Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807032813/rz2150sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807032813/rz2150Isup2.hkl |
CCDC reference: 657701
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.005 Å
- Disorder in main residue
- R factor = 0.053
- wR factor = 0.159
- Data-to-parameter ratio = 13.5
checkCIF/PLATON results
No syntax errors found Datablock: I
Alert level C PLAT220_ALERT_2_C Large Non-Solvent O Ueq(max)/Ueq(min) ... 2.56 Ratio PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O8 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O10 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C6 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for P2 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C9 PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 3.66 PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.28 PLAT301_ALERT_3_C Main Residue Disorder ......................... 5.00 Perc. PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 5 PLAT415_ALERT_2_C Short Inter D-H..H-X H7B .. H13A .. 2.12 Ang.
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 38
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 11 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 9 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The title salt was prepared by mixing ethanol solutions of 1-oxo-2,6,7-trioxa-1-phospha-bicyclo[2.2.2]octane-4-carboxylic acid (1.94 g in 10 ml) and 1,10-phenanthroline (1.8 g in 10 ml). The solution was stirred at room temperature for 10 min, after which the crystalline product was separated by filtration. The pure product (1.0 g) was heated and dissolved in water (25 ml). Single crystals suitable for X-ray analysis were obtained from this aqueous solution by slow evaporation of the solvent over a period of five days at room temperature.
All H atoms were included in the refinement in the riding model approximation, with N–H = 0.90 Å, C–H = 0.93–0.97 Å, and Uiso(H) = 1.2 Ueq(C, N).
Caged bicyclic phosphates are widely used as flame retardants in some polymers. As a low-toxicity and environmentally friendly flame retardant system, the phosphorus-nitrogen combination has been extensively studied. We report here the crystal structure of a new bicyclic phosphate cage compound.
