Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025263/pk2021sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025263/pk2021Isup2.hkl |
CCDC reference: 654705
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.007 Å
- Disorder in main residue
- R factor = 0.057
- wR factor = 0.206
- Data-to-parameter ratio = 15.1
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT241_ALERT_2_B Check High Ueq as Compared to Neighbors for N6
Alert level C PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 0.50 Ratio PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.12 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C25 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C26 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for C30 PLAT301_ALERT_3_C Main Residue Disorder ......................... 7.00 Perc. PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 50.00 Perc. PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 7
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 64
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 10 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 4 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
An ethanol solution (20 ml) of dmbpy (36.8 mg, 0.2 mmol) was added to a mixed aqueous solution (10 ml) of the hexahydrate of zinc(II) perchlorate (37.2 mg, 0.1 mmol) and sodium dicyanamide (17.8 mg, 0.2 mmol) under continuous stirring. After 30 min, the reaction mixture was filtered. Colorless crystals of (I) suitable for X-ray diffraction analysis were obtained by slow evaporation of the filtrate at room temperature. Yield 67%. Spectroscopic analysis: IR (KBr, νcm-1): 3433, 2295, 2231, 2200,2170, 1616, 1562, 1485, 1354, 1120, 1016, 921, 837. (IR spectra were recorded on a BIO-RAD FTS 3000 infrared spectrophotometer). Analysis, required for C58H54N20OZn2: C 59.14, H 4.62, N 23.78%; found: C 59.32, H 4.39, N 23.85%.
The dca ligand containing atom N8 is disordered over two positions with refined site-occupancy factors of 0.64 (2) and 0.36 (2). All H atoms were located in a difference Fourier map and were refined using a riding model, with distances between 0.93–0.97 Å (CH) and an OH distance of 0.82 Å. Uiso(H) values were set to either 1.2Ueq or 1.5Ueq (CH3, OH) of the attached atom.
Polypyridine complexes of transition metals have received much attention in recent years on account of their photophysical properties (Yiting et al., 2001). Hydrogen bonds and π···π stacking interactions have also proven to play important roles in the control of molecular arrangement in the crystalline state and the properties of matter (Jones & Rao, 2001).
The crystal structure of (I) contains half an ethanol molecule for each zinc(II) complex. The Zn atom is coordinated by six N atoms from two chelating dmbpy ligands and two dca ligands that are cis to one another (Fig.1). The Zn—N bond distances range from 2.101 (4) to 2.226 (3) Å and the cis N—Zn—N angles range from 74.87 (13) to 96.25 (13) °, indicating a distorted octahedral coordinated geometry around Zn atom. The dmbpy ligands are planar (maximum deviation from the least-squares planes are 0.0499 (44) Å (for the ligand containing N1 and 0.0436 (50) Å for the ligand containing N3.
The dihedral angle between the two dmbpy ligands is 79.31 (7) °. in the two dca ligands, all the C—N triple bond distances less than 1.13 Å. As depicted in Fig. 2, the complexes are linked via weak π···π stacking interactions between parallel dmbpy ligands to generate a one-dimensional chain along the [100] direction. The center-to-center distance between the pyridyl ring containing atom N1 and that containing N2i atom (i = 1 - x, 1 - y, 1 - z) is 4.175 (3) Å and that between the rings containing atom N3 and atom N4ii (ii = - x, 1 - y, -z) is 3.838 (3) Å. The one-dimensional chains are parallel in the crystal structure of (I) and the ethanol resides in a vacancy between the main complexes.
For related literature, see: Jones & Rao (2001); Yiting et al. (2001).
Data collection: APEX2 (Bruker, 2003); cell refinement: APEX2 or 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: SHELXTL (Bruker 2003); software used to prepare material for publication: SHELXTL.
