Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802021293/lh6017sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802021293/lh6017Isup2.hkl |
CCDC reference: 202301
Disodium maleonitriledithiolate (Na2mnt) was prepared following the procedure in the literature (Davison et al., 1967). 4,4'-Bipyridinium chloride was prepared using 4,4'-bipyridine and one equivalent of dilute hydrochloride acid. A similar method for synthesizing [Bu4N]2[Zn(mnt)2] (Davison et al., 1967) was used to prepare [4,4'-bipyH]2[Zn(mnt)2]. Good quality light-red single crystals suitable for X-ray analysis were obtained about a week after dispersing ethyl ether into an acetonitrile solution of (I).
All H atoms were placed in geometrically calculated positions (C—H = 0.93 and 0.97 Å), with Uiso = 1.2Ueq(parent atom).
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SMART; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.
(C10H9N2)2[Zn(C4N2S2)2]·C2H3N | V = 1567.8 (3) Å3 |
Mr = 701.17 | Z = 2 |
Triclinic, P1 | F(000) = 716 |
Hall symbol: -P 1 | Dx = 1.485 Mg m−3 |
a = 9.591 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.086 (1) Å | θ = 2.5–25.0° |
c = 16.659 (2) Å | µ = 1.09 mm−1 |
α = 88.22 (1)° | T = 293 K |
β = 76.84 (1)° | Needle, light-red |
γ = 88.00 (1)° | 0.15 × 0.10 × 0.10 mm |
Bruker SMART CCD diffractometer | 5422 independent reflections |
Radiation source: fine-focus sealed tube | 3920 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.062 |
ω scans | θmax = 25.0°, θmin = 2.1° |
Absorption correction: empirical (using intensity measurements) (North et al., 1984) | h = −11→9 |
Tmin = 0.847, Tmax = 0.901 | k = −10→11 |
7842 measured reflections | l = −19→19 |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.025P)2] where P = (Fo2 + 2Fc2)/3 |
5422 reflections | (Δ/σ)max = 0.001 |
398 parameters | Δρmax = 0.41 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
(C10H9N2)2[Zn(C4N2S2)2]·C2H3N | γ = 88.00 (1)° |
Mr = 701.17 | V = 1567.8 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.591 (1) Å | Mo Kα radiation |
b = 10.086 (1) Å | µ = 1.09 mm−1 |
c = 16.659 (2) Å | T = 293 K |
α = 88.22 (1)° | 0.15 × 0.10 × 0.10 mm |
β = 76.84 (1)° |
Bruker SMART CCD diffractometer | 5422 independent reflections |
Absorption correction: empirical (using intensity measurements) (North et al., 1984) | 3920 reflections with I > 2σ(I) |
Tmin = 0.847, Tmax = 0.901 | Rint = 0.062 |
7842 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.41 e Å−3 |
5422 reflections | Δρmin = −0.28 e Å−3 |
