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The anion of the title compound, {(C16H36N)[Zn(C8H4O4)1.5(C2H6OS)]·0.67C2H6OS·0.25C4H4N2}n, exists as a polyanionic layer in which the dimethyl sulfoxide-coordinated Zn atom is bridged by two terephthalate anions (one of which lies on a general position and the other about a center of inversion). The honeycomb layers are wavy, and the sterically bulky cation as well as the dimethyl sulfoxide and pyrazine solvent mol­ecules occupy the space between adjacent layers. These do not inter­act with the layers. The geometry of the Zn atom is tetra­hedral.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807050672/hb2568sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807050672/hb2568Isup2.hkl
Contains datablock I

CCDC reference: 667202

Key indicators

  • Single-crystal X-ray study
  • T = 223 K
  • Mean [sigma](C-C) = 0.005 Å
  • Disorder in main residue
  • R factor = 0.060
  • wR factor = 0.181
  • Data-to-parameter ratio = 20.5

checkCIF/PLATON results

No syntax errors found



Alert level A PLAT220_ALERT_2_A Large Non-Solvent C Ueq(max)/Ueq(min) ... 5.80 Ratio
Author Response: There are two lattice molecules, a DMSO that lies on a general position, and a pyrazine that lies on a special position. There are no hydrogen bonds between either and the main molecule. Both can be treated as disordered molecules with the use of restraints, but this is not necessary.
PLAT222_ALERT_3_A Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       7.33 Ratio
Author Response: As above.

Alert level B PLAT242_ALERT_2_B Check Low Ueq as Compared to Neighbors for C27 PLAT242_ALERT_2_B Check Low Ueq as Compared to Neighbors for C31
Alert level C ABSMU01_ALERT_1_C The ratio of given/expected absorption coefficient lies outside the range 0.99 <> 1.01 Calculated value of mu = 0.776 Value of mu given = 0.797 DENSD01_ALERT_1_C The ratio of the submitted crystal density and that calculated from the formula is outside the range 0.99 <> 1.01 Crystal density given = 1.267 Calculated crystal density = 1.222 PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT044_ALERT_1_C Calculated and Reported Dx Differ .............. ? PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 0.25 Ratio PLAT046_ALERT_1_C Reported Z, MW and D(calc) are Inconsistent .... 1.22 PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ............. 0.89 PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.98 PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)... ? PLAT077_ALERT_4_C Unitcell contains non-integer number of atoms .. ? PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.35 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C19 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for S2 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for N2 PLAT245_ALERT_2_C U(iso) H31D Smaller than U(eq) C32 by ... 0.04 AngSq PLAT245_ALERT_2_C U(iso) H31B Smaller than U(eq) C32' by ... 0.04 AngSq PLAT301_ALERT_3_C Main Residue Disorder ......................... 1.00 Perc. PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 60.00 Perc.
Alert level G FORMU01_ALERT_1_G There is a discrepancy between the atom counts in the _chemical_formula_sum and _chemical_formula_moiety. This is usually due to the moiety formula being in the wrong format. Atom count from _chemical_formula_sum: C32.33 H53 N1.5 O7.67 S1.67 Atom count from _chemical_formula_moiety:C30.335 H49.675 N1.335 O7.1 FORMU01_ALERT_2_G There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:C32.33 H53 N1.5 O7.67 S1.67 Zn Atom count from the _atom_site data: C32.34 H53.02 N1.5 O7.67 S1.67 CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected. CELLZ01_ALERT_1_G ALERT: check formula stoichiometry or atom site occupancies. From the CIF: _cell_formula_units_Z 4 From the CIF: _chemical_formula_sum C32.33 H53 N1.50 O7.67 S1.67 Zn TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff C 129.32 129.36 -0.04 H 212.00 212.08 -0.08 N 6.00 6.00 0.00 O 30.68 30.68 0.00 S 6.68 6.68 0.00 Zn 4.00 4.00 0.00 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 105
2 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 19 ALERT level C = Check and explain 5 ALERT level G = General alerts; check 11 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 8 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 ALERT type 3 Indicator that the structure quality may be low 5 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

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.

Related literature top

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).

Experimental top

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).

Refinement top

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.

