Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105000478/fg1805sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105000478/fg1805Isup2.hkl |
CCDC reference: 252238
Ligand L was synthesized according to the method reported by Berends & Stephan (1984). A mixture of Co(NO3)2.6H2O (0.291 g, 1 mmol) and L (0.435 g, 1.5 mmol) in ethanol (20 ml) was refluxed for 30 min, and a purple solution was obtained. Purple crystals were obtained after leaving the solution to stand at room temperature for several days. The same product, (I), was isolated using different cobalt(II)/L molar ratios of 1:1, 1:1.5 and 1:2; this result may be caused by the low solubility of complex (I). Yield 64% based on Co. Analysis calcualted for C58H66Co2N16O14: C 52.41, H 5.00, N 16.86%; found: C 52.35, H 4.92, N 16.41%. IR (cm−1, KBr): 3436 (s), 3121 (w), 2943 (w), 2340 (w), 1641 (w), 1529 (m), 1458 (s), 1382 (vs), 1240 (w), 1103(s), 1038 (w), 948 (w), 837 (w), 757 (w), 622 (m).
All H atoms were visible in difference maps and were allowed for in the refinement as riding atoms, with C—H distances of 0.95–0.99 Å, N—H distances of 0.88 Å and an O—H distance of 0.84 Å, and with Uiso(H) values of 1.2–1.5 times Ueq(C, N,O).
Data collection: PROCESS-AUTO (Rigaku Corporation, 1998); cell refinement: PROCESS-AUTO; data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) in WinGX (Farrugia, 1999); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.
[Co2(NO3)2(C18H18N4)3](NO3)2·2C2H6O | Z = 1 |
Mr = 1329.13 | F(000) = 692 |
Triclinic, P1 | Dx = 1.427 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.7260 (17) Å | Cell parameters from 7174 reflections |
b = 11.295 (2) Å | θ = 2.3–27.5° |
c = 16.284 (3) Å | µ = 0.61 mm−1 |
α = 90.16 (3)° | T = 193 K |
β = 96.76 (3)° | Block, purple |
γ = 103.85 (3)° | 0.51 × 0.44 × 0.23 mm |
V = 1546.6 (5) Å3 |
Rigaku R-AXIS RAPID diffractometer | 6778 independent reflections |
Radiation source: rotating anode | 4638 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
ω scans | θmax = 27.5°, θmin = 2.3° |
Absorption correction: multi-scan (Higashi, 1995) | h = 0→11 |
Tmin = 0.725, Tmax = 0.867 | k = −14→13 |
13292 measured reflections | l = −21→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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.089 | H-atom parameters constrained |
S = 0.91 | w = 1/[σ2(Fo2) + (0.0475P)2] where P = (Fo2 + 2Fc2)/3 |
6778 reflections | (Δ/σ)max < 0.001 |
408 parameters | Δρmax = 0.50 e Å−3 |
0 restraints | Δρmin = −0.38 e Å−3 |
[Co2(NO3)2(C18H18N4)3](NO3)2·2C2H6O | γ = 103.85 (3)° |
Mr = 1329.13 | V = 1546.6 (5) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.7260 (17) Å | Mo Kα radiation |
b = 11.295 (2) Å | µ = 0.61 mm−1 |
c = 16.284 (3) Å | T = 193 K |
α = 90.16 (3)° | 0.51 × 0.44 × 0.23 mm |
β = 96.76 (3)° |
Rigaku R-AXIS RAPID diffractometer | 6778 independent reflections |
Absorption correction: multi-scan (Higashi, 1995) | 4638 reflections with I > 2σ(I) |
Tmin = 0.725, Tmax = 0.867 | Rint = 0.032 |
