Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680704055X/bg3051sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680704055X/bg3051Isup2.hkl |
CCDC reference: 655854
The N-heterocycle was prepared according to a reported procedure (Chawla & Gill, 1997). Zinc nitrate hexahydrate (0.074 g, 0.25 mmol), succinic acid (0.0148 g, 0.125 mmol),1, 3-bis(benzimidazol-2-ylmethyl)benzene (0.039 g, 0.125 mmol), ethanol (2 ml) and water (15 ml) were placed in a 23 -ml, Teflon-lined, stainless-steel Parr bomb. (Neither sodium hydroxide nor postassium hydroxide was added.) The bomb was heated at 433 K for 5 days and cooled to room temperature at 5 K h-1. Brown block-shaped crystals picked out by hand (in 10% yield).
The amino H-atoms were located in a difference Fourier map, and were refined with a distance restraint of 0.85 (1) Å; their temperature factors were freely refined. The carbon-bound H-atoms were generated geometrically (C–H 0.93 to 0.97 Å); they were included in the refinement in the riding model approximation, with U(H) set to 1.2Ueq(C).
The reaction between 1,3-bis(benzimidazol-2-ylmethyl)benzene and zinc terephthalate affords the expected 1:1 adduct as a methanol solvate. The compound adopts a layer structure owing to bridging by both the N-heterocycle and the terephthalate dianion (Meng et al., 2007). The succinate dianion is not rigid like the terephthalate dianion. It typically lies on a center-of-inversion in most metal succinates (CSD Version 5.28, May 2007) and functions as a bridging dianion; however, the succinate group chelates to the zinc atom in the zinc succinate adduct of this heterocycle. Both the cation and the dianion lie on a twofold rotation axis in the monomeric compound (Scheme I, Fig. 1).
Chelation by a succinate group has been documented in only three cases: the polymeric hexaaquatricobalt(III) (Forster et al., 2004) and monomeric tetraaquanickel(II) (Gupta & Devi, 1978) derivatives, and the salt, diaquabis(phenanthrolinato)manganese(II) bis(phenanthroline)succinatomanganate(II) succinate heptahydrate (Zheng, Lin & Sun, 2001). The title compound has the metal center connected to two N-heterocycles; expansion of the coordination number is precluded as the second tertiary N-donor site of both ligands is already engaged in hydrogen bonding interactions. This possibly forces the succinate group to bind in the uncommon chelating mode. The amino –NH group of one heterocycle in hydrogen-bonded to the carbonyl oxygen atom [3.158 (2) Å]; that of the second heterocycle engages in an intermolecular N–H···N interaction [2.839 (2) Å] to furnish a linear chain motif.
The zinc-oxygen bond distance is similar to that found in zinc succinate itself; the metal center in this compound shows tetrahedral coordination and the anion behaves as a bridging group to result in the formation of a polymeric network motif (Bowden et al., 2003; Zheng, Peters & von Schnering, 2001). The distance is, however, shorter than those found in other higher-than-four-coordinateamine adducts (Tao et al., 2001; Yin et al., 2002; Ying et al., 2003; Zeng et al., 2007; Zheng, 2004; Zheng et al., 2002; Zhou et al., 2005).
For the structure of the adduct the N-heterocycle with zinc terephthalate, see Meng et al. (2007). For the rare examples of chelation by a succinate group, see Forster et al. (2004); Gupta & Devi (1978); Zheng, Lin & Sun (2001). For the structure of zinc succinate, see Bowden et al. (2003); Zheng, Peters & von Schnering (2001). For higher-than-four-coordinate amine adducts of zinc succinate, see Tao et al. (2001); Yin et al. (2002); Ying et al. (2003); Zeng et al. (2007); Zheng (2004); Zheng et al. (2002); Zhou et al. (2005). For the synthesis of the N-heterocycle, see Chawla & Gill (1997).
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).