398 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Zn1 | 0.91975 (4) | 0.22278 (4) | 0.19796 (2) | 0.05554 (14) | |
S1 | 1.06773 (10) | 0.12157 (9) | 0.08465 (5) | 0.0628 (2) | |
S2 | 0.79122 (9) | 0.34407 (9) | 0.11682 (5) | 0.0623 (2) | |
S3 | 0.81168 (11) | 0.08240 (10) | 0.30560 (5) | 0.0763 (3) | |
S4 | 1.02371 (9) | 0.34514 (8) | 0.28479 (4) | 0.0543 (2) | |
N1 | 1.1847 (3) | 0.2131 (3) | −0.13412 (17) | 0.0767 (9) | |
N2 | 0.8497 (3) | 0.4513 (3) | −0.09892 (18) | 0.0796 (9) | |
N3 | 0.8170 (3) | 0.0126 (3) | 0.51978 (18) | 0.0757 (9) | |
N4 | 1.0675 (4) | 0.3286 (4) | 0.49470 (18) | 0.0936 (11) | |
N5 | 0.4833 (3) | 0.6824 (3) | 0.08961 (15) | 0.0588 (7) | |
H5A | 0.4756 | 0.6427 | 0.1368 | 0.071* | 0.25 |
N6 | 0.5655 (3) | 1.0253 (3) | −0.28556 (14) | 0.0583 (7) | |
H6A | 0.5770 | 1.0714 | −0.3308 | 0.070* | 0.75 |
N7 | 0.5453 (3) | 0.1932 (3) | 0.58722 (14) | 0.0631 (8) | |
H7A | 0.5516 | 0.1507 | 0.6319 | 0.076* | 0.25 |
N8 | 0.4902 (3) | 0.5494 (2) | 0.22851 (14) | 0.0556 (7) | |
H8A | 0.4823 | 0.5967 | 0.1858 | 0.067* | 0.75 |
N9 | 0.7971 (4) | 0.2318 (4) | 0.7203 (2) | 0.0999 (12) | |
C1 | 1.1096 (4) | 0.2169 (3) | −0.0705 (2) | 0.0580 (8) | |
C2 | 1.0191 (3) | 0.2256 (3) | 0.01010 (17) | 0.0513 (8) | |
C3 | 0.9067 (3) | 0.3142 (3) | 0.02262 (17) | 0.0503 (8) | |
C4 | 0.8787 (3) | 0.3906 (3) | −0.0455 (2) | 0.0587 (9) | |
C5 | 1.0230 (4) | 0.2906 (3) | 0.4423 (2) | 0.0615 (9) | |
C6 | 0.9717 (3) | 0.2488 (3) | 0.37373 (16) | 0.0504 (8) | |
C7 | 0.8874 (3) | 0.1403 (3) | 0.38149 (17) | 0.0541 (8) | |
C8 | 0.8512 (3) | 0.0701 (3) | 0.45923 (19) | 0.0594 (9) | |
C9 | 0.5818 (4) | 0.6421 (3) | 0.02533 (19) | 0.0608 (9) | |
H9 | 0.6422 | 0.5706 | 0.0321 | 0.073* | |
C10 | 0.5982 (3) | 0.7022 (3) | −0.05117 (17) | 0.0532 (8) | |
H10 | 0.6674 | 0.6709 | −0.0956 | 0.064* | |
C11 | 0.5102 (3) | 0.8097 (3) | −0.06097 (16) | 0.0434 (7) | |
C12 | 0.4076 (3) | 0.8492 (3) | 0.00666 (16) | 0.0519 (8) | |
H12 | 0.3456 | 0.9205 | 0.0019 | 0.062* | |
C13 | 0.3967 (4) | 0.7838 (3) | 0.08111 (17) | 0.0584 (9) | |
H13 | 0.3269 | 0.8114 | 0.1264 | 0.070* | |
C14 | 0.4437 (4) | 1.0370 (3) | −0.23035 (18) | 0.0562 (8) | |
H14 | 0.3722 | 1.0950 | −0.2410 | 0.067* | |
C15 | 0.4203 (3) | 0.9660 (3) | −0.15794 (16) | 0.0520 (8) | |
H15 | 0.3330 | 0.9740 | −0.1199 | 0.062* | |
C16 | 0.5280 (3) | 0.8816 (3) | −0.14158 (16) | 0.0434 (7) | |
C17 | 0.6534 (3) | 0.8714 (3) | −0.20085 (16) | 0.0534 (8) | |
H17 | 0.7271 | 0.8145 | −0.1920 | 0.064* | |
C18 | 0.6704 (4) | 0.9448 (3) | −0.27331 (17) | 0.0595 (9) | |
H18 | 0.7553 | 0.9377 | −0.3134 | 0.071* | |