13292 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.089 | H-atom parameters constrained |
S = 0.91 | Δρmax = 0.50 e Å−3 |
6778 reflections | Δρmin = −0.38 e Å−3 |
408 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 | ||
Co1 | 0.38487 (3) | 0.20527 (3) | 0.241430 (17) | 0.02794 (9) | |
O1 | 0.55379 (17) | 0.21259 (14) | 0.16743 (9) | 0.0407 (4) | |
O2 | 0.62483 (19) | 0.38065 (15) | 0.23991 (10) | 0.0475 (4) | |
O3 | 0.7784 (2) | 0.33985 (19) | 0.15424 (11) | 0.0661 (6) | |
N1 | 0.66240 (19) | 0.22300 (15) | 0.46911 (10) | 0.0279 (4) | |
H1 | 0.7230 | 0.2638 | 0.5120 | 0.033* | |
N3 | 0.48729 (19) | 0.18275 (15) | 0.35654 (10) | 0.0260 (4) | |
N4 | 0.6567 (2) | 0.31293 (19) | 0.18709 (11) | 0.0392 (5) | |
N11 | 0.1090 (2) | 0.46147 (17) | 0.24837 (11) | 0.0363 (4) | |
H11 | 0.0476 | 0.4990 | 0.2723 | 0.044* | |
N13 | 0.26112 (19) | 0.33477 (15) | 0.23022 (10) | 0.0300 (4) | |
N21 | −0.0036 (2) | −0.09084 (16) | 0.18100 (11) | 0.0375 (4) | |
H21 | −0.0933 | −0.1381 | 0.1932 | 0.045* | |
N23 | 0.22122 (19) | 0.05359 (16) | 0.19455 (10) | 0.0310 (4) | |
C2 | 0.5671 (2) | 0.26780 (18) | 0.41333 (11) | 0.0251 (4) | |
C3A | 0.5389 (2) | 0.07649 (18) | 0.37810 (12) | 0.0271 (4) | |
C4 | 0.4998 (3) | −0.0395 (2) | 0.33952 (14) | 0.0372 (5) | |
H4 | 0.4233 | −0.0592 | 0.2919 | 0.045* | |
C5 | 0.5775 (3) | −0.1240 (2) | 0.37380 (15) | 0.0422 (6) | |
H5 | 0.5526 | −0.2038 | 0.3493 | 0.051* | |
C6 | 0.6905 (3) | −0.0964 (2) | 0.44278 (15) | 0.0418 (6) | |
H6 | 0.7431 | −0.1568 | 0.4634 | 0.050* | |
C7 | 0.7281 (3) | 0.0167 (2) | 0.48204 (14) | 0.0357 (5) | |
H7A | 0.8039 | 0.0356 | 0.5300 | 0.043* | |
C7A | 0.6495 (2) | 0.10213 (18) | 0.44798 (12) | 0.0271 (4) | |
C8 | 0.5572 (2) | 0.39773 (18) | 0.41748 (12) | 0.0279 (4) | |
H8A | 0.4794 | 0.4115 | 0.3714 | 0.033* | |
H8B | 0.6621 | 0.4510 | 0.4098 | 0.033* | |
C9 | 0.5077 (2) | 0.43462 (18) | 0.49955 (12) | 0.0285 (5) | |
H9A | 0.4046 | 0.3796 | 0.5085 | 0.034* | |
H9B | 0.5878 | 0.4246 | 0.5457 | 0.034* | |
C12 | 0.1723 (2) | 0.37263 (19) | 0.28129 (13) | 0.0306 (5) | |
C13A | 0.2509 (2) | 0.40393 (19) | 0.15928 (12) | 0.0299 (5) | |
C14 | 0.3181 (3) | 0.4019 (2) | 0.08585 (13) | 0.0350 (5) | |
H14 | 0.3829 | 0.3475 | 0.0771 | 0.042* | |
C15 | 0.2861 (3) | 0.4825 (2) | 0.02645 (14) | 0.0424 (6) | |
H15 | 0.3293 | 0.4831 | −0.0245 | 0.051* | |
C16 | 0.1923 (3) | 0.5628 (2) | 0.03924 (15) | 0.0500 (6) | |
H16 | 0.1745 | 0.6175 | −0.0030 | 0.060* | |
C17 | 0.1244 (3) | 0.5655 (2) | 0.11095 (15) | 0.0471 (6) | |
H17 | 0.0594 | 0.6199 | 0.1192 | 0.057* | |
C17A | 0.1560 (3) | 0.4841 (2) | 0.17074 (13) | 0.0350 (5) | |
C18 | 0.1380 (2) | 0.3197 (2) | 0.36263 (13) | 0.0344 (5) | |
H18A | 0.1466 | 0.3868 | 0.4035 | 0.041* | |
H18B | 0.2188 | 0.2744 | 0.3821 | 0.041* | |
C19 | −0.0282 (3) | 0.2333 (2) | 0.35838 (14) | 0.0393 (5) | |
H19A | −0.0414 | 0.1967 | 0.4130 | 0.047* | |
H19B | −0.1091 | 0.2813 | 0.3467 | 0.047* | |
C22 | 0.0928 (2) | −0.00061 (19) | 0.22955 (13) | 0.0331 (5) | |
