0.82 | C5—C6 | 1.506 (4) |
O2'—H2' | 0.82 | C5—H5A | 0.97 |
O3—N8 | 1.131 (3) | C5—H5B | 0.97 |
N1—C1 | 1.473 (4) | C6—H6A | 0.97 |
N1—C8 | 1.501 (4) | C6—H6B | 0.97 |
N1—H1 | 0.91 | C7—H7A | 0.97 |
N2—C2 | 1.477 (4) | C7—H7B | 0.97 |
N2—C3 | 1.491 (3) | C8—H8A | 0.97 |
N2—H2 | 0.91 | C8—H8B | 0.97 |
N3—C3 | 1.425 (4) | C9—H9A | 0.97 |
N3—C4 | 1.430 (4) | C9—H9B | 0.97 |
N3—C9 | 1.472 (3) | C11—H11A | 0.97 |
N4—C5 | 1.477 (4) | C11—H11B | 0.97 |
N4—Cu—N1 | 175.33 (9) | Cu—N5—H5 | 107.4 |
N4—Cu—N2 | 92.65 (9) | C7—N6—C8 | 117.1 (2) |
N1—Cu—N2 | 85.91 (9) | C7—N6—C11 | 119.8 (3) |
N4—Cu—N5 | 85.69 (9) | C8—N6—C11 | 119.8 (3) |
N1—Cu—N5 | 95.31 (9) | C14—N9—Cuii | 133.9 (2) |
N2—Cu—N5 | 174.37 (9) | C13—N7—Cu | 147.2 (2) |
N4—Cu—N7 | 93.66 (8) | O3—N8—Fe | 175.9 (2) |
N1—Cu—N7 | 90.87 (9) | N1—C1—C2 | 108.9 (2) |
N2—Cu—N7 | 93.45 (8) | N1—C1—H1A | 109.9 |
N5—Cu—N7 | 92.03 (9) | C2—C1—H1A | 109.9 |
N4—Cu—N9i | 89.56 (8) | N1—C1—H1B | 109.9 |
N1—Cu—N9i | 85.82 (8) | C2—C1—H1B | 109.9 |
N2—Cu—N9i | 80.74 (8) | H1A—C1—H1B | 108.3 |
N5—Cu—N9i | 93.86 (8) | N2—C2—C1 | 107.9 (2) |
N7—Cu—N9i | 173.49 (8) | N2—C2—H2A | 110.1 |
N8—Fe—C15 | 91.89 (12) | C1—C2—H2A | 110.1 |
N8—Fe—C13 | 177.34 (11) | N2—C2—H2B | 110.1 |
C15—Fe—C13 | 85.94 (12) | C1—C2—H2B | 110.1 |
N8—Fe—C17 | 96.26 (12) | H2A—C2—H2B | 108.4 |
C15—Fe—C17 | 89.43 (12) | N3—C3—N2 | 114.5 (2) |
C13—Fe—C17 | 85.27 (11) | N3—C3—H3A | 108.6 |
N8—Fe—C16 | 94.96 (12) | N2—C3—H3A | 108.6 |
C15—Fe—C16 | 88.68 (12) | N3—C3—H3B | 108.6 |
C13—Fe—C16 | 83.46 (11) | N2—C3—H3B | 108.6 |
C17—Fe—C16 | 168.68 (12) | H3A—C3—H3B | 107.6 |
N8—Fe—C14 | 95.88 (11) | N3—C4—N4 | 114.0 (2) |
C15—Fe—C14 | 172.16 (12) | N3—C4—H4A | 108.8 |
C13—Fe—C14 | 86.32 (11) | N4—C4—H4A | 108.8 |
C17—Fe—C14 | 88.70 (11) | N3—C4—H4B | 108.8 |
C16—Fe—C14 | 91.67 (11) | N4—C4—H4B | 108.8 |
C10—O1—H11 | 109.5 | H4A—C4—H4B | 107.7 |
C12—O2—H12 | 109.5 | N4—C5—C6 | 106.8 (2) |
C10—O1'—H1' | 109.5 | N4—C5—H5A | 110.4 |
C12—O2'—H2' | 109.5 | C6—C5—H5A | 110.4 |
O1—C10—C9 | 116.7 (4) | N4—C5—H5B | 110.4 |
O1—C10—H10A | 108.1 | C6—C5—H5B | 110.4 |
C9—C10—H10A | 108.1 | H5A—C5—H5B | 108.6 |
O1—C10—H10B | 108.1 | N5—C6—C5 | 107.5 (2) |
C9—C10—H10B | 108.1 | N5—C6—H6A | 110.2 |
H10A—C10—H10B | 107.3 | C5—C6—H6A | 110.2 |
O2—C12—C11 | 108.3 (4) | N5—C6—H6B | 110.2 |
O2—C12—H12A | 110.0 | C5—C6—H6B | 110.2 |
C11—C12—H12A | 110.0 | H6A—C6—H6B | 108.5 |
O2—C12—H12B | 110.0 | N6—C7—N5 | 114.2 (2) |
C11—C12—H12B | 110.0 | N6—C7—H7A | 108.7 |
H12A—C12—H12B | 108.4 | N5—C7—H7A | 108.7 |
C1—N1—C8 | 112.6 (2) | N6—C7—H7B | 108.7 |
