Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199015176/sk1341sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199015176/sk1341Isup2.hkl |
CCDC reference: 143222
K4Fe(CN)6 (184 mg, 0.5 mmol) in water (10 cm3) was added to dien (0.30 ml, 4.0 mmol) in H2O (20 cm3) containing Zn(NO3)2 (188 mg, 1.0 mmol). The mixture was refluxed with stirring for 30 min and then allowed to stand in air at room temperature for 2 d. Colourless, single crystals suitable for X-ray analysis were obtained and washed with ethanol.
After checking their presence in the difference map, all H atoms were geometrically fixed and allowed to ride on their attached atoms except H atoms of the water molecules which were refined isotropically.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 1990).
Fig. 1. The structure of (I) showing 30% probability displacement ellipsoids and the atom-numbering scheme. |
[Zn(C4H13N3)2]2[Fe(CN)6]·4H2O | F(000) = 872 |
Mr = 827.47 | Dx = 1.465 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 9.2597 (2) Å | Cell parameters from 5929 reflections |
b = 14.5473 (3) Å | θ = 2.9–33.2° |
c = 13.9263 (2) Å | µ = 1.70 mm−1 |
β = 90.726 (1)° | T = 293 K |
V = 1875.77 (6) Å3 | Slab, colourless |
Z = 2 | 0.48 × 0.32 × 0.18 mm |
Siemens SMART CCD area detector diffractometer | 6906 independent reflections |
Radiation source: fine-focus sealed tube | 5745 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
Detector resolution: 8.33 pixels mm-1 | θmax = 33.1°, θmin = 2.9° |
ω scans | h = −14→11 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −22→17 |
Tmin = 0.495, Tmax = 0.749 | l = −21→21 |
17004 measured reflections |
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)] = 0.028 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.069 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0304P)2 + 0.3241P] where P = (Fo2 + 2Fc2)/3 |
6906 reflections | (Δ/σ)max < 0.001 |
230 parameters | Δρmax = 0.27 e Å−3 |
4 restraints | Δρmin = −0.60 e Å−3 |
[Zn(C4H13N3)2]2[Fe(CN)6]·4H2O | V = 1875.77 (6) Å3 |
Mr = 827.47 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.2597 (2) Å | µ = 1.70 mm−1 |
b = 14.5473 (3) Å | T = 293 K |
c = 13.9263 (2) Å | 0.48 × 0.32 × 0.18 mm |
β = 90.726 (1)° |
Siemens SMART CCD area detector diffractometer | 6906 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 5745 reflections with I > 2σ(I) |
Tmin = 0.495, Tmax = 0.749 | Rint = 0.021 |
17004 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | 4 restraints |
