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The crystal structure of 7-methoxy-1H-indazole, C8H8N2O, an inhibitor of nitric oxide synthase, shows that the methoxy group lies in the plane of the indazole system with its methyl group located trans to the indazole N-H group. The crystal packing consists principally of hydrogen-bonded trimers. Intermolecular hydrogen-bonding interactions are formed between the indazole N atoms, with the N-H group as a hydrogen-bond donor and the remaining N atom as an acceptor.
Supporting information
CCDC reference: 199444
The title compound was synthesized from 2-methoxy-6-methylaniline using the
method of Bartsh & Yang (1984). Crystals of (I) suitable for single-crystal
X-ray diffraction were obtained by slow evaporation of a solution in
cyclohexane at room temperature.
The result of the Flack test (Flack, 1983) is not significant, as the number of
Friedel pairs measured is low and thus not sufficient for a meaningful Flack
parameter. However, (I) does not contain any asymmetric centres, and the
knowledge of its absolute configuration does not reveal any new information on
its structure. H atoms were treated as riding, with C—H distances in the
range 0.93–0.96 Å and N—H distances of 0.86 Å. Is this added text OK?
Data collection: CAD-4-PC Software (Enraf-Nonius, 1996); cell refinement: CAD-4-PC Software; data reduction: JANA98 (Petříček & Dušek, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
7-methoxy-1
H-indazole
top
Crystal data top
C8H8N2O | F(000) = 1404 |
Mr = 148.16 | Dx = 1.278 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 25 reflections |
a = 14.1297 (5) Å | θ = 18–25° |
b = 16.0074 (7) Å | µ = 0.09 mm−1 |
c = 15.699 (1) Å | T = 293 K |
β = 102.533 (4)° | Prism, translucent dark yellow |
V = 3466.2 (3) Å3 | 0.5 × 0.4 × 0.3 mm |
Z = 18 | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.026 |
Radiation source: fine-focus sealed tube | θmax = 30.0°, θmin = 2.2° |
Graphite monochromator | h = −19→19 |
θ/2θ scans | k = 0→22 |
10744 measured reflections | l = 0→22 |
10405 independent reflections | 3 standard reflections every 60 min |
4332 reflections with I > 2σ(I) | intensity decay: 5.8% |
Refinement top
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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.128 | H-atom parameters constrained |
S = 0.98 | w = 1/[σ2(Fo2) + (0.0529P)2] where P = (Fo2 + 2Fc2)/3 |
10405 reflections | (Δ/σ)max = 0.001 |
901 parameters | Δρmax = 0.12 e Å−3 |
1 restraint | Δρmin = −0.10 e Å−3 |
Crystal data top
C8H8N2O | V = 3466.2 (3) Å3 |
Mr = 148.16 | Z = 18 |
Monoclinic, P21 | Mo Kα radiation |
a = 14.1297 (5) Å | µ = 0.09 mm−1 |
b = 16.0074 (7) Å | T = 293 K |
c = 15.699 (1) Å | 0.5 × 0.4 × 0.3 mm |
β = 102.533 (4)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.026 |
10744 measured reflections | 3 standard reflections every 60 min |
10405 independent reflections | intensity decay: 5.8% |
4332 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.053 | 1 restraint |
wR(F2) = 0.128 | H-atom parameters constrained |
S = 0.98 | Δρmax = 0.12 e Å−3 |
10405 reflections | Δρmin = −0.10 e Å−3 |
901 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1A | 0.2087 (2) | 0.3827 (2) | 0.8152 (2) | 0.0659 (10) | |
N2A | 0.2716 (2) | 0.4343 (2) | 0.8667 (2) | 0.0747 (9) | |
H2A | 0.3326 | 0.4366 | 0.8676 | 0.090* | |
N3A | 0.2263 (3) | 0.4823 (2) | 0.9168 (2) | 0.0808 (9) | |
C4A | 0.1345 (3) | 0.4597 (3) | 0.8969 (3) | 0.0869 (12) | |
H4A | 0.0864 | 0.4829 | 0.9216 | 0.104* | |
C5A | 0.1181 (3) | 0.3962 (2) | 0.8335 (2) | 0.0723 (10) | |
C6A | 0.0379 (3) | 0.3482 (3) | 0.7901 (3) | 0.0931 (13) | |
H6A | −0.0235 | 0.3559 | 0.8011 | 0.112* | |
C7A | 0.0544 (3) | 0.2901 (3) | 0.7314 (3) | 0.0939 (14) | |
H7A | 0.0028 | 0.2574 | 0.7027 | 0.113* | |
C8A | 0.1455 (3) | 0.2778 (2) | 0.7126 (3) | 0.0840 (12) | |
H8A | 0.1528 | 0.2379 | 0.6714 | 0.101* | |
C9A | 0.2242 (3) | 0.3233 (2) | 0.7536 (3) | 0.0712 (10) | |
O10A | 0.31709 (19) | 0.31719 (17) | 0.74411 (19) | 0.0853 (8) | |
C11A | 0.3365 (3) | 0.2588 (3) | 0.6814 (3) | 0.0939 (13) | |
H11A | 0.3272 | 0.2031 | 0.7006 | 0.141* | |
H12A | 0.4022 | 0.2653 | 0.6753 | 0.141* | |
H13A | 0.2931 | 0.2688 | 0.6262 | 0.141* | |
C1B | 0.6990 (2) | 0.1344 (2) | 0.8818 (2) | 0.0640 (9) | |
N2B | 0.66845 (19) | 0.08728 (19) | 0.94318 (19) | 0.0705 (8) | |
H2B | 0.7062 | 0.0615 | 0.9854 | 0.085* | |
N3B | 0.5701 (2) | 0.0867 (2) | 0.9283 (2) | 0.0744 (8) | |
C4B | 0.5398 (3) | 0.1327 (3) | 0.8583 (3) | 0.0745 (10) | |
H4B | 0.4748 | 0.1429 | 0.8337 | 0.089* | |
C5B | 0.6176 (3) | 0.1645 (2) | 0.8248 (2) | 0.0713 (10) | |
C6B | 0.6302 (4) | 0.2146 (3) | 0.7553 (3) | 0.0938 (13) | |
H6B | 0.5771 | 0.2362 | 0.7158 | 0.113* | |
C7B | 0.7214 (5) | 0.2305 (3) | 0.7471 (4) | 0.1104 (17) | |
H7B | 0.7301 | 0.2631 | 0.7003 | 0.133* | |
C8B | 0.8029 (4) | 0.2011 (3) | 0.8047 (4) | 0.1020 (15) | |
H8B | 0.8643 | 0.2150 | 0.7969 | 0.122* | |
C9B | 0.7931 (3) | 0.1512 (3) | 0.8736 (3) | 0.0828 (12) | |
O10B | 0.86536 (19) | 0.1177 (2) | 0.9360 (2) | 0.1086 (10) | |
