Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112033392/sf3176sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112033392/sf3176Isup2.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270112033392/sf3176Isup3.cml |
CCDC reference: 908137
For related literature, see: Bernstein et al. (1995); Birum & Jansen (1978); Dai et al. (2012); Desiraju (2007); Dong et al. (2012); Eppel & Bernstein (2009); Hu et al. (2011); Ikonen et al. (2010); Janczak & Perpétuo (2002, 2004); Moulton & Zaworotko (2001); Reddy et al. (2006); Seddon & Zaworotko (1999); Sun et al. (2011); Zhang & Chen (2005).
(2-Carboxyethyl)(phenyl)phosphinic acid (H2L) was synthesized according to the published procedure of Birum & Jansen (1978). Compound (I) was prepared by mixing hot aqueous solutions of melamine and H2L in a 1:1 molar ratio. The hot mixtures were stirred at room temperature and filtered. After a few days, colorless block-shaped crystals of (I) were deposited from the filtrates in a ca 70% yield based on H2L. Analysis calculated for C24H38N12O10P2: C 40.23, H 5.35, N 23.46%; found: C 40.11, H 5.50, N 23.38%. IR data (KBr, cm-1): 3362 (s), 3147 (s), 2954 (m), 2471 (m), 1895 (m), 1665 (s), 1578 (m), 1508 (s), 1436 (m), 1343 (m), 1315 (m), 1248 (m), 1189 (m), 1155 (s), 1122 (s), 1017 (s), 907 (m), 859 (m), 777 (m), 721 (s), 698 (m), 546 (m), 512 (m).
All C-bound and N-bound H atoms, except for H2B and H8C, were positioned geometrically (C—H = 0.93 or 0.97 Å and N—H = 0.86 Å) and included in the refinement in the riding-model approximation, with Uiso(H) = 1.2Ueq(C) or 1.2Ueq(N). Atoms H2B and H8C and all O-bound H atoms were located in a difference map and refined with Uiso(H) values set at 1.2Ueq(N) or 1.5Ueq(O). The O—H distance of each carboxy group was restrained to be 0.93 (1) Å, while the O—H and H···H distances in each water molecule were restrained to be 0.85 (1) and 1.38 (1) Å, respectively.
Data collection: SMART (Bruker, 2008); cell refinement: SMART (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXTL (Bruker, 2008).
C3H7N6+·C9H10O4P−·H2O | Z = 4 |
Mr = 358.30 | F(000) = 752 |
Triclinic, P1 | Dx = 1.450 Mg m−3 |
a = 7.2280 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.4251 (2) Å | Cell parameters from 4106 reflections |
c = 18.9837 (3) Å | θ = 3.3–26.9° |
α = 105.388 (1)° | µ = 0.21 mm−1 |
β = 91.348 (1)° | T = 296 K |
γ = 92.604 (1)° | Block, colourless |
V = 1640.96 (4) Å3 | 0.35 × 0.15 × 0.15 mm |
Bruker SMART CCD area-detector diffractometer | 6378 independent reflections |
Radiation source: fine-focus sealed tube | 4783 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ω scans | θmax = 26.0°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −8→8 |
Tmin = 0.673, Tmax = 0.746 | k = −15→12 |
14192 measured reflections | l = −19→23 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.115 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | w = 1/[σ2(Fo2) + (0.056P)2 + 0.0025P] where P = (Fo2 + 2Fc2)/3 |
6378 reflections | (Δ/σ)max < 0.001 |
457 parameters | Δρmax = 0.31 e Å−3 |
8 restraints | Δρmin = −0.37 e Å−3 |
C3H7N6+·C9H10O4P−·H2O | γ = 92.604 (1)° |
