Supplementary Material
Chiral bis(aminoalcohol) silver complex derived from (+)-camphor
JAIME GONZÁLEZ, MARISOL REYES-LEZAMA, DAVID CORONA and ERICK CUEVAS-YAÑEZ*
CONTENTS:
1. General considerations
2. Spectroscopic data of compounds
3. 1H NMR and 13C NMR spectra for compounds
4. Selected X-ray data of silver complex
1. General considerations
The starting materials were purchased from Aldrich Chemical Co. and were used without further purification. Solvents were distilled before use. Silica plates of 0.20 mm thickness were used for thin layer chromatography. Melting points were determined with a Fisher-Johns melting point apparatus and they are uncorrected.
1H and 13C NMR spectra were recorded using a Varian 500; the chemical shifts (δ) are given in ppm relative to TMS as internal standard (0.00). For analytical purposes the mass spectra were recorded on a Shimadzu GCMS-QP2010 Plus and on a JEOL JMS-5X 10217 in the EI mode, 70 eV, 200 °C via direct inlet probe. Only the molecular and parent ions (m/z) are reported. IR spectra were recorded on a Bruker TENSOR 27 FT instrument.
For the RX difraction studies, crystals of compound 3 were obtained by slow evaporation of a dilute MeOH solution, and the reflections were acquired with a Bruker difractometer. Three standard reflections every 97 reflections were used to monitor the crystal stability. The structure was solved by direct methods; missing atoms were found by difference-Fourier synthesis, and refined on F2 by a full-matrix least-squares procedure using anisotropic displacement parameters using SHELX-97. Crystallographic data for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Centre (CCDC No. 911160). Copies of available materials can be obtained free of charge on application to the Director, CCDC, 12 Union Road, Cambridge CB2 IEZ, UK (facsimile: (44) 01223 336033); e-mail: .
2. Spectroscopic data of compounds
(1R, 2R, 4R-2-amino-1,7,7-trimethylbicyclo[2.2.1]hept-2-yl)methanol (1).
m.p. 108-110 °C; [α]D20 = -35.5 (c 0.0012 in DMSO).
1H NMR (300 MHz, CDCl3): δ 3.38 (q, J = 5.9Hz, 2H), 1.90 (s, broad, 3H), 1.73 (d, J = 2.5Hz, 2H), 1.68 (t, J = 3.5 Hz, 2H), 1.45 (d, J = 6.4 Hz, 2H), 1.36 (d, J = 12.8 Hz, 1H), 1.07 (s, 3H), 0.88 (s, 3H), 0.86 (s, 3H).
13C NMR (75 MHz, CDCl3): δ. 69.0 (CH2), 61.5 (C), 50.9 (C), 49.9 (C), 44.9 (CH2), 44.6 (CH), 30.6 (CH2), 27.2 (CH2), 21.9 (CH3), 21.0 (CH3), 12.0 (CH3).
IR (KBr) νmax 3400, 3124, 2991, 2938, 1700, 1592 cm-1.
MS [EI+] m/z (%):183 [M]+ (73).
Anal. calcd. for C11H21NO (%): C 72.08, H 11.55, N 7.64; found: C 72.05; H 11.50; N 7.67.
bis-(1R, 2R, 4R-2-amino-1,7,7-trimethylbicyclo[2.2.1]hept-2-yl)methanol silver complex (2).
m.p. 77-82 °C; [α]D20 = -37.5 (c 0.0028 in DMSO).
1H NMR (500 MHz, CDCl3): δ 4.84 (s, broad 1H, OH), 3.62 (dd, J = 5.9 Hz, 2H, assigned to H8, scheme 3), 3.51 (s, broad, 2H, NH2), 1.83 (dt, J = 12.8, 6.5 Hz, 1H, assigned to H3β, scheme 3), 1.74 (m, 3H, assigned to H5 and H4, scheme 3), 1.61 (ddd, J = 13.5, 9.2, 2.9 Hz, 1H, assigned to H6, scheme 3), 1.52 (ddd, J = 13.7, 11.4, 3.0 Hz, 1H, assigned to H6, scheme3), 1.27 (d, J = 13.2 Hz, 1H, assigned to H3α, scheme 3), 1.05 (s, 3H, assigned to H9, scheme 3), 1.03 (s, 3H, assigned to H11, scheme 3), 0.88 (s, 3H, assigned to H10, scheme 3).
