The structure of the title compound, C
23H
27N
2O
2+·I
−, was determined from a 0.14 × 0.10 × 0.003 mm crystal using synchrotron X-radiation. The cation charge is delocalized and there is strong O—H
I
− intermolecular hydrogen bonding.
Supporting information
CCDC reference: 209997
Key indicators
- Single-crystal synchrotron study
- T = 100 K
- Mean (C-C) = 0.004 Å
- R factor = 0.025
- wR factor = 0.071
- Data-to-parameter ratio = 8.8
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level A:
ABSTM_02 Alert A The ratio of Tmax/Tmin expected RT(exp) is > 1.30
An absorption correction should be applied.
Tmin and Tmax expected: 0.695 0.991
RT(exp) = 1.426
THETM_01 Alert A The value of sine(theta_max)/wavelength is less than 0.550
Calculated sin(theta_max)/wavelength = 0.5264
| Author response: The CCD plate was placed as close to the crystal as was
practicable (60 mm); the incomplete shell corresponds to
all the available data using the highest wavelength
possible on the X9B beamline.
|
Alert Level C:
REFLT_03
From the CIF: _diffrn_reflns_theta_max 28.98
From the CIF: _reflns_number_total 2300
TEST2: Reflns within _diffrn_reflns_theta_max
Count of symmetry unique reflns 2525
Completeness (_total/calc) 91.09%
Alert C: < 95% complete
REFNR_01 Alert C Ratio of reflections to parameters is < 10 for a
centrosymmetric structure
sine(theta)/lambda 0.5264
Proportion of unique data used 1.0000
Ratio reflections to parameters 8.7786
General Notes
ABSMU_01 Radiation type not identified. Calculation of
_exptl_absorpt_correction_mu not performed.
2 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check
The compound was prepared as previously described [compound29a in Kay et al. (2001)].
It was not possible to carry out an analytical absorption correction, as the crystal was not uniform or accurately measurable, and no empirical correction method was available for this experimental arrangement. H atoms on O1, O2 and C9 were refined freely, while others were constrained to geometrically calculated positions, riding on their parent atoms. For all H atoms, Uiso(H) = 1.2Ueq of the parent atom.
Data collection: DENZO (Otinowski & Minor, 1997); cell refinement: DENZO; data reduction: DENZO; 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.
1-(2-Hydroxyethyl)-4-{4,5,6,7-tetrahydro-1-[1-(2-hydroxyethyl)- pyridin-4(1
H)-ylidene]-1
H-inden-3-yl}pyridinium iodide
top
Crystal data top
C23H27N2O2+·I− | F(000) = 992 |
Mr = 490.37 | Dx = 1.573 Mg m−3 |
Monoclinic, P21/c | Synchrotron radiation, λ = 0.9204 Å |
a = 9.0520 (18) Å | Cell parameters from 340 reflections |
b = 24.134 (5) Å | θ = 3.8–22.5° |