[Zn(C4H4O4)(C20H14N4)2] | F(000) = 1656 |
Mr = 802.15 | Dx = 1.458 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 4938 reflections |
a = 21.453 (2) Å | θ = 2.3–25.0° |
b = 10.272 (1) Å | µ = 0.73 mm−1 |
c = 17.587 (2) Å | T = 291 K |
β = 109.411 (1)° | Block, brown |
V = 3655.2 (6) Å3 | 0.46 × 0.34 × 0.22 mm |
Z = 4 |
Bruker APEXII area-detector diffractometer | 4186 independent reflections |
Radiation source: fine-focus sealed tube | 3354 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
φ and ω scans | θmax = 27.5°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −27→27 |
Tmin = 0.687, Tmax = 0.856 | k = −13→13 |
14308 measured reflections | l = −22→22 |
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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.103 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0519P)2 + 1.7754P] where P = (Fo2 + 2Fc2)/3 |
4186 reflections | (Δ/σ)max = 0.001 |
266 parameters | Δρmax = 0.41 e Å−3 |
2 restraints | Δρmin = −0.24 e Å−3 |
[Zn(C4H4O4)(C20H14N4)2] | V = 3655.2 (6) Å3 |
Mr = 802.15 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 21.453 (2) Å | µ = 0.73 mm−1 |
b = 10.272 (1) Å | T = 291 K |
c = 17.587 (2) Å | 0.46 × 0.34 × 0.22 mm |
β = 109.411 (1)° |
Bruker APEXII area-detector diffractometer | 4186 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3354 reflections with I > 2σ(I) |
Tmin = 0.687, Tmax = 0.856 | Rint = 0.034 |
14308 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 2 restraints |
wR(F2) = 0.103 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.41 e Å−3 |
4186 reflections | Δρmin = −0.24 e Å−3 |
266 parameters |
x | y | z | Uiso*/Ueq | ||
Zn1 | 0.5000 | 0.19880 (3) | 0.7500 | 0.04623 (12) | |
O1 | 0.53016 (8) | 0.09147 (13) | 0.67838 (9) | 0.0592 (4) | |
O2 | 0.56800 (11) | −0.08025 (16) | 0.63523 (13) | 0.0907 (6) | |
N1 | 0.42681 (7) | 0.32303 (14) | 0.69164 (9) | 0.0425 (3) | |
N2 | 0.38107 (8) | 0.50277 (17) | 0.62655 (10) | 0.0507 (4) | |
H2n | 0.3757 (12) | 0.5670 (17) | 0.5949 (12) | 0.072 (8)* | |
N3 | 0.59125 (9) | 0.13643 (17) | 0.53998 (11) | 0.0522 (4) | |
H3n | 0.5727 (11) | 0.103 (2) | 0.5708 (13) | 0.074 (8)* | |
N4 | 0.63664 (8) | 0.28509 (16) | 0.48210 (10) | 0.0512 (4) | |
C1 | 0.36481 (9) | 0.33981 (19) | 0.70053 (11) | 0.0440 (4) | |
C2 | 0.33136 (10) | 0.2633 (2) | 0.74022 (13) | 0.0553 (5) | |
H2 | 0.3501 | 0.1882 | 0.7680 | 0.066* | |
C3 | 0.26909 (12) | 0.3049 (3) | 0.73619 (15) | 0.0675 (6) | |
H3 | 0.2454 | 0.2565 | 0.7620 | 0.081* | |
C4 | 0.24068 (11) | 0.4171 (3) | 0.69462 (15) | 0.0727 (7) | |
H4 | 0.1986 | 0.4415 | 0.6935 | 0.087* | |
