The preparation and structural characterization of the diazo-diphenanthroline compound, (E)-6,6′-(diazene-1,2-diyl)bis(1,10-phenanthrolin-5-ol) are described. The fully conjugated bis-phenanthroline molecule is expected to offer exciting new physical and chemical properties, and should form the basis of novel metal coordination complexes as a consequence of the dual N,N′-1,10-phenanthroline chelating moieties situated on the opposite ends of the molecule.
Supporting information
CCDC reference: 1937969
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean
(C-C) = 0.004 Å
- R factor = 0.044
- wR factor = 0.111
- Data-to-parameter ratio = 14.8
checkCIF/PLATON results
No syntax errors found
Alert level C
HYDTR01_ALERT_1_C The hydrogen treatment should only be one of the following
keywords
* refall
* refxyz
* refU
* noref
* undef
* constr
* none
* mixed
Hydrogen treatment given as heteroxyz
PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors of C21 Check
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L= 0.600 2 Report
Alert level G
PLAT333_ALERT_2_G Large Aver C6-Ring C-C Dist C4 -C12 . 1.43 Ang.
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min). 2 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 5 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ... 2 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density. 7 Info
0 ALERT level A = Most likely a serious problem - resolve or explain
0 ALERT level B = A potentially serious problem, consider carefully
3 ALERT level C = Check. Ensure it is not caused by an omission or oversight
5 ALERT level G = General information/check it is not something unexpected
1 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: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXT (Sheldrick 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).
(
E)-6,6'-(Diazene-1,2-diyl)bis(1,10-phenanthrolin-5-ol)
trichloromethane disolvate
top
Crystal data top
C24H14N6O2·2CHCl3 | F(000) = 664 |
Mr = 657.15 | Dx = 1.604 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 5.9406 (7) Å | Cell parameters from 5155 reflections |
b = 18.856 (2) Å | θ = 2.7–26.1° |
c = 12.2375 (16) Å | µ = 0.67 mm−1 |
β = 96.863 (4)° | T = 150 K |
V = 1361.0 (3) Å3 | Lath, purple |
Z = 2 | 0.43 × 0.05 × 0.04 mm |
Data collection top
Bruker–Nonius X8 APEXII CCD diffractometer | 2732 independent reflections |
Radiation source: fine-focus sealed-tube | 2068 reflections with I > 2σ(I) |
Detector resolution: 9.1 pixels mm-1 | Rint = 0.045 |
thin–slice ω and φ scans | θmax = 26.2°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2012) | h = −5→7 |
Tmin = 0.657, Tmax = 0.745 | k = −23→23 |
18529 measured reflections | l = −15→14 |
Refinement top
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.044 | Hydrogen site location: mixed |