wR(F2) = 0.069 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.27 e Å−3 |
6906 reflections | Δρmin = −0.60 e Å−3 |
230 parameters |
Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 30 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was -35°. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible. |
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. The structure was solved by direct methods and refined by full-matrix least-squares techniques. |
x | y | z | Uiso*/Ueq | ||
Zn1 | 0.412304 (15) | 0.227177 (10) | 0.204060 (10) | 0.02518 (4) | |
Fe1 | 1.0000 | 0.0000 | 0.0000 | 0.01959 (5) | |
O1W | 0.50283 (16) | 0.20972 (13) | 0.85242 (13) | 0.0701 (4) | |
O2W | 0.43026 (19) | 0.38773 (11) | 0.78911 (11) | 0.0642 (4) | |
N1 | 0.34670 (15) | 0.26535 (8) | 0.35151 (8) | 0.0358 (2) | |
H1C | 0.4140 | 0.3019 | 0.3788 | 0.043* | |
H1D | 0.2624 | 0.2961 | 0.3495 | 0.043* | |
N2 | 0.42214 (12) | 0.09400 (7) | 0.27286 (8) | 0.0286 (2) | |
H2C | 0.3358 | 0.0653 | 0.2634 | 0.034* | |
N3 | 0.49066 (13) | 0.13912 (8) | 0.08448 (8) | 0.0327 (2) | |
H3C | 0.4279 | 0.1420 | 0.0347 | 0.039* | |
H3D | 0.5767 | 0.1599 | 0.0645 | 0.039* | |
N4 | 0.64048 (12) | 0.27629 (8) | 0.22467 (9) | 0.0336 (2) | |
H4C | 0.6621 | 0.2794 | 0.2878 | 0.040* | |
H4D | 0.7018 | 0.2364 | 0.1973 | 0.040* | |
N5 | 0.40335 (12) | 0.36001 (8) | 0.13572 (8) | 0.0308 (2) | |
H5C | 0.3823 | 0.4026 | 0.1813 | 0.037* | |
N6 | 0.18753 (13) | 0.22679 (9) | 0.15007 (9) | 0.0368 (2) | |
H6C | 0.1771 | 0.1847 | 0.1031 | 0.044* | |
H6D | 0.1271 | 0.2122 | 0.1979 | 0.044* | |
N7 | 0.84889 (13) | 0.00760 (8) | −0.19849 (8) | 0.0343 (2) | |
N8 | 0.82607 (14) | 0.15881 (9) | 0.08924 (10) | 0.0393 (3) | |
N9 | 0.77735 (13) | −0.14191 (9) | 0.07207 (9) | 0.0365 (2) | |
C1 | 0.33112 (17) | 0.18023 (11) | 0.40788 (10) | 0.0384 (3) | |
H1A | 0.2346 | 0.1556 | 0.3988 | 0.046* | |
H1B | 0.3450 | 0.1936 | 0.4756 | 0.046* | |
C2 | 0.44214 (17) | 0.10974 (10) | 0.37595 (10) | 0.0382 (3) | |
H2A | 0.5389 | 0.1324 | 0.3890 | 0.046* | |
H2B | 0.4293 | 0.0527 | 0.4108 | 0.046* | |
C3 | 0.53451 (15) | 0.03997 (10) | 0.22496 (11) | 0.0362 (3) | |
H3A | 0.5327 | −0.0231 | 0.2476 | 0.043* | |
H3B | 0.6290 | 0.0656 | 0.2393 | 0.043* | |
C4 | 0.50522 (16) | 0.04274 (10) | 0.11723 (11) | 0.0368 (3) | |
H4A | 0.5840 | 0.0133 | 0.0838 | 0.044* | |
H4B | 0.4171 | 0.0093 | 0.1024 | 0.044* | |
C5 | 0.65649 (16) | 0.36762 (11) | 0.18071 (12) | 0.0419 (3) | |
H5A | 0.7537 | 0.3743 | 0.1565 | 0.050* | |
