The title compound, C
13H
16N
22+·0.5P
4O
124−, has been prepared at room temperature and studied by single-crystal X-ray diffraction. The asymmetric unit consists of one 4,4′-diphenylmethylendiammonium organic cation and two PO
4 tetrahedra that form one half of a cyclic P
4O
124− anion that lies about an inversion centre. The P
4O
12 rings are linked through N—H
O hydrogen bonds to build layers parallel to the
ab plane. The two NH
3+ groups at the 4- and 4′-positions of the cations link these layers into a three-dimensional network.
Supporting information
CCDC reference: 283990
Key indicators
- Single-crystal X-ray study
- T = 300 K
- Mean (C-C) = 0.004 Å
- R factor = 0.038
- wR factor = 0.118
- Data-to-parameter ratio = 12.9
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.70
PLAT128_ALERT_4_C Non-standard setting of Space group P21/c .... P21/a
PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C42
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 16
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
6 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
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
0 ALERT type 3 Indicator that the structure quality may be low
2 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: CAD-4 EXPRESS (Duisenberg, 1992; Macíček & Yordanov, 1992); cell refinement: CAD-4 EXPRESS; data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ATOMS for Windows (Dowty, 1995) and ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
Bis(4,4'-diphenylmethylendiammonium) cyclotetraphosphate
top
Crystal data top
C13H16N22+·0.5P4O124− | F(000) = 744 |
Mr = 358.22 | Dx = 1.47 Mg m−3 |
Monoclinic, P21/a | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yab | Cell parameters from 25 reflections |
a = 8.467 (2) Å | θ = 10–15° |
b = 13.808 (3) Å | µ = 0.30 mm−1 |
c = 14.453 (2) Å | T = 300 K |
β = 106.62 (2)° | Prism, colourless |
V = 1619.2 (6) Å3 | 0.30 × 0.15 × 0.10 mm |
Z = 4 | |
Data collection top
Enraf–Nonius CAD-4 diffractometer | Rint = 0.013 |
Radiation source: fine-focus sealed tube | θmax = 27.0°, θmin = 2.1° |
Graphite monochromator | h = 0→10 |
ω/2θ scans | k = −1→17 |
4086 measured reflections | l = −18→17 |
3528 independent reflections | 2 standard reflections every 60 min |
2874 reflections with I > 2σ(I) | intensity decay: 1.0% |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.038 | All H-atom parameters refined |
wR(F2) = 0.118 | w = 1/[σ2(Fo2) + (0.1136P)2 + 1.5906P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.001 |
3528 reflections | Δρmax = 0.70 e Å−3 |
273 parameters | Δρmin = −0.26 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.007 (2) |
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 | |
P1 | 0.11661 (6) | 0.88542 (4) | 0.60555 (4) | 0.03273 (16) | |
P2 | 0.20536 (6) | 1.01465 (4) | 0.46622 (4) | 0.03204 (16) | |