Fig. 1. View of the assymmetric unit of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. | |
Fig. 2. The molecular packing, viewed along c axis. |
[Zn(C2N3)2(C12H12N2)2]·0.5C2H6O | F(000) = 1220 |
Mr = 589.00 | Dx = 1.322 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5956 reflections |
a = 15.694 (2) Å | θ = 2.8–25.4° |
b = 14.713 (2) Å | µ = 0.87 mm−1 |
c = 13.8868 (19) Å | T = 294 K |
β = 112.674 (2)° | Block, colourless |
V = 2958.7 (7) Å3 | 0.24 × 0.20 × 0.16 mm |
Z = 4 |
Bruker APEX II CCD area-detector diffractometer | 6059 independent reflections |
Radiation source: fine-focus sealed tube | 4171 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
φ and ω scans | θmax = 26.4°, θmin = 1.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −19→9 |
Tmin = 0.772, Tmax = 0.870 | k = −18→17 |
16800 measured reflections | l = −17→17 |
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)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.206 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.1227P)2 + 1.4831P] where P = (Fo2 + 2Fc2)/3 |
6059 reflections | (Δ/σ)max = 0.003 |
402 parameters | Δρmax = 0.95 e Å−3 |
64 restraints | Δρmin = −0.45 e Å−3 |
[Zn(C2N3)2(C12H12N2)2]·0.5C2H6O | V = 2958.7 (7) Å3 |
Mr = 589.00 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 15.694 (2) Å | µ = 0.87 mm−1 |
b = 14.713 (2) Å | T = 294 K |
c = 13.8868 (19) Å | 0.24 × 0.20 × 0.16 mm |
β = 112.674 (2)° |
Bruker APEX II CCD area-detector diffractometer | 6059 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4171 reflections with I > 2σ(I) |
Tmin = 0.772, Tmax = 0.870 | Rint = 0.031 |
16800 measured reflections |
R[F2 > 2σ(F2)] = 0.057 | 64 restraints |
wR(F2) = 0.206 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.95 e Å−3 |
6059 reflections | Δρmin = −0.45 e Å−3 |
402 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 > 2σ(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 | 0.26488 (3) | 0.45836 (3) | 0.21113 (3) | 0.0488 (2) | |
N1 | 0.3197 (2) | 0.5743 (2) | 0.3162 (3) | 0.0502 (8) | |
N2 | 0.3189 (2) | 0.3995 (2) | 0.3645 (3) | 0.0510 (8) | |
N3 | 0.1999 (2) | 0.5370 (2) | 0.0733 (3) | 0.0481 (8) | |
N4 | 0.1283 (2) | 0.4973 (3) | 0.2124 (3) | 0.0524 (8) | |
N5 | 0.3916 (3) | 0.4500 (3) | 0.1909 (3) | 0.0656 (10) | |
N6 | 0.5474 (4) | 0.4465 (4) | 0.1965 (5) | 0.0952 (15) | |
N7 | 0.6198 (5) | 0.5372 (4) | 0.1048 (5) | 0.1123 (19) | |
N8 | 0.2159 (3) | 0.3333 (3) | 0.1376 (3) | 0.0706 (10) | |
C1 | 0.3184 (3) | 0.6601 (3) | 0.2883 (4) | 0.0604 (11) | |
H1 | 0.2911 | 0.6742 | 0.2176 | 0.073* | |
C2 | 0.3553 (3) | 0.7299 (3) | 0.3580 (4) | 0.0632 (11) | |
H2 | 0.3533 | 0.7894 | 0.3344 | 0.076* | |
C3 | 0.3950 (3) | 0.7109 (3) | 0.4623 (4) | 0.0613 (11) | |
C4 | 0.3968 (3) | 0.6203 (3) | 0.4924 (3) | 0.0599 (11) | |
H4 | 0.4233 | 0.6047 | 0.5627 | 0.072* | |