H5B | 0.6416 | 0.4147 | 0.2289 | 0.050* | |
C6 | 0.54826 (17) | 0.38039 (11) | 0.09906 (11) | 0.0413 (3) | |
H6A | 0.5520 | 0.4431 | 0.0755 | 0.050* | |
H6B | 0.5708 | 0.3392 | 0.0465 | 0.050* | |
C7 | 0.28480 (18) | 0.35933 (12) | 0.06478 (11) | 0.0432 (3) | |
H7A | 0.3110 | 0.3224 | 0.0097 | 0.052* | |
H7B | 0.2646 | 0.4214 | 0.0430 | 0.052* | |
C8 | 0.15277 (17) | 0.31902 (12) | 0.11259 (13) | 0.0453 (4) | |
H8A | 0.1229 | 0.3586 | 0.1648 | 0.054* | |
H8B | 0.0737 | 0.3149 | 0.0664 | 0.054* | |
C9 | 0.90170 (12) | 0.00658 (8) | −0.12216 (8) | 0.0240 (2) | |
C10 | 0.88819 (12) | 0.09894 (8) | 0.05271 (8) | 0.0255 (2) | |
C11 | 0.86031 (12) | −0.08761 (8) | 0.04569 (8) | 0.0242 (2) | |
H2W1 | 0.419 (2) | 0.1824 (15) | 0.8717 (16) | 0.069 (7)* | |
H2W2 | 0.504 (2) | 0.4287 (16) | 0.7773 (19) | 0.081 (8)* | |
H1W2 | 0.391 (3) | 0.377 (2) | 0.7261 (15) | 0.121 (12)* | |
H1W1 | 0.474 (3) | 0.2693 (13) | 0.849 (2) | 0.094 (10)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.02592 (7) | 0.02505 (7) | 0.02458 (7) | 0.00178 (5) | 0.00011 (5) | −0.00136 (5) |
Fe1 | 0.01778 (10) | 0.02023 (10) | 0.02076 (9) | 0.00013 (7) | 0.00094 (7) | 0.00058 (7) |
O1W | 0.0440 (7) | 0.0761 (11) | 0.0904 (12) | −0.0016 (7) | 0.0130 (7) | 0.0272 (9) |
O2W | 0.0774 (10) | 0.0593 (9) | 0.0560 (8) | −0.0102 (8) | 0.0066 (7) | 0.0109 (7) |
N1 | 0.0436 (7) | 0.0343 (6) | 0.0295 (5) | 0.0004 (5) | 0.0036 (5) | −0.0067 (4) |
N2 | 0.0283 (5) | 0.0281 (5) | 0.0293 (5) | −0.0007 (4) | −0.0013 (4) | −0.0026 (4) |
N3 | 0.0327 (5) | 0.0375 (6) | 0.0280 (5) | 0.0033 (4) | 0.0000 (4) | −0.0065 (4) |
N4 | 0.0280 (5) | 0.0372 (6) | 0.0357 (5) | 0.0015 (4) | −0.0004 (4) | −0.0101 (5) |
N5 | 0.0349 (6) | 0.0294 (5) | 0.0280 (5) | 0.0016 (4) | 0.0019 (4) | −0.0021 (4) |
N6 | 0.0289 (5) | 0.0418 (7) | 0.0396 (6) | −0.0026 (5) | −0.0029 (5) | −0.0040 (5) |
N7 | 0.0353 (6) | 0.0357 (6) | 0.0317 (5) | −0.0057 (5) | −0.0069 (4) | 0.0055 (4) |
N8 | 0.0351 (6) | 0.0374 (6) | 0.0458 (7) | 0.0074 (5) | 0.0093 (5) | −0.0051 (5) |
N9 | 0.0364 (6) | 0.0396 (6) | 0.0336 (5) | −0.0119 (5) | 0.0003 (5) | 0.0053 (5) |
C1 | 0.0447 (8) | 0.0448 (8) | 0.0259 (5) | −0.0036 (6) | 0.0055 (5) | −0.0014 (5) |
C2 | 0.0467 (8) | 0.0390 (7) | 0.0287 (6) | −0.0001 (6) | −0.0052 (6) | 0.0041 (5) |
C3 | 0.0342 (7) | 0.0283 (6) | 0.0459 (7) | 0.0068 (5) | 0.0007 (6) | 0.0004 (5) |
C4 | 0.0364 (7) | 0.0319 (6) | 0.0422 (7) | 0.0007 (5) | 0.0052 (6) | −0.0137 (6) |