13C NMR (125 MHz, CDCl3): δ 66.7 (CH2), 60.9 (C), 48.8 (C), 47.3 (CH2), 42.1 (C), 41.7 (CH), 28.8 (CH2), 24.1 (CH2), 18.9 (CH3), 18.0 (CH3), 9.9 (CH3).
IR (KBr) νmax 3406, 3367, 3248, 29952, 2874, 1714, 1596 cm-1.
HRMS (ESI+): for C22H42AgN2O2 calcd. 473.2297, found 473.2292.
Anal. calcd. for C22H42AgN2O2 (%): C 55.69, H 8.92, N 6.74; found: C 55.71; H 8.97; N 6.68.
3. 1H NMR and 13C NMR spectra for compounds.
(1R, 2R, 4R-2-amino-1,7,7-trimethylbicyclo[2.2.1]hept-2-yl)methanol (1).
bis-(1R, 2R, 4R-2-amino-1,7,7-trimethylbicyclo[2.2.1]hept-2-yl)methanol silver complex (2).
COSY spectrum for silver complex 2
NOESY spectrum for silver complex 2
4. Selected X-ray data of silver complex
Table S1. Crystal data and structure refinement for bis-(2-amino-1,7,7-trimethylbicyclo[2.2.1]hept-2-yl)methanol silver complex (2).
Identification code / Complex 2Empirical formula / C22H42AgN3O5
Formula weight / 536.46
Temperature / 293(2) K
Wavelength / 0.71073 Å
Crystal system / Orthorhombic
Space group / P2(1)2(1)2(1)
Unit cell dimensions / a = 7.3336(10) Å / a = 90°
b = 12.1467(16) Å / b = 90°
c = 28.836(4) Å / g = 90°
Volume / 2568.7(6) Å3
Z / 4
Density (calculated) / 1.387 Mg/m3
Absorption coefficient / 0.819 mm-1
F(000) / 1128
Crystal size / 0.36 × 0.25 × 0.15 mm3
Theta range for data collection / 1.82 to 25.11°
Index ranges / -8<=h<=8, -14<=k<=14, -34<=l<=34
Reflections collected / 36189
Independent reflections / 4583 [R(int) = 0.0787]
Completeness to theta = 25.11° / 99.8 %
Absorption correction / Semi-empirical from equivalents
Max. and min. transmission / 0.8870 and 0.7592
Refinement method / Full-matrix least-squares on F2
Data / restraints / parameters / 4583 / 149 / 340
Goodness-of-fit on F2 / 1.033
Final R indices [I 2s (I)] / R1 = 0.0357, wR2 = 0.0807
R indices (all data) / R1 = 0.0405, wR2 = 0.0836
Absolute structure parameter / 0.06(3)
Largest diff. peak and hole / 0.509 and -0.701 (eÅ-3)
ORTEP diagram and atom labelling system for 2.
Table S2. Atomic coordinates (×104) and equivalent isotropic displacement parameters (Å2×103)
for 2. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
______
x y z U(eq)
______
Ag(1) / 4900(1) / 1160(1) / 390(1) / 54(1)O(1) / 8379(4) / -141(3) / 1348(1) / 82(1)
O(2) / 835(4) / -682(3) / -321(1) / 80(1)
N(1) / 5634(4) / 1477(2) / 1094(1) / 45(1)
N(2) / 4120(4) / 665(2) / -291(1) / 41(1)
N(3) / -20(50) / 1470(17) / 411(7) / 67(2)