C5 | 0.27305 (11) | 0.4924 (3) | 0.65541 (15) | 0.0651 (6) | |
H5 | 0.2539 | 0.5670 | 0.6274 | 0.078* | |
C6 | 0.33596 (10) | 0.4519 (2) | 0.65957 (12) | 0.0494 (4) | |
C7 | 0.43377 (9) | 0.42315 (17) | 0.64697 (11) | 0.0428 (4) | |
C8 | 0.49252 (9) | 0.44713 (18) | 0.62339 (11) | 0.0440 (4) | |
C9 | 0.51755 (9) | 0.34797 (18) | 0.58804 (11) | 0.0440 (4) | |
H9 | 0.4968 | 0.2672 | 0.5787 | 0.053* | |
C10 | 0.57367 (9) | 0.36922 (19) | 0.56657 (11) | 0.0453 (4) | |
C11 | 0.60443 (10) | 0.4902 (2) | 0.58136 (13) | 0.0530 (5) | |
H11 | 0.6423 | 0.5046 | 0.5680 | 0.064* | |
C12 | 0.57930 (11) | 0.5891 (2) | 0.61573 (13) | 0.0578 (5) | |
H12 | 0.6001 | 0.6698 | 0.6251 | 0.069* | |
C13 | 0.52322 (10) | 0.56822 (19) | 0.63630 (12) | 0.0517 (5) | |
H13 | 0.5060 | 0.6353 | 0.6588 | 0.062* | |
C14 | 0.60041 (9) | 0.2648 (2) | 0.52894 (11) | 0.0464 (4) | |
C15 | 0.62476 (10) | 0.0671 (2) | 0.49841 (12) | 0.0523 (5) | |
C16 | 0.63407 (12) | −0.0656 (2) | 0.49111 (15) | 0.0683 (6) | |
H16 | 0.6147 | −0.1273 | 0.5148 | 0.082* | |
C17 | 0.67363 (13) | −0.1007 (3) | 0.44680 (16) | 0.0766 (7) | |
H17 | 0.6812 | −0.1886 | 0.4405 | 0.092* | |
C18 | 0.70266 (12) | −0.0080 (3) | 0.41107 (16) | 0.0782 (8) | |
H18 | 0.7290 | −0.0358 | 0.3816 | 0.094* | |
C19 | 0.69331 (11) | 0.1232 (3) | 0.41826 (15) | 0.0682 (6) | |
H19 | 0.7127 | 0.1844 | 0.3942 | 0.082* | |
C20 | 0.65334 (10) | 0.1610 (2) | 0.46324 (12) | 0.0520 (5) | |
C21 | 0.54524 (11) | −0.02897 (19) | 0.68279 (14) | 0.0541 (5) | |
C22 | 0.53548 (11) | −0.1074 (2) | 0.75113 (15) | 0.0629 (6) | |
H22A | 0.5632 | −0.0715 | 0.8022 | 0.075* | |
H22B | 0.5495 | −0.1965 | 0.7479 | 0.075* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0571 (2) | 0.03012 (16) | 0.0570 (2) | 0.000 | 0.02633 (15) | 0.000 |
O1 | 0.0847 (10) | 0.0345 (7) | 0.0713 (10) | 0.0041 (7) | 0.0431 (8) | 0.0002 (6) |
O2 | 0.1373 (17) | 0.0521 (9) | 0.1215 (16) | 0.0084 (10) | 0.0953 (15) | −0.0045 (10) |
N1 | 0.0465 (8) | 0.0398 (8) | 0.0440 (8) | −0.0014 (6) | 0.0189 (7) | −0.0029 (6) |
N2 | 0.0524 (9) | 0.0507 (10) | 0.0522 (10) | 0.0089 (8) | 0.0216 (8) | 0.0085 (8) |
N3 | 0.0616 (10) | 0.0489 (10) | 0.0520 (10) | −0.0035 (8) | 0.0267 (8) | −0.0015 (8) |
N4 | 0.0473 (9) | 0.0584 (10) | 0.0526 (10) | 0.0051 (7) | 0.0229 (7) | 0.0056 (8) |
C1 | 0.0455 (10) | 0.0478 (10) | 0.0410 (10) | −0.0036 (8) | 0.0176 (8) | −0.0075 (8) |
C2 | 0.0577 (12) | 0.0611 (12) | 0.0519 (12) | −0.0071 (10) | 0.0247 (10) | −0.0024 (10) |
C3 | 0.0583 (13) | 0.0902 (18) | 0.0639 (14) | −0.0106 (12) | 0.0335 (11) | −0.0048 (12) |