Structure description top

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).

Computing details top

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).

Figures top
[Figure 1] Fig. 1. View of a portion of the layer structure of (I); displacement ellipsoids are drawn at the 50% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius. Symmetry code: i = 1/2 + x, 3/2 - y, 1/2 - z.] The solvent DMSO and pyrazine molecules, and the minor disorder component are not shown.
[Figure 2] Fig. 2. Extended layer structure of (I).
Poly[tetra-n-butylammonium [(dimethyl sulfoxide-κO) sesqui(µ2-terephthalato-κ2O:O')zincate(II)] 0.67-dimethyl sulfoxide 0.25-pyrazine solvate] top
Crystal data top
(C16H36N)[Zn(C8H4O4)1.5(C2H6OS)]·0.67C2H6OS·0.25C4H4N2F(000) = 1558
Mr = 704.26Dx = 1.267 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 6737 reflections
a = 11.1722 (5) Åθ = 2.2–27.6°
b = 24.8188 (11) ŵ = 0.80 mm1
c = 13.9443 (6) ÅT = 223 K
β = 97.968 (1)°Irregular block, colorless
V = 3829.2 (3) Å30.48 × 0.47 × 0.38 mm
Z = 4
Data collection top
Bruker APEX area-detector
diffractometer
8752 independent reflections
Radiation source: fine-focus sealed tube7451 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.038
φ and ω scansθmax = 27.5°, θmin = 1.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1414
Tmin = 0.626, Tmax = 0.752k = 3232
43211 measured reflectionsl = 1818
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.060Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.181H-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 parametersΔρmax = 1.44 e Å3
105 restraintsΔρmin = 0.61 e Å3
Crystal data top
(C16H36N)[Zn(C8H4O4)1.5(C2H6OS)]·0.67C2H6OS·0.25C4H4N2V = 3829.2 (3) Å3
Mr = 704.26Z = 4
Monoclinic, P21/nMo Kα radiation
a = 11.1722 (5) ŵ = 0.80 mm1
b = 24.8188 (11) ÅT = 223 K
c = 13.9443 (6) Å0.48 × 0.47 × 0.38 mm
β = 97.968 (1)°
Data collection top
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 = 0.752Rint = 0.038
43211 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.060105 restraints
wR(F2) = 0.181H-atom parameters constrained
S = 1.05Δρmax = 1.44 e Å3
8752 reflectionsΔρmin = 0.61 e Å3
427 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Zn10.64399 (3)0.642867 (13)0.33508 (2)0.02661 (13)
S10.38991 (8)0.57300 (4)0.32477 (7)0.0474 (2)
S20.5688 (3)0.98156 (14)0.66626 (17)0.1035 (8)0.67
O10.59927 (19)0.67880 (9)0.45005 (15)0.0349 (5)
O20.5151 (2)0.74012 (12)0.34659 (16)0.0518 (7)
