The reaction of aminophosphinic acid with CdCl
2·2.5H
2O or CoCl
2·6H
2O in concentrated hydrochloric acid yielded the isostructural compounds 1,4-bis{[hydroxy(phenyl)phosphoryl]methyl}piperazine-1,4-diium tetrachloridocadmate(II) dihydrate, (C
18H
26N
2O
4P
2)[CdCl
4]·2H
2O, (I), and 1,4-bis{[hydroxy(phenyl)phosphoryl]methyl}piperazine-1,4-diium tetrachloridocobaltate(II) dihydrate, (C
18H
26N
2O
4P
2)[CoCl
4]·2H
2O, (II). The asymmetric unit of each contains two half dications, both located on crystallographic centres of inversion, a tetrachloridometallate(II) dianion and two solvent water molecules. The residues are linked into two-dimensional layers in the
ab plane by O—H
O hydrogen bonds.
Supporting information
CCDC references: 956994; 956995
PBPA hydrochloride was synthesized according to the method of Choi et
al. (1994) using a typical Mannich reaction in which phosphorous acid was
replaced by phenylphosphinic acid. Phenylphosphinic acid (1.42 g, 0.01 mol)
and piperazine (4.307 g, 0.05 mol) were dissolved in hydrochloric acid (6
M, 50 ml) and refluxed for 1 h under a nitrogen atmosphere.
Formaldehyde (50 ml) in hydrochloric acid (37%) was added dropwise with
vigorous stirring and the temperature was maintained at 378–383 K for 4 h.
This solution was then concentrated under reduced pressure and allowed to cool
to room temperature. Acetone (100 ml) was added and the white precipitate was
collected by filtration. Colourless crystals of (I) and (II) suitable for
single-crystal diffraction studies were obtained by slow evaporation from
solutions of the white precipitate and CdCl2.2.5H2O (2.284 g, 0.01 mol) or
CoCl2.6H2O (2.379 g, 0.01 mol) in hydrochloric acid (4 M, 40 ml),
respectively. The crystalline product was filtered off, washed with water and
dried in air.
C-bound H atoms were positioned geometrically and refined as riding, with C—H
= 0.95 Å and Uiso(H) = 1.2Ueq(C). The positions of N-bound
H atoms were constrained to N—H = 0.91 Å, with Uiso(H) =
1.2Ueq(N). The positions of O-bound H atoms were constrained to O—H
= 0.82 Å, with Uiso(H) = 1.5Ueq(O). Water H atoms were
located in difference Fourier syntheses and constrained to O—H and H···H
distances of 0.85 and 1.35 Å, respectively; Uiso(H) values were set
at 1.5Ueq(O).
For both compounds, data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008 and PLATON (Spek, 2009).
(I) 1,4-Bis{[hydroxy(phenyl)phosphoryl]methyl}piperazine-1,4-diium
tetrachloridocadmate(II) dihydrate
top
Crystal data top
(C18H26N2O4P2)[CdCl4]·2H2O | Z = 2 |
Mr = 686.58 | F(000) = 692 |
Triclinic, P1 | Dx = 1.693 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.6159 (3) Å | Cell parameters from 4676 reflections |
