The crystal structure of the title compound, C
15H
18N
2O·H
2O, exhibits four independent hydrogen bonds, of types N—H
O and O—H
O. The water molecules participate in extensive hydrogen bonding and link molecules into a two-dimensional network.
Supporting information
CCDC reference: 627639
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.010 Å
- R factor = 0.066
- wR factor = 0.161
- Data-to-parameter ratio = 7.5
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ?
PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax .LT. 18) ..... 7.51
PLAT150_ALERT_1_C Volume as Calculated Differs from that Given ... 1419.00 Ang-3
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.11
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 10
PLAT414_ALERT_2_C Short Intra D-H..H-X H2A .. H3 .. 1.94 Ang.
PLAT420_ALERT_2_C D-H Without Acceptor N2 - H2A ... ?
PLAT480_ALERT_4_C Long H...A H-Bond Reported H2A .. N2 .. 2.68 Ang.
Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
correct. If it is not, please give the correct count in the
_publ_section_exptl_refinement section of the submitted CIF.
From the CIF: _diffrn_reflns_theta_max 25.00
From the CIF: _reflns_number_total 1292
Count of symmetry unique reflns 1314
Completeness (_total/calc) 98.33%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 0
Fraction of Friedel pairs measured 0.000
Are heavy atom types Z>Si present no
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C6 = . R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C10 = . R
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
8 ALERT level C = Check and explain
3 ALERT level G = General alerts; check
4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
3 ALERT type 2 Indicator that the structure model may be wrong or deficient
2 ALERT type 3 Indicator that the structure quality may be low
2 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.
(6
R,10
R,14E)-6-Amino-12-ethylidene-8-methyl-6,7,10,12-tetrahydro-6,10- methanocycloocta[
b]pyridin-2(1
H)-one monohydrate
top
Crystal data top
C15H18N2O·H2O | F(000) = 560 |
Mr = 260.33 | Dx = 1.219 Mg m−3 |
Monoclinic, C2 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C 2y | Cell parameters from 682 reflections |
a = 14.00 (2) Å | θ = 2.3–20.1° |
b = 12.35 (2) Å | µ = 0.08 mm−1 |
c = 8.838 (14) Å | T = 298 K |
β = 111.731 (19)° | Block, white |
V = 1419 (4) Å3 | 0.20 × 0.17 × 0.11 mm |
Z = 4 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 1292 independent reflections |
Radiation source: fine-focus sealed tube | 751 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.079 |
Detector resolution: 10 pixels mm-1 | θmax = 25.0°, θmin = 2.3° |
