Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807050672/hb2568sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807050672/hb2568Isup2.hkl |
CCDC reference: 667202
Pyrazine (0.4 mmol), tetra-n-butylammonium terephthalate (0.4 mmol), zinc nitrate hexahydrate (0.4 mmol) and dimethylsulfoxide (2 ml) was placed in a thin glass tube. The contents were set aside for a month for the formation of colourless blocks of (I).
There is some disorder in the terminal carbon atom of one of the four butyl chains of the cation. For the cation, the four N–C bonds were restrained to within 0.01 Å of each other as were the C–C distances. The C32 atom is disordered over two sites; the Uij values for C28 were set to those of C28'.
As one of the geometrically generated H atoms of the uncoordinated DMSO (S2/O8/C15/C16) molecule is too close to one of the geometrically generated H of the C28' atom, the occupancy of this DMSO molecule is not unity, and refining gave a value close to 0.667. Furthermore, the refinement of the occupancy of the C28/C28' pair of atoms gave a ratio of nearly 0.67/0.33. Consequently, the occupany of the DMSO was fixed as 2/3; the occupancy of C32 would then also be 2/3.
The pyrazine molecule lies on an inversion centre; its C—C and C—N bond distances were restrained to 1.35 (1) Å; the Uij values were restrained to be nearly isotropic. The carbon-bound H atoms were placed at calculated positions (C–H 0.93 to 0.98 Å) and were included in the refinement in the riding model approximation, with Uiso(H) = 1.2 to 1.5Ueq(C). The final difference Fourier map had a large peak in the vicinity of S1, but was otherwise essentially featureless.
Dimethyl sulfoxide (DMSO) occassionally gets trapped in organic molecular crystals through multi-point recognition between the solvent and molecule (Nangia & Desiraju, 1999). Similarly, coordination polymers synthesized using DMSO as solvent sometimes intercalate DMSO as solvated molecule (Wang et al., 2001, Yang et al., 2005). Our attempt to synthesize porous coordination polymers with the zinc ion, terephthalate dianion and pyrazine in DMSO resulted in the formation of the title compound, (I).
The zinc atom exists in a tetrahedral geometry (Table 1), being coordinated to one oxygen atom from a DMSO moleucle and three oxygen atoms from three different terephthalate anions (Fig. 1). The manner of bridging generates a wavy, honeycomb polyanionic layer (Figure 2). The space between adjacent layers is occupied by the bulky cation as well as the DMSO and pyrazine solvent molecules. The guest cations and molecules take up more than 60% of the unit cell volume. These guests interact with the layers through weak van der Waals interactions.
For other zinc terephthalate adducts of DMSO, see Wang et al. (2001) and Yang et al. (2005). For a report of the intercalation of DMSO in organic compounds, see Nangia & Desiraju (1999).
Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001) and OLEX (Dolomanov et al., 2003); software used to prepare material for publication: publCIF (Westrip, 2007).
(C16H36N)[Zn(C8H4O4)1.5(C2H6OS)]·0.67C2H6OS·0.25C4H4N2 | F(000) = 1558 |
Mr = 704.26 | Dx = 1.267 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 6737 reflections |