b = 14.5242 (7) Å | θ = 2.8–29.5° |
c = 14.5449 (7) Å | µ = 1.36 mm−1 |
α = 87.035 (4)° | T = 293 K |
β = 81.713 (4)° | Plate, colourless |
γ = 76.947 (4)° | 0.30 × 0.25 × 0.20 mm |
V = 1347.03 (11) Å3 | |
Data collection top
Agilent Xcalibur (Atlas, Gemini ultra) diffractometer | 4832 independent reflections |
Radiation source: fine-focus sealed tube | 3928 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
Detector resolution: 10.4170 pixels mm-1 | θmax = 25.2°, θmin = 2.8° |
ω scans | h = −7→7 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | k = −16→17 |
Tmin = 0.686, Tmax = 0.772 | l = −16→17 |
10146 measured reflections | |
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.069 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0288P)2] where P = (Fo2 + 2Fc2)/3 |
4832 reflections | (Δ/σ)max < 0.001 |
300 parameters | Δρmax = 0.36 e Å−3 |
0 restraints | Δρmin = −0.53 e Å−3 |
Crystal data top
(C18H26N2O4P2)[CdCl4]·2H2O | γ = 76.947 (4)° |
Mr = 686.58 | V = 1347.03 (11) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.6159 (3) Å | Mo Kα radiation |
b = 14.5242 (7) Å | µ = 1.36 mm−1 |
c = 14.5449 (7) Å | T = 293 K |
α = 87.035 (4)° | 0.30 × 0.25 × 0.20 mm |
β = 81.713 (4)° | |
Data collection top
Agilent Xcalibur (Atlas, Gemini ultra) diffractometer | 4832 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | 3928 reflections with I > 2σ(I) |
Tmin = 0.686, Tmax = 0.772 | Rint = 0.036 |
10146 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.069 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.36 e Å−3 |
4832 reflections | Δρmin = −0.53 e Å−3 |
300 parameters | |
Special details top
Experimental. CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm. |
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. |
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 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.0564 (5) | 0.1126 (2) | 0.84464 (19) | 0.0332 (7) | |
C2 | 0.2323 (6) | 0.0943 (3) | 0.8900 (2) | 0.0488 (9) | |
H2 | 0.3649 | 0.0778 | 0.8559 | 0.059* | |
C3 | 0.2123 (7) | 0.1005 (3) | 0.9844 (3) | 0.0640 (12) | |
H3 | 0.3309 | 0.0888 | 1.0143 | 0.077* | |
C4 | 0.0179 (8) | 0.1238 (3) | 1.0347 (2) | 0.0642 (12) | |
H4 | 0.0054 | 0.1279 | 1.0990 | 0.077* | |
C5 | −0.1576 (7) | 0.1411 (3) | 0.9925 (3) | 0.0618 (12) | |
H5 | −0.2888 | 0.1572 | 1.0278 | 0.074* | |
C6 | −0.1412 (6) | 0.1348 (3) | 0.8958 (2) | 0.0492 (10) | |
H6 | −0.2606 | 0.1452 | 0.8666 | 0.059* | |
C7 | 0.0797 (5) | −0.0091 (2) | 0.69128 (18) | 0.0273 (7) | |
H7A | 0.2124 | −0.0498 | 0.7020 | 0.033* | |
H7B | −0.0290 | −0.0300 | 0.7336 | 0.033* | |
C8 | 0.1984 (4) | 0.0102 (2) | 0.52114 (18) | 0.0264 (7) | |
H8A | 0.3399 | −0.0169 | 0.5338 | 0.032* | |