C11B | 0.9628 (3) | 0.1340 (4) | 0.9307 (4) | 0.146 (2) | |
H11B | 0.9768 | 0.1055 | 0.8811 | 0.219* | |
H12B | 1.0059 | 0.1145 | 0.9829 | 0.219* | |
H13B | 0.9715 | 0.1930 | 0.9246 | 0.219* | |
C1C | 0.2245 (2) | 0.0522 (2) | 0.6196 (2) | 0.0596 (9) | |
N2C | 0.13110 (19) | 0.05753 (18) | 0.62580 (18) | 0.0664 (8) | |
H2C | 0.1078 | 0.0345 | 0.6663 | 0.080* | |
N3C | 0.0786 (2) | 0.1040 (2) | 0.5599 (2) | 0.0748 (8) | |
C4C | 0.1396 (3) | 0.1271 (3) | 0.5126 (2) | 0.0790 (11) | |
H4C | 0.1224 | 0.1597 | 0.4626 | 0.095* | |
C5C | 0.2344 (3) | 0.0970 (2) | 0.5459 (2) | 0.0689 (9) | |
C6C | 0.3254 (3) | 0.1025 (3) | 0.5246 (3) | 0.0897 (12) | |
H6C | 0.3336 | 0.1321 | 0.4757 | 0.108* | |
C7C | 0.4018 (3) | 0.0632 (3) | 0.5773 (4) | 0.0993 (14) | |
H7C | 0.4627 | 0.0660 | 0.5639 | 0.119* | |
C8C | 0.3908 (3) | 0.0191 (3) | 0.6508 (3) | 0.0882 (12) | |
H8C | 0.4446 | −0.0067 | 0.6855 | 0.106* | |
C9C | 0.3030 (2) | 0.0125 (2) | 0.6734 (3) | 0.0687 (9) | |
O10C | 0.28336 (17) | −0.02998 (17) | 0.74296 (18) | 0.0832 (8) | |
C11C | 0.3636 (3) | −0.0667 (3) | 0.8038 (3) | 0.1031 (14) | |
H11C | 0.3956 | −0.1065 | 0.7740 | 0.155* | |
H12C | 0.3401 | −0.0943 | 0.8494 | 0.155* | |
H13C | 0.4085 | −0.0237 | 0.8286 | 0.155* | |
C1D | 0.3744 (2) | 0.0019 (2) | 0.0494 (2) | 0.0584 (8) | |
N2D | 0.47078 (19) | 0.00718 (19) | 0.05081 (18) | 0.0670 (8) | |
H2D | 0.4954 | 0.0378 | 0.0161 | 0.080* | |
N3D | 0.5229 (2) | −0.0420 (2) | 0.1138 (2) | 0.0752 (9) | |
C4D | 0.4595 (3) | −0.0773 (3) | 0.1526 (3) | 0.0781 (11) | |
H4D | 0.4760 | −0.1140 | 0.1995 | 0.094* | |
C5D | 0.3639 (3) | −0.0532 (2) | 0.1150 (2) | 0.0656 (9) | |
C6D | 0.2699 (3) | −0.0701 (3) | 0.1274 (3) | 0.0841 (12) | |
H6D | 0.2602 | −0.1069 | 0.1706 | 0.101* | |
C7D | 0.1945 (3) | −0.0314 (3) | 0.0749 (3) | 0.0924 (13) | |
H7D | 0.1322 | −0.0422 | 0.0826 | 0.111* | |
C8D | 0.2061 (3) | 0.0240 (3) | 0.0094 (3) | 0.0840 (12) | |
H8D | 0.1519 | 0.0489 | −0.0256 | 0.101* | |
C9D | 0.2956 (2) | 0.0421 (3) | −0.0039 (2) | 0.0695 (10) | |
O10D | 0.31827 (18) | 0.09507 (19) | −0.06448 (18) | 0.0938 (8) | |
C11D | 0.2405 (3) | 0.1399 (4) | −0.1187 (3) | 0.1230 (18) | |
H11D | 0.1988 | 0.1014 | −0.1561 | 0.184* | |
H12D | 0.2663 | 0.1795 | −0.1536 | 0.184* | |
H13D | 0.2041 | 0.1688 | −0.0828 | 0.184* | |
C1E | 0.0900 (2) | 0.4343 (2) | 0.1973 (2) | 0.0625 (9) | |
N2E | 0.0620 (2) | 0.4817 (2) | 0.25877 (19) | 0.0727 (8) | |
H2E | 0.1010 | 0.5094 | 0.2985 | 0.087* | |
N3E | −0.0352 (2) | 0.4797 (2) | 0.2496 (2) | 0.0755 (9) | |
C4E | −0.0689 (3) | 0.4316 (3) | 0.1828 (3) | 0.0739 (10) | |
H4E | −0.1343 | 0.4196 | 0.1622 | 0.089* | |
C5E | 0.0062 (3) | 0.4002 (2) | 0.1457 (2) | 0.0653 (9) | |
C6E | 0.0131 (3) | 0.3483 (3) | 0.0745 (2) | 0.0796 (11) | |
H6E | −0.0416 | 0.3243 | 0.0393 | 0.096* | |
C7E | 0.1029 (3) | 0.3350 (3) | 0.0597 (3) | 0.0889 (12) | |
H7E | 0.1090 | 0.3016 | 0.0128 | 0.107* | |
C8E | 0.1867 (3) | 0.3692 (3) | 0.1117 (3) | 0.0841 (12) | |
H8E | 0.2467 | 0.3577 | 0.0991 | 0.101* | |
C9E | 0.1814 (3) | 0.4195 (3) | 0.1813 (3) | 0.0737 (11) | |
O10E | 0.25551 (19) | 0.45844 (18) | 0.2381 (2) | 0.0953 (9) | |
C11E | 0.3526 (3) | 0.4398 (4) | 0.2296 (4) | 0.128 (2) | |
H11E | 0.3662 | 0.3818 | 0.2423 | 0.191* | |
H12E | 0.3977 | 0.4735 | 0.2698 | 0.191* | |
H13E | 0.3587 | 0.4516 | 0.1711 | 0.191* | |
C1F | 0.8030 (3) | 0.1801 (2) | 0.4961 (2) | 0.0678 (10) | |
N2F | 0.8733 (2) | 0.1344 (2) | 0.5507 (2) | 0.0753 (8) | |
H2F | 0.9341 | 0.1361 | 0.5506 | 0.090* | |
N3F | 0.8333 (3) | 0.0865 (2) | 0.6044 (2) | 0.0841 (9) | |
C4F | 0.7403 (3) | 0.1017 (3) | 0.5852 (3) | 0.0863 (12) | |
H4F | 0.6959 | 0.0760 | 0.6126 | 0.104* | |
C5F | 0.7150 (3) | 0.1617 (3) | 0.5180 (3) | 0.0777 (11) | |
C6F | 0.6303 (3) | 0.2019 (3) | 0.4721 (3) | 0.0949 (14) | |
H6F | 0.5702 | 0.1911 | 0.4848 | 0.114* | |
C7F | 0.6400 (3) | 0.2564 (3) | 0.4092 (3) | 0.1009 (15) | |
H7F | 0.5847 | 0.2832 | 0.3784 | 0.121* | |
C8F | 0.7290 (3) | 0.2748 (3) | 0.3877 (3) | 0.0875 (13) | |
H8F | 0.7314 | 0.3135 | 0.3440 | 0.105* | |
C9F | 0.8121 (3) | 0.2363 (2) | 0.4303 (3) | 0.0747 (11) | |
O10F | 0.9036 (2) | 0.24647 (19) | 0.41661 (19) | 0.0951 (9) | |
C11F | 0.9155 (3) | 0.3015 (4) | 0.3490 (3) | 0.1221 (18) | |
H11F | 0.8743 | 0.2841 | 0.2950 | 0.183* | |
H12F | 0.9818 | 0.3006 | 0.3436 | 0.183* | |
H13F | 0.8983 | 0.3572 | 0.3627 | 0.183* | |
C1G | 0.3367 (3) | 0.4235 (2) | 0.5427 (2) | 0.0644 (9) | |
N2G | 0.3922 (2) | 0.4718 (2) | 0.6043 (2) | 0.0755 (9) | |
H2G | 0.3700 | 0.5049 | 0.6385 | 0.091* | |
N3G | 0.4876 (2) | 0.4614 (2) | 0.6050 (2) | 0.0845 (9) | |
C4G | 0.4915 (3) | 0.4068 (3) | 0.5437 (3) | 0.0838 (12) | |
H4G | 0.5488 | 0.3884 | 0.5300 | 0.101* | |
C5G | 0.3982 (3) | 0.3793 (2) | 0.5009 (2) | 0.0706 (10) | |
C6G | 0.3588 (4) | 0.3235 (3) | 0.4345 (3) | 0.0904 (12) | |
H6G | 0.3985 | 0.2931 | 0.4057 | 0.109* | |
C7G | 0.2620 (4) | 0.3148 (3) | 0.4131 (3) | 0.1090 (16) | |
H7G | 0.2353 | 0.2783 | 0.3682 | 0.131* | |
C8G | 0.1997 (3) | 0.3583 (3) | 0.4554 (3) | 0.0997 (15) | |
H8G | 0.1331 | 0.3498 | 0.4385 | 0.120* | |
C9G | 0.2355 (3) | 0.4138 (3) | 0.5218 (3) | 0.0769 (11) | |