Mr = 358.30 | V = 1640.96 (4) Å3 |
Triclinic, P1 | Z = 4 |
a = 7.2280 (1) Å | Mo Kα radiation |
b = 12.4251 (2) Å | µ = 0.21 mm−1 |
c = 18.9837 (3) Å | T = 296 K |
α = 105.388 (1)° | 0.35 × 0.15 × 0.15 mm |
β = 91.348 (1)° |
Bruker SMART CCD area-detector diffractometer | 6378 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | 4783 reflections with I > 2σ(I) |
Tmin = 0.673, Tmax = 0.746 | Rint = 0.026 |
14192 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 8 restraints |
wR(F2) = 0.115 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | Δρmax = 0.31 e Å−3 |
6378 reflections | Δρmin = −0.37 e Å−3 |
457 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 | ||
P1 | 0.53508 (8) | 0.92005 (4) | 0.22888 (3) | 0.03041 (15) | |
P2 | 0.06311 (8) | 0.42633 (4) | 0.20166 (3) | 0.03250 (15) | |
N1 | 0.7524 (2) | 0.90493 (12) | 0.53207 (8) | 0.0335 (4) | |
N2 | 0.6745 (3) | 0.95091 (14) | 0.42338 (9) | 0.0367 (4) | |
H2B | 0.641 (3) | 0.9239 (16) | 0.3783 (11) | 0.044* | |
N3 | 0.7930 (2) | 1.09446 (12) | 0.52305 (8) | 0.0326 (4) | |
N4 | 0.8718 (3) | 1.04513 (13) | 0.62684 (8) | 0.0450 (5) | |
H4B | 0.8809 | 0.9966 | 0.6515 | 0.054* | |
H4C | 0.9068 | 1.1139 | 0.6465 | 0.054* | |
N5 | 0.7095 (3) | 1.13171 (14) | 0.41506 (8) | 0.0472 (5) | |
H5B | 0.7397 | 1.2015 | 0.4334 | 0.057* | |
H5C | 0.6670 | 1.1083 | 0.3706 | 0.057* | |
N6 | 0.6421 (3) | 0.77001 (13) | 0.43095 (9) | 0.0508 (5) | |
H6B | 0.6499 | 0.7203 | 0.4548 | 0.061* | |
H6C | 0.6024 | 0.7509 | 0.3861 | 0.061* | |
N7 | 0.2677 (2) | 0.41348 (12) | 0.49784 (8) | 0.0355 (4) | |
N8 | 0.1550 (3) | 0.46825 (15) | 0.39698 (9) | 0.0398 (5) | |
H8C | 0.110 (3) | 0.4465 (17) | 0.3549 (11) | 0.048* | |
N9 | 0.2306 (2) | 0.60849 (13) | 0.50500 (8) | 0.0346 (4) | |
N10 | 0.3370 (3) | 0.55108 (13) | 0.60225 (8) | 0.0420 (5) | |
H10A | 0.3449 | 0.6201 | 0.6271 | 0.050* | |
H10B | 0.3681 | 0.4999 | 0.6224 | 0.050* | |
N11 | 0.1250 (3) | 0.65278 (15) | 0.40180 (9) | 0.0505 (5) | |
H11B | 0.1325 | 0.7227 | 0.4246 | 0.061* | |
H11C | 0.0869 | 0.6318 | 0.3567 | 0.061* | |
N12 | 0.1865 (3) | 0.28298 (14) | 0.39018 (9) | 0.0555 (6) | |
H12B | 0.2164 | 0.2305 | 0.4094 | 0.067* | |
H12C | 0.1450 | 0.2668 | 0.3456 | 0.067* | |
C1 | 0.6643 (3) | 0.90063 (15) | 0.14637 (10) | 0.0320 (5) | |
C2 | 0.7385 (3) | 0.79907 (16) | 0.11263 (10) | 0.0381 (5) | |
H2A | 0.7310 | 0.7410 | 0.1350 | 0.046* | |
C3 | 0.8229 (3) | 0.78321 (19) | 0.04640 (11) | 0.0480 (6) | |
H3A | 0.8736 | 0.7153 | 0.0250 | 0.058* | |
C4 | 0.8322 (3) | 0.8677 (2) | 0.01207 (11) | 0.0475 (6) | |
H4A | 0.8858 | 0.8562 | −0.0332 | 0.057* | |
C5 | 0.7620 (4) | 0.9690 (2) | 0.04471 (12) | 0.0518 (6) | |
H5A | 0.7703 | 1.0265 | 0.0218 | 0.062* | |
C6 | 0.6794 (3) | 0.98609 (17) | 0.11119 (11) | 0.0438 (6) | |
H6A | 0.6332 | 1.0553 | 0.1329 | 0.053* | |
C7 | 0.3001 (3) | 0.87998 (15) | 0.19500 (10) | 0.0360 (5) | |
H7A | 0.2981 | 0.8057 | 0.1616 | 0.043* | |
H7B | 0.2247 | 0.8756 | 0.2358 | 0.043* | |
C8 | 0.2117 (3) | 0.95782 (17) | 0.15582 (10) | 0.0417 (5) | |
H8A | 0.2967 | 0.9716 | 0.1200 | 0.050* | |
H8B | 0.1005 | 0.9199 | 0.1294 | 0.050* | |
