Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101012136/gd1164sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101012136/gd1164Isup2.hkl |
CCDC reference: 175059
Colourless crystals of (I) were grown by slow evaporation from a solution of ZnCl2 and 2,6-Cl2-pyrazine (1:2) in ethanol under a flow of nitrogen.
All H atoms were introduced in idealized positions (C—H = 0.98 Å) and included as riding with Uiso(H) = 1.3Ueq(non-H).
Data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT+ (Bruker, 1999); program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: PLATON (Spek, 1990); software used to prepare material for publication: SHELXTL.
[ZnCl2(C4H2Cl2N2)2] | Z = 6 |
Mr = 434.22 | F(000) = 1272 |
Triclinic, P1 | Dx = 1.903 Mg m−3 |
a = 12.4478 (7) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.4880 (8) Å | Cell parameters from 31443 reflections |
c = 15.6692 (9) Å | θ = 1.4–28.3° |
α = 75.954 (1)° | µ = 2.67 mm−1 |
β = 76.134 (1)° | T = 293 K |
γ = 79.438 (1)° | Block, colourless |
V = 2273.7 (2) Å3 | 0.36 × 0.30 × 0.20 mm |
Bruker SMART APEX CCD area-detector diffractometer | 11257 independent reflections |
Radiation source: fine-focus sealed tube | 6480 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
ω scans | θmax = 28.3°, θmin = 1.4° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −16→16 |
Tmin = 0.398, Tmax = 0.587 | k = −16→16 |
31443 measured reflections | l = −20→20 |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.077 | H-atom parameters constrained |
S = 0.81 | w = 1/[σ2(Fo2) + (0.0309P)2] where P = (Fo2 + 2Fc2)/3 |
11257 reflections | (Δ/σ)max = 0.001 |
515 parameters | Δρmax = 0.50 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
[ZnCl2(C4H2Cl2N2)2] | γ = 79.438 (1)° |
Mr = 434.22 | V = 2273.7 (2) Å3 |
Triclinic, P1 | Z = 6 |
a = 12.4478 (7) Å | Mo Kα radiation |
b = 12.4880 (8) Å | µ = 2.67 mm−1 |
c = 15.6692 (9) Å | T = 293 K |
α = 75.954 (1)° | 0.36 × 0.30 × 0.20 mm |
β = 76.134 (1)° |
Bruker SMART APEX CCD area-detector diffractometer | 11257 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 6480 reflections with I > 2σ(I) |
Tmin = 0.398, Tmax = 0.587 | Rint = 0.046 |
31443 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.077 | H-atom parameters constrained |
S = 0.81 | Δρmax = 0.50 e Å−3 |
11257 reflections | Δρmin = −0.37 e Å−3 |
515 parameters |