The content of the asymmetric unit of the title salt is shown in Fig. 1. In the 1,10-phenanthrolinium cation, the C—N—C bond angle of 123.0 (3)° at the protonated N1 atom is significantly larger than that at the non-protonated N2 atom (116.4 (3)°). This widening is not unexpected, as analogous differences were already observed in previously reported monoprotonated phenanthrolines (Hensen et al., 1998, 2000; Guo, 2005). In the anion, the oxygen atoms O11 and O12 of the carboxylate group are positionally disordered over two position, with site occupation factors of 0.701 (15) and 0.299 (15) for the major and minor components respectively. In the crystal structure, ions and neutral molecules are linked into an extended three-dimensional network by O—H···O and N—H···O hydrogen bonding interactions (Table 1, Fig. 2).
For related literature, see: Guo (2005); Hensen et al. (1998, 2000).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C12H9N2+·C5H6O6P−·C5H7O6P·H2O | F(000) = 1216 |
Mr = 586.37 | Dx = 1.594 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2791 reflections |
a = 9.2841 (18) Å | θ = 2.5–26.3° |
b = 8.5863 (16) Å | µ = 0.25 mm−1 |
c = 31.124 (6) Å | T = 294 K |
β = 99.917 (5)° | Prism, colorless |
V = 2444.0 (8) Å3 | 0.20 × 0.16 × 0.12 mm |
Z = 4 |
Bruker SMART CCD area detector diffractometer | 5008 independent reflections |
Radiation source: fine-focus sealed tube | 2956 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
φ and ω scans | θmax = 26.4°, θmin = 1.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −11→8 |
Tmin = 0.948, Tmax = 0.972 | k = −10→10 |
13684 measured reflections | l = −38→36 |
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) = 0.159 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0773P)2 + 0.655P] where P = (Fo2 + 2Fc2)/3 |
5008 reflections | (Δ/σ)max = 0.001 |
371 parameters | Δρmax = 0.35 e Å−3 |
38 restraints | Δρmin = −0.32 e Å−3 |
C12H9N2+·C5H6O6P−·C5H7O6P·H2O | V = 2444.0 (8) Å3 |
Mr = 586.37 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.2841 (18) Å | µ = 0.25 mm−1 |
b = 8.5863 (16) Å | T = 294 K |
c = 31.124 (6) Å | 0.20 × 0.16 × 0.12 mm |
β = 99.917 (5)° |
Bruker SMART CCD area detector diffractometer | 5008 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2956 reflections with I > 2σ(I) |
Tmin = 0.948, Tmax = 0.972 | Rint = 0.043 |
13684 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 38 restraints |
wR(F2) = 0.159 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.35 e Å−3 |
5008 reflections | Δρmin = −0.32 e Å−3 |
371 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
P1 | 1.15068 (9) | 0.02050 (10) | 0.95898 (3) | 0.0336 (2) | |
O1 | 1.2593 (2) | 0.0302 (3) | 0.99848 (7) | 0.0451 (6) | |
O2 | 1.2147 (2) | 0.0221 (3) | 0.91570 (7) | 0.0514 (7) | |
O3 | 1.0366 (2) | 0.1551 (3) | 0.95336 (7) | 0.0440 (6) | |
O4 | 1.0576 (2) | −0.1324 (3) | 0.95573 (7) | 0.0460 (6) | |
O5 | 0.8678 (3) | −0.0305 (3) | 0.81115 (7) | 0.0533 (7) | |
O6 | 0.7046 (2) | −0.0035 (3) | 0.85531 (7) | 0.0554 (7) | |