O30.1890 (2)0.83652 (10)0.70662 (17)0.0425 (5)
O40.3049 (2)0.78816 (13)0.81478 (17)0.0531 (7)
O50.7673 (2)0.58738 (9)0.37480 (16)0.0396 (5)
O60.6877 (2)0.54688 (10)0.49407 (19)0.0460 (6)
O70.4824 (2)0.60747 (10)0.28330 (17)0.0445 (6)
O80.5191 (8)1.0295 (4)0.6328 (7)0.150 (4)0.67
N10.9806 (2)0.68523 (11)0.59716 (18)0.0379 (6)
C10.5326 (3)0.72000 (13)0.4272 (2)0.0333 (6)
C20.4686 (3)0.74255 (13)0.5077 (2)0.0326 (6)
C30.4834 (3)0.71959 (14)0.5987 (2)0.0406 (7)
H30.53600.69010.61220.049*
C40.4214 (3)0.73963 (15)0.6704 (2)0.0414 (7)
H40.43390.72420.73260.050*
C50.3412 (3)0.78209 (13)0.6515 (2)0.0330 (6)
C60.3251 (3)0.80457 (15)0.5598 (2)0.0422 (8)
H60.27040.83320.54570.051*
C70.3888 (3)0.78525 (15)0.4887 (2)0.0444 (8)
H70.37790.80120.42700.053*
C80.2740 (3)0.80337 (14)0.7308 (2)0.0380 (7)
C90.7701 (2)0.55514 (11)0.4462 (2)0.0302 (6)
C100.8894 (2)0.52593 (11)0.4732 (2)0.0284 (6)
C110.9800 (3)0.52863 (12)0.4141 (2)0.0319 (6)
H110.96650.54800.35560.038*
C121.0895 (3)0.50312 (12)0.4406 (2)0.0330 (6)
H121.15010.50540.40030.040*
C130.4011 (3)0.58585 (16)0.4505 (3)0.0484 (8)
H13A0.36990.62160.46070.073*
H13B0.48500.58380.47940.073*
H13C0.35430.55930.48030.073*
C140.4521 (4)0.50670 (17)0.3325 (3)0.0630 (11)
H14A0.45360.49260.26780.095*
H14B0.40280.48350.36710.095*
H14C0.53380.50790.36680.095*
C150.4521 (17)0.9380 (6)0.6315 (9)0.180 (8)0.67
H15A0.38800.94420.67050.270*0.67
H15B0.48070.90120.64040.270*0.67
H15C0.42130.94390.56370.270*0.67
C160.6612 (17)0.9648 (10)0.5953 (10)0.226 (11)0.67
H16A0.73200.98770.60650.339*0.67
H16B0.62310.96880.52880.339*0.67
H16C0.68500.92750.60700.339*0.67
C170.8735 (3)0.65174 (13)0.6193 (2)0.0385 (7)
H17A0.80380.66050.57110.046*
H17B0.89270.61370.61090.046*
C180.8364 (4)0.65861 (16)0.7188 (3)0.0487 (9)
H18A0.80680.69530.72630.058*
H18B0.90580.65240.76870.058*
C190.7367 (3)0.61794 (15)0.7296 (3)0.0486 (8)
H19A0.67250.62180.67450.058*
H19B0.76990.58150.72720.058*
C200.6817 (5)0.6240 (2)0.8225 (4)0.0817 (16)
H20A0.61940.59700.82460.123*
H20B0.64650.65960.82490.123*
H20C0.74410.61930.87760.123*
C210.9985 (3)0.66980 (14)0.4949 (2)0.0410 (7)
H21A1.01470.63100.49420.049*
H21B0.92190.67590.45280.049*
C221.0968 (3)0.69794 (15)0.4500 (2)0.0471 (8)
H22A1.17310.69630.49400.056*
H22B1.07550.73590.43820.056*
C231.1112 (3)0.67031 (16)0.3550 (2)0.0466 (8)
H23A1.03200.66820.31500.056*
H23B1.13990.63340.36860.056*
C241.1989 (4)0.6992 (2)0.2981 (3)0.0621 (11)
H24A1.20360.68000.23810.093*
H24B1.27830.70040.33630.093*
H24C1.17060.73570.28350.093*