C4 | 0.0502 (12) | 0.101 (2) | 0.0736 (16) | 0.0080 (13) | 0.0293 (11) | −0.0012 (14) |
C5 | 0.0545 (12) | 0.0783 (16) | 0.0647 (14) | 0.0146 (11) | 0.0227 (11) | 0.0048 (12) |
C6 | 0.0501 (10) | 0.0562 (11) | 0.0440 (11) | 0.0029 (9) | 0.0183 (8) | −0.0036 (9) |
C7 | 0.0469 (10) | 0.0404 (9) | 0.0427 (10) | 0.0007 (7) | 0.0171 (8) | −0.0021 (7) |
C8 | 0.0476 (10) | 0.0435 (9) | 0.0422 (10) | 0.0011 (8) | 0.0165 (8) | 0.0040 (8) |
C9 | 0.0480 (10) | 0.0406 (9) | 0.0457 (10) | −0.0011 (8) | 0.0187 (8) | 0.0020 (8) |
C10 | 0.0460 (10) | 0.0477 (10) | 0.0435 (10) | 0.0017 (8) | 0.0168 (8) | 0.0050 (8) |
C11 | 0.0501 (11) | 0.0536 (11) | 0.0595 (13) | −0.0060 (9) | 0.0240 (9) | 0.0037 (9) |
C12 | 0.0638 (13) | 0.0445 (11) | 0.0680 (14) | −0.0121 (9) | 0.0257 (11) | −0.0024 (10) |
C13 | 0.0600 (12) | 0.0428 (10) | 0.0554 (12) | 0.0005 (9) | 0.0234 (9) | −0.0026 (9) |
C14 | 0.0460 (10) | 0.0497 (10) | 0.0445 (10) | 0.0013 (8) | 0.0165 (8) | 0.0042 (8) |
C15 | 0.0547 (11) | 0.0551 (12) | 0.0445 (11) | 0.0024 (9) | 0.0132 (9) | −0.0076 (9) |
C16 | 0.0784 (15) | 0.0582 (13) | 0.0654 (15) | −0.0043 (11) | 0.0200 (12) | −0.0161 (11) |
C17 | 0.0726 (16) | 0.0720 (16) | 0.0787 (17) | 0.0062 (13) | 0.0165 (13) | −0.0310 (14) |
C18 | 0.0580 (14) | 0.101 (2) | 0.0755 (17) | 0.0090 (13) | 0.0218 (12) | −0.0330 (15) |
C19 | 0.0555 (13) | 0.0870 (17) | 0.0666 (15) | 0.0038 (12) | 0.0261 (11) | −0.0113 (13) |
C20 | 0.0434 (10) | 0.0651 (12) | 0.0458 (11) | 0.0061 (9) | 0.0128 (8) | −0.0026 (9) |
C21 | 0.0615 (12) | 0.0404 (10) | 0.0692 (14) | −0.0018 (9) | 0.0334 (11) | −0.0061 (9) |
C22 | 0.0720 (14) | 0.0428 (11) | 0.0751 (15) | 0.0132 (10) | 0.0261 (12) | 0.0016 (10) |
Zn1—O1i | 1.940 (1) | C7—C8 | 1.473 (2) |
Zn1—O1 | 1.940 (1) | C8—C9 | 1.391 (3) |
Zn1—N1i | 2.019 (2) | C8—C13 | 1.390 (3) |
Zn1—N1 | 2.019 (2) | C9—C10 | 1.394 (3) |
O1—C21 | 1.275 (2) | C9—H9 | 0.9300 |
O2—C21 | 1.219 (2) | C10—C11 | 1.390 (3) |
N1—C7 | 1.332 (2) | C10—C14 | 1.473 (3) |
N1—C1 | 1.401 (2) | C11—C12 | 1.380 (3) |
N2—C7 | 1.344 (2) | C11—H11 | 0.9300 |
N2—C6 | 1.386 (3) | C12—C13 | 1.383 (3) |
N2—H2N | 0.846 (10) | C12—H12 | 0.9300 |
N3—C14 | 1.357 (3) | C13—H13 | 0.9300 |
N3—C15 | 1.381 (3) | C15—C16 | 1.390 (3) |
N3—H3N | 0.846 (10) | C15—C20 | 1.393 (3) |
N4—C14 | 1.324 (2) | C16—C17 | 1.377 (3) |
N4—C20 | 1.394 (3) | C16—H16 | 0.9300 |
C1—C6 | 1.390 (3) | C17—C18 | 1.396 (4) |
C1—C2 | 1.397 (3) | C17—H17 | 0.9300 |
C2—C3 | 1.382 (3) | C18—C19 | 1.375 (4) |
C2—H2 | 0.9300 | C18—H18 | 0.9300 |
C3—C4 | 1.392 (4) | C19—C20 | 1.401 (3) |
C3—H3 | 0.9300 | C19—H19 | 0.9300 |
C4—C5 | 1.369 (3) | C21—C22 | 1.518 (3) |