H6C | 0.6335 | −0.0100 | 0.8339 | 0.066* | |
C1 | 1.1025 (4) | 0.0206 (5) | 0.87599 (10) | 0.0477 (9) | |
H1A | 1.1220 | −0.0637 | 0.8571 | 0.057* | |
H1B | 1.1055 | 0.1178 | 0.8603 | 0.057* | |
C2 | 0.9191 (3) | 0.1378 (4) | 0.91576 (10) | 0.0387 (8) | |
H2A | 0.9109 | 0.2321 | 0.8983 | 0.046* | |
H2B | 0.8268 | 0.1210 | 0.9256 | 0.046* | |
C3 | 0.9521 (4) | −0.1485 (4) | 0.91557 (10) | 0.0426 (8) | |
H3A | 0.8552 | −0.1652 | 0.9224 | 0.051* | |
H3B | 0.9772 | −0.2377 | 0.8992 | 0.051* | |
C4 | 0.9527 (3) | −0.0008 (3) | 0.88813 (9) | 0.0308 (7) | |
C5 | 0.8348 (4) | −0.0131 (4) | 0.84658 (10) | 0.0370 (8) | |
P2 | 0.91080 (11) | 0.49646 (13) | 0.82372 (3) | 0.0523 (3) | |
O7 | 1.0150 (3) | 0.4764 (4) | 0.86362 (9) | 0.0841 (10) | |
O8 | 0.8420 (4) | 0.3432 (3) | 0.80474 (10) | 0.0960 (11) | |
O9 | 0.7750 (3) | 0.5977 (4) | 0.82963 (7) | 0.0649 (8) | |
O10 | 0.9709 (3) | 0.5822 (4) | 0.78669 (8) | 0.0795 (10) | |
C6 | 0.7333 (5) | 0.3608 (5) | 0.76470 (14) | 0.0862 (13) | |
H6A | 0.6396 | 0.3205 | 0.7694 | 0.103* | |
H6B | 0.7638 | 0.3021 | 0.7412 | 0.103* | |
C7 | 0.6693 (4) | 0.6187 (5) | 0.78974 (10) | 0.0575 (10) | |
H7A | 0.6594 | 0.7287 | 0.7828 | 0.069* | |
H7B | 0.5747 | 0.5798 | 0.7940 | 0.069* | |
C8 | 0.8643 (4) | 0.5989 (6) | 0.74632 (11) | 0.0712 (12) | |
H8A | 0.8993 | 0.5447 | 0.7228 | 0.085* | |
H8B | 0.8530 | 0.7081 | 0.7386 | 0.085* | |
C9 | 0.7185 (4) | 0.5323 (4) | 0.75239 (10) | 0.0440 (8) | |
C10 | 0.6033 (4) | 0.5554 (5) | 0.71121 (11) | 0.0549 (10) | |
O11 | 0.5054 (7) | 0.4583 (8) | 0.7037 (2) | 0.0620 (19) | 0.701 (15) |
O12 | 0.6099 (9) | 0.6825 (11) | 0.6909 (3) | 0.123 (4) | 0.701 (15) |
O11' | 0.4766 (12) | 0.5159 (19) | 0.7151 (4) | 0.048 (3) | 0.299 (15) |
O12' | 0.6430 (10) | 0.553 (3) | 0.6759 (3) | 0.075 (7) | 0.299 (15) |
N1 | 0.5028 (3) | 0.8006 (3) | 0.96061 (8) | 0.0342 (6) | |
H1 | 0.5655 | 0.8589 | 0.9790 | 0.041* | |
N2 | 0.5012 (3) | 0.7655 (3) | 1.04740 (8) | 0.0381 (7) | |
C11 | 0.5104 (4) | 0.8262 (4) | 0.91909 (10) | 0.0386 (8) | |
H11 | 0.5743 | 0.9009 | 0.9116 | 0.046* | |
C12 | 0.4235 (4) | 0.7417 (4) | 0.88690 (10) | 0.0422 (8) | |
H12 | 0.4296 | 0.7583 | 0.8577 | 0.051* | |
C13 | 0.3281 (4) | 0.6333 (4) | 0.89802 (10) | 0.0399 (8) | |
H13 | 0.2697 | 0.5762 | 0.8763 | 0.048* | |
C14 | 0.3182 (3) | 0.6079 (4) | 0.94211 (9) | 0.0339 (7) | |
C15 | 0.2217 (4) | 0.4975 (4) | 0.95668 (11) | 0.0402 (8) | |
H15 | 0.1603 | 0.4379 | 0.9363 | 0.048* | |
C16 | 0.2182 (4) | 0.4786 (4) | 0.99920 (11) | 0.0405 (8) | |
H16 | 0.1543 | 0.4060 | 1.0078 | 0.049* | |
C17 | 0.3105 (3) | 0.5678 (4) | 1.03176 (10) | 0.0345 (7) | |
C18 | 0.3133 (4) | 0.5502 (4) | 1.07702 (11) | 0.0410 (8) | |
