Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109024445/fn3025sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109024445/fn3025Isup2.hkl |
CCDC reference: 746046
A mixture of Zn(CH3COO)2.H2O (1.1120 g), H3BO3 (1.2291 g) and H2O (50 ml) was placed in a beaker and stirred at 363 K until the solution had evaporated to 2–3 ml, then teta (1 ml) was added and thorough mixing was carried out. The resulting viscous milky liquid was sealed in a Teflon-lined autoclave, heated at 453 K for 7 d and then cooled to room temperature. Colourless transparent block-like crystals of (I) were obtained, and these were washed with deionized water and dried at ambient temperature.
All H atoms were placed at calculated positions and were included in the refinement in the riding-model approximation, with hydroxyl O—H = 0.84Å, imine N—H = 0.93Å, amine N—H = 0.92Å, methylene C—H = 0.99Å and methyl C—H = 0.98Å, and with Uiso(H) = 1.5Ueq(O), 1.2Ueq(N), 1.2Ueq(C) or 1.5Ueq(methyl C).
Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
[Zn(C2H3O2)(C6H18N4)](B5H4O10) | Z = 2 |
Mr = 488.74 | F(000) = 504 |
Triclinic, P1 | Dx = 1.558 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.7778 (18) Å | Cell parameters from 8475 reflections |
b = 10.260 (2) Å | θ = 3.0–27.5° |
c = 12.882 (3) Å | µ = 1.24 mm−1 |
α = 69.08 (3)° | T = 295 K |
β = 87.10 (3)° | Block-like, colourless |
γ = 74.26 (3)° | 0.57 × 0.41 × 0.27 mm |
V = 1041.6 (4) Å3 |
Rigaku R-AXIS RAPID diffractometer | 4703 independent reflections |
Radiation source: fine-focus sealed tube | 3988 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
ω scans | θmax = 27.5°, θmin = 3.0° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −10→11 |
Tmin = 0.538, Tmax = 0.730 | k = −12→13 |
10240 measured reflections | l = −16→16 |
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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.080 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0381P)2 + 0.3178P] where P = (Fo2 + 2Fc2)/3 |
4703 reflections | (Δ/σ)max = 0.001 |
284 parameters | Δρmax = 0.28 e Å−3 |
1 restraint | Δρmin = −0.24 e Å−3 |
[Zn(C2H3O2)(C6H18N4)](B5H4O10) | γ = 74.26 (3)° |
Mr = 488.74 | V = 1041.6 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.7778 (18) Å | Mo Kα radiation |
b = 10.260 (2) Å | µ = 1.24 mm−1 |
c = 12.882 (3) Å | T = 295 K |
α = 69.08 (3)° | 0.57 × 0.41 × 0.27 mm |