C23A | 0.2040 (2) | −0.00653 (19) | 0.11675 (12) | 0.0303 (5) | |
C24 | 0.3010 (3) | 0.0122 (2) | 0.05355 (13) | 0.0382 (5) | |
H24 | 0.3986 | 0.0726 | 0.0587 | 0.046* | |
C25 | 0.2479 (3) | −0.0618 (2) | −0.01738 (14) | 0.0436 (6) | |
H25 | 0.3113 | −0.0523 | −0.0616 | 0.052* | |
C26 | 0.1040 (3) | −0.1498 (2) | −0.02532 (15) | 0.0471 (6) | |
H26 | 0.0713 | −0.1976 | −0.0752 | 0.057* | |
C27 | 0.0087 (3) | −0.1693 (2) | 0.03654 (15) | 0.0427 (6) | |
H27 | −0.0894 | −0.2293 | 0.0309 | 0.051* | |
C27A | 0.0629 (3) | −0.0966 (2) | 0.10836 (13) | 0.0349 (5) | |
C28 | 0.0505 (3) | 0.0420 (2) | 0.30816 (13) | 0.0379 (5) | |
H28A | 0.1488 | 0.0834 | 0.3438 | 0.046* | |
H28B | −0.0042 | −0.0292 | 0.3378 | 0.046* | |
C29 | −0.0586 (3) | 0.1307 (2) | 0.29234 (14) | 0.0384 (5) | |
H29A | −0.0437 | 0.1675 | 0.2379 | 0.046* | |
H29B | −0.1707 | 0.0838 | 0.2897 | 0.046* | |
O7 | 1.2465 (2) | 0.27097 (18) | 0.77199 (14) | 0.0697 (6) | |
H7 | 1.2161 | 0.3255 | 0.7442 | 0.105* | |
C31 | 1.3980 (3) | 0.3190 (3) | 0.81330 (17) | 0.0602 (8) | |
H31A | 1.3984 | 0.3917 | 0.8475 | 0.072* | |
H31B | 1.4753 | 0.3437 | 0.7729 | 0.072* | |
C32 | 1.4426 (4) | 0.2229 (3) | 0.8669 (2) | 0.0830 (10) | |
H32A | 1.5494 | 0.2544 | 0.8963 | 0.124* | |
H32B | 1.4415 | 0.1513 | 0.8325 | 0.124* | |
H32C | 1.3662 | 0.1998 | 0.9070 | 0.124* | |
O4 | 1.08359 (19) | 0.41372 (17) | 0.66994 (11) | 0.0530 (5) | |
O5 | 0.8646 (2) | 0.37899 (19) | 0.58905 (13) | 0.0783 (7) | |
O6 | 1.0218 (3) | 0.2621 (2) | 0.58139 (14) | 0.0945 (8) | |
N5 | 0.9904 (3) | 0.3510 (2) | 0.61269 (12) | 0.0487 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.03030 (16) | 0.02959 (17) | 0.02396 (15) | 0.00660 (12) | 0.00482 (11) | −0.00539 (11) |
O1 | 0.0386 (9) | 0.0460 (10) | 0.0353 (9) | 0.0028 (8) | 0.0111 (7) | −0.0107 (7) |
O2 | 0.0565 (11) | 0.0439 (10) | 0.0404 (10) | 0.0054 (8) | 0.0127 (8) | −0.0096 (8) |
O3 | 0.0430 (10) | 0.0944 (16) | 0.0539 (12) | −0.0058 (10) | 0.0239 (9) | −0.0079 (11) |
N1 | 0.0305 (9) | 0.0313 (10) | 0.0220 (9) | 0.0082 (8) | 0.0026 (7) | −0.0061 (7) |
N3 | 0.0310 (9) | 0.0241 (9) | 0.0241 (9) | 0.0079 (7) | 0.0058 (7) | −0.0040 (7) |
N4 | 0.0350 (11) | 0.0541 (13) | 0.0273 (10) | 0.0061 (9) | 0.0087 (8) | 0.0015 (9) |
N11 | 0.0359 (10) | 0.0390 (11) | 0.0373 (11) | 0.0147 (9) | 0.0068 (8) | −0.0053 (8) |
N13 | 0.0340 (10) | 0.0298 (10) | 0.0258 (9) | 0.0063 (8) | 0.0051 (8) | −0.0048 (8) |
N21 | 0.0336 (10) | 0.0345 (11) | 0.0398 (11) | 0.0004 (8) | 0.0023 (8) | −0.0045 (9) |
N23 | 0.0320 (10) | 0.0325 (10) | 0.0272 (9) | 0.0059 (8) | 0.0029 (8) | −0.0059 (8) |
C2 | 0.0283 (10) | 0.0266 (11) | 0.0220 (10) | 0.0073 (8) | 0.0084 (8) | −0.0028 (8) |
C3A | 0.0305 (11) | 0.0271 (11) | 0.0263 (10) | 0.0089 (9) | 0.0106 (9) | −0.0019 (8) |
C4 | 0.0438 (13) | 0.0312 (13) | 0.0370 (13) | 0.0093 (10) | 0.0064 (10) | −0.0076 (10) |
C5 | 0.0559 (15) | 0.0271 (13) | 0.0483 (15) | 0.0134 (11) | 0.0183 (12) | −0.0026 (11) |
C6 | 0.0500 (15) | 0.0362 (14) | 0.0482 (15) | 0.0222 (11) | 0.0182 (12) | 0.0115 (11) |