C5 | 0.0350 (7) | 0.0420 (8) | 0.0490 (8) | −0.0114 (6) | 0.0050 (6) | −0.0056 (7) |
C6 | 0.0443 (8) | 0.0411 (8) | 0.0388 (7) | −0.0074 (6) | 0.0090 (6) | 0.0045 (6) |
C7 | 0.0463 (8) | 0.0454 (8) | 0.0376 (7) | 0.0050 (6) | −0.0083 (6) | 0.0098 (6) |
C8 | 0.0317 (7) | 0.0540 (9) | 0.0501 (9) | 0.0111 (6) | −0.0080 (6) | 0.0037 (7) |
C9 | 0.0221 (5) | 0.0213 (5) | 0.0287 (5) | −0.0021 (4) | 0.0017 (4) | 0.0016 (4) |
C10 | 0.0223 (5) | 0.0274 (5) | 0.0268 (5) | 0.0000 (4) | 0.0013 (4) | 0.0017 (4) |
C11 | 0.0243 (5) | 0.0257 (5) | 0.0227 (5) | 0.0006 (4) | −0.0008 (4) | −0.0002 (4) |
Zn1—N5 | 2.155 (1) | N5—C6 | 1.4719 (19) |
Zn1—N2 | 2.163 (1) | N5—H5C | 0.9100 |
Zn1—N6 | 2.204 (1) | N6—C8 | 1.474 (2) |
Zn1—N1 | 2.219 (1) | N6—H6C | 0.9000 |
Zn1—N3 | 2.230 (1) | N6—H6D | 0.9000 |
Zn1—N4 | 2.245 (1) | N7—C9 | 1.1645 (16) |
Fe1—C9 | 1.922 (1) | N8—C10 | 1.1643 (16) |
Fe1—C9i | 1.9217 (12) | N9—C11 | 1.1645 (16) |
Fe1—C10 | 1.924 (1) | C1—C2 | 1.522 (2) |
Fe1—C10i | 1.9240 (12) | C1—H1A | 0.9700 |
Fe1—C11i | 1.9296 (12) | C1—H1B | 0.9700 |
Fe1—C11 | 1.930 (1) | C2—H2A | 0.9700 |
O1W—H2W1 | 0.913 (16) | C2—H2B | 0.9700 |
O1W—H1W1 | 0.908 (17) | C3—C4 | 1.522 (2) |
O2W—H2W2 | 0.922 (17) | C3—H3A | 0.9700 |
O2W—H1W2 | 0.958 (17) | C3—H3B | 0.9700 |
N1—C1 | 1.4742 (19) | C4—H4A | 0.9700 |
N1—H1C | 0.9000 | C4—H4B | 0.9700 |
N1—H1D | 0.9000 | C5—C6 | 1.518 (2) |
N2—C2 | 1.4633 (17) | C5—H5A | 0.9700 |
N2—C3 | 1.4708 (17) | C5—H5B | 0.9700 |
N2—H2C | 0.9100 | C6—H6A | 0.9700 |
N3—C4 | 1.4800 (19) | C6—H6B | 0.9700 |
N3—H3C | 0.9000 | C7—C8 | 1.517 (2) |
N3—H3D | 0.9000 | C7—H7A | 0.9700 |
N4—C5 | 1.471 (2) | C7—H7B | 0.9700 |
N4—H4C | 0.9000 | C8—H8A | 0.9700 |
N4—H4D | 0.9000 | C8—H8B | 0.9700 |
N5—C7 | 1.4676 (18) | ||
N5—Zn1—N2 | 179.77 (4) | C6—N5—H5C | 108.0 |
N5—Zn1—N6 | 79.68 (5) | Zn1—N5—H5C | 108.0 |
N2—Zn1—N6 | 100.55 (4) | C8—N6—Zn1 | 108.64 (9) |
N5—Zn1—N1 | 100.07 (4) | C8—N6—H6C | 110.0 |
N2—Zn1—N1 | 79.91 (4) | Zn1—N6—H6C | 110.0 |
N6—Zn1—N1 | 92.75 (5) | C8—N6—H6D | 110.0 |
N5—Zn1—N3 | 101.32 (4) | Zn1—N6—H6D | 110.0 |
N2—Zn1—N3 | 78.70 (4) | H6C—N6—H6D | 108.3 |
N6—Zn1—N3 | 93.36 (5) | N1—C1—C2 | 109.83 (12) |
N1—Zn1—N3 | 158.48 (5) | N1—C1—H1A | 109.7 |
N5—Zn1—N4 | 78.58 (4) | C2—C1—H1A | 109.7 |
N2—Zn1—N4 | 101.20 (4) | N1—C1—H1B | 109.7 |
N6—Zn1—N4 | 158.04 (5) | C2—C1—H1B | 109.7 |
N1—Zn1—N4 | 94.03 (5) | H1A—C1—H1B | 108.2 |
N3—Zn1—N4 | 87.92 (4) | N2—C2—C1 | 108.33 (11) |
C9—Fe1—C9i | 180.00 (3) | N2—C2—H2A | 110.0 |
C9—Fe1—C10 | 92.83 (5) | C1—C2—H2A | 110.0 |