H8B | 0.1758 | 0.0784 | 0.5235 | 0.032* | |
C9 | −0.1740 (4) | 0.0174 (2) | 0.57428 (19) | 0.0281 (7) | |
H9A | −0.2031 | 0.0858 | 0.5779 | 0.034* | |
H9B | −0.2730 | −0.0057 | 0.6204 | 0.034* | |
C10 | 0.3315 (5) | 0.3629 (2) | 0.8662 (2) | 0.0344 (8) | |
C11 | 0.4496 (6) | 0.3744 (3) | 0.9321 (2) | 0.0637 (12) | |
H11 | 0.5890 | 0.3773 | 0.9148 | 0.076* | |
C12 | 0.3634 (7) | 0.3821 (4) | 1.0255 (3) | 0.0797 (15) | |
H12 | 0.4453 | 0.3898 | 1.0701 | 0.096* | |
C13 | 0.1602 (7) | 0.3781 (3) | 1.0510 (2) | 0.0628 (12) | |
H13 | 0.1024 | 0.3837 | 1.1132 | 0.075* | |
C14 | 0.0398 (6) | 0.3660 (3) | 0.9855 (3) | 0.0613 (12) | |
H14 | −0.0991 | 0.3626 | 1.0033 | 0.074* | |
C15 | 0.1246 (6) | 0.3587 (3) | 0.8929 (2) | 0.0499 (9) | |
H15 | 0.0423 | 0.3509 | 0.8484 | 0.060* | |
C16 | 0.3829 (4) | 0.4684 (2) | 0.69595 (17) | 0.0262 (7) | |
H16A | 0.2396 | 0.4987 | 0.7191 | 0.031* | |
H16B | 0.4736 | 0.5051 | 0.7161 | 0.031* | |
C17 | 0.6241 (4) | 0.4226 (2) | 0.54754 (18) | 0.0291 (7) | |
H17A | 0.6542 | 0.3567 | 0.5673 | 0.035* | |
H17B | 0.7270 | 0.4523 | 0.5679 | 0.035* | |
C18 | 0.3599 (4) | 0.5708 (2) | 0.55706 (18) | 0.0267 (7) | |
H18A | 0.4565 | 0.6042 | 0.5774 | 0.032* | |
H18B | 0.2193 | 0.6012 | 0.5839 | 0.032* | |
Cd1 | 0.43344 (4) | 0.253741 (17) | 0.279474 (15) | 0.03649 (9) | |
Cl1 | 0.18030 (12) | 0.40601 (6) | 0.30776 (5) | 0.0405 (2) | |
Cl2 | 0.44108 (13) | 0.19941 (6) | 0.44738 (5) | 0.0417 (2) | |
Cl3 | 0.77149 (13) | 0.28882 (7) | 0.22373 (6) | 0.0489 (2) | |
Cl4 | 0.37448 (15) | 0.11487 (7) | 0.21324 (6) | 0.0501 (2) | |
N1 | 0.0450 (3) | −0.02374 (16) | 0.59388 (14) | 0.0228 (5) | |
H1 | 0.0669 | −0.0873 | 0.5871 | 0.027* | |
N2 | 0.4087 (3) | 0.47040 (16) | 0.59151 (14) | 0.0229 (5) | |
H2A | 0.3149 | 0.4404 | 0.5732 | 0.028* | |
O1 | 0.3066 (3) | 0.11996 (15) | 0.68167 (15) | 0.0372 (5) | |
H1A | 0.3180 | 0.1741 | 0.6888 | 0.056* | |
O2 | −0.0884 (4) | 0.17847 (16) | 0.68263 (14) | 0.0453 (6) | |
O3 | 0.6827 (3) | 0.32796 (16) | 0.74527 (15) | 0.0399 (6) | |
H3A | 0.7340 | 0.2771 | 0.7202 | 0.060* | |
O4 | 0.3562 (4) | 0.28648 (16) | 0.69451 (14) | 0.0431 (6) | |
O1W | 0.1184 (3) | 0.38355 (19) | 0.53961 (17) | 0.0542 (7) | |
H2W | 0.1400 | 0.3699 | 0.4824 | 0.081* | |
H1W | 0.1458 | 0.3308 | 0.5685 | 0.081* | |
O2W | 0.0491 (3) | 0.78983 (15) | 0.58781 (16) | 0.0464 (6) | |
H3W | 0.0815 | 0.7635 | 0.6388 | 0.070* | |
H4W | −0.0794 | 0.7895 | 0.5886 | 0.070* | |
P1 | 0.08217 (12) | 0.11015 (6) | 0.72146 (5) | 0.02879 (19) | |
P2 | 0.44266 (12) | 0.35047 (6) | 0.74696 (5) | 0.02890 (19) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0464 (19) | 0.0285 (18) | 0.0258 (15) | −0.0088 (15) | −0.0063 (14) | −0.0042 (13) |
