Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802021177/ob6192sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802021177/ob6192Isup2.hkl |
CCDC reference: 202302
All the chemicals used are commercially available, except for HCPz3, which was prepared according to the literature method of Reger (2000). Elemental analyses were carried on a Perkin-Elmer 240 C elemental analyzer. To an ethanol (25 ml) solution containing Ce(NO3)3·6H2O (0.5 mmol) was added stepwise HCPz3 (0.5 mmol) and nBu4NBr (0.5 mmol), and the reaction mixture refluxed for 30 min with stirring and then filtered. The filtrate was allowed to stand in air for several days, producing colorless rod-like crystals of (I) (yield ca 70%). Analysis calculated: C 36.96, H 5.49, N 18.24%; found: C 36.91, H 5.55, N 18.28%. 1H NMR (500 MHz, DMSO): δ (p.p.m.) 7.89 and 7.66 (d, d, 3H, 3H, 3-H and 5-H on Pz), 6.42 (t, 3H, 4-H on Pz), 8.97 (s, 1H on HCPz3), 3.16 and 0.93 (t, t, 8H, 8H, CH2 and CH3 on nBu4N), 1.56 and 1.30 (m, m, 8H, 8H, CH2 and CH2 on nBu4N).
Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. View of the [(HCPz3)Ce(NO3)4]− anion, with displacement ellipsoids at the 20% probability level. | |
Fig. 2. The crystal packing of compound (I), showing C—H···O short contacts along the c axis. |
(C16H36N)[Ce(NO3)4(C10H10N6)] | F(000) = 1732 |
Mr = 844.86 | Dx = 1.507 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4597 reflections |
a = 12.484 (1) Å | θ = 2.2–23.8° |
b = 16.742 (1) Å | µ = 1.29 mm−1 |
c = 18.267 (1) Å | T = 293 K |
β = 102.82 (1)° | Rod-like, colorless |
V = 3722.8 (4) Å3 | 0.3 × 0.2 × 0.2 mm |
Z = 4 |
Bruker SMART APEX CCD area-detector diffractometer | 6546 independent reflections |
Radiation source: fine-focus sealed tube | 4018 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.1° |
Absorption correction: multi-scan (Sheldrick, 1990) | h = −14→14 |
Tmin = 0.740, Tmax = 0.771 | k = 0→19 |
18988 measured reflections | l = 0→21 |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.092 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.03P)2 + 1.99P] where P = (Fo2 + 2Fc2)/3 |
6546 reflections | (Δ/σ)max < 0.001 |
431 parameters | Δρmax = 0.67 e Å−3 |
0 restraints | Δρmin = −0.59 e Å−3 |
(C16H36N)[Ce(NO3)4(C10H10N6)] | V = 3722.8 (4) Å3 |
Mr = 844.86 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.484 (1) Å | µ = 1.29 mm−1 |
b = 16.742 (1) Å | T = 293 K |
c = 18.267 (1) Å | 0.3 × 0.2 × 0.2 mm |
β = 102.82 (1)° |
Bruker SMART APEX CCD area-detector diffractometer | 6546 independent reflections |
Absorption correction: multi-scan (Sheldrick, 1990) | 4018 reflections with I > 2σ(I) |
Tmin = 0.740, Tmax = 0.771 | Rint = 0.037 |
18988 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.092 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.67 e Å−3 |
6546 reflections | Δρmin = −0.59 e Å−3 |
431 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. The structure was solved by direct method and refined by full-matrix least-square calculation on F2 using SHELXTL. All non-hydrogen atoms were refined anisotropically. 