C251.0928 (3)0.67370 (15)0.6683 (3)0.0476 (8)
H25A1.07820.68540.73280.057*
H25B1.15940.69550.65030.057*
C261.1329 (4)0.61516 (19)0.6747 (4)0.0784 (15)
H26A1.06940.59290.69630.094*
H26B1.14700.60240.61070.094*
C271.2475 (5)0.6102 (3)0.7453 (5)0.111 (2)
H27A1.30830.63440.72440.133*
H27B1.23110.62270.80890.133*
C281.2987 (10)0.5555 (4)0.7559 (10)0.224 (7)
H28A1.37080.55590.80350.337*
H28B1.31930.54340.69410.337*
H28C1.23970.53120.77720.337*
C290.9563 (3)0.74534 (13)0.6051 (2)0.0433 (8)
H29A0.95320.75410.67320.052*
H29B1.02440.76520.58480.052*
C300.8404 (3)0.76503 (14)0.5455 (3)0.0507 (9)
H30A0.77070.75150.57370.061*
H30B0.83530.75090.47940.061*
C310.8365 (5)0.82621 (16)0.5425 (4)0.0676 (12)
H31A0.84260.83990.60880.081*0.33
H31B0.75830.83770.50780.081*0.33
H31C0.85780.84060.60800.081*0.67
H31D0.89560.83960.50250.081*0.67
C320.9368 (9)0.8511 (4)0.4936 (10)0.124 (4)0.67
H32A0.92960.89000.49410.186*0.67
H32B0.93020.83850.42720.186*0.67
H32C1.01460.84060.52820.186*0.67
C32'0.7109 (11)0.8452 (9)0.501 (2)0.124 (4)0.33
H32D0.70920.88430.49910.186*0.33
H32E0.65270.83220.54090.186*0.33
H32F0.69050.83130.43550.186*0.33
N20.4355 (13)0.5001 (6)0.0732 (9)0.121 (4)0.50
C330.5243 (17)0.5325 (8)0.0698 (14)0.143 (6)0.50
H330.54280.55810.11930.171*0.50
C340.415 (2)0.4692 (8)0.0040 (14)0.160 (7)0.50
H340.34680.44650.00870.192*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.02605 (19)0.0307 (2)0.02437 (19)0.00432 (12)0.00790 (13)0.00481 (11)
S10.0347 (4)0.0568 (5)0.0500 (5)0.0105 (4)0.0032 (4)0.0037 (4)
S20.122 (2)0.121 (2)0.0642 (13)0.0155 (17)0.0000 (13)0.0061 (13)
O10.0355 (11)0.0379 (11)0.0336 (11)0.0072 (9)0.0129 (9)0.0017 (9)
O20.0593 (15)0.0694 (17)0.0298 (12)0.0266 (13)0.0177 (11)0.0070 (11)
O30.0408 (12)0.0531 (14)0.0364 (12)0.0006 (11)0.0155 (10)0.0137 (10)
O40.0504 (14)0.0816 (19)0.0298 (12)0.0007 (13)0.0150 (10)0.0096 (12)
O50.0367 (11)0.0418 (12)0.0417 (12)0.0163 (9)0.0103 (9)0.0117 (10)
O60.0299 (11)0.0521 (14)0.0580 (15)0.0089 (10)0.0130 (10)0.0165 (12)
O70.0396 (12)0.0562 (15)0.0369 (12)0.0133 (11)0.0029 (10)0.0057 (10)
O80.117 (6)0.156 (8)0.166 (8)0.031 (6)0.015 (6)0.084 (7)
N10.0393 (14)0.0420 (15)0.0326 (13)0.0105 (11)0.0052 (11)0.0086 (11)
C10.0305 (14)0.0401 (16)0.0309 (15)0.0048 (12)0.0099 (11)0.0010 (12)
C20.0324 (14)0.0384 (16)0.0280 (14)0.0042 (12)0.0079 (11)0.0014 (11)
C30.0427 (17)0.0472 (18)0.0334 (16)0.0118 (14)0.0104 (13)0.0022 (13)
C40.0436 (18)0.056 (2)0.0264 (14)0.0049 (15)0.0098 (13)0.0029 (13)