C2 | 0.056 (2) | 0.055 (2) | 0.0353 (19) | −0.0051 (19) | −0.0142 (17) | −0.0094 (16) |
C3 | 0.087 (3) | 0.063 (3) | 0.044 (2) | −0.005 (2) | −0.030 (2) | −0.0099 (19) |
C4 | 0.114 (4) | 0.047 (3) | 0.0302 (19) | −0.011 (3) | −0.014 (2) | −0.0033 (17) |
C5 | 0.080 (3) | 0.057 (3) | 0.041 (2) | −0.014 (2) | 0.019 (2) | −0.0072 (18) |
C6 | 0.055 (2) | 0.050 (2) | 0.040 (2) | −0.0105 (19) | 0.0017 (17) | −0.0006 (17) |
C7 | 0.0372 (17) | 0.0245 (17) | 0.0229 (14) | −0.0108 (13) | −0.0072 (13) | 0.0014 (12) |
C8 | 0.0227 (14) | 0.0317 (18) | 0.0268 (15) | −0.0118 (13) | −0.0019 (12) | 0.0005 (12) |
C9 | 0.0232 (15) | 0.0325 (18) | 0.0288 (15) | −0.0086 (13) | 0.0001 (12) | −0.0030 (13) |
C10 | 0.0424 (19) | 0.0329 (19) | 0.0277 (16) | −0.0090 (15) | −0.0057 (14) | 0.0056 (13) |
C11 | 0.050 (2) | 0.107 (4) | 0.036 (2) | −0.021 (2) | −0.0055 (18) | −0.006 (2) |
C12 | 0.076 (3) | 0.133 (5) | 0.034 (2) | −0.026 (3) | −0.015 (2) | −0.005 (2) |
C13 | 0.076 (3) | 0.079 (3) | 0.030 (2) | −0.018 (2) | 0.003 (2) | 0.0043 (19) |
C14 | 0.055 (2) | 0.078 (3) | 0.049 (2) | −0.025 (2) | 0.014 (2) | −0.001 (2) |
C15 | 0.053 (2) | 0.061 (3) | 0.040 (2) | −0.0235 (19) | −0.0047 (17) | −0.0052 (17) |
C16 | 0.0288 (15) | 0.0271 (17) | 0.0222 (14) | −0.0065 (13) | −0.0007 (12) | −0.0035 (12) |
C17 | 0.0254 (15) | 0.0268 (17) | 0.0312 (15) | 0.0011 (13) | −0.0019 (12) | 0.0005 (13) |
C18 | 0.0278 (15) | 0.0194 (16) | 0.0299 (15) | −0.0006 (12) | −0.0010 (12) | −0.0006 (12) |
Cd1 | 0.03733 (14) | 0.03385 (15) | 0.03849 (14) | −0.00974 (11) | −0.00116 (10) | −0.00550 (10) |
Cl1 | 0.0332 (4) | 0.0403 (5) | 0.0473 (5) | −0.0030 (4) | −0.0092 (4) | −0.0070 (4) |
Cl2 | 0.0446 (5) | 0.0425 (5) | 0.0373 (4) | −0.0109 (4) | −0.0043 (4) | 0.0063 (4) |
Cl3 | 0.0424 (5) | 0.0586 (6) | 0.0470 (5) | −0.0212 (4) | 0.0087 (4) | −0.0098 (4) |
Cl4 | 0.0627 (6) | 0.0465 (6) | 0.0475 (5) | −0.0234 (5) | −0.0069 (4) | −0.0110 (4) |
N1 | 0.0271 (12) | 0.0177 (13) | 0.0258 (12) | −0.0087 (10) | −0.0044 (10) | −0.0010 (10) |
N2 | 0.0215 (12) | 0.0244 (14) | 0.0237 (12) | −0.0060 (10) | −0.0028 (9) | −0.0050 (10) |
O1 | 0.0464 (13) | 0.0291 (13) | 0.0394 (12) | −0.0183 (10) | 0.0015 (10) | −0.0062 (10) |
O2 | 0.0566 (14) | 0.0349 (14) | 0.0400 (12) | 0.0083 (11) | −0.0181 (11) | −0.0103 (10) |
O3 | 0.0390 (12) | 0.0318 (14) | 0.0457 (13) | 0.0005 (10) | −0.0055 (10) | −0.0083 (10) |
O4 | 0.0623 (15) | 0.0331 (13) | 0.0396 (12) | −0.0216 (12) | −0.0069 (11) | −0.0049 (10) |
O1W | 0.0409 (14) | 0.0589 (17) | 0.0671 (16) | −0.0104 (12) | −0.0147 (12) | −0.0228 (13) |
O2W | 0.0415 (13) | 0.0308 (13) | 0.0696 (15) | −0.0122 (11) | −0.0112 (11) | 0.0030 (11) |
P1 | 0.0378 (4) | 0.0243 (4) | 0.0250 (4) | −0.0059 (4) | −0.0066 (3) | −0.0040 (3) |