β = 87.10 (3)° |
Rigaku R-AXIS RAPID diffractometer | 4703 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 3988 reflections with I > 2σ(I) |
Tmin = 0.538, Tmax = 0.730 | Rint = 0.018 |
10240 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 1 restraint |
wR(F2) = 0.080 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.28 e Å−3 |
4703 reflections | Δρmin = −0.24 e Å−3 |
284 parameters |
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. |
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 > 2sigma(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) | |
Zn1 | 0.47591 (3) | 0.39003 (2) | 0.350305 (18) | 0.04313 (9) | |
C1 | 0.1771 (3) | 0.2654 (3) | 0.6031 (2) | 0.0708 (7) | |
H1B | 0.1162 | 0.1988 | 0.6018 | 0.106* | |
H1C | 0.1042 | 0.3589 | 0.5981 | 0.106* | |
H1D | 0.2423 | 0.2244 | 0.6727 | 0.106* | |
C2 | 0.2816 (3) | 0.2868 (3) | 0.50683 (18) | 0.0568 (6) | |
C3 | 0.2488 (4) | 0.5959 (3) | 0.1623 (3) | 0.0779 (8) | |
H3B | 0.2119 | 0.6929 | 0.1035 | 0.093* | |
H3C | 0.1559 | 0.5575 | 0.1867 | 0.093* | |
C4 | 0.3658 (4) | 0.4975 (3) | 0.11786 (19) | 0.0682 (7) | |
H4B | 0.3161 | 0.4872 | 0.0550 | 0.082* | |
H4C | 0.4563 | 0.5385 | 0.0901 | 0.082* | |
C5 | 0.5621 (3) | 0.2575 (3) | 0.1824 (2) | 0.0641 (6) | |
H5A | 0.6449 | 0.3087 | 0.1542 | 0.077* | |
H5B | 0.5346 | 0.2235 | 0.1248 | 0.077* | |
C6 | 0.6231 (3) | 0.1301 (3) | 0.2882 (2) | 0.0690 (7) | |
H6A | 0.5438 | 0.0740 | 0.3124 | 0.083* | |
H6B | 0.7220 | 0.0654 | 0.2746 | 0.083* | |
C7 | 0.8104 (3) | 0.2086 (3) | 0.3724 (2) | 0.0641 (7) | |
H7A | 0.8417 | 0.2431 | 0.2945 | 0.077* | |
H7B | 0.8905 | 0.1175 | 0.4143 | 0.077* | |
C8 | 0.8042 (3) | 0.3203 (3) | 0.4231 (2) | 0.0709 (8) | |
H8B | 0.7860 | 0.2810 | 0.5035 | 0.085* | |
H8C | 0.9065 | 0.3453 | 0.4150 | 0.085* | |
N1 | 0.3239 (2) | 0.6074 (2) | 0.25698 (17) | 0.0606 (5) | |
H1E | 0.2481 | 0.6379 | 0.3015 | 0.073* | |
H1F | 0.3835 | 0.6728 | 0.2322 | 0.073* | |
N2 | 0.4221 (2) | 0.35553 (19) | 0.20610 (14) | 0.0509 (4) | |
H2A | 0.3404 | 0.3107 | 0.2208 | 0.061* | |
N3 | 0.6537 (2) | 0.1813 (2) | 0.37538 (15) | 0.0555 (5) | |
H3D | 0.6431 | 0.1144 | 0.4447 | 0.067* | |
N4 | 0.6745 (2) | 0.4519 (2) | 0.36706 (14) | 0.0544 (5) | |
H4A | 0.7039 | 0.5028 | 0.2982 | 0.065* | |
H4D | 0.6534 | 0.5109 | 0.4085 | 0.065* | |
O1 | 0.09555 (18) | 0.54868 (13) | −0.13616 (11) | 0.0498 (4) | |