O(3) / -220(30) / 451(14) / 466(8) / 69(3)
O(4) / 420(30) / 1791(15) / 11(7) / 82(4)
O(5) / -170(30) / 2067(18) / 760(7) / 71(3)
N(3A) / -120(30) / 1571(13) / 457(6) / 67(2)
O(3A) / -750(20) / 608(12) / 422(7) / 70(3)
O(4A) / 1020(20) / 1954(11) / 176(7) / 84(3)
O(5A) / -730(20) / 2161(13) / 766(5) / 73(3)
C(1) / 5431(4) / 939(3) / 1952(1) / 44(1)
C(2) / 5506(6) / -130(3) / 2242(1) / 66(1)
C(3) / 3581(8) / -610(4) / 2193(2) / 82(1)
C(4) / 2575(6) / 263(4) / 1908(2) / 70(1)
C(5) / 3235(5) / 189(4) / 1407(2) / 60(1)
C(6) / 3461(6) / 1341(4) / 2071(1) / 57(1)
C(7) / 3189(9) / 1579(5) / 2589(2) / 91(2)
C(8) / 2790(7) / 2369(4) / 1816(2) / 74(1)
C(9) / 7009(6) / 1725(4) / 2056(2) / 66(1)
C(10) / 5249(5) / 568(2) / 1430(1) / 45(1)
C(11) / 6515(6) / -371(3) / 1282(2) / 62(1)
C(12) / 4168(5) / -705(3) / -959(1) / 41(1)
C(13) / 3663(6) / -1928(3) / -1038(2) / 64(1)
C(14) / 5311(7) / -2558(3) / -841(2) / 79(1)
C(15) / 6638(5) / -1633(3) / -706(1) / 57(1)
C(16) / 5937(4) / -1107(3) / -265(1) / 45(1)
C(17) / 6258(5) / -748(4) / -1072(1) / 58(1)
C(19) / 6674(8) / -1119(6) / -1576(2) / 109(2)
C(18) / 7295(6) / 334(4) / -990(2) / 75(1)
C(20) / 3047(6) / 102(4) / -1238(1) / 60(1)
C(21) / 4154(4) / -522(2) / -418(1) / 34(1)
C(22) / 2551(4) / -1027(3) / -158(1) / 56(1)
______
Table S3. Bond lengths [Å] and angles [°] for 2.
______
Ag(1)-N(2) / 2.131(3)Ag(1)-N(1) / 2.135(3)
O(1)-C(11) / 1.408(6)
O(1)-H(1A) / 0.848(10)
O(2)-C(22) / 1.408(5)
O(2)-H(2A) / 0.838(10)
N(1)-C(10) / 1.495(4)
N(1)-H(1') / 0.85(2)
N(1)-H(1) / 0.84(2)
N(2)-C(21) / 1.489(4)
N(2)-H(2') / 0.85(2)
N(2)-H(2) / 0.84(2)
N(3)-O(5) / 1.247(11)
N(3)-O(3) / 1.256(12)
N(3)-O(4) / 1.260(12)
N(3A)-O(5A) / 1.228(10)
N(3A)-O(4A) / 1.250(11)
N(3A)-O(3A) / 1.263(10)
C(1)-C(9) / 1.530(5)
C(1)-C(2) / 1.546(5)
C(1)-C(6) / 1.562(5)
C(1)-C(10) / 1.578(4)
C(2)-C(3) / 1.535(7)
C(2)-H(2C) / 0.9700
C(2)-H(2D) / 0.9700
C(3)-C(4) / 1.531(7)
C(3)-H(3A) / 0.9700
C(3)-H(3B) / 0.9700
C(4)-C(5) / 1.526(6)
C(4)-C(6) / 1.536(6)
C(4)-H(4A) / 0.9800
C(5)-C(10) / 1.549(5)
C(5)-H(5A) / 0.9700
C(5)-H(5B) / 0.9700
C(6)-C(8) / 1.530(6)
C(6)-C(7) / 1.537(6)
C(7)-H(7A) / 0.9600
C(7)-H(7B) / 0.9600
C(7)-H(7C) / 0.9600
C(8)-H(8A) / 0.9600
C(8)-H(8B) / 0.9600
C(8)-H(8C) / 0.9600
C(9)-H(9A) / 0.9600
C(9)-H(9B) / 0.9600
C(9)-H(9C) / 0.9600
C(10)-C(11) / 1.531(5)
C(11)-H(11A) / 0.9700
C(11)-H(11B) / 0.9700
C(12)-C(20) / 1.513(5)
C(12)-C(13) / 1.548(5)
C(12)-C(17) / 1.568(5)
C(12)-C(21) / 1.575(4)