C19 | 0.4485 (4) | 0.1632 (3) | 0.54675 (19) | 0.0661 (10) | |
H19 | 0.3863 | 0.0955 | 0.5680 | 0.079* | |
C20 | 0.4343 (4) | 0.2266 (3) | 0.47433 (18) | 0.0604 (9) | |
H20 | 0.3652 | 0.2015 | 0.4470 | 0.073* | |
C21 | 0.5257 (3) | 0.3289 (3) | 0.44337 (16) | 0.0460 (7) | |
C22 | 0.6255 (3) | 0.3600 (3) | 0.48591 (16) | 0.0521 (8) | |
H22 | 0.6885 | 0.4279 | 0.4666 | 0.063* | |
C23 | 0.6329 (4) | 0.2907 (3) | 0.55766 (17) | 0.0581 (9) | |
H23 | 0.7014 | 0.3131 | 0.5861 | 0.070* | |
C24 | 0.6120 (3) | 0.5451 (3) | 0.25274 (17) | 0.0555 (8) | |
H24 | 0.6889 | 0.5924 | 0.2227 | 0.067* | |
C25 | 0.6279 (3) | 0.4727 (3) | 0.32097 (16) | 0.0531 (8) | |
H25 | 0.7149 | 0.4707 | 0.3368 | 0.064* | |
C26 | 0.5141 (3) | 0.4025 (3) | 0.36623 (15) | 0.0431 (7) | |
C27 | 0.3889 (3) | 0.4082 (3) | 0.33878 (17) | 0.0533 (8) | |
H27 | 0.3099 | 0.3621 | 0.3675 | 0.064* | |
C28 | 0.3801 (4) | 0.4811 (3) | 0.26978 (17) | 0.0572 (8) | |
H28 | 0.2955 | 0.4828 | 0.2514 | 0.069* | |
C29 | 0.9131 (5) | 0.2524 (4) | 0.7086 (2) | 0.0702 (10) | |
C30 | 1.0621 (4) | 0.2822 (4) | 0.6940 (2) | 0.0901 (12) | |
H30A | 1.0973 | 0.3052 | 0.6368 | 0.135* | |
H30B | 1.1149 | 0.2059 | 0.7084 | 0.135* | |
H30C | 1.0738 | 0.3554 | 0.7272 | 0.135* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0570 (2) | 0.0684 (3) | 0.0416 (2) | −0.00790 (19) | −0.01190 (17) | 0.00498 (17) |
S1 | 0.0768 (6) | 0.0640 (6) | 0.0471 (4) | 0.0075 (5) | −0.0145 (4) | 0.0019 (4) |
S2 | 0.0538 (5) | 0.0840 (7) | 0.0483 (4) | 0.0032 (5) | −0.0111 (4) | 0.0029 (4) |
S3 | 0.0933 (7) | 0.0840 (7) | 0.0547 (5) | −0.0366 (6) | −0.0206 (5) | 0.0159 (5) |
S4 | 0.0548 (5) | 0.0620 (5) | 0.0469 (4) | −0.0085 (4) | −0.0130 (4) | 0.0045 (4) |
N1 | 0.086 (2) | 0.085 (2) | 0.0505 (16) | 0.0032 (18) | 0.0002 (17) | 0.0075 (16) |
N2 | 0.086 (2) | 0.089 (2) | 0.0659 (18) | −0.0002 (18) | −0.0234 (18) | 0.0176 (17) |
N3 | 0.072 (2) | 0.085 (2) | 0.0616 (18) | 0.0034 (17) | −0.0019 (16) | 0.0172 (17) |
N4 | 0.115 (3) | 0.113 (3) | 0.0601 (19) | −0.004 (2) | −0.034 (2) | −0.0041 (19) |
N5 | 0.0713 (19) | 0.0681 (19) | 0.0423 (15) | −0.0221 (16) | −0.0237 (15) | 0.0208 (14) |
N6 | 0.0751 (19) | 0.0627 (18) | 0.0387 (14) | −0.0054 (15) | −0.0183 (14) | 0.0187 (13) |
N7 | 0.078 (2) | 0.070 (2) | 0.0375 (14) | 0.0151 (17) | −0.0106 (15) | 0.0199 (13) |
N8 | 0.0724 (19) | 0.0597 (17) | 0.0349 (13) | −0.0077 (15) | −0.0143 (13) | 0.0198 (12) |
N9 | 0.093 (3) | 0.119 (3) | 0.089 (2) | −0.027 (2) | −0.018 (2) | 0.000 (2) |
C1 | 0.064 (2) | 0.056 (2) | 0.054 (2) | −0.0075 (17) | −0.0144 (18) | 0.0054 (17) |