H1A | 0.0301 | 0.5811 | −0.0955 | 0.075* | |
O2 | 0.29160 (16) | 0.34529 (13) | −0.13194 (10) | 0.0456 (3) | |
O3 | 0.50676 (18) | 0.15544 (15) | −0.13021 (13) | 0.0585 (4) | |
H3A | 0.5552 | 0.0703 | −0.0907 | 0.088* | |
O4 | 0.11629 (13) | 0.32734 (11) | 0.01583 (9) | 0.0317 (3) | |
O5 | 0.33931 (14) | 0.12480 (12) | 0.02258 (9) | 0.0332 (3) | |
O6 | 0.08432 (15) | 0.08712 (12) | 0.06758 (9) | 0.0348 (3) | |
O7 | 0.22590 (14) | 0.14987 (12) | 0.19056 (9) | 0.0331 (3) | |
O8 | −0.0341 (2) | −0.10567 (19) | 0.14699 (12) | 0.0655 (5) | |
H8A | −0.0621 | −0.0813 | 0.0798 | 0.098* | |
O9 | 0.1077 (2) | −0.04509 (15) | 0.26163 (11) | 0.0527 (4) | |
O10 | 0.2170 (2) | 0.02584 (17) | 0.38478 (11) | 0.0574 (4) | |
H10A | 0.2475 | 0.0955 | 0.3873 | 0.086* | |
O11 | 0.3670 (2) | 0.36977 (18) | 0.49334 (13) | 0.0627 (4) | |
O12A | 0.275 (4) | 0.261 (4) | 0.422 (3) | 0.0827 (18) | 0.22 |
O12B | 0.252 (3) | 0.255 (2) | 0.4256 (15) | 0.0827 (18) | 0.37 |
O12C | 0.3153 (10) | 0.1835 (7) | 0.4675 (5) | 0.0827 (18) | 0.40 |
B1 | 0.1642 (2) | 0.4062 (2) | −0.08186 (16) | 0.0328 (4) | |
B2 | 0.3790 (3) | 0.2040 (2) | −0.07763 (17) | 0.0374 (4) | |
B3 | 0.1909 (2) | 0.17166 (19) | 0.07556 (15) | 0.0289 (4) | |
B4 | 0.1852 (3) | 0.0462 (2) | 0.27743 (16) | 0.0376 (4) | |
B5 | 0.0522 (3) | −0.0197 (2) | 0.15673 (17) | 0.0395 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.05178 (15) | 0.04918 (14) | 0.03022 (12) | −0.02143 (10) | 0.00767 (9) | −0.01131 (9) |
C1 | 0.0847 (18) | 0.0874 (18) | 0.0548 (14) | −0.0532 (15) | 0.0293 (13) | −0.0236 (13) |
C2 | 0.0679 (14) | 0.0746 (15) | 0.0402 (11) | −0.0370 (12) | 0.0132 (10) | −0.0232 (10) |
C3 | 0.0707 (17) | 0.0708 (17) | 0.0738 (18) | −0.0147 (14) | −0.0208 (14) | −0.0043 (14) |
C4 | 0.094 (2) | 0.0737 (16) | 0.0379 (12) | −0.0390 (15) | −0.0124 (12) | −0.0072 (11) |
C5 | 0.0814 (17) | 0.0749 (16) | 0.0536 (14) | −0.0330 (14) | 0.0148 (12) | −0.0365 (12) |
C6 | 0.0727 (16) | 0.0531 (14) | 0.0873 (19) | −0.0224 (12) | 0.0250 (14) | −0.0312 (13) |
C7 | 0.0469 (12) | 0.0741 (16) | 0.0479 (13) | −0.0123 (11) | 0.0034 (10) | 0.0023 (11) |
C8 | 0.0585 (14) | 0.105 (2) | 0.0423 (13) | −0.0367 (14) | −0.0054 (11) | −0.0057 (13) |
N1 | 0.0673 (13) | 0.0516 (11) | 0.0573 (12) | −0.0164 (9) | 0.0119 (10) | −0.0137 (9) |
N2 | 0.0629 (11) | 0.0570 (10) | 0.0402 (9) | −0.0321 (9) | 0.0040 (8) | −0.0145 (8) |