c = 9.5330 (19) Å | µ = 3.03 mm−1 |
β = 96.22 (3)° | T = 100 K |
V = 2070.3 (7) Å3 | Plate, black |
Z = 4 | 0.14 × 0.10 × 0.003 mm |
Data collection top
Quantum4 CCD detector diffractometer | 2191 reflections with I > 2σ(I) |
None monochromator | Rint = 0.000 |
Detector resolution: 4000 pixels mm-1 | θmax = 29.0°, θmin = 3.0° |
ϕ scans | h = 0→9 |
2300 measured reflections | k = 0→25 |
2300 independent reflections | l = −10→9 |
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)] = 0.025 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.071 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.025P)2 + 2.8457P] where P = (Fo2 + 2Fc2)/3 |
2300 reflections | (Δ/σ)max = 0.002 |
262 parameters | Δρmax = 0.51 e Å−3 |
0 restraints | Δρmin = −0.58 e Å−3 |
Crystal data top
C23H27N2O2+·I− | V = 2070.3 (7) Å3 |
Mr = 490.37 | Z = 4 |
Monoclinic, P21/c | Synchrotron radiation, λ = 0.9204 Å |
a = 9.0520 (18) Å | µ = 3.03 mm−1 |
b = 24.134 (5) Å | T = 100 K |
c = 9.5330 (19) Å | 0.14 × 0.10 × 0.003 mm |
β = 96.22 (3)° | |
Data collection top
Quantum4 CCD detector diffractometer | 2191 reflections with I > 2σ(I) |
2300 measured reflections | Rint = 0.000 |
2300 independent reflections | θmax = 29.0° |
Refinement top
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.071 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.51 e Å−3 |
2300 reflections | Δρmin = −0.58 e Å−3 |
262 parameters | |
Special details top
Experimental. Crystal decay was monitored and corrected by the inter-frame analysis (DENZO: Otwinowski & Minor, 1997). |
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 | |
I1 | 0.69464 (2) | 0.845714 (9) | 0.61325 (2) | 0.02629 (16) | |
O1 | −0.0167 (3) | 0.74846 (10) | 1.2136 (3) | 0.0338 (7) | |
H1O | −0.076 (5) | 0.7281 (18) | 1.185 (5) | 0.041* | |
O2 | 0.5846 (3) | 1.27037 (10) | 1.0761 (3) | 0.0377 (7) | |
H2O | 0.507 (5) | 1.2868 (18) | 1.053 (5) | 0.045* | |
N1 | −0.1179 (3) | 0.86075 (10) | 1.1480 (3) | 0.0170 (6) | |
N2 | 0.6417 (3) | 1.15909 (9) | 0.9625 (3) | 0.0170 (7) | |
C1 | −0.1224 (4) | 0.85604 (12) | 1.0073 (4) | 0.0165 (8) | |
H1 | −0.1878 | 0.8298 | 0.9592 | 0.020* | |
C2 | −0.0353 (3) | 0.88799 (12) | 0.9317 (3) | 0.0165 (7) | |
H2 | −0.0429 | 0.8839 | 0.8321 | 0.020* | |
C3 | 0.0664 (3) | 0.92725 (11) | 0.9976 (3) | 0.0145 (7) | |
C4 | 0.0594 (4) | 0.93277 (12) | 1.1460 (3) | 0.0171 (7) | |
H4 | 0.1200 | 0.9597 | 1.1971 | 0.020* | |
C5 | −0.0312 (4) | 0.90080 (12) | 1.2159 (4) | 0.0186 (7) | |
H5 | −0.0344 | 0.9063 | 1.3142 | 0.022* | |
C6 | −0.2003 (4) | 0.82163 (13) | 1.2311 (4) | 0.0231 (8) | |
H6A | −0.2767 | 0.8020 | 1.1675 | 0.028* | |