P2 | 0.0367 (4) | 0.0232 (4) | 0.0279 (4) | −0.0092 (4) | −0.0041 (3) | −0.0006 (3) |
Geometric parameters (Å, º) top
C1—C6 | 1.386 (4) | C13—H13 | 0.93 |
C1—C2 | 1.387 (5) | C14—C15 | 1.382 (5) |
C1—P1 | 1.776 (3) | C14—H14 | 0.93 |
C2—C3 | 1.366 (5) | C15—H15 | 0.93 |
C2—H2 | 0.93 | C16—N2 | 1.503 (3) |
C3—C4 | 1.364 (6) | C16—P2 | 1.814 (3) |
C3—H3 | 0.93 | C16—H16A | 0.97 |
C4—C5 | 1.359 (6) | C16—H16B | 0.97 |
C4—H4 | 0.93 | C17—N2 | 1.503 (3) |
C5—C6 | 1.400 (5) | C17—C18ii | 1.509 (4) |
C5—H5 | 0.93 | C17—H17A | 0.97 |
C6—H6 | 0.93 | C17—H17B | 0.97 |
C7—N1 | 1.501 (3) | C18—N2 | 1.496 (3) |
C7—P1 | 1.813 (3) | C18—C17ii | 1.509 (4) |
C7—H7A | 0.97 | C18—H18A | 0.97 |
C7—H7B | 0.97 | C18—H18B | 0.97 |
C8—N1 | 1.501 (3) | Cd1—Cl4 | 2.4110 (9) |
C8—C9i | 1.505 (4) | Cd1—Cl3 | 2.4224 (8) |
C8—H8A | 0.97 | Cd1—Cl1 | 2.4673 (8) |
C8—H8B | 0.97 | Cd1—Cl2 | 2.5314 (8) |
C9—N1 | 1.500 (3) | N1—H1 | 0.91 |
C9—C8i | 1.505 (4) | N2—H2A | 0.91 |
C9—H9A | 0.97 | O1—P1 | 1.549 (2) |
C9—H9B | 0.97 | O1—H1A | 0.82 |
C10—C11 | 1.360 (5) | O2—P1 | 1.482 (2) |
C10—C15 | 1.382 (5) | O3—P2 | 1.544 (2) |
C10—P2 | 1.785 (3) | O3—H3A | 0.82 |
C11—C12 | 1.395 (5) | O4—P2 | 1.488 (2) |
C11—H11 | 0.93 | O1W—H2W | 0.85 |
C12—C13 | 1.355 (6) | O1W—H1W | 0.85 |
C12—H12 | 0.93 | O2W—H3W | 0.85 |
C13—C14 | 1.369 (6) | O2W—H4W | 0.8499 |
| | | |
C6—C1—C2 | 119.6 (3) | C14—C15—H15 | 119.9 |
C6—C1—P1 | 119.7 (3) | N2—C16—P2 | 113.89 (19) |
C2—C1—P1 | 120.6 (2) | N2—C16—H16A | 108.8 |
C3—C2—C1 | 120.5 (3) | P2—C16—H16A | 108.8 |
C3—C2—H2 | 119.8 | N2—C16—H16B | 108.8 |
C1—C2—H2 | 119.8 | P2—C16—H16B | 108.8 |
C4—C3—C2 | 119.9 (4) | H16A—C16—H16B | 107.7 |
C4—C3—H3 | 120.1 | N2—C17—C18ii | 110.7 (2) |
C2—C3—H3 | 120.1 | N2—C17—H17A | 109.5 |
C5—C4—C3 | 121.1 (3) | C18ii—C17—H17A | 109.5 |
C5—C4—H4 | 119.5 | N2—C17—H17B | 109.5 |
C3—C4—H4 | 119.5 | C18ii—C17—H17B | 109.5 |
C4—C5—C6 | 120.1 (3) | H17A—C17—H17B | 108.1 |
C4—C5—H5 | 119.9 | N2—C18—C17ii | 111.9 (2) |
C6—C5—H5 | 119.9 | N2—C18—H18A | 109.2 |
C1—C6—C5 | 118.8 (4) | C17ii—C18—H18A | 109.2 |
C1—C6—H6 | 120.6 | N2—C18—H18B | 109.2 |
C5—C6—H6 | 120.6 | C17ii—C18—H18B | 109.2 |
N1—C7—P1 | 117.00 (19) | H18A—C18—H18B | 107.9 |
N1—C7—H7A | 108.0 | Cl4—Cd1—Cl3 | 114.14 (3) |
P1—C7—H7A | 108.0 | Cl4—Cd1—Cl1 | 126.99 (3) |
N1—C7—H7B | 108.0 | Cl3—Cd1—Cl1 | 107.34 (3) |
P1—C7—H7B | 108.0 | Cl4—Cd1—Cl2 | 100.33 (3) |
H7A—C7—H7B | 107.3 | Cl3—Cd1—Cl2 | 106.91 (3) |
N1—C8—C9i | 110.9 (2) | Cl1—Cd1—Cl2 | 97.59 (3) |
N1—C8—H8A | 109.5 | C9—N1—C7 | 113.9 (2) |
C9i—C8—H8A | 109.5 | C9—N1—C8 | 109.7 (2) |
N1—C8—H8B | 109.5 | C7—N1—C8 | 113.3 (2) |
C9i—C8—H8B | 109.5 | C9—N1—H1 | 106.5 |
H8A—C8—H8B | 108.1 | C7—N1—H1 | 106.5 |