C5 | 0.3590 (3) | 0.5535 (3) | 0.4176 (3) | 0.0478 (9) | |
C6 | 0.3579 (3) | 0.4568 (3) | 0.4447 (3) | 0.0493 (9) | |
C7 | 0.3940 (3) | 0.4249 (3) | 0.5452 (3) | 0.0582 (10) | |
H7 | 0.4213 | 0.4654 | 0.5998 | 0.070* | |
C8 | 0.3906 (3) | 0.3331 (3) | 0.5671 (4) | 0.0639 (11) | |
C9 | 0.3523 (3) | 0.2761 (3) | 0.4843 (4) | 0.0664 (12) | |
H9 | 0.3504 | 0.2139 | 0.4952 | 0.080* | |
C10 | 0.3168 (3) | 0.3102 (3) | 0.3857 (4) | 0.0601 (11) | |
H10 | 0.2900 | 0.2702 | 0.3304 | 0.072* | |
C11 | 0.4351 (4) | 0.7839 (4) | 0.5419 (5) | 0.0880 (17) | |
H11A | 0.4643 | 0.8288 | 0.5149 | 0.132* | |
H11B | 0.4800 | 0.7578 | 0.6043 | 0.132* | |
H11C | 0.3868 | 0.8118 | 0.5578 | 0.132* | |
C12 | 0.4267 (4) | 0.3001 (4) | 0.6780 (4) | 0.0894 (17) | |
H12A | 0.3817 | 0.3117 | 0.7077 | 0.134* | |
H12B | 0.4830 | 0.3316 | 0.7177 | 0.134* | |
H12C | 0.4386 | 0.2360 | 0.6796 | 0.134* | |
C13 | 0.2371 (3) | 0.5524 (3) | 0.0024 (3) | 0.0574 (11) | |
H13 | 0.2918 | 0.5230 | 0.0103 | 0.069* | |
C14 | 0.1983 (4) | 0.6092 (3) | −0.0804 (4) | 0.0670 (12) | |
H14 | 0.2261 | 0.6174 | −0.1280 | 0.080* | |
C15 | 0.1173 (4) | 0.6545 (3) | −0.0936 (4) | 0.0666 (12) | |
C16 | 0.0785 (3) | 0.6362 (3) | −0.0229 (4) | 0.0620 (11) | |
H16 | 0.0228 | 0.6635 | −0.0306 | 0.074* | |
C17 | 0.1205 (3) | 0.5779 (3) | 0.0597 (3) | 0.0470 (9) | |
C18 | 0.0799 (3) | 0.5560 (3) | 0.1380 (3) | 0.0476 (9) | |
C19 | −0.0018 (3) | 0.5927 (3) | 0.1341 (4) | 0.0567 (10) | |
H19 | −0.0341 | 0.6329 | 0.0807 | 0.068* | |
C20 | −0.0367 (3) | 0.5707 (3) | 0.2085 (4) | 0.0625 (11) | |
C21 | 0.0135 (4) | 0.5108 (4) | 0.2844 (4) | 0.0731 (13) | |
H21 | −0.0071 | 0.4938 | 0.3363 | 0.088* | |
C22 | 0.0943 (4) | 0.4759 (4) | 0.2837 (4) | 0.0676 (12) | |
H22 | 0.1271 | 0.4350 | 0.3359 | 0.081* | |
C23 | 0.0748 (5) | 0.7225 (4) | −0.1791 (5) | 0.102 (2) | |
H23A | 0.0182 | 0.6984 | −0.2292 | 0.153* | |
H23B | 0.1167 | 0.7350 | −0.2127 | 0.153* | |
H23C | 0.0621 | 0.7776 | −0.1501 | 0.153* | |
C24 | −0.1243 (4) | 0.6141 (4) | 0.2073 (5) | 0.0829 (16) | |
H24A | −0.1688 | 0.5672 | 0.2003 | 0.124* | |
H24B | −0.1481 | 0.6550 | 0.1491 | 0.124* | |
H24C | −0.1121 | 0.6470 | 0.2709 | 0.124* | |
C25 | 0.4622 (3) | 0.4524 (3) | 0.1893 (3) | 0.0533 (10) | |
C26 | 0.5817 (4) | 0.4974 (4) | 0.1456 (5) | 0.0753 (14) | |
C27 | 0.1844 (4) | 0.2722 (3) | 0.0877 (4) | 0.0698 (13) | |
N9 | 0.1507 (7) | 0.2111 (7) | 0.0119 (11) | 0.088 (3) | 0.64 (2) |
C28 | 0.0769 (4) | 0.1747 (4) | −0.0020 (5) | 0.0834 (16) | 0.64 (2) |
N10 | 0.0048 (6) | 0.1397 (7) | −0.0195 (11) | 0.105 (4) | 0.64 (2) |
N9' | 0.1659 (9) | 0.1872 (10) | 0.0591 (15) | 0.070 (5) | 0.36 (2) |
C28' | 0.0769 (4) | 0.1747 (4) | −0.0020 (5) | 0.0834 (16) | 0.36 (2) |
N10' | 0.0058 (8) | 0.1591 (13) | −0.0634 (15) | 0.094 (6) | 0.36 (2) |
C29 | 0.7949 (9) | 0.0355 (7) | 0.9106 (12) | 0.096 (4) | 0.50 |