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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 3.8608 (0.0180) x + 15.3608 (0.0140) y − 5.7084 (0.0323) z = 11.5998 (0.0121) * −0.0531 (0.0016) Ce1 * 0.0667 (0.0019) O1 * 0.0574 (0.0018) O2 * −0.0658 (0.0027) O3 * −0.0052 (0.0037) N7 Rms deviation of fitted atoms = 0.0546 3.9089 (0.0218) x − 1.9296 (0.0176) y + 15.5218 (0.0190) z = 2.5577 (0.0116) Angle to previous plane (with approximate e.s.d.) = 75.84 (13) * 0.0153 (0.0014) Ce1 * −0.0085 (0.0017) O4 * −0.0084 (0.0018) O5 * 0.0289 (0.0024) O6 * −0.0272 (0.0036) N8 Rms deviation of fitted atoms = 0.0198 4.9515 (0.0149) x + 15.1257 (0.0063) y − 4.5045 (0.0344) z = 11.9365 (0.0097) Angle to previous plane (with approximate e.s.d.) = 82.34 (13) * −0.0347 (0.0015) Ce1 * 0.0375 (0.0019) O7 * 0.0386 (0.0019) O8 * −0.0462 (0.0025) O9 * 0.0047 (0.0039) N9 Rms deviation of fitted atoms = 0.0354 4.9620 (0.0225) x + 3.5227 (0.0182) y + 14.2977 (0.0192) z = 6.7222 (0.0125) Angle to previous plane (with approximate e.s.d.) = 78.32 (13) * 0.0124 (0.0014) Ce1 * −0.0068 (0.0017) O10 * −0.0079 (0.0017) O11 * 0.0229 (0.0024) O12 * −0.0207 (0.0036) N10 Rms deviation of fitted atoms = 0.0156 3.8608 (0.0180) x + 15.3608 (0.0140) y − 5.7084 (0.0323) z = 11.5998 (0.0121) Angle to previous plane (with approximate e.s.d.) = 84.69 (12) * −0.0531 (0.0016) Ce1 * 0.0667 (0.0019) O1 * 0.0574 (0.0018) O2 * −0.0658 (0.0027) O3 * −0.0052 (0.0037) N7 Rms deviation of fitted atoms = 0.0546 4.9515 (0.0149) x + 15.1257 (0.0063) y − 4.5045 (0.0344) z = 11.9365 (0.0097) Angle to previous plane (with approximate e.s.d.) = 7.13 (16) * −0.0347 (0.0015) Ce1 * 0.0375 (0.0019) O7 * 0.0386 (0.0019) O8 * −0.0462 (0.0025) O9 * 0.0047 (0.0039) N9 Rms deviation of fitted atoms = 0.0354 3.9089 (0.0218) x − 1.9296 (0.0176) y + 15.5218 (0.0190) z = 2.5577 (0.0116) Angle to previous plane (with approximate e.s.d.) = 82.34 (13) * 0.0153 (0.0014) Ce1 * −0.0085 (0.0017) O4 * −0.0084 (0.0018) O5 * 0.0289 (0.0024) O6 * −0.0272 (0.0036) N8 Rms deviation of fitted atoms = 0.0198 4.9620 (0.0225) x + 3.5227 (0.0182) y + 14.2977 (0.0192) z = 6.7222 (0.0125) Angle to previous plane (with approximate e.s.d.) = 19.58 (19) * 0.0124 (0.0014) Ce1 * −0.0068 (0.0017) O10 * −0.0079 (0.0017) O11 * 0.0229 (0.0024) O12 * −0.0207 (0.0036) N10 Rms deviation of fitted atoms = 0.0156 4.0705 (0.0228) x + 15.8142 (0.0113) y − 2.0003 (0.0435) z = 13.0596 (0.0189) Angle to previous plane (with approximate e.s.d.) = 72.88 (16) * −0.0404 (0.0032) N1 * −0.0539 (0.0039) N2 * 0.0404 (0.0034) C17 * 0.0265 (0.0036) C18 * −0.0293 (0.0035) C19 * 0.0567 (0.0027) C26 Rms deviation of fitted atoms = 0.0427 − 8.7565 (0.0166) x + 11.1267 (0.0271) y − 1.7441 (0.0446) z = 5.1909 (0.0371) Angle to previous plane (with approximate e.s.d.) = 65.87 (14) * −0.0034 (0.0034) N3 * −0.0048 (0.0041) N4 * 0.0000 (0.0037) C20 * 0.0104 (0.0040) C21 * −0.0098 (0.0039) C22 * 0.0077 (0.0027) C26 Rms deviation of fitted atoms = 0.0070 11.8325 (0.0074) x + 5.3375 (0.0285) y − 3.8004 (0.0447) z = 6.6262 (0.0235) Angle to previous plane (with approximate e.s.d.) = 63.03 (12) * −0.0302 (0.0032) N5 * −0.0495 (0.0039) N6 * 0.0236 (0.0035) C23 * 0.0426 (0.0037) C24 * −0.0417 (0.0036) C25 * 0.0553 (0.0027) C26 Rms deviation of fitted atoms = 0.0419 4.0705 (0.0228) x + 15.8142 (0.0113) y − 2.0003 (0.0435) z = 13.0596 (0.0189) Angle to previous plane (with approximate e.s.d.) = 52.40 (17) * −0.0404 (0.0032) N1 * −0.0539 (0.0039) N2 * 0.0404 (0.0034) C17 * 0.0265 (0.0036) C18 * −0.0293 (0.0035) C19 * 0.0567 (0.0027) C26 Rms deviation of fitted atoms = 0.0427 |
x | y | z | Uiso*/Ueq | ||
Ce1 | 0.27896 (2) | 0.751820 (18) | 0.188978 (13) | 0.04547 (10) | |
C17 | 0.0804 (4) | 0.8436 (3) | 0.2842 (3) | 0.0556 (13) | |
H17 | 0.0327 | 0.8537 | 0.2383 | 0.067* | |
C18 | 0.0574 (5) | 0.8576 (3) | 0.3545 (3) | 0.0583 (14) | |
H18 | −0.0082 | 0.8772 | 0.3635 | 0.070* | |
C19 | 0.1450 (4) | 0.8379 (3) | 0.4056 (3) | 0.0573 (14) | |
H19 | 0.1531 | 0.8412 | 0.4573 | 0.069* | |