C(13)-C(14) / 1.539(6)
C(13)-H(13A) / 0.9700
C(13)-H(13B) / 0.9700
C(14)-C(15) / 1.537(6)
C(14)-H(14A) / 0.9700
C(14)-H(14B) / 0.9700
C(15)-C(16) / 1.512(5)
C(15)-C(17) / 1.534(6)
C(15)-H(15A) / 0.9800
C(16)-C(21) / 1.552(4)
C(16)-H(16A) / 0.9700
C(16)-H(16B) / 0.9700
C(17)-C(18) / 1.536(7)
C(17)-C(19) / 1.551(6)
C(19)-H(19A) / 0.9600
C(19)-H(19B) / 0.9600
C(19)-H(19C) / 0.9600
C(18)-H(18A) / 0.9600
C(18)-H(18B) / 0.9600
C(18)-H(18C) / 0.9600
C(20)-H(20A) / 0.9600
C(20)-H(20B) / 0.9600
C(20)-H(20C) / 0.9600
C(21)-C(22) / 1.523(4)
C(22)-H(22A) / 0.9700
C(22)-H(22B) / 0.9700
N(2)-Ag(1)-N(1) / 173.82(11)
C(11)-O(1)-H(1A) / 105.3(16)
C(22)-O(2)-H(2A) / 105(2)
C(10)-N(1)-Ag(1) / 115.8(2)
C(10)-N(1)-H(1') / 114(2)
Ag(1)-N(1)-H(1') / 105(2)
C(10)-N(1)-H(1) / 112(3)
Ag(1)-N(1)-H(1) / 103(3)
H(1')-N(1)-H(1) / 106(3)
C(21)-N(2)-Ag(1) / 119.8(2)
C(21)-N(2)-H(2') / 115(2)
Ag(1)-N(2)-H(2') / 99(2)
C(21)-N(2)-H(2) / 112(3)
Ag(1)-N(2)-H(2) / 104(3)
H(2')-N(2)-H(2) / 106(3)
O(5)-N(3)-O(3) / 117.4(16)
O(5)-N(3)-O(4) / 125.6(15)
O(3)-N(3)-O(4) / 116.9(14)
O(5A)-N(3A)-O(4A) / 119.8(11)
O(5A)-N(3A)-O(3A) / 117.5(12)
O(4A)-N(3A)-O(3A) / 122.6(12)
C(9)-C(1)-C(2) / 113.0(3)
C(9)-C(1)-C(6) / 117.5(3)
C(2)-C(1)-C(6) / 100.2(3)
C(9)-C(1)-C(10) / 115.4(3)
C(2)-C(1)-C(10) / 106.3(3)
C(6)-C(1)-C(10) / 102.7(3)
C(3)-C(2)-C(1) / 103.6(3)
C(3)-C(2)-H(2C) / 111.0
C(1)-C(2)-H(2C) / 111.0
C(3)-C(2)-H(2D) / 111.0
C(1)-C(2)-H(2D) / 111.0
H(2C)-C(2)-H(2D) / 109.0
C(4)-C(3)-C(2) / 103.3(3)
C(4)-C(3)-H(3A) / 111.1
C(2)-C(3)-H(3A) / 111.1
C(4)-C(3)-H(3B) / 111.1
C(2)-C(3)-H(3B) / 111.1
H(3A)-C(3)-H(3B) / 109.1
C(5)-C(4)-C(3) / 108.3(4)
C(5)-C(4)-C(6) / 101.8(3)
C(3)-C(4)-C(6) / 102.9(4)
C(5)-C(4)-H(4A) / 114.2
C(3)-C(4)-H(4A) / 114.2
C(6)-C(4)-H(4A) / 114.2
C(4)-C(5)-C(10) / 104.2(3)
C(4)-C(5)-H(5A) / 110.9
C(10)-C(5)-H(5A) / 110.9
C(4)-C(5)-H(5B) / 110.9
C(10)-C(5)-H(5B) / 110.9
H(5A)-C(5)-H(5B) / 108.9
C(8)-C(6)-C(4) / 114.4(4)
C(8)-C(6)-C(7) / 105.8(4)
C(4)-C(6)-C(7) / 113.7(4)
C(8)-C(6)-C(1) / 116.6(3)
C(4)-C(6)-C(1) / 93.3(3)
C(7)-C(6)-C(1) / 113.1(4)
C(6)-C(7)-H(7A) / 109.5
C(6)-C(7)-H(7B) / 109.5
H(7A)-C(7)-H(7B) / 109.5
C(6)-C(7)-H(7C) / 109.5
H(7A)-C(7)-H(7C) / 109.5
H(7B)-C(7)-H(7C) / 109.5
C(6)-C(8)-H(8A) / 109.5
C(6)-C(8)-H(8B) / 109.5
H(8A)-C(8)-H(8B) / 109.5
C(6)-C(8)-H(8C) / 109.5
H(8A)-C(8)-H(8C) / 109.5
H(8B)-C(8)-H(8C) / 109.5
C(1)-C(9)-H(9A) / 109.5
C(1)-C(9)-H(9B) / 109.5
H(9A)-C(9)-H(9B) / 109.5