C1—N1—Cu | 107.53 (17) | N5—C7—H7B | 108.7 |
C8—N1—Cu | 114.65 (19) | H7A—C7—H7B | 107.6 |
C1—N1—H1 | 107.2 | N6—C8—N1 | 114.2 (2) |
C8—N1—H1 | 107.2 | N6—C8—H8A | 108.7 |
Cu—N1—H1 | 107.2 | N1—C8—H8A | 108.7 |
C2—N2—C3 | 113.1 (2) | N6—C8—H8B | 108.7 |
C2—N2—Cu | 107.32 (17) | N1—C8—H8B | 108.7 |
C3—N2—Cu | 114.69 (18) | H8A—C8—H8B | 107.6 |
C2—N2—H2 | 107.1 | N3—C9—C10 | 112.8 (3) |
C3—N2—H2 | 107.1 | N3—C9—H9A | 109.0 |
Cu—N2—H2 | 107.1 | C10—C9—H9A | 109.0 |
C3—N3—C4 | 116.2 (2) | N3—C9—H9B | 109.0 |
C3—N3—C9 | 115.5 (3) | C10—C9—H9B | 109.0 |
C4—N3—C9 | 115.4 (3) | H9A—C9—H9B | 107.8 |
C5—N4—C4 | 112.4 (2) | N6—C11—C12 | 117.3 (3) |
C5—N4—Cu | 107.04 (16) | N6—C11—H11A | 108.0 |
C4—N4—Cu | 114.22 (18) | C12—C11—H11A | 108.0 |
C5—N4—H4 | 107.6 | N6—C11—H11B | 108.0 |
C4—N4—H4 | 107.6 | C12—C11—H11B | 108.0 |
Cu—N4—H4 | 107.6 | H11A—C11—H11B | 107.2 |
C6—N5—C7 | 112.9 (2) | N7—C13—Fe | 176.3 (2) |
C6—N5—Cu | 106.71 (17) | N9—C14—Fe | 177.0 (3) |
C7—N5—Cu | 114.66 (18) | N10—C15—Fe | 176.7 (3) |
C6—N5—H5 | 107.4 | N11—C16—Fe | 176.7 (3) |
C7—N5—H5 | 107.4 | N12—C17—Fe | 178.5 (3) |
Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) −x+1/2, y−1/2, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 0.91 | 2.20 | 2.958 (5) | 141 |
N4—H4···N11iii | 0.91 | 2.25 | 3.103 (3) | 156 |
N5—H5···N12iv | 0.91 | 2.38 | 3.139 (3) | 141 |
O1—H11···N10v | 0.82 | 2.03 | 2.836 (4) | 170 |
O2—H12···N10 | 0.82 | 2.44 | 3.202 (4) | 155 |
C5—H5B···O2iii | 0.97 | 2.51 | 3.370 (5) | 148 |
C8—H8A···O1i | 0.97 | 2.44 | 3.376 (4) | 162 |
C9—H9A···N12i | 0.97 | 2.62 | 3.517 (4) | 155 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (iii) x+1/2, −y+1/2, z+1/2; (iv) −x+1, −y, −z+1; (v) x, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | [CuFe(CN)5(C12H30N6O2)(NO)] |
Mr | 569.92 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 296 |
a, b, c (Å) | 12.885 (2), 14.089 (2), 13.519 (3) |
β (°) | 93.35 (1) |
V (Å3) | 2450.0 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.51 |
Crystal size (mm) | 0.40 × 0.36 × 0.36 |
Data collection | |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | Empirical (using intensity measurements) (North et al., 1968) |
Tmin, Tmax | 0.549, 0.582 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4892, 4324, 3303 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.076, 0.97 |
No. of reflections | 4324 |
No. of parameters | 332 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.42, −0.31 |
Computer programs: XSCANS (Siemens, 1991), XSCANS, SHELXTL (Sheldrick, 1990), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL.