O10G | 0.18607 (19) | 0.4600 (2) | 0.5695 (2) | 0.0974 (9) | |
C11G | 0.0826 (3) | 0.4504 (4) | 0.5512 (4) | 0.136 (2) | |
H11G | 0.0564 | 0.4626 | 0.4908 | 0.204* | |
H12G | 0.0555 | 0.4880 | 0.5871 | 0.204* | |
H13G | 0.0667 | 0.3939 | 0.5635 | 0.204* | |
C1H | 0.3774 (3) | 0.6832 (2) | 0.8382 (2) | 0.0703 (10) | |
N2H | 0.4141 (2) | 0.6364 (2) | 0.7806 (2) | 0.0753 (8) | |
H2H | 0.4743 | 0.6355 | 0.7779 | 0.090* | |
N3H | 0.3435 (3) | 0.5915 (2) | 0.7278 (2) | 0.0794 (9) | |
C4H | 0.2627 (3) | 0.6105 (3) | 0.7530 (3) | 0.0818 (11) | |
H4H | 0.2023 | 0.5884 | 0.7276 | 0.098* | |
C5H | 0.2784 (3) | 0.6677 (3) | 0.8223 (2) | 0.0735 (10) | |
C6H | 0.2226 (3) | 0.7085 (3) | 0.8739 (3) | 0.0934 (14) | |
H6H | 0.1560 | 0.7002 | 0.8643 | 0.112* | |
C7H | 0.2687 (4) | 0.7603 (3) | 0.9381 (3) | 0.0951 (14) | |
H7H | 0.2327 | 0.7876 | 0.9727 | 0.114* | |
C8H | 0.3691 (4) | 0.7740 (3) | 0.9538 (3) | 0.0866 (12) | |
H8H | 0.3978 | 0.8097 | 0.9987 | 0.104* | |
C9H | 0.4255 (3) | 0.7364 (2) | 0.9051 (3) | 0.0749 (10) | |
O10H | 0.5226 (2) | 0.74407 (19) | 0.91276 (19) | 0.0964 (9) | |
C11H | 0.5735 (4) | 0.7918 (4) | 0.9847 (3) | 0.1197 (17) | |
H11H | 0.5526 | 0.8489 | 0.9780 | 0.180* | |
H12H | 0.6418 | 0.7888 | 0.9869 | 0.180* | |
H13H | 0.5604 | 0.7698 | 1.0379 | 0.180* | |
C1I | 0.2637 (2) | 0.0685 (2) | 0.2889 (2) | 0.0626 (9) | |
N2I | 0.3612 (2) | 0.06746 (19) | 0.29795 (18) | 0.0695 (8) | |
H2I | 0.3991 | 0.0314 | 0.3286 | 0.083* | |
N3I | 0.3916 (2) | 0.1302 (2) | 0.2527 (2) | 0.0836 (9) | |
C4I | 0.3121 (3) | 0.1707 (3) | 0.2157 (3) | 0.0869 (12) | |
H4I | 0.3115 | 0.2171 | 0.1799 | 0.104* | |
C5I | 0.2283 (3) | 0.1361 (3) | 0.2361 (2) | 0.0751 (10) | |
C6I | 0.1287 (3) | 0.1522 (3) | 0.2155 (3) | 0.0955 (13) | |
H6I | 0.1033 | 0.1975 | 0.1809 | 0.115* | |
C7I | 0.0709 (3) | 0.0993 (4) | 0.2481 (3) | 0.1013 (14) | |
H7I | 0.0044 | 0.1089 | 0.2348 | 0.122* | |
C8I | 0.1064 (3) | 0.0308 (3) | 0.3007 (3) | 0.0846 (12) | |
H8I | 0.0634 | −0.0035 | 0.3216 | 0.101* | |
C9I | 0.2027 (3) | 0.0139 (2) | 0.3217 (2) | 0.0685 (9) | |
O10I | 0.24879 (18) | −0.05057 (17) | 0.37102 (17) | 0.0869 (8) | |
C11I | 0.1925 (3) | −0.1009 (3) | 0.4157 (3) | 0.1010 (14) | |
H11I | 0.1636 | −0.0664 | 0.4531 | 0.151* | |
H12I | 0.2333 | −0.1419 | 0.4501 | 0.151* | |
H13I | 0.1424 | −0.1285 | 0.3740 | 0.151* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1A | 0.061 (2) | 0.052 (2) | 0.073 (2) | −0.0132 (18) | −0.0093 (19) | 0.017 (2) |
N2A | 0.0588 (18) | 0.068 (2) | 0.089 (2) | −0.0086 (17) | −0.0024 (17) | 0.0021 (19) |
N3A | 0.086 (2) | 0.069 (2) | 0.084 (2) | −0.0134 (18) | 0.0124 (18) | −0.0064 (19) |
C4A | 0.075 (3) | 0.090 (3) | 0.094 (3) | −0.012 (2) | 0.015 (2) | 0.006 (3) |
C5A | 0.067 (2) | 0.070 (3) | 0.073 (2) | −0.017 (2) | −0.0001 (19) | 0.012 (2) |
C6A | 0.064 (3) | 0.101 (3) | 0.106 (3) | −0.023 (2) | 0.002 (2) | 0.008 (3) |
C7A | 0.079 (3) | 0.084 (3) | 0.105 (4) | −0.027 (3) | −0.012 (3) | 0.005 (3) |
C8A | 0.093 (3) | 0.062 (3) | 0.083 (3) | −0.012 (2) | −0.014 (2) | 0.003 (2) |
C9A | 0.070 (3) | 0.052 (2) | 0.079 (3) | −0.0040 (19) | −0.011 (2) | 0.013 (2) |
O10A | 0.0752 (18) | 0.0684 (18) | 0.105 (2) | −0.0020 (14) | 0.0032 (15) | −0.0129 (16) |
C11A | 0.108 (3) | 0.078 (3) | 0.093 (3) | 0.005 (3) | 0.016 (3) | −0.002 (3) |
C1B | 0.062 (2) | 0.060 (2) | 0.073 (2) | −0.0045 (19) | 0.0218 (19) | −0.008 (2) |
N2B | 0.0545 (18) | 0.073 (2) | 0.080 (2) | 0.0023 (15) | 0.0055 (14) | 0.0054 (18) |
N3B | 0.0608 (19) | 0.082 (2) | 0.080 (2) | −0.0014 (16) | 0.0139 (15) | 0.0049 (19) |
C4B | 0.063 (2) | 0.078 (3) | 0.079 (3) | 0.004 (2) | 0.007 (2) | 0.003 (2) |
C5B | 0.078 (3) | 0.065 (2) | 0.072 (2) | −0.003 (2) | 0.019 (2) | −0.002 (2) |
C6B | 0.128 (4) | 0.075 (3) | 0.082 (3) | 0.007 (3) | 0.030 (3) | 0.007 (3) |
C7B | 0.153 (5) | 0.091 (4) | 0.107 (4) | −0.017 (4) | 0.071 (4) | −0.005 (3) |
C8B | 0.106 (4) | 0.088 (3) | 0.130 (4) | −0.029 (3) | 0.065 (4) | −0.031 (3) |
C9B | 0.069 (3) | 0.077 (3) | 0.107 (3) | −0.009 (2) | 0.030 (2) | −0.022 (3) |
O10B | 0.0592 (17) | 0.117 (3) | 0.151 (3) | 0.0003 (17) | 0.0238 (17) | −0.021 (2) |
C11B | 0.062 (3) | 0.158 (5) | 0.226 (6) | −0.014 (3) | 0.046 (3) | −0.068 (5) |
C1C | 0.059 (2) | 0.056 (2) | 0.063 (2) | −0.0102 (17) | 0.0107 (17) | −0.0046 (18) |
N2C | 0.0602 (18) | 0.0639 (18) | 0.0706 (19) | −0.0061 (15) | 0.0048 (15) | 0.0098 (16) |
N3C | 0.0687 (19) | 0.072 (2) | 0.077 (2) | −0.0042 (17) | −0.0002 (17) | 0.0069 (18) |
C4C | 0.089 (3) | 0.076 (3) | 0.064 (2) | −0.012 (2) | 0.001 (2) | 0.006 (2) |
C5C | 0.076 (3) | 0.068 (2) | 0.063 (2) | −0.011 (2) | 0.0157 (19) | −0.005 (2) |
C6C | 0.101 (3) | 0.094 (3) | 0.082 (3) | −0.023 (3) | 0.037 (3) | −0.009 (3) |
C7C | 0.077 (3) | 0.107 (4) | 0.122 (4) | −0.007 (3) | 0.038 (3) | −0.007 (3) |
C8C | 0.066 (3) | 0.089 (3) | 0.108 (3) | 0.004 (2) | 0.014 (2) | 0.002 (3) |
C9C | 0.058 (2) | 0.063 (2) | 0.083 (3) | −0.0038 (18) | 0.012 (2) | 0.002 (2) |
O10C | 0.0694 (16) | 0.0814 (19) | 0.0928 (18) | 0.0025 (14) | 0.0042 (14) | 0.0222 (17) |
C11C | 0.093 (3) | 0.090 (3) | 0.111 (3) | 0.020 (3) | −0.012 (2) | 0.022 (3) |