N1—C9—C8i | 109.6 (2) | C8—N1—H1 | 106.5 |
N1—C9—H9A | 109.7 | C18—N2—C17 | 109.1 (2) |
C8i—C9—H9A | 109.7 | C18—N2—C16 | 109.3 (2) |
N1—C9—H9B | 109.7 | C17—N2—C16 | 113.6 (2) |
C8i—C9—H9B | 109.7 | C18—N2—H2A | 108.2 |
H9A—C9—H9B | 108.2 | C17—N2—H2A | 108.2 |
C11—C10—C15 | 119.2 (3) | C16—N2—H2A | 108.2 |
C11—C10—P2 | 120.7 (3) | P1—O1—H1A | 109.5 |
C15—C10—P2 | 120.1 (3) | P2—O3—H3A | 109.5 |
C10—C11—C12 | 120.5 (4) | H2W—O1W—H1W | 105.2 |
C10—C11—H11 | 119.7 | H3W—O2W—H4W | 105.2 |
C12—C11—H11 | 119.7 | O2—P1—O1 | 115.04 (13) |
C13—C12—C11 | 120.0 (4) | O2—P1—C1 | 112.74 (13) |
C13—C12—H12 | 120.0 | O1—P1—C1 | 108.41 (14) |
C11—C12—H12 | 120.0 | O2—P1—C7 | 109.88 (14) |
C12—C13—C14 | 120.1 (3) | O1—P1—C7 | 103.21 (13) |
C12—C13—H13 | 119.9 | C1—P1—C7 | 106.85 (13) |
C14—C13—H13 | 119.9 | O4—P2—O3 | 116.81 (13) |
C13—C14—C15 | 120.1 (4) | O4—P2—C10 | 114.27 (14) |
C13—C14—H14 | 120.0 | O3—P2—C10 | 106.45 (14) |
C15—C14—H14 | 120.0 | O4—P2—C16 | 108.72 (14) |
C10—C15—C14 | 120.1 (4) | O3—P2—C16 | 104.15 (13) |
C10—C15—H15 | 119.9 | C10—P2—C16 | 105.42 (13) |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···O4 | 0.85 | 2.43 | 3.038 (3) | 129 |
O1W—H2W···Cl2 | 0.85 | 2.82 | 3.237 (2) | 112 |
O1W—H2W···Cl1 | 0.85 | 2.55 | 3.346 (3) | 155 |
O1—H1A···O4 | 0.82 | 1.72 | 2.533 (3) | 175 |
N2—H2A···O1W | 0.91 | 1.82 | 2.732 (3) | 178 |
O2W—H4W···Cl2iii | 0.85 | 2.49 | 3.323 (2) | 167 |
O2W—H3W···Cl3ii | 0.85 | 2.36 | 3.198 (3) | 167 |
O3—H3A···O2iv | 0.82 | 1.69 | 2.482 (3) | 161 |
N1—H1···O2Wv | 0.91 | 1.81 | 2.708 (3) | 167 |
Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) −x, −y+1, −z+1; (iv) x+1, y, z; (v) x, y−1, z. |
(II) 1,4-Bis{[hydroxy(phenyl)phosphoryl]methyl}piperazine-1,4-diium
tetrachloridocobaltate(II) dihydrate
top
Crystal data top
(C18H26N2O4P2)[CoCl4]·2H2O | Z = 2 |
Mr = 633.11 | F(000) = 650 |
Triclinic, P1 | Dx = 1.576 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.6448 (4) Å | Cell parameters from 2119 reflections |
b = 14.4213 (14) Å | θ = 2.9–29.5° |
c = 14.4804 (16) Å | µ = 1.20 mm−1 |
α = 87.523 (8)° | T = 293 K |
β = 80.727 (7)° | Plate, purple |
γ = 76.990 (7)° | 0.30 × 0.25 × 0.20 mm |
V = 1334.3 (2) Å3 | |
Data collection top
Agilent Xcalibur (Atlas, Gemini ultra) diffractometer | 4786 independent reflections |
Radiation source: fine-focus sealed tube | 2993 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.061 |
Detector resolution: 10.4170 pixels mm-1 | θmax = 25.2°, θmin = 2.9° |
ω scans | h = −7→7 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | k = −14→17 |
Tmin = 0.715, Tmax = 0.795 | l = −16→17 |
10695 measured reflections | |
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)] = 0.069 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.157 | H-atom parameters constrained |