Experimental. The values of Tmin and Tmax are 0.718023 and 1.000000 from SADABS. |
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 | ||
Zn1 | 0.69780 (3) | 0.87835 (3) | 0.24338 (3) | 0.04852 (12) | |
Zn2 | 0.31282 (3) | 0.15000 (3) | 0.28837 (3) | 0.04466 (11) | |
Zn3 | 0.99635 (3) | 0.51099 (3) | 0.21669 (3) | 0.04580 (12) | |
Cl1 | 0.71674 (9) | 0.76978 (9) | 0.37249 (7) | 0.0674 (3) | |
Cl2 | 0.80248 (8) | 0.86944 (9) | 0.11061 (7) | 0.0664 (3) | |
Cl3 | 0.68225 (13) | 1.33685 (10) | 0.09425 (9) | 0.0955 (4) | |
Cl4 | 0.53836 (12) | 1.22161 (10) | 0.43821 (8) | 0.0930 (4) | |
Cl5 | 0.37496 (10) | 0.89265 (11) | 0.04109 (7) | 0.0832 (4) | |
Cl6 | 0.25755 (9) | 0.78485 (11) | 0.38853 (7) | 0.0770 (3) | |
Cl7 | 0.33155 (9) | 0.04644 (8) | 0.41871 (7) | 0.0612 (3) | |
Cl8 | 0.42443 (8) | 0.14275 (8) | 0.15803 (6) | 0.0568 (3) | |
Cl9 | 0.34596 (10) | 0.60185 (9) | 0.13283 (7) | 0.0717 (3) | |
Cl10 | 0.18459 (11) | 0.50373 (9) | 0.47549 (7) | 0.0810 (4) | |
Cl11 | −0.02003 (11) | 0.25743 (11) | 0.08050 (8) | 0.0898 (4) | |
Cl12 | −0.13942 (9) | 0.08871 (11) | 0.41955 (7) | 0.0756 (3) | |
Cl13 | 0.99787 (9) | 0.39144 (8) | 0.34470 (7) | 0.0576 (3) | |
Cl14 | 1.10453 (9) | 0.49922 (9) | 0.08680 (7) | 0.0657 (3) | |
Cl15 | 1.07935 (11) | 0.95749 (9) | 0.10210 (8) | 0.0834 (4) | |
Cl16 | 0.97284 (10) | 0.80013 (10) | 0.44686 (7) | 0.0798 (4) | |
Cl17 | 0.64420 (9) | 0.67235 (10) | 0.02764 (7) | 0.0741 (3) | |
Cl18 | 0.53714 (9) | 0.53455 (10) | 0.37272 (8) | 0.0798 (4) | |
N1 | 0.6746 (2) | 1.0437 (2) | 0.2562 (2) | 0.0471 (8) | |
N2 | 0.6161 (3) | 1.2652 (3) | 0.2662 (2) | 0.0625 (9) | |
N3 | 0.5395 (2) | 0.8608 (2) | 0.23055 (19) | 0.0417 (7) | |
N4 | 0.3269 (3) | 0.8406 (3) | 0.2159 (2) | 0.0531 (8) | |
N5 | 0.3029 (2) | 0.3157 (2) | 0.29860 (19) | 0.0422 (7) | |
N6 | 0.2689 (3) | 0.5382 (2) | 0.3049 (2) | 0.0520 (8) | |
N7 | 0.1527 (2) | 0.1465 (2) | 0.2706 (2) | 0.0438 (7) | |
N8 | −0.0667 (3) | 0.1695 (3) | 0.2509 (2) | 0.0526 (8) | |
N9 | 1.0172 (2) | 0.6626 (2) | 0.24006 (19) | 0.0427 (7) | |
N10 | 1.0256 (3) | 0.8688 (3) | 0.2731 (2) | 0.0557 (8) | |
N11 | 0.8283 (2) | 0.5395 (2) | 0.20641 (19) | 0.0448 (7) | |
N12 | 0.6051 (3) | 0.5992 (3) | 0.2001 (2) | 0.0536 (8) | |
C1 | 0.6939 (3) | 1.1248 (3) | 0.1838 (3) | 0.0548 (10) | |
H1 | 0.7303 | 1.1062 | 0.1255 | 0.071* | |
C2 | 0.6631 (3) | 1.2341 (3) | 0.1903 (3) | 0.0569 (11) | |