C50.0288 (14)0.0431 (17)0.0286 (14)0.0046 (12)0.0092 (11)0.0096 (12)
C60.0461 (18)0.0479 (19)0.0347 (16)0.0172 (15)0.0126 (14)0.0006 (14)
C70.055 (2)0.052 (2)0.0281 (15)0.0188 (16)0.0132 (14)0.0054 (13)
C80.0319 (15)0.0488 (18)0.0354 (16)0.0121 (13)0.0119 (12)0.0157 (13)
C90.0274 (13)0.0252 (13)0.0378 (15)0.0023 (10)0.0037 (11)0.0016 (11)
C100.0258 (12)0.0233 (12)0.0365 (15)0.0015 (10)0.0055 (11)0.0000 (10)
C110.0339 (14)0.0291 (14)0.0335 (14)0.0056 (11)0.0080 (12)0.0066 (11)
C120.0309 (14)0.0314 (14)0.0387 (15)0.0043 (11)0.0125 (12)0.0046 (12)
C130.0408 (18)0.054 (2)0.054 (2)0.0038 (15)0.0181 (16)0.0072 (17)
C140.069 (3)0.049 (2)0.074 (3)0.012 (2)0.019 (2)0.006 (2)
C150.26 (2)0.166 (13)0.096 (9)0.097 (14)0.041 (11)0.013 (8)
C160.23 (2)0.34 (3)0.098 (10)0.12 (2)0.002 (11)0.045 (14)
C170.0384 (16)0.0379 (16)0.0398 (17)0.0107 (13)0.0070 (13)0.0077 (13)
C180.055 (2)0.049 (2)0.0441 (19)0.0156 (17)0.0165 (16)0.0104 (15)
C190.050 (2)0.0446 (19)0.053 (2)0.0083 (16)0.0139 (16)0.0013 (16)
C200.095 (4)0.082 (3)0.078 (3)0.040 (3)0.047 (3)0.017 (3)
C210.0430 (17)0.0466 (19)0.0340 (16)0.0096 (14)0.0078 (13)0.0116 (13)
C220.0471 (19)0.052 (2)0.0436 (19)0.0092 (16)0.0125 (15)0.0061 (15)
C230.0387 (17)0.058 (2)0.0449 (19)0.0006 (15)0.0111 (15)0.0018 (16)
C240.055 (2)0.077 (3)0.058 (2)0.001 (2)0.0230 (19)0.005 (2)
C250.0404 (18)0.059 (2)0.0416 (18)0.0096 (16)0.0001 (14)0.0061 (16)
C260.060 (3)0.073 (3)0.094 (4)0.012 (2)0.017 (3)0.007 (3)
C270.089 (5)0.098 (5)0.133 (6)0.014 (4)0.029 (4)0.010 (4)
C280.152 (9)0.199 (12)0.287 (16)0.094 (9)0.093 (10)0.078 (11)
C290.0515 (19)0.0412 (18)0.0379 (17)0.0113 (15)0.0091 (14)0.0084 (14)
C300.060 (2)0.046 (2)0.046 (2)0.0014 (17)0.0043 (17)0.0071 (15)
C310.089 (3)0.045 (2)0.070 (3)0.001 (2)0.015 (2)0.004 (2)
C320.123 (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)
N20.147 (8)0.129 (8)0.090 (6)0.034 (7)0.027 (6)0.004 (6)
C330.163 (10)0.151 (10)0.117 (9)0.015 (8)0.031 (8)0.029 (8)
C340.172 (11)0.167 (11)0.142 (10)0.029 (9)0.029 (9)0.017 (9)
Geometric parameters (Å, º) top
Zn1—O11.959 (2)C18—H18A0.9800
Zn1—O51.972 (2)C18—H18B0.9800
Zn1—O3i1.993 (2)C19—C201.516 (5)
Zn1—O72.047 (2)C19—H19A0.9800
S1—O71.516 (2)C19—H19B0.9800
S1—C131.769 (4)C20—H20A0.9700
S1—C141.784 (5)C20—H20B0.9700
S2—O81.368 (10)C20—H20C0.9700
S2—C161.581 (17)C21—C221.509 (4)
S2—C151.712 (13)C21—H21A0.9800
O1—C11.279 (4)C21—H21B0.9800
O2—C11.220 (4)C22—C231.519 (4)
O3—C81.266 (4)C22—H22A0.9800
O3—Zn1ii1.993 (2)C22—H22B0.9800