C1D | 0.056 (2) | 0.060 (2) | 0.057 (2) | 0.0030 (17) | 0.0087 (16) | −0.0032 (19) |
N2D | 0.0623 (19) | 0.0666 (19) | 0.0687 (18) | 0.0027 (15) | 0.0065 (15) | 0.0106 (17) |
N3D | 0.071 (2) | 0.071 (2) | 0.077 (2) | 0.0084 (18) | 0.0010 (17) | 0.0079 (18) |
C4D | 0.094 (3) | 0.066 (2) | 0.069 (2) | 0.004 (2) | 0.007 (2) | 0.014 (2) |
C5D | 0.077 (3) | 0.059 (2) | 0.060 (2) | −0.0040 (19) | 0.0140 (18) | −0.001 (2) |
C6D | 0.093 (3) | 0.087 (3) | 0.079 (3) | −0.009 (3) | 0.034 (2) | 0.000 (2) |
C7D | 0.065 (3) | 0.119 (4) | 0.098 (3) | −0.003 (3) | 0.027 (2) | −0.007 (3) |
C8D | 0.061 (2) | 0.104 (3) | 0.084 (3) | 0.007 (2) | 0.011 (2) | −0.003 (3) |
C9D | 0.061 (2) | 0.078 (3) | 0.067 (2) | 0.001 (2) | 0.0079 (19) | 0.000 (2) |
O10D | 0.0797 (17) | 0.103 (2) | 0.0937 (19) | 0.0184 (16) | 0.0072 (15) | 0.0335 (19) |
C11D | 0.111 (4) | 0.119 (4) | 0.121 (4) | 0.028 (3) | −0.013 (3) | 0.043 (3) |
C1E | 0.061 (2) | 0.059 (2) | 0.068 (2) | 0.0045 (18) | 0.0154 (18) | 0.010 (2) |
N2E | 0.064 (2) | 0.075 (2) | 0.076 (2) | −0.0016 (16) | 0.0097 (15) | −0.0043 (18) |
N3E | 0.063 (2) | 0.082 (2) | 0.081 (2) | −0.0009 (17) | 0.0145 (16) | −0.011 (2) |
C4E | 0.057 (2) | 0.082 (3) | 0.080 (3) | −0.002 (2) | 0.010 (2) | −0.005 (2) |
C5E | 0.071 (2) | 0.065 (2) | 0.060 (2) | 0.0005 (19) | 0.0153 (19) | −0.0010 (19) |
C6E | 0.082 (3) | 0.082 (3) | 0.076 (3) | −0.001 (2) | 0.018 (2) | −0.003 (2) |
C7E | 0.105 (4) | 0.081 (3) | 0.086 (3) | 0.006 (3) | 0.030 (3) | −0.003 (2) |
C8E | 0.084 (3) | 0.078 (3) | 0.101 (3) | 0.021 (2) | 0.045 (3) | 0.018 (3) |
C9E | 0.061 (2) | 0.068 (3) | 0.093 (3) | 0.005 (2) | 0.018 (2) | 0.025 (2) |
O10E | 0.0626 (17) | 0.089 (2) | 0.133 (2) | −0.0035 (15) | 0.0184 (16) | 0.0163 (19) |
C11E | 0.057 (3) | 0.125 (4) | 0.200 (6) | 0.005 (3) | 0.027 (3) | 0.036 (4) |
C1F | 0.077 (3) | 0.055 (2) | 0.064 (2) | 0.0117 (19) | −0.001 (2) | −0.012 (2) |
N2F | 0.0712 (19) | 0.066 (2) | 0.082 (2) | 0.0118 (17) | 0.0015 (17) | −0.0001 (18) |
N3F | 0.083 (2) | 0.077 (2) | 0.088 (2) | 0.0151 (19) | 0.0100 (19) | 0.007 (2) |
C4F | 0.089 (3) | 0.083 (3) | 0.089 (3) | 0.013 (2) | 0.022 (2) | −0.007 (3) |
C5F | 0.080 (3) | 0.073 (3) | 0.077 (3) | 0.023 (2) | 0.009 (2) | −0.007 (2) |
C6F | 0.079 (3) | 0.107 (4) | 0.094 (3) | 0.035 (3) | 0.011 (2) | −0.003 (3) |
C7F | 0.091 (4) | 0.109 (4) | 0.094 (3) | 0.045 (3) | 0.002 (3) | −0.005 (3) |
C8F | 0.106 (3) | 0.073 (3) | 0.074 (3) | 0.023 (3) | −0.001 (2) | 0.000 (2) |
C9F | 0.084 (3) | 0.061 (2) | 0.072 (3) | 0.003 (2) | 0.001 (2) | −0.014 (2) |
O10F | 0.094 (2) | 0.093 (2) | 0.089 (2) | −0.0021 (17) | 0.0019 (16) | 0.0138 (18) |
C11F | 0.124 (4) | 0.126 (4) | 0.104 (3) | −0.035 (3) | −0.002 (3) | 0.027 (4) |
C1G | 0.062 (2) | 0.063 (2) | 0.066 (2) | −0.0048 (19) | 0.0095 (19) | 0.006 (2) |
N2G | 0.068 (2) | 0.079 (2) | 0.083 (2) | −0.0018 (17) | 0.0255 (16) | −0.0090 (19) |
N3G | 0.067 (2) | 0.092 (3) | 0.098 (2) | −0.0099 (18) | 0.0232 (17) | −0.021 (2) |
C4G | 0.073 (3) | 0.088 (3) | 0.098 (3) | −0.002 (2) | 0.034 (2) | −0.017 (3) |
C5G | 0.081 (3) | 0.060 (2) | 0.072 (2) | −0.008 (2) | 0.019 (2) | −0.002 (2) |
C6G | 0.108 (3) | 0.075 (3) | 0.086 (3) | 0.002 (3) | 0.015 (3) | −0.009 (2) |
C7G | 0.118 (4) | 0.086 (3) | 0.108 (4) | −0.006 (3) | −0.007 (3) | −0.011 (3) |
C8G | 0.072 (3) | 0.083 (3) | 0.125 (4) | −0.011 (3) | −0.019 (3) | 0.014 (3) |
C9G | 0.063 (2) | 0.072 (3) | 0.094 (3) | 0.002 (2) | 0.015 (2) | 0.023 (2) |
O10G | 0.0695 (18) | 0.105 (2) | 0.122 (2) | 0.0181 (16) | 0.0298 (16) | 0.023 (2) |
C11G | 0.062 (3) | 0.154 (5) | 0.196 (6) | 0.020 (3) | 0.038 (3) | 0.065 (5) |
C1H | 0.093 (3) | 0.060 (2) | 0.065 (2) | 0.022 (2) | 0.032 (2) | 0.008 (2) |
N2H | 0.084 (2) | 0.071 (2) | 0.0754 (19) | 0.0166 (18) | 0.0261 (17) | 0.0036 (18) |
N3H | 0.092 (2) | 0.075 (2) | 0.075 (2) | 0.011 (2) | 0.0256 (19) | 0.0019 (18) |
C4H | 0.083 (3) | 0.084 (3) | 0.081 (3) | 0.008 (2) | 0.023 (2) | 0.011 (3) |
C5H | 0.089 (3) | 0.070 (3) | 0.066 (2) | 0.019 (2) | 0.026 (2) | 0.012 (2) |
C6H | 0.096 (3) | 0.106 (4) | 0.087 (3) | 0.031 (3) | 0.039 (3) | 0.019 (3) |
C7H | 0.124 (4) | 0.094 (3) | 0.078 (3) | 0.039 (3) | 0.045 (3) | 0.011 (3) |
C8H | 0.124 (4) | 0.067 (3) | 0.074 (3) | 0.023 (3) | 0.034 (3) | 0.006 (2) |
C9H | 0.097 (3) | 0.064 (2) | 0.069 (3) | 0.016 (2) | 0.028 (2) | 0.007 (2) |
O10H | 0.101 (2) | 0.097 (2) | 0.097 (2) | −0.0003 (18) | 0.0344 (18) | −0.0164 (18) |
C11H | 0.129 (4) | 0.124 (4) | 0.108 (4) | −0.019 (4) | 0.029 (3) | −0.021 (4) |
C1I | 0.056 (2) | 0.066 (2) | 0.063 (2) | 0.0024 (18) | 0.0064 (17) | −0.0033 (19) |
N2I | 0.069 (2) | 0.066 (2) | 0.0726 (19) | 0.0042 (16) | 0.0141 (15) | 0.0128 (16) |
N3I | 0.081 (2) | 0.076 (2) | 0.095 (2) | −0.002 (2) | 0.0219 (18) | 0.017 (2) |
C4I | 0.097 (3) | 0.073 (3) | 0.093 (3) | −0.002 (3) | 0.024 (2) | 0.021 (2) |
C5I | 0.080 (3) | 0.067 (2) | 0.076 (2) | 0.006 (2) | 0.011 (2) | 0.008 (2) |
C6I | 0.084 (3) | 0.088 (3) | 0.108 (3) | 0.013 (3) | 0.007 (2) | 0.020 (3) |
C7I | 0.065 (3) | 0.116 (4) | 0.117 (4) | 0.019 (3) | 0.006 (2) | 0.009 (3) |