C3 | 0.5997 (3) | 1.1846 (3) | 0.3372 (3) | 0.0562 (10) | |
C4 | 0.6278 (3) | 1.0733 (3) | 0.3348 (3) | 0.0529 (10) | |
H4 | 0.6138 | 1.0163 | 0.3901 | 0.069* | |
C5 | 0.5130 (3) | 0.8786 (3) | 0.1509 (2) | 0.0441 (9) | |
H5 | 0.5688 | 0.8995 | 0.0960 | 0.057* | |
C6 | 0.4071 (3) | 0.8679 (3) | 0.1452 (2) | 0.0484 (9) | |
C7 | 0.3567 (3) | 0.8227 (3) | 0.2940 (2) | 0.0478 (9) | |
C8 | 0.4614 (3) | 0.8325 (3) | 0.3040 (2) | 0.0472 (9) | |
H8 | 0.4782 | 0.8191 | 0.3640 | 0.061* | |
C9 | 0.3279 (3) | 0.3931 (3) | 0.2241 (2) | 0.0474 (9) | |
H9 | 0.3575 | 0.3712 | 0.1660 | 0.062* | |
C10 | 0.3120 (3) | 0.5036 (3) | 0.2291 (2) | 0.0462 (9) | |
C11 | 0.2457 (3) | 0.4607 (3) | 0.3762 (2) | 0.0484 (9) | |
C12 | 0.2633 (3) | 0.3481 (3) | 0.3764 (2) | 0.0449 (9) | |
H12 | 0.2469 | 0.2932 | 0.4326 | 0.058* | |
C13 | 0.1243 (3) | 0.1909 (3) | 0.1906 (3) | 0.0530 (10) | |
H13 | 0.1815 | 0.2160 | 0.1379 | 0.069* | |
C14 | 0.0158 (3) | 0.2011 (3) | 0.1828 (3) | 0.0540 (10) | |
C15 | −0.0360 (3) | 0.1263 (3) | 0.3287 (2) | 0.0464 (9) | |
C16 | 0.0727 (3) | 0.1132 (3) | 0.3398 (2) | 0.0443 (9) | |
H16 | 0.0907 | 0.0792 | 0.3989 | 0.058* | |
C17 | 1.0447 (3) | 0.7472 (3) | 0.1734 (2) | 0.0483 (9) | |
H17 | 1.0627 | 0.7373 | 0.1112 | 0.063* | |
C18 | 1.0480 (3) | 0.8490 (3) | 0.1909 (3) | 0.0504 (10) | |
C19 | 1.0007 (3) | 0.7828 (3) | 0.3380 (3) | 0.0505 (10) | |
C20 | 0.9948 (3) | 0.6794 (3) | 0.3242 (2) | 0.0456 (9) | |
H20 | 0.9745 | 0.6186 | 0.3754 | 0.059* | |
C21 | 0.7970 (3) | 0.5831 (3) | 0.1287 (2) | 0.0464 (9) | |
H21 | 0.8529 | 0.5945 | 0.0726 | 0.060* | |
C22 | 0.6851 (3) | 0.6122 (3) | 0.1277 (3) | 0.0500 (10) | |
C23 | 0.6386 (3) | 0.5530 (3) | 0.2760 (3) | 0.0512 (10) | |
C24 | 0.7491 (3) | 0.5231 (3) | 0.2812 (3) | 0.0513 (10) | |
H24 | 0.7698 | 0.4898 | 0.3394 | 0.067* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0427 (3) | 0.0440 (2) | 0.0577 (3) | −0.00338 (19) | −0.0124 (2) | −0.0081 (2) |
Zn2 | 0.0441 (3) | 0.0397 (2) | 0.0465 (3) | −0.00325 (19) | −0.0053 (2) | −0.0076 (2) |
Zn3 | 0.0494 (3) | 0.0440 (2) | 0.0455 (3) | 0.0009 (2) | −0.0132 (2) | −0.0141 (2) |
Cl1 | 0.0674 (7) | 0.0678 (7) | 0.0636 (7) | −0.0012 (6) | −0.0266 (6) | 0.0001 (6) |
Cl2 | 0.0498 (6) | 0.0742 (7) | 0.0678 (7) | −0.0065 (5) | 0.0024 (5) | −0.0160 (6) |
Cl3 | 0.1446 (13) | 0.0554 (7) | 0.0773 (9) | −0.0239 (7) | −0.0212 (8) | 0.0094 (6) |