O4—C81.234 (4)C23—C241.524 (4)
O5—C91.274 (4)C23—H23A0.9800
O6—C91.228 (4)C23—H23B0.9800
N1—C251.515 (4)C24—H24A0.9700
N1—C211.517 (4)C24—H24B0.9700
N1—C171.523 (4)C24—H24C0.9700
N1—C291.523 (4)C25—C261.519 (5)
C1—C21.519 (4)C25—H25A0.9800
C2—C31.380 (4)C25—H25B0.9800
C2—C71.387 (4)C26—C271.508 (5)
C3—C41.385 (4)C26—H26A0.9800
C3—H30.9400C26—H26B0.9800
C4—C51.385 (5)C27—C281.473 (7)
C4—H40.9400C27—H27A0.9800
C5—C61.383 (4)C27—H27B0.9800
C5—C81.516 (4)C28—H28A0.9700
C6—C71.384 (4)C28—H28B0.9700
C6—H60.9400C28—H28C0.9700
C7—H70.9400C29—C301.519 (4)
C8—Zn1ii2.567 (3)C29—H29A0.9800
C9—C101.518 (4)C29—H29B0.9800
C10—C111.392 (4)C30—C311.519 (5)
C10—C12iii1.393 (4)C30—H30A0.9800
C11—C121.382 (4)C30—H30B0.9800
C11—H110.9400C31—C32'1.518 (8)
C12—C10iii1.393 (4)C31—C321.520 (7)
C12—H120.9400C31—H31A0.9800
C13—H13A0.9700C31—H31B0.9800
C13—H13B0.9700C31—H31C0.9800
C13—H13C0.9700C31—H31D0.9800
C14—H14A0.9700C32—H32A0.9700
C14—H14B0.9700C32—H32B0.9700
C14—H14C0.9700C32—H32C0.9700
C15—H15A0.9700C32'—H32D0.9700
C15—H15B0.9700C32'—H32E0.9700
C15—H15C0.9700C32'—H32F0.9700
C16—H16A0.9700N2—C331.283 (15)
C16—H16B0.9700N2—C341.316 (15)
C16—H16C0.9700C33—C34iv1.218 (16)
C17—C181.511 (4)C33—H330.9400
C17—H17A0.9800C34—C33iv1.218 (16)
C17—H17B0.9800C34—H340.9400
C18—C191.526 (4)
O1—Zn1—O5109.61 (9)C18—C19—H19B108.8
O1—Zn1—O3i138.01 (10)H19A—C19—H19B107.6
O5—Zn1—O3i100.27 (10)C19—C20—H20A109.5
O1—Zn1—O799.87 (10)C19—C20—H20B109.5
O5—Zn1—O7110.29 (10)H20A—C20—H20B109.5
O3i—Zn1—O796.49 (10)C19—C20—H20C109.5
O7—S1—C13108.55 (16)H20A—C20—H20C109.5
O7—S1—C14105.26 (19)H20B—C20—H20C109.5
C13—S1—C1497.7 (2)C22—C21—N1118.2 (3)
O8—S2—C16106.6 (9)C22—C21—H21A107.8
O8—S2—C15101.3 (7)N1—C21—H21A107.8
C16—S2—C15101.2 (11)C22—C21—H21B107.8
C1—O1—Zn1111.44 (18)N1—C21—H21B107.8
C8—O3—Zn1ii101.6 (2)H21A—C21—H21B107.1
C9—O5—Zn1126.77 (19)C21—C22—C23108.9 (3)
S1—O7—Zn1136.20 (14)C21—C22—H22A109.9
C25—N1—C21111.3 (3)C23—C22—H22A109.9
C25—N1—C17111.5 (3)C21—C22—H22B109.9
C21—N1—C17105.2 (2)C23—C22—H22B109.9
C25—N1—C29106.1 (2)H22A—C22—H22B108.3
C21—N1—C29111.3 (3)C22—C23—C24113.3 (3)
C17—N1—C29111.5 (2)C22—C23—H23A108.9
O2—C1—O1124.8 (3)C24—C23—H23A108.9
O2—C1—C2119.9 (3)C22—C23—H23B108.9
O1—C1—C2115.3 (3)C24—C23—H23B108.9
C3—C2—C7118.9 (3)H23A—C23—H23B107.7
C3—C2—C1121.3 (3)C23—C24—H24A109.5
C7—C2—C1119.7 (3)C23—C24—H24B109.5
C2—C3—C4120.5 (3)H24A—C24—H24B109.5
C2—C3—H3119.8C23—C24—H24C109.5
C4—C3—H3119.8H24A—C24—H24C109.5
C5—C4—C3120.7 (3)H24B—C24—H24C109.5