H29A | 0.8388 | 0.0226 | 0.8797 | 0.144* | 0.50 |
H29B | 0.7404 | −0.0005 | 0.8772 | 0.144* | 0.50 |
H29C | 0.8216 | 0.0212 | 0.9837 | 0.144* | 0.50 |
C30 | 0.7712 (7) | 0.1294 (7) | 0.8976 (9) | 0.077 (3) | 0.50 |
H30A | 0.7052 | 0.1346 | 0.8578 | 0.092* | 0.50 |
H30B | 0.7842 | 0.1559 | 0.9658 | 0.092* | 0.50 |
O1 | 0.8149 (5) | 0.1774 (6) | 0.8501 (7) | 0.098 (2) | 0.50 |
H1A | 0.8307 | 0.1439 | 0.8128 | 0.147* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0478 (3) | 0.0516 (3) | 0.0448 (3) | −0.0035 (2) | 0.0155 (2) | −0.00216 (19) |
N1 | 0.055 (2) | 0.0476 (18) | 0.0453 (18) | −0.0068 (15) | 0.0164 (15) | −0.0053 (15) |
N2 | 0.0515 (19) | 0.0518 (19) | 0.0479 (18) | −0.0030 (15) | 0.0170 (15) | −0.0007 (15) |
N3 | 0.0490 (19) | 0.0537 (19) | 0.0415 (17) | −0.0028 (15) | 0.0173 (15) | −0.0023 (14) |
N4 | 0.0475 (19) | 0.062 (2) | 0.050 (2) | −0.0020 (16) | 0.0210 (16) | 0.0010 (17) |
N5 | 0.057 (2) | 0.078 (3) | 0.065 (2) | 0.0031 (19) | 0.0269 (19) | 0.0028 (19) |
N6 | 0.0927 (17) | 0.0955 (18) | 0.0974 (18) | 0.0011 (10) | 0.0367 (11) | 0.0035 (10) |
N7 | 0.111 (2) | 0.114 (2) | 0.114 (2) | 0.0007 (10) | 0.0455 (12) | 0.0008 (10) |
N8 | 0.0700 (13) | 0.0688 (13) | 0.0706 (13) | −0.0009 (9) | 0.0245 (9) | −0.0025 (9) |
C1 | 0.072 (3) | 0.053 (2) | 0.056 (2) | −0.006 (2) | 0.023 (2) | −0.002 (2) |
C2 | 0.068 (3) | 0.051 (2) | 0.066 (3) | −0.007 (2) | 0.022 (2) | −0.004 (2) |
C3 | 0.054 (3) | 0.056 (2) | 0.068 (3) | −0.007 (2) | 0.017 (2) | −0.014 (2) |
C4 | 0.054 (2) | 0.066 (3) | 0.049 (2) | 0.000 (2) | 0.0090 (19) | −0.007 (2) |
C5 | 0.043 (2) | 0.053 (2) | 0.045 (2) | −0.0018 (17) | 0.0147 (17) | −0.0053 (17) |
C6 | 0.044 (2) | 0.055 (2) | 0.049 (2) | 0.0001 (17) | 0.0187 (18) | 0.0022 (18) |
C7 | 0.058 (3) | 0.066 (3) | 0.045 (2) | −0.002 (2) | 0.0135 (19) | 0.002 (2) |
C8 | 0.058 (3) | 0.073 (3) | 0.059 (3) | 0.002 (2) | 0.020 (2) | 0.013 (2) |
C9 | 0.073 (3) | 0.053 (2) | 0.075 (3) | 0.004 (2) | 0.030 (3) | 0.012 (2) |
C10 | 0.068 (3) | 0.050 (2) | 0.062 (3) | −0.006 (2) | 0.025 (2) | −0.001 (2) |
C11 | 0.092 (4) | 0.071 (3) | 0.078 (4) | −0.006 (3) | 0.007 (3) | −0.028 (3) |
C12 | 0.096 (4) | 0.095 (4) | 0.068 (3) | 0.006 (3) | 0.022 (3) | 0.030 (3) |
C13 | 0.057 (3) | 0.070 (3) | 0.049 (2) | 0.001 (2) | 0.024 (2) | −0.001 (2) |
C14 | 0.084 (3) | 0.069 (3) | 0.057 (3) | 0.000 (3) | 0.037 (3) | 0.004 (2) |
C15 | 0.081 (3) | 0.062 (3) | 0.054 (3) | 0.000 (2) | 0.024 (2) | 0.004 (2) |
C16 | 0.066 (3) | 0.057 (3) | 0.063 (3) | 0.009 (2) | 0.026 (2) | 0.002 (2) |
C17 | 0.050 (2) | 0.045 (2) | 0.047 (2) | −0.0037 (17) | 0.0192 (17) | −0.0072 (17) |
C18 | 0.045 (2) | 0.048 (2) | 0.047 (2) | −0.0049 (17) | 0.0153 (17) | −0.0085 (17) |
C19 | 0.054 (2) | 0.057 (2) | 0.060 (3) | 0.0001 (19) | 0.023 (2) | −0.008 (2) |
C20 | 0.053 (3) | 0.066 (3) | 0.074 (3) | −0.007 (2) | 0.031 (2) | −0.014 (2) |