C9i—Fe1—C10 | 87.17 (5) | N2—C2—H2B | 110.0 |
C9—Fe1—C10i | 87.17 (5) | C1—C2—H2B | 110.0 |
C9i—Fe1—C10i | 92.83 (5) | H2A—C2—H2B | 108.4 |
C10—Fe1—C10i | 180.00 (10) | N2—C3—C4 | 108.34 (11) |
C9—Fe1—C11i | 89.26 (5) | N2—C3—H3A | 110.0 |
C9i—Fe1—C11i | 90.74 (5) | C4—C3—H3A | 110.0 |
C10—Fe1—C11i | 89.88 (5) | N2—C3—H3B | 110.0 |
C10i—Fe1—C11i | 90.12 (5) | C4—C3—H3B | 110.0 |
C9—Fe1—C11 | 90.74 (5) | H3A—C3—H3B | 108.4 |
C9i—Fe1—C11 | 89.26 (5) | N3—C4—C3 | 110.08 (11) |
C10—Fe1—C11 | 90.12 (5) | N3—C4—H4A | 109.6 |
C10i—Fe1—C11 | 89.88 (5) | C3—C4—H4A | 109.6 |
C11i—Fe1—C11 | 180.00 (5) | N3—C4—H4B | 109.6 |
H2W1—O1W—H1W1 | 100 (2) | C3—C4—H4B | 109.6 |
H2W2—O2W—H1W2 | 102 (3) | H4A—C4—H4B | 108.2 |
C1—N1—Zn1 | 108.20 (8) | N4—C5—C6 | 110.69 (12) |
C1—N1—H1C | 110.1 | N4—C5—H5A | 109.5 |
Zn1—N1—H1C | 110.1 | C6—C5—H5A | 109.5 |
C1—N1—H1D | 110.1 | N4—C5—H5B | 109.5 |
Zn1—N1—H1D | 110.1 | C6—C5—H5B | 109.5 |
H1C—N1—H1D | 108.4 | H5A—C5—H5B | 108.1 |
C2—N2—C3 | 116.56 (11) | N5—C6—C5 | 108.16 (12) |
C2—N2—Zn1 | 107.37 (8) | N5—C6—H6A | 110.1 |
C3—N2—Zn1 | 107.69 (8) | C5—C6—H6A | 110.1 |
C2—N2—H2C | 108.3 | N5—C6—H6B | 110.1 |
C3—N2—H2C | 108.3 | C5—C6—H6B | 110.1 |
Zn1—N2—H2C | 108.3 | H6A—C6—H6B | 108.4 |
C4—N3—Zn1 | 110.08 (8) | N5—C7—C8 | 107.88 (12) |
C4—N3—H3C | 109.6 | N5—C7—H7A | 110.1 |
Zn1—N3—H3C | 109.6 | C8—C7—H7A | 110.1 |
C4—N3—H3D | 109.6 | N5—C7—H7B | 110.1 |
Zn1—N3—H3D | 109.6 | C8—C7—H7B | 110.1 |
H3C—N3—H3D | 108.2 | H7A—C7—H7B | 108.4 |
C5—N4—Zn1 | 109.50 (9) | N6—C8—C7 | 109.49 (12) |
C5—N4—H4C | 109.8 | N6—C8—H8A | 109.8 |
Zn1—N4—H4C | 109.8 | C7—C8—H8A | 109.8 |
C5—N4—H4D | 109.8 | N6—C8—H8B | 109.8 |
Zn1—N4—H4D | 109.8 | C7—C8—H8B | 109.8 |
H4C—N4—H4D | 108.2 | H8A—C8—H8B | 108.2 |
C7—N5—C6 | 116.44 (12) | N7—C9—Fe1 | 175.92 (12) |
C7—N5—Zn1 | 108.39 (9) | N8—C10—Fe1 | 175.97 (11) |
C6—N5—Zn1 | 107.68 (9) | N9—C11—Fe1 | 178.55 (12) |
C7—N5—H5C | 108.0 | ||
N5—Zn1—N1—C1 | 173.99 (10) | N2—Zn1—N6—C8 | 171.66 (10) |
N2—Zn1—N1—C1 | −6.24 (9) | N1—Zn1—N6—C8 | 91.42 (11) |
N6—Zn1—N1—C1 | 94.00 (10) | N3—Zn1—N6—C8 | −109.22 (10) |
N3—Zn1—N1—C1 | −12.35 (19) | N4—Zn1—N6—C8 | −16.46 (19) |
N4—Zn1—N1—C1 | −106.91 (10) | Zn1—N1—C1—C2 | 34.27 (13) |
N5—Zn1—N2—C2 | 59 (12) | C3—N2—C2—C1 | 169.96 (12) |
N6—Zn1—N2—C2 | −114.40 (9) | Zn1—N2—C2—C1 | 49.14 (13) |
N1—Zn1—N2—C2 | −23.47 (9) | N1—C1—C2—N2 | −57.05 (15) |
N3—Zn1—N2—C2 | 154.25 (10) | C2—N2—C3—C4 | −172.21 (12) |
N4—Zn1—N2—C2 | 68.68 (9) | Zn1—N2—C3—C4 | −51.57 (12) |