Cu—N4 | 1.999 (2) | Fe—C17 | 1.946 (3) |
Cu—N1 | 2.009 (2) | Fe—C16 | 1.947 (3) |
Cu—N2 | 2.013 (2) | Fe—C14 | 1.948 (3) |
Cu—N5 | 2.016 (2) | O3—N8 | 1.131 (3) |
Cu—N7 | 2.383 (2) | N7—C13 | 1.152 (3) |
Cu—N9i | 2.902 (3) | N9—C14 | 1.145 (3) |
Fe—N8 | 1.656 (2) | N10—C15 | 1.138 (4) |
Fe—C15 | 1.938 (3) | N11—C16 | 1.134 (4) |
Fe—C13 | 1.942 (3) | N12—C17 | 1.144 (4) |
N4—Cu—N1 | 175.33 (9) | C14—N9—Cuii | 133.9 (2) |
N4—Cu—N2 | 92.65 (9) | C13—N7—Cu | 147.2 (2) |
N1—Cu—N2 | 85.91 (9) | O3—N8—Fe | 175.9 (2) |
N4—Cu—N5 | 85.69 (9) | N7—C13—Fe | 176.3 (2) |
N1—Cu—N5 | 95.31 (9) | N9—C14—Fe | 177.0 (3) |
N2—Cu—N5 | 174.37 (9) | N10—C15—Fe | 176.7 (3) |
N8—Fe—C13 | 177.34 (11) | N11—C16—Fe | 176.7 (3) |
C17—Fe—C16 | 168.68 (12) | N12—C17—Fe | 178.5 (3) |
C15—Fe—C14 | 172.16 (12) |
Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) −x+1/2, y−1/2, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 0.91 | 2.20 | 2.958 (5) | 141 |
N4—H4···N11iii | 0.91 | 2.25 | 3.103 (3) | 156 |
N5—H5···N12iv | 0.91 | 2.38 | 3.139 (3) | 141 |
O1—H11···N10v | 0.82 | 2.03 | 2.836 (4) | 170 |
O2—H12···N10 | 0.82 | 2.44 | 3.202 (4) | 155 |
C5—H5B···O2iii | 0.97 | 2.51 | 3.370 (5) | 148 |
C8—H8A···O1i | 0.97 | 2.44 | 3.376 (4) | 162 |
C9—H9A···N12i | 0.97 | 2.62 | 3.517 (4) | 155 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (iii) x+1/2, −y+1/2, z+1/2; (iv) −x+1, −y, −z+1; (v) x, y, z+1. |
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The coordination chemistry of cyanide-bridged metal complexes, especially ferro- and ferricyanides, has become of remarkable interest in recent years due to their unusual electronic state, magnetic behaviour and photochemical properties (Alcock et al., 1993; Entley & Giroloni, 1994; Clemente-Leon et al., 2001). Several studies have been carried out with the [Fe(CN)5(NO)]2− anion (Olabe et al., 1984; Zhan et al., 1999), but the interesting cyanide-bridged polymeric complexes based on azamacrocylic nickel(II) or copper(II) and the nitroprusside were only developed very recently (Kou et al., 2000; Lu et al., 2000). We report here the preparation and structure of a new cyano-bridged Cu—Fe complex, the title compound, (I). \sch