a = 11.1722 (5) Å | θ = 2.2–27.6° |
b = 24.8188 (11) Å | µ = 0.80 mm−1 |
c = 13.9443 (6) Å | T = 223 K |
β = 97.968 (1)° | Irregular block, colorless |
V = 3829.2 (3) Å3 | 0.48 × 0.47 × 0.38 mm |
Z = 4 |
Bruker APEX area-detector diffractometer | 8752 independent reflections |
Radiation source: fine-focus sealed tube | 7451 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
φ and ω scans | θmax = 27.5°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −14→14 |
Tmin = 0.626, Tmax = 0.752 | k = −32→32 |
43211 measured reflections | l = −18→18 |
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)] = 0.060 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.181 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.1092P)2 + 3.742P] where P = (Fo2 + 2Fc2)/3 |
8752 reflections | (Δ/σ)max = 0.001 |
427 parameters | Δρmax = 1.44 e Å−3 |
105 restraints | Δρmin = −0.61 e Å−3 |
(C16H36N)[Zn(C8H4O4)1.5(C2H6OS)]·0.67C2H6OS·0.25C4H4N2 | V = 3829.2 (3) Å3 |
Mr = 704.26 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.1722 (5) Å | µ = 0.80 mm−1 |
b = 24.8188 (11) Å | T = 223 K |
c = 13.9443 (6) Å | 0.48 × 0.47 × 0.38 mm |
β = 97.968 (1)° |
Bruker APEX area-detector diffractometer | 8752 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 7451 reflections with I > 2σ(I) |
Tmin = 0.626, Tmax = 0.752 | Rint = 0.038 |
43211 measured reflections |
R[F2 > 2σ(F2)] = 0.060 | 105 restraints |
wR(F2) = 0.181 | H-atom parameters constrained |
S = 1.05 | Δρmax = 1.44 e Å−3 |
8752 reflections | Δρmin = −0.61 e Å−3 |
427 parameters |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Zn1 | 0.64399 (3) | 0.642867 (13) | 0.33508 (2) | 0.02661 (13) | |
S1 | 0.38991 (8) | 0.57300 (4) | 0.32477 (7) | 0.0474 (2) | |
S2 | 0.5688 (3) | 0.98156 (14) | 0.66626 (17) | 0.1035 (8) | 0.67 |
O1 | 0.59927 (19) | 0.67880 (9) | 0.45005 (15) | 0.0349 (5) | |
O2 | 0.5151 (2) | 0.74012 (12) | 0.34659 (16) | 0.0518 (7) | |
O3 | 0.1890 (2) | 0.83652 (10) | 0.70662 (17) | 0.0425 (5) | |
O4 | 0.3049 (2) | 0.78816 (13) | 0.81478 (17) | 0.0531 (7) | |
O5 | 0.7673 (2) | 0.58738 (9) | 0.37480 (16) | 0.0396 (5) | |
O6 | 0.6877 (2) | 0.54688 (10) | 0.49407 (19) | 0.0460 (6) | |
O7 | 0.4824 (2) | 0.60747 (10) | 0.28330 (17) | 0.0445 (6) | |
O8 | 0.5191 (8) | 1.0295 (4) | 0.6328 (7) | 0.150 (4) | 0.67 |
N1 | 0.9806 (2) | 0.68523 (11) | 0.59716 (18) | 0.0379 (6) | |
C1 | 0.5326 (3) | 0.72000 (13) | 0.4272 (2) | 0.0333 (6) | |
C2 | 0.4686 (3) | 0.74255 (13) | 0.5077 (2) | 0.0326 (6) | |
C3 | 0.4834 (3) | 0.71959 (14) | 0.5987 (2) | 0.0406 (7) | |
H3 | 0.5360 | 0.6901 | 0.6122 | 0.049* | |
C4 | 0.4214 (3) | 0.73963 (15) | 0.6704 (2) | 0.0414 (7) | |
H4 | 0.4339 | 0.7242 | 0.7326 | 0.050* | |
C5 | 0.3412 (3) | 0.78209 (13) | 0.6515 (2) | 0.0330 (6) | |
C6 | 0.3251 (3) | 0.80457 (15) | 0.5598 (2) | 0.0422 (8) | |
H6 | 0.2704 | 0.8332 | 0.5457 | 0.051* | |
C7 | 0.3888 (3) | 0.78525 (15) | 0.4887 (2) | 0.0444 (8) | |
H7 | 0.3779 | 0.8012 | 0.4270 | 0.053* | |
C8 | 0.2740 (3) | 0.80337 (14) | 0.7308 (2) | 0.0380 (7) | |
C9 | 0.7701 (2) | 0.55514 (11) | 0.4462 (2) | 0.0302 (6) | |
C10 | 0.8894 (2) | 0.52593 (11) | 0.4732 (2) | 0.0284 (6) | |
C11 | 0.9800 (3) | 0.52863 (12) | 0.4141 (2) | 0.0319 (6) | |
H11 | 0.9665 | 0.5480 | 0.3556 | 0.038* | |