φ and ω scans | h = −16→11 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | k = −14→13 |
Tmin = 0.984, Tmax = 0.991 | l = −10→10 |
3603 measured reflections | |
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)] = 0.066 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.161 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0786P)2] where P = (Fo2 + 2Fc2)/3 |
1292 reflections | (Δ/σ)max < 0.001 |
172 parameters | Δρmax = 0.25 e Å−3 |
1 restraint | Δρmin = −0.24 e Å−3 |
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. |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.8847 (4) | 0.3330 (4) | 0.8217 (5) | 0.0421 (14) | |
H1 | 0.9473 | 0.3537 | 0.8468 | 0.051* | |
N2 | 0.6021 (4) | 0.1441 (5) | 0.4456 (6) | 0.0591 (18) | |
H2A | 0.5822 | 0.1478 | 0.5264 | 0.071* | |
H2B | 0.5527 | 0.1330 | 0.3538 | 0.071* | |
O1 | 0.9042 (3) | 0.3612 (4) | 1.0844 (5) | 0.0550 (13) | |
O2 | 0.9567 (4) | 0.5875 (5) | 0.1216 (7) | 0.094 (2) | |
H16 | 0.9401 | 0.5210 | 0.1163 | 0.113* | |
H17 | 0.9290 | 0.6109 | 0.0246 | 0.113* | |
C1 | 0.8459 (4) | 0.3315 (5) | 0.9425 (7) | 0.0457 (18) | |
C2 | 0.7446 (4) | 0.2966 (6) | 0.8981 (7) | 0.0474 (18) | |
H2 | 0.7143 | 0.2937 | 0.9756 | 0.057* | |
C3 | 0.6898 (5) | 0.2667 (6) | 0.7417 (7) | 0.0523 (19) | |
H3 | 0.6223 | 0.2433 | 0.7142 | 0.063* | |
C4 | 0.7324 (5) | 0.2700 (5) | 0.6200 (7) | 0.0411 (16) | |
C5 | 0.8307 (4) | 0.3038 (5) | 0.6632 (6) | 0.0373 (15) | |
C6 | 0.6691 (4) | 0.2336 (5) | 0.4429 (7) | 0.0417 (17) | |
C7 | 0.6021 (5) | 0.3287 (6) | 0.3509 (7) | 0.0497 (18) | |
H7A | 0.5489 | 0.3009 | 0.2533 | 0.060* | |
H7B | 0.5684 | 0.3599 | 0.4189 | 0.060* | |
C8 | 0.6585 (6) | 0.4162 (5) | 0.3032 (7) | 0.0463 (17) | |
C9 | 0.7546 (6) | 0.4023 (5) | 0.3150 (7) | 0.0467 (17) | |
H9 | 0.7870 | 0.4595 | 0.2849 | 0.056* | |
C10 | 0.8144 (4) | 0.3007 (5) | 0.3736 (6) | 0.0419 (16) | |
H10 | 0.8546 | 0.2856 | 0.3058 | 0.050* | |
C11 | 0.8886 (4) | 0.3112 (6) | 0.5531 (7) | 0.0464 (16) | |
H11A | 0.9396 | 0.2540 | 0.5788 | 0.056* | |
H11B | 0.9242 | 0.3802 | 0.5690 | 0.056* | |
C12 | 0.7430 (5) | 0.2054 (6) | 0.3622 (7) | 0.0426 (17) | |
C13 | 0.6013 (6) | 0.5188 (6) | 0.2430 (9) | 0.075 (3) | |
H13A | 0.6321 | 0.5573 | 0.1782 | 0.112* | |
H13B | 0.6041 | 0.5629 | 0.3341 | 0.112* | |
H13C | 0.5310 | 0.5026 | 0.1780 | 0.112* | |
C14 | 0.7476 (5) | 0.1136 (6) | 0.2939 (8) | 0.0520 (17) | |
H14 | 0.6989 | 0.0624 | 0.2942 | 0.062* | |
C15 | 0.8197 (7) | 0.0789 (7) | 0.2155 (11) | 0.086 (3) | |
H15A | 0.8561 | 0.0154 | 0.2693 | 0.128* | |
H15B | 0.8678 | 0.1360 | 0.2237 | 0.128* | |
H15C | 0.7817 | 0.0628 | 0.1028 | 0.128* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.037 (3) | 0.068 (4) | 0.023 (2) | −0.008 (3) | 0.013 (2) | −0.001 (3) |