C7 | 0.0373 (13) | 0.0409 (14) | 0.0337 (12) | 0.0158 (10) | 0.0103 (10) | 0.0065 (10) |
C7A | 0.0285 (11) | 0.0285 (12) | 0.0275 (11) | 0.0094 (9) | 0.0113 (9) | −0.0006 (9) |
C8 | 0.0328 (11) | 0.0258 (11) | 0.0258 (10) | 0.0082 (9) | 0.0045 (9) | −0.0058 (8) |
C9 | 0.0329 (11) | 0.0285 (11) | 0.0247 (10) | 0.0089 (9) | 0.0024 (9) | −0.0067 (9) |
C12 | 0.0276 (11) | 0.0323 (12) | 0.0309 (11) | 0.0058 (9) | 0.0027 (9) | −0.0069 (9) |
C13A | 0.0291 (11) | 0.0302 (12) | 0.0272 (11) | 0.0030 (9) | −0.0003 (9) | −0.0026 (9) |
C14 | 0.0360 (12) | 0.0376 (13) | 0.0302 (12) | 0.0058 (10) | 0.0049 (10) | −0.0032 (10) |
C15 | 0.0474 (14) | 0.0494 (16) | 0.0278 (12) | 0.0062 (12) | 0.0050 (10) | 0.0021 (11) |
C16 | 0.0576 (16) | 0.0510 (16) | 0.0403 (14) | 0.0135 (13) | 0.0001 (12) | 0.0130 (12) |
C17 | 0.0496 (15) | 0.0484 (16) | 0.0464 (15) | 0.0195 (12) | 0.0027 (12) | 0.0061 (12) |
C17A | 0.0344 (12) | 0.0365 (13) | 0.0331 (12) | 0.0076 (10) | 0.0021 (10) | −0.0022 (10) |
C18 | 0.0380 (12) | 0.0398 (13) | 0.0270 (11) | 0.0118 (10) | 0.0057 (9) | −0.0061 (10) |
C19 | 0.0350 (12) | 0.0506 (15) | 0.0334 (12) | 0.0088 (11) | 0.0127 (10) | −0.0009 (11) |
C22 | 0.0336 (12) | 0.0313 (12) | 0.0332 (12) | 0.0070 (9) | 0.0006 (10) | −0.0009 (10) |
C23A | 0.0342 (12) | 0.0290 (12) | 0.0282 (11) | 0.0112 (9) | −0.0008 (9) | −0.0055 (9) |
C24 | 0.0398 (13) | 0.0400 (14) | 0.0370 (13) | 0.0147 (10) | 0.0034 (10) | −0.0046 (10) |
C25 | 0.0516 (15) | 0.0520 (16) | 0.0322 (12) | 0.0236 (12) | 0.0027 (11) | −0.0115 (11) |
C26 | 0.0594 (16) | 0.0460 (15) | 0.0375 (14) | 0.0236 (13) | −0.0096 (12) | −0.0170 (11) |
C27 | 0.0441 (14) | 0.0347 (14) | 0.0457 (14) | 0.0094 (11) | −0.0087 (11) | −0.0124 (11) |
C27A | 0.0378 (12) | 0.0306 (12) | 0.0366 (12) | 0.0115 (10) | −0.0014 (10) | −0.0054 (10) |
C28 | 0.0397 (13) | 0.0404 (14) | 0.0309 (12) | 0.0020 (10) | 0.0085 (10) | −0.0002 (10) |
C29 | 0.0321 (12) | 0.0426 (14) | 0.0378 (13) | 0.0014 (10) | 0.0089 (10) | −0.0034 (10) |
O7 | 0.0482 (11) | 0.0663 (14) | 0.0835 (15) | −0.0024 (10) | −0.0045 (10) | 0.0274 (12) |
C31 | 0.0580 (17) | 0.0555 (18) | 0.0573 (18) | −0.0028 (14) | 0.0016 (14) | −0.0090 (14) |
C32 | 0.069 (2) | 0.082 (2) | 0.085 (2) | 0.0071 (18) | −0.0194 (18) | 0.003 (2) |
O4 | 0.0396 (9) | 0.0627 (12) | 0.0554 (11) | 0.0182 (8) | −0.0112 (8) | −0.0279 (9) |
O5 | 0.0603 (13) | 0.0878 (16) | 0.0884 (15) | 0.0448 (12) | −0.0388 (12) | −0.0535 (12) |
O6 | 0.1020 (17) | 0.0955 (17) | 0.0945 (17) | 0.0632 (15) | −0.0334 (14) | −0.0599 (14) |
N5 | 0.0488 (13) | 0.0542 (14) | 0.0445 (12) | 0.0211 (11) | −0.0061 (10) | −0.0192 (10) |
Co1—O1 | 1.9980 (15) | C14—C15 | 1.380 (3) |
Co1—N13 | 2.0125 (17) | C14—H14 | 0.95 |
Co1—N3 | 2.0233 (17) | C15—C16 | 1.389 (3) |
Co1—N23 | 2.0303 (18) | C15—H15 | 0.95 |
O1—N4 | 1.279 (2) | C16—C17 | 1.374 (3) |
O2—N4 | 1.248 (2) | C16—H16 | 0.95 |
O3—N4 | 1.219 (2) | C17—C17A | 1.390 (3) |
N1—C2 | 1.341 (2) | C17—H17 | 0.95 |
N1—C7A | 1.382 (2) | C18—C19 | 1.536 (3) |
N1—H1 | 0.88 | C18—H18A | 0.99 |