C12 | 1.0895 (3) | 0.50312 (12) | 0.4406 (2) | 0.0330 (6) | |
H12 | 1.1501 | 0.5054 | 0.4003 | 0.040* | |
C13 | 0.4011 (3) | 0.58585 (16) | 0.4505 (3) | 0.0484 (8) | |
H13A | 0.3699 | 0.6216 | 0.4607 | 0.073* | |
H13B | 0.4850 | 0.5838 | 0.4794 | 0.073* | |
H13C | 0.3543 | 0.5593 | 0.4803 | 0.073* | |
C14 | 0.4521 (4) | 0.50670 (17) | 0.3325 (3) | 0.0630 (11) | |
H14A | 0.4536 | 0.4926 | 0.2678 | 0.095* | |
H14B | 0.4028 | 0.4835 | 0.3671 | 0.095* | |
H14C | 0.5338 | 0.5079 | 0.3668 | 0.095* | |
C15 | 0.4521 (17) | 0.9380 (6) | 0.6315 (9) | 0.180 (8) | 0.67 |
H15A | 0.3880 | 0.9442 | 0.6705 | 0.270* | 0.67 |
H15B | 0.4807 | 0.9012 | 0.6404 | 0.270* | 0.67 |
H15C | 0.4213 | 0.9439 | 0.5637 | 0.270* | 0.67 |
C16 | 0.6612 (17) | 0.9648 (10) | 0.5953 (10) | 0.226 (11) | 0.67 |
H16A | 0.7320 | 0.9877 | 0.6065 | 0.339* | 0.67 |
H16B | 0.6231 | 0.9688 | 0.5288 | 0.339* | 0.67 |
H16C | 0.6850 | 0.9275 | 0.6070 | 0.339* | 0.67 |
C17 | 0.8735 (3) | 0.65174 (13) | 0.6193 (2) | 0.0385 (7) | |
H17A | 0.8038 | 0.6605 | 0.5711 | 0.046* | |
H17B | 0.8927 | 0.6137 | 0.6109 | 0.046* | |
C18 | 0.8364 (4) | 0.65861 (16) | 0.7188 (3) | 0.0487 (9) | |
H18A | 0.8068 | 0.6953 | 0.7263 | 0.058* | |
H18B | 0.9058 | 0.6524 | 0.7687 | 0.058* | |
C19 | 0.7367 (3) | 0.61794 (15) | 0.7296 (3) | 0.0486 (8) | |
H19A | 0.6725 | 0.6218 | 0.6745 | 0.058* | |
H19B | 0.7699 | 0.5815 | 0.7272 | 0.058* | |
C20 | 0.6817 (5) | 0.6240 (2) | 0.8225 (4) | 0.0817 (16) | |
H20A | 0.6194 | 0.5970 | 0.8246 | 0.123* | |
H20B | 0.6465 | 0.6596 | 0.8249 | 0.123* | |
H20C | 0.7441 | 0.6193 | 0.8776 | 0.123* | |
C21 | 0.9985 (3) | 0.66980 (14) | 0.4949 (2) | 0.0410 (7) | |
H21A | 1.0147 | 0.6310 | 0.4942 | 0.049* | |
H21B | 0.9219 | 0.6759 | 0.4528 | 0.049* | |
C22 | 1.0968 (3) | 0.69794 (15) | 0.4500 (2) | 0.0471 (8) | |
H22A | 1.1731 | 0.6963 | 0.4940 | 0.056* | |
H22B | 1.0755 | 0.7359 | 0.4382 | 0.056* | |
C23 | 1.1112 (3) | 0.67031 (16) | 0.3550 (2) | 0.0466 (8) | |
H23A | 1.0320 | 0.6682 | 0.3150 | 0.056* | |
H23B | 1.1399 | 0.6334 | 0.3686 | 0.056* | |
C24 | 1.1989 (4) | 0.6992 (2) | 0.2981 (3) | 0.0621 (11) | |
H24A | 1.2036 | 0.6800 | 0.2381 | 0.093* | |
H24B | 1.2783 | 0.7004 | 0.3363 | 0.093* | |
H24C | 1.1706 | 0.7357 | 0.2835 | 0.093* | |
C25 | 1.0928 (3) | 0.67370 (15) | 0.6683 (3) | 0.0476 (8) | |
H25A | 1.0782 | 0.6854 | 0.7328 | 0.057* | |
H25B | 1.1594 | 0.6955 | 0.6503 | 0.057* | |
C26 | 1.1329 (4) | 0.61516 (19) | 0.6747 (4) | 0.0784 (15) | |
H26A | 1.0694 | 0.5929 | 0.6963 | 0.094* | |
H26B | 1.1470 | 0.6024 | 0.6107 | 0.094* | |
C27 | 1.2475 (5) | 0.6102 (3) | 0.7453 (5) | 0.111 (2) | |
H27A | 1.3083 | 0.6344 | 0.7244 | 0.133* | |
H27B | 1.2311 | 0.6227 | 0.8089 | 0.133* | |
C28 | 1.2987 (10) | 0.5555 (4) | 0.7559 (10) | 0.224 (7) | |
H28A | 1.3708 | 0.5559 | 0.8035 | 0.337* | |
H28B | 1.3193 | 0.5434 | 0.6941 | 0.337* | |
H28C | 1.2397 | 0.5312 | 0.7772 | 0.337* | |
C29 | 0.9563 (3) | 0.74534 (13) | 0.6051 (2) | 0.0433 (8) | |
H29A | 0.9532 | 0.7541 | 0.6732 | 0.052* | |
H29B | 1.0244 | 0.7652 | 0.5848 | 0.052* | |
C30 | 0.8404 (3) | 0.76503 (14) | 0.5455 (3) | 0.0507 (9) | |
H30A | 0.7707 | 0.7515 | 0.5737 | 0.061* | |
H30B | 0.8353 | 0.7509 | 0.4794 | 0.061* | |
C31 | 0.8365 (5) | 0.82621 (16) | 0.5425 (4) | 0.0676 (12) | |