C20 | 0.4892 (4) | 0.8975 (3) | 0.2935 (3) | 0.0656 (15) | |
H20 | 0.5130 | 0.9090 | 0.2498 | 0.079* | |
C21 | 0.5249 (5) | 0.9368 (3) | 0.3594 (3) | 0.0694 (16) | |
H21 | 0.5745 | 0.9790 | 0.3688 | 0.083* | |
C22 | 0.4732 (5) | 0.9020 (3) | 0.4081 (3) | 0.0669 (16) | |
H22 | 0.4811 | 0.9148 | 0.4585 | 0.080* | |
C23 | 0.3969 (4) | 0.6060 (3) | 0.3372 (3) | 0.0578 (14) | |
H23 | 0.4038 | 0.5690 | 0.3006 | 0.069* | |
C24 | 0.4292 (4) | 0.5921 (3) | 0.4132 (3) | 0.0602 (14) | |
H24 | 0.4624 | 0.5465 | 0.4370 | 0.072* | |
C25 | 0.4024 (4) | 0.6588 (3) | 0.4456 (3) | 0.0591 (14) | |
H25 | 0.4111 | 0.6675 | 0.4968 | 0.071* | |
C26 | 0.3352 (4) | 0.7938 (3) | 0.4003 (3) | 0.0569 (13) | |
H26 | 0.3483 | 0.8040 | 0.4544 | 0.068* | |
N1 | 0.1811 (3) | 0.8137 (2) | 0.2931 (2) | 0.0526 (11) | |
N2 | 0.2214 (4) | 0.8120 (2) | 0.3686 (2) | 0.0544 (11) | |
N3 | 0.4163 (3) | 0.8406 (3) | 0.2984 (2) | 0.0604 (12) | |
N4 | 0.4086 (4) | 0.8457 (3) | 0.3702 (2) | 0.0605 (12) | |
N5 | 0.3549 (3) | 0.6787 (3) | 0.3225 (2) | 0.0550 (11) | |
N6 | 0.3607 (3) | 0.7108 (3) | 0.3907 (2) | 0.0554 (11) | |
N7 | 0.0659 (3) | 0.7650 (2) | 0.0718 (2) | 0.0550 (11) | |
N8 | 0.1809 (4) | 0.5866 (3) | 0.1904 (2) | 0.0585 (11) | |
N9 | 0.4582 (4) | 0.6755 (3) | 0.1210 (3) | 0.0585 (12) | |
N10 | 0.3256 (3) | 0.9148 (3) | 0.1303 (2) | 0.0574 (11) | |
O1 | 0.1584 (2) | 0.74174 (18) | 0.05932 (15) | 0.04547 (10) | |
O2 | 0.0681 (2) | 0.79130 (19) | 0.13329 (16) | 0.04547 (10) | |
O3 | −0.0148 (3) | 0.7626 (3) | 0.0214 (2) | 0.1093 (17) | |
O4 | 0.2709 (3) | 0.5962 (2) | 0.17014 (18) | 0.0587 (9) | |
O5 | 0.1366 (2) | 0.64561 (19) | 0.21009 (16) | 0.04547 (10) | |
O6 | 0.1454 (3) | 0.5187 (2) | 0.1945 (2) | 0.0854 (12) | |
O7 | 0.3677 (3) | 0.6951 (2) | 0.07995 (17) | 0.0563 (9) | |
O8 | 0.4732 (3) | 0.6932 (2) | 0.18926 (19) | 0.0576 (9) | |
O9 | 0.5279 (3) | 0.6416 (2) | 0.0950 (2) | 0.0752 (11) | |
O10 | 0.2484 (2) | 0.90512 (18) | 0.16047 (15) | 0.04547 (10) | |
O11 | 0.3836 (3) | 0.8539 (2) | 0.12609 (18) | 0.0578 (9) | |
O12 | 0.3508 (3) | 0.9800 (2) | 0.1086 (2) | 0.0870 (13) | |
N11 | 0.1736 (4) | 0.1421 (3) | 0.2403 (3) | 0.0833 (15) | |
C1 | 0.1556 (5) | 0.0313 (4) | 0.4948 (3) | 0.096 (2) | |
H1A | 0.1307 | 0.0831 | 0.5065 | 0.144* | |
H1B | 0.2029 | 0.0091 | 0.5387 | 0.144* | |
H1C | 0.0934 | −0.0031 | 0.4784 | 0.144* | |
C2 | 0.2181 (5) | 0.0392 (4) | 0.4330 (3) | 0.0864 (19) | |
H2A | 0.2848 | 0.0696 | 0.4517 | 0.104* | |
H2B | 0.2392 | −0.0135 | 0.4193 | 0.104* | |
C3 | 0.1522 (5) | 0.0796 (4) | 0.3645 (3) | 0.0833 (18) | |
H3A | 0.0856 | 0.0494 | 0.3452 | 0.100* | |
H3B | 0.1312 | 0.1326 | 0.3776 | 0.100* | |
C4 | 0.2174 (5) | 0.0858 (4) | 0.3058 (3) | 0.0816 (18) | |
H4A | 0.2234 | 0.0328 | 0.2856 | 0.098* | |
H4B | 0.2911 | 0.1030 | 0.3297 | 0.098* | |
C5 | 0.2568 (5) | 0.1428 (4) | 0.1911 (3) | 0.0847 (19) | |
H5A | 0.3283 | 0.1551 | 0.2225 | 0.102* | |
H5B | 0.2608 | 0.0894 | 0.1713 | 0.102* | |
C6 | 0.2348 (5) | 0.2002 (4) | 0.1266 (4) | 0.091 (2) | |
H6A | 0.1673 | 0.1851 | 0.0917 | 0.109* | |
H6B | 0.2251 | 0.2534 | 0.1450 | 0.109* | |
C7 | 0.3263 (5) | 0.2012 (4) | 0.0865 (4) | 0.094 (2) | |
H7A | 0.3951 | 0.2117 | 0.1219 | 0.113* | |
H7B | 0.3319 | 0.1494 | 0.0637 | 0.113* | |
C8 | 0.3068 (6) | 0.2622 (4) | 0.0290 (4) | 0.104 (2) | |
H8A | 0.2332 | 0.2573 | −0.0005 | 0.156* | |
H8B | 0.3580 | 0.2559 | −0.0028 | 0.156* | |
H8C | 0.3163 | 0.3139 | 0.0522 | 0.156* | |
C9 | 0.3220 (6) | 0.3919 (4) | 0.3758 (4) | 0.109 (2) | |
H9A | 0.3575 | 0.3614 | 0.4188 | 0.163* | |
H9B | 0.2976 | 0.4420 | 0.3920 | 0.163* | |
H9C | 0.3729 | 0.4017 | 0.3444 | 0.163* | |