N3—C2 | 1.336 (2) | C18—H18B | 0.99 |
N3—C3A | 1.411 (2) | C19—C29 | 1.532 (3) |
N11—C12 | 1.341 (3) | C19—H19A | 0.99 |
N11—C17A | 1.380 (3) | C19—H19B | 0.99 |
N11—H11 | 0.88 | C22—C28 | 1.483 (3) |
N13—C12 | 1.335 (2) | C23A—C27A | 1.389 (3) |
N13—C13A | 1.402 (3) | C23A—C24 | 1.393 (3) |
N21—C22 | 1.341 (3) | C24—C25 | 1.390 (3) |
N21—C27A | 1.385 (3) | C24—H24 | 0.95 |
N21—H21 | 0.88 | C25—C26 | 1.394 (4) |
N23—C22 | 1.334 (3) | C25—H25 | 0.95 |
N23—C23A | 1.411 (2) | C26—C27 | 1.366 (3) |
C2—C8 | 1.492 (3) | C26—H26 | 0.95 |
C3A—C7A | 1.384 (3) | C27—C27A | 1.394 (3) |
C3A—C4 | 1.399 (3) | C27—H27 | 0.95 |
C4—C5 | 1.381 (3) | C28—C29 | 1.542 (3) |
C4—H4 | 0.95 | C28—H28A | 0.99 |
C5—C6 | 1.386 (3) | C28—H28B | 0.99 |
C5—H5 | 0.95 | C29—H29A | 0.99 |
C6—C7 | 1.376 (3) | C29—H29B | 0.99 |
C6—H6 | 0.95 | O7—C31 | 1.393 (3) |
C7—C7A | 1.392 (3) | O7—H7 | 0.84 |
C7—H7A | 0.95 | C31—C32 | 1.489 (4) |
C8—C9 | 1.538 (3) | C31—H31A | 0.99 |
C8—H8A | 0.99 | C31—H31B | 0.99 |
C8—H8B | 0.99 | C32—H32A | 0.98 |
C9—C9i | 1.515 (4) | C32—H32B | 0.98 |
C9—H9A | 0.99 | C32—H32C | 0.98 |
C9—H9B | 0.99 | O4—N5 | 1.255 (2) |
C12—C18 | 1.488 (3) | O5—N5 | 1.233 (2) |
C13A—C17A | 1.392 (3) | O6—N5 | 1.227 (3) |
C13A—C14 | 1.394 (3) | ||
O1—Co1—N13 | 117.59 (7) | C16—C15—H15 | 119.2 |
O1—Co1—N3 | 105.64 (7) | C17—C16—C15 | 122.1 (2) |
N13—Co1—N3 | 116.37 (7) | C17—C16—H16 | 118.9 |
O1—Co1—N23 | 100.93 (7) | C15—C16—H16 | 118.9 |
N13—Co1—N23 | 102.62 (7) | C16—C17—C17A | 116.3 (2) |
N3—Co1—N23 | 112.74 (7) | C16—C17—H17 | 121.9 |
N4—O1—Co1 | 105.64 (12) | C17A—C17—H17 | 121.9 |
C2—N1—C7A | 108.62 (16) | N11—C17A—C17 | 132.2 (2) |
C2—N1—H1 | 125.7 | N11—C17A—C13A | 105.44 (19) |
C7A—N1—H1 | 125.7 | C17—C17A—C13A | 122.3 (2) |
C2—N3—C3A | 105.18 (16) | C12—C18—C19 | 112.54 (18) |
C2—N3—Co1 | 128.76 (14) | C12—C18—H18A | 109.1 |
C3A—N3—Co1 | 122.18 (12) | C19—C18—H18A | 109.1 |
O3—N4—O2 | 122.7 (2) | C12—C18—H18B | 109.1 |
O3—N4—O1 | 120.49 (19) | C19—C18—H18B | 109.1 |
O2—N4—O1 | 116.82 (17) | H18A—C18—H18B | 107.8 |
C12—N11—C17A | 108.60 (18) | C29—C19—C18 | 113.47 (18) |
C12—N11—H11 | 125.7 | C29—C19—H19A | 108.9 |
C17A—N11—H11 | 125.7 | C18—C19—H19A | 108.9 |
C12—N13—C13A | 105.52 (17) | C29—C19—H19B | 108.9 |
C12—N13—Co1 | 131.42 (15) | C18—C19—H19B | 108.9 |
C13A—N13—Co1 | 123.04 (13) | H19A—C19—H19B | 107.7 |
C22—N21—C27A | 108.06 (18) | N23—C22—N21 | 112.04 (19) |
C22—N21—H21 | 126.0 | N23—C22—C28 | 124.43 (19) |
C27A—N21—H21 | 126.0 | N21—C22—C28 | 123.2 (2) |
C22—N23—C23A | 105.40 (17) | C27A—C23A—C24 | 120.65 (19) |
C22—N23—Co1 | 124.70 (14) | C27A—C23A—N23 | 108.54 (19) |
C23A—N23—Co1 | 129.39 (14) | C24—C23A—N23 | 130.8 (2) |
N3—C2—N1 | 111.61 (17) | C25—C24—C23A | 116.7 (2) |
N3—C2—C8 | 126.53 (18) | C25—C24—H24 | 121.7 |
N1—C2—C8 | 121.87 (17) | C23A—C24—H24 | 121.7 |
C7A—C3A—C4 | 120.24 (19) | C24—C25—C26 | 121.8 (2) |
C7A—C3A—N3 | 109.01 (17) | C24—C25—H25 | 119.1 |
C4—C3A—N3 | 130.71 (18) | C26—C25—H25 | 119.1 |
C5—C4—C3A | 117.0 (2) | C27—C26—C25 | 122.0 (2) |