H31A | 0.8426 | 0.8399 | 0.6088 | 0.081* | 0.33 |
H31B | 0.7583 | 0.8377 | 0.5078 | 0.081* | 0.33 |
H31C | 0.8578 | 0.8406 | 0.6080 | 0.081* | 0.67 |
H31D | 0.8956 | 0.8396 | 0.5025 | 0.081* | 0.67 |
C32 | 0.9368 (9) | 0.8511 (4) | 0.4936 (10) | 0.124 (4) | 0.67 |
H32A | 0.9296 | 0.8900 | 0.4941 | 0.186* | 0.67 |
H32B | 0.9302 | 0.8385 | 0.4272 | 0.186* | 0.67 |
H32C | 1.0146 | 0.8406 | 0.5282 | 0.186* | 0.67 |
C32' | 0.7109 (11) | 0.8452 (9) | 0.501 (2) | 0.124 (4) | 0.33 |
H32D | 0.7092 | 0.8843 | 0.4991 | 0.186* | 0.33 |
H32E | 0.6527 | 0.8322 | 0.5409 | 0.186* | 0.33 |
H32F | 0.6905 | 0.8313 | 0.4355 | 0.186* | 0.33 |
N2 | 0.4355 (13) | 0.5001 (6) | 0.0732 (9) | 0.121 (4) | 0.50 |
C33 | 0.5243 (17) | 0.5325 (8) | 0.0698 (14) | 0.143 (6) | 0.50 |
H33 | 0.5428 | 0.5581 | 0.1193 | 0.171* | 0.50 |
C34 | 0.415 (2) | 0.4692 (8) | −0.0040 (14) | 0.160 (7) | 0.50 |
H34 | 0.3468 | 0.4465 | −0.0087 | 0.192* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.02605 (19) | 0.0307 (2) | 0.02437 (19) | 0.00432 (12) | 0.00790 (13) | 0.00481 (11) |
S1 | 0.0347 (4) | 0.0568 (5) | 0.0500 (5) | −0.0105 (4) | 0.0032 (4) | 0.0037 (4) |
S2 | 0.122 (2) | 0.121 (2) | 0.0642 (13) | −0.0155 (17) | 0.0000 (13) | −0.0061 (13) |
O1 | 0.0355 (11) | 0.0379 (11) | 0.0336 (11) | 0.0072 (9) | 0.0129 (9) | −0.0017 (9) |
O2 | 0.0593 (15) | 0.0694 (17) | 0.0298 (12) | 0.0266 (13) | 0.0177 (11) | 0.0070 (11) |
O3 | 0.0408 (12) | 0.0531 (14) | 0.0364 (12) | −0.0006 (11) | 0.0155 (10) | −0.0137 (10) |
O4 | 0.0504 (14) | 0.0816 (19) | 0.0298 (12) | −0.0007 (13) | 0.0150 (10) | −0.0096 (12) |
O5 | 0.0367 (11) | 0.0418 (12) | 0.0417 (12) | 0.0163 (9) | 0.0103 (9) | 0.0117 (10) |
O6 | 0.0299 (11) | 0.0521 (14) | 0.0580 (15) | 0.0089 (10) | 0.0130 (10) | 0.0165 (12) |
O7 | 0.0396 (12) | 0.0562 (15) | 0.0369 (12) | −0.0133 (11) | 0.0029 (10) | 0.0057 (10) |
O8 | 0.117 (6) | 0.156 (8) | 0.166 (8) | 0.031 (6) | −0.015 (6) | −0.084 (7) |
N1 | 0.0393 (14) | 0.0420 (15) | 0.0326 (13) | −0.0105 (11) | 0.0052 (11) | −0.0086 (11) |
C1 | 0.0305 (14) | 0.0401 (16) | 0.0309 (15) | 0.0048 (12) | 0.0099 (11) | −0.0010 (12) |
C2 | 0.0324 (14) | 0.0384 (16) | 0.0280 (14) | 0.0042 (12) | 0.0079 (11) | −0.0014 (11) |
C3 | 0.0427 (17) | 0.0472 (18) | 0.0334 (16) | 0.0118 (14) | 0.0104 (13) | 0.0022 (13) |
C4 | 0.0436 (18) | 0.056 (2) | 0.0264 (14) | 0.0049 (15) | 0.0098 (13) | 0.0029 (13) |
C5 | 0.0288 (14) | 0.0431 (17) | 0.0286 (14) | −0.0046 (12) | 0.0092 (11) | −0.0096 (12) |
C6 | 0.0461 (18) | 0.0479 (19) | 0.0347 (16) | 0.0172 (15) | 0.0126 (14) | 0.0006 (14) |
C7 | 0.055 (2) | 0.052 (2) | 0.0281 (15) | 0.0188 (16) | 0.0132 (14) | 0.0054 (13) |
C8 | 0.0319 (15) | 0.0488 (18) | 0.0354 (16) | −0.0121 (13) | 0.0119 (12) | −0.0157 (13) |
C9 | 0.0274 (13) | 0.0252 (13) | 0.0378 (15) | 0.0023 (10) | 0.0037 (11) | −0.0016 (11) |
C10 | 0.0258 (12) | 0.0233 (12) | 0.0365 (15) | 0.0015 (10) | 0.0055 (11) | 0.0000 (10) |
C11 | 0.0339 (14) | 0.0291 (14) | 0.0335 (14) | 0.0056 (11) | 0.0080 (12) | 0.0066 (11) |
C12 | 0.0309 (14) | 0.0314 (14) | 0.0387 (15) | 0.0043 (11) | 0.0125 (12) | 0.0046 (12) |
C13 | 0.0408 (18) | 0.054 (2) | 0.054 (2) | −0.0038 (15) | 0.0181 (16) | 0.0072 (17) |
C14 | 0.069 (3) | 0.049 (2) | 0.074 (3) | −0.012 (2) | 0.019 (2) | −0.006 (2) |