N3 | 0.0561 (11) | 0.0501 (10) | 0.0452 (10) | −0.0172 (8) | 0.0106 (8) | 0.0017 (8) |
N4 | 0.0685 (12) | 0.0705 (12) | 0.0317 (9) | −0.0397 (10) | 0.0092 (8) | −0.0127 (8) |
O1 | 0.0584 (9) | 0.0290 (6) | 0.0390 (7) | 0.0022 (6) | 0.0219 (6) | 0.0019 (5) |
O2 | 0.0542 (8) | 0.0292 (6) | 0.0338 (7) | 0.0007 (6) | 0.0203 (6) | 0.0004 (5) |
O3 | 0.0614 (9) | 0.0342 (7) | 0.0520 (9) | 0.0041 (6) | 0.0341 (7) | 0.0007 (6) |
O4 | 0.0361 (6) | 0.0234 (5) | 0.0291 (6) | −0.0051 (5) | 0.0102 (5) | −0.0049 (4) |
O5 | 0.0367 (6) | 0.0246 (5) | 0.0302 (6) | −0.0040 (5) | 0.0107 (5) | −0.0046 (4) |
O6 | 0.0450 (7) | 0.0334 (6) | 0.0275 (6) | −0.0184 (5) | 0.0060 (5) | −0.0074 (5) |
O7 | 0.0416 (7) | 0.0324 (6) | 0.0248 (6) | −0.0144 (5) | 0.0058 (5) | −0.0072 (4) |
O8 | 0.1065 (14) | 0.0759 (11) | 0.0381 (8) | −0.0690 (10) | 0.0191 (9) | −0.0178 (8) |
O9 | 0.0865 (11) | 0.0504 (8) | 0.0276 (7) | −0.0418 (8) | 0.0099 (7) | −0.0051 (6) |
O10 | 0.0852 (11) | 0.0619 (9) | 0.0249 (7) | −0.0351 (9) | 0.0012 (7) | −0.0039 (6) |
O11 | 0.0790 (11) | 0.0727 (10) | 0.0506 (9) | −0.0443 (9) | 0.0298 (8) | −0.0248 (8) |
O12A | 0.125 (6) | 0.113 (4) | 0.050 (3) | −0.079 (4) | 0.028 (3) | −0.044 (2) |
O12B | 0.125 (6) | 0.113 (4) | 0.050 (3) | −0.079 (4) | 0.028 (3) | −0.044 (2) |
O12C | 0.125 (6) | 0.113 (4) | 0.050 (3) | −0.079 (4) | 0.028 (3) | −0.044 (2) |
B1 | 0.0382 (10) | 0.0263 (9) | 0.0276 (9) | −0.0062 (8) | 0.0073 (8) | −0.0051 (7) |
B2 | 0.0418 (11) | 0.0286 (9) | 0.0341 (10) | −0.0053 (8) | 0.0118 (8) | −0.0064 (8) |
B3 | 0.0342 (9) | 0.0246 (8) | 0.0254 (9) | −0.0089 (7) | 0.0073 (7) | −0.0061 (6) |
B4 | 0.0463 (11) | 0.0349 (10) | 0.0272 (9) | −0.0124 (9) | 0.0054 (8) | −0.0055 (7) |
B5 | 0.0536 (12) | 0.0384 (11) | 0.0313 (10) | −0.0229 (9) | 0.0136 (9) | −0.0120 (8) |
Zn1—O11 | 2.0020 (16) | C7—H7B | 0.9900 |
Zn1—N4 | 2.0549 (19) | C8—N4 | 1.481 (3) |
Zn1—N2 | 2.1090 (18) | C8—H8B | 0.9900 |
Zn1—N1 | 2.198 (2) | C8—H8C | 0.9900 |
Zn1—N3 | 2.207 (2) | N1—H1E | 0.9200 |
Zn1—O12A | 2.44 (2) | N1—H1F | 0.9200 |
C1—C2 | 1.493 (3) | N2—H2A | 0.9300 |
C1—H1B | 0.9800 | N3—H3D | 0.9300 |
C1—H1C | 0.9800 | N4—H4A | 0.9200 |
C1—H1D | 0.9800 | N4—H4D | 0.9200 |
C2—O12A | 1.22 (3) | O1—B1 | 1.350 (2) |
C2—O11 | 1.242 (3) | O1—H1A | 0.8400 |
C2—O12B | 1.259 (19) | O2—B1 | 1.376 (2) |
C2—O12C | 1.290 (6) | O2—B2 | 1.381 (2) |
C3—N1 | 1.471 (4) | O3—B2 | 1.351 (2) |