N5—Zn1—N2—C3 | −67 (12) | Zn1—N3—C4—C3 | −27.37 (14) |
N6—Zn1—N2—C3 | 119.33 (9) | N2—C3—C4—N3 | 52.98 (15) |
N1—Zn1—N2—C3 | −149.73 (9) | Zn1—N4—C5—C6 | −26.94 (14) |
N3—Zn1—N2—C3 | 27.98 (8) | C7—N5—C6—C5 | −173.94 (13) |
N4—Zn1—N2—C3 | −57.59 (9) | Zn1—N5—C6—C5 | −52.06 (13) |
N5—Zn1—N3—C4 | 179.76 (9) | N4—C5—C6—N5 | 53.11 (16) |
N2—Zn1—N3—C4 | −0.01 (9) | C6—N5—C7—C8 | 168.98 (13) |
N6—Zn1—N3—C4 | −100.11 (9) | Zn1—N5—C7—C8 | 47.47 (14) |
N1—Zn1—N3—C4 | 6.14 (18) | Zn1—N6—C8—C7 | 36.23 (15) |
N4—Zn1—N3—C4 | 101.84 (9) | N5—C7—C8—N6 | −56.67 (17) |
N5—Zn1—N4—C5 | −0.69 (9) | C9i—Fe1—C9—N7 | −99.0 (15) |
N2—Zn1—N4—C5 | 179.35 (9) | C10—Fe1—C9—N7 | 162.6 (15) |
N6—Zn1—N4—C5 | 7.48 (18) | C10i—Fe1—C9—N7 | −17.4 (15) |
N1—Zn1—N4—C5 | −100.16 (10) | C11i—Fe1—C9—N7 | 72.8 (15) |
N3—Zn1—N4—C5 | 101.30 (10) | C11—Fe1—C9—N7 | −107.2 (15) |
N2—Zn1—N5—C7 | 165 (100) | C9—Fe1—C10—N8 | −170.3 (16) |
N6—Zn1—N5—C7 | −21.57 (10) | C9i—Fe1—C10—N8 | 9.7 (16) |
N1—Zn1—N5—C7 | −112.55 (10) | C10i—Fe1—C10—N8 | 115 (100) |
N3—Zn1—N5—C7 | 69.82 (10) | C11i—Fe1—C10—N8 | −81.1 (16) |
N4—Zn1—N5—C7 | 155.34 (10) | C11—Fe1—C10—N8 | 98.9 (16) |
N2—Zn1—N5—C6 | 38 (12) | C9—Fe1—C11—N9 | 74 (5) |
N6—Zn1—N5—C6 | −148.32 (9) | C9i—Fe1—C11—N9 | −106 (5) |
N1—Zn1—N5—C6 | 120.70 (9) | C10—Fe1—C11—N9 | 167 (5) |
N3—Zn1—N5—C6 | −56.93 (9) | C10i—Fe1—C11—N9 | −13 (5) |
N4—Zn1—N5—C6 | 28.58 (9) | C11i—Fe1—C11—N9 | −97 (100) |
N5—Zn1—N6—C8 | −8.31 (10) |
Symmetry code: (i) −x+2, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3D···N8 | 0.90 | 2.33 | 3.119 (2) | 146 |
N4—H4D···N8 | 0.90 | 2.22 | 3.084 (2) | 162 |
N4—H4C···N9ii | 0.90 | 2.32 | 3.155 (2) | 153 |
N1—H1D···O1Wiii | 0.90 | 2.41 | 3.205 (2) | 148 |
N5—H5C···N7iv | 0.91 | 2.15 | 3.054 (2) | 172 |
N2—H2C···N7v | 0.91 | 2.20 | 3.081 (2) | 163 |
N3—H3C···N9v | 0.90 | 2.40 | 3.283 (2) | 167 |
N6—H6C···N9v | 0.90 | 2.56 | 3.351 (2) | 147 |
O1W—H1W1···O2W | 0.91 (2) | 1.95 (2) | 2.814 (2) | 157 |
O2W—H1W2···N8iv | 0.96 (2) | 2.06 (2) | 3.011 (2) | 173 |
O1W—H2W1···N9vi | 0.92 (2) | 2.07 (2) | 2.980 (2) | 170 |
O2W—H2W2···N7ii | 0.92 (2) | 2.10 (2) | 2.980 (2) | 159 |
Symmetry codes: (ii) −x+3/2, y+1/2, −z+1/2; (iii) x−1/2, −y+1/2, z−1/2; (iv) x−1/2, −y+1/2, z+1/2; (v) −x+1, −y, −z; (vi) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C4H13N3)2]2[Fe(CN)6]·4H2O |
Mr | 827.47 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 9.2597 (2), 14.5473 (3), 13.9263 (2) |
β (°) | 90.726 (1) |