C10 | 0.2285 (5) | 0.3479 (4) | 0.3339 (4) | 0.097 (2) | |
H10A | 0.1958 | 0.3776 | 0.2888 | 0.116* | |
H10B | 0.1739 | 0.3433 | 0.3640 | 0.116* | |
C11 | 0.2581 (5) | 0.2674 (4) | 0.3124 (4) | 0.091 (2) | |
H11A | 0.2897 | 0.2368 | 0.3571 | 0.109* | |
H11B | 0.3126 | 0.2714 | 0.2821 | 0.109* | |
C12 | 0.1566 (5) | 0.2253 (4) | 0.2683 (4) | 0.087 (2) | |
H12A | 0.1036 | 0.2219 | 0.2998 | 0.105* | |
H12B | 0.1244 | 0.2582 | 0.2254 | 0.105* | |
C13 | 0.0590 (5) | 0.1200 (4) | 0.1958 (4) | 0.093 (2) | |
H13A | 0.0096 | 0.1182 | 0.2300 | 0.111* | |
H13B | 0.0331 | 0.1617 | 0.1593 | 0.111* | |
C14 | 0.0530 (5) | 0.0413 (5) | 0.1552 (4) | 0.102 (2) | |
H14A | 0.0835 | −0.0003 | 0.1907 | 0.123* | |
H14B | 0.0971 | 0.0441 | 0.1178 | 0.123* | |
C15 | −0.0646 (6) | 0.0198 (5) | 0.1173 (4) | 0.110 (2) | |
H15A | −0.0650 | −0.0347 | 0.0993 | 0.132* | |
H15B | −0.1083 | 0.0209 | 0.1550 | 0.132* | |
C16 | −0.1203 (6) | 0.0711 (5) | 0.0532 (4) | 0.132 (3) | |
H16A | −0.1293 | 0.1240 | 0.0711 | 0.158* | |
H16B | −0.1911 | 0.0490 | 0.0311 | 0.158* | |
H16C | −0.0765 | 0.0732 | 0.0162 | 0.158* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ce1 | 0.03753 (15) | 0.06274 (18) | 0.03704 (15) | −0.00008 (15) | 0.01023 (10) | −0.00146 (16) |
C17 | 0.056 (3) | 0.066 (4) | 0.048 (3) | 0.003 (3) | 0.019 (3) | −0.005 (3) |
C18 | 0.060 (4) | 0.068 (4) | 0.050 (3) | 0.002 (3) | 0.020 (3) | −0.007 (3) |
C19 | 0.063 (4) | 0.066 (4) | 0.047 (3) | 0.000 (3) | 0.020 (3) | −0.004 (3) |
C20 | 0.061 (4) | 0.073 (4) | 0.058 (3) | −0.015 (3) | 0.003 (3) | −0.002 (3) |
C21 | 0.065 (4) | 0.074 (4) | 0.063 (4) | −0.015 (3) | 0.000 (3) | −0.006 (3) |
C22 | 0.065 (4) | 0.072 (4) | 0.058 (4) | −0.011 (3) | 0.001 (3) | −0.008 (3) |
C23 | 0.063 (4) | 0.062 (4) | 0.047 (3) | 0.003 (3) | 0.007 (3) | 0.002 (3) |
C24 | 0.066 (4) | 0.063 (4) | 0.048 (3) | 0.002 (3) | 0.006 (3) | 0.004 (3) |
C25 | 0.065 (4) | 0.065 (4) | 0.044 (3) | 0.001 (3) | 0.006 (3) | 0.004 (3) |
C26 | 0.061 (4) | 0.063 (4) | 0.045 (3) | −0.001 (3) | 0.009 (3) | −0.002 (3) |
N1 | 0.056 (3) | 0.063 (3) | 0.042 (2) | 0.002 (2) | 0.017 (2) | −0.002 (2) |
N2 | 0.060 (3) | 0.063 (3) | 0.043 (2) | 0.001 (2) | 0.017 (2) | −0.003 (2) |
N3 | 0.056 (3) | 0.070 (3) | 0.051 (3) | −0.011 (2) | 0.002 (2) | −0.001 (2) |
N4 | 0.060 (3) | 0.067 (3) | 0.051 (3) | −0.009 (2) | 0.004 (2) | −0.005 (2) |
N5 | 0.057 (3) | 0.063 (3) | 0.043 (3) | 0.003 (2) | 0.007 (2) | 0.001 (2) |
N6 | 0.061 (3) | 0.063 (3) | 0.041 (3) | 0.002 (2) | 0.008 (2) | 0.002 (2) |
N7 | 0.043 (2) | 0.077 (3) | 0.043 (2) | 0.006 (2) | 0.004 (2) | −0.008 (2) |
N8 | 0.053 (3) | 0.062 (3) | 0.062 (3) | −0.002 (2) | 0.015 (2) | −0.006 (2) |
N9 | 0.043 (3) | 0.081 (3) | 0.054 (3) | 0.009 (2) | 0.017 (2) | 0.000 (2) |
N10 | 0.050 (3) | 0.069 (3) | 0.057 (3) | −0.002 (2) | 0.020 (2) | 0.006 (2) |
O1 | 0.03753 (15) | 0.06274 (18) | 0.03704 (15) | −0.00008 (15) | 0.01023 (10) | −0.00146 (16) |
O2 | 0.03753 (15) | 0.06274 (18) | 0.03704 (15) | −0.00008 (15) | 0.01023 (10) | −0.00146 (16) |
O3 | 0.058 (3) | 0.181 (5) | 0.071 (3) | 0.020 (3) | −0.024 (2) | −0.024 (3) |
O4 | 0.053 (2) | 0.062 (2) | 0.063 (2) | 0.0034 (18) | 0.0185 (19) | −0.0075 (18) |
O5 | 0.03753 (15) | 0.06274 (18) | 0.03704 (15) | −0.00008 (15) | 0.01023 (10) | −0.00146 (16) |
O6 | 0.086 (3) | 0.067 (3) | 0.102 (3) | −0.021 (2) | 0.019 (2) | −0.003 (2) |
O7 | 0.045 (2) | 0.078 (3) | 0.049 (2) | 0.0098 (19) | 0.0169 (17) | −0.0004 (18) |
O8 | 0.040 (2) | 0.080 (3) | 0.053 (2) | 0.0077 (18) | 0.0122 (17) | 0.005 (2) |