H6B | −0.2513 | 0.8425 | 1.3013 | 0.028* | |
C7 | −0.0947 (4) | 0.77996 (14) | 1.3062 (4) | 0.0300 (9) | |
H7A | −0.0222 | 0.7999 | 1.3734 | 0.036* | |
H7B | −0.1518 | 0.7545 | 1.3614 | 0.036* | |
C8 | 0.1659 (3) | 0.95914 (11) | 0.9251 (3) | 0.0140 (7) | |
C9 | 0.2564 (4) | 1.00253 (12) | 0.9852 (3) | 0.0148 (7) | |
H9 | 0.255 (4) | 1.0142 (13) | 1.079 (4) | 0.018* | |
C10 | 0.3347 (4) | 1.02670 (12) | 0.8816 (3) | 0.0151 (7) | |
C11 | 0.5656 (4) | 1.13870 (13) | 1.0664 (3) | 0.0180 (8) | |
H11 | 0.5817 | 1.1543 | 1.1583 | 0.022* | |
C12 | 0.4667 (4) | 1.09638 (11) | 1.0416 (3) | 0.0157 (7) | |
H12 | 0.4151 | 1.0833 | 1.1167 | 0.019* | |
C13 | 0.4385 (3) | 1.07131 (12) | 0.9067 (3) | 0.0149 (7) | |
C14 | 0.5184 (4) | 1.09497 (12) | 0.8020 (3) | 0.0177 (7) | |
H14 | 0.5036 | 1.0808 | 0.7086 | 0.021* | |
C15 | 0.6160 (4) | 1.13758 (13) | 0.8313 (3) | 0.0179 (7) | |
H15 | 0.6670 | 1.1524 | 0.7578 | 0.022* | |
C16 | 0.1935 (3) | 0.95565 (12) | 0.7769 (3) | 0.0145 (7) | |
C17 | 0.1388 (4) | 0.91208 (13) | 0.6690 (3) | 0.0188 (8) | |
H17A | 0.0333 | 0.9193 | 0.6347 | 0.023* | |
H17B | 0.1452 | 0.8750 | 0.7137 | 0.023* | |
C18 | 0.2322 (4) | 0.91294 (13) | 0.5443 (3) | 0.0215 (8) | |
H18A | 0.3314 | 0.8969 | 0.5736 | 0.026* | |
H18B | 0.1834 | 0.8901 | 0.4664 | 0.026* | |
C19 | 0.2495 (4) | 0.97176 (13) | 0.4936 (4) | 0.0227 (8) | |
H19A | 0.1503 | 0.9889 | 0.4720 | 0.027* | |
H19B | 0.2991 | 0.9715 | 0.4060 | 0.027* | |
C20 | 0.3416 (4) | 1.00582 (13) | 0.6064 (3) | 0.0204 (8) | |
H20A | 0.4476 | 0.9954 | 0.6086 | 0.024* | |
H20B | 0.3324 | 1.0456 | 0.5822 | 0.024* | |
C21 | 0.2910 (3) | 0.99639 (12) | 0.7499 (3) | 0.0146 (7) | |
C23 | 0.6751 (4) | 1.26098 (13) | 0.9666 (4) | 0.0272 (9) | |
H23A | 0.7512 | 1.2905 | 0.9670 | 0.033* | |
H23B | 0.6138 | 1.2616 | 0.8741 | 0.033* | |
C22 | 0.7489 (4) | 1.20558 (12) | 0.9896 (4) | 0.0222 (8) | |
H22A | 0.8280 | 1.2020 | 0.9262 | 0.027* | |
H22B | 0.7962 | 1.2033 | 1.0881 | 0.027* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
I1 | 0.0229 (2) | 0.0389 (2) | 0.0163 (2) | −0.00270 (9) | −0.00135 (14) | −0.00171 (8) |
O1 | 0.0292 (16) | 0.0273 (14) | 0.0458 (17) | 0.0000 (11) | 0.0083 (14) | 0.0059 (12) |
O2 | 0.0477 (18) | 0.0355 (15) | 0.0289 (15) | 0.0186 (13) | −0.0008 (15) | −0.0034 (11) |
N1 | 0.0173 (16) | 0.0170 (13) | 0.0172 (17) | 0.0009 (12) | 0.0041 (14) | 0.0023 (12) |
N2 | 0.0146 (16) | 0.0153 (14) | 0.0211 (17) | 0.0010 (10) | 0.0010 (14) | 0.0005 (11) |
C1 | 0.017 (2) | 0.0126 (15) | 0.019 (2) | 0.0015 (13) | −0.0012 (16) | −0.0033 (13) |
C2 | 0.0170 (18) | 0.0182 (16) | 0.0133 (17) | 0.0023 (14) | −0.0027 (15) | −0.0024 (13) |