H18 | 0.2517 | 0.4791 | 1.0873 | 0.049* | |
C19 | 0.4072 (4) | 0.6385 (4) | 1.10530 (10) | 0.0450 (9) | |
H19 | 0.4103 | 0.6283 | 1.1352 | 0.054* | |
C20 | 0.4988 (4) | 0.7445 (4) | 1.08938 (10) | 0.0437 (8) | |
H20 | 0.5617 | 0.8039 | 1.1094 | 0.052* | |
C21 | 0.4079 (3) | 0.6769 (3) | 1.01926 (9) | 0.0316 (7) | |
C22 | 0.4103 (3) | 0.6958 (3) | 0.97354 (9) | 0.0307 (7) | |
O13 | 0.3103 (4) | 0.5046 (4) | 0.79112 (13) | 0.1197 (14) | |
H13A | 0.3580 | 0.5070 | 0.7702 | 0.144* | |
H13B | 0.2572 | 0.4255 | 0.7859 | 0.144* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0254 (4) | 0.0425 (5) | 0.0304 (4) | −0.0021 (4) | −0.0018 (3) | −0.0021 (4) |
O1 | 0.0347 (13) | 0.0596 (15) | 0.0368 (13) | −0.0045 (11) | −0.0062 (10) | −0.0028 (11) |
O2 | 0.0258 (12) | 0.0915 (19) | 0.0353 (13) | −0.0075 (13) | 0.0008 (10) | −0.0068 (12) |
O3 | 0.0435 (13) | 0.0436 (13) | 0.0386 (13) | 0.0066 (11) | −0.0103 (11) | −0.0131 (10) |
O4 | 0.0449 (13) | 0.0411 (13) | 0.0435 (13) | −0.0065 (11) | −0.0160 (11) | 0.0080 (10) |
O5 | 0.0522 (16) | 0.0778 (18) | 0.0279 (13) | −0.0068 (14) | 0.0014 (11) | −0.0081 (12) |
O6 | 0.0284 (13) | 0.096 (2) | 0.0361 (13) | −0.0018 (13) | −0.0098 (10) | −0.0016 (12) |
C1 | 0.0307 (18) | 0.079 (3) | 0.0318 (18) | −0.0028 (18) | 0.0019 (14) | −0.0056 (17) |
C2 | 0.0358 (18) | 0.0419 (19) | 0.0338 (17) | 0.0050 (16) | −0.0065 (14) | 0.0004 (14) |
C3 | 0.0415 (19) | 0.0357 (18) | 0.0437 (19) | −0.0049 (16) | −0.0126 (16) | −0.0013 (15) |
C4 | 0.0280 (16) | 0.0373 (17) | 0.0253 (14) | 0.0001 (14) | −0.0009 (13) | −0.0020 (13) |
C5 | 0.0346 (19) | 0.0387 (19) | 0.0347 (18) | −0.0041 (15) | −0.0020 (15) | 0.0002 (14) |
P2 | 0.0441 (6) | 0.0700 (7) | 0.0351 (5) | −0.0119 (5) | −0.0156 (4) | 0.0103 (5) |
O7 | 0.0680 (19) | 0.121 (3) | 0.0496 (17) | −0.0271 (19) | −0.0275 (15) | 0.0276 (16) |
O8 | 0.114 (2) | 0.0543 (17) | 0.091 (2) | 0.0021 (17) | −0.0649 (19) | 0.0064 (15) |
O9 | 0.0637 (18) | 0.098 (2) | 0.0291 (13) | −0.0002 (17) | −0.0041 (12) | −0.0061 (13) |
O10 | 0.0362 (15) | 0.152 (3) | 0.0465 (15) | −0.0141 (18) | −0.0035 (12) | 0.0238 (17) |
C6 | 0.097 (3) | 0.062 (2) | 0.078 (2) | 0.005 (2) | −0.049 (2) | −0.005 (2) |
C7 | 0.049 (2) | 0.080 (3) | 0.0385 (19) | 0.008 (2) | −0.0056 (17) | 0.0008 (18) |
C8 | 0.044 (2) | 0.132 (3) | 0.0354 (19) | 0.002 (2) | −0.0004 (17) | 0.020 (2) |
C9 | 0.0395 (16) | 0.0621 (18) | 0.0262 (14) | 0.0012 (15) | −0.0059 (13) | 0.0023 (14) |
C10 | 0.047 (2) | 0.082 (3) | 0.0306 (19) | 0.003 (2) | −0.0077 (17) | 0.0063 (19) |
O11 | 0.057 (3) | 0.054 (3) | 0.061 (4) | −0.004 (3) | −0.029 (3) | −0.002 (3) |
O12 | 0.142 (6) | 0.109 (6) | 0.086 (5) | −0.055 (5) | −0.069 (4) | 0.050 (5) |