Cl4 | 0.1363 (12) | 0.0781 (8) | 0.0651 (8) | 0.0123 (8) | −0.0284 (8) | −0.0282 (7) |
Cl5 | 0.0848 (8) | 0.1192 (10) | 0.0502 (7) | −0.0306 (7) | −0.0270 (6) | −0.0008 (7) |
Cl6 | 0.0692 (7) | 0.1116 (9) | 0.0542 (7) | −0.0437 (7) | 0.0138 (5) | −0.0276 (7) |
Cl7 | 0.0709 (7) | 0.0541 (6) | 0.0521 (6) | −0.0095 (5) | −0.0140 (5) | 0.0033 (5) |
Cl8 | 0.0536 (6) | 0.0572 (6) | 0.0504 (6) | 0.0039 (5) | 0.0003 (5) | −0.0131 (5) |
Cl9 | 0.1060 (9) | 0.0579 (6) | 0.0510 (6) | −0.0336 (6) | −0.0150 (6) | 0.0049 (5) |
Cl10 | 0.1290 (11) | 0.0618 (7) | 0.0473 (7) | −0.0117 (7) | −0.0017 (7) | −0.0190 (5) |
Cl11 | 0.1017 (10) | 0.1114 (10) | 0.0609 (8) | −0.0313 (8) | −0.0413 (7) | 0.0105 (7) |
Cl12 | 0.0508 (6) | 0.1122 (9) | 0.0586 (7) | −0.0246 (6) | 0.0002 (5) | −0.0092 (6) |
Cl13 | 0.0718 (7) | 0.0451 (5) | 0.0540 (6) | 0.0029 (5) | −0.0216 (5) | −0.0061 (5) |
Cl14 | 0.0668 (7) | 0.0786 (7) | 0.0540 (6) | −0.0065 (6) | −0.0019 (5) | −0.0307 (6) |
Cl15 | 0.1020 (10) | 0.0591 (7) | 0.0849 (9) | −0.0280 (6) | −0.0241 (7) | 0.0109 (6) |
Cl16 | 0.0837 (8) | 0.1051 (9) | 0.0636 (7) | −0.0230 (7) | 0.0006 (6) | −0.0494 (7) |
Cl17 | 0.0694 (7) | 0.0970 (9) | 0.0537 (7) | 0.0147 (6) | −0.0266 (5) | −0.0167 (6) |
Cl18 | 0.0634 (7) | 0.0951 (9) | 0.0660 (8) | −0.0119 (6) | 0.0049 (6) | −0.0054 (7) |
N1 | 0.0476 (19) | 0.0442 (18) | 0.054 (2) | −0.0073 (14) | −0.0197 (16) | −0.0082 (16) |
N2 | 0.081 (3) | 0.046 (2) | 0.065 (2) | −0.0041 (18) | −0.031 (2) | −0.0092 (19) |
N3 | 0.0402 (17) | 0.0398 (16) | 0.0445 (19) | −0.0038 (13) | −0.0068 (14) | −0.0103 (14) |
N4 | 0.046 (2) | 0.058 (2) | 0.057 (2) | −0.0107 (16) | −0.0085 (17) | −0.0149 (17) |
N5 | 0.0417 (17) | 0.0395 (17) | 0.0426 (18) | −0.0069 (13) | −0.0061 (14) | −0.0046 (14) |
N6 | 0.068 (2) | 0.0454 (18) | 0.045 (2) | −0.0092 (16) | −0.0144 (17) | −0.0107 (16) |
N7 | 0.0473 (18) | 0.0408 (17) | 0.0426 (19) | −0.0084 (14) | −0.0070 (15) | −0.0073 (14) |
N8 | 0.056 (2) | 0.056 (2) | 0.052 (2) | −0.0139 (16) | −0.0170 (17) | −0.0124 (17) |
N9 | 0.0433 (18) | 0.0394 (17) | 0.0439 (19) | 0.0005 (13) | −0.0102 (14) | −0.0086 (15) |
N10 | 0.054 (2) | 0.053 (2) | 0.066 (2) | −0.0078 (16) | −0.0142 (18) | −0.0223 (19) |
N11 | 0.0468 (19) | 0.0438 (17) | 0.0442 (19) | −0.0017 (14) | −0.0104 (15) | −0.0121 (15) |
N12 | 0.051 (2) | 0.056 (2) | 0.055 (2) | −0.0016 (16) | −0.0161 (17) | −0.0136 (17) |