C3 | 0.0153 (18) | 0.0123 (15) | 0.0150 (18) | 0.0053 (13) | −0.0023 (15) | 0.0008 (12) |
C4 | 0.0158 (18) | 0.0196 (17) | 0.0149 (18) | 0.0011 (13) | −0.0026 (15) | −0.0024 (13) |
C5 | 0.0173 (17) | 0.0243 (18) | 0.0137 (16) | 0.0038 (14) | −0.0006 (16) | 0.0016 (14) |
C6 | 0.023 (2) | 0.0242 (18) | 0.0242 (19) | −0.0021 (15) | 0.0093 (17) | 0.0047 (14) |
C7 | 0.036 (2) | 0.0253 (19) | 0.029 (2) | −0.0008 (16) | 0.0070 (19) | 0.0096 (15) |
C8 | 0.0118 (18) | 0.0143 (16) | 0.0151 (18) | 0.0053 (13) | −0.0025 (15) | 0.0016 (12) |
C9 | 0.0155 (18) | 0.0163 (16) | 0.0117 (18) | 0.0057 (13) | −0.0022 (15) | −0.0010 (13) |
C10 | 0.0153 (17) | 0.0154 (16) | 0.0140 (18) | 0.0030 (13) | −0.0007 (15) | 0.0004 (12) |
C11 | 0.0178 (19) | 0.0199 (16) | 0.0155 (18) | 0.0028 (15) | −0.0012 (16) | −0.0026 (14) |
C12 | 0.0140 (18) | 0.0178 (17) | 0.0153 (17) | 0.0019 (14) | 0.0019 (15) | 0.0007 (13) |
C13 | 0.0127 (17) | 0.0147 (16) | 0.0173 (18) | 0.0054 (13) | 0.0010 (15) | 0.0024 (13) |
C14 | 0.0191 (19) | 0.0198 (17) | 0.0141 (18) | 0.0012 (14) | 0.0004 (15) | −0.0017 (13) |
C15 | 0.0182 (19) | 0.0211 (17) | 0.0144 (18) | 0.0023 (15) | 0.0014 (16) | 0.0047 (14) |
C16 | 0.0124 (18) | 0.0174 (16) | 0.0131 (17) | 0.0049 (13) | −0.0012 (15) | −0.0011 (13) |
C17 | 0.0176 (19) | 0.0201 (17) | 0.0180 (18) | 0.0002 (13) | −0.0008 (16) | −0.0022 (14) |
C18 | 0.022 (2) | 0.0291 (18) | 0.0129 (18) | 0.0001 (15) | −0.0020 (16) | −0.0058 (14) |
C19 | 0.024 (2) | 0.0307 (19) | 0.0133 (18) | −0.0020 (15) | 0.0025 (16) | −0.0028 (14) |
C20 | 0.0208 (19) | 0.0256 (18) | 0.0147 (18) | −0.0034 (14) | 0.0014 (15) | −0.0010 (14) |
C21 | 0.0123 (18) | 0.0179 (16) | 0.0132 (17) | 0.0052 (13) | −0.0007 (15) | −0.0020 (13) |
C23 | 0.031 (2) | 0.0209 (18) | 0.029 (2) | −0.0004 (15) | −0.0011 (19) | −0.0002 (15) |
C22 | 0.0176 (19) | 0.0188 (18) | 0.029 (2) | −0.0055 (14) | −0.0009 (17) | −0.0001 (14) |
Geometric parameters (Å, º) top
O1—C7 | 1.412 (5) | C23—C22 | 1.500 (5) |
O2—C23 | 1.413 (5) | O1—H1O | 0.75 (4) |
N1—C1 | 1.342 (4) | O2—H2O | 0.82 (5) |
N1—C5 | 1.364 (4) | C1—H1 | 0.950 |
N1—C6 | 1.484 (4) | C2—H2 | 0.950 |
N2—C15 | 1.351 (4) | C4—H4 | 0.950 |
N2—C11 | 1.358 (4) | C5—H5 | 0.950 |
N2—C22 | 1.488 (4) | C6—H6A | 0.990 |
C1—C2 | 1.363 (5) | C6—H6B | 0.990 |
C2—C3 | 1.420 (4) | C7—H7A | 0.990 |
C3—C8 | 1.420 (4) | C7—H7B | 0.990 |
C3—C4 | 1.429 (5) | C9—H9 | 0.94 (4) |
C4—C5 | 1.352 (5) | C11—H11 | 0.950 |
C6—C7 | 1.513 (5) | C12—H12 | 0.950 |
C8—C9 | 1.412 (5) | C14—H14 | 0.950 |
C8—C16 | 1.464 (4) | C15—H15 | 0.950 |
C9—C10 | 1.403 (5) | C17—H17A | 0.990 |
C10—C13 | 1.432 (5) | C17—H17B | 0.990 |