O9 | 0.053 (2) | 0.100 (3) | 0.076 (3) | 0.017 (2) | 0.022 (2) | −0.011 (2) |
O10 | 0.03753 (15) | 0.06274 (18) | 0.03704 (15) | −0.00008 (15) | 0.01023 (10) | −0.00146 (16) |
O11 | 0.047 (2) | 0.072 (2) | 0.060 (2) | −0.0013 (19) | 0.0231 (18) | 0.0039 (19) |
O12 | 0.087 (3) | 0.076 (3) | 0.102 (3) | −0.009 (2) | 0.030 (3) | 0.025 (2) |
N11 | 0.057 (3) | 0.106 (4) | 0.093 (4) | 0.003 (3) | 0.030 (3) | 0.005 (3) |
C1 | 0.081 (5) | 0.116 (6) | 0.097 (5) | −0.014 (4) | 0.034 (4) | 0.014 (4) |
C2 | 0.067 (4) | 0.104 (5) | 0.094 (5) | −0.006 (4) | 0.029 (4) | 0.008 (4) |
C3 | 0.062 (4) | 0.102 (5) | 0.092 (5) | −0.003 (4) | 0.031 (4) | 0.006 (4) |
C4 | 0.058 (4) | 0.101 (5) | 0.092 (5) | 0.001 (4) | 0.031 (4) | 0.004 (4) |
C5 | 0.059 (4) | 0.109 (5) | 0.092 (5) | 0.005 (4) | 0.030 (4) | 0.009 (4) |
C6 | 0.065 (4) | 0.116 (5) | 0.096 (5) | 0.003 (4) | 0.029 (4) | 0.015 (4) |
C7 | 0.068 (4) | 0.120 (6) | 0.099 (5) | 0.001 (4) | 0.030 (4) | 0.020 (5) |
C8 | 0.080 (5) | 0.127 (6) | 0.107 (5) | −0.008 (4) | 0.027 (4) | 0.028 (5) |
C9 | 0.084 (5) | 0.104 (6) | 0.136 (6) | 0.006 (4) | 0.018 (5) | −0.006 (5) |
C10 | 0.072 (5) | 0.101 (6) | 0.116 (6) | 0.013 (4) | 0.020 (4) | 0.000 (4) |
C11 | 0.067 (4) | 0.101 (6) | 0.107 (5) | 0.012 (4) | 0.023 (4) | 0.000 (4) |
C12 | 0.062 (4) | 0.104 (6) | 0.099 (5) | 0.009 (4) | 0.027 (4) | 0.004 (4) |
C13 | 0.060 (4) | 0.119 (6) | 0.102 (5) | −0.003 (4) | 0.027 (4) | 0.002 (5) |
C14 | 0.070 (5) | 0.127 (6) | 0.112 (6) | −0.009 (4) | 0.023 (4) | −0.003 (5) |
C15 | 0.075 (5) | 0.136 (7) | 0.118 (6) | −0.014 (5) | 0.018 (5) | −0.002 (5) |
C16 | 0.091 (6) | 0.157 (8) | 0.137 (7) | −0.008 (5) | 0.003 (5) | 0.007 (6) |
Ce1—O1 | 2.514 (3) | N11—C12 | 1.515 (7) |
Ce1—O11 | 2.572 (3) | N11—C4 | 1.526 (7) |
Ce1—O5 | 2.602 (3) | N11—C13 | 1.527 (7) |
Ce1—O8 | 2.615 (3) | C1—C2 | 1.515 (7) |
Ce1—O4 | 2.626 (3) | C1—H1A | 0.9600 |
Ce1—O10 | 2.630 (3) | C1—H1B | 0.9600 |
Ce1—O7 | 2.660 (3) | C1—H1C | 0.9600 |
Ce1—O2 | 2.685 (3) | C2—C3 | 1.498 (7) |
Ce1—N1 | 2.686 (4) | C2—H2A | 0.9700 |
Ce1—N5 | 2.705 (4) | C2—H2B | 0.9700 |
Ce1—N3 | 2.761 (4) | C3—C4 | 1.488 (7) |
C17—N1 | 1.329 (6) | C3—H3A | 0.9700 |
C17—C18 | 1.397 (6) | C3—H3B | 0.9700 |
C17—H17 | 0.9300 | C4—H4A | 0.9700 |
C18—C19 | 1.312 (6) | C4—H4B | 0.9700 |
C18—H18 | 0.9300 | C5—C6 | 1.498 (8) |
C19—N2 | 1.357 (6) | C5—H5A | 0.9700 |
C19—H19 | 0.9300 | C5—H5B | 0.9700 |
C20—N3 | 1.335 (6) | C6—C7 | 1.487 (7) |
C20—C21 | 1.357 (7) | C6—H6A | 0.9700 |
C20—H20 | 0.9300 | C6—H6B | 0.9700 |
C21—C22 | 1.342 (7) | C7—C8 | 1.446 (8) |
C21—H21 | 0.9300 | C7—H7A | 0.9700 |
C22—N4 | 1.331 (6) | C7—H7B | 0.9700 |
C22—H22 | 0.9300 | C8—H8A | 0.9600 |
C23—N5 | 1.329 (6) | C8—H8B | 0.9600 |
C23—C24 | 1.377 (6) | C8—H8C | 0.9600 |
C23—H23 | 0.9300 | C9—C10 | 1.447 (8) |
C24—C25 | 1.339 (6) | C9—H9A | 0.9600 |
C24—H24 | 0.9300 | C9—H9B | 0.9600 |
C25—N6 | 1.342 (6) | C9—H9C | 0.9600 |
C25—H25 | 0.9300 | C10—C11 | 1.475 (8) |
C26—N2 | 1.443 (6) | C10—H10A | 0.9700 |
C26—N6 | 1.444 (6) | C10—H10B | 0.9700 |
C26—N4 | 1.456 (6) | C11—C12 | 1.516 (8) |
C26—H26 | 0.9800 | C11—H11A | 0.9700 |
N1—N2 | 1.359 (5) | C11—H11B | 0.9700 |
N3—N4 | 1.341 (5) | C12—H12A | 0.9700 |
N5—N6 | 1.345 (5) | C12—H12B | 0.9700 |
N7—O2 | 1.201 (4) | C13—C14 | 1.505 (8) |
N7—O3 | 1.205 (5) | C13—H13A | 0.9700 |
N7—O1 | 1.286 (5) | C13—H13B | 0.9700 |
N8—O5 | 1.224 (5) | C14—C15 | 1.521 (8) |
N8—O6 | 1.228 (5) | C14—H14A | 0.9700 |
N8—O4 | 1.269 (5) | C14—H14B | 0.9700 |
N9—O9 | 1.220 (5) | C15—C16 | 1.493 (9) |
N9—O7 | 1.253 (5) | C15—H15A | 0.9700 |
N9—O8 | 1.255 (5) | C15—H15B | 0.9700 |