V (Å3) | 1875.77 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.70 |
Crystal size (mm) | 0.48 × 0.32 × 0.18 |
Data collection | |
Diffractometer | Siemens SMART CCD area detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.495, 0.749 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17004, 6906, 5745 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.769 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.069, 1.07 |
No. of reflections | 6906 |
No. of parameters | 230 |
No. of restraints | 4 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.27, −0.60 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL and PLATON (Spek, 1990).
Zn1—N5 | 2.155 (1) | Zn1—N4 | 2.245 (1) |
Zn1—N2 | 2.163 (1) | Fe1—C9 | 1.922 (1) |
Zn1—N6 | 2.204 (1) | Fe1—C10 | 1.924 (1) |
Zn1—N1 | 2.219 (1) | Fe1—C11 | 1.930 (1) |
Zn1—N3 | 2.230 (1) | ||
N5—Zn1—N2 | 179.77 (4) | N1—Zn1—N3 | 158.48 (5) |
N5—Zn1—N6 | 79.68 (5) | N5—Zn1—N4 | 78.58 (4) |
N2—Zn1—N6 | 100.55 (4) | N2—Zn1—N4 | 101.20 (4) |
N5—Zn1—N1 | 100.07 (4) | N6—Zn1—N4 | 158.04 (5) |
N2—Zn1—N1 | 79.91 (4) | N1—Zn1—N4 | 94.03 (5) |
N6—Zn1—N1 | 92.75 (5) | N3—Zn1—N4 | 87.92 (4) |
N5—Zn1—N3 | 101.32 (4) | C9—Fe1—C10 | 92.83 (5) |
N2—Zn1—N3 | 78.70 (4) | C9—Fe1—C11 | 90.74 (5) |
N6—Zn1—N3 | 93.36 (5) | C10—Fe1—C11 | 90.12 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3D···N8 | 0.90 | 2.33 | 3.119 (2) | 146 |
N4—H4D···N8 | 0.90 | 2.22 | 3.084 (2) | 162 |
N4—H4C···N9i | 0.90 | 2.32 | 3.155 (2) | 153 |
N1—H1D···O1Wii | 0.90 | 2.41 | 3.205 (2) | 148 |
N5—H5C···N7iii | 0.91 | 2.15 | 3.054 (2) | 172 |
N2—H2C···N7iv | 0.91 | 2.20 | 3.081 (2) | 163 |
N3—H3C···N9iv | 0.90 | 2.40 | 3.283 (2) | 167 |
N6—H6C···N9iv | 0.90 | 2.56 | 3.351 (2) | 147 |
O1W—H1W1···O2W | 0.91 (2) | 1.95 (2) | 2.814 (2) | 157 |
O2W—H1W2···N8iii | 0.96 (2) | 2.06 (2) | 3.011 (2) | 173 |
O1W—H2W1···N9v | 0.92 (2) | 2.07 (2) | 2.980 (2) | 170 |
O2W—H2W2···N7i | 0.92 (2) | 2.10 (2) | 2.980 (2) | 159 |
Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) x−1/2, −y+1/2, z−1/2; (iii) x−1/2, −y+1/2, z+1/2; (iv) −x+1, −y, −z; (v) −x+1, −y, −z+1. |
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Coordination polymers with supramolecular structures are one of the most interesting topics in current chemistry and crystal engineering, both for the theoretical aspects related to the topologies of novel frameworks with inner cavities and channels (Carlucci et al., 1995; Yaghi & Li 1995) and for their potential applications in catalysis (Fujita et al., 