C1 | 0.060 (3) | 0.053 (3) | 0.052 (3) | −0.012 (2) | −0.015 (2) | −0.005 (2) |
C2 | 0.072 (3) | 0.043 (2) | 0.060 (3) | −0.013 (2) | −0.023 (2) | −0.003 (2) |
C3 | 0.064 (3) | 0.055 (3) | 0.057 (3) | 0.002 (2) | −0.029 (2) | −0.016 (2) |
C4 | 0.058 (3) | 0.052 (2) | 0.054 (3) | −0.008 (2) | −0.023 (2) | −0.008 (2) |
C5 | 0.045 (2) | 0.041 (2) | 0.042 (2) | −0.0063 (17) | −0.0037 (17) | −0.0059 (17) |
C6 | 0.051 (2) | 0.050 (2) | 0.044 (2) | −0.0077 (18) | −0.0109 (19) | −0.0089 (18) |
C7 | 0.044 (2) | 0.053 (2) | 0.046 (2) | −0.0144 (18) | 0.0046 (18) | −0.0171 (19) |
C8 | 0.053 (2) | 0.046 (2) | 0.042 (2) | −0.0069 (18) | −0.0060 (19) | −0.0118 (18) |
C9 | 0.049 (2) | 0.049 (2) | 0.044 (2) | −0.0069 (18) | −0.0064 (18) | −0.0130 (19) |
C10 | 0.052 (2) | 0.045 (2) | 0.040 (2) | −0.0131 (18) | −0.0094 (18) | 0.0008 (18) |
C11 | 0.059 (2) | 0.048 (2) | 0.041 (2) | −0.0084 (19) | −0.0122 (19) | −0.0108 (19) |
C12 | 0.051 (2) | 0.046 (2) | 0.036 (2) | −0.0052 (18) | −0.0094 (17) | −0.0054 (17) |
C13 | 0.057 (3) | 0.055 (2) | 0.046 (2) | −0.012 (2) | −0.005 (2) | −0.011 (2) |
C14 | 0.062 (3) | 0.056 (2) | 0.049 (3) | −0.012 (2) | −0.018 (2) | −0.010 (2) |
C15 | 0.042 (2) | 0.052 (2) | 0.046 (2) | −0.0118 (18) | −0.0048 (18) | −0.0138 (19) |
C16 | 0.046 (2) | 0.045 (2) | 0.041 (2) | −0.0064 (17) | −0.0078 (18) | −0.0097 (17) |
C17 | 0.051 (2) | 0.050 (2) | 0.044 (2) | −0.0004 (18) | −0.0131 (18) | −0.0096 (19) |
C18 | 0.044 (2) | 0.044 (2) | 0.060 (3) | −0.0045 (17) | −0.0151 (19) | −0.003 (2) |
C19 | 0.040 (2) | 0.063 (3) | 0.050 (2) | −0.0036 (19) | −0.0063 (18) | −0.022 (2) |
C20 | 0.046 (2) | 0.049 (2) | 0.043 (2) | −0.0042 (17) | −0.0075 (17) | −0.0140 (18) |
C21 | 0.054 (2) | 0.047 (2) | 0.040 (2) | −0.0015 (18) | −0.0120 (18) | −0.0143 (18) |
C22 | 0.058 (3) | 0.049 (2) | 0.048 (2) | 0.0042 (19) | −0.019 (2) | −0.0186 (19) |
C23 | 0.052 (3) | 0.046 (2) | 0.053 (3) | −0.0095 (19) | −0.002 (2) | −0.0118 (19) |
C24 | 0.058 (3) | 0.054 (2) | 0.042 (2) | −0.005 (2) | −0.014 (2) | −0.0079 (19) |
Zn1—N1 | 2.084 (3) | N7—C16 | 1.325 (4) |
Zn1—N3 | 2.084 (3) | N7—C13 | 1.344 (4) |
Zn2—N5 | 2.094 (3) | N8—C15 | 1.324 (4) |
Zn2—N7 | 2.086 (3) | N8—C14 | 1.329 (5) |
Zn3—N9 | 2.085 (3) | N9—C17 | 1.323 (4) |
Zn3—N11 | 2.095 (3) | N9—C20 | 1.340 (4) |
Zn1—Cl1 | 2.1833 (11) | N10—C19 | 1.313 (5) |
Zn1—Cl2 | 2.1905 (11) | N10—C18 | 1.325 (5) |
Zn2—Cl7 | 2.1757 (10) | N11—C21 | 1.326 (4) |