C9 | 0.1613 (3) | 1.06804 (17) | 0.20392 (11) | 0.0366 (5) | |
C10 | −0.1031 (3) | 0.39956 (16) | 0.12557 (10) | 0.0328 (5) | |
C11 | −0.1959 (3) | 0.29639 (17) | 0.09751 (11) | 0.0428 (5) | |
H11A | −0.1776 | 0.2388 | 0.1194 | 0.051* | |
C12 | −0.3159 (4) | 0.2786 (2) | 0.03703 (13) | 0.0566 (7) | |
H12A | −0.3784 | 0.2093 | 0.0187 | 0.068* | |
C13 | −0.3432 (4) | 0.3623 (2) | 0.00405 (13) | 0.0604 (7) | |
H13A | −0.4232 | 0.3497 | −0.0367 | 0.072* | |
C14 | −0.2525 (4) | 0.4648 (2) | 0.03116 (13) | 0.0602 (7) | |
H14A | −0.2708 | 0.5217 | 0.0087 | 0.072* | |
C15 | −0.1340 (3) | 0.48383 (18) | 0.09171 (11) | 0.0467 (6) | |
H15A | −0.0741 | 0.5539 | 0.1101 | 0.056* | |
C16 | 0.2819 (3) | 0.41621 (16) | 0.15769 (10) | 0.0365 (5) | |
H16A | 0.2895 | 0.3412 | 0.1261 | 0.044* | |
H16B | 0.2879 | 0.4678 | 0.1273 | 0.044* | |
C17 | 0.4468 (3) | 0.44217 (15) | 0.21179 (11) | 0.0391 (5) | |
H17A | 0.4254 | 0.4026 | 0.2488 | 0.047* | |
H17B | 0.5559 | 0.4130 | 0.1861 | 0.047* | |
C18 | 0.4869 (3) | 0.56317 (16) | 0.24917 (11) | 0.0360 (5) | |
C19 | 0.6910 (3) | 0.87479 (16) | 0.46298 (10) | 0.0330 (5) | |
C20 | 0.7282 (3) | 1.06109 (16) | 0.45480 (10) | 0.0326 (5) | |
C21 | 0.8046 (3) | 1.01435 (15) | 0.55929 (10) | 0.0303 (5) | |
C22 | 0.2040 (3) | 0.38766 (16) | 0.42896 (10) | 0.0371 (5) | |
C23 | 0.1715 (3) | 0.57849 (16) | 0.43558 (10) | 0.0345 (5) | |
C24 | 0.2775 (3) | 0.52399 (16) | 0.53364 (10) | 0.0314 (5) | |
O1 | 0.5526 (2) | 1.04009 (10) | 0.27145 (7) | 0.0407 (4) | |
O2 | 0.5939 (2) | 0.83649 (10) | 0.26998 (7) | 0.0378 (4) | |
O3 | 0.1075 (2) | 1.08447 (11) | 0.26516 (7) | 0.0478 (4) | |
O4 | 0.1755 (3) | 1.14779 (13) | 0.17030 (8) | 0.0640 (5) | |
H4D | 0.128 (4) | 1.2165 (17) | 0.1990 (14) | 0.096* | |
O5 | 0.0475 (2) | 0.54070 (11) | 0.25065 (7) | 0.0502 (4) | |
O6 | 0.0457 (2) | 0.33445 (11) | 0.24030 (7) | 0.0452 (4) | |
O7 | 0.4748 (3) | 0.62976 (12) | 0.20648 (8) | 0.0533 (5) | |
H7C | 0.516 (4) | 0.7035 (15) | 0.2339 (12) | 0.080* | |
O8 | 0.5325 (3) | 0.59681 (12) | 0.31291 (8) | 0.0603 (5) | |
O1W | 0.6868 (3) | 1.25393 (13) | 0.28193 (10) | 0.0614 (5) | |
H1WA | 0.655 (4) | 1.1872 (15) | 0.2717 (15) | 0.092* | |
H1WB | 0.796 (3) | 1.265 (2) | 0.2677 (15) | 0.092* | |
O2W | −0.0427 (3) | 0.75858 (13) | 0.27911 (10) | 0.0578 (5) | |
H2WA | −0.031 (4) | 0.6908 (14) | 0.2638 (14) | 0.087* | |
H2WB | −0.151 (3) | 0.777 (2) | 0.2709 (14) | 0.087* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0414 (3) | 0.0239 (3) | 0.0262 (3) | −0.0005 (2) | −0.0019 (2) | 0.0079 (2) |
P2 | 0.0406 (3) | 0.0292 (3) | 0.0273 (3) | 0.0048 (2) | −0.0011 (2) | 0.0066 (2) |
N1 | 0.0465 (11) | 0.0239 (9) | 0.0288 (9) | −0.0011 (8) | −0.0015 (8) | 0.0053 (7) |
N2 | 0.0522 (12) | 0.0322 (10) | 0.0237 (8) | −0.0011 (9) | −0.0046 (8) | 0.0050 (8) |
N3 | 0.0438 (11) | 0.0266 (9) | 0.0280 (9) | −0.0004 (8) | −0.0009 (8) | 0.0090 (7) |
N4 | 0.0781 (15) | 0.0262 (9) | 0.0293 (9) | −0.0059 (9) | −0.0114 (9) | 0.0077 (7) |
N5 | 0.0759 (15) | 0.0359 (10) | 0.0324 (9) | −0.0042 (10) | −0.0106 (9) | 0.0157 (8) |
N6 | 0.0848 (17) | 0.0260 (10) | 0.0366 (10) | −0.0040 (10) | −0.0123 (10) | 0.0023 (8) |