C5—C4—H4119.7N1—C25—C26115.4 (3)
C3—C4—H4119.7N1—C25—H25A108.4
C6—C5—C4118.8 (3)C26—C25—H25A108.4
C6—C5—C8121.3 (3)N1—C25—H25B108.4
C4—C5—C8119.9 (3)C26—C25—H25B108.4
C5—C6—C7120.5 (3)H25A—C25—H25B107.5
C5—C6—H6119.7C27—C26—C25109.4 (4)
C7—C6—H6119.7C27—C26—H26A109.8
C6—C7—C2120.6 (3)C25—C26—H26A109.8
C6—C7—H7119.7C27—C26—H26B109.8
C2—C7—H7119.7C25—C26—H26B109.8
O4—C8—O3123.5 (3)H26A—C26—H26B108.2
O4—C8—C5119.0 (3)C28—C27—C26115.0 (6)
O3—C8—C5117.5 (3)C28—C27—H27A108.5
O4—C8—Zn1ii74.17 (18)C26—C27—H27A108.5
O3—C8—Zn1ii49.51 (14)C28—C27—H27B108.5
C5—C8—Zn1ii166.2 (3)C26—C27—H27B108.5
O6—C9—O5126.2 (3)H27A—C27—H27B107.5
O6—C9—C10119.0 (3)C27—C28—H28A109.5
O5—C9—C10114.8 (2)C27—C28—H28B109.5
C11—C10—C12iii119.1 (3)H28A—C28—H28B109.5
C11—C10—C9121.0 (3)C27—C28—H28C109.5
C12iii—C10—C9119.9 (3)H28A—C28—H28C109.5
C12—C11—C10120.5 (3)H28B—C28—H28C109.5
C12—C11—H11119.7C30—C29—N1115.0 (3)
C10—C11—H11119.7C30—C29—H29A108.5
C11—C12—C10iii120.4 (3)N1—C29—H29A108.5
C11—C12—H12119.8C30—C29—H29B108.5
C10iii—C12—H12119.8N1—C29—H29B108.5
S1—C13—H13A109.5H29A—C29—H29B107.5
S1—C13—H13B109.5C29—C30—C31110.8 (3)
H13A—C13—H13B109.5C29—C30—H30A109.5
S1—C13—H13C109.5C31—C30—H30A109.5
H13A—C13—H13C109.5C29—C30—H30B109.5
H13B—C13—H13C109.5C31—C30—H30B109.5
S1—C14—H14A109.5H30A—C30—H30B108.1
S1—C14—H14B109.5C32'—C31—C30110.0 (10)
H14A—C14—H14B109.5C32'—C31—C32113.7 (10)
S1—C14—H14C109.5C30—C31—C32113.4 (6)
H14A—C14—H14C109.5C30—C31—H31A108.9
H14B—C14—H14C109.5C32—C31—H31A108.9
S2—C15—H15A109.5C30—C31—H31B108.9
S2—C15—H15B109.5C32—C31—H31B108.9
H15A—C15—H15B109.5H31A—C31—H31B107.7
S2—C15—H15C109.5C32'—C31—H31C109.7
H15A—C15—H15C109.5C30—C31—H31C109.7
H15B—C15—H15C109.5C32'—C31—H31D109.7
S2—C16—H16A109.5C30—C31—H31D109.7
S2—C16—H16B109.5H31C—C31—H31D108.2
H16A—C16—H16B109.5C31—C32—H32A109.5
S2—C16—H16C109.5C31—C32—H32B109.5
H16A—C16—H16C109.5H32A—C32—H32B109.5
H16B—C16—H16C109.5C31—C32—H32C109.5
C18—C17—N1116.6 (3)H32A—C32—H32C109.5
C18—C17—H17A108.1H32B—C32—H32C109.5
N1—C17—H17A108.1C31—C32'—H32D109.5
C18—C17—H17B108.1C31—C32'—H32E109.5
N1—C17—H17B108.1H32D—C32'—H32E109.5
H17A—C17—H17B107.3C31—C32'—H32F109.5
C17—C18—C19108.3 (3)H32D—C32'—H32F109.5
C17—C18—H18A110.0H32E—C32'—H32F109.5
C19—C18—H18A110.0C33—N2—C34112.6 (14)
C17—C18—H18B110.0C34iv—C33—N2121 (2)
C19—C18—H18B110.0C34iv—C33—H33119.3
H18A—C18—H18B108.4N2—C33—H33119.3
C20—C19—C18114.0 (3)C33iv—C34—N2126 (2)
C20—C19—H19A108.8C33iv—C34—H34117.1
C18—C19—H19A108.8N2—C34—H34117.1
C20—C19—H19B108.8