O11' | 0.039 (5) | 0.058 (6) | 0.043 (5) | −0.005 (4) | −0.003 (3) | −0.008 (4) |
O12' | 0.034 (5) | 0.167 (19) | 0.023 (5) | −0.007 (7) | 0.004 (4) | 0.017 (6) |
N1 | 0.0300 (14) | 0.0383 (15) | 0.0320 (14) | −0.0016 (12) | −0.0013 (11) | −0.0033 (12) |
N2 | 0.0384 (16) | 0.0431 (16) | 0.0301 (14) | −0.0013 (13) | −0.0012 (12) | −0.0031 (12) |
C11 | 0.0359 (18) | 0.0440 (19) | 0.0356 (18) | −0.0008 (16) | 0.0054 (15) | 0.0050 (15) |
C12 | 0.041 (2) | 0.054 (2) | 0.0303 (17) | 0.0072 (18) | 0.0030 (15) | 0.0022 (15) |
C13 | 0.0374 (18) | 0.046 (2) | 0.0321 (17) | 0.0033 (16) | −0.0059 (15) | −0.0053 (14) |
C14 | 0.0286 (16) | 0.0368 (18) | 0.0338 (17) | 0.0035 (15) | −0.0022 (14) | −0.0037 (14) |
C15 | 0.0321 (18) | 0.0385 (19) | 0.0459 (19) | −0.0049 (15) | −0.0049 (15) | −0.0050 (15) |
C16 | 0.0355 (19) | 0.0371 (19) | 0.048 (2) | −0.0038 (15) | 0.0040 (16) | 0.0040 (15) |
C17 | 0.0321 (17) | 0.0329 (17) | 0.0376 (18) | 0.0078 (14) | 0.0038 (14) | 0.0015 (14) |
C18 | 0.044 (2) | 0.0394 (19) | 0.0413 (19) | 0.0061 (16) | 0.0128 (16) | 0.0061 (15) |
C19 | 0.050 (2) | 0.054 (2) | 0.0322 (18) | 0.0080 (19) | 0.0088 (16) | 0.0034 (16) |
C20 | 0.042 (2) | 0.051 (2) | 0.0351 (19) | 0.0040 (17) | −0.0004 (16) | −0.0075 (16) |
C21 | 0.0294 (16) | 0.0341 (17) | 0.0296 (16) | 0.0061 (14) | 0.0003 (13) | −0.0016 (13) |
C22 | 0.0267 (15) | 0.0322 (16) | 0.0312 (16) | 0.0027 (14) | −0.0011 (13) | 0.0002 (13) |
O13 | 0.093 (3) | 0.120 (3) | 0.149 (4) | −0.018 (2) | 0.029 (3) | −0.022 (2) |
P1—O1 | 1.452 (2) | C8—H8A | 0.9700 |
P1—O3 | 1.557 (2) | C8—H8B | 0.9700 |
P1—O2 | 1.563 (2) | C9—C10 | 1.535 (4) |
P1—O4 | 1.565 (2) | C10—O12' | 1.218 (8) |
O2—C1 | 1.473 (4) | C10—O11 | 1.225 (6) |
O3—C2 | 1.463 (3) | C10—O11' | 1.250 (11) |
O4—C3 | 1.455 (3) | C10—O12 | 1.268 (6) |
O5—C5 | 1.204 (4) | N1—C11 | 1.325 (4) |
O6—C5 | 1.286 (4) | N1—C22 | 1.352 (4) |
O6—H6C | 0.8548 | N1—H1 | 0.8964 |
C1—C4 | 1.513 (4) | N2—C20 | 1.323 (4) |
C1—H1A | 0.9700 | N2—C21 | 1.354 (4) |
C1—H1B | 0.9700 | C11—C12 | 1.379 (4) |
C2—C4 | 1.532 (4) | C11—H11 | 0.9300 |
C2—H2A | 0.9700 | C12—C13 | 1.369 (5) |
C2—H2B | 0.9700 | C12—H12 | 0.9300 |
C3—C4 | 1.529 (4) | C13—C14 | 1.408 (4) |
C3—H3A | 0.9700 | C13—H13 | 0.9300 |
C3—H3B | 0.9700 | C14—C22 | 1.404 (4) |
C4—C5 | 1.547 (4) | C14—C15 | 1.430 (4) |
P2—O7 | 1.447 (3) | C15—C16 | 1.339 (5) |
P2—O8 | 1.536 (3) | C15—H15 | 0.9300 |
P2—O10 | 1.550 (3) | C16—C17 | 1.431 (4) |
P2—O9 | 1.568 (3) | C16—H16 | 0.9300 |
O8—C6 | 1.470 (4) | C17—C21 | 1.403 (4) |
O9—C7 | 1.455 (4) | C17—C18 | 1.413 (4) |
O10—C8 | 1.467 (4) | C18—C19 | 1.359 (5) |
C6—C9 | 1.522 (5) | C18—H18 | 0.9300 |
C6—H6A | 0.9700 | C19—C20 | 1.393 (5) |