The asymmetric unit of (I) consists of one [Cu(L)]2+ cation linked to an [Fe(CN)5(NO)]2− anion. As shown in Fig. 1, two cyano N atoms in cis mode coordinate to the adjacent Cu atoms, to form a one-dimensional zigzag chain which extends in the b direction. The coordination environment of the Cu atom can be described as elongated octahedral. The basal plane is constructed by the coordination of four secondary N atoms of the tetradentate azamacrocycle ligand (L), with two N atoms of the cyanide group occupying the axial positions. The Cu—N(azamacrocycle) bond distances range from 1.999 (2) to 2.016 (2) Å, close to the values of 2.002 and 2.018 Å in [CuL(H2O)]n[(CuL)Fe(CN)6]2n (Lu et al., 2000). The axial Cu—N7 and Cu—N9i bonds [Table 1; symmetry code: (i) 1/2 − x, 1/2 + y, 3/2 − z]) are elongated significantly, owning to the Jahn-Teller effect of the d9 electronic configuration of CuII. This was also present in [CuL(H2O)]n[(CuL)Fe(CN)6]2n (Lu et al., 2000) and {[Cu(en)2[Fe(CN)5(NO)]2}[Cu(en)2] (where en is ethylenediammine; Zhan et al., 1999).
The average bite distances of the five- and six-membered chelate rings are 2.736 (3) and 2.939 (3) Å, repectively, and the average bite angles of the five- and six-membered chelate rings are 85.80 (9) and 92.47 (9)°, respectively. These values are similar to those in [Cu(L)(SCN)2] (Shen, 2002). The six-membered chelate rings adopt a chair conformation and the alkyl chains on the bridgehead N atoms are axial. The five-membered chelate rings assume a gauche conformation. The average N—C bond distance on the azamacrocycle is 1.46 (3) Å.
The FeII atom in (I) is in a slightly deformed octahedral arrangement. The equatorial plane is defined by four cyanide C atoms, and the two axial sites are occupied by a cyanide C atom and the nitrosyl N atom. The Fe—C, Fe—N, C—N and N—O bond lengths in the [Fe(CN)5(NO)] moiety are comparable with those found in previously reported multinuclear [Fe(CN)5(NO)]2− complexes (Zhan et al., 1999; Shen et al., 2002). The Fe—N distance [1.656 (2) Å] is much shorter than the other five Fe—C distances, which are in the range 1.938 (3)–1.948 (2) Å. Hence,the NO ligand is perfectly localized in the structure.
According to molecular orbital theory, M—NO+ should be nearly linear, and the observed Fe—N—O bond angle in (I) is 175.9 (2)°. The Fe—C—N bond angles [in the range 176.3 (2)–178.5 (3)°] are also essentially linear. The Cu—N7—C13 and Cu—N9i—C14i bond angles are 147.2 (2) and 133.9 (2)°, respectively, resulting in a one-dimensional zigzag chain being formed.
Hydrogen-bonding interactions (Table 2) play an important role in the solid-state structure of (I). As shown in Fig. 2, the one-dimensional zigzag chains are linked to form a three-dimensional network via N—H···N and O—H···N hydrogen bonds. In addition, there are some weak C—H···O interactions (Table 2).