C4—H4 | 0.9300 | C22—C22i | 1.509 (4) |
C5—C6 | 1.391 (3) | C22—H22A | 0.9700 |
C5—H5 | 0.9300 | C22—H22B | 0.9700 |
O1i—Zn1—O1 | 110.7 (1) | C10—C9—H9 | 119.9 |
O1—Zn1—N1 | 113.6 (1) | C11—C10—C9 | 119.24 (18) |
O1—Zn1—N1i | 108.6 (1) | C11—C10—C14 | 120.22 (17) |
O1i—Zn1—N1 | 108.6 (1) | C9—C10—C14 | 120.54 (17) |
O1i—Zn1—N1i | 113.6 (1) | C12—C11—C10 | 120.65 (18) |
N1i—Zn1—N1 | 101.6 (1) | C12—C11—H11 | 119.7 |
C21—O1—Zn1 | 130.16 (14) | C10—C11—H11 | 119.7 |
C7—N1—C1 | 105.51 (15) | C13—C12—C11 | 120.04 (19) |
C7—N1—Zn1 | 124.55 (12) | C13—C12—H12 | 120.0 |
C1—N1—Zn1 | 128.90 (12) | C11—C12—H12 | 120.0 |
C7—N2—C6 | 107.51 (16) | C12—C13—C8 | 120.13 (18) |
C7—N2—H2n | 124.7 (17) | C12—C13—H13 | 119.9 |
C6—N2—H2n | 127.5 (17) | C8—C13—H13 | 119.9 |
C14—N3—C15 | 107.46 (17) | N4—C14—N3 | 112.65 (18) |
C14—N3—H3n | 127.5 (18) | N4—C14—C10 | 124.18 (18) |
C15—N3—H3n | 124.7 (18) | N3—C14—C10 | 123.16 (17) |
C14—N4—C20 | 104.75 (17) | N3—C15—C16 | 132.1 (2) |
C6—C1—N1 | 108.65 (16) | N3—C15—C20 | 105.13 (17) |
C6—C1—C2 | 120.71 (18) | C16—C15—C20 | 122.7 (2) |
N1—C1—C2 | 130.62 (18) | C15—C16—C17 | 116.3 (2) |
C3—C2—C1 | 116.7 (2) | C15—C16—H16 | 121.8 |
C3—C2—H2 | 121.7 | C17—C16—H16 | 121.8 |
C1—C2—H2 | 121.7 | C16—C17—C18 | 121.8 (2) |
C2—C3—C4 | 122.0 (2) | C16—C17—H17 | 119.1 |
C2—C3—H3 | 119.0 | C18—C17—H17 | 119.1 |
C4—C3—H3 | 119.0 | C19—C18—C17 | 121.8 (2) |
C5—C4—C3 | 121.7 (2) | C19—C18—H18 | 119.1 |
C5—C4—H4 | 119.1 | C17—C18—H18 | 119.1 |
C3—C4—H4 | 119.1 | C18—C19—C20 | 117.3 (3) |
C4—C5—C6 | 116.8 (2) | C18—C19—H19 | 121.3 |
C4—C5—H5 | 121.6 | C20—C19—H19 | 121.3 |
C6—C5—H5 | 121.6 | N4—C20—C19 | 129.9 (2) |
N2—C6—C1 | 106.09 (16) | N4—C20—C15 | 109.99 (17) |
N2—C6—C5 | 131.7 (2) | C19—C20—C15 | 120.1 (2) |
C1—C6—C5 | 122.2 (2) | O2—C21—O1 | 121.9 (2) |
N1—C7—N2 | 112.23 (16) | O2—C21—C22 | 120.37 (19) |
N1—C7—C8 | 124.70 (16) | O1—C21—C22 | 117.68 (17) |
N2—C7—C8 | 123.06 (17) | C21—C22—C22i | 112.5 (2) |
C9—C8—C13 | 119.72 (17) | C21—C22—H22A | 109.1 |
C9—C8—C7 | 119.80 (16) | C22i—C22—H22A | 109.1 |
C13—C8—C7 | 120.47 (17) | C21—C22—H22B | 109.1 |
C8—C9—C10 | 120.20 (17) | C22i—C22—H22B | 109.1 |
C8—C9—H9 | 119.9 | H22A—C22—H22B | 107.8 |
O1i—Zn1—O1—C21 | −16.11 (17) | C7—C8—C9—C10 | −179.10 (17) |
N1i—Zn1—O1—C21 | 109.22 (19) | C8—C9—C10—C11 | 0.4 (3) |
N1—Zn1—O1—C21 | −138.57 (19) | C8—C9—C10—C14 | −179.86 (17) |
O1i—Zn1—N1—C7 | 169.60 (14) | C9—C10—C11—C12 | −1.0 (3) |
O1—Zn1—N1—C7 | −66.76 (15) | C14—C10—C11—C12 | 179.24 (19) |
N1i—Zn1—N1—C7 | 49.62 (13) | C10—C11—C12—C13 | 0.4 (3) |
O1i—Zn1—N1—C1 | 2.97 (17) | C11—C12—C13—C8 | 0.8 (3) |