C2 | 0.061 (2) | 0.057 (2) | 0.0377 (15) | −0.0126 (17) | −0.0122 (15) | 0.0031 (14) |
C3 | 0.0518 (19) | 0.059 (2) | 0.0419 (16) | −0.0109 (16) | −0.0145 (15) | 0.0046 (15) |
C4 | 0.054 (2) | 0.068 (2) | 0.0540 (19) | −0.0071 (17) | −0.0131 (17) | 0.0038 (18) |
C5 | 0.060 (2) | 0.074 (2) | 0.0475 (18) | 0.0026 (18) | −0.0079 (17) | 0.0014 (18) |
C6 | 0.0452 (18) | 0.066 (2) | 0.0391 (15) | 0.0077 (16) | −0.0080 (14) | −0.0026 (15) |
C7 | 0.0519 (19) | 0.063 (2) | 0.0445 (17) | 0.0031 (17) | −0.0056 (15) | 0.0059 (15) |
C8 | 0.055 (2) | 0.071 (2) | 0.0478 (18) | 0.0044 (17) | −0.0044 (16) | 0.0083 (18) |
C9 | 0.074 (2) | 0.057 (2) | 0.057 (2) | −0.0033 (18) | −0.0290 (19) | 0.0237 (17) |
C10 | 0.062 (2) | 0.055 (2) | 0.0423 (16) | −0.0027 (17) | −0.0151 (15) | 0.0157 (15) |
C11 | 0.0505 (18) | 0.0471 (18) | 0.0350 (15) | −0.0102 (15) | −0.0148 (14) | 0.0104 (13) |
C12 | 0.064 (2) | 0.0516 (19) | 0.0412 (16) | −0.0065 (16) | −0.0141 (16) | 0.0100 (14) |
C13 | 0.068 (2) | 0.070 (2) | 0.0373 (17) | −0.0145 (19) | −0.0130 (16) | 0.0110 (16) |
C14 | 0.067 (2) | 0.056 (2) | 0.0491 (18) | 0.0029 (17) | −0.0240 (17) | 0.0166 (16) |
C15 | 0.0544 (19) | 0.062 (2) | 0.0398 (16) | −0.0013 (16) | −0.0130 (15) | 0.0133 (15) |
C16 | 0.0553 (18) | 0.0433 (17) | 0.0344 (14) | −0.0042 (14) | −0.0170 (14) | 0.0074 (13) |
C17 | 0.063 (2) | 0.057 (2) | 0.0398 (16) | 0.0044 (16) | −0.0137 (16) | 0.0108 (15) |
C18 | 0.067 (2) | 0.071 (2) | 0.0387 (16) | 0.0004 (19) | −0.0089 (16) | 0.0126 (16) |
C19 | 0.068 (2) | 0.069 (2) | 0.0543 (19) | −0.0067 (19) | −0.0039 (19) | 0.0314 (18) |
C20 | 0.066 (2) | 0.065 (2) | 0.0504 (18) | −0.0059 (18) | −0.0175 (17) | 0.0232 (17) |
C21 | 0.0520 (19) | 0.0488 (19) | 0.0335 (14) | 0.0041 (15) | −0.0041 (14) | 0.0104 (13) |
C22 | 0.065 (2) | 0.0502 (19) | 0.0400 (16) | 0.0013 (16) | −0.0118 (16) | 0.0088 (14) |
C23 | 0.072 (2) | 0.063 (2) | 0.0413 (17) | 0.0115 (18) | −0.0185 (16) | 0.0054 (16) |
C24 | 0.056 (2) | 0.069 (2) | 0.0389 (16) | −0.0107 (17) | −0.0061 (15) | 0.0174 (15) |
C25 | 0.0526 (19) | 0.067 (2) | 0.0392 (16) | −0.0047 (16) | −0.0101 (15) | 0.0124 (15) |
C26 | 0.0548 (19) | 0.0419 (17) | 0.0308 (13) | −0.0026 (14) | −0.0073 (14) | 0.0092 (12) |
C27 | 0.059 (2) | 0.057 (2) | 0.0433 (16) | −0.0161 (16) | −0.0107 (16) | 0.0168 (15) |
C28 | 0.063 (2) | 0.067 (2) | 0.0462 (17) | −0.0095 (18) | −0.0227 (16) | 0.0179 (16) |
C29 | 0.093 (3) | 0.065 (3) | 0.056 (2) | −0.010 (2) | −0.024 (2) | 0.0030 (18) |
C30 | 0.084 (3) | 0.095 (3) | 0.097 (3) | −0.009 (2) | −0.035 (3) | 0.013 (2) |