C3—C4 | 1.481 (4) | O3—H3A | 0.8400 |
C3—H3B | 0.9900 | O4—B1 | 1.349 (2) |
C3—H3C | 0.9900 | O4—B3 | 1.476 (2) |
C4—N2 | 1.464 (3) | O5—B2 | 1.344 (2) |
C4—H4B | 0.9900 | O5—B3 | 1.483 (2) |
C4—H4C | 0.9900 | O6—B5 | 1.355 (2) |
C5—N2 | 1.458 (3) | O6—B3 | 1.467 (2) |
C5—C6 | 1.508 (4) | O7—B4 | 1.351 (2) |
C5—H5A | 0.9900 | O7—B3 | 1.453 (2) |
C5—H5B | 0.9900 | O8—B5 | 1.349 (3) |
C6—N3 | 1.462 (3) | O8—H8A | 0.8400 |
C6—H6A | 0.9900 | O9—B5 | 1.370 (3) |
C6—H6B | 0.9900 | O9—B4 | 1.371 (3) |
C7—N3 | 1.473 (3) | O10—B4 | 1.354 (2) |
C7—C8 | 1.496 (4) | O10—H10A | 0.8400 |
C7—H7A | 0.9900 | ||
O11—Zn1—N4 | 105.65 (8) | N4—C8—H8B | 109.7 |
O11—Zn1—N2 | 132.06 (7) | C7—C8—H8B | 109.7 |
N4—Zn1—N2 | 122.28 (8) | N4—C8—H8C | 109.7 |
O11—Zn1—N1 | 95.43 (8) | C7—C8—H8C | 109.7 |
N4—Zn1—N1 | 97.20 (8) | H8B—C8—H8C | 108.2 |
N2—Zn1—N1 | 80.78 (8) | C3—N1—Zn1 | 106.70 (16) |
O11—Zn1—N3 | 106.94 (8) | C3—N1—H1E | 110.4 |
N4—Zn1—N3 | 81.88 (8) | Zn1—N1—H1E | 110.4 |
N2—Zn1—N3 | 80.46 (8) | C3—N1—H1F | 110.4 |
N1—Zn1—N3 | 157.06 (8) | Zn1—N1—H1F | 110.4 |
O11—Zn1—O12A | 52.7 (8) | H1E—N1—H1F | 108.6 |
N4—Zn1—O12A | 153.3 (8) | C5—N2—C4 | 115.5 (2) |
N2—Zn1—O12A | 80.7 (8) | C5—N2—Zn1 | 108.01 (14) |
N1—Zn1—O12A | 100.2 (10) | C4—N2—Zn1 | 107.75 (14) |
N3—Zn1—O12A | 89.7 (10) | C5—N2—H2A | 108.5 |
C2—C1—H1B | 109.5 | C4—N2—H2A | 108.5 |
C2—C1—H1C | 109.5 | Zn1—N2—H2A | 108.5 |
H1B—C1—H1C | 109.5 | C6—N3—C7 | 113.9 (2) |
C2—C1—H1D | 109.5 | C6—N3—Zn1 | 107.72 (15) |
H1B—C1—H1D | 109.5 | C7—N3—Zn1 | 106.71 (15) |
H1C—C1—H1D | 109.5 | C6—N3—H3D | 109.5 |
O12A—C2—O11 | 109.4 (11) | C7—N3—H3D | 109.5 |
O11—C2—O12B | 118.7 (6) | Zn1—N3—H3D | 109.5 |
O11—C2—O12C | 122.0 (4) | C8—N4—Zn1 | 108.74 (15) |
O12A—C2—C1 | 129.5 (13) | C8—N4—H4A | 109.9 |
O11—C2—C1 | 119.1 (2) | Zn1—N4—H4A | 109.9 |
O12B—C2—C1 | 119.4 (8) | C8—N4—H4D | 109.9 |
O12C—C2—C1 | 114.8 (4) | Zn1—N4—H4D | 109.9 |
N1—C3—C4 | 108.9 (2) | H4A—N4—H4D | 108.3 |
N1—C3—H3B | 109.9 | B1—O1—H1A | 109.5 |
C4—C3—H3B | 109.9 | B1—O2—B2 | 119.50 (14) |
N1—C3—H3C | 109.9 | B2—O3—H3A | 109.5 |
C4—C3—H3C | 109.9 | B1—O4—B3 | 123.88 (13) |
H3B—C3—H3C | 108.3 | B2—O5—B3 | 123.93 (14) |
N2—C4—C3 | 109.4 (2) | B5—O6—B3 | 122.65 (15) |
N2—C4—H4B | 109.8 | B4—O7—B3 | 122.58 (15) |
C3—C4—H4B | 109.8 | B5—O8—H8A | 109.5 |
N2—C4—H4C | 109.8 | B5—O9—B4 | 119.42 (15) |
C3—C4—H4C | 109.8 | B4—O10—H10A | 109.5 |