N2 | 0.055 (4) | 0.092 (5) | 0.034 (3) | −0.032 (3) | 0.021 (3) | −0.011 (3) |
O1 | 0.050 (3) | 0.088 (4) | 0.026 (2) | −0.003 (3) | 0.0133 (19) | −0.005 (2) |
O2 | 0.096 (4) | 0.111 (5) | 0.055 (4) | 0.001 (4) | 0.003 (3) | −0.013 (3) |
C1 | 0.043 (4) | 0.066 (5) | 0.028 (3) | 0.005 (4) | 0.014 (3) | 0.003 (3) |
C2 | 0.033 (4) | 0.084 (5) | 0.029 (3) | 0.000 (4) | 0.017 (3) | −0.004 (4) |
C3 | 0.041 (4) | 0.087 (6) | 0.033 (3) | −0.014 (4) | 0.019 (3) | 0.000 (4) |
C4 | 0.043 (4) | 0.054 (4) | 0.026 (3) | 0.002 (3) | 0.012 (3) | −0.001 (3) |
C5 | 0.036 (3) | 0.056 (4) | 0.021 (3) | −0.003 (3) | 0.012 (2) | 0.000 (3) |
C6 | 0.037 (3) | 0.052 (4) | 0.034 (4) | −0.002 (3) | 0.011 (3) | −0.001 (3) |
C7 | 0.044 (4) | 0.072 (5) | 0.031 (3) | 0.007 (4) | 0.011 (3) | 0.001 (3) |
C8 | 0.053 (5) | 0.052 (4) | 0.025 (3) | 0.005 (4) | 0.004 (3) | −0.001 (3) |
C9 | 0.065 (5) | 0.050 (4) | 0.020 (3) | −0.003 (4) | 0.010 (3) | 0.000 (3) |
C10 | 0.046 (3) | 0.063 (4) | 0.018 (3) | −0.001 (4) | 0.013 (2) | 0.002 (3) |
C11 | 0.046 (4) | 0.059 (4) | 0.030 (3) | −0.004 (4) | 0.010 (3) | −0.006 (3) |
C12 | 0.042 (4) | 0.054 (4) | 0.023 (3) | −0.003 (3) | 0.002 (3) | 0.003 (3) |
C13 | 0.078 (6) | 0.076 (6) | 0.054 (5) | 0.007 (5) | 0.007 (5) | −0.002 (4) |
C14 | 0.051 (4) | 0.065 (5) | 0.044 (4) | −0.010 (4) | 0.021 (3) | −0.011 (4) |
C15 | 0.084 (6) | 0.089 (7) | 0.092 (6) | 0.019 (6) | 0.042 (5) | −0.015 (6) |
Geometric parameters (Å, º) top
N1—C1 | 1.365 (7) | C7—H7A | 0.9700 |
N1—C5 | 1.371 (7) | C7—H7B | 0.9700 |
N1—H1 | 0.8600 | C8—C9 | 1.321 (9) |
N2—C6 | 1.455 (8) | C8—C13 | 1.488 (10) |
N2—H2A | 0.8598 | C9—C10 | 1.490 (9) |
N2—H2B | 0.8601 | C9—H9 | 0.9300 |
O1—C1 | 1.271 (7) | C10—C12 | 1.523 (9) |
O2—H16 | 0.8504 | C10—C11 | 1.547 (7) |
O2—H17 | 0.8500 | C10—H10 | 0.9800 |
C1—C2 | 1.393 (8) | C11—H11A | 0.9700 |
C2—C3 | 1.360 (8) | C11—H11B | 0.9700 |
C2—H2 | 0.9300 | C12—C14 | 1.297 (9) |
C3—C4 | 1.410 (9) | C13—H13A | 0.9600 |
C3—H3 | 0.9300 | C13—H13B | 0.9600 |
C4—C5 | 1.351 (8) | C13—H13C | 0.9600 |
C4—C6 | 1.553 (8) | C14—C15 | 1.483 (10) |
C5—C11 | 1.482 (8) | C14—H14 | 0.9300 |
C6—C12 | 1.498 (9) | C15—H15A | 0.9600 |
C6—C7 | 1.535 (9) | C15—H15B | 0.9600 |
C7—C8 | 1.488 (10) | C15—H15C | 0.9600 |
| | | |
C1—N1—C5 | 124.6 (5) | C9—C8—C7 | 120.9 (6) |
C1—N1—H1 | 117.7 | C13—C8—C7 | 116.6 (7) |
C5—N1—H1 | 117.7 | C8—C9—C10 | 124.2 (6) |
C6—N2—H2A | 112.5 | C8—C9—H9 | 117.9 |
C6—N2—H2B | 113.9 | C10—C9—H9 | 117.9 |
H2A—N2—H2B | 113.3 | C9—C10—C12 | 110.9 (5) |
H16—O2—H17 | 105.0 | C9—C10—C11 | 111.3 (5) |
O1—C1—N1 | 118.2 (6) | C12—C10—C11 | 107.9 (5) |
O1—C1—C2 | 125.6 (6) | C9—C10—H10 | 108.9 |
N1—C1—C2 | 116.2 (5) | C12—C10—H10 | 108.9 |
C3—C2—C1 | 120.2 (6) | C11—C10—H10 | 108.9 |