1994), host–guest chemistry (Yaghi et al., 1997; Kawata et al., 1996; Zhang et al., 1996) and molecular electronics (Fallah et al., 1996; Miyasaka et al., 1996). Cyanide is a versatile ligand capable of bridging different metal centres in an asymmetric mode. The most outstanding known example of such behaviour is represented by the mixed-valence polymeric structure of Prussian blue (Buser et al., 1977), where cyanide is C-end attached to low-spin FeII and N-end to high-spin FeIII. We have become interested in these type of complexes and now report the crystal structure of [Zn(dien)2]2Fe(CN)6·4H2O (dien = diethylenetriamine, NH2CH2CH2NHCH2CH2NH2), (I). \sch
The crystal structure of (I) is formed by [Zn(dien)2]2+ cations, water molecules and half of the [Fe(CN)6]4- anions. The Fe atom lies on the inversion centre so that the [Fe(CN)6]4- anion has an inversion symmetry. The bond lengths and angles of the [Zn(dien)2]2+ are comparable with the reported values (Hodgson & Penfold, 1974). The environment around the Zn atom formed by the N atoms of the diethylenetriamine moieties can be described as distorted octahedral [N—Zn—N = 78.58 (4)–179.77 (4)°]. The [Fe(CN)6]4- assumes an octahedrally coordinated geometry with six CN- groups. The bond lengths and angles observed show only small differences with the reported values, even in the presence of different cation (Orpen et al., 1989; Cauzzi et al., 1993).
In the crystal the water molecules are involved in O—H···O intramolecular hydrogen bonds (O1W-H1W1···O2W). Two of the N atoms from the [Zn(dien)2]2+ cations, N3 and N4 formed N—H···N intramolecular hydrogen bonds with N8 from the [Fe(CN)6]4- anions. In addition to the O—H···O intramolecular hydrogen bonds, both the water molecules are also involved in intermolecular O—H···N hydrogen bonds with N atoms from the [Fe(CN)6]4- anions [O1W-H2W1···N9(1 - x, -y, 1 - z); O2W-H1W2···N8(-1/2 + x,1/2 - y,1/2 + z); O2W-H2W2···N7(3/2 - x,1/2 + y,1/2 - z)]. These O—H···O intramolecular and O—H···N intermolecular hydrogen bonds involving water molecules and [Fe(CN)6]4- anions form an infinite chain in the [101] direction where cyanide ligands are connected through the water molecules. The [Zn(dien)2]2+ cations are also involved in N—H···O and N—H···N intermolecular hydrogen bondings with the water molecules and the anions, respectively. These O—H···O, N—H···N intramolecular and O—H···N, N—H···O, N—H···N intermolecular hydrogen bonds form a three dimensional framework.