H4B—C4—H4C | 108.2 | C2—O11—Zn1 | 109.38 (15) |
N2—C5—C6 | 108.7 (2) | C2—O12A—Zn1 | 87.8 (14) |
N2—C5—H5A | 110.0 | O4—B1—O1 | 123.64 (16) |
C6—C5—H5A | 110.0 | O4—B1—O2 | 121.14 (15) |
N2—C5—H5B | 110.0 | O1—B1—O2 | 115.20 (15) |
C6—C5—H5B | 110.0 | O5—B2—O3 | 123.72 (17) |
H5A—C5—H5B | 108.3 | O5—B2—O2 | 120.72 (16) |
N3—C6—C5 | 109.85 (19) | O3—B2—O2 | 115.52 (16) |
N3—C6—H6A | 109.7 | O7—B3—O6 | 111.59 (13) |
C5—C6—H6A | 109.7 | O7—B3—O4 | 108.49 (14) |
N3—C6—H6B | 109.7 | O6—B3—O4 | 109.59 (14) |
C5—C6—H6B | 109.7 | O7—B3—O5 | 109.93 (14) |
H6A—C6—H6B | 108.2 | O6—B3—O5 | 107.71 (13) |
N3—C7—C8 | 109.6 (2) | O4—B3—O5 | 109.51 (13) |
N3—C7—H7A | 109.7 | O7—B4—O10 | 122.83 (18) |
C8—C7—H7A | 109.7 | O7—B4—O9 | 121.46 (17) |
N3—C7—H7B | 109.7 | O10—B4—O9 | 115.72 (16) |
C8—C7—H7B | 109.7 | O8—B5—O6 | 122.21 (18) |
H7A—C7—H7B | 108.2 | O8—B5—O9 | 117.05 (16) |
N4—C8—C7 | 109.72 (19) | O6—B5—O9 | 120.74 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O4i | 0.84 | 1.87 | 2.703 (2) | 174 |
O3—H3A···O5ii | 0.84 | 1.85 | 2.692 (3) | 171 |
O8—H8A···O6iii | 0.84 | 1.94 | 2.751 (2) | 162 |
N1—H1F···O3iv | 0.92 | 2.21 | 3.112 (3) | 165 |
N2—H2A···O7 | 0.93 | 2.30 | 3.125 (3) | 148 |
N3—H3D···O10v | 0.93 | 2.34 | 3.116 (3) | 141 |
N4—H4A···O2iv | 0.92 | 2.16 | 3.054 (3) | 164 |
N4—H4D···O11vi | 0.92 | 2.02 | 2.939 (4) | 173 |
O10—H10A···O12a | 0.84 | 1.98 | 2.799 (2) | 164 |
O10—H10A···O12b | 0.84 | 1.88 | 2.682 (2) | 159 |
O10—H10A···O12c | 0.84 | 1.80 | 2.565 (2) | 149 |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1, −y, −z; (iii) −x, −y, −z; (iv) −x+1, −y+1, −z; (v) −x+1, −y, −z+1; (vi) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C2H3O2)(C6H18N4)](B5H4O10) |
Mr | 488.74 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 295 |
a, b, c (Å) | 8.7778 (18), 10.260 (2), 12.882 (3) |
α, β, γ (°) | 69.08 (3), 87.10 (3), 74.26 (3) |
V (Å3) | 1041.6 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.24 |
Crystal size (mm) | 0.57 × 0.41 × 0.27 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.538, 0.730 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10240, 4703, 3988 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.080, 1.04 |
No. of reflections | 4703 |
No. of parameters | 284 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.28, −0.24 |
Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPII (Johnson, 1976).