Zn1—S3 | 2.3223 (9) | C11—C12 | 1.376 (4) |
Zn1—S2 | 2.3225 (10) | C11—C16 | 1.484 (4) |
Zn1—S1 | 2.3277 (10) | C12—C13 | 1.371 (4) |
Zn1—S4 | 2.3373 (9) | C12—H12 | 0.9300 |
S1—C2 | 1.735 (3) | C13—H13 | 0.9300 |
S2—C3 | 1.731 (3) | C14—C15 | 1.361 (4) |
S3—C7 | 1.721 (3) | C14—H14 | 0.9300 |
S4—C6 | 1.731 (3) | C15—C16 | 1.385 (4) |
N1—C1 | 1.139 (4) | C15—H15 | 0.9300 |
N2—C4 | 1.145 (4) | C16—C17 | 1.374 (4) |
N3—C8 | 1.135 (4) | C17—C18 | 1.377 (4) |
N4—C5 | 1.137 (4) | C17—H17 | 0.9300 |
N5—C13 | 1.320 (4) | C18—H18 | 0.9300 |
N5—C9 | 1.321 (4) | C19—C20 | 1.380 (4) |
N5—H5A | 0.8600 | C19—H19 | 0.9300 |
N6—C14 | 1.316 (4) | C20—C21 | 1.386 (4) |
N6—C18 | 1.318 (4) | C20—H20 | 0.9300 |
N6—H6A | 0.8600 | C21—C22 | 1.364 (4) |
N7—C19 | 1.313 (4) | C21—C26 | 1.488 (4) |
N7—C23 | 1.325 (4) | C22—C23 | 1.380 (4) |
N7—H7A | 0.8600 | C22—H22 | 0.9300 |
N8—C24 | 1.318 (4) | C23—H23 | 0.9300 |
N8—C28 | 1.324 (3) | C24—C25 | 1.367 (4) |
N8—H8A | 0.8600 | C24—H24 | 0.9300 |
N9—C29 | 1.111 (4) | C25—C26 | 1.381 (4) |
C1—C2 | 1.426 (4) | C25—H25 | 0.9300 |
C2—C3 | 1.358 (4) | C26—C27 | 1.378 (4) |
C3—C4 | 1.422 (4) | C27—C28 | 1.362 (4) |
C5—C6 | 1.424 (5) | C27—H27 | 0.9300 |
C6—C7 | 1.368 (4) | C28—H28 | 0.9300 |
C7—C8 | 1.434 (4) | C29—C30 | 1.435 (5) |
C9—C10 | 1.372 (4) | C30—H30A | 0.9600 |
C9—H9 | 0.9300 | C30—H30B | 0.9600 |
C10—C11 | 1.380 (4) | C30—H30C | 0.9600 |
C10—H10 | 0.9300 | ||
S3—Zn1—S2 | 122.76 (4) | N6—C14—C15 | 121.3 (3) |
S3—Zn1—S1 | 116.27 (4) | N6—C14—H14 | 119.3 |
S2—Zn1—S1 | 92.95 (3) | C15—C14—H14 | 119.3 |
S3—Zn1—S4 | 92.22 (3) | C14—C15—C16 | 119.2 (3) |
S2—Zn1—S4 | 116.18 (4) | C14—C15—H15 | 120.4 |
S1—Zn1—S4 | 118.89 (3) | C16—C15—H15 | 120.4 |
C2—S1—Zn1 | 96.49 (11) | C17—C16—C15 | 117.9 (2) |
C3—S2—Zn1 | 97.14 (11) | C17—C16—C11 | 121.4 (3) |
C7—S3—Zn1 | 98.70 (11) | C15—C16—C11 | 120.7 (3) |
C6—S4—Zn1 | 98.18 (11) | C16—C17—C18 | 120.3 (3) |
C13—N5—C9 | 119.7 (3) | C16—C17—H17 | 119.8 |
C13—N5—H5A | 120.1 | C18—C17—H17 | 119.8 |
C9—N5—H5A | 120.1 | N6—C18—C17 | 119.6 (3) |
C14—N6—C18 | 121.7 (3) | N6—C18—H18 | 120.2 |
C14—N6—H6A | 119.1 | C17—C18—H18 | 120.2 |
C18—N6—H6A | 119.1 | N7—C19—C20 | 123.5 (3) |
C19—N7—C23 | 118.4 (3) | N7—C19—H19 | 118.2 |
C19—N7—H7A | 120.8 | C20—C19—H19 | 118.2 |
C23—N7—H7A | 120.8 | C19—C20—C21 | 118.2 (3) |
C24—N8—C28 | 120.1 (2) | C19—C20—H20 | 120.9 |
C24—N8—H8A | 119.9 | C21—C20—H20 | 120.9 |
C28—N8—H8A | 119.9 | C22—C21—C20 | 118.0 (3) |
N1—C1—C2 | 177.7 (4) | C22—C21—C26 | 121.3 (3) |