S = 0.99 | w = 1/[σ2(Fo2) + (0.0602P)2] where P = (Fo2 + 2Fc2)/3 |
4786 reflections | (Δ/σ)max < 0.001 |
300 parameters | Δρmax = 1.06 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
Crystal data top
(C18H26N2O4P2)[CoCl4]·2H2O | γ = 76.990 (7)° |
Mr = 633.11 | V = 1334.3 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.6448 (4) Å | Mo Kα radiation |
b = 14.4213 (14) Å | µ = 1.20 mm−1 |
c = 14.4804 (16) Å | T = 293 K |
α = 87.523 (8)° | 0.30 × 0.25 × 0.20 mm |
β = 80.727 (7)° | |
Data collection top
Agilent Xcalibur (Atlas, Gemini ultra) diffractometer | 4786 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | 2993 reflections with I > 2σ(I) |
Tmin = 0.715, Tmax = 0.795 | Rint = 0.061 |
10695 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.069 | 0 restraints |
wR(F2) = 0.157 | H-atom parameters constrained |
S = 0.99 | Δρmax = 1.06 e Å−3 |
4786 reflections | Δρmin = −0.37 e Å−3 |
300 parameters | |
Special details top
Experimental. CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm. |
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. |
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 >
2sigma(F2) is used only for calculating R-factors(gt) etc. and is not
relevant to the choice of reflections for refinement. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.0647 (10) | 0.1116 (4) | 0.8477 (4) | 0.0379 (15) | |
C2 | 0.2435 (11) | 0.0933 (5) | 0.8902 (5) | 0.0515 (18) | |
H2 | 0.3750 | 0.0762 | 0.8541 | 0.062* | |
C3 | 0.2246 (14) | 0.1007 (6) | 0.9859 (5) | 0.065 (2) | |
H3 | 0.3436 | 0.0901 | 1.0144 | 0.078* | |
C4 | 0.0325 (15) | 0.1234 (5) | 1.0383 (5) | 0.064 (2) | |
H4 | 0.0212 | 0.1267 | 1.1030 | 0.077* | |
C5 | −0.1461 (13) | 0.1417 (5) | 0.9979 (5) | 0.061 (2) | |
H5 | −0.2767 | 0.1577 | 1.0350 | 0.073* | |
C6 | −0.1302 (11) | 0.1360 (5) | 0.9009 (5) | 0.0505 (18) | |
H6 | −0.2497 | 0.1485 | 0.8727 | 0.061* | |
C7 | 0.0818 (9) | −0.0093 (4) | 0.6916 (4) | 0.0285 (13) | |
H7A | 0.2133 | −0.0512 | 0.7010 | 0.034* | |
H7B | −0.0280 | −0.0295 | 0.7348 | 0.034* | |
C8 | 0.1979 (8) | 0.0103 (4) | 0.5195 (4) | 0.0282 (13) | |
H8A | 0.3392 | −0.0166 | 0.5312 | 0.034* | |
H8B | 0.1746 | 0.0790 | 0.5224 | 0.034* | |
C9 | −0.1750 (8) | 0.0179 (4) | 0.5757 (4) | 0.0313 (14) | |
H9A | −0.2735 | −0.0056 | 0.6227 | 0.038* | |
H9B | −0.2049 | 0.0867 | 0.5800 | 0.038* | |
C10 | 0.3287 (10) | 0.3637 (4) | 0.8688 (4) | 0.0371 (15) | |
C11 | 0.4441 (11) | 0.3708 (6) | 0.9371 (5) | 0.060 (2) | |
H11 | 0.5850 | 0.3715 | 0.9207 | 0.072* | |
C12 | 0.3535 (14) | 0.3771 (6) | 1.0310 (5) | 0.076 (3) | |
H12 | 0.4324 | 0.3834 | 1.0770 | 0.091* | |