C6—H6B | 0.9700 | C19—H19 | 0.9300 |
C7—C9 | 1.514 (5) | C20—H20 | 0.9300 |
C7—H7A | 0.9700 | C21—C22 | 1.436 (4) |
C7—H7B | 0.9700 | O13—H13A | 0.8488 |
C8—C9 | 1.511 (5) | O13—H13B | 0.8393 |
O1—P1—O3 | 114.37 (13) | C9—C8—H8A | 109.7 |
O1—P1—O2 | 114.69 (14) | O10—C8—H8B | 109.7 |
O3—P1—O2 | 104.42 (13) | C9—C8—H8B | 109.7 |
O1—P1—O4 | 113.44 (13) | H8A—C8—H8B | 108.2 |
O3—P1—O4 | 104.95 (13) | C8—C9—C7 | 107.8 (3) |
O2—P1—O4 | 103.81 (13) | C8—C9—C6 | 110.7 (4) |
C1—O2—P1 | 113.86 (19) | C7—C9—C6 | 107.9 (3) |
C2—O3—P1 | 114.43 (18) | C8—C9—C10 | 110.9 (3) |
C3—O4—P1 | 114.66 (18) | C7—C9—C10 | 108.6 (3) |
C5—O6—H6C | 117.4 | C6—C9—C10 | 110.8 (3) |
O2—C1—C4 | 109.8 (2) | O12'—C10—O11 | 98.3 (8) |
O2—C1—H1A | 109.7 | O12'—C10—O11' | 121.3 (8) |
C4—C1—H1A | 109.7 | O12'—C10—O12 | 61.1 (7) |
O2—C1—H1B | 109.7 | O11—C10—O12 | 126.0 (4) |
C4—C1—H1B | 109.7 | O11'—C10—O12 | 114.1 (7) |
H1A—C1—H1B | 108.2 | O12'—C10—C9 | 118.4 (5) |
O3—C2—C4 | 109.4 (2) | O11—C10—C9 | 117.4 (4) |
O3—C2—H2A | 109.8 | O11'—C10—C9 | 114.6 (6) |
C4—C2—H2A | 109.8 | O12—C10—C9 | 116.1 (4) |
O3—C2—H2B | 109.8 | C11—N1—C22 | 123.0 (3) |
C4—C2—H2B | 109.8 | C11—N1—H1 | 113.2 |
H2A—C2—H2B | 108.2 | C22—N1—H1 | 123.8 |
O4—C3—C4 | 109.5 (2) | C20—N2—C21 | 116.4 (3) |
O4—C3—H3A | 109.8 | N1—C11—C12 | 119.9 (3) |
C4—C3—H3A | 109.8 | N1—C11—H11 | 120.0 |
O4—C3—H3B | 109.8 | C12—C11—H11 | 120.0 |
C4—C3—H3B | 109.8 | C13—C12—C11 | 119.8 (3) |
H3A—C3—H3B | 108.2 | C13—C12—H12 | 120.1 |
C1—C4—C3 | 109.4 (3) | C11—C12—H12 | 120.1 |
C1—C4—C2 | 109.3 (3) | C12—C13—C14 | 120.4 (3) |
C3—C4—C2 | 108.1 (3) | C12—C13—H13 | 119.8 |
C1—C4—C5 | 110.4 (2) | C14—C13—H13 | 119.8 |
C3—C4—C5 | 109.9 (2) | C22—C14—C13 | 117.5 (3) |
C2—C4—C5 | 109.8 (2) | C22—C14—C15 | 118.4 (3) |
O5—C5—O6 | 126.8 (3) | C13—C14—C15 | 124.2 (3) |
O5—C5—C4 | 121.3 (3) | C16—C15—C14 | 121.1 (3) |
O6—C5—C4 | 112.0 (3) | C16—C15—H15 | 119.4 |
O7—P2—O8 | 113.61 (17) | C14—C15—H15 | 119.4 |
O7—P2—O10 | 114.93 (16) | C15—C16—C17 | 121.4 (3) |
O8—P2—O10 | 107.47 (19) | C15—C16—H16 | 119.3 |
O7—P2—O9 | 113.40 (18) | C17—C16—H16 | 119.3 |
O8—P2—O9 | 103.32 (18) | C21—C17—C18 | 116.5 (3) |
O10—P2—O9 | 102.94 (17) | C21—C17—C16 | 119.8 (3) |
C6—O8—P2 | 114.7 (2) | C18—C17—C16 | 123.7 (3) |
C7—O9—P2 | 114.0 (2) | C19—C18—C17 | 119.1 (3) |
C8—O10—P2 | 114.0 (2) | C19—C18—H18 | 120.5 |
O8—C6—C9 | 109.4 (3) | C17—C18—H18 | 120.5 |
O8—C6—H6A | 109.8 | C18—C19—C20 | 119.8 (3) |
C9—C6—H6A | 109.8 | C18—C19—H19 | 120.1 |
O8—C6—H6B | 109.8 | C20—C19—H19 | 120.1 |
C9—C6—H6B | 109.8 | N2—C20—C19 | 123.7 (3) |
H6A—C6—H6B | 108.2 | N2—C20—H20 | 118.1 |
O9—C7—C9 | 110.2 (3) | C19—C20—H20 | 118.1 |
O9—C7—H7A | 109.6 | N2—C21—C17 | 124.5 (3) |