wR(F2) = 0.111 | Heteroxyz |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0444P)2 + 1.8407P] where P = (Fo2 + 2Fc2)/3 |
2732 reflections | (Δ/σ)max = 0.001 |
184 parameters | Δρmax = 0.87 e Å−3 |
0 restraints | Δρmin = −0.59 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.3174 (4) | 0.63628 (11) | 0.66898 (18) | 0.0216 (5) | |
C1 | 0.3648 (5) | 0.69741 (14) | 0.6234 (2) | 0.0240 (6) | |
H1 | 0.269904 | 0.736919 | 0.632910 | 0.029* | |
C2 | 0.5456 (5) | 0.70706 (14) | 0.5623 (2) | 0.0255 (6) | |
H2 | 0.572645 | 0.752054 | 0.531450 | 0.031* | |
C3 | 0.6846 (4) | 0.65044 (14) | 0.5473 (2) | 0.0219 (6) | |
H3 | 0.810516 | 0.656051 | 0.507047 | 0.026* | |
C4 | 0.6383 (4) | 0.58421 (13) | 0.5923 (2) | 0.0174 (5) | |
C5 | 0.7702 (4) | 0.52078 (13) | 0.5757 (2) | 0.0177 (5) | |
N2 | 0.9396 (3) | 0.52817 (11) | 0.50912 (17) | 0.0195 (5) | |
C6 | 0.7175 (4) | 0.45623 (14) | 0.6231 (2) | 0.0195 (5) | |
O1 | 0.8303 (3) | 0.39726 (10) | 0.61010 (16) | 0.0246 (4) | |
H1A | 0.937 (6) | 0.4088 (17) | 0.569 (3) | 0.037* | |
C7 | 0.5313 (4) | 0.45226 (13) | 0.6889 (2) | 0.0191 (5) | |
C8 | 0.4726 (5) | 0.38783 (14) | 0.7366 (2) | 0.0239 (6) | |
H8 | 0.554738 | 0.345644 | 0.726050 | 0.029* | |
C9 | 0.2948 (5) | 0.38714 (15) | 0.7985 (2) | 0.0274 (6) | |
H9 | 0.251833 | 0.344474 | 0.831710 | 0.033* | |
C10 | 0.1781 (5) | 0.45015 (15) | 0.8118 (2) | 0.0253 (6) | |
H10 | 0.057433 | 0.449191 | 0.856178 | 0.030* | |
N3 | 0.2257 (4) | 0.51143 (12) | 0.76615 (18) | 0.0224 (5) | |
C11 | 0.4006 (4) | 0.51294 (13) | 0.7050 (2) | 0.0182 (5) | |
C12 | 0.4522 (4) | 0.58002 (13) | 0.6541 (2) | 0.0185 (5) | |
C21 | 0.0382 (5) | 0.64497 (15) | 0.8784 (2) | 0.0271 (6) | |
H21 | 0.087592 | 0.621547 | 0.811921 | 0.032* | |
Cl1 | −0.23375 (13) | 0.61485 (6) | 0.89683 (7) | 0.0493 (3) | |
Cl2 | 0.03861 (18) | 0.73803 (4) | 0.85952 (7) | 0.0508 (3) | |
Cl3 | 0.23081 (12) | 0.62261 (4) | 0.99506 (6) | 0.0333 (2) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0234 (11) | 0.0211 (12) | 0.0208 (12) | 0.0047 (9) | 0.0050 (9) | −0.0007 (9) |
C1 | 0.0290 (14) | 0.0208 (15) | 0.0229 (14) | 0.0070 (11) | 0.0065 (11) | −0.0003 (11) |
C2 | 0.0330 (15) | 0.0159 (13) | 0.0279 (15) | 0.0000 (11) | 0.0054 (12) | 0.0012 (11) |
C3 | 0.0231 (13) | 0.0216 (14) | 0.0219 (14) | −0.0011 (11) | 0.0064 (11) | −0.0016 (11) |
C4 | 0.0192 (13) | 0.0169 (13) | 0.0160 (12) | 0.0001 (10) | 0.0008 (10) | −0.0016 (10) |
C5 | 0.0158 (12) | 0.0196 (13) | 0.0169 (13) | 0.0011 (10) | −0.0011 (10) | −0.0021 (10) |
N2 | 0.0180 (11) | 0.0213 (11) | 0.0193 (11) | 0.0023 (8) | 0.0020 (9) | −0.0036 (9) |
C6 | 0.0192 (13) | 0.0203 (14) | 0.0180 (13) | 0.0023 (10) | −0.0011 (10) | −0.0020 (10) |
O1 | 0.0258 (10) | 0.0197 (10) | 0.0293 (11) | 0.0053 (8) | 0.0072 (8) | 0.0007 (8) |
C7 | 0.0212 (13) | 0.0203 (13) | 0.0151 (13) | 0.0003 (10) | −0.0007 (10) | 0.0007 (10) |