C8I | 0.070 (3) | 0.093 (3) | 0.091 (3) | −0.003 (2) | 0.017 (2) | 0.002 (3) |
C9I | 0.069 (2) | 0.068 (2) | 0.068 (2) | 0.003 (2) | 0.0135 (18) | 0.002 (2) |
O10I | 0.0880 (17) | 0.0794 (19) | 0.0952 (19) | 0.0033 (15) | 0.0238 (15) | 0.0269 (17) |
C11I | 0.120 (3) | 0.086 (3) | 0.103 (3) | −0.016 (3) | 0.036 (3) | 0.022 (3) |
Geometric parameters (Å, º) top
C1A—N2A | 1.347 (4) | C6E—H6E | 0.9300 |
C1A—C5A | 1.389 (5) | C7E—C8E | 1.395 (6) |
C1A—C9A | 1.407 (5) | C7E—H7E | 0.9300 |
N2A—N3A | 1.356 (4) | C8E—C9E | 1.372 (6) |
N2A—H2A | 0.8600 | C8E—H8E | 0.9300 |
N3A—C4A | 1.317 (5) | C9E—O10E | 1.369 (5) |
C4A—C5A | 1.406 (5) | O10E—C11E | 1.438 (5) |
C4A—H4A | 0.9300 | C11E—H11E | 0.9600 |
C5A—C6A | 1.415 (5) | C11E—H12E | 0.9600 |
C6A—C7A | 1.365 (6) | C11E—H13E | 0.9600 |
C6A—H6A | 0.9300 | C1F—N2F | 1.373 (4) |
C7A—C8A | 1.396 (6) | C1F—C5F | 1.390 (5) |
C7A—H7A | 0.9300 | C1F—C9F | 1.397 (5) |
C8A—C9A | 1.368 (5) | N2F—N3F | 1.351 (4) |
C8A—H8A | 0.9300 | N2F—H2F | 0.8600 |
C9A—O10A | 1.357 (4) | N3F—C4F | 1.305 (5) |
O10A—C11A | 1.426 (5) | C4F—C5F | 1.414 (6) |
C11A—H11A | 0.9600 | C4F—H4F | 0.9300 |
C11A—H12A | 0.9600 | C5F—C6F | 1.411 (5) |
C11A—H13A | 0.9600 | C6F—C7F | 1.347 (6) |
C1B—N2B | 1.366 (4) | C6F—H6F | 0.9300 |
C1B—C5B | 1.382 (5) | C7F—C8F | 1.402 (6) |
C1B—C9B | 1.389 (5) | C7F—H7F | 0.9300 |
N2B—N3B | 1.359 (4) | C8F—C9F | 1.365 (5) |
N2B—H2B | 0.8600 | C8F—H8F | 0.9300 |
N3B—C4B | 1.314 (4) | C9F—O10F | 1.366 (5) |
C4B—C5B | 1.412 (5) | O10F—C11F | 1.417 (5) |
C4B—H4B | 0.9300 | C11F—H11F | 0.9600 |
C5B—C6B | 1.396 (5) | C11F—H12F | 0.9600 |
C6B—C7B | 1.348 (6) | C11F—H13F | 0.9600 |
C6B—H6B | 0.9300 | C1G—N2G | 1.349 (4) |
C7B—C8B | 1.383 (7) | C1G—C5G | 1.391 (5) |
C7B—H7B | 0.9300 | C1G—C9G | 1.405 (5) |
C8B—C9B | 1.375 (6) | N2G—N3G | 1.357 (4) |
C8B—H8B | 0.9300 | N2G—H2G | 0.8600 |
C9B—O10B | 1.362 (5) | N3G—C4G | 1.309 (5) |
O10B—C11B | 1.421 (5) | C4G—C5G | 1.413 (5) |
C11B—H11B | 0.9600 | C4G—H4G | 0.9300 |
C11B—H12B | 0.9600 | C5G—C6G | 1.393 (5) |
C11B—H13B | 0.9600 | C6G—C7G | 1.342 (6) |
C1C—N2C | 1.347 (4) | C6G—H6G | 0.9300 |
C1C—C9C | 1.393 (5) | C7G—C8G | 1.399 (7) |
C1C—C5C | 1.395 (5) | C7G—H7G | 0.9300 |
N2C—N3C | 1.356 (4) | C8G—C9G | 1.379 (6) |
N2C—H2C | 0.8600 | C8G—H8G | 0.9300 |
N3C—C4C | 1.307 (4) | C9G—O10G | 1.350 (5) |
C4C—C5C | 1.413 (5) | O10G—C11G | 1.436 (5) |
C4C—H4C | 0.9300 | C11G—H11G | 0.9600 |
C5C—C6C | 1.400 (5) | C11G—H12G | 0.9600 |
C6C—C7C | 1.363 (6) | C11G—H13G | 0.9600 |
C6C—H6C | 0.9300 | C1H—N2H | 1.362 (4) |
C7C—C8C | 1.390 (6) | C1H—C5H | 1.388 (5) |
C7C—H7C | 0.9300 | C1H—C9H | 1.407 (5) |
C8C—C9C | 1.366 (5) | N2H—N3H | 1.357 (4) |
C8C—H8C | 0.9300 | N2H—H2H | 0.8600 |
C9C—O10C | 1.366 (4) | N3H—C4H | 1.322 (4) |
O10C—C11C | 1.439 (4) | C4H—C5H | 1.403 (5) |
C11C—H11C | 0.9600 | C4H—H4H | 0.9300 |
C11C—H12C | 0.9600 | C5H—C6H | 1.408 (5) |
C11C—H13C | 0.9600 | C6H—C7H | 1.357 (6) |
C1D—N2D | 1.360 (4) | C6H—H6H | 0.9300 |
C1D—C5D | 1.389 (5) | C7H—C8H | 1.403 (6) |
C1D—C9D | 1.396 (5) | C7H—H7H | 0.9300 |
N2D—N3D | 1.351 (4) | C8H—C9H | 1.358 (5) |
N2D—H2D | 0.8600 | C8H—H8H | 0.9300 |
N3D—C4D | 1.315 (5) | C9H—O10H | 1.356 (5) |
C4D—C5D | 1.406 (5) | O10H—C11H | 1.423 (5) |
C4D—H4D | 0.9300 | C11H—H11H | 0.9600 |
C5D—C6D | 1.409 (5) | C11H—H12H | 0.9600 |
C6D—C7D | 1.349 (6) | C11H—H13H | 0.9600 |
C6D—H6D | 0.9300 | C1I—N2I | 1.354 (4) |
C7D—C8D | 1.395 (6) | C1I—C5I | 1.388 (5) |
C7D—H7D | 0.9300 | C1I—C9I | 1.402 (5) |
C8D—C9D | 1.357 (5) | N2I—N3I | 1.352 (4) |
C8D—H8D | 0.9300 | N2I—H2I | 0.8600 |
C9D—O10D | 1.363 (4) | N3I—C4I | 1.318 (5) |
O10D—C11D | 1.429 (5) | C4I—C5I | 1.405 (5) |
C11D—H11D | 0.9600 | C4I—H4I | 0.9300 |
C11D—H12D | 0.9600 | C5I—C6I | 1.399 (5) |
C11D—H13D | 0.9600 | C6I—C7I | 1.351 (6) |
C1E—N2E | 1.352 (4) | C6I—H6I | 0.9300 |
C1E—C9E | 1.389 (5) | C7I—C8I | 1.399 (6) |
C1E—C5E | 1.393 (5) | C7I—H7I | 0.9300 |
N2E—N3E | 1.350 (4) | C8I—C9I | 1.356 (5) |
N2E—H2E | 0.8600 | C8I—H8I | 0.9300 |
N3E—C4E | 1.306 (5) | C9I—O10I | 1.367 (4) |
C4E—C5E | 1.409 (5) | O10I—C11I | 1.420 (5) |
C4E—H4E | 0.9300 | C11I—H11I | 0.9600 |
C5E—C6E | 1.413 (5) | C11I—H12I | 0.9600 |
C6E—C7E | 1.356 (5) | C11I—H13I | 0.9600 |
| | | |
N2A—C1A—C5A | 107.3 (4) | C6E—C7E—C8E | 123.1 (4) |
N2A—C1A—C9A | 130.3 (3) | C6E—C7E—H7E | 118.5 |
C5A—C1A—C9A | 122.4 (3) | C8E—C7E—H7E | 118.5 |
C1A—N2A—N3A | 111.3 (3) | C9E—C8E—C7E | 120.7 (4) |
C1A—N2A—H2A | 124.4 | C9E—C8E—H8E | 119.7 |
N3A—N2A—H2A | 124.4 | C7E—C8E—H8E | 119.7 |
C4A—N3A—N2A | 105.7 (3) | O10E—C9E—C8E | 128.3 (4) |
N3A—C4A—C5A | 111.7 (4) | O10E—C9E—C1E | 114.5 (4) |
N3A—C4A—H4A | 124.2 | C8E—C9E—C1E | 117.2 (4) |
C5A—C4A—H4A | 124.2 | C9E—O10E—C11E | 117.1 (4) |
C1A—C5A—C4A | 104.0 (3) | O10E—C11E—H11E | 109.5 |
C1A—C5A—C6A | 119.5 (4) | O10E—C11E—H12E | 109.5 |
C4A—C5A—C6A | 136.5 (4) | H11E—C11E—H12E | 109.5 |
C7A—C6A—C5A | 117.4 (4) | O10E—C11E—H13E | 109.5 |
C7A—C6A—H6A | 121.3 | H11E—C11E—H13E | 109.5 |
C5A—C6A—H6A | 121.3 | H12E—C11E—H13E | 109.5 |
C6A—C7A—C8A | 122.6 (4) | N2F—C1F—C5F | 107.3 (4) |
C6A—C7A—H7A | 118.7 | N2F—C1F—C9F | 129.3 (4) |
C8A—C7A—H7A | 118.7 | C5F—C1F—C9F | 123.4 (4) |