C9—C7—H7A | 109.6 | N2—C21—C22 | 117.4 (3) |
O9—C7—H7B | 109.6 | C17—C21—C22 | 118.1 (3) |
C9—C7—H7B | 109.6 | N1—C22—C14 | 119.5 (3) |
H7A—C7—H7B | 108.1 | N1—C22—C21 | 119.3 (3) |
O10—C8—C9 | 110.0 (3) | C14—C22—C21 | 121.2 (3) |
O10—C8—H8A | 109.7 | H13A—O13—H13B | 103.8 |
O1—P1—O2—C1 | −176.9 (2) | O8—C6—C9—C7 | −60.0 (5) |
O3—P1—O2—C1 | −51.0 (3) | O8—C6—C9—C10 | −178.8 (4) |
O4—P1—O2—C1 | 58.7 (3) | C8—C9—C10—O12' | 32.4 (13) |
O1—P1—O3—C2 | −174.5 (2) | C7—C9—C10—O12' | 150.7 (13) |
O2—P1—O3—C2 | 59.3 (2) | C6—C9—C10—O12' | −91.0 (13) |
O4—P1—O3—C2 | −49.6 (2) | C8—C9—C10—O11 | 150.2 (7) |
O1—P1—O4—C3 | −177.4 (2) | C7—C9—C10—O11 | −91.5 (7) |
O3—P1—O4—C3 | 57.0 (2) | C6—C9—C10—O11 | 26.8 (7) |
O2—P1—O4—C3 | −52.3 (2) | C8—C9—C10—O11' | −173.8 (10) |
P1—O2—C1—C4 | −6.5 (4) | C7—C9—C10—O11' | −55.5 (10) |
P1—O3—C2—C4 | −7.5 (3) | C6—C9—C10—O11' | 62.8 (10) |
P1—O4—C3—C4 | −4.5 (3) | C8—C9—C10—O12 | −37.3 (8) |
O2—C1—C4—C3 | −55.4 (3) | C7—C9—C10—O12 | 81.0 (8) |
O2—C1—C4—C2 | 62.7 (3) | C6—C9—C10—O12 | −160.7 (8) |
O2—C1—C4—C5 | −176.4 (3) | C22—N1—C11—C12 | −1.3 (5) |
O4—C3—C4—C1 | 61.9 (3) | N1—C11—C12—C13 | 0.9 (5) |
O4—C3—C4—C2 | −57.0 (3) | C11—C12—C13—C14 | 0.2 (5) |
O4—C3—C4—C5 | −176.9 (3) | C12—C13—C14—C22 | −0.8 (5) |
O3—C2—C4—C1 | −54.9 (3) | C12—C13—C14—C15 | 179.9 (3) |
O3—C2—C4—C3 | 64.1 (3) | C22—C14—C15—C16 | 0.4 (5) |
O3—C2—C4—C5 | −176.1 (2) | C13—C14—C15—C16 | 179.7 (3) |
C1—C4—C5—O5 | 12.0 (4) | C14—C15—C16—C17 | 0.0 (5) |
C3—C4—C5—O5 | −108.7 (3) | C15—C16—C17—C21 | −0.4 (5) |
C2—C4—C5—O5 | 132.6 (3) | C15—C16—C17—C18 | −178.7 (3) |
C1—C4—C5—O6 | −168.5 (3) | C21—C17—C18—C19 | 0.4 (4) |
C3—C4—C5—O6 | 70.9 (3) | C16—C17—C18—C19 | 178.7 (3) |
C2—C4—C5—O6 | −47.9 (4) | C17—C18—C19—C20 | 0.0 (5) |
O7—P2—O8—C6 | 178.7 (3) | C21—N2—C20—C19 | 0.0 (5) |
O10—P2—O8—C6 | −53.0 (4) | C18—C19—C20—N2 | −0.3 (5) |
O9—P2—O8—C6 | 55.4 (4) | C20—N2—C21—C17 | 0.5 (4) |
O7—P2—O9—C7 | −180.0 (3) | C20—N2—C21—C22 | −179.0 (3) |
O8—P2—O9—C7 | −56.5 (3) | C18—C17—C21—N2 | −0.7 (4) |
O10—P2—O9—C7 | 55.2 (3) | C16—C17—C21—N2 | −179.1 (3) |
O7—P2—O10—C8 | 179.0 (3) | C18—C17—C21—C22 | 178.8 (3) |
O8—P2—O10—C8 | 51.5 (3) | C16—C17—C21—C22 | 0.4 (4) |
O9—P2—O10—C8 | −57.2 (3) | C11—N1—C22—C14 | 0.6 (4) |
P2—O8—C6—C9 | 0.3 (5) | C11—N1—C22—C21 | −179.2 (3) |
P2—O9—C7—C9 | 1.1 (4) | C13—C14—C22—N1 | 0.5 (4) |
P2—O10—C8—C9 | 2.4 (5) | C15—C14—C22—N1 | 179.8 (3) |
O10—C8—C9—C7 | 58.6 (4) | C13—C14—C22—C21 | −179.7 (3) |
O10—C8—C9—C6 | −59.2 (5) | C15—C14—C22—C21 | −0.4 (4) |
O10—C8—C9—C10 | 177.4 (3) | N2—C21—C22—N1 | −0.7 (4) |
O9—C7—C9—C8 | −60.6 (4) | C17—C21—C22—N1 | 179.8 (3) |
O9—C7—C9—C6 | 59.0 (4) | N2—C21—C22—C14 | 179.5 (3) |