C5—C4—H4 | 121.5 | C27—C26—H26 | 119.0 |
C3A—C4—H4 | 121.5 | C25—C26—H26 | 119.0 |
C4—C5—C6 | 122.2 (2) | C26—C27—C27A | 116.5 (2) |
C4—C5—H5 | 118.9 | C26—C27—H27 | 121.8 |
C6—C5—H5 | 118.9 | C27A—C27—H27 | 121.8 |
C7—C6—C5 | 121.3 (2) | N21—C27A—C23A | 105.96 (18) |
C7—C6—H6 | 119.3 | N21—C27A—C27 | 131.5 (2) |
C5—C6—H6 | 119.3 | C23A—C27A—C27 | 122.5 (2) |
C6—C7—C7A | 116.7 (2) | C22—C28—C29 | 111.30 (18) |
C6—C7—H7A | 121.7 | C22—C28—H28A | 109.4 |
C7A—C7—H7A | 121.7 | C29—C28—H28A | 109.4 |
N1—C7A—C3A | 105.56 (18) | C22—C28—H28B | 109.4 |
N1—C7A—C7 | 131.85 (19) | C29—C28—H28B | 109.4 |
C3A—C7A—C7 | 122.54 (19) | H28A—C28—H28B | 108.0 |
C2—C8—C9 | 113.38 (17) | C19—C29—C28 | 113.92 (18) |
C2—C8—H8A | 108.9 | C19—C29—H29A | 108.8 |
C9—C8—H8A | 108.9 | C28—C29—H29A | 108.8 |
C2—C8—H8B | 108.9 | C19—C29—H29B | 108.8 |
C9—C8—H8B | 108.9 | C28—C29—H29B | 108.8 |
H8A—C8—H8B | 107.7 | H29A—C29—H29B | 107.7 |
C9i—C9—C8 | 112.1 (2) | C31—O7—H7 | 109.5 |
C9i—C9—H9A | 109.2 | O7—C31—C32 | 107.9 (2) |
C8—C9—H9A | 109.2 | O7—C31—H31A | 110.1 |
C9i—C9—H9B | 109.2 | C32—C31—H31A | 110.1 |
C8—C9—H9B | 109.2 | O7—C31—H31B | 110.1 |
H9A—C9—H9B | 107.9 | C32—C31—H31B | 110.1 |
N13—C12—N11 | 111.55 (19) | H31A—C31—H31B | 108.4 |
N13—C12—C18 | 125.29 (19) | C31—C32—H32A | 109.5 |
N11—C12—C18 | 123.06 (19) | C31—C32—H32B | 109.5 |
C17A—C13A—C14 | 120.6 (2) | H32A—C32—H32B | 109.5 |
C17A—C13A—N13 | 108.89 (18) | C31—C32—H32C | 109.5 |
C14—C13A—N13 | 130.5 (2) | H32A—C32—H32C | 109.5 |
C15—C14—C13A | 117.0 (2) | H32B—C32—H32C | 109.5 |
C15—C14—H14 | 121.5 | O6—N5—O5 | 120.2 (2) |
C13A—C14—H14 | 121.5 | O6—N5—O4 | 121.0 (2) |
C14—C15—C16 | 121.7 (2) | O5—N5—O4 | 118.81 (19) |
C14—C15—H15 | 119.2 | ||
N13—Co1—O1—N4 | 63.25 (15) | C13A—N13—C12—C18 | 175.70 (19) |
N3—Co1—O1—N4 | −68.56 (14) | Co1—N13—C12—C18 | −2.7 (3) |
N23—Co1—O1—N4 | 173.86 (13) | C17A—N11—C12—N13 | 0.6 (2) |
O1—Co1—N3—C2 | 89.12 (17) | C17A—N11—C12—C18 | −176.08 (19) |
N13—Co1—N3—C2 | −43.37 (18) | C12—N13—C13A—C17A | 0.8 (2) |
N23—Co1—N3—C2 | −161.55 (16) | Co1—N13—C13A—C17A | 179.41 (13) |
O1—Co1—N3—C3A | −65.30 (16) | C12—N13—C13A—C14 | −179.1 (2) |
N13—Co1—N3—C3A | 162.20 (14) | Co1—N13—C13A—C14 | −0.6 (3) |
N23—Co1—N3—C3A | 44.02 (16) | C17A—C13A—C14—C15 | 0.1 (3) |
Co1—O1—N4—O3 | 176.75 (18) | N13—C13A—C14—C15 | −179.9 (2) |
Co1—O1—N4—O2 | −4.1 (2) | C13A—C14—C15—C16 | 0.5 (3) |
O1—Co1—N13—C12 | −161.34 (17) | C14—C15—C16—C17 | −0.9 (4) |
N3—Co1—N13—C12 | −34.6 (2) | C15—C16—C17—C17A | 0.7 (4) |
N23—Co1—N13—C12 | 89.01 (18) | C12—N11—C17A—C17 | 179.8 (2) |
O1—Co1—N13—C13A | 20.50 (17) | C12—N11—C17A—C13A | 0.0 (2) |
N3—Co1—N13—C13A | 147.27 (14) | C16—C17—C17A—N11 | −179.8 (2) |
N23—Co1—N13—C13A | −89.15 (16) | C16—C17—C17A—C13A | 0.0 (3) |
O1—Co1—N23—C22 | 170.74 (17) | C14—C13A—C17A—N11 | 179.48 (18) |
N13—Co1—N23—C22 | −67.49 (18) | N13—C13A—C17A—N11 | −0.5 (2) |
N3—Co1—N23—C22 | 58.48 (18) | C14—C13A—C17A—C17 | −0.4 (3) |
O1—Co1—N23—C23A | −18.60 (18) | N13—C13A—C17A—C17 | 179.6 (2) |