O11 | 0.2490 (2) | 0.90244 (14) | 0.69594 (11) | 0.0511 (4) | |
O21 | 0.0412 (2) | 0.78737 (11) | 0.58536 (12) | 0.0482 (4) | |
OL12 | 0.17918 (19) | 0.91247 (11) | 0.51327 (11) | 0.0399 (4) | |
OL21 | −0.02220 (16) | 0.96524 (10) | 0.60152 (10) | 0.0352 (3) | |
O12 | 0.2564 (2) | 1.09101 (13) | 0.54004 (12) | 0.0491 (4) | |
O22 | 0.30822 (19) | 0.99134 (12) | 0.40131 (12) | 0.0423 (4) | |
N1 | 0.5686 (2) | 0.87388 (15) | 0.69741 (14) | 0.0382 (4) | |
C11 | 0.6914 (3) | 0.86918 (16) | 0.79187 (15) | 0.0384 (5) | |
C21 | 0.6502 (3) | 0.8928 (2) | 0.87429 (18) | 0.0561 (7) | |
C31 | 0.7707 (4) | 0.8878 (3) | 0.9630 (2) | 0.0693 (9) | |
C41 | 0.9317 (3) | 0.8611 (2) | 0.96941 (18) | 0.0586 (7) | |
C51 | 0.9698 (4) | 0.8388 (2) | 0.8848 (2) | 0.0612 (7) | |
C61 | 0.8512 (3) | 0.8419 (2) | 0.79639 (19) | 0.0546 (6) | |
C | 1.0660 (5) | 0.8618 (4) | 1.0655 (2) | 0.0865 (13) | |
N2 | 0.9548 (3) | 0.68773 (17) | 1.40265 (15) | 0.0424 (4) | |
C12 | 0.9659 (2) | 0.73140 (15) | 1.31231 (14) | 0.0359 (4) | |
C22 | 0.9452 (4) | 0.82934 (18) | 1.29834 (18) | 0.0537 (6) | |
C32 | 0.9746 (5) | 0.8708 (2) | 1.2175 (2) | 0.0690 (9) | |
C42 | 1.0210 (3) | 0.8150 (2) | 1.14995 (17) | 0.0553 (7) | |
C52 | 1.0329 (4) | 0.7159 (2) | 1.1633 (2) | 0.0616 (7) | |
C62 | 1.0073 (4) | 0.6731 (2) | 1.24524 (19) | 0.0574 (7) | |
H1N1 | 0.599 (3) | 0.918 (2) | 0.661 (2) | 0.055 (8)* | |
H2N1 | 0.570 (3) | 0.819 (2) | 0.664 (2) | 0.050 (7)* | |
H3N1 | 0.4710 (15) | 0.889 (2) | 0.701 (2) | 0.060 (9)* | |
H1N2 | 0.936 (4) | 0.732 (3) | 1.444 (2) | 0.074 (10)* | |
H2N2 | 0.878 (4) | 0.643 (2) | 1.393 (2) | 0.057 (8)* | |
H3N2 | 1.065 (5) | 0.659 (3) | 1.430 (3) | 0.087 (11)* | |
HC21 | 0.531 (5) | 0.917 (3) | 0.867 (3) | 0.092 (11)* | |
HC31 | 0.740 (4) | 0.910 (3) | 1.024 (3) | 0.091 (11)* | |
HC51 | 1.091 (5) | 0.831 (3) | 0.889 (3) | 0.099 (12)* | |
HC61 | 0.875 (4) | 0.825 (2) | 0.742 (2) | 0.065 (9)* | |
H1C | 1.078 (6) | 0.9300 (7) | 1.079 (3) | 0.114 (16)* | |
H2C | 1.164 (6) | 0.842 (3) | 1.062 (3) | 0.110 (15)* | |
HC22 | 0.922 (4) | 0.870 (2) | 1.353 (2) | 0.071 (9)* | |
HC32 | 0.967 (4) | 0.947 (3) | 1.215 (3) | 0.094 (11)* | |
HC52 | 1.063 (4) | 0.674 (2) | 1.117 (2) | 0.073 (9)* | |
HC62 | 1.033 (4) | 0.604 (3) | 1.259 (3) | 0.089 (11)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P1 | 0.0330 (3) | 0.0338 (3) | 0.0320 (3) | 0.0079 (2) | 0.0103 (2) | 0.0055 (2) |
P2 | 0.0269 (3) | 0.0376 (3) | 0.0328 (3) | 0.0019 (2) | 0.0105 (2) | −0.0001 (2) |
O11 | 0.0411 (9) | 0.0715 (12) | 0.0359 (8) | 0.0154 (8) | 0.0034 (7) | 0.0041 (8) |
O21 | 0.0629 (10) | 0.0317 (8) | 0.0533 (9) | 0.0033 (7) | 0.0220 (8) | 0.0054 (7) |
OL12 | 0.0461 (8) | 0.0392 (8) | 0.0393 (8) | 0.0079 (7) | 0.0200 (7) | 0.0060 (6) |
OL21 | 0.0295 (7) | 0.0358 (7) | 0.0391 (7) | 0.0046 (6) | 0.0076 (6) | −0.0040 (6) |