O9—C7—C9—C10 | 179.2 (3) | C17—C21—C22—C14 | 0.0 (4) |
O8—C6—C9—C8 | 57.7 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
O13—H13B···O12i | 0.84 | 2.47 | 2.893 (9) | 112 |
N1—H1···O1ii | 0.90 | 1.91 | 2.765 (3) | 159 |
O6—H6C···O11i | 0.85 | 1.61 | 2.459 (5) | 173 |
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+2, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C12H9N2+·C5H6O6P−·C5H7O6P·H2O |
Mr | 586.37 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 294 |
a, b, c (Å) | 9.2841 (18), 8.5863 (16), 31.124 (6) |
β (°) | 99.917 (5) |
V (Å3) | 2444.0 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.25 |
Crystal size (mm) | 0.20 × 0.16 × 0.12 |
Data collection | |
Diffractometer | Bruker SMART CCD area detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.948, 0.972 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13684, 5008, 2956 |
Rint | 0.043 |
(sin θ/λ)max (Å−1) | 0.626 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.159, 1.03 |
No. of reflections | 5008 |
No. of parameters | 371 |
No. of restraints | 38 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.35, −0.32 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXTL (Bruker, 2000), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O13—H13B···O12i | 0.84 | 2.47 | 2.893 (9) | 112.4 |
N1—H1···O1ii | 0.90 | 1.91 | 2.765 (3) | 158.6 |
O6—H6C···O11i | 0.85 | 1.61 | 2.459 (5) | 173.1 |
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+2, −y+1, −z+2. |
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Caged bicyclic phosphates are widely used as flame retardants in some polymers. As a low-toxicity and environmentally friendly flame retardant system, the phosphorus-nitrogen combination has been extensively studied. We report here the crystal structure of a new bicyclic phosphate cage compound.
The content of the asymmetric unit of the title salt is shown in Fig. 1. In the 1,10-phenanthrolinium cation, the C—N—C bond angle of 123.0 (3)° at the protonated N1 atom is significantly larger than that at the non-protonated N2 atom (116.4 (3)°). This widening is not unexpected, as analogous differences were already observed in previously reported monoprotonated phenanthrolines (Hensen et al., 1998, 2000; Guo, 2005). In the anion, the oxygen atoms O11 and O12 of the carboxylate group are positionally disordered over two position, with site occupation factors of 0.701 (15) and 0.299 (15) for the major and minor components respectively. In the crystal structure, ions and neutral molecules are linked into an extended three-dimensional network by O—H···O and N—H···O hydrogen bonding interactions (Table 1, Fig. 2).