C15 | 0.26 (2) | 0.166 (13) | 0.096 (9) | −0.097 (14) | −0.041 (11) | 0.013 (8) |
C16 | 0.23 (2) | 0.34 (3) | 0.098 (10) | 0.12 (2) | 0.002 (11) | 0.045 (14) |
C17 | 0.0384 (16) | 0.0379 (16) | 0.0398 (17) | −0.0107 (13) | 0.0070 (13) | −0.0077 (13) |
C18 | 0.055 (2) | 0.049 (2) | 0.0441 (19) | −0.0156 (17) | 0.0165 (16) | −0.0104 (15) |
C19 | 0.050 (2) | 0.0446 (19) | 0.053 (2) | −0.0083 (16) | 0.0139 (16) | −0.0013 (16) |
C20 | 0.095 (4) | 0.082 (3) | 0.078 (3) | −0.040 (3) | 0.047 (3) | −0.017 (3) |
C21 | 0.0430 (17) | 0.0466 (19) | 0.0340 (16) | −0.0096 (14) | 0.0078 (13) | −0.0116 (13) |
C22 | 0.0471 (19) | 0.052 (2) | 0.0436 (19) | −0.0092 (16) | 0.0125 (15) | −0.0061 (15) |
C23 | 0.0387 (17) | 0.058 (2) | 0.0449 (19) | 0.0006 (15) | 0.0111 (15) | −0.0018 (16) |
C24 | 0.055 (2) | 0.077 (3) | 0.058 (2) | 0.001 (2) | 0.0230 (19) | 0.005 (2) |
C25 | 0.0404 (18) | 0.059 (2) | 0.0416 (18) | −0.0096 (16) | −0.0001 (14) | −0.0061 (16) |
C26 | 0.060 (3) | 0.073 (3) | 0.094 (4) | 0.012 (2) | −0.017 (3) | −0.007 (3) |
C27 | 0.089 (5) | 0.098 (5) | 0.133 (6) | 0.014 (4) | −0.029 (4) | 0.010 (4) |
C28 | 0.152 (9) | 0.199 (12) | 0.287 (16) | 0.094 (9) | −0.093 (10) | −0.078 (11) |
C29 | 0.0515 (19) | 0.0412 (18) | 0.0379 (17) | −0.0113 (15) | 0.0091 (14) | −0.0084 (14) |
C30 | 0.060 (2) | 0.046 (2) | 0.046 (2) | −0.0014 (17) | 0.0043 (17) | −0.0071 (15) |
C31 | 0.089 (3) | 0.045 (2) | 0.070 (3) | 0.001 (2) | 0.015 (2) | 0.004 (2) |
C32 | 0.123 (8) | 0.094 (7) | 0.154 (10) | 0.011 (6) | 0.018 (7) | 0.054 (6) |
C32' | 0.123 (8) | 0.094 (7) | 0.154 (10) | 0.011 (6) | 0.018 (7) | 0.054 (6) |
N2 | 0.147 (8) | 0.129 (8) | 0.090 (6) | −0.034 (7) | 0.027 (6) | −0.004 (6) |
C33 | 0.163 (10) | 0.151 (10) | 0.117 (9) | −0.015 (8) | 0.031 (8) | 0.029 (8) |
C34 | 0.172 (11) | 0.167 (11) | 0.142 (10) | −0.029 (9) | 0.029 (9) | 0.017 (9) |
Zn1—O1 | 1.959 (2) | C18—H18A | 0.9800 |
Zn1—O5 | 1.972 (2) | C18—H18B | 0.9800 |
Zn1—O3i | 1.993 (2) | C19—C20 | 1.516 (5) |
Zn1—O7 | 2.047 (2) | C19—H19A | 0.9800 |
S1—O7 | 1.516 (2) | C19—H19B | 0.9800 |
S1—C13 | 1.769 (4) | C20—H20A | 0.9700 |
S1—C14 | 1.784 (5) | C20—H20B | 0.9700 |
S2—O8 | 1.368 (10) | C20—H20C | 0.9700 |
S2—C16 | 1.581 (17) | C21—C22 | 1.509 (4) |
S2—C15 | 1.712 (13) | C21—H21A | 0.9800 |
O1—C1 | 1.279 (4) | C21—H21B | 0.9800 |
O2—C1 | 1.220 (4) | C22—C23 | 1.519 (4) |
O3—C8 | 1.266 (4) | C22—H22A | 0.9800 |
O3—Zn1ii | 1.993 (2) | C22—H22B | 0.9800 |
O4—C8 | 1.234 (4) | C23—C24 | 1.524 (4) |
O5—C9 | 1.274 (4) | C23—H23A | 0.9800 |
O6—C9 | 1.228 (4) | C23—H23B | 0.9800 |
N1—C25 | 1.515 (4) | C24—H24A | 0.9700 |
N1—C21 | 1.517 (4) | C24—H24B | 0.9700 |
N1—C17 | 1.523 (4) | C24—H24C | 0.9700 |
N1—C29 | 1.523 (4) | C25—C26 | 1.519 (5) |
C1—C2 | 1.519 (4) | C25—H25A | 0.9800 |
C2—C3 | 1.380 (4) | C25—H25B | 0.9800 |
C2—C7 | 1.387 (4) | C26—C27 | 1.508 (5) |
C3—C4 | 1.385 (4) | C26—H26A | 0.9800 |
C3—H3 | 0.9400 | C26—H26B | 0.9800 |
C4—C5 | 1.385 (5) | C27—C28 | 1.473 (7) |
C4—H4 | 0.9400 | C27—H27A | 0.9800 |
C5—C6 | 1.383 (4) | C27—H27B | 0.9800 |
C5—C8 | 1.516 (4) | C28—H28A | 0.9700 |
C6—C7 | 1.384 (4) | C28—H28B | 0.9700 |
C6—H6 | 0.9400 | C28—H28C | 0.9700 |
C7—H7 | 0.9400 | C29—C30 | 1.519 (4) |
C8—Zn1ii | 2.567 (3) | C29—H29A | 0.9800 |
C9—C10 | 1.518 (4) | C29—H29B | 0.9800 |