C10—C21 | 1.470 (4) | C18—H18A | 0.990 |
C11—C12 | 1.362 (5) | C18—H18B | 0.990 |
C12—C13 | 1.419 (5) | C19—H19A | 0.990 |
C13—C14 | 1.415 (5) | C19—H19B | 0.990 |
C14—C15 | 1.365 (5) | C20—H20A | 0.990 |
C16—C21 | 1.364 (5) | C20—H20B | 0.990 |
C16—C17 | 1.516 (4) | C23—H23A | 0.990 |
C17—C18 | 1.532 (5) | C23—H23B | 0.990 |
C18—C19 | 1.513 (5) | C22—H22A | 0.990 |
C19—C20 | 1.528 (5) | C22—H22B | 0.990 |
C20—C21 | 1.506 (5) | | |
| | | |
C1—N1—C5 | 119.2 (3) | N1—C6—H6A | 109.6 |
C1—N1—C6 | 121.1 (3) | C7—C6—H6A | 109.6 |
C5—N1—C6 | 119.6 (3) | N1—C6—H6B | 109.6 |
C15—N2—C11 | 119.1 (3) | C7—C6—H6B | 109.6 |
C15—N2—C22 | 119.6 (3) | H6A—C6—H6B | 108.1 |
C11—N2—C22 | 121.3 (3) | O1—C7—H7A | 108.9 |
N1—C1—C2 | 121.6 (3) | C6—C7—H7A | 108.9 |
C1—C2—C3 | 121.9 (3) | O1—C7—H7B | 108.9 |
C8—C3—C2 | 124.2 (3) | C6—C7—H7B | 108.9 |
C8—C3—C4 | 122.0 (3) | H7A—C7—H7B | 107.7 |
C2—C3—C4 | 113.8 (3) | C10—C9—H9 | 127 (2) |
C5—C4—C3 | 121.9 (3) | C8—C9—H9 | 123 (2) |
C4—C5—N1 | 121.3 (3) | N2—C11—H11 | 119.3 |
N1—C6—C7 | 110.3 (3) | C12—C11—H11 | 119.3 |
O1—C7—C6 | 113.3 (3) | C11—C12—H12 | 119.1 |
C9—C8—C3 | 125.1 (3) | C13—C12—H12 | 119.1 |
C9—C8—C16 | 106.4 (3) | C15—C14—H14 | 119.0 |
C3—C8—C16 | 128.5 (3) | C13—C14—H14 | 119.0 |
C10—C9—C8 | 109.7 (3) | N2—C15—H15 | 119.3 |
C9—C10—C13 | 124.6 (3) | C14—C15—H15 | 119.3 |
C9—C10—C21 | 106.6 (3) | C16—C17—H17A | 109.6 |
C13—C10—C21 | 128.9 (3) | C18—C17—H17A | 109.6 |
N2—C11—C12 | 121.4 (3) | C16—C17—H17B | 109.6 |
C11—C12—C13 | 121.8 (3) | C18—C17—H17B | 109.6 |
C14—C13—C12 | 114.3 (3) | H17A—C17—H17B | 108.1 |
C14—C13—C10 | 124.2 (3) | C19—C18—H18A | 109.6 |
C12—C13—C10 | 121.5 (3) | C17—C18—H18A | 109.6 |
C15—C14—C13 | 121.9 (3) | C19—C18—H18B | 109.6 |
N2—C15—C14 | 121.4 (3) | C17—C18—H18B | 109.6 |
C21—C16—C8 | 108.8 (3) | H18A—C18—H18B | 108.1 |
C21—C16—C17 | 122.8 (3) | C18—C19—H19A | 109.6 |
C8—C16—C17 | 128.1 (3) | C20—C19—H19A | 109.6 |
C16—C17—C18 | 110.5 (3) | C18—C19—H19B | 109.6 |
C19—C18—C17 | 110.2 (3) | C20—C19—H19B | 109.6 |
C18—C19—C20 | 110.3 (3) | H19A—C19—H19B | 108.1 |
C21—C20—C19 | 111.2 (3) | C21—C20—H20A | 109.4 |
C16—C21—C10 | 108.5 (3) | C19—C20—H20A | 109.4 |
C16—C21—C20 | 123.2 (3) | C21—C20—H20B | 109.4 |
C10—C21—C20 | 128.3 (3) | C19—C20—H20B | 109.4 |
O2—C23—C22 | 108.7 (3) | H20A—C20—H20B | 108.0 |
N2—C22—C23 | 112.0 (3) | O2—C23—H23A | 110.0 |
C7—O1—H1O | 101 (3) | C22—C23—H23A | 110.0 |
C23—O2—H2O | 116 (3) | O2—C23—H23B | 110.0 |
N1—C1—H1 | 119.2 | C22—C23—H23B | 110.0 |
C2—C1—H1 | 119.2 | H23A—C23—H23B | 108.3 |
C1—C2—H2 | 119.1 | N2—C22—H22A | 109.2 |
C3—C2—H2 | 119.1 | C23—C22—H22A | 109.2 |
C5—C4—H4 | 119.0 | N2—C22—H22B | 109.2 |