N13—Co1—N23—C23A | 103.17 (17) | N13—C12—C18—C19 | −101.2 (2) |
N3—Co1—N23—C23A | −130.86 (17) | N11—C12—C18—C19 | 75.0 (3) |
C3A—N3—C2—N1 | −0.9 (2) | C12—C18—C19—C29 | 54.7 (3) |
Co1—N3—C2—N1 | −158.62 (13) | C23A—N23—C22—N21 | 0.7 (2) |
C3A—N3—C2—C8 | 178.94 (18) | Co1—N23—C22—N21 | 173.21 (13) |
Co1—N3—C2—C8 | 21.2 (3) | C23A—N23—C22—C28 | −172.60 (19) |
C7A—N1—C2—N3 | 1.5 (2) | Co1—N23—C22—C28 | −0.1 (3) |
C7A—N1—C2—C8 | −178.33 (17) | C27A—N21—C22—N23 | −0.9 (2) |
C2—N3—C3A—C7A | −0.1 (2) | C27A—N21—C22—C28 | 172.5 (2) |
Co1—N3—C3A—C7A | 159.51 (13) | C22—N23—C23A—C27A | −0.2 (2) |
C2—N3—C3A—C4 | −177.8 (2) | Co1—N23—C23A—C27A | −172.27 (14) |
Co1—N3—C3A—C4 | −18.2 (3) | C22—N23—C23A—C24 | 179.3 (2) |
C7A—C3A—C4—C5 | −0.7 (3) | Co1—N23—C23A—C24 | 7.3 (3) |
N3—C3A—C4—C5 | 176.7 (2) | C27A—C23A—C24—C25 | 1.0 (3) |
C3A—C4—C5—C6 | −0.6 (3) | N23—C23A—C24—C25 | −178.5 (2) |
C4—C5—C6—C7 | 1.7 (4) | C23A—C24—C25—C26 | 0.6 (3) |
C5—C6—C7—C7A | −1.3 (3) | C24—C25—C26—C27 | −1.0 (4) |
C2—N1—C7A—C3A | −1.5 (2) | C25—C26—C27—C27A | −0.1 (3) |
C2—N1—C7A—C7 | 176.0 (2) | C22—N21—C27A—C23A | 0.7 (2) |
C4—C3A—C7A—N1 | 178.91 (18) | C22—N21—C27A—C27 | −176.8 (2) |
N3—C3A—C7A—N1 | 0.9 (2) | C24—C23A—C27A—N21 | −179.90 (19) |
C4—C3A—C7A—C7 | 1.1 (3) | N23—C23A—C27A—N21 | −0.3 (2) |
N3—C3A—C7A—C7 | −176.84 (18) | C24—C23A—C27A—C27 | −2.2 (3) |
C6—C7—C7A—N1 | −177.2 (2) | N23—C23A—C27A—C27 | 177.46 (19) |
C6—C7—C7A—C3A | −0.1 (3) | C26—C27—C27A—N21 | 178.8 (2) |
N3—C2—C8—C9 | 122.4 (2) | C26—C27—C27A—C23A | 1.7 (3) |
N1—C2—C8—C9 | −57.8 (2) | N23—C22—C28—C29 | 91.5 (3) |
C2—C8—C9—C9i | −177.7 (2) | N21—C22—C28—C29 | −81.0 (3) |
C13A—N13—C12—N11 | −0.9 (2) | C18—C19—C29—C28 | 63.8 (3) |
Co1—N13—C12—N11 | −179.28 (13) | C22—C28—C29—C19 | −144.45 (19) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O5 | 0.88 | 1.91 | 2.777 (3) | 168 |
N11—H11···O4i | 0.88 | 1.99 | 2.869 (2) | 178 |
N21—H21···O7ii | 0.88 | 1.89 | 2.747 (3) | 163 |
O7—H7···O4 | 0.84 | 2.01 | 2.817 (3) | 162 |
C16—H16···O3iii | 0.95 | 2.57 | 3.358 (3) | 140 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+1; (iii) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Co2(NO3)2(C18H18N4)3](NO3)2·2C2H6O |
Mr | 1329.13 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 193 |
a, b, c (Å) | 8.7260 (17), 11.295 (2), 16.284 (3) |
α, β, γ (°) | 90.16 (3), 96.76 (3), 103.85 (3) |
V (Å3) | 1546.6 (5) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.61 |
Crystal size (mm) | 0.51 × 0.44 × 0.23 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (Higashi, 1995) |
Tmin, Tmax | 0.725, 0.867 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13292, 6778, 4638 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.089, 0.91 |
No. of reflections | 6778 |
No. of parameters | 408 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.50, −0.38 |
Computer programs: PROCESS-AUTO (Rigaku Corporation, 1998), PROCESS-AUTO, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997) in WinGX (Farrugia, 1999), PLATON (Spek, 2003), SHELXL97.