C10—C11 | 1.392 (4) | C30—C31 | 1.519 (5) |
C10—C12iii | 1.393 (4) | C30—H30A | 0.9800 |
C11—C12 | 1.382 (4) | C30—H30B | 0.9800 |
C11—H11 | 0.9400 | C31—C32' | 1.518 (8) |
C12—C10iii | 1.393 (4) | C31—C32 | 1.520 (7) |
C12—H12 | 0.9400 | C31—H31A | 0.9800 |
C13—H13A | 0.9700 | C31—H31B | 0.9800 |
C13—H13B | 0.9700 | C31—H31C | 0.9800 |
C13—H13C | 0.9700 | C31—H31D | 0.9800 |
C14—H14A | 0.9700 | C32—H32A | 0.9700 |
C14—H14B | 0.9700 | C32—H32B | 0.9700 |
C14—H14C | 0.9700 | C32—H32C | 0.9700 |
C15—H15A | 0.9700 | C32'—H32D | 0.9700 |
C15—H15B | 0.9700 | C32'—H32E | 0.9700 |
C15—H15C | 0.9700 | C32'—H32F | 0.9700 |
C16—H16A | 0.9700 | N2—C33 | 1.283 (15) |
C16—H16B | 0.9700 | N2—C34 | 1.316 (15) |
C16—H16C | 0.9700 | C33—C34iv | 1.218 (16) |
C17—C18 | 1.511 (4) | C33—H33 | 0.9400 |
C17—H17A | 0.9800 | C34—C33iv | 1.218 (16) |
C17—H17B | 0.9800 | C34—H34 | 0.9400 |
C18—C19 | 1.526 (4) | ||
O1—Zn1—O5 | 109.61 (9) | C18—C19—H19B | 108.8 |
O1—Zn1—O3i | 138.01 (10) | H19A—C19—H19B | 107.6 |
O5—Zn1—O3i | 100.27 (10) | C19—C20—H20A | 109.5 |
O1—Zn1—O7 | 99.87 (10) | C19—C20—H20B | 109.5 |
O5—Zn1—O7 | 110.29 (10) | H20A—C20—H20B | 109.5 |
O3i—Zn1—O7 | 96.49 (10) | C19—C20—H20C | 109.5 |
O7—S1—C13 | 108.55 (16) | H20A—C20—H20C | 109.5 |
O7—S1—C14 | 105.26 (19) | H20B—C20—H20C | 109.5 |
C13—S1—C14 | 97.7 (2) | C22—C21—N1 | 118.2 (3) |
O8—S2—C16 | 106.6 (9) | C22—C21—H21A | 107.8 |
O8—S2—C15 | 101.3 (7) | N1—C21—H21A | 107.8 |
C16—S2—C15 | 101.2 (11) | C22—C21—H21B | 107.8 |
C1—O1—Zn1 | 111.44 (18) | N1—C21—H21B | 107.8 |
C8—O3—Zn1ii | 101.6 (2) | H21A—C21—H21B | 107.1 |
C9—O5—Zn1 | 126.77 (19) | C21—C22—C23 | 108.9 (3) |
S1—O7—Zn1 | 136.20 (14) | C21—C22—H22A | 109.9 |
C25—N1—C21 | 111.3 (3) | C23—C22—H22A | 109.9 |
C25—N1—C17 | 111.5 (3) | C21—C22—H22B | 109.9 |
C21—N1—C17 | 105.2 (2) | C23—C22—H22B | 109.9 |
C25—N1—C29 | 106.1 (2) | H22A—C22—H22B | 108.3 |
C21—N1—C29 | 111.3 (3) | C22—C23—C24 | 113.3 (3) |
C17—N1—C29 | 111.5 (2) | C22—C23—H23A | 108.9 |
O2—C1—O1 | 124.8 (3) | C24—C23—H23A | 108.9 |
O2—C1—C2 | 119.9 (3) | C22—C23—H23B | 108.9 |
O1—C1—C2 | 115.3 (3) | C24—C23—H23B | 108.9 |
C3—C2—C7 | 118.9 (3) | H23A—C23—H23B | 107.7 |
C3—C2—C1 | 121.3 (3) | C23—C24—H24A | 109.5 |
C7—C2—C1 | 119.7 (3) | C23—C24—H24B | 109.5 |
C2—C3—C4 | 120.5 (3) | H24A—C24—H24B | 109.5 |
C2—C3—H3 | 119.8 | C23—C24—H24C | 109.5 |
C4—C3—H3 | 119.8 | H24A—C24—H24C | 109.5 |
C5—C4—C3 | 120.7 (3) | H24B—C24—H24C | 109.5 |
C5—C4—H4 | 119.7 | N1—C25—C26 | 115.4 (3) |
C3—C4—H4 | 119.7 | N1—C25—H25A | 108.4 |
C6—C5—C4 | 118.8 (3) | C26—C25—H25A | 108.4 |
C6—C5—C8 | 121.3 (3) | N1—C25—H25B | 108.4 |
C4—C5—C8 | 119.9 (3) | C26—C25—H25B | 108.4 |
C5—C6—C7 | 120.5 (3) | H25A—C25—H25B | 107.5 |
C5—C6—H6 | 119.7 | C27—C26—C25 | 109.4 (4) |
C7—C6—H6 | 119.7 | C27—C26—H26A | 109.8 |
C6—C7—C2 | 120.6 (3) | C25—C26—H26A | 109.8 |
C6—C7—H7 | 119.7 | C27—C26—H26B | 109.8 |
C2—C7—H7 | 119.7 | C25—C26—H26B | 109.8 |
O4—C8—O3 | 123.5 (3) | H26A—C26—H26B | 108.2 |
O4—C8—C5 | 119.0 (3) | C28—C27—C26 | 115.0 (6) |
O3—C8—C5 | 117.5 (3) | C28—C27—H27A | 108.5 |
O4—C8—Zn1ii | 74.17 (18) | C26—C27—H27A | 108.5 |
O3—C8—Zn1ii | 49.51 (14) | C28—C27—H27B | 108.5 |
C5—C8—Zn1ii | 166.2 (3) | C26—C27—H27B | 108.5 |