N7 | 0.0490 (12) | 0.0268 (9) | 0.0291 (9) | 0.0000 (8) | −0.0036 (8) | 0.0056 (7) |
N8 | 0.0536 (13) | 0.0411 (11) | 0.0229 (9) | −0.0018 (9) | −0.0049 (8) | 0.0067 (8) |
N9 | 0.0481 (12) | 0.0300 (9) | 0.0274 (9) | 0.0023 (8) | −0.0027 (8) | 0.0107 (7) |
N10 | 0.0679 (14) | 0.0283 (9) | 0.0300 (9) | 0.0015 (9) | −0.0120 (9) | 0.0095 (7) |
N11 | 0.0770 (16) | 0.0452 (11) | 0.0332 (10) | 0.0077 (10) | −0.0090 (10) | 0.0175 (9) |
N12 | 0.0882 (17) | 0.0350 (11) | 0.0362 (10) | −0.0002 (11) | −0.0068 (10) | −0.0013 (8) |
C1 | 0.0362 (12) | 0.0298 (11) | 0.0298 (10) | −0.0045 (9) | −0.0052 (9) | 0.0094 (8) |
C2 | 0.0490 (14) | 0.0316 (11) | 0.0340 (11) | −0.0006 (10) | 0.0021 (10) | 0.0096 (9) |
C3 | 0.0551 (16) | 0.0415 (13) | 0.0413 (12) | −0.0012 (12) | 0.0055 (11) | 0.0007 (10) |
C4 | 0.0502 (15) | 0.0594 (15) | 0.0306 (11) | −0.0093 (12) | 0.0058 (10) | 0.0095 (11) |
C5 | 0.0693 (18) | 0.0511 (15) | 0.0426 (13) | −0.0036 (13) | 0.0062 (12) | 0.0266 (11) |
C6 | 0.0562 (16) | 0.0325 (12) | 0.0449 (12) | 0.0013 (11) | 0.0056 (11) | 0.0140 (10) |
C7 | 0.0436 (14) | 0.0265 (11) | 0.0353 (11) | 0.0018 (10) | 0.0044 (10) | 0.0035 (9) |
C8 | 0.0452 (14) | 0.0429 (13) | 0.0339 (11) | 0.0061 (11) | −0.0056 (10) | 0.0048 (10) |
C9 | 0.0398 (13) | 0.0384 (12) | 0.0337 (12) | 0.0043 (10) | −0.0050 (10) | 0.0136 (10) |
C10 | 0.0345 (12) | 0.0308 (11) | 0.0319 (10) | 0.0045 (9) | 0.0040 (9) | 0.0059 (9) |
C11 | 0.0471 (15) | 0.0306 (12) | 0.0485 (13) | 0.0031 (11) | −0.0008 (11) | 0.0067 (10) |
C12 | 0.0490 (16) | 0.0427 (14) | 0.0642 (16) | −0.0030 (12) | −0.0133 (13) | −0.0080 (12) |
C13 | 0.0544 (17) | 0.0668 (18) | 0.0519 (14) | 0.0071 (14) | −0.0222 (13) | 0.0033 (13) |
C14 | 0.0703 (19) | 0.0596 (16) | 0.0552 (15) | 0.0046 (14) | −0.0190 (14) | 0.0247 (13) |
C15 | 0.0523 (16) | 0.0395 (13) | 0.0501 (13) | −0.0032 (11) | −0.0126 (12) | 0.0171 (11) |
C16 | 0.0465 (14) | 0.0305 (11) | 0.0302 (10) | −0.0023 (10) | −0.0010 (10) | 0.0052 (9) |
C17 | 0.0398 (13) | 0.0290 (11) | 0.0458 (12) | 0.0030 (10) | −0.0027 (10) | 0.0052 (9) |
C18 | 0.0415 (14) | 0.0301 (11) | 0.0374 (12) | 0.0015 (10) | −0.0037 (10) | 0.0113 (9) |
C19 | 0.0389 (13) | 0.0268 (11) | 0.0318 (11) | 0.0015 (9) | 0.0017 (9) | 0.0051 (9) |
C20 | 0.0399 (13) | 0.0291 (11) | 0.0294 (10) | 0.0021 (9) | 0.0035 (9) | 0.0086 (9) |
C21 | 0.0367 (12) | 0.0271 (11) | 0.0266 (10) | 0.0027 (9) | 0.0031 (9) | 0.0061 (8) |
C22 | 0.0447 (14) | 0.0318 (12) | 0.0326 (11) | −0.0026 (10) | 0.0032 (10) | 0.0053 (9) |
C23 | 0.0377 (13) | 0.0362 (12) | 0.0316 (11) | 0.0023 (10) | 0.0026 (9) | 0.0127 (9) |
C24 | 0.0373 (13) | 0.0294 (11) | 0.0281 (10) | 0.0005 (9) | 0.0006 (9) | 0.0092 (9) |
O1 | 0.0578 (10) | 0.0245 (7) | 0.0365 (8) | −0.0032 (7) | −0.0027 (7) | 0.0038 (6) |
O2 | 0.0523 (10) | 0.0312 (8) | 0.0335 (7) | 0.0015 (7) | −0.0024 (7) | 0.0151 (6) |
O3 | 0.0732 (12) | 0.0379 (9) | 0.0361 (8) | 0.0115 (8) | 0.0111 (8) | 0.0142 (7) |
O4 | 0.1109 (16) | 0.0458 (10) | 0.0450 (9) | 0.0226 (10) | 0.0208 (10) | 0.0243 (8) |
O5 | 0.0642 (11) | 0.0395 (9) | 0.0383 (8) | 0.0137 (8) | −0.0071 (8) | −0.0055 (7) |