C21 | 0.065 (3) | 0.091 (4) | 0.077 (3) | −0.005 (3) | 0.042 (3) | 0.008 (3) |
C22 | 0.064 (3) | 0.082 (3) | 0.064 (3) | −0.003 (2) | 0.032 (2) | 0.011 (2) |
C23 | 0.125 (5) | 0.097 (4) | 0.084 (4) | 0.032 (4) | 0.040 (4) | 0.037 (3) |
C24 | 0.063 (3) | 0.096 (4) | 0.102 (4) | 0.002 (3) | 0.045 (3) | −0.011 (3) |
C25 | 0.045 (2) | 0.056 (2) | 0.054 (2) | 0.0052 (18) | 0.0142 (19) | 0.0010 (18) |
C26 | 0.061 (3) | 0.084 (4) | 0.092 (4) | 0.006 (3) | 0.041 (3) | 0.006 (3) |
C27 | 0.067 (3) | 0.057 (3) | 0.079 (3) | −0.010 (2) | 0.021 (3) | −0.016 (2) |
N9 | 0.089 (3) | 0.088 (3) | 0.088 (3) | −0.0007 (10) | 0.0342 (16) | −0.0016 (10) |
C28 | 0.078 (4) | 0.084 (4) | 0.091 (4) | −0.009 (3) | 0.035 (3) | −0.024 (3) |
N10 | 0.105 (4) | 0.105 (4) | 0.105 (4) | −0.0011 (10) | 0.0398 (17) | −0.0005 (10) |
N9' | 0.070 (5) | 0.069 (5) | 0.071 (5) | 0.0000 (10) | 0.026 (2) | 0.0000 (10) |
C28' | 0.078 (4) | 0.084 (4) | 0.091 (4) | −0.009 (3) | 0.035 (3) | −0.024 (3) |
N10' | 0.094 (6) | 0.094 (6) | 0.094 (6) | −0.0005 (10) | 0.036 (2) | −0.0002 (10) |
C29 | 0.069 (6) | 0.106 (7) | 0.119 (8) | −0.011 (5) | 0.041 (6) | 0.008 (6) |
C30 | 0.055 (5) | 0.095 (6) | 0.080 (6) | −0.001 (5) | 0.026 (4) | 0.003 (5) |
O1 | 0.071 (4) | 0.098 (5) | 0.107 (5) | 0.004 (4) | 0.014 (4) | 0.040 (4) |
Zn1—N8 | 2.101 (4) | C12—H12A | 0.9600 |
Zn1—N5 | 2.117 (4) | C12—H12B | 0.9600 |
Zn1—N3 | 2.130 (3) | C12—H12C | 0.9600 |
Zn1—N2 | 2.148 (3) | C13—C14 | 1.360 (6) |
Zn1—N1 | 2.194 (3) | C13—H13 | 0.9300 |
Zn1—N4 | 2.226 (3) | C14—C15 | 1.384 (7) |
N1—C1 | 1.319 (5) | C14—H14 | 0.9300 |
N1—C5 | 1.336 (5) | C15—C16 | 1.367 (6) |
N2—C6 | 1.342 (5) | C15—C23 | 1.498 (7) |
N2—C10 | 1.349 (5) | C16—C17 | 1.380 (6) |
N3—C17 | 1.330 (5) | C16—H16 | 0.9300 |
N3—C13 | 1.342 (5) | C17—C18 | 1.492 (5) |
N4—C22 | 1.331 (6) | C18—C19 | 1.373 (6) |
N4—C18 | 1.336 (5) | C19—C20 | 1.382 (6) |
N5—C25 | 1.118 (6) | C19—H19 | 0.9300 |
N6—C26 | 1.281 (7) | C20—C21 | 1.366 (7) |
N6—C25 | 1.305 (7) | C20—C24 | 1.510 (6) |
N7—C26 | 1.132 (7) | C21—C22 | 1.372 (7) |
N8—C27 | 1.127 (6) | C21—H21 | 0.9300 |
C1—C2 | 1.377 (6) | C22—H22 | 0.9300 |
C1—H1 | 0.9300 | C23—H23A | 0.9600 |
C2—C3 | 1.367 (7) | C23—H23B | 0.9600 |
C2—H2 | 0.9300 | C23—H23C | 0.9600 |
C3—C4 | 1.393 (6) | C24—H24A | 0.9600 |
C3—C11 | 1.495 (6) | C24—H24B | 0.9600 |
C4—C5 | 1.386 (6) | C24—H24C | 0.9600 |
C4—H4 | 0.9300 | C27—N9' | 1.311 (14) |
C5—C6 | 1.475 (5) | C27—N9 | 1.329 (10) |
C6—C7 | 1.371 (6) | N9—C28 | 1.222 (10) |
C7—C8 | 1.390 (6) | C28—N10 | 1.181 (8) |
C7—H7 | 0.9300 | C29—C30 | 1.425 (9) |
C8—C9 | 1.361 (7) | C29—H29A | 0.9600 |
C8—C12 | 1.503 (7) | C29—H29B | 0.9600 |
C9—C10 | 1.360 (6) | C29—H29C | 0.9600 |
C9—H9 | 0.9300 | C30—O1 | 1.324 (8) |
C10—H10 | 0.9300 | C30—H30A | 0.9700 |
C11—H11A | 0.9600 | C30—H30B | 0.9700 |
C11—H11B | 0.9600 | O1—H1A | 0.8200 |
C11—H11C | 0.9600 | ||