O6—C9—O5 | 126.2 (3) | H27A—C27—H27B | 107.5 |
O6—C9—C10 | 119.0 (3) | C27—C28—H28A | 109.5 |
O5—C9—C10 | 114.8 (2) | C27—C28—H28B | 109.5 |
C11—C10—C12iii | 119.1 (3) | H28A—C28—H28B | 109.5 |
C11—C10—C9 | 121.0 (3) | C27—C28—H28C | 109.5 |
C12iii—C10—C9 | 119.9 (3) | H28A—C28—H28C | 109.5 |
C12—C11—C10 | 120.5 (3) | H28B—C28—H28C | 109.5 |
C12—C11—H11 | 119.7 | C30—C29—N1 | 115.0 (3) |
C10—C11—H11 | 119.7 | C30—C29—H29A | 108.5 |
C11—C12—C10iii | 120.4 (3) | N1—C29—H29A | 108.5 |
C11—C12—H12 | 119.8 | C30—C29—H29B | 108.5 |
C10iii—C12—H12 | 119.8 | N1—C29—H29B | 108.5 |
S1—C13—H13A | 109.5 | H29A—C29—H29B | 107.5 |
S1—C13—H13B | 109.5 | C29—C30—C31 | 110.8 (3) |
H13A—C13—H13B | 109.5 | C29—C30—H30A | 109.5 |
S1—C13—H13C | 109.5 | C31—C30—H30A | 109.5 |
H13A—C13—H13C | 109.5 | C29—C30—H30B | 109.5 |
H13B—C13—H13C | 109.5 | C31—C30—H30B | 109.5 |
S1—C14—H14A | 109.5 | H30A—C30—H30B | 108.1 |
S1—C14—H14B | 109.5 | C32'—C31—C30 | 110.0 (10) |
H14A—C14—H14B | 109.5 | C32'—C31—C32 | 113.7 (10) |
S1—C14—H14C | 109.5 | C30—C31—C32 | 113.4 (6) |
H14A—C14—H14C | 109.5 | C30—C31—H31A | 108.9 |
H14B—C14—H14C | 109.5 | C32—C31—H31A | 108.9 |
S2—C15—H15A | 109.5 | C30—C31—H31B | 108.9 |
S2—C15—H15B | 109.5 | C32—C31—H31B | 108.9 |
H15A—C15—H15B | 109.5 | H31A—C31—H31B | 107.7 |
S2—C15—H15C | 109.5 | C32'—C31—H31C | 109.7 |
H15A—C15—H15C | 109.5 | C30—C31—H31C | 109.7 |
H15B—C15—H15C | 109.5 | C32'—C31—H31D | 109.7 |
S2—C16—H16A | 109.5 | C30—C31—H31D | 109.7 |
S2—C16—H16B | 109.5 | H31C—C31—H31D | 108.2 |
H16A—C16—H16B | 109.5 | C31—C32—H32A | 109.5 |
S2—C16—H16C | 109.5 | C31—C32—H32B | 109.5 |
H16A—C16—H16C | 109.5 | H32A—C32—H32B | 109.5 |
H16B—C16—H16C | 109.5 | C31—C32—H32C | 109.5 |
C18—C17—N1 | 116.6 (3) | H32A—C32—H32C | 109.5 |
C18—C17—H17A | 108.1 | H32B—C32—H32C | 109.5 |
N1—C17—H17A | 108.1 | C31—C32'—H32D | 109.5 |
C18—C17—H17B | 108.1 | C31—C32'—H32E | 109.5 |
N1—C17—H17B | 108.1 | H32D—C32'—H32E | 109.5 |
H17A—C17—H17B | 107.3 | C31—C32'—H32F | 109.5 |
C17—C18—C19 | 108.3 (3) | H32D—C32'—H32F | 109.5 |
C17—C18—H18A | 110.0 | H32E—C32'—H32F | 109.5 |
C19—C18—H18A | 110.0 | C33—N2—C34 | 112.6 (14) |
C17—C18—H18B | 110.0 | C34iv—C33—N2 | 121 (2) |
C19—C18—H18B | 110.0 | C34iv—C33—H33 | 119.3 |
H18A—C18—H18B | 108.4 | N2—C33—H33 | 119.3 |
C20—C19—C18 | 114.0 (3) | C33iv—C34—N2 | 126 (2) |
C20—C19—H19A | 108.8 | C33iv—C34—H34 | 117.1 |
C18—C19—H19A | 108.8 | N2—C34—H34 | 117.1 |
C20—C19—H19B | 108.8 | ||
O5—Zn1—O1—C1 | 170.8 (2) | C6—C5—C8—Zn1ii | −7.4 (11) |
O3i—Zn1—O1—C1 | 38.0 (3) | C4—C5—C8—Zn1ii | 172.1 (7) |
O7—Zn1—O1—C1 | −73.4 (2) | Zn1—O5—C9—O6 | 12.2 (5) |
C8i—Zn1—O1—C1 | 63.7 (2) | Zn1—O5—C9—C10 | −166.51 (19) |
O1—Zn1—O5—C9 | 40.6 (3) | O6—C9—C10—C11 | 171.8 (3) |
O3i—Zn1—O5—C9 | −169.3 (3) | O5—C9—C10—C11 | −9.4 (4) |
O7—Zn1—O5—C9 | −68.4 (3) | O6—C9—C10—C12iii | −9.7 (4) |
C13—S1—O7—Zn1 | 25.2 (3) | O5—C9—C10—C12iii | 169.1 (3) |
C14—S1—O7—Zn1 | −78.6 (3) | C12iii—C10—C11—C12 | −0.4 (5) |
O1—Zn1—O7—S1 | −49.4 (3) | C9—C10—C11—C12 | 178.2 (3) |
O5—Zn1—O7—S1 | 65.9 (3) | C10—C11—C12—C10iii | 0.4 (5) |
O3i—Zn1—O7—S1 | 169.4 (2) | C25—N1—C17—C18 | 58.4 (4) |
Zn1—O1—C1—O2 | −11.5 (4) | C21—N1—C17—C18 | 179.2 (3) |
Zn1—O1—C1—C2 | 165.9 (2) | C29—N1—C17—C18 | −60.0 (4) |
O2—C1—C2—C3 | 177.8 (3) | N1—C17—C18—C19 | −174.6 (3) |