C3—C2—C1 | 118.7 (3) | C20—C21—C26 | 120.7 (3) |
C3—C2—S1 | 125.9 (2) | C21—C22—C23 | 120.0 (3) |
C1—C2—S1 | 115.4 (2) | C21—C22—H22 | 120.0 |
C2—C3—C4 | 119.2 (3) | C23—C22—H22 | 120.0 |
C2—C3—S2 | 125.1 (2) | N7—C23—C22 | 121.9 (3) |
C4—C3—S2 | 115.7 (2) | N7—C23—H23 | 119.1 |
N2—C4—C3 | 176.9 (4) | C22—C23—H23 | 119.1 |
N4—C5—C6 | 176.7 (4) | N8—C24—C25 | 121.6 (3) |
C7—C6—C5 | 120.0 (3) | N8—C24—H24 | 119.2 |
C7—C6—S4 | 125.1 (2) | C25—C24—H24 | 119.2 |
C5—C6—S4 | 114.8 (2) | C24—C25—C26 | 119.6 (3) |
C6—C7—C8 | 119.3 (3) | C24—C25—H25 | 120.2 |
C6—C7—S3 | 125.3 (2) | C26—C25—H25 | 120.2 |
C8—C7—S3 | 115.3 (3) | C27—C26—C25 | 117.3 (2) |
N3—C8—C7 | 176.8 (4) | C27—C26—C21 | 121.9 (3) |
N5—C9—C10 | 122.3 (3) | C25—C26—C21 | 120.8 (3) |
N5—C9—H9 | 118.9 | C28—C27—C26 | 120.4 (3) |
C10—C9—H9 | 118.9 | C28—C27—H27 | 119.8 |
C9—C10—C11 | 118.9 (3) | C26—C27—H27 | 119.8 |
C9—C10—H10 | 120.6 | N8—C28—C27 | 121.0 (3) |
C11—C10—H10 | 120.6 | N8—C28—H28 | 119.5 |
C12—C11—C10 | 117.8 (2) | C27—C28—H28 | 119.5 |
C12—C11—C16 | 121.3 (3) | N9—C29—C30 | 178.6 (5) |
C10—C11—C16 | 120.8 (3) | C29—C30—H30A | 109.5 |
C13—C12—C11 | 120.1 (3) | C29—C30—H30B | 109.5 |
C13—C12—H12 | 119.9 | H30A—C30—H30B | 109.5 |
C11—C12—H12 | 119.9 | C29—C30—H30C | 109.5 |
N5—C13—C12 | 121.2 (3) | H30A—C30—H30C | 109.5 |
N5—C13—H13 | 119.4 | H30B—C30—H30C | 109.5 |
C12—C13—H13 | 119.4 |
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5A···N8 | 0.86 | 1.80 | 2.651 (3) | 170 |
N8—H8A···N5 | 0.86 | 1.80 | 2.651 (3) | 173 |
N6—H6A···N7i | 0.86 | 1.88 | 2.709 (3) | 162 |
N7—H7A···N6ii | 0.86 | 1.86 | 2.709 (3) | 167 |
Symmetry codes: (i) x, y+1, z−1; (ii) x, y−1, z+1. |
Experimental details
Crystal data | |
Chemical formula | (C10H9N2)2[Zn(C4N2S2)2]·C2H3N |
Mr | 701.17 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 9.591 (1), 10.086 (1), 16.659 (2) |
α, β, γ (°) | 88.22 (1), 76.84 (1), 88.00 (1) |
V (Å3) | 1567.8 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.09 |
Crystal size (mm) | 0.15 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART CCD diffractometer |
Absorption correction | Empirical (using intensity measurements) (North et al., 1984) |
Tmin, Tmax | 0.847, 0.901 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7842, 5422, 3920 |
Rint | 0.062 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.088, 1.01 |
No. of reflections | 5422 |
No. of parameters | 398 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.41, −0.28 |
Computer programs: SMART (Bruker, 1998), SMART, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.