C(1)-C(9)-H(9C) / 109.5
H(9A)-C(9)-H(9C) / 109.5
H(9B)-C(9)-H(9C) / 109.5
N(1)-C(10)-C(11) / 104.8(3)
N(1)-C(10)-C(5) / 111.8(3)
C(11)-C(10)-C(5) / 110.2(3)
N(1)-C(10)-C(1) / 113.0(3)
C(11)-C(10)-C(1) / 115.3(3)
C(5)-C(10)-C(1) / 101.9(3)
O(1)-C(11)-C(10) / 113.8(3)
O(1)-C(11)-H(11A) / 108.8
C(10)-C(11)-H(11A) / 108.8
O(1)-C(11)-H(11B) / 108.8
C(10)-C(11)-H(11B) / 108.8
H(11A)-C(11)-H(11B) / 107.7
C(20)-C(12)-C(13) / 114.4(3)
C(20)-C(12)-C(17) / 116.2(3)
C(13)-C(12)-C(17) / 99.9(3)
C(20)-C(12)-C(21) / 115.6(3)
C(13)-C(12)-C(21) / 106.3(3)
C(17)-C(12)-C(21) / 102.6(2)
C(14)-C(13)-C(12) / 103.5(3)
C(14)-C(13)-H(13A) / 111.1
C(12)-C(13)-H(13A) / 111.1
C(14)-C(13)-H(13B) / 111.1
C(12)-C(13)-H(13B) / 111.1
H(13A)-C(13)-H(13B) / 109.0
C(15)-C(14)-C(13) / 103.2(3)
C(15)-C(14)-H(14A) / 111.1
C(13)-C(14)-H(14A) / 111.1
C(15)-C(14)-H(14B) / 111.1
C(13)-C(14)-H(14B) / 111.1
H(14A)-C(14)-H(14B) / 109.1
C(16)-C(15)-C(17) / 102.7(3)
C(16)-C(15)-C(14) / 107.9(3)
C(17)-C(15)-C(14) / 102.9(3)
C(16)-C(15)-H(15A) / 114.0
C(17)-C(15)-H(15A) / 114.0
C(14)-C(15)-H(15A) / 114.0
C(15)-C(16)-C(21) / 104.0(3)
C(15)-C(16)-H(16A) / 111.0
C(21)-C(16)-H(16A) / 111.0
C(15)-C(16)-H(16B) / 111.0
C(21)-C(16)-H(16B) / 111.0
H(16A)-C(16)-H(16B) / 109.0
C(15)-C(17)-C(18) / 113.8(4)
C(15)-C(17)-C(19) / 113.9(4)
C(18)-C(17)-C(19) / 107.2(4)
C(15)-C(17)-C(12) / 93.2(3)
C(18)-C(17)-C(12) / 115.1(4)
C(19)-C(17)-C(12) / 113.4(4)
C(17)-C(19)-H(19A) / 109.5
C(17)-C(19)-H(19B) / 109.5
H(19A)-C(19)-H(19B) / 109.5
C(17)-C(19)-H(19C) / 109.5
H(19A)-C(19)-H(19C) / 109.5
H(19B)-C(19)-H(19C) / 109.5
C(17)-C(18)-H(18A) / 109.5
C(17)-C(18)-H(18B) / 109.5
H(18A)-C(18)-H(18B) / 109.5
C(17)-C(18)-H(18C) / 109.5
H(18A)-C(18)-H(18C) / 109.5
H(18B)-C(18)-H(18C) / 109.5
C(12)-C(20)-H(20A) / 109.5
C(12)-C(20)-H(20B) / 109.5
H(20A)-C(20)-H(20B) / 109.5
C(12)-C(20)-H(20C) / 109.5
H(20A)-C(20)-H(20C) / 109.5
H(20B)-C(20)-H(20C) / 109.5
N(2)-C(21)-C(22) / 104.8(3)
N(2)-C(21)-C(16) / 112.8(3)
C(22)-C(21)-C(16) / 109.0(3)
N(2)-C(21)-C(12) / 112.4(3)
C(22)-C(21)-C(12) / 115.9(3)
C(16)-C(21)-C(12) / 102.2(2)
O(2)-C(22)-C(21) / 113.9(3)
O(2)-C(22)-H(22A) / 108.8
C(21)-C(22)-H(22A) / 108.8
O(2)-C(22)-H(22B) / 108.8
C(21)-C(22)-H(22B) / 108.8
H(22A)-C(22)-H(22B) / 107.7
______
Table S4. Anisotropic displacement parameters (Å2×103) for 3. The anisotropic displacement factor exponent takes the form: -2p2[ h2 a*2U11 + ... + 2 h k a* b* U12 ].