C3—C4—H4 | 119.0 | C23—C22—H22B | 109.2 |
C4—C5—H5 | 119.4 | H22A—C22—H22B | 107.9 |
N1—C5—H5 | 119.4 | | |
| | | |
C5—N1—C1—C2 | 4.2 (4) | C21—C10—C13—C12 | 179.4 (3) |
C6—N1—C1—C2 | −173.1 (3) | C12—C13—C14—C15 | 1.2 (4) |
N1—C1—C2—C3 | 1.1 (5) | C10—C13—C14—C15 | 179.9 (3) |
C1—C2—C3—C8 | 176.1 (3) | C11—N2—C15—C14 | −1.8 (5) |
C1—C2—C3—C4 | −4.7 (4) | C22—N2—C15—C14 | −179.9 (3) |
C8—C3—C4—C5 | −177.3 (3) | C13—C14—C15—N2 | 0.4 (5) |
C2—C3—C4—C5 | 3.4 (4) | C9—C8—C16—C21 | −2.2 (3) |
C3—C4—C5—N1 | 1.5 (5) | C3—C8—C16—C21 | 176.2 (3) |
C1—N1—C5—C4 | −5.5 (4) | C9—C8—C16—C17 | 172.3 (3) |
C6—N1—C5—C4 | 171.8 (3) | C3—C8—C16—C17 | −9.2 (5) |
C1—N1—C6—C7 | 103.4 (4) | C21—C16—C17—C18 | 12.4 (4) |
C5—N1—C6—C7 | −73.9 (4) | C8—C16—C17—C18 | −161.4 (3) |
N1—C6—C7—O1 | −59.0 (4) | C16—C17—C18—C19 | −47.6 (4) |
C2—C3—C8—C9 | 172.8 (3) | C17—C18—C19—C20 | 66.3 (4) |
C4—C3—C8—C9 | −6.4 (5) | C18—C19—C20—C21 | −45.8 (4) |
C2—C3—C8—C16 | −5.4 (5) | C8—C16—C21—C10 | 2.0 (3) |
C4—C3—C8—C16 | 175.4 (3) | C17—C16—C21—C10 | −172.8 (3) |
C3—C8—C9—C10 | −177.0 (3) | C8—C16—C21—C20 | −178.6 (3) |
C16—C8—C9—C10 | 1.5 (3) | C17—C16—C21—C20 | 6.5 (5) |
C8—C9—C10—C13 | −178.9 (3) | C9—C10—C21—C16 | −1.1 (3) |
C8—C9—C10—C21 | −0.3 (3) | C13—C10—C21—C16 | 177.4 (3) |
C15—N2—C11—C12 | 1.4 (4) | C9—C10—C21—C20 | 179.6 (3) |
C22—N2—C11—C12 | 179.6 (3) | C13—C10—C21—C20 | −1.9 (5) |
N2—C11—C12—C13 | 0.3 (5) | C19—C20—C21—C16 | 10.4 (4) |
C11—C12—C13—C14 | −1.5 (4) | C19—C20—C21—C10 | −170.3 (3) |
C11—C12—C13—C10 | 179.8 (3) | C15—N2—C22—C23 | 89.5 (4) |
C9—C10—C13—C14 | 179.2 (3) | C11—N2—C22—C23 | −88.7 (4) |
C21—C10—C13—C14 | 0.9 (5) | O2—C23—C22—N2 | 70.7 (4) |
C9—C10—C13—C12 | −2.3 (5) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2O···I1i | 0.82 (4) | 2.69 (5) | 3.459 (3) | 158 (2) |
O1—H1O···I1ii | 0.76 (4) | 2.76 (5) | 3.517 (3) | 173 (5) |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x−1, −y+3/2, z+1/2. |
Experimental details
Crystal data |
Chemical formula | C23H27N2O2+·I− |
Mr | 490.37 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 9.0520 (18), 24.134 (5), 9.5330 (19) |
β (°) | 96.22 (3) |
V (Å3) | 2070.3 (7) |
Z | 4 |
Radiation type | Synchrotron, λ = 0.9204 Å |
µ (mm−1) | 3.03 |
Crystal size (mm) | 0.14 × 0.10 × 0.003 |
|
Data collection |
Diffractometer | Quantum4 CCD detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2300, 2300, 2191 |
Rint | 0.000 |
θmax (°) | 29.0 |
(sin θ/λ)max (Å−1) | 0.526 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.071, 1.06 |
No. of reflections | 2300 |
No. of parameters | 262 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.51, −0.58 |