Zn2—Cl8 | 2.1894 (10) | N11—C24 | 1.339 (4) |
Zn3—Cl13 | 2.1924 (10) | N12—C22 | 1.316 (5) |
Zn3—Cl14 | 2.1764 (11) | N12—C23 | 1.318 (5) |
Cl3—C2 | 1.723 (4) | C1—C2 | 1.370 (5) |
Cl4—C3 | 1.718 (4) | C1—H1 | 0.9800 |
Cl5—C6 | 1.714 (4) | C3—C4 | 1.377 (5) |
Cl6—C7 | 1.714 (4) | C4—H4 | 0.9800 |
Cl9—C10 | 1.716 (3) | C5—C6 | 1.375 (5) |
Cl10—C11 | 1.725 (4) | C5—H5 | 0.9800 |
Cl11—C14 | 1.716 (4) | C7—C8 | 1.380 (5) |
Cl12—C15 | 1.709 (4) | C8—H8 | 0.9800 |
Cl15—C18 | 1.715 (4) | C9—C10 | 1.376 (5) |
Cl16—C19 | 1.716 (4) | C9—H9 | 0.9800 |
Cl17—C22 | 1.718 (4) | C11—C12 | 1.382 (5) |
Cl18—C23 | 1.721 (4) | C12—H12 | 0.9800 |
N1—C1 | 1.331 (4) | C13—C14 | 1.366 (5) |
N1—C4 | 1.338 (4) | C13—H13 | 0.9800 |
N2—C2 | 1.310 (5) | C15—C16 | 1.381 (5) |
N2—C3 | 1.309 (5) | C16—H16 | 0.9800 |
N3—C5 | 1.324 (4) | C17—C18 | 1.373 (5) |
N3—C8 | 1.337 (4) | C17—H17 | 0.9800 |
N4—C7 | 1.318 (4) | C19—C20 | 1.379 (5) |
N4—C6 | 1.323 (4) | C20—H20 | 0.9800 |
N5—C12 | 1.330 (4) | C21—C22 | 1.377 (5) |
N5—C9 | 1.335 (4) | C21—H21 | 0.9800 |
N6—C11 | 1.302 (4) | C23—C24 | 1.374 (5) |
N6—C10 | 1.321 (4) | C24—H24 | 0.9800 |
N1—Zn1—N3 | 101.30 (11) | N4—C6—C5 | 123.8 (4) |
N5—Zn2—N7 | 101.26 (11) | N4—C6—Cl5 | 117.4 (3) |
N9—Zn3—N11 | 101.53 (11) | C5—C6—Cl5 | 118.9 (3) |
Cl1—Zn1—Cl2 | 127.86 (5) | N4—C7—C8 | 124.3 (3) |
Cl7—Zn2—Cl8 | 127.53 (4) | N4—C7—Cl6 | 117.1 (3) |
Cl13—Zn3—Cl14 | 127.47 (4) | C8—C7—Cl6 | 118.6 (3) |
N3—Zn1—Cl1 | 104.02 (8) | N3—C8—C7 | 118.9 (3) |
N1—Zn1—Cl1 | 108.99 (9) | N3—C8—H8 | 120.5 |
N3—Zn1—Cl2 | 103.96 (8) | C7—C8—H8 | 120.5 |
N1—Zn1—Cl2 | 107.43 (9) | N5—C9—C10 | 119.7 (3) |
N7—Zn2—Cl7 | 108.37 (9) | N5—C9—H9 | 120.1 |
N5—Zn2—Cl7 | 107.06 (8) | C10—C9—H9 | 120.1 |
N7—Zn2—Cl8 | 106.07 (9) | N6—C10—C9 | 122.8 (3) |
N5—Zn2—Cl8 | 103.54 (8) | N6—C10—Cl9 | 118.0 (3) |
N9—Zn3—Cl14 | 104.94 (9) | C9—C10—Cl9 | 119.2 (3) |
N11—Zn3—Cl14 | 110.53 (9) | N6—C11—C12 | 124.3 (3) |
N9—Zn3—Cl13 | 105.69 (8) | N6—C11—Cl10 | 116.8 (3) |
N11—Zn3—Cl13 | 103.80 (9) | C12—C11—Cl10 | 118.9 (3) |
C1—N1—C4 | 117.6 (3) | N5—C12—C11 | 118.7 (3) |
C1—N1—Zn1 | 120.3 (3) | N5—C12—H12 | 120.7 |
C4—N1—Zn1 | 121.6 (3) | C11—C12—H12 | 120.7 |
C2—N2—C3 | 115.7 (3) | N7—C13—C14 | 120.0 (4) |
C5—N3—C8 | 118.5 (3) | N7—C13—H13 | 120.0 |
C5—N3—Zn1 | 121.6 (2) | C14—C13—H13 | 120.0 |
C8—N3—Zn1 | 119.9 (2) | N8—C14—C13 | 123.8 (4) |