O6 | 0.0571 (11) | 0.0462 (9) | 0.0405 (8) | 0.0094 (8) | 0.0057 (7) | 0.0243 (7) |
O7 | 0.0880 (14) | 0.0325 (8) | 0.0407 (9) | −0.0096 (9) | −0.0127 (8) | 0.0155 (7) |
O8 | 0.1060 (16) | 0.0327 (9) | 0.0400 (9) | −0.0055 (9) | −0.0281 (9) | 0.0097 (7) |
O1W | 0.0844 (15) | 0.0326 (9) | 0.0639 (11) | −0.0072 (10) | 0.0180 (10) | 0.0076 (8) |
O2W | 0.0593 (12) | 0.0346 (9) | 0.0751 (11) | 0.0035 (9) | −0.0190 (10) | 0.0086 (8) |
P1—O1 | 1.4940 (13) | C2—C3 | 1.381 (3) |
P1—O2 | 1.5238 (13) | C2—H2A | 0.9300 |
P1—C7 | 1.802 (2) | C3—C4 | 1.375 (3) |
P1—C1 | 1.809 (2) | C3—H3A | 0.9300 |
P2—O5 | 1.4884 (13) | C4—C5 | 1.373 (3) |
P2—O6 | 1.5142 (13) | C4—H4A | 0.9300 |
P2—C16 | 1.799 (2) | C5—C6 | 1.378 (3) |
P2—C10 | 1.808 (2) | C5—H5A | 0.9300 |
N1—C19 | 1.325 (2) | C6—H6A | 0.9300 |
N1—C21 | 1.352 (2) | C7—C8 | 1.521 (3) |
N2—C19 | 1.363 (2) | C7—H7A | 0.9700 |
N2—C20 | 1.374 (2) | C7—H7B | 0.9700 |
N2—H2B | 0.86 (2) | C8—C9 | 1.497 (3) |
N3—C20 | 1.319 (2) | C8—H8A | 0.9700 |
N3—C21 | 1.356 (2) | C8—H8B | 0.9700 |
N4—C21 | 1.312 (2) | C9—O3 | 1.203 (2) |
N4—H4B | 0.8600 | C9—O4 | 1.315 (2) |
N4—H4C | 0.8600 | C10—C11 | 1.386 (3) |
N5—C20 | 1.309 (2) | C10—C15 | 1.390 (3) |
N5—H5B | 0.8600 | C11—C12 | 1.386 (3) |
N5—H5C | 0.8600 | C11—H11A | 0.9300 |
N6—C19 | 1.311 (2) | C12—C13 | 1.368 (3) |
N6—H6B | 0.8600 | C12—H12A | 0.9300 |
N6—H6C | 0.8600 | C13—C14 | 1.370 (3) |
N7—C22 | 1.327 (2) | C13—H13A | 0.9300 |
N7—C24 | 1.359 (2) | C14—C15 | 1.379 (3) |
N8—C22 | 1.357 (2) | C14—H14A | 0.9300 |
N8—C23 | 1.370 (2) | C15—H15A | 0.9300 |
N8—H8C | 0.82 (2) | C16—C17 | 1.520 (3) |
N9—C23 | 1.325 (2) | C16—H16A | 0.9700 |
N9—C24 | 1.356 (2) | C16—H16B | 0.9700 |
N10—C24 | 1.312 (2) | C17—C18 | 1.494 (3) |
N10—H10A | 0.8600 | C17—H17A | 0.9700 |
N10—H10B | 0.8600 | C17—H17B | 0.9700 |
N11—C23 | 1.307 (2) | C18—O8 | 1.203 (2) |
N11—H11B | 0.8600 | C18—O7 | 1.307 (2) |
N11—H11C | 0.8600 | O4—H4D | 0.967 (17) |
N12—C22 | 1.312 (2) | O7—H7C | 0.956 (16) |
N12—H12B | 0.8600 | O1W—H1WA | 0.820 (16) |
N12—H12C | 0.8600 | O1W—H1WB | 0.856 (17) |
C1—C2 | 1.392 (3) | O2W—H2WA | 0.824 (16) |
C1—C6 | 1.398 (3) | O2W—H2WB | 0.847 (17) |
O1—P1—O2 | 115.60 (8) | C9—C8—C7 | 115.43 (16) |
O1—P1—C7 | 110.97 (9) | C9—C8—H8A | 108.4 |
O2—P1—C7 | 107.24 (9) | C7—C8—H8A | 108.4 |
O1—P1—C1 | 109.70 (8) | C9—C8—H8B | 108.4 |
O2—P1—C1 | 109.24 (8) | C7—C8—H8B | 108.4 |
C7—P1—C1 | 103.35 (9) | H8A—C8—H8B | 107.5 |
O5—P2—O6 | 113.92 (8) | O3—C9—O4 | 122.19 (18) |
O5—P2—C16 | 110.26 (10) | O3—C9—C8 | 125.95 (18) |
O6—P2—C16 | 108.06 (9) | O4—C9—C8 | 111.80 (17) |
O5—P2—C10 | 110.79 (9) | C11—C10—C15 | 118.35 (19) |
O6—P2—C10 | 110.30 (9) | C11—C10—P2 | 122.49 (15) |
C16—P2—C10 | 102.90 (9) | C15—C10—P2 | 119.10 (15) |
C19—N1—C21 | 115.77 (16) | C12—C11—C10 | 120.3 (2) |
C19—N2—C20 | 119.52 (16) | C12—C11—H11A | 119.9 |
C19—N2—H2B | 115.7 (14) | C10—C11—H11A | 119.9 |
C20—N2—H2B | 124.5 (14) | C13—C12—C11 | 120.5 (2) |
C20—N3—C21 | 116.36 (16) | C13—C12—H12A | 119.8 |
C21—N4—H4B | 120.0 | C11—C12—H12A | 119.8 |
C21—N4—H4C | 120.0 | C12—C13—C14 | 119.9 (2) |
H4B—N4—H4C | 120.0 | C12—C13—H13A | 120.0 |