N10—O10 | 1.222 (4) | C16—H16A | 0.9600 |
N10—O12 | 1.226 (5) | C16—H16B | 0.9600 |
N10—O11 | 1.262 (5) | C16—H16C | 0.9600 |
N11—C5 | 1.515 (6) | ||
O1—Ce1—O11 | 83.17 (10) | O5—N8—O6 | 122.4 (5) |
O1—Ce1—O5 | 78.93 (9) | O5—N8—O4 | 118.0 (4) |
O11—Ce1—O5 | 162.09 (10) | O6—N8—O4 | 119.3 (5) |
O1—Ce1—O8 | 109.74 (10) | O5—N8—Ce1 | 58.3 (2) |
O11—Ce1—O8 | 71.81 (11) | O6—N8—Ce1 | 176.5 (4) |
O5—Ce1—O8 | 113.98 (10) | O4—N8—Ce1 | 59.7 (2) |
O1—Ce1—O4 | 79.19 (10) | O9—N9—O7 | 121.1 (4) |
O11—Ce1—O4 | 127.54 (11) | O9—N9—O8 | 122.3 (4) |
O5—Ce1—O4 | 48.25 (10) | O7—N9—O8 | 116.6 (4) |
O8—Ce1—O4 | 68.69 (11) | O10—N10—O12 | 123.3 (5) |
O1—Ce1—O10 | 81.30 (9) | O10—N10—O11 | 116.1 (4) |
O11—Ce1—O10 | 47.81 (10) | O12—N10—O11 | 120.5 (4) |
O5—Ce1—O10 | 128.50 (10) | N7—O1—Ce1 | 100.7 (2) |
O8—Ce1—O10 | 117.42 (10) | N7—O2—Ce1 | 94.7 (3) |
O4—Ce1—O10 | 160.44 (10) | N8—O4—Ce1 | 95.6 (3) |
O1—Ce1—O7 | 62.13 (10) | N8—O5—Ce1 | 98.1 (3) |
O11—Ce1—O7 | 64.27 (11) | N9—O7—Ce1 | 96.7 (3) |
O5—Ce1—O7 | 106.17 (10) | N9—O8—Ce1 | 98.8 (3) |
O8—Ce1—O7 | 47.72 (10) | N10—O10—Ce1 | 97.2 (3) |
O4—Ce1—O7 | 63.77 (10) | N10—O11—Ce1 | 98.9 (3) |
O10—Ce1—O7 | 105.46 (10) | C5—N11—C12 | 111.1 (5) |
O1—Ce1—O2 | 47.78 (9) | C5—N11—C4 | 107.2 (4) |
O11—Ce1—O2 | 102.67 (10) | C12—N11—C4 | 110.8 (5) |
O5—Ce1—O2 | 65.18 (9) | C5—N11—C13 | 111.8 (5) |
O8—Ce1—O2 | 157.46 (10) | C12—N11—C13 | 102.5 (5) |
O4—Ce1—O2 | 100.87 (10) | C4—N11—C13 | 113.4 (5) |
O10—Ce1—O2 | 66.29 (9) | C2—C1—H1A | 109.5 |
O7—Ce1—O2 | 109.90 (10) | C2—C1—H1B | 109.5 |
O1—Ce1—N1 | 114.94 (11) | H1A—C1—H1B | 109.5 |
O11—Ce1—N1 | 114.56 (12) | C2—C1—H1C | 109.5 |
O5—Ce1—N1 | 74.10 (11) | H1A—C1—H1C | 109.5 |
O8—Ce1—N1 | 135.28 (12) | H1B—C1—H1C | 109.5 |
O4—Ce1—N1 | 117.72 (11) | C3—C2—C1 | 112.6 (5) |
O10—Ce1—N1 | 72.24 (11) | C3—C2—H2A | 109.1 |
O7—Ce1—N1 | 176.74 (11) | C1—C2—H2A | 109.1 |
O2—Ce1—N1 | 67.16 (11) | C3—C2—H2B | 109.1 |
O1—Ce1—N5 | 146.67 (11) | C1—C2—H2B | 109.1 |
O11—Ce1—N5 | 126.33 (11) | H2A—C2—H2B | 107.8 |
O5—Ce1—N5 | 70.81 (11) | C4—C3—C2 | 110.3 (5) |
O8—Ce1—N5 | 71.88 (12) | C4—C3—H3A | 109.6 |
O4—Ce1—N5 | 70.42 (11) | C2—C3—H3A | 109.6 |
O10—Ce1—N5 | 128.80 (11) | C4—C3—H3B | 109.6 |
O7—Ce1—N5 | 113.11 (12) | C2—C3—H3B | 109.6 |
O2—Ce1—N5 | 124.81 (11) | H3A—C3—H3B | 108.1 |
N1—Ce1—N5 | 70.10 (13) | C3—C4—N11 | 116.8 (5) |
O1—Ce1—N3 | 149.74 (11) | C3—C4—H4A | 108.1 |
O11—Ce1—N3 | 70.72 (12) | N11—C4—H4A | 108.1 |
O5—Ce1—N3 | 126.55 (11) | C3—C4—H4B | 108.1 |
O8—Ce1—N3 | 76.94 (12) | N11—C4—H4B | 108.1 |
O4—Ce1—N3 | 128.94 (11) | H4A—C4—H4B | 107.3 |
O10—Ce1—N3 | 69.96 (11) | C6—C5—N11 | 116.2 (5) |
O7—Ce1—N3 | 116.05 (12) | C6—C5—H5A | 108.2 |
O2—Ce1—N3 | 122.74 (11) | N11—C5—H5A | 108.2 |
N1—Ce1—N3 | 65.59 (13) | C6—C5—H5B | 108.2 |
N5—Ce1—N3 | 63.53 (13) | N11—C5—H5B | 108.2 |
O1—Ce1—N8 | 77.76 (10) | H5A—C5—H5B | 107.4 |
O11—Ce1—N8 | 149.06 (11) | C7—C6—C5 | 111.7 (5) |
O5—Ce1—N8 | 23.59 (9) | C7—C6—H6A | 109.3 |
O8—Ce1—N8 | 91.93 (11) | C5—C6—H6A | 109.3 |
O4—Ce1—N8 | 24.65 (10) | C7—C6—H6B | 109.3 |
O10—Ce1—N8 | 148.45 (11) | C5—C6—H6B | 109.3 |
O7—Ce1—N8 | 85.22 (11) | H6A—C6—H6B | 108.0 |
O2—Ce1—N8 | 82.17 (11) | C8—C7—C6 | 110.0 (6) |
N1—Ce1—N8 | 95.63 (12) | C8—C7—H7A | 109.7 |
N5—Ce1—N8 | 68.91 (12) | C6—C7—H7A | 109.7 |
N3—Ce1—N8 | 132.32 (12) | C8—C7—H7B | 109.7 |
N1—C17—C18 | 109.4 (5) | C6—C7—H7B | 109.7 |
N1—C17—H17 | 125.3 | H7A—C7—H7B | 108.2 |
C18—C17—H17 | 125.3 | C7—C8—H8A | 109.5 |
C19—C18—C17 | 107.6 (5) | C7—C8—H8B | 109.5 |
C19—C18—H18 | 126.2 | H8A—C8—H8B | 109.5 |
C17—C18—H18 | 126.2 | C7—C8—H8C | 109.5 |