O1—Zn1—N1—C1 | 126.61 (15) | C9—C8—C13—C12 | −1.5 (3) |
N1i—Zn1—N1—C1 | −117.01 (16) | C7—C8—C13—C12 | 178.48 (19) |
C7—N1—C1—C6 | 0.3 (2) | C20—N4—C14—N3 | −1.5 (2) |
Zn1—N1—C1—C6 | 168.86 (13) | C20—N4—C14—C10 | 177.43 (17) |
C7—N1—C1—C2 | 178.8 (2) | C15—N3—C14—N4 | 1.0 (2) |
Zn1—N1—C1—C2 | −12.6 (3) | C15—N3—C14—C10 | −177.96 (17) |
C6—C1—C2—C3 | 0.1 (3) | C11—C10—C14—N4 | −25.1 (3) |
N1—C1—C2—C3 | −178.3 (2) | C9—C10—C14—N4 | 155.19 (19) |
C1—C2—C3—C4 | 0.1 (3) | C11—C10—C14—N3 | 153.8 (2) |
C2—C3—C4—C5 | 0.0 (4) | C9—C10—C14—N3 | −26.0 (3) |
C3—C4—C5—C6 | −0.4 (4) | C14—N3—C15—C16 | 177.5 (2) |
C7—N2—C6—C1 | 0.4 (2) | C14—N3—C15—C20 | 0.0 (2) |
C7—N2—C6—C5 | −177.9 (2) | N3—C15—C16—C17 | −177.0 (2) |
N1—C1—C6—N2 | −0.4 (2) | C20—C15—C16—C17 | 0.1 (3) |
C2—C1—C6—N2 | −179.12 (18) | C15—C16—C17—C18 | −0.1 (4) |
N1—C1—C6—C5 | 178.12 (19) | C16—C17—C18—C19 | 0.0 (4) |
C2—C1—C6—C5 | −0.6 (3) | C17—C18—C19—C20 | 0.1 (4) |
C4—C5—C6—N2 | 178.8 (2) | C14—N4—C20—C19 | −177.1 (2) |
C4—C5—C6—C1 | 0.7 (3) | C14—N4—C20—C15 | 1.5 (2) |
C1—N1—C7—N2 | 0.0 (2) | C18—C19—C20—N4 | 178.3 (2) |
Zn1—N1—C7—N2 | −169.24 (13) | C18—C19—C20—C15 | −0.1 (3) |
C1—N1—C7—C8 | 178.83 (17) | N3—C15—C20—N4 | −0.9 (2) |
Zn1—N1—C7—C8 | 9.6 (3) | C16—C15—C20—N4 | −178.69 (19) |
C6—N2—C7—N1 | −0.3 (2) | N3—C15—C20—C19 | 177.84 (19) |
C6—N2—C7—C8 | −179.10 (17) | C16—C15—C20—C19 | 0.0 (3) |
N1—C7—C8—C9 | 51.0 (3) | Zn1—O1—C21—O2 | −174.73 (18) |
N2—C7—C8—C9 | −130.3 (2) | Zn1—O1—C21—C22 | 3.8 (3) |
N1—C7—C8—C13 | −129.0 (2) | O2—C21—C22—C22i | −121.7 (2) |
N2—C7—C8—C13 | 49.7 (3) | O1—C21—C22—C22i | 59.7 (3) |
C13—C8—C9—C10 | 0.8 (3) |
Symmetry code: (i) −x+1, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2n···N4ii | 0.85 (1) | 1.99 (1) | 2.839 (2) | 178 (2) |
N3—H3n···O1 | 0.85 (1) | 2.36 (1) | 3.158 (2) | 158 (2) |
Symmetry code: (ii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C4H4O4)(C20H14N4)2] |
Mr | 802.15 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 291 |
a, b, c (Å) | 21.453 (2), 10.272 (1), 17.587 (2) |
β (°) | 109.411 (1) |
V (Å3) | 3655.2 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.73 |
Crystal size (mm) | 0.46 × 0.34 × 0.22 |
Data collection | |
Diffractometer | Bruker APEXII area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.687, 0.856 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14308, 4186, 3354 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.103, 1.02 |
No. of reflections | 4186 |
No. of parameters | 266 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.41, −0.24 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), X-SEED (Barbour, 2001), publCIF (Westrip, 2007).