C20—N5—H5B | 120.0 | C14—C13—H13A | 120.0 |
C20—N5—H5C | 120.0 | C13—C14—C15 | 120.1 (2) |
H5B—N5—H5C | 120.0 | C13—C14—H14A | 119.9 |
C19—N6—H6B | 120.0 | C15—C14—H14A | 119.9 |
C19—N6—H6C | 120.0 | C14—C15—C10 | 120.8 (2) |
H6B—N6—H6C | 120.0 | C14—C15—H15A | 119.6 |
C22—N7—C24 | 115.94 (16) | C10—C15—H15A | 119.6 |
C22—N8—C23 | 120.20 (16) | C17—C16—P2 | 112.83 (13) |
C22—N8—H8C | 116.3 (15) | C17—C16—H16A | 109.0 |
C23—N8—H8C | 123.4 (15) | P2—C16—H16A | 109.0 |
C23—N9—C24 | 115.80 (16) | C17—C16—H16B | 109.0 |
C24—N10—H10A | 120.0 | P2—C16—H16B | 109.0 |
C24—N10—H10B | 120.0 | H16A—C16—H16B | 107.8 |
H10A—N10—H10B | 120.0 | C18—C17—C16 | 115.44 (17) |
C23—N11—H11B | 120.0 | C18—C17—H17A | 108.4 |
C23—N11—H11C | 120.0 | C16—C17—H17A | 108.4 |
H11B—N11—H11C | 120.0 | C18—C17—H17B | 108.4 |
C22—N12—H12B | 120.0 | C16—C17—H17B | 108.4 |
C22—N12—H12C | 120.0 | H17A—C17—H17B | 107.5 |
H12B—N12—H12C | 120.0 | O8—C18—O7 | 122.34 (18) |
C2—C1—C6 | 117.75 (18) | O8—C18—C17 | 123.01 (18) |
C2—C1—P1 | 122.03 (14) | O7—C18—C17 | 114.61 (17) |
C6—C1—P1 | 120.02 (15) | N6—C19—N1 | 120.42 (17) |
C3—C2—C1 | 121.03 (19) | N6—C19—N2 | 118.02 (17) |
C3—C2—H2A | 119.5 | N1—C19—N2 | 121.56 (17) |
C1—C2—H2A | 119.5 | N5—C20—N3 | 121.40 (18) |
C4—C3—C2 | 120.1 (2) | N5—C20—N2 | 117.67 (17) |
C4—C3—H3A | 120.0 | N3—C20—N2 | 120.93 (17) |
C2—C3—H3A | 120.0 | N4—C21—N1 | 116.69 (16) |
C5—C4—C3 | 119.9 (2) | N4—C21—N3 | 117.50 (16) |
C5—C4—H4A | 120.0 | N1—C21—N3 | 125.81 (16) |
C3—C4—H4A | 120.0 | N12—C22—N7 | 120.49 (19) |
C4—C5—C6 | 120.4 (2) | N12—C22—N8 | 118.42 (18) |
C4—C5—H5A | 119.8 | N7—C22—N8 | 121.09 (17) |
C6—C5—H5A | 119.8 | N11—C23—N9 | 121.28 (18) |
C5—C6—C1 | 120.78 (19) | N11—C23—N8 | 117.68 (17) |
C5—C6—H6A | 119.6 | N9—C23—N8 | 121.04 (17) |
C1—C6—H6A | 119.6 | N10—C24—N9 | 117.22 (17) |
C8—C7—P1 | 115.26 (14) | N10—C24—N7 | 116.87 (17) |
C8—C7—H7A | 108.5 | N9—C24—N7 | 125.91 (17) |
P1—C7—H7A | 108.5 | C9—O4—H4D | 111.7 (17) |
C8—C7—H7B | 108.5 | C18—O7—H7C | 108.3 (15) |
P1—C7—H7B | 108.5 | H1WA—O1W—H1WB | 112 (3) |
H7A—C7—H7B | 107.5 | H2WA—O2W—H2WB | 113 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O1 | 0.82 (2) | 1.94 (2) | 2.742 (2) | 166 (3) |
N2—H2B···O2 | 0.86 (2) | 2.07 (2) | 2.914 (2) | 169 (2) |
O2W—H2WA···O5 | 0.82 (2) | 1.93 (2) | 2.729 (2) | 164 (3) |
N5—H5C···O1 | 0.86 | 1.99 | 2.847 (2) | 173 |
N6—H6C···O8 | 0.86 | 2.08 | 2.735 (2) | 133 |
O7—H7C···O2 | 0.96 (2) | 1.68 (2) | 2.6265 (19) | 172 (2) |
N8—H8C···O6 | 0.82 (2) | 2.28 (2) | 3.063 (2) | 160 (2) |
N11—H11C···O5 | 0.86 | 2.04 | 2.867 (2) | 162 |
O1W—H1WB···O6i | 0.86 (2) | 2.10 (2) | 2.939 (2) | 165 (3) |
O2W—H2WB···O2ii | 0.85 (2) | 2.02 (2) | 2.858 (2) | 170 (3) |
N4—H4B···O3iii | 0.86 | 2.09 | 2.929 (2) | 165 |
N4—H4C···O2Wiii | 0.86 | 2.02 | 2.824 (2) | 155 |
O4—H4D···O6iv | 0.97 (2) | 1.61 (2) | 2.578 (2) | 175 (3) |
N5—H5B···N9iii | 0.86 | 2.34 | 3.186 (2) | 169 |
N6—H6B···N7v | 0.86 | 2.19 | 3.030 (2) | 166 |
N10—H10A···O1Wiii | 0.86 | 2.03 | 2.822 (2) | 154 |
N10—H10B···O8v | 0.86 | 2.07 | 2.918 (2) | 168 |
N11—H11B···N3iii | 0.86 | 2.26 | 3.109 (2) | 169 |