O12 | 0.0424 (9) | 0.0561 (10) | 0.0465 (9) | −0.0081 (8) | 0.0092 (7) | −0.0137 (8) |
O22 | 0.0377 (8) | 0.0471 (9) | 0.0481 (9) | 0.0078 (7) | 0.0219 (7) | 0.0072 (7) |
N1 | 0.0414 (10) | 0.0374 (10) | 0.0360 (9) | −0.0012 (8) | 0.0113 (8) | −0.0014 (8) |
C11 | 0.0434 (11) | 0.0361 (10) | 0.0345 (10) | −0.0042 (9) | 0.0095 (9) | 0.0024 (8) |
C21 | 0.0471 (14) | 0.084 (2) | 0.0400 (12) | −0.0065 (13) | 0.0169 (11) | 0.0005 (12) |
C31 | 0.0645 (18) | 0.110 (3) | 0.0357 (12) | −0.0199 (17) | 0.0179 (12) | 0.0014 (14) |
C41 | 0.0529 (15) | 0.0745 (18) | 0.0433 (13) | −0.0190 (13) | 0.0059 (11) | 0.0185 (13) |
C51 | 0.0508 (15) | 0.0733 (19) | 0.0553 (15) | 0.0083 (14) | 0.0084 (12) | 0.0119 (14) |
C61 | 0.0547 (15) | 0.0643 (17) | 0.0442 (13) | 0.0124 (13) | 0.0135 (11) | −0.0017 (12) |
C | 0.066 (2) | 0.136 (4) | 0.0465 (16) | −0.040 (2) | −0.0013 (14) | 0.031 (2) |
N2 | 0.0440 (11) | 0.0438 (11) | 0.0389 (10) | −0.0080 (9) | 0.0109 (8) | 0.0013 (8) |
C12 | 0.0351 (10) | 0.0376 (11) | 0.0315 (9) | −0.0037 (8) | 0.0036 (8) | 0.0014 (8) |
C22 | 0.0758 (18) | 0.0384 (12) | 0.0402 (12) | 0.0001 (12) | 0.0056 (12) | −0.0037 (10) |
C32 | 0.107 (3) | 0.0411 (14) | 0.0454 (14) | −0.0135 (15) | 0.0003 (15) | 0.0072 (11) |
C42 | 0.0476 (13) | 0.0740 (18) | 0.0358 (11) | −0.0176 (13) | −0.0018 (10) | 0.0132 (12) |
C52 | 0.0714 (18) | 0.0737 (19) | 0.0442 (13) | 0.0168 (15) | 0.0236 (13) | 0.0052 (13) |
C62 | 0.0814 (19) | 0.0430 (13) | 0.0501 (14) | 0.0158 (13) | 0.0227 (13) | 0.0055 (11) |
Geometric parameters (Å, º) top
P1—O11 | 1.477 (2) | C51—C61 | 1.382 (4) |
P1—O21 | 1.490 (2) | C51—HC51 | 1.02 (4) |
P1—OL21 | 1.600 (2) | C61—HC61 | 0.90 (3) |
P1—OL12 | 1.613 (2) | C—C42 | 1.522 (4) |
P2—O12 | 1.474 (2) | C—H1C | 0.96 (1) |
P2—O22 | 1.486 (2) | C—H2C | 0.89 (4) |
P2—OL21i | 1.604 (2) | N2—C12 | 1.465 (3) |
P2—OL12 | 1.609 (2) | N2—H1N2 | 0.90 (4) |
OL21—P2i | 1.604 (2) | N2—H2N2 | 0.88 (3) |
N1—C11 | 1.462 (3) | N2—H3N2 | 0.99 (4) |
N1—H1N1 | 0.89 (3) | C12—C22 | 1.371 (3) |
N1—H2N1 | 0.90 (3) | C12—C62 | 1.380 (3) |
N1—H3N1 | 0.88 (1) | C22—C32 | 1.385 (4) |
C11—C21 | 1.373 (3) | C22—HC22 | 1.03 (3) |
C11—C61 | 1.388 (4) | C32—C42 | 1.386 (4) |
C21—C31 | 1.393 (4) | C32—HC32 | 1.06 (4) |
C21—HC21 | 1.04 (4) | C42—C52 | 1.382 (4) |
C31—C41 | 1.389 (4) | C52—C62 | 1.394 (4) |
C31—HC31 | 1.04 (4) | C52—HC52 | 0.97 (3) |
C41—C51 | 1.385 (4) | C62—HC62 | 0.98 (4) |
C41—C | 1.522 (4) | | |
| | | |
O11—P1—O21 | 119.5 (1) | C41—C51—HC51 | 117 (2) |
O11—P1—OL21 | 106.64 (9) | C51—C61—C11 | 119.5 (3) |
O21—P1—OL21 | 110.47 (9) | C51—C61—HC61 | 121 (2) |
O11—P1—OL12 | 110.4 (1) | C11—C61—HC61 | 119 (2) |
O21—P1—OL12 | 105.79 (9) | C42—C—C41 | 115.9 (3) |
OL21—P1—OL12 | 102.82 (8) | C42—C—H1C | 107 (3) |
O12—P2—O22 | 120.5 (1) | C41—C—H1C | 102 (3) |
O12—P2—OL21i | 110.49 (9) | C42—C—H2C | 111 (3) |