N8—Zn1—N5 | 94.05 (16) | C8—C12—H12B | 109.5 |
N8—Zn1—N3 | 94.59 (14) | H12A—C12—H12B | 109.5 |
N5—Zn1—N3 | 93.49 (14) | C8—C12—H12C | 109.5 |
N8—Zn1—N2 | 93.40 (14) | H12A—C12—H12C | 109.5 |
N5—Zn1—N2 | 94.37 (14) | H12B—C12—H12C | 109.5 |
N3—Zn1—N2 | 168.36 (13) | N3—C13—C14 | 123.0 (4) |
N8—Zn1—N1 | 168.71 (14) | N3—C13—H13 | 118.5 |
N5—Zn1—N1 | 89.18 (14) | C14—C13—H13 | 118.5 |
N3—Zn1—N1 | 96.01 (13) | C13—C14—C15 | 119.8 (4) |
N2—Zn1—N1 | 75.55 (12) | C13—C14—H14 | 120.1 |
N8—Zn1—N4 | 93.27 (15) | C15—C14—H14 | 120.1 |
N5—Zn1—N4 | 166.71 (14) | C16—C15—C14 | 116.8 (4) |
N3—Zn1—N4 | 74.87 (13) | C16—C15—C23 | 121.0 (5) |
N2—Zn1—N4 | 96.25 (13) | C14—C15—C23 | 122.2 (5) |
N1—Zn1—N4 | 85.78 (13) | C15—C16—C17 | 121.1 (4) |
C1—N1—C5 | 118.5 (4) | C15—C16—H16 | 119.5 |
C1—N1—Zn1 | 126.2 (3) | C17—C16—H16 | 119.5 |
C5—N1—Zn1 | 115.2 (3) | N3—C17—C16 | 121.4 (4) |
C6—N2—C10 | 118.1 (4) | N3—C17—C18 | 116.1 (4) |
C6—N2—Zn1 | 116.7 (3) | C16—C17—C18 | 122.5 (4) |
C10—N2—Zn1 | 125.2 (3) | N4—C18—C19 | 121.9 (4) |
C17—N3—C13 | 117.9 (4) | N4—C18—C17 | 115.4 (3) |
C17—N3—Zn1 | 118.1 (3) | C19—C18—C17 | 122.8 (4) |
C13—N3—Zn1 | 123.9 (3) | C18—C19—C20 | 120.7 (4) |
C22—N4—C18 | 117.2 (4) | C18—C19—H19 | 119.6 |
C22—N4—Zn1 | 127.5 (3) | C20—C19—H19 | 119.6 |
C18—N4—Zn1 | 114.9 (3) | C21—C20—C19 | 116.9 (4) |
C25—N5—Zn1 | 172.1 (4) | C21—C20—C24 | 122.2 (5) |
C26—N6—C25 | 123.7 (5) | C19—C20—C24 | 120.9 (5) |
C27—N8—Zn1 | 171.7 (4) | C20—C21—C22 | 119.7 (4) |
N1—C1—C2 | 123.6 (4) | C20—C21—H21 | 120.2 |
N1—C1—H1 | 118.2 | C22—C21—H21 | 120.2 |
C2—C1—H1 | 118.2 | N4—C22—C21 | 123.6 (5) |
C3—C2—C1 | 119.2 (4) | N4—C22—H22 | 118.2 |
C3—C2—H2 | 120.4 | C21—C22—H22 | 118.2 |
C1—C2—H2 | 120.4 | C15—C23—H23A | 109.5 |
C2—C3—C4 | 117.5 (4) | C15—C23—H23B | 109.5 |
C2—C3—C11 | 121.7 (5) | H23A—C23—H23B | 109.5 |
C4—C3—C11 | 120.7 (5) | C15—C23—H23C | 109.5 |
C5—C4—C3 | 120.0 (4) | H23A—C23—H23C | 109.5 |
C5—C4—H4 | 120.0 | H23B—C23—H23C | 109.5 |
C3—C4—H4 | 120.0 | C20—C24—H24A | 108.7 |
N1—C5—C4 | 121.2 (4) | C20—C24—H24B | 109.4 |
N1—C5—C6 | 116.3 (4) | H24A—C24—H24B | 109.5 |
C4—C5—C6 | 122.5 (4) | C20—C24—H24C | 110.2 |
N2—C6—C7 | 120.5 (4) | H24A—C24—H24C | 109.5 |
N2—C6—C5 | 116.2 (4) | H24B—C24—H24C | 109.5 |
C7—C6—C5 | 123.3 (4) | N5—C25—N6 | 172.4 (5) |
C6—C7—C8 | 121.3 (4) | N7—C26—N6 | 173.0 (7) |
C6—C7—H7 | 119.3 | N8—C27—N9' | 160.3 (10) |
C8—C7—H7 | 119.3 | N8—C27—N9 | 166.7 (8) |
C9—C8—C7 | 117.1 (4) | C28—N9—C27 | 119.0 (8) |
C9—C8—C12 | 122.4 (5) | N10—C28—N9 | 177.5 (10) |
C7—C8—C12 | 120.4 (5) | C30—C29—H29A | 109.5 |
C10—C9—C8 | 119.9 (4) | C30—C29—H29B | 109.5 |
C10—C9—H9 | 120.0 | H29A—C29—H29B | 109.5 |
C8—C9—H9 | 120.0 | C30—C29—H29C | 109.5 |
N2—C10—C9 | 123.0 (4) | H29A—C29—H29C | 109.5 |
N2—C10—H10 | 118.5 | H29B—C29—H29C | 109.5 |
C9—C10—H10 | 118.5 | O1—C30—C29 | 114.8 (9) |