C7—N4—C6 | 114.6 (3) | N8—C14—Cl11 | 116.4 (3) |
C12—N5—C9 | 118.6 (3) | C13—C14—Cl11 | 119.8 (3) |
C12—N5—Zn2 | 121.9 (2) | N8—C15—C16 | 123.6 (3) |
C9—N5—Zn2 | 119.3 (2) | N8—C15—Cl12 | 116.8 (3) |
C11—N6—C10 | 115.8 (3) | C16—C15—Cl12 | 119.5 (3) |
C16—N7—C13 | 117.9 (3) | N7—C16—C15 | 120.0 (3) |
C16—N7—Zn2 | 121.1 (2) | N7—C16—H16 | 120.0 |
C13—N7—Zn2 | 120.6 (2) | C15—C16—H16 | 120.0 |
C15—N8—C14 | 114.8 (3) | N9—C17—C18 | 120.4 (3) |
C17—N9—C20 | 117.9 (3) | N9—C17—H17 | 119.8 |
C17—N9—Zn3 | 121.9 (2) | C18—C17—H17 | 119.8 |
C20—N9—Zn3 | 120.1 (2) | N10—C18—C17 | 123.4 (4) |
C19—N10—C18 | 114.9 (3) | N10—C18—Cl15 | 117.9 (3) |
C21—N11—C24 | 118.4 (3) | C17—C18—Cl15 | 118.7 (3) |
C21—N11—Zn3 | 122.0 (2) | N10—C19—C20 | 124.1 (4) |
C24—N11—Zn3 | 119.4 (2) | N10—C19—Cl16 | 118.2 (3) |
C22—N12—C23 | 115.4 (3) | C20—C19—Cl16 | 117.8 (3) |
N1—C1—C2 | 120.4 (4) | N9—C20—C19 | 119.4 (3) |
N1—C1—H1 | 119.8 | N9—C20—H20 | 120.3 |
C2—C1—H1 | 119.8 | C19—C20—H20 | 120.3 |
N2—C2—C1 | 123.1 (4) | N11—C21—C22 | 119.3 (3) |
N2—C2—Cl3 | 117.6 (3) | N11—C21—H21 | 120.4 |
C1—C2—Cl3 | 119.3 (3) | C22—C21—H21 | 120.4 |
N2—C3—C4 | 123.8 (4) | N12—C22—C21 | 123.9 (4) |
N2—C3—Cl4 | 117.3 (3) | N12—C22—Cl17 | 116.6 (3) |
C4—C3—Cl4 | 118.9 (3) | C21—C22—Cl17 | 119.5 (3) |
N1—C4—C3 | 119.2 (4) | N12—C23—C24 | 123.2 (4) |
N1—C4—H4 | 120.4 | N12—C23—Cl18 | 117.2 (3) |
C3—C4—H4 | 120.4 | C24—C23—Cl18 | 119.6 (3) |
N3—C5—C6 | 119.9 (3) | N11—C24—C23 | 119.7 (3) |
N3—C5—H5 | 120.0 | N11—C24—H24 | 120.1 |
C6—C5—H5 | 120.0 | C23—C24—H24 | 120.1 |
Experimental details
Crystal data | |
Chemical formula | [ZnCl2(C4H2Cl2N2)2] |
Mr | 434.22 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 12.4478 (7), 12.4880 (8), 15.6692 (9) |
α, β, γ (°) | 75.954 (1), 76.134 (1), 79.438 (1) |
V (Å3) | 2273.7 (2) |
Z | 6 |
Radiation type | Mo Kα |
µ (mm−1) | 2.67 |
Crystal size (mm) | 0.36 × 0.30 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.398, 0.587 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 31443, 11257, 6480 |
Rint | 0.046 |
(sin θ/λ)max (Å−1) | 0.668 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.077, 0.81 |
No. of reflections | 11257 |
No. of parameters | 515 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.50, −0.37 |
Computer programs: SMART (Bruker, 2001), SMART, SAINT+ (Bruker, 1999), SHELXTL (Sheldrick, 1997), SHELXTL, PLATON (Spek, 1990).