O22—P2—OL21i | 106.92 (9) | C41—C—H2C | 114 (3) |
O12—P2—OL12 | 111.6 (1) | H1C—C—H2C | 106 (4) |
O22—P2—OL12 | 104.67 (8) | C12—N2—H1N2 | 113 (2) |
OL21i—P2—OL12 | 100.59 (8) | C12—N2—H2N2 | 112 (2) |
P2—OL12—P1 | 132.1 (1) | H1N2—N2—H2N2 | 109 (3) |
P1—OL21—P2i | 135.5 (1) | C12—N2—H3N2 | 103 (2) |
C11—N1—H1N1 | 109 (2) | H1N2—N2—H3N2 | 110 (3) |
C11—N1—H2N1 | 111 (2) | H2N2—N2—H3N2 | 110 (3) |
H1N1—N1—H2N1 | 102 (2) | C22—C12—C62 | 121.3 (2) |
C11—N1—H3N1 | 113 (2) | C22—C12—N2 | 119.9 (2) |
H1N1—N1—H3N1 | 108 (3) | C62—C12—N2 | 118.7 (2) |
H2N1—N1—H3N1 | 114 (3) | C12—C22—C32 | 119.0 (3) |
C21—C11—C61 | 120.6 (2) | C12—C22—HC22 | 118 (2) |
C21—C11—N1 | 120.7 (2) | C32—C22—HC22 | 123 (2) |
C61—C11—N1 | 118.7 (2) | C42—C32—C22 | 121.4 (3) |
C11—C21—C31 | 119.1 (3) | C42—C32—HC32 | 124 (2) |
C11—C21—HC21 | 118 (2) | C22—C32—HC32 | 115 (2) |
C31—C21—HC21 | 123 (2) | C52—C42—C32 | 118.4 (2) |
C41—C31—C21 | 121.4 (3) | C52—C42—C | 120.5 (3) |
C41—C31—HC31 | 120 (2) | C32—C42—C | 121.0 (3) |
C21—C31—HC31 | 118 (2) | C42—C52—C62 | 121.0 (3) |
C51—C41—C31 | 118.2 (2) | C42—C52—HC52 | 121 (2) |
C51—C41—C | 120.3 (3) | C62—C52—HC52 | 118 (2) |
C31—C41—C | 121.4 (3) | C12—C62—C52 | 118.8 (3) |
C61—C51—C41 | 121.2 (3) | C12—C62—HC62 | 121 (2) |
C61—C51—HC51 | 121 (2) | C52—C62—HC62 | 120 (2) |
| | | |
O12—P2—OL12—P1 | 32.50 (17) | C21—C11—C61—C51 | −0.2 (4) |
O22—P2—OL12—P1 | 164.49 (13) | N1—C11—C61—C51 | 178.8 (3) |
OL21i—P2—OL12—P1 | −84.71 (14) | C51—C41—C—C42 | −136.9 (4) |
O11—P1—OL12—P2 | −76.64 (16) | C31—C41—C—C42 | 46.7 (6) |
O21—P1—OL12—P2 | 152.74 (13) | C62—C12—C22—C32 | −3.2 (4) |
OL21—P1—OL12—P2 | 36.82 (15) | N2—C12—C22—C32 | 172.7 (3) |
O11—P1—OL21—P2i | −172.08 (14) | C12—C22—C32—C42 | 1.3 (5) |
O21—P1—OL21—P2i | −40.78 (17) | C22—C32—C42—C52 | 1.9 (5) |
OL12—P1—OL21—P2i | 71.73 (15) | C22—C32—C42—C | −175.2 (3) |
C61—C11—C21—C31 | −0.8 (4) | C41—C—C42—C52 | 83.0 (5) |
N1—C11—C21—C31 | −179.8 (3) | C41—C—C42—C32 | −100.0 (4) |
C11—C21—C31—C41 | 1.1 (5) | C32—C42—C52—C62 | −3.3 (5) |
C21—C31—C41—C51 | −0.4 (5) | C—C42—C52—C62 | 173.8 (3) |
C21—C31—C41—C | 176.1 (3) | C22—C12—C62—C52 | 1.8 (4) |
C31—C41—C51—C61 | −0.6 (5) | N2—C12—C62—C52 | −174.1 (3) |
C—C41—C51—C61 | −177.1 (3) | C42—C52—C62—C12 | 1.5 (5) |
C41—C51—C61—C11 | 0.9 (5) | | |
Symmetry code: (i) −x, −y+2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N1···O22ii | 0.89 (4) | 1.85 (4) | 2.728 (3) | 172 (3) |
N1—H2N1···O21iii | 0.90 (3) | 1.83 (3) | 2.724 (3) | 171 (3) |
N1—H3N1···O11 | 0.88 (1) | 1.86 (2) | 2.728 (3) | 170 (3) |
N2—H1N2···O21iv | 0.90 (4) | 2.13 (4) | 2.880 (3) | 141 (3) |
N2—H2N2···O22v | 0.88 (4) | 1.96 (4) | 2.764 (3) | 151 (3) |
N2—H3N2···O12vi | 0.99 (4) | 1.72 (4) | 2.700 (3) | 169 (4) |
Symmetry codes: (ii) −x+1, −y+2, −z+1; (iii) x+1/2, −y+3/2, z; (iv) x+1, y, z+1; (v) x+1/2, −y+3/2, z+1; (vi) −x+3/2, y−1/2, −z+2. |