______
U11 U22 U33 U23 U13 U12
______
Ag(1) / 62(1) / 61(1) / 39(1) / -7(1) / -5(1) / -2(1)O(1) / 68(2) / 92(2) / 87(2) / -2(2) / 1(2) / 26(2)
O(2) / 38(1) / 125(3) / 78(2) / -17(2) / 3(1) / -9(2)
N(1) / 54(2) / 42(2) / 40(1) / -3(1) / -3(1) / -2(1)
N(2) / 45(1) / 39(1) / 40(2) / 1(1) / -4(1) / 4(1)
N(3) / 54(5) / 57(4) / 91(4) / 9(4) / 13(5) / 16(5)
O(3) / 77(9) / 51(4) / 80(5) / 4(3) / 13(7) / 13(6)
O(4) / 74(8) / 67(6) / 106(6) / 21(5) / 31(6) / 19(6)
O(5) / 50(8) / 58(4) / 105(5) / -8(4) / 1(6) / 17(6)
N(3A) / 54(4) / 55(4) / 90(4) / 9(3) / 12(4) / 9(4)
O(3A) / 62(6) / 56(5) / 92(6) / -11(4) / 18(5) / 5(4)
O(4A) / 64(5) / 66(4) / 121(8) / 19(5) / 29(5) / 10(4)
O(5A) / 52(7) / 47(4) / 120(5) / -1(3) / 24(5) / 7(5)
C(1) / 53(2) / 40(2) / 38(2) / 1(1) / -5(1) / 0(1)
C(2) / 85(3) / 58(2) / 54(2) / 11(2) / -10(2) / 7(2)
C(3) / 108(4) / 61(3) / 78(3) / 24(3) / 2(3) / -16(3)
C(4) / 59(3) / 73(3) / 77(3) / 18(2) / 0(2) / -16(2)
C(5) / 59(2) / 56(2) / 67(3) / 3(2) / -11(2) / -13(2)
C(6) / 70(2) / 56(2) / 46(2) / 9(2) / 9(2) / 2(2)
C(7) / 125(5) / 95(4) / 54(2) / 0(3) / 28(3) / 16(3)
C(8) / 81(3) / 60(3) / 82(3) / 11(2) / 19(3) / 30(2)
C(9) / 77(3) / 67(3) / 55(2) / -13(2) / -12(2) / -15(2)
C(10) / 56(2) / 36(2) / 45(2) / 0(1) / -8(2) / -2(2)
C(11) / 81(3) / 45(2) / 59(3) / -5(2) / -4(2) / 4(2)
C(12) / 45(2) / 47(2) / 33(2) / -4(1) / -5(1) / 5(1)
C(13) / 72(3) / 52(2) / 67(3) / -18(2) / -16(2) / -2(2)
C(14) / 89(4) / 46(2) / 102(3) / -21(2) / -17(3) / 16(2)
C(15) / 44(2) / 60(2) / 68(2) / -5(2) / -6(2) / 17(2)
C(16) / 47(2) / 41(2) / 48(2) / 8(2) / -10(1) / 7(2)
C(17) / 45(2) / 83(3) / 47(2) / 0(2) / 10(2) / 13(2)
C(19) / 100(4) / 163(6) / 63(3) / -5(4) / 31(3) / 36(4)
C(18) / 48(2) / 88(3) / 88(3) / 24(3) / 13(2) / -10(2)
C(20) / 62(2) / 78(3) / 39(2) / -6(2) / -17(2) / 20(2)
C(21) / 38(1) / 33(2) / 33(2) / 3(1) / 1(1) / -4(1)
C(22) / 46(2) / 62(2) / 59(2) / 3(2) / 8(2) / -14(2)
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