Zn1—O11 | 2.0020 (16) | O4—B3 | 1.476 (2) |
Zn1—N4 | 2.0549 (19) | O5—B2 | 1.344 (2) |
Zn1—N2 | 2.1090 (18) | O5—B3 | 1.483 (2) |
Zn1—N1 | 2.198 (2) | O6—B5 | 1.355 (2) |
Zn1—N3 | 2.207 (2) | O6—B3 | 1.467 (2) |
Zn1—O12A | 2.44 (2) | O7—B4 | 1.351 (2) |
O1—B1 | 1.350 (2) | O7—B3 | 1.453 (2) |
O2—B1 | 1.376 (2) | O9—B5 | 1.370 (3) |
O2—B2 | 1.381 (2) | O9—B4 | 1.371 (3) |
O3—B2 | 1.351 (2) | O10—B4 | 1.354 (2) |
O4—B1 | 1.349 (2) | ||
O11—Zn1—N4 | 105.65 (8) | O1—B1—O2 | 115.20 (15) |
O11—Zn1—N2 | 132.06 (7) | O5—B2—O3 | 123.72 (17) |
N4—Zn1—N2 | 122.28 (8) | O5—B2—O2 | 120.72 (16) |
O11—Zn1—N1 | 95.43 (8) | O3—B2—O2 | 115.52 (16) |
N4—Zn1—N1 | 97.20 (8) | O7—B3—O6 | 111.59 (13) |
N2—Zn1—N1 | 80.78 (8) | O7—B3—O4 | 108.49 (14) |
O11—Zn1—N3 | 106.94 (8) | O6—B3—O4 | 109.59 (14) |
N4—Zn1—N3 | 81.88 (8) | O7—B3—O5 | 109.93 (14) |
N2—Zn1—N3 | 80.46 (8) | O6—B3—O5 | 107.71 (13) |
N1—Zn1—N3 | 157.06 (8) | O4—B3—O5 | 109.51 (13) |
O11—Zn1—O12A | 52.7 (8) | O7—B4—O10 | 122.83 (18) |
N4—Zn1—O12A | 153.3 (8) | O7—B4—O9 | 121.46 (17) |
N2—Zn1—O12A | 80.7 (8) | O10—B4—O9 | 115.72 (16) |
N1—Zn1—O12A | 100.2 (10) | O8—B5—O6 | 122.21 (18) |
N3—Zn1—O12A | 89.7 (10) | O8—B5—O9 | 117.05 (16) |
O4—B1—O1 | 123.64 (16) | O6—B5—O9 | 120.74 (18) |
O4—B1—O2 | 121.14 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O4i | 0.84 | 1.87 | 2.703 (2) | 174 |
O3—H3A···O5ii | 0.84 | 1.85 | 2.692 (3) | 171 |
O8—H8A···O6iii | 0.84 | 1.94 | 2.751 (2) | 162 |
N1—H1F···O3iv | 0.92 | 2.21 | 3.112 (3) | 165 |
N2—H2A···O7 | 0.93 | 2.30 | 3.125 (3) | 148 |
N3—H3D···O10v | 0.93 | 2.34 | 3.116 (3) | 141 |
N4—H4A···O2iv | 0.92 | 2.16 | 3.054 (3) | 164 |
N4—H4D···O11vi | 0.92 | 2.02 | 2.939 (4) | 173 |
O10—H10A···O12a | 0.84 | 1.98 | 2.799 (2) | 164 |
O10—H10A···O12b | 0.84 | 1.88 | 2.682 (2) | 159 |
O10—H10A···O12c | 0.84 | 1.80 | 2.565 (2) | 149 |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1, −y, −z; (iii) −x, −y, −z; (iv) −x+1, −y+1, −z; (v) −x+1, −y, −z+1; (vi) −x+1, −y+1, −z+1. |
Borate materials have attracted a great deal of attention in the past because of their rich structural chemistry and potential applications in mineralogy and industry (Christ & Clark, 1977; Becker, 1998; Burns, 1995; Grice et al., 1999; Chen et al., 1995). Borate materials with various alkali metals, alkaline earth metals, main group metals, rare earths and transition metals have been widely explored. In contrast, less work has been carried out on organic borates. To date, only a few organic amines have been successfully introduced into borate systems, such as [NH3CH2CH2NH3][B6O9(OH)2] (Li et al., 2006), [H3N(C6H10)NH3][B4O5(OH)4] and [H3N(C6H10)NH3][B5O8(OH)] (Wang