N12—H12B···N1v | 0.86 | 2.27 | 3.117 (2) | 170 |
N12—H12C···O3vi | 0.86 | 2.37 | 2.957 (2) | 126 |
Symmetry codes: (i) x+1, y+1, z; (ii) x−1, y, z; (iii) −x+1, −y+2, −z+1; (iv) x, y+1, z; (v) −x+1, −y+1, −z+1; (vi) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | C3H7N6+·C9H10O4P−·H2O |
Mr | 358.30 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 7.2280 (1), 12.4251 (2), 18.9837 (3) |
α, β, γ (°) | 105.388 (1), 91.348 (1), 92.604 (1) |
V (Å3) | 1640.96 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.21 |
Crystal size (mm) | 0.35 × 0.15 × 0.15 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2008) |
Tmin, Tmax | 0.673, 0.746 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14192, 6378, 4783 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.115, 1.10 |
No. of reflections | 6378 |
No. of parameters | 457 |
No. of restraints | 8 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.31, −0.37 |
Computer programs: SMART (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2010), SHELXTL (Bruker, 2008).
P1—O1 | 1.4940 (13) | C9—O3 | 1.203 (2) |
P1—O2 | 1.5238 (13) | C9—O4 | 1.315 (2) |
P2—O5 | 1.4884 (13) | C18—O8 | 1.203 (2) |
P2—O6 | 1.5142 (13) | C18—O7 | 1.307 (2) |
C19—N1—C21 | 115.77 (16) | C22—N7—C24 | 115.94 (16) |
C19—N2—C20 | 119.52 (16) | C22—N8—C23 | 120.20 (16) |
C20—N3—C21 | 116.36 (16) | C23—N9—C24 | 115.80 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O1 | 0.820 (16) | 1.940 (17) | 2.742 (2) | 166 (3) |
N2—H2B···O2 | 0.86 (2) | 2.07 (2) | 2.914 (2) | 169 (2) |
O2W—H2WA···O5 | 0.824 (16) | 1.928 (17) | 2.729 (2) | 164 (3) |
N5—H5C···O1 | 0.86 | 1.99 | 2.847 (2) | 173.3 |
N6—H6C···O8 | 0.86 | 2.08 | 2.735 (2) | 132.7 |
O7—H7C···O2 | 0.956 (16) | 1.677 (17) | 2.6265 (19) | 172 (2) |
N8—H8C···O6 | 0.82 (2) | 2.28 (2) | 3.063 (2) | 160 (2) |
N11—H11C···O5 | 0.86 | 2.04 | 2.867 (2) | 161.7 |
O1W—H1WB···O6i | 0.856 (17) | 2.103 (17) | 2.939 (2) | 165 (3) |
O2W—H2WB···O2ii | 0.847 (17) | 2.020 (17) | 2.858 (2) | 170 (3) |
N4—H4B···O3iii | 0.86 | 2.09 | 2.929 (2) | 164.7 |
N4—H4C···O2Wiii | 0.86 | 2.02 | 2.824 (2) | 155.4 |
O4—H4D···O6iv | 0.967 (17) | 1.613 (17) | 2.578 (2) | 175 (3) |
N5—H5B···N9iii | 0.86 | 2.34 | 3.186 (2) | 169.1 |
N6—H6B···N7v | 0.86 | 2.19 | 3.030 (2) | 166.2 |
N10—H10A···O1Wiii | 0.86 | 2.03 | 2.822 (2) | 153.5 |
N10—H10B···O8v | 0.86 | 2.07 | 2.918 (2) | 168.4 |
N11—H11B···N3iii | 0.86 | 2.26 | 3.109 (2) | 169.2 |
N12—H12B···N1v | 0.86 | 2.27 | 3.117 (2) | 170.4 |
N12—H12C···O3vi | 0.86 | 2.37 | 2.957 (2) | 125.6 |
Symmetry codes: (i) x+1, y+1, z; (ii) x−1, y, z; (iii) −x+1, −y+2, −z+1; (iv) x, y+1, z; (v) −x+1, −y+1, −z+1; (vi) x, y−1, z. |
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The understanding of intermolecular interactions in molecular crystals is very significant for the design of novel materials with tailored structures and properties (Seddon & Zaworotko, 1999; Desiraju, 2007). Specifically, the hydrogen bond is one of the most important intermolecular interactions owing to its directionality and energetic favourability (Moulton & Zaworotko, 2001; Reddy et al., 2006).