Selected geometric parameters (Å, º) topO1—C7 | 1.412 (5) | C8—C9 | 1.412 (5) |
N1—C1 | 1.342 (4) | C8—C16 | 1.464 (4) |
N1—C6 | 1.484 (4) | C9—C10 | 1.403 (5) |
C1—C2 | 1.363 (5) | C10—C21 | 1.470 (4) |
C2—C3 | 1.420 (4) | C16—C21 | 1.364 (5) |
C3—C8 | 1.420 (4) | C17—C18 | 1.532 (5) |
| | | |
C10—C9—C8 | 109.7 (3) | C10—C21—C20 | 128.3 (3) |
| | | |
C4—C3—C8—C9 | −6.4 (5) | C3—C8—C16—C17 | −9.2 (5) |
C21—C10—C13—C14 | 0.9 (5) | C17—C16—C21—C20 | 6.5 (5) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2O···I1i | 0.82 (4) | 2.69 (5) | 3.459 (3) | 158 (2) |
O1—H1O···I1ii | 0.76 (4) | 2.76 (5) | 3.517 (3) | 173 (5) |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x−1, −y+3/2, z+1/2. |
The title compound, (I), was prepared as part of a study into the use of zwitterionic merocyanines as potential non-linear optical (NLO) chromophores (Kay et al., 2001). Initial single-crystal and powder diffraction studies using conventional X-ray sources showed that the larger crystals suffered from both twinning and different hydration states. Access to the X9B beamline at the National Synchrotron Light Source gave sufficient data with a crystallite 0.14 × 0.10 × 0.003 mm, leading to the ordered structure reported here. The crystal contained independent C23H27N2O2+ cations (Fig. 1) linked in pairs about inversion centres by hydrogen bonds (O—H···I−, Table 2). Similar hydroxyethyl O—H···I− interactions have been found in the Cambridge Structural Database (Allen, 2002) by use of Conquest (Bruno et al., 2002), in entries QIGHET, a zwitterionic cyanine dye (Lacroix et al., 2001), NUYDOA (Grobosch et al., 1998) and ABILIG (Wang et al., 2001). The pairs form a `herring-bone' pattern along the b axis, with the normals to the cation molecular planes approximately in the [101] and [101] directions.
The bond distances illustrate both self-consistency (e.g. C8—C16 and C10—C21 in Table 1) and the molecule delocalization, spreading the overall positive charge, e.g. C8—C9 = 1.412 (5) Å and C9—C13 = 1.403 (5) Å. The main molecular fragment excluding the hydoxyethyl and atoms C1/C2/C17/C18/C19 is approximately planar, with an r.m.s. displacement of 0.023 (3) Å. The two pyridine rings are subtly different, with their mean planes inclined at 5.6 (2) and 1.5 (2)° (for the C3 and C13 rings, respectively) to the planar central five-membered ring (atoms C8/C9/C10/C21/C16). Likewise, there is a small difference in the dihedral angles within the hydroxyethyl groups, with N—C—C—O(H) values of 70.7 (4) and −59.1 (4)°. Such deviations are consistent with the observed intermoleculer hydrogen bonding.