C8 | 0.0277 (14) | 0.0199 (14) | 0.0236 (14) | 0.0023 (11) | 0.0004 (11) | 0.0027 (11) |
C9 | 0.0319 (15) | 0.0274 (15) | 0.0230 (14) | −0.0046 (12) | 0.0036 (12) | 0.0063 (12) |
C10 | 0.0244 (14) | 0.0290 (15) | 0.0236 (14) | −0.0027 (11) | 0.0077 (11) | 0.0032 (12) |
N3 | 0.0235 (11) | 0.0250 (12) | 0.0190 (11) | −0.0009 (9) | 0.0039 (9) | 0.0005 (9) |
C11 | 0.0207 (13) | 0.0198 (13) | 0.0141 (12) | 0.0010 (10) | 0.0016 (10) | −0.0020 (10) |
C12 | 0.0199 (13) | 0.0196 (13) | 0.0156 (13) | 0.0008 (10) | 0.0008 (10) | −0.0015 (10) |
C21 | 0.0290 (15) | 0.0290 (16) | 0.0242 (15) | 0.0014 (12) | 0.0077 (12) | −0.0021 (12) |
Cl1 | 0.0258 (4) | 0.0875 (7) | 0.0346 (5) | −0.0121 (4) | 0.0037 (3) | −0.0095 (4) |
Cl2 | 0.0818 (7) | 0.0295 (4) | 0.0438 (5) | 0.0156 (4) | 0.0196 (5) | 0.0009 (4) |
Cl3 | 0.0273 (4) | 0.0379 (4) | 0.0339 (4) | −0.0051 (3) | 0.0008 (3) | 0.0002 (3) |
Geometric parameters (Å, º) top
N1—C1 | 1.326 (3) | O1—H1A | 0.88 (3) |
N1—C12 | 1.355 (3) | C7—C11 | 1.409 (4) |
C1—C2 | 1.392 (4) | C7—C8 | 1.409 (4) |
C1—H1 | 0.9500 | C8—C9 | 1.371 (4) |
C2—C3 | 1.375 (4) | C8—H8 | 0.9500 |
C2—H2 | 0.9500 | C9—C10 | 1.395 (4) |
C3—C4 | 1.405 (4) | C9—H9 | 0.9500 |
C3—H3 | 0.9500 | C10—N3 | 1.328 (3) |
C4—C12 | 1.414 (3) | C10—H10 | 0.9500 |
C4—C5 | 1.457 (3) | N3—C11 | 1.352 (3) |
C5—N2 | 1.376 (3) | C11—C12 | 1.459 (4) |
C5—C6 | 1.400 (4) | C21—Cl1 | 1.752 (3) |
N2—N2i | 1.316 (4) | C21—Cl2 | 1.770 (3) |
C6—O1 | 1.318 (3) | C21—Cl3 | 1.771 (3) |
C6—C7 | 1.446 (4) | C21—H21 | 1.0000 |
| | | |
C1—N1—C12 | 117.7 (2) | C8—C7—C6 | 121.2 (2) |
N1—C1—C2 | 123.8 (2) | C9—C8—C7 | 118.8 (2) |
N1—C1—H1 | 118.1 | C9—C8—H8 | 120.6 |
C2—C1—H1 | 118.1 | C7—C8—H8 | 120.6 |
C3—C2—C1 | 118.9 (3) | C8—C9—C10 | 118.9 (3) |
C3—C2—H2 | 120.5 | C8—C9—H9 | 120.6 |
C1—C2—H2 | 120.5 | C10—C9—H9 | 120.6 |
C2—C3—C4 | 119.3 (2) | N3—C10—C9 | 123.9 (2) |
C2—C3—H3 | 120.3 | N3—C10—H10 | 118.0 |
C4—C3—H3 | 120.3 | C9—C10—H10 | 118.0 |
C3—C4—C12 | 117.4 (2) | C10—N3—C11 | 117.9 (2) |
C3—C4—C5 | 122.8 (2) | N3—C11—C7 | 122.2 (2) |
C12—C4—C5 | 119.8 (2) | N3—C11—C12 | 118.0 (2) |
N2—C5—C6 | 123.3 (2) | C7—C11—C12 | 119.8 (2) |
N2—C5—C4 | 116.3 (2) | N1—C12—C4 | 122.7 (2) |
C6—C5—C4 | 120.4 (2) | N1—C12—C11 | 117.6 (2) |
N2i—N2—C5 | 118.1 (3) | C4—C12—C11 | 119.6 (2) |
O1—C6—C5 | 122.8 (2) | Cl1—C21—Cl2 | 110.73 (16) |
O1—C6—C7 | 117.2 (2) | Cl1—C21—Cl3 | 109.64 (15) |
C5—C6—C7 | 120.0 (2) | Cl2—C21—Cl3 | 109.29 (16) |
C6—O1—H1A | 106 (2) | Cl1—C21—H21 | 109.1 |
C11—C7—C8 | 118.3 (2) | Cl2—C21—H21 | 109.1 |
C11—C7—C6 | 120.4 (2) | Cl3—C21—H21 | 109.1 |
Symmetry code: (i) −x+2, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···N2i | 0.88 (3) | 1.74 (3) | 2.540 (3) | 149 (3) |
C21—H21···N1 | 1.00 | 2.36 | 3.219 (3) | 143 |
C21—H21···N3 | 1.00 | 2.33 | 3.136 (4) | 137 |
Symmetry code: (i) −x+2, −y+1, −z+1. |