O5—Zn1—O1—C1170.8 (2)C6—C5—C8—Zn1ii7.4 (11)
O3i—Zn1—O1—C138.0 (3)C4—C5—C8—Zn1ii172.1 (7)
O7—Zn1—O1—C173.4 (2)Zn1—O5—C9—O612.2 (5)
C8i—Zn1—O1—C163.7 (2)Zn1—O5—C9—C10166.51 (19)
O1—Zn1—O5—C940.6 (3)O6—C9—C10—C11171.8 (3)
O3i—Zn1—O5—C9169.3 (3)O5—C9—C10—C119.4 (4)
O7—Zn1—O5—C968.4 (3)O6—C9—C10—C12iii9.7 (4)
C13—S1—O7—Zn125.2 (3)O5—C9—C10—C12iii169.1 (3)
C14—S1—O7—Zn178.6 (3)C12iii—C10—C11—C120.4 (5)
O1—Zn1—O7—S149.4 (3)C9—C10—C11—C12178.2 (3)
O5—Zn1—O7—S165.9 (3)C10—C11—C12—C10iii0.4 (5)
O3i—Zn1—O7—S1169.4 (2)C25—N1—C17—C1858.4 (4)
Zn1—O1—C1—O211.5 (4)C21—N1—C17—C18179.2 (3)
Zn1—O1—C1—C2165.9 (2)C29—N1—C17—C1860.0 (4)
O2—C1—C2—C3177.8 (3)N1—C17—C18—C19174.6 (3)
O1—C1—C2—C30.3 (5)C17—C18—C19—C20174.2 (4)
O2—C1—C2—C71.2 (5)C25—N1—C21—C2261.2 (4)
O1—C1—C2—C7176.3 (3)C17—N1—C21—C22178.0 (3)
C7—C2—C3—C41.3 (5)C29—N1—C21—C2257.0 (4)
C1—C2—C3—C4177.9 (3)N1—C21—C22—C23171.3 (3)
C2—C3—C4—C51.7 (5)C21—C22—C23—C24173.8 (3)
C3—C4—C5—C60.7 (5)C21—N1—C25—C2660.2 (4)
C3—C4—C5—C8179.8 (3)C17—N1—C25—C2657.0 (4)
C4—C5—C6—C70.6 (5)C29—N1—C25—C26178.6 (4)
C8—C5—C6—C7178.9 (3)N1—C25—C26—C27178.0 (5)
C5—C6—C7—C20.9 (6)C25—C26—C27—C28178.0 (9)
C3—C2—C7—C60.0 (6)C25—N1—C29—C30175.0 (3)
C1—C2—C7—C6176.7 (3)C21—N1—C29—C3063.8 (4)
Zn1ii—O3—C8—O44.9 (4)C17—N1—C29—C3053.5 (4)
Zn1ii—O3—C8—C5174.4 (2)N1—C29—C30—C31168.9 (3)
C6—C5—C8—O4168.5 (3)C29—C30—C31—C32'168.5 (12)
C4—C5—C8—O410.9 (5)C29—C30—C31—C3262.9 (8)
C6—C5—C8—O310.8 (5)C34—N2—C33—C34iv5 (4)
C4—C5—C8—O3169.7 (3)C33—N2—C34—C33iv5 (4)
Symmetry codes: (i) x+1/2, y+3/2, z1/2; (ii) x1/2, 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
Mr704.26
Crystal system, space groupMonoclinic, P21/n
Temperature (K)223
a, b, c (Å)11.1722 (5), 24.8188 (11), 13.9443 (6)
β (°) 97.968 (1)
V3)3829.2 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.80
Crystal size (mm)0.48 × 0.47 × 0.38
Data collection
DiffractometerBruker APEX area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.626, 0.752
No. of measured, independent and
observed [I > 2σ(I)] reflections
43211, 8752, 7451
Rint0.038
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.060, 0.181, 1.05
No. of reflections8752
No. of parameters427
No. of restraints105
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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).

Selected bond lengths (Å) top
Zn1—O11.959 (2)Zn1—O3i1.993 (2)
Zn1—O51.972 (2)Zn1—O72.047 (2)
Symmetry code: (i) x+1/2, y+3/2, z1/2.
 

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