O1—C1—C2—C3 | 0.3 (5) | C17—C18—C19—C20 | −174.2 (4) |
O2—C1—C2—C7 | 1.2 (5) | C25—N1—C21—C22 | −61.2 (4) |
O1—C1—C2—C7 | −176.3 (3) | C17—N1—C21—C22 | 178.0 (3) |
C7—C2—C3—C4 | −1.3 (5) | C29—N1—C21—C22 | 57.0 (4) |
C1—C2—C3—C4 | −177.9 (3) | N1—C21—C22—C23 | 171.3 (3) |
C2—C3—C4—C5 | 1.7 (5) | C21—C22—C23—C24 | 173.8 (3) |
C3—C4—C5—C6 | −0.7 (5) | C21—N1—C25—C26 | −60.2 (4) |
C3—C4—C5—C8 | 179.8 (3) | C17—N1—C25—C26 | 57.0 (4) |
C4—C5—C6—C7 | −0.6 (5) | C29—N1—C25—C26 | 178.6 (4) |
C8—C5—C6—C7 | 178.9 (3) | N1—C25—C26—C27 | 178.0 (5) |
C5—C6—C7—C2 | 0.9 (6) | C25—C26—C27—C28 | −178.0 (9) |
C3—C2—C7—C6 | 0.0 (6) | C25—N1—C29—C30 | −175.0 (3) |
C1—C2—C7—C6 | 176.7 (3) | C21—N1—C29—C30 | 63.8 (4) |
Zn1ii—O3—C8—O4 | 4.9 (4) | C17—N1—C29—C30 | −53.5 (4) |
Zn1ii—O3—C8—C5 | −174.4 (2) | N1—C29—C30—C31 | −168.9 (3) |
C6—C5—C8—O4 | −168.5 (3) | C29—C30—C31—C32' | −168.5 (12) |
C4—C5—C8—O4 | 10.9 (5) | C29—C30—C31—C32 | 62.9 (8) |
C6—C5—C8—O3 | 10.8 (5) | C34—N2—C33—C34iv | −5 (4) |
C4—C5—C8—O3 | −169.7 (3) | C33—N2—C34—C33iv | 5 (4) |
Symmetry codes: (i) x+1/2, −y+3/2, z−1/2; (ii) x−1/2, −y+3/2, z+1/2; (iii) −x+2, −y+1, −z+1; (iv) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | (C16H36N)[Zn(C8H4O4)1.5(C2H6OS)]·0.67C2H6OS·0.25C4H4N2 |
Mr | 704.26 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 223 |
a, b, c (Å) | 11.1722 (5), 24.8188 (11), 13.9443 (6) |
β (°) | 97.968 (1) |
V (Å3) | 3829.2 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.80 |
Crystal size (mm) | 0.48 × 0.47 × 0.38 |
Data collection | |
Diffractometer | Bruker APEX area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.626, 0.752 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 43211, 8752, 7451 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.060, 0.181, 1.05 |
No. of reflections | 8752 |
No. of parameters | 427 |
No. of restraints | 105 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.44, −0.61 |
Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), X-SEED (Barbour, 2001) and OLEX (Dolomanov et al., 2003), publCIF (Westrip, 2007).
Zn1—O1 | 1.959 (2) | Zn1—O3i | 1.993 (2) |
Zn1—O5 | 1.972 (2) | Zn1—O7 | 2.047 (2) |
Symmetry code: (i) x+1/2, −y+3/2, z−1/2. |
Dimethyl sulfoxide (DMSO) occassionally gets trapped in organic molecular crystals through multi-point recognition between the solvent and molecule (Nangia & Desiraju, 1999). Similarly, coordination polymers synthesized using DMSO as solvent sometimes intercalate DMSO as solvated molecule (Wang et al., 2001, Yang et al., 2005). Our attempt to synthesize porous coordination polymers with the zinc ion, terephthalate dianion and pyrazine in DMSO resulted in the formation of the title compound, (I).
The zinc atom exists in a tetrahedral geometry (Table 1), being coordinated to one oxygen atom from a DMSO moleucle and three oxygen atoms from three different terephthalate anions (Fig. 1). The manner of bridging generates a wavy, honeycomb polyanionic layer (Figure 2). The space between adjacent layers is occupied by the bulky cation as well as the DMSO and pyrazine solvent molecules. The guest cations and molecules take up more than 60% of the unit cell volume. These guests interact with the layers through weak van der Waals interactions.