C9A—C8A—C7A | 121.2 (4) | N3F—N2F—C1F | 110.3 (3) |
C9A—C8A—H8A | 119.4 | N3F—N2F—H2F | 124.8 |
C7A—C8A—H8A | 119.4 | C1F—N2F—H2F | 124.8 |
O10A—C9A—C8A | 128.1 (4) | C4F—N3F—N2F | 106.7 (3) |
O10A—C9A—C1A | 115.0 (3) | N3F—C4F—C5F | 112.2 (4) |
C8A—C9A—C1A | 116.9 (4) | N3F—C4F—H4F | 123.9 |
C9A—O10A—C11A | 117.3 (3) | C5F—C4F—H4F | 123.9 |
O10A—C11A—H11A | 109.5 | C1F—C5F—C6F | 118.8 (4) |
O10A—C11A—H12A | 109.5 | C1F—C5F—C4F | 103.5 (3) |
H11A—C11A—H12A | 109.5 | C6F—C5F—C4F | 137.7 (5) |
O10A—C11A—H13A | 109.5 | C7F—C6F—C5F | 117.4 (4) |
H11A—C11A—H13A | 109.5 | C7F—C6F—H6F | 121.3 |
H12A—C11A—H13A | 109.5 | C5F—C6F—H6F | 121.3 |
N2B—C1B—C5B | 107.6 (3) | C6F—C7F—C8F | 123.5 (4) |
N2B—C1B—C9B | 128.9 (4) | C6F—C7F—H7F | 118.3 |
C5B—C1B—C9B | 123.5 (4) | C8F—C7F—H7F | 118.3 |
N3B—N2B—C1B | 110.5 (3) | C9F—C8F—C7F | 120.6 (4) |
N3B—N2B—H2B | 124.7 | C9F—C8F—H8F | 119.7 |
C1B—N2B—H2B | 124.7 | C7F—C8F—H8F | 119.7 |
C4B—N3B—N2B | 106.0 (3) | C8F—C9F—O10F | 127.7 (4) |
N3B—C4B—C5B | 112.0 (3) | C8F—C9F—C1F | 116.4 (4) |
N3B—C4B—H4B | 124.0 | O10F—C9F—C1F | 115.8 (3) |
C5B—C4B—H4B | 124.0 | C9F—O10F—C11F | 117.5 (3) |
C1B—C5B—C6B | 118.5 (4) | O10F—C11F—H11F | 109.5 |
C1B—C5B—C4B | 103.8 (3) | O10F—C11F—H12F | 109.5 |
C6B—C5B—C4B | 137.7 (4) | H11F—C11F—H12F | 109.5 |
C7B—C6B—C5B | 118.1 (5) | O10F—C11F—H13F | 109.5 |
C7B—C6B—H6B | 121.0 | H11F—C11F—H13F | 109.5 |
C5B—C6B—H6B | 121.0 | H12F—C11F—H13F | 109.5 |
C6B—C7B—C8B | 123.4 (5) | N2G—C1G—C5G | 107.8 (3) |
C6B—C7B—H7B | 118.3 | N2G—C1G—C9G | 129.3 (4) |
C8B—C7B—H7B | 118.3 | C5G—C1G—C9G | 122.9 (4) |
C9B—C8B—C7B | 120.1 (4) | C1G—N2G—N3G | 110.9 (3) |
C9B—C8B—H8B | 120.0 | C1G—N2G—H2G | 124.6 |
C7B—C8B—H8B | 120.0 | N3G—N2G—H2G | 124.6 |
O10B—C9B—C8B | 127.3 (4) | C4G—N3G—N2G | 106.0 (3) |
O10B—C9B—C1B | 116.1 (4) | N3G—C4G—C5G | 112.0 (3) |
C8B—C9B—C1B | 116.5 (4) | N3G—C4G—H4G | 124.0 |
C9B—O10B—C11B | 118.1 (4) | C5G—C4G—H4G | 124.0 |
O10B—C11B—H11B | 109.5 | C1G—C5G—C6G | 119.3 (4) |
O10B—C11B—H12B | 109.5 | C1G—C5G—C4G | 103.3 (3) |
H11B—C11B—H12B | 109.5 | C6G—C5G—C4G | 137.4 (4) |
O10B—C11B—H13B | 109.5 | C7G—C6G—C5G | 118.3 (4) |
H11B—C11B—H13B | 109.5 | C7G—C6G—H6G | 120.9 |
H12B—C11B—H13B | 109.5 | C5G—C6G—H6G | 120.9 |
N2C—C1C—C9C | 130.5 (3) | C6G—C7G—C8G | 122.8 (5) |
N2C—C1C—C5C | 107.7 (3) | C6G—C7G—H7G | 118.6 |
C9C—C1C—C5C | 121.8 (3) | C8G—C7G—H7G | 118.6 |
C1C—N2C—N3C | 111.2 (3) | C9G—C8G—C7G | 120.9 (4) |
C1C—N2C—H2C | 124.4 | C9G—C8G—H8G | 119.5 |
N3C—N2C—H2C | 124.4 | C7G—C8G—H8G | 119.5 |
C4C—N3C—N2C | 105.6 (3) | O10G—C9G—C8G | 128.5 (4) |
N3C—C4C—C5C | 112.5 (3) | O10G—C9G—C1G | 115.7 (4) |
N3C—C4C—H4C | 123.7 | C8G—C9G—C1G | 115.8 (4) |
C5C—C4C—H4C | 123.7 | C9G—O10G—C11G | 117.2 (4) |
C1C—C5C—C6C | 119.6 (4) | O10G—C11G—H11G | 109.5 |
C1C—C5C—C4C | 103.0 (3) | O10G—C11G—H12G | 109.5 |
C6C—C5C—C4C | 137.5 (4) | H11G—C11G—H12G | 109.5 |
C7C—C6C—C5C | 118.2 (4) | O10G—C11G—H13G | 109.5 |
C7C—C6C—H6C | 120.9 | H11G—C11G—H13G | 109.5 |
C5C—C6C—H6C | 120.9 | H12G—C11G—H13G | 109.5 |
C6C—C7C—C8C | 121.5 (4) | N2H—C1H—C5H | 107.2 (4) |
C6C—C7C—H7C | 119.2 | N2H—C1H—C9H | 129.5 (4) |
C8C—C7C—H7C | 119.2 | C5H—C1H—C9H | 123.2 (3) |
C9C—C8C—C7C | 121.7 (4) | N3H—N2H—C1H | 111.2 (3) |
C9C—C8C—H8C | 119.1 | N3H—N2H—H2H | 124.4 |
C7C—C8C—H8C | 119.1 | C1H—N2H—H2H | 124.4 |
C8C—C9C—O10C | 126.8 (4) | C4H—N3H—N2H | 105.2 (3) |
C8C—C9C—C1C | 117.2 (4) | N3H—C4H—C5H | 112.4 (4) |
O10C—C9C—C1C | 116.0 (3) | N3H—C4H—H4H | 123.8 |
C9C—O10C—C11C | 117.8 (3) | C5H—C4H—H4H | 123.8 |
O10C—C11C—H11C | 109.5 | C1H—C5H—C4H | 103.9 (3) |
O10C—C11C—H12C | 109.5 | C1H—C5H—C6H | 118.8 (4) |
H11C—C11C—H12C | 109.5 | C4H—C5H—C6H | 137.4 (4) |
O10C—C11C—H13C | 109.5 | C7H—C6H—C5H | 118.2 (4) |
H11C—C11C—H13C | 109.5 | C7H—C6H—H6H | 120.9 |
H12C—C11C—H13C | 109.5 | C5H—C6H—H6H | 120.9 |
N2D—C1D—C5D | 107.2 (3) | C6H—C7H—C8H | 122.0 (4) |
N2D—C1D—C9D | 130.3 (3) | C6H—C7H—H7H | 119.0 |
C5D—C1D—C9D | 122.5 (3) | C8H—C7H—H7H | 119.0 |
N3D—N2D—C1D | 111.1 (3) | C9H—C8H—C7H | 121.8 (4) |
N3D—N2D—H2D | 124.4 | C9H—C8H—H8H | 119.1 |
C1D—N2D—H2D | 124.4 | C7H—C8H—H8H | 119.1 |
C4D—N3D—N2D | 105.8 (3) | O10H—C9H—C8H | 128.0 (4) |
N3D—C4D—C5D | 112.1 (3) | O10H—C9H—C1H | 115.9 (3) |
N3D—C4D—H4D | 123.9 | C8H—C9H—C1H | 116.1 (4) |
C5D—C4D—H4D | 123.9 | C9H—O10H—C11H | 116.5 (3) |
C1D—C5D—C4D | 103.8 (3) | O10H—C11H—H11H | 109.5 |
C1D—C5D—C6D | 118.7 (3) | O10H—C11H—H12H | 109.5 |
C4D—C5D—C6D | 137.5 (4) | H11H—C11H—H12H | 109.5 |
C7D—C6D—C5D | 118.1 (4) | O10H—C11H—H13H | 109.5 |
C7D—C6D—H6D | 121.0 | H11H—C11H—H13H | 109.5 |
C5D—C6D—H6D | 121.0 | H12H—C11H—H13H | 109.5 |
C6D—C7D—C8D | 122.6 (4) | N2I—C1I—C5I | 107.4 (3) |
C6D—C7D—H7D | 118.7 | N2I—C1I—C9I | 130.3 (3) |
C8D—C7D—H7D | 118.7 | C5I—C1I—C9I | 122.3 (3) |
C9D—C8D—C7D | 120.9 (4) | N3I—N2I—C1I | 111.5 (3) |
C9D—C8D—H8D | 119.6 | N3I—N2I—H2I | 124.2 |
C7D—C8D—H8D | 119.6 | C1I—N2I—H2I | 124.2 |
C8D—C9D—O10D | 127.5 (4) | C4I—N3I—N2I | 105.0 (3) |
C8D—C9D—C1D | 117.2 (4) | N3I—C4I—C5I | 112.6 (4) |
O10D—C9D—C1D | 115.3 (3) | N3I—C4I—H4I | 123.7 |
C9D—O10D—C11D | 117.4 (3) | C5I—C4I—H4I | 123.7 |