C18—C19—N2 | 107.0 (5) | H8A—C8—H8C | 109.5 |
C18—C19—H19 | 126.5 | H8B—C8—H8C | 109.5 |
N2—C19—H19 | 126.5 | C10—C9—H9A | 109.5 |
N3—C20—C21 | 112.4 (5) | C10—C9—H9B | 109.5 |
N3—C20—H20 | 123.8 | H9A—C9—H9B | 109.5 |
C21—C20—H20 | 123.8 | C10—C9—H9C | 109.5 |
C22—C21—C20 | 105.5 (5) | H9A—C9—H9C | 109.5 |
C22—C21—H21 | 127.3 | H9B—C9—H9C | 109.5 |
C20—C21—H21 | 127.3 | C9—C10—C11 | 112.7 (6) |
N4—C22—C21 | 106.8 (5) | C9—C10—H10A | 109.1 |
N4—C22—H22 | 126.6 | C11—C10—H10A | 109.1 |
C21—C22—H22 | 126.6 | C9—C10—H10B | 109.1 |
N5—C23—C24 | 111.9 (5) | C11—C10—H10B | 109.1 |
N5—C23—H23 | 124.0 | H10A—C10—H10B | 107.8 |
C24—C23—H23 | 124.0 | C10—C11—C12 | 109.7 (6) |
C25—C24—C23 | 105.0 (5) | C10—C11—H11A | 109.7 |
C25—C24—H24 | 127.5 | C12—C11—H11A | 109.7 |
C23—C24—H24 | 127.5 | C10—C11—H11B | 109.7 |
C24—C25—N6 | 107.7 (5) | C12—C11—H11B | 109.7 |
C24—C25—H25 | 126.1 | H11A—C11—H11B | 108.2 |
N6—C25—H25 | 126.1 | N11—C12—C11 | 116.3 (5) |
N2—C26—N6 | 112.3 (4) | N11—C12—H12A | 108.2 |
N2—C26—N4 | 111.6 (4) | C11—C12—H12A | 108.2 |
N6—C26—N4 | 110.7 (4) | N11—C12—H12B | 108.2 |
N2—C26—H26 | 107.3 | C11—C12—H12B | 108.2 |
N6—C26—H26 | 107.3 | H12A—C12—H12B | 107.4 |
N4—C26—H26 | 107.3 | C14—C13—N11 | 114.3 (5) |
C17—N1—N2 | 105.0 (4) | C14—C13—H13A | 108.7 |
C17—N1—Ce1 | 128.7 (3) | N11—C13—H13A | 108.7 |
N2—N1—Ce1 | 125.9 (3) | C14—C13—H13B | 108.7 |
C19—N2—N1 | 110.9 (4) | N11—C13—H13B | 108.7 |
C19—N2—C26 | 127.3 (4) | H13A—C13—H13B | 107.6 |
N1—N2—C26 | 121.4 (4) | C13—C14—C15 | 111.6 (6) |
C20—N3—N4 | 102.7 (4) | C13—C14—H14A | 109.3 |
C20—N3—Ce1 | 131.3 (4) | C15—C14—H14A | 109.3 |
N4—N3—Ce1 | 125.1 (3) | C13—C14—H14B | 109.3 |
C22—N4—N3 | 112.7 (5) | C15—C14—H14B | 109.3 |
C22—N4—C26 | 125.9 (5) | H14A—C14—H14B | 108.0 |
N3—N4—C26 | 121.4 (4) | C16—C15—C14 | 117.2 (7) |
C23—N5—N6 | 103.9 (4) | C16—C15—H15A | 108.0 |
C23—N5—Ce1 | 129.9 (3) | C14—C15—H15A | 108.0 |
N6—N5—Ce1 | 126.2 (3) | C16—C15—H15B | 108.0 |
C25—N6—N5 | 111.4 (4) | C14—C15—H15B | 108.0 |
C25—N6—C26 | 126.3 (5) | H15A—C15—H15B | 107.2 |
N5—N6—C26 | 121.9 (4) | C15—C16—H16A | 109.5 |
O2—N7—O3 | 124.7 (4) | C15—C16—H16B | 109.5 |
O2—N7—O1 | 116.2 (4) | H16A—C16—H16B | 109.5 |
O3—N7—O1 | 119.0 (4) | C15—C16—H16C | 109.5 |
O2—N7—Ce1 | 62.0 (2) | H16A—C16—H16C | 109.5 |
O3—N7—Ce1 | 172.4 (3) | H16B—C16—H16C | 109.5 |
O1—N7—Ce1 | 54.63 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4B···O9i | 0.97 | 2.46 | 3.421 (7) | 173 |
C5—H5B···O12ii | 0.97 | 2.55 | 3.445 (8) | 153 |
C13—H13A···O5iii | 0.97 | 2.37 | 3.311 (7) | 163 |
C19—H19···O1iv | 0.93 | 2.31 | 3.080 (6) | 140 |
C25—H25···O11iv | 0.93 | 2.49 | 3.365 (6) | 158 |
C26—H26···O7iv | 0.98 | 2.25 | 3.221 (6) | 170 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x, y−1, z; (iii) −x, y−1/2, −z+1/2; (iv) x, −y+3/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | (C16H36N)[Ce(NO3)4(C10H10N6)] |
Mr | 844.86 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 12.484 (1), 16.742 (1), 18.267 (1) |
β (°) | 102.82 (1) |
V (Å3) | 3722.8 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.29 |
Crystal size (mm) | 0.3 × 0.2 × 0.2 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (Sheldrick, 1990) |
Tmin, Tmax | 0.740, 0.771 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18988, 6546, 4018 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.092, 1.02 |
No. of reflections | 6546 |
No. of parameters | 431 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.67, −0.59 |
Computer programs: SMART (Bruker, 2000), SMART, SAINT (Bruker, 2000), SHELXTL (Bruker, 2000), SHELXTL.