Zn1—N1 | 2.084 (3) | Zn1—Cl1 | 2.1833 (11) |
Zn1—N3 | 2.084 (3) | Zn1—Cl2 | 2.1905 (11) |
Zn2—N5 | 2.094 (3) | Zn2—Cl7 | 2.1757 (10) |
Zn2—N7 | 2.086 (3) | Zn2—Cl8 | 2.1894 (10) |
Zn3—N9 | 2.085 (3) | Zn3—Cl13 | 2.1924 (10) |
Zn3—N11 | 2.095 (3) | Zn3—Cl14 | 2.1764 (11) |
N1—Zn1—N3 | 101.30 (11) | Cl1—Zn1—Cl2 | 127.86 (5) |
N5—Zn2—N7 | 101.26 (11) | Cl7—Zn2—Cl8 | 127.53 (4) |
N9—Zn3—N11 | 101.53 (11) | Cl13—Zn3—Cl14 | 127.47 (4) |
Dataset | Rint(LMS) | Rint(crystal) | volume fraction of 2nd twin individual |
1 | 0.343 | 0.046 | 0.1016 (4) |
2 | 0.154 | 0.061 | 0.3673 (8) |
3 | 0.075 | 0.047 | 0.4765 (8) |
4 | 0.067 | 0.048 | 0.4974 (9) |
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Our interest in intermolecular interactions recently induced us to synthesize and study the first one-dimensional chain polymers of the type [Zn(µ-Cl)2py2]∞ (py is 3,5-dichloropyridine or 3,5-dibromopyridine), (II) (Hu & Englert, 2001). 2,6-Dichloropyrazine, the ligand involved in the present study, was expected to have similar steric requirements to the 3,5-dihalopyridines. Furthermore, coordination of a metal should only occur in the 4- and not in the 1-position. Despite these similarities between the dihalopyridine and dihalopyrazine ligands, reaction of zinc dichloride with the latter does not result in the formation of a chain polymer, but of the title tetrahedral mononuclear complex, (I), underlining the restricted range of existence for the above-mentioned type of coordination polymers. \sch
We studied five crystals of (I) by X-ray diffraction and obtained four data sets of comparable accuracy; the intensity data from a fifth sample proved to be less satisfactory in terms of internal consistency and will not be reported. All crystals were twinned. A metrically possible transformation to a monoclinic centred cell is incompatible with the symmetry of the diffraction pattern. The twinning can be classified as metric merohedry (Nespolo & Ferraris, 2000) with monoclinic lattice metric symmetry (LMS). Metric merohedry means that all reflections of the twin components will overlap. In other words, the reciprocal lattice of the twin mimics that of a single-crystal, and in the limiting case of a very small twin component twinning might be completely overlooked. In the present case, the twin law interchanges a and b according to the matrix (010, 100, 001). Internal agreement factors (Rint) for merging the intensity data under the LMS differ strongly between these independent data sets, and we wish to point out that this variation represents a warning sign for merohedral twinning. A synopsis of Rint, obtained under both the triclinic crystal symmetry and the monoclinic LMS, and the volume ratio between the twin components, is provided in Table 2. The discrepancy between Rint for merging in the LMS and the crystal symmetry may serve as an indicator for the volume ratio between the twin individuals. In the following discussion, in Table 1 and in the supplementary material, numerical values and their standard deviations refer to the data set with the smallest contribution of a second individual.
The asymmetric unit of (I) contains three independent molecules (Fig. 1). They are similar not only in terms of bond lengths and angles, but also with respect to the dihedral angles subtended by the planes through the pyrazine ligands [87.40 (18), 87.39 (18) and 89.64 (18)°]. A packing diagram is shown in Fig. 2. No particularly short intermolecular interactions occur; the shortest Cl···Cl distance is ca 3.39 Å.