O10D—C11D—H11D | 109.5 | C1I—C5I—C6I | 119.8 (4) |
O10D—C11D—H12D | 109.5 | C1I—C5I—C4I | 103.4 (3) |
H11D—C11D—H12D | 109.5 | C6I—C5I—C4I | 136.8 (4) |
O10D—C11D—H13D | 109.5 | C7I—C6I—C5I | 117.2 (4) |
H11D—C11D—H13D | 109.5 | C7I—C6I—H6I | 121.4 |
H12D—C11D—H13D | 109.5 | C5I—C6I—H6I | 121.4 |
N2E—C1E—C9E | 130.8 (4) | C6I—C7I—C8I | 123.1 (4) |
N2E—C1E—C5E | 106.9 (3) | C6I—C7I—H7I | 118.4 |
C9E—C1E—C5E | 122.3 (4) | C8I—C7I—H7I | 118.4 |
N3E—N2E—C1E | 111.1 (3) | C9I—C8I—C7I | 120.8 (4) |
N3E—N2E—H2E | 124.5 | C9I—C8I—H8I | 119.6 |
C1E—N2E—H2E | 124.5 | C7I—C8I—H8I | 119.6 |
C4E—N3E—N2E | 106.5 (3) | C8I—C9I—O10I | 128.1 (4) |
N3E—C4E—C5E | 111.5 (3) | C8I—C9I—C1I | 116.8 (4) |
N3E—C4E—H4E | 124.3 | O10I—C9I—C1I | 115.1 (3) |
C5E—C4E—H4E | 124.3 | C9I—O10I—C11I | 117.3 (3) |
C1E—C5E—C4E | 104.0 (3) | O10I—C11I—H11I | 109.5 |
C1E—C5E—C6E | 119.6 (3) | O10I—C11I—H12I | 109.5 |
C4E—C5E—C6E | 136.3 (4) | H11I—C11I—H12I | 109.5 |
C7E—C6E—C5E | 117.1 (4) | O10I—C11I—H13I | 109.5 |
C7E—C6E—H6E | 121.5 | H11I—C11I—H13I | 109.5 |
C5E—C6E—H6E | 121.5 | H12I—C11I—H13I | 109.5 |
| | | |
C8A—C9A—O10A—C11A | 2.7 (6) | C8F—C9F—O10F—C11F | −1.8 (6) |
C8B—C9B—O10B—C11B | −0.8 (6) | C8G—C9G—O10G—C11G | 1.2 (6) |
C8C—C9C—O10C—C11C | 5.4 (6) | C8H—C9H—O10H—C11H | 5.5 (6) |
C8D—C9D—O10D—C11D | 2.7 (6) | C8I—C9I—O10I—C11I | −8.8 (5) |
C8E—C9E—O10E—C11E | −5.7 (6) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2A—H2A···N3Di | 0.86 | 2.03 | 2.879 (4) | 170 |
N2B—H2B···N3Aii | 0.86 | 2.06 | 2.907 (4) | 168 |
N2C—H2C···N3Eiii | 0.86 | 2.04 | 2.891 (4) | 172 |
N2D—H2D···N3Biv | 0.86 | 2.06 | 2.909 (4) | 167 |
N2E—H2E···N3Fi | 0.86 | 2.02 | 2.871 (4) | 168 |
N2F—H2F···N3Cv | 0.86 | 2.08 | 2.914 (4) | 163 |
N2G—H2G···N3H | 0.86 | 2.06 | 2.911 (4) | 169 |
N2H—H2H···N3Ii | 0.86 | 2.06 | 2.906 (5) | 169 |
N2I—H2I···N3Gvi | 0.86 | 2.04 | 2.890 (4) | 168 |
Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) −x+1, y−1/2, −z+2; (iii) −x, y−1/2, −z+1; (iv) x, y, z−1; (v) x+1, y, z; (vi) −x+1, y−1/2, −z+1. |
Experimental details
Crystal data |
Chemical formula | C8H8N2O |
Mr | 148.16 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 293 |
a, b, c (Å) | 14.1297 (5), 16.0074 (7), 15.699 (1) |
β (°) | 102.533 (4) |
V (Å3) | 3466.2 (3) |
Z | 18 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.5 × 0.4 × 0.3 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10744, 10405, 4332 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.703 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.128, 0.98 |
No. of reflections | 10405 |
No. of parameters | 901 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.12, −0.10 |
Selected torsion angles (º) topC8A—C9A—O10A—C11A | 2.7 (6) | C8F—C9F—O10F—C11F | −1.8 (6) |
C8B—C9B—O10B—C11B | −0.8 (6) | C8G—C9G—O10G—C11G | 1.2 (6) |
C8C—C9C—O10C—C11C | 5.4 (6) | C8H—C9H—O10H—C11H | 5.5 (6) |
C8D—C9D—O10D—C11D | 2.7 (6) | C8I—C9I—O10I—C11I | −8.8 (5) |
C8E—C9E—O10E—C11E | −5.7 (6) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2A—H2A···N3Di | 0.86 | 2.03 | 2.879 (4) | 170 |
N2B—H2B···N3Aii | 0.86 | 2.06 | 2.907 (4) | 168 |
N2C—H2C···N3Eiii | 0.86 | 2.04 | 2.891 (4) | 172 |
N2D—H2D···N3Biv | 0.86 | 2.06 | 2.909 (4) | 167 |
N2E—H2E···N3Fi | 0.86 | 2.02 | 2.871 (4) | 168 |
N2F—H2F···N3Cv | 0.86 | 2.08 | 2.914 (4) | 163 |
N2G—H2G···N3H | 0.86 | 2.06 | 2.911 (4) | 169 |
N2H—H2H···N3Ii | 0.86 | 2.06 | 2.906 (5) | 169 |
N2I—H2I···N3Gvi | 0.86 | 2.04 | 2.890 (4) | 168 |
Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) −x+1, y−1/2, −z+2; (iii) −x, y−1/2, −z+1; (iv) x, y, z−1; (v) x+1, y, z; (vi) −x+1, y−1/2, −z+1. |
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Nitric oxide (NO) is an important biological messenger involved in numerous physiological processes, including neurotransmission, blood-pressure and blood-flow regulation, platelet aggregation, and inflammation (Bredt, 1999). On the other hand, overproduction of NO plays a role in a variety of disorders, such as septic shock, pain, ischaemia and several neurodegenerative diseases (Dawson & Dawson, 1996). NO is synthesized in several cell types from L-arginine by different isoforms of nitric oxide synthase (NOS). Its substrate binding site (heme cavity) is located in the catalytic heme domain. The guanidinium side chain of the substrate interacts with a glutamic acid residue in the binding site and its terminal guanidinium N atom is therefore located approximately 4.0 Å from the heme Fe atom and can be hydroxylated by the Fe-bound O atom. To date, three isoforms of NOS have been cloned, namely neuronal (nNOS) and endothelial (eNOS), which are both constitutive and calcium-dependent, and an inducible, calcium-independent form (iNOS) (Stuehr, 1997). Development of inhibitors selective for one of these isoforms is of considerable interest, both for therapeutical purposes and for their use as specific pharmacological tools. Among the synthetic inhibitors, 7-nitroindazole (7-NI) has been identified as a potential selective inhibitor of neuronal NOS activity and is now considered as a very important tool in pharmacological studies (Moore et al., 1991; Babbedge et al., 1993).