Ce1—O1 | 2.514 (3) | Ce1—O7 | 2.660 (3) |
Ce1—O11 | 2.572 (3) | Ce1—O2 | 2.685 (3) |
Ce1—O5 | 2.602 (3) | Ce1—N1 | 2.686 (4) |
Ce1—O8 | 2.615 (3) | Ce1—N5 | 2.705 (4) |
Ce1—O4 | 2.626 (3) | Ce1—N3 | 2.761 (4) |
Ce1—O10 | 2.630 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4B···O9i | 0.97 | 2.46 | 3.421 (7) | 173 |
C5—H5B···O12ii | 0.97 | 2.55 | 3.445 (8) | 153 |
C13—H13A···O5iii | 0.97 | 2.37 | 3.311 (7) | 163 |
C19—H19···O1iv | 0.93 | 2.31 | 3.080 (6) | 140 |
C25—H25···O11iv | 0.93 | 2.49 | 3.365 (6) | 158 |
C26—H26···O7iv | 0.98 | 2.25 | 3.221 (6) | 170 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x, y−1, z; (iii) −x, y−1/2, −z+1/2; (iv) x, −y+3/2, z+1/2. |
The coordination chemistry of the neutral isoelectronic carbon-centred analogue tris(pyrazolyl)methane (HCPz3) is relatively underdeveloped, even though it was introduced by Trofimenko as early as 1986 (Trofimenko, 1986). So far, many transition metal complexes with HCPz3 have been prepared (Astley et al., 1993; Bhambri et al., 1997; Reger et al., 1996) and main group element complexes have also appeared (Pettinari et al., 1999; Reger et al., 1997). However, no rare earth complexes with this remarkable tridentate ligand has been reported. Herein we report the title CeIII complex, (I).
The crystal structure of (I) consists of discrete [(HCPz3)Ce(NO3)4]− and nBu4N+ ions. The structure of the anion is shown in Fig. 1. The cerium(III) ion is surrounded by three N atoms from the tridentate HCPz3 ligand and eight O atoms belonging to four bidentate chelating nitrate ligands. This structure is similar to the 11–coordinate Ce-nitrate complexes CeIII(NO3)4(R3TPTZ) [R is (CH3)3C and TPTZ is 2,4,6-tris(2-pyridyl)-1,3,5-triazine; Gabriel et al., 1996] and (Hpy)[CeIV(NO3)4(terpy)].py (terpy is terpyridine; Grigoriev et al., 2001). The Ce—O bond distances are in the range 2.514 (3)–2.685 (3) Å, and the shortest and longest Ce—O distances are slightly shorter than those in CeIII(NO3)4(R3TPTZ) [Ce—O 2.522 (7)–2.699 (9) Å] and (Hpy)[CeIV(NO3)4(terpy)].py [Ce—O 2.570 (2)–2.709 (2)°]. They are also comparable to those in ten-coordinate CeIII complexes, for example [(C6H5)3C2H5P]2Ce(NO3)5 [mean 2.57 (3) Å; Al-Karaghouli et al., 1973] and [Ce(ntb)(NO3)3]·H2O [ntb is tris(benzimidazol-2-ylmethyl)amine; mean 2.597 (2) Å; Su et al., 1998]. The nitrate ligands are coordinated to the cerium(III) ion in a slightly asymmetrical manner, with differences in the Ce···O distancess of 0.176 (2), 0.022 (2), 0.065 (2) and 0.065 (2) Å for the individual nitrate groups. CeIII is approximately coplanar with the nitrate ligands. The average dihedral angle of the chelating nitrate ligands is 48°. The CeIII—N distances are in the range 2.686 (4)–2.761 (4) Å; however, the shortest and longest Ce—N distances are slightly longer than those in CeIII(NO3)4(R3TPTZ) [Ce—N 2.673 (7)–2.734 (7) Å] and (Hpy)[CeIV(NO3)4(terpy)].py [Ce—N 2.624 (2)–2.706 (2) Å]. The three dihedral angles of the tridentate ligand are in the range 63.53 (13)–70.10 (13)°, and are larger than those of CeIII(NO3)4(R3TPTZ) [dihedral angle 59.4 (2)–62.4 (2)°] and (Hpy)[CeIV(NO3)4(terpy)].py [dihedral angle 57.68 (7)–61.37 (7)°]. There are intermolecular C—H···O close contacts leading to a three-dimensional polymeric network (Fig. 2 and Table 2).