Zn1—S3 | 2.3223 (9) | Zn1—S1 | 2.3277 (10) |
Zn1—S2 | 2.3225 (10) | Zn1—S4 | 2.3373 (9) |
S3—Zn1—S2 | 122.76 (4) | S3—Zn1—S4 | 92.22 (3) |
S3—Zn1—S1 | 116.27 (4) | S2—Zn1—S4 | 116.18 (4) |
S2—Zn1—S1 | 92.95 (3) | S1—Zn1—S4 | 118.89 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5A···N8 | 0.86 | 1.80 | 2.651 (3) | 170 |
N8—H8A···N5 | 0.86 | 1.80 | 2.651 (3) | 173 |
N6—H6A···N7i | 0.86 | 1.88 | 2.709 (3) | 162 |
N7—H7A···N6ii | 0.86 | 1.86 | 2.709 (3) | 167 |
Symmetry codes: (i) x, y+1, z−1; (ii) x, y−1, z+1. |
In recent years, the principles of supramolecular chemistry, in which a great deal new concepts concern intermolecular non-covalent interactions, such as hydrogen-bonding and π-π-stacking interactions, have been introduced into the area of materials science (Saadeh et al., 2000; Lawrence et al., 1999). Some of the resulting materials have exhibited novel properties (Gardner et al., 1995; Venkataraman et al., 1995; Fujita et al., 1994; Yaghi et al., 1995).
More recently, we have paid attention to the construction of [M(mnt)2]− (M = NiIII, PdIII and PtIII) with pyridinium derivatives, in which the CN groups of the mnt2− ligand and the H—N groups of the pyridinium derivatives may exist with hydrogen-bonding interactions, and have found that there are strong bifurcated hydrogen-bonding interactions between these molecules (Ren Chen et al., 2002; Ren, Lu et al., 2002). We have obtained one-dimensional to three-dimensional molecular magnets based on this class of building block. It has been known that a number of salts consisting of pyridinium and some anions with tetrahedral configurations, namely, tetrafluoroborate, perchlorate, periodate, fluorosulfonate and perrhenate, appear to be ferroelectric (Czarnecki et al., 1994a,b; Wasicki et al., 1997; Pajak et al., 1998, 2000, 2002; Szafranski et al., 2002). It is also worth noting that there exist bifuracated hydrogen-bonding interactions between O or F atoms of anions and H atom of pyridiniums in those ferroelectric materials referred to above. The molecular geometries of the anion of [M(mnt)2]2−, where M denotes Zn2+ or Cd2+ ions, are tetrahedral and similar to those inorganic anions referred to above, so it is expected that new ferroelectric material families based on ion-pair complexes, which form bipyridinum derivatives and [Zn(mnt)2]2− ([Cd(mnt)2]2−) can be obtained. In this communication, we report the crystal structure of [4,4'-bipyH]2[Zn(mnt)2], (I).
The structure of (I) is composed of 4,4'-bipyH+ monovalent cations and [Zn(mnt)2]2−, together with an acetonitrile solvent molecule (Fig. 1). The anion consists a ZnII ion surrounded by four S atoms of two mnt2− ligands, forming a distorted tetrahedron (ZnS4). The Zn—S distances range from 2.3223 (9) to 2.3373 (9) Å, with internal S—Zn—S chelating angles ranging between 92.22 (3) and 92.95 (3)° (Table 1). The dihedral angle between the Zn1/S1/C2/C3/S2 and Zn1/S3/C6/C7/S4 least-squares planes is 87.61 (4)° and hence almost perpendicular to each other. These results are in agreement with that of [Et4N]2[Zn(mnt)2] (Stach et al., 1986). In (I), the cations of the two bipyridyl rings twist away from one another, and the dihedral angles between the two bipyridyl rings of 4,4'-bipyridine is 18.9 (2)° for the molecule containing N5, and 22.2 (2)° for the molecule containing N7. The H atoms bonded to the N atoms of 4,4'-bipyridine are disordered, this was also found in other compounds containing bipyridine (Lough et al., 2000). The relative occupancies of the H atoms are 0.25/0.75 for H5A/H6A and 0.25/0.75 for H7A/H8A. The adjacent 4,4'-bipyridinium molecules are linked by strong hydrogen-bonding interactions to form an one-dimensional chains along the c axis of the unit cell (Fig. 2). The corresponding hydrogen-bonding parameters are listed in Table 2, but there are no hydrogen-bonding interactions between N atoms of CN (mnt) and N atoms of 4,4'-bipyridinium. The anions and cations form alternating layers, which are nearly parallel bc plane of the crystallographic unit cell (Fig. 3).