The recently determined X-ray structure of the catalytic heme domain of eNOS, complexed with a derivative of the 7-nitroindazole inhibitor (3-bromo-7-NI) (Raman et al., 2001), showed that 3-bromo-7-NI does not interact directly either with the glutamic acid or with the heme Fe atom, but stacks parallel to the heme plane within the van der Waals contact distance. Its position in the substrate-binding site is ensured by two hydrogen bonds, one between the indazole N—H and the carbonyl O of Trp 358, and a second between one O atom from the nitro group and the peptide N—H of Met 360. The fixation of 3-bromo-7-NI causes a displacement of glutamic acid side chains in the substrate-binding cavity from its original (potential substrate-binding position) at the edge of the cavity.
The synthesis and pharmacological evaluation of several substituted indazoles and potential analogues of 7-NI has recently been reported by our group (Schumann et al., 2001). Among them, 7-methoxyindazole (7-MI), (I), the most active compound of the series in an in vitro enzymatic assay of nNOS activity (6.3 nM, cf. 0.9 nM for 7-NI), is considered as a novel lead in the field of NOS-inhibitory drugs development. The aim of the present study was to determine the three-dimensional arrangement of (I) and whether the new inhibition mechanism described for 7-NI can be considered as a potential mechanism for (I) as well. In order to find an answer to this question, we have studied the X-ray structure of (I). \sch
There are 18 molecules in the unit cell in the crystal structure, i.e. nine molecules of (I) per asymmetric unit (named A—I). In all these nine structures, the methoxy group lies in the plane of the indazole with its methyl located trans to N2—H2 (Fig. 1), which is to be expected considering that atom H2 of the N2—H2 group constitutes a steric hindrance for the opposite conformation. The C8—C9—O10—C11 torsion angle, characterizing the conformation of the methoxy group with respect to the indazole ring, is close to 0° for all nine molecules, but varies slightly (Table 1), with extremes from -9.6° in molecule I to 4.8° in molecule A.
The observed C9—O10 (mean 1.37 Å) and O10—C11 (mean 1.42 Å) bond lengths in the methoxy group are comparable with values for aromatic methoxy groups deposited in the Cambridge Structural Database (CSD, Version?; Allen & Kennard, 1993). However, greater differences are observed between the methoxy group bond angles (C1—C9—O10 and C8—C9—C10) in the structures of (I). Generally in the CSD structures, the bond angle toward which the CH3 of the methoxy group is rotated (hereinafter the first bond angle) is about 124° and the second bond angle is about 115°. In the structure of (I), the first bond angle (C8—C9—C10) has an average of about 128.4° and the second (C1—C9—O10) of about 115.0°. The more significant deviation of methoxy group in (I) is probably a result of the electrostatic attraction between atom O10 of the methoxy group and atom H2 of the indazole. If the N2—H2 in (I) is replaced by a Carom—H group, the modelled three-dimensional structure [MOPAC, method Austin Model 1 (AM1); Stewart, 1990] gives C8—C9—C10 and C1—C9—O10 bond angles of 125° and 116°, respectively.
The crystal packing consists of trimers of (I), connected by symmetry-equivalent hydrogen bonds from each indazole, N2—H2···N3 (Fig. 2, Table 2). One molecule of a trimer interacts through N2—H2 with the second molecule and through N3 with the third, and vice versa. The nine molecules are arranged in three trimers: 1s t trimer molecule A + molecule B + molecule D (x + 1, y, z + 1); 2nd trimer molecule C + molecule E + molecule F (x + 1, y, z + 1); 3rd trimer molecule H + molecule G + molecule I (x + 1, y, z + 1). The molecules in the trimers are not strictly coplanar, deviating slightly from a planar arrangement (1s t trimer: 〈 AB ≈ 14°, 〈 AD ≈ 7°, 〈 BD ≈ 6°; 2nd trimer: 〈 EF ≈ 5°, 〈 CF ≈ 10°, 〈 CE ≈ 9°; 1s t Should this be 3rd? trimer: 〈 IG ≈ 13°, 〈 IH ≈ 15°, 〈 GH ≈ 6°). In the crystal packing, the coplanar trimers stack in parallel planes, with an interplanar spacing of 3.5 Å between the trimers. Two kinds of these trimer strips are observed in the crystal in projection along the a axis (Fig. 3), without any direct interaction between them. The difference between the strips is given by the initial trimer orientation. The planes of the trimer indazole rings in neighbouring strips are approximately perpendicular to each other (80°).
Superposition of the X-ray structure of (I) on that of 7-NI (Sopková-de Oliveira Santos et al., 2000) shows that the substitutions at the 7-position are of approximately the same size. Therefore, (I) could be positioned in the substrate-binding site in a similar way to 7-NI, without any motion of the side chains in the substrate-binding cavity. However, the replacement of a nitro by methoxy group will suppress the potentially strong hydrogen acceptor, NO2. This could be a reason for the weaker affinity of (I) compared with 7-NI.