C3—C2—H2 | 119.9 | C5—C11—C10 | 110.2 (5) |
C1—C2—H2 | 119.9 | C5—C11—H11A | 109.6 |
C2—C3—C4 | 121.9 (6) | C10—C11—H11A | 109.6 |
C2—C3—H3 | 119.0 | C5—C11—H11B | 109.6 |
C4—C3—H3 | 119.0 | C10—C11—H11B | 109.6 |
C5—C4—C3 | 117.9 (6) | H11A—C11—H11B | 108.1 |
C5—C4—C6 | 121.0 (5) | C14—C12—C6 | 125.8 (6) |
C3—C4—C6 | 121.1 (6) | C14—C12—C10 | 124.2 (6) |
C4—C5—N1 | 119.2 (5) | C6—C12—C10 | 109.9 (6) |
C4—C5—C11 | 125.6 (5) | C8—C13—H13A | 109.5 |
N1—C5—C11 | 115.2 (5) | C8—C13—H13B | 109.5 |
N2—C6—C12 | 113.2 (5) | H13A—C13—H13B | 109.5 |
N2—C6—C7 | 108.6 (5) | C8—C13—H13C | 109.5 |
C12—C6—C7 | 108.6 (5) | H13A—C13—H13C | 109.5 |
N2—C6—C4 | 109.5 (5) | H13B—C13—H13C | 109.5 |
C12—C6—C4 | 108.1 (5) | C12—C14—C15 | 129.0 (7) |
C7—C6—C4 | 108.7 (5) | C12—C14—H14 | 115.5 |
C8—C7—C6 | 114.9 (5) | C15—C14—H14 | 115.5 |
C8—C7—H7A | 108.5 | C14—C15—H15A | 109.5 |
C6—C7—H7A | 108.5 | C14—C15—H15B | 109.5 |
C8—C7—H7B | 108.5 | H15A—C15—H15B | 109.5 |
C6—C7—H7B | 108.5 | C14—C15—H15C | 109.5 |
H7A—C7—H7B | 107.5 | H15A—C15—H15C | 109.5 |
C9—C8—C13 | 122.4 (7) | H15B—C15—H15C | 109.5 |
| | | |
C5—N1—C1—O1 | −179.7 (6) | C6—C7—C8—C9 | 11.2 (9) |
C5—N1—C1—C2 | 0.6 (9) | C6—C7—C8—C13 | −168.6 (6) |
O1—C1—C2—C3 | −179.9 (7) | C13—C8—C9—C10 | −179.6 (6) |
N1—C1—C2—C3 | −0.2 (10) | C7—C8—C9—C10 | 0.7 (9) |
C1—C2—C3—C4 | −0.2 (11) | C8—C9—C10—C12 | 19.4 (7) |
C2—C3—C4—C5 | 0.3 (10) | C8—C9—C10—C11 | −100.7 (7) |
C2—C3—C4—C6 | 178.9 (6) | C4—C5—C11—C10 | 13.2 (9) |
C3—C4—C5—N1 | 0.1 (9) | N1—C5—C11—C10 | −167.8 (5) |
C6—C4—C5—N1 | −178.5 (5) | C9—C10—C11—C5 | 75.4 (7) |
C3—C4—C5—C11 | 179.1 (7) | C12—C10—C11—C5 | −46.4 (7) |
C6—C4—C5—C11 | 0.5 (10) | N2—C6—C12—C14 | 2.6 (9) |
C1—N1—C5—C4 | −0.5 (9) | C7—C6—C12—C14 | −118.0 (7) |
C1—N1—C5—C11 | −179.6 (6) | C4—C6—C12—C14 | 124.2 (7) |
C5—C4—C6—N2 | 143.9 (6) | N2—C6—C12—C10 | −176.6 (5) |
C3—C4—C6—N2 | −34.6 (8) | C7—C6—C12—C10 | 62.7 (6) |
C5—C4—C6—C12 | 20.2 (8) | C4—C6—C12—C10 | −55.0 (6) |
C3—C4—C6—C12 | −158.4 (6) | C9—C10—C12—C14 | 129.5 (6) |
C5—C4—C6—C7 | −97.6 (7) | C11—C10—C12—C14 | −108.4 (7) |
C3—C4—C6—C7 | 83.8 (7) | C9—C10—C12—C6 | −51.2 (6) |
N2—C6—C7—C8 | −166.0 (5) | C11—C10—C12—C6 | 70.9 (6) |
C12—C6—C7—C8 | −42.5 (7) | C6—C12—C14—C15 | −178.4 (7) |
C4—C6—C7—C8 | 74.9 (7) | C10—C12—C14—C15 | 0.7 (11) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H17···O2i | 0.85 | 2.42 | 2.833 (13) | 111 |
O2—H16···O1ii | 0.85 | 2.03 | 2.877 (9) | 174 |
N2—H2B···O2iii | 0.86 | 2.07 | 2.918 (9) | 168 |
N2—H2A···N2iv | 0.86 | 2.68 | 3.333 (12) | 134 |
N1—H1···O1v | 0.86 | 1.94 | 2.780 (8) | 165 |
Symmetry codes: (i) −x+2, y, −z; (ii) x, y, z−1; (iii) x−1/2, y−1/2, z; (iv) −x+1, y, −z+1; (v) −x+2, y, −z+2. |