Co1—O1 | 1.9980 (15) | Co1—N3 | 2.0233 (17) |
Co1—N13 | 2.0125 (17) | Co1—N23 | 2.0303 (18) |
O1—Co1—N13 | 117.59 (7) | N13—Co1—N23 | 102.62 (7) |
O1—Co1—N3 | 105.64 (7) | N3—Co1—N23 | 112.74 (7) |
N13—Co1—N3 | 116.37 (7) | N4—O1—Co1 | 105.64 (12) |
O1—Co1—N23 | 100.93 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O5 | 0.88 | 1.91 | 2.777 (3) | 168 |
N11—H11···O4i | 0.88 | 1.99 | 2.869 (2) | 178 |
N21—H21···O7ii | 0.88 | 1.89 | 2.747 (3) | 163 |
O7—H7···O4 | 0.84 | 2.01 | 2.817 (3) | 162 |
C16—H16···O3iii | 0.95 | 2.57 | 3.358 (3) | 140 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+1; (iii) −x+1, −y+1, −z. |
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The role of coordination bonds in crystal engineering is currently of great interest because of their use in constructing novel compounds with special properties, such as electrical conductivity, magnetism, host–guest chemistry and catalysis (Fujita et al., 1994; Inoue et al., 1996). So far, much of the work has been focused on coordination compounds with rigid ligands, such as 4,4'-bipyridine and pyrazine (Carlucci et al., 1994; Robinson & Zaworotko, 1995; Gable et al., 1990). We are interested in utilizing substituted benzimidazole or imidazole ligands to construct new coordination compounds (Yang et al., 2003). Our previous investigation of cobalt(II) complexes with the flexible ligand 1,1'-(1,4-butanediyl)bis(benzimidazole) (L') gave one- and two-dimensional coordination polymers (Ma et al., 2000). In the present work, the assembly of 2,2'-(1,4-butanediyl)bis(benzimidazole) (L) with cobalt(II) nitrate resulted in a dinuclear complex, [Co2L3(NO3)2]2+·2NO3−·2C2H5OH, (I). The structure of the free ligand L has been reported (Chen et al., 2002) and that of a Cu complex, catena[µ2-[1,4-bis(2-benzimidazolyl)butane]bis(azido-N)copper(II)] is known (van Albada et al., 2000); in both cases, the ligand L lies about an inversion centre.
The [Co2L3(NO3)2]2+ cation in complex (I) (Fig. 1) lies about an inversion centre (chosen for convenience to be (1/2,1/2, 1/2)]. The unique cobalt(II) ion is in a distorted tetrahedral coordination environment, with three N atoms from two L ligands and one O atom from a nitrate anion (see Table 1 for selected geometric parameters). The L ligands in (I) display two different coordination modes; one L ligand lies about an inversion centre and bridges two cobalt(II) atoms, while the other L ligand chelates the cobalt(II) atom, leading to a complex with two unanticipated nine-membered chelate rings. The Co—N distances (Table 1) are shorter than those found in other related cobalt(II) complexes (2.132 and 2.159 Å; Ma et al., 2000). The distance between Co1 and Co1i [symmetry code: (i) 1 − x, 1 − y, 1 − z] is 10.420 (2) Å. We have previously reported two related complexes, [CoL2'(H2O)2]2+·2NO3−·8H2O with a (4,4)-network and [CoL'(H2O)2(CH3CO2)2]·H2O with an infinite chain structure, where L' is 1,1'-(1,4-butanediyl)bis(benzimidazole) (Ma et al., 2000).
The uncoordinated nitrate moiety plays the role of counter-anion and determines the cation complex conformation by acting as an acceptor for pairs of N—H···O hydrogen bonds (Table 2) from N1—H1 and N11i—H11i. The unique ethanol molecule is also linked to the counter-anion by an O—H···O hydrogen bond (Table 2). In the crystal structure, the {[Co2L3(NO3)2]2+·2NO3−·2C2H5OH} units are linked to form chains in the [010] direction by an N—H···O hydrogen bond involving the N21/H21 group and the adjacent ethanol O atom (see Table 2). Chains are linked to form sheets in the (100) plane by C—H···O hydrogen bonds (Table 2) between aromatic atoms C16 and H16 and nitro atom O3 of a symmetry-related cation (Fig. 2)