As an excellent H-atom donor and acceptor, melamine, a famous organic base with a 1,3,5-triazine skeleton, has been widely utilized to create one-, two- and three-dimensional networks in combination with various carboxylic acids such as glutaric acid, maleic acid, terephthalic acid, benzene-1,3,5-tricarboxylic acid, malonic acid, 3,5-dinitrobenzoic acid, bile acid and tris(2-carboxyethyl)isocyanuric acid (Janczak & Perpétuo, 2002; Janczak & Perpétuo, 2004; Zhang & Chen, 2005; Eppel & Bernstein, 2009; Ikonen et al., 2010; Dai et al., 2012). However, the use of phosphinic acid, a formally analogous acid of carboxylic acid [i.e. both contain one (P/C)═O group and one (P/C)–OH group], as the counterpart component, has never been investigated.
Recently, we have undertaken a study of the coordination and supramolecular chemistry of (2-carboxyethyl)(phenyl)phosphinic acid (H2L), an an asymmetric binary acid containing both carboxy and phosphinic acid groups separated by a flexible –CH2CH2– spacer, with the latter being additionally bonded to a phenyl group (Sun et al., 2011; Hu et al., 2011; Dong et al., 2012). As an expansion of our work, we report here a cocrystal of melamine (ma) and H2L obtained from a water solution, namely, melaminium (2-carboxyethyl)(phenyl)phosphinate monohydrate, (maH)(HL).H2O, (I), which exhibits an interesting architecture with diversified hydrogen-bonding modes.
Compound (I) crystallizes in the triclinic space group P1. The asymmetric unit contains two (2-carboxyethyl)(phenyl)phosphinate (HL-) anions, two melaminium (2,4,6-triamino-1,3,5-triazin-1-ium, maH+) cations and two water molecules (Fig. 1). Judging from the P—O and C—O bond lengths of the HL- anion (Table 1), the phosphinic H atom of each H2L molecule is transferred to a ring N atom of each melamine molecule (N2 and N8), while the carboxy group remains protonated. The 1H-protonation of two melamine molecules in (I) is also evidenced by the fact that the internal C—N—C angle involving the protonated ring N atom is significantly greater than the remaining two C—N—C angles involving the nonprotonated ring N atoms (Table 1).
Extensive hydrogen-bond interactions are observed in (I) (Fig. 2 and Table 2). A close analysis reveals that there are two types of secondary building units (SBUs) in the crystal structure, namely cationic [(maH+)2]∞ ribbons and anionic {[(HL)2(H2O)2]2-}∞ layers (denoted A and B, respectively). SBU A, a one-dimensional [maH+]∞ ribbon running along the b axis, is formed by pairs of almost linear N—H···N hydrogen bonds (Fig. 2a and Table 2) between two crystallographically independent maH+ cations. Such a ribbon has been observed frequently in cocrystals of melamine (Janczak & Perpétuo, 2002; Janczak & Perpétuo, 2004; Zhang & Chen, 2005; Eppel & Bernstein, 2009; Ikonen et al., 2010; Dai et al., 2012) and it features an R22(8) ring motif, discussed here according to the graph-set analysis nomenclature of Bernstein et al. (1995). On the other hand, SBU B, an anionic {[(HL)2(H2O)2]2-}∞ layer, is formed by six types of O—H···O hydrogen bonds among two unique HL- anions and two unique water molecules, in almost linear geometries (Fig. 3 and Table 2). The layer features two edge-sharing but essentially similar R65(24) ring motifs, both with five phosphinate O atoms acting as hydrogen-bond acceptors and two carboxy –OH groups as well as two water molecules serving as hydrogen-bond donors. The two hydrogen-bond ring motifs are conformational isomeric and they differ slightly in their geometric parameters. For example, the O4···O7 distance between two carboxy O atoms is 6.131 (3) Å in one ring containing one P1 and two P2 atoms, whereas the distance is 7.080 (3) Å in the other ring containing one P2 and two P1 atoms.
The combination of these cationic A ribbons and a couple of charge-balanced B layers via the hydrogen-bond and electrostatic interactions generates a two-dimensional sandwich-like `B–A∞–B' layer, in which π–π packing interactions are also present between the melaminium rings of adjacent A ribbons along the a axis (Fig. 4). Furthermore, these large-scale `B–A∞–B' layers stack along the c axis through van der Waals interactions to form a three-dimensional supramolecular structure.