C3—C11—H11A | 109.5 | O1—C30—H30A | 108.6 |
C3—C11—H11B | 109.5 | C29—C30—H30A | 108.6 |
H11A—C11—H11B | 109.5 | O1—C30—H30B | 108.6 |
C3—C11—H11C | 109.5 | C29—C30—H30B | 108.6 |
H11A—C11—H11C | 109.5 | H30A—C30—H30B | 107.5 |
H11B—C11—H11C | 109.5 | C30—O1—H1A | 109.6 |
C8—C12—H12A | 109.5 | ||
N8—Zn1—N1—C1 | −167.9 (7) | C3—C4—C5—N1 | −0.7 (7) |
N5—Zn1—N1—C1 | 85.3 (4) | C3—C4—C5—C6 | −179.3 (4) |
N3—Zn1—N1—C1 | −8.1 (4) | C10—N2—C6—C7 | −0.4 (6) |
N2—Zn1—N1—C1 | −180.0 (4) | Zn1—N2—C6—C7 | 179.9 (3) |
N4—Zn1—N1—C1 | −82.4 (4) | C10—N2—C6—C5 | 179.6 (4) |
N8—Zn1—N1—C5 | 13.2 (9) | Zn1—N2—C6—C5 | −0.1 (5) |
N5—Zn1—N1—C5 | −93.6 (3) | N1—C5—C6—N2 | 1.1 (5) |
N3—Zn1—N1—C5 | 173.0 (3) | C4—C5—C6—N2 | 179.8 (4) |
N2—Zn1—N1—C5 | 1.1 (3) | N1—C5—C6—C7 | −178.9 (4) |
N4—Zn1—N1—C5 | 98.7 (3) | C4—C5—C6—C7 | −0.2 (7) |
N8—Zn1—N2—C6 | −178.2 (3) | N2—C6—C7—C8 | −0.6 (7) |
N5—Zn1—N2—C6 | 87.5 (3) | C5—C6—C7—C8 | 179.4 (4) |
N3—Zn1—N2—C6 | −44.8 (8) | C6—C7—C8—C9 | 1.8 (7) |
N1—Zn1—N2—C6 | −0.5 (3) | C6—C7—C8—C12 | −177.2 (5) |
N4—Zn1—N2—C6 | −84.5 (3) | C7—C8—C9—C10 | −2.1 (7) |
N8—Zn1—N2—C10 | 2.1 (4) | C12—C8—C9—C10 | 177.0 (5) |
N5—Zn1—N2—C10 | −92.2 (4) | C6—N2—C10—C9 | 0.1 (7) |
N3—Zn1—N2—C10 | 135.5 (6) | Zn1—N2—C10—C9 | 179.8 (3) |
N1—Zn1—N2—C10 | 179.8 (4) | C8—C9—C10—N2 | 1.2 (7) |
N4—Zn1—N2—C10 | 95.8 (4) | C17—N3—C13—C14 | 1.6 (6) |
N8—Zn1—N3—C17 | 99.3 (3) | Zn1—N3—C13—C14 | −174.2 (3) |
N5—Zn1—N3—C17 | −166.3 (3) | N3—C13—C14—C15 | 0.6 (7) |
N2—Zn1—N3—C17 | −33.9 (8) | C13—C14—C15—C16 | −2.5 (7) |
N1—Zn1—N3—C17 | −76.8 (3) | C13—C14—C15—C23 | 175.8 (5) |
N4—Zn1—N3—C17 | 7.2 (3) | C14—C15—C16—C17 | 2.4 (7) |
N8—Zn1—N3—C13 | −85.0 (3) | C23—C15—C16—C17 | −175.9 (5) |
N5—Zn1—N3—C13 | 9.4 (3) | C13—N3—C17—C16 | −1.7 (6) |
N2—Zn1—N3—C13 | 141.8 (6) | Zn1—N3—C17—C16 | 174.3 (3) |
N1—Zn1—N3—C13 | 98.9 (3) | C13—N3—C17—C18 | 177.7 (3) |
N4—Zn1—N3—C13 | −177.1 (3) | Zn1—N3—C17—C18 | −6.3 (4) |
N8—Zn1—N4—C22 | 85.9 (4) | C15—C16—C17—N3 | −0.4 (7) |
N5—Zn1—N4—C22 | −150.8 (6) | C15—C16—C17—C18 | −179.7 (4) |
N3—Zn1—N4—C22 | 179.7 (4) | C22—N4—C18—C19 | −0.3 (6) |
N2—Zn1—N4—C22 | −7.9 (4) | Zn1—N4—C18—C19 | −174.1 (3) |
N1—Zn1—N4—C22 | −82.9 (4) | C22—N4—C18—C17 | −179.9 (4) |
N8—Zn1—N4—C18 | −101.0 (3) | Zn1—N4—C18—C17 | 6.3 (4) |
N5—Zn1—N4—C18 | 22.3 (8) | N3—C17—C18—N4 | −0.3 (5) |
N3—Zn1—N4—C18 | −7.1 (3) | C16—C17—C18—N4 | 179.1 (4) |
N2—Zn1—N4—C18 | 165.2 (3) | N3—C17—C18—C19 | −179.8 (4) |
N1—Zn1—N4—C18 | 90.3 (3) | C16—C17—C18—C19 | −0.5 (6) |
C5—N1—C1—C2 | −0.1 (7) | N4—C18—C19—C20 | 0.7 (6) |
Zn1—N1—C1—C2 | −179.0 (3) | C17—C18—C19—C20 | −179.8 (4) |
N1—C1—C2—C3 | −0.7 (8) | C18—C19—C20—C21 | −0.5 (7) |
C1—C2—C3—C4 | 0.8 (7) | C18—C19—C20—C24 | 177.3 (4) |
C1—C2—C3—C11 | −179.2 (5) | C19—C20—C21—C22 | 0.0 (8) |
C2—C3—C4—C5 | −0.1 (7) | C24—C20—C21—C22 | −177.7 (5) |