et al., 2004) and [C6H13N2][B5O6(OH)4] (Liu et al., 2008), or metals coordinated by amines, such as [Cu(en)2][B7O13H3]n (en is ethylenediamine; Sung et al., 2000), [Mn(C10H18N6)][B5O6(OH)4]2 (Zhang et al., 2004), [Ni(C4H10N2)(C2H8N2)2][B5O6(OH)4]2 (Liu et al., 2006) and [Zn(dien)2][B5O6(OH)4]2 and [B5O7(OH)3Zn(tren)] [dien is diethylenetriamine and tren is tris(2-aminoethyl)amine; Wang et al., 2005]. However, borates involving organic acids are extremely rare (Tombul et al., 2007). We describe here the synthesis and crystal structure of the title novel metallo-organically templated borate, [Zn(CH3COO)(teta)][B5O6(OH)4] (teta is triethylenetetramine), (I), in which the [Zn(CH3COO)(teta)]+ complex cation contains both organic amine and organic acid ligands.
The asymmetric unit of (I) consists of a [Zn(CH3COO)(teta)]+ cation and a [B5O6(OH)4]- polyborate anion (Fig. 1). In the [Zn(CH3COO)(teta)]+ metal complex cation, the Zn centre is coordinated by four N atoms from teta and one carboxylate O atom, forming a square pyramid with an O atom as the vertex. The Zn—N bond lengths are in the range 2.049 (19)–2.207 (2) Å and the N—Zn—N angles are between 80.46 (8) and 157.06 (8) °. The Zn—O bond length is 2.0020 (16) Å . The second O atom of the carboxylate group is equally disordered over three positions (see Experimental).
The [B5O6(OH)4]- borate polyanion is formed by two [B3O3] rings linked by a common BO4 tetrahedron. Each ring is composed of two BO3 triangles and a slightly distorted common BO4 tetrahedron. The terminal O atoms are protonated. The trigonally coordinated B atoms have B—O distances in the range 1.344 (2)–1.381 (2) Å and the tetrahedral B atoms have longer B—O distances in the range 1.453 (2)–1.483 (2) Å. The O—B—O angles of the BO3 triangles lie in the range 115.20 (15)–123.64 (16) ° and those of the BO4 tetrahedra range from 107.71 (13) to 111.59 (13) °.
Extensive hydrogen-bond interactions are important in the formation and stability of low-dimensional structures (Chang et al., 2001; Dalrymple & Shimizu, 2007).The overall sheet-like structure of (I) is formed by extensive multipoint hydrogen bonding involving the [B5O6(OH)4]- borate polyanions. The [B5O6(OH)4]- polyanions and the templating [Zn(CH3COO)(teta)]+ cations are further connected by hydrogen bonds to form a three-dimensional supramolecular network [N1—H1F···O3, N2—H2A···O7, N3—H3D···O10 and N4—H4A···O2; N···O = 3.054 (3)–3.125 (3) Å; Table 2]. The [Zn(CH3COO)(teta)]+ cations are located in the free space of the network and interact with the inorganic framework by extensive hydrogen bonding (Fig. 2 and Table 2).