Zn1—O1 | 1.940 (1) | Zn1—N1 | 2.019 (2) |
O1i—Zn1—O1 | 110.7 (1) | O1i—Zn1—N1 | 108.6 (1) |
O1—Zn1—N1 | 113.6 (1) | O1i—Zn1—N1i | 113.6 (1) |
O1—Zn1—N1i | 108.6 (1) |
Symmetry code: (i) −x+1, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2n···N4ii | 0.85 (1) | 1.99 (1) | 2.839 (2) | 178 (2) |
N3—H3n···O1 | 0.85 (1) | 2.36 (1) | 3.158 (2) | 158 (2) |
Symmetry code: (ii) −x+1, −y+1, −z+1. |
The reaction between 1,3-bis(benzimidazol-2-ylmethyl)benzene and zinc terephthalate affords the expected 1:1 adduct as a methanol solvate. The compound adopts a layer structure owing to bridging by both the N-heterocycle and the terephthalate dianion (Meng et al., 2007). The succinate dianion is not rigid like the terephthalate dianion. It typically lies on a center-of-inversion in most metal succinates (CSD Version 5.28, May 2007) and functions as a bridging dianion; however, the succinate group chelates to the zinc atom in the zinc succinate adduct of this heterocycle. Both the cation and the dianion lie on a twofold rotation axis in the monomeric compound (Scheme I, Fig. 1).
Chelation by a succinate group has been documented in only three cases: the polymeric hexaaquatricobalt(III) (Forster et al., 2004) and monomeric tetraaquanickel(II) (Gupta & Devi, 1978) derivatives, and the salt, diaquabis(phenanthrolinato)manganese(II) bis(phenanthroline)succinatomanganate(II) succinate heptahydrate (Zheng, Lin & Sun, 2001). The title compound has the metal center connected to two N-heterocycles; expansion of the coordination number is precluded as the second tertiary N-donor site of both ligands is already engaged in hydrogen bonding interactions. This possibly forces the succinate group to bind in the uncommon chelating mode. The amino –NH group of one heterocycle in hydrogen-bonded to the carbonyl oxygen atom [3.158 (2) Å]; that of the second heterocycle engages in an intermolecular N–H···N interaction [2.839 (2) Å] to furnish a linear chain motif.
The zinc-oxygen bond distance is similar to that found in zinc succinate itself; the metal center in this compound shows tetrahedral coordination and the anion behaves as a bridging group to result in the formation of a polymeric network motif (Bowden et al., 2003; Zheng, Peters & von Schnering, 2001). The distance is, however, shorter than those found in other higher-than-four-coordinateamine adducts (Tao et al., 2001; Yin et al., 2002; Ying et al., 2003; Zeng et al., 2007; Zheng, 2004; Zheng et al., 2002; Zhou et al., 2005).