C11—C3—C4—C5 | 179.8 (5) | C18—N4—C22—C21 | −0.2 (7) |
C1—N1—C5—C4 | 0.8 (6) | Zn1—N4—C22—C21 | 172.8 (4) |
Zn1—N1—C5—C4 | 179.8 (3) | C20—C21—C22—N4 | 0.4 (8) |
C1—N1—C5—C6 | 179.5 (4) | N8—C27—N9—C28 | −134 (3) |
Zn1—N1—C5—C6 | −1.5 (5) | N9'—C27—N9—C28 | 72.4 (17) |
Experimental details
Crystal data | |
Chemical formula | [Zn(C2N3)2(C12H12N2)2]·0.5C2H6O |
Mr | 589.00 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 294 |
a, b, c (Å) | 15.694 (2), 14.713 (2), 13.8868 (19) |
β (°) | 112.674 (2) |
V (Å3) | 2958.7 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.87 |
Crystal size (mm) | 0.24 × 0.20 × 0.16 |
Data collection | |
Diffractometer | Bruker APEX II CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.772, 0.870 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16800, 6059, 4171 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.626 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.057, 0.206, 1.08 |
No. of reflections | 6059 |
No. of parameters | 402 |
No. of restraints | 64 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.95, −0.45 |
Computer programs: APEX2 (Bruker, 2003), APEX2 or SAINT? (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker 2003), SHELXTL.
Polypyridine complexes of transition metals have received much attention in recent years on account of their photophysical properties (Yiting et al., 2001). Hydrogen bonds and π···π stacking interactions have also proven to play important roles in the control of molecular arrangement in the crystalline state and the properties of matter (Jones & Rao, 2001).
The crystal structure of (I) contains half an ethanol molecule for each zinc(II) complex. The Zn atom is coordinated by six N atoms from two chelating dmbpy ligands and two dca ligands that are cis to one another (Fig.1). The Zn—N bond distances range from 2.101 (4) to 2.226 (3) Å and the cis N—Zn—N angles range from 74.87 (13) to 96.25 (13) °, indicating a distorted octahedral coordinated geometry around Zn atom. The dmbpy ligands are planar (maximum deviation from the least-squares planes are 0.0499 (44) Å (for the ligand containing N1 and 0.0436 (50) Å for the ligand containing N3.
The dihedral angle between the two dmbpy ligands is 79.31 (7) °. in the two dca ligands, all the C—N triple bond distances less than 1.13 Å. As depicted in Fig. 2, the complexes are linked via weak π···π stacking interactions between parallel dmbpy ligands to generate a one-dimensional chain along the [100] direction. The center-to-center distance between the pyridyl ring containing atom N1 and that containing N2i atom (i = 1 - x, 1 - y, 1 - z) is 4.175 (3) Å and that between the rings containing atom N3 and atom N4ii (ii = - x, 1 - y, -z) is 3.838 (3) Å. The one-dimensional chains are parallel in the crystal structure of (I) and the ethanol resides in a vacancy between the main complexes.