C13 | 0.1473 (13) | 0.3737 (5) | 1.0551 (5) | 0.065 (2) | |
H13 | 0.0881 | 0.3756 | 1.1179 | 0.077* | |
C14 | 0.0285 (12) | 0.3678 (6) | 0.9892 (5) | 0.064 (2) | |
H14 | −0.1124 | 0.3676 | 1.0065 | 0.077* | |
C15 | 0.1178 (10) | 0.3619 (5) | 0.8952 (5) | 0.0499 (18) | |
H15 | 0.0368 | 0.3567 | 0.8498 | 0.060* | |
C16 | 0.3799 (9) | 0.4699 (4) | 0.6981 (4) | 0.0303 (13) | |
H16A | 0.2355 | 0.4990 | 0.7220 | 0.036* | |
H16B | 0.4670 | 0.5085 | 0.7181 | 0.036* | |
C17 | 0.6281 (8) | 0.4255 (4) | 0.5483 (4) | 0.0328 (14) | |
H17A | 0.6640 | 0.3597 | 0.5687 | 0.039* | |
H17B | 0.7251 | 0.4588 | 0.5682 | 0.039* | |
C18 | 0.3533 (9) | 0.5702 (4) | 0.5569 (4) | 0.0293 (13) | |
H18A | 0.4451 | 0.6065 | 0.5765 | 0.035* | |
H18B | 0.2110 | 0.5992 | 0.5841 | 0.035* | |
Co1 | 0.43731 (12) | 0.25133 (6) | 0.28903 (6) | 0.0370 (3) | |
Cl1 | 0.1941 (2) | 0.39248 (11) | 0.30934 (11) | 0.0430 (4) | |
Cl2 | 0.4480 (2) | 0.19886 (11) | 0.44188 (11) | 0.0448 (4) | |
Cl3 | 0.7480 (2) | 0.28356 (12) | 0.22824 (12) | 0.0493 (5) | |
Cl4 | 0.3704 (3) | 0.12799 (12) | 0.21842 (12) | 0.0549 (5) | |
N1 | 0.0462 (7) | −0.0236 (3) | 0.5931 (3) | 0.0262 (11) | |
H1 | 0.0682 | −0.0876 | 0.5854 | 0.031* | |
N2 | 0.4086 (7) | 0.4704 (3) | 0.5925 (3) | 0.0263 (11) | |
H2A | 0.3202 | 0.4373 | 0.5743 | 0.032* | |
O1 | 0.3144 (6) | 0.1183 (3) | 0.6809 (3) | 0.0415 (11) | |
H1A | 0.3258 | 0.1734 | 0.6850 | 0.062* | |
O2 | −0.0824 (7) | 0.1810 (3) | 0.6858 (3) | 0.0501 (12) | |
O3 | 0.6850 (6) | 0.3327 (3) | 0.7478 (3) | 0.0390 (10) | |
H3A | 0.7428 | 0.2857 | 0.7160 | 0.059* | |
O4 | 0.3662 (7) | 0.2855 (3) | 0.6954 (3) | 0.0462 (12) | |
O1W | 0.1196 (6) | 0.3810 (3) | 0.5436 (3) | 0.0547 (13) | |
H1W | 0.1471 | 0.3282 | 0.5725 | 0.082* | |
H2W | 0.1415 | 0.3673 | 0.4858 | 0.082* | |
O2W | 0.0528 (7) | 0.7890 (3) | 0.5862 (3) | 0.0495 (12) | |
H3W | 0.0851 | 0.7627 | 0.6370 | 0.074* | |
H4W | −0.0753 | 0.7887 | 0.5870 | 0.074* | |
P1 | 0.0885 (2) | 0.11056 (11) | 0.72246 (11) | 0.0326 (4) | |
P2 | 0.4450 (2) | 0.35160 (10) | 0.74902 (11) | 0.0314 (4) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.049 (4) | 0.027 (3) | 0.034 (4) | −0.003 (3) | 0.000 (3) | −0.008 (3) |
C2 | 0.061 (5) | 0.055 (5) | 0.038 (4) | −0.009 (4) | −0.010 (4) | −0.012 (3) |
C3 | 0.084 (6) | 0.071 (6) | 0.041 (5) | −0.010 (5) | −0.022 (5) | 0.000 (4) |
C4 | 0.101 (7) | 0.058 (5) | 0.032 (4) | −0.013 (5) | −0.009 (5) | −0.005 (4) |
C5 | 0.072 (5) | 0.066 (5) | 0.036 (5) | −0.007 (4) | 0.010 (4) | −0.007 (4) |
C6 | 0.054 (4) | 0.050 (4) | 0.043 (5) | −0.007 (4) | 0.001 (4) | 0.000 (3) |
C7 | 0.040 (3) | 0.030 (3) | 0.017 (3) | −0.011 (3) | −0.005 (3) | 0.004 (2) |
C8 | 0.024 (3) | 0.032 (3) | 0.030 (3) | −0.006 (3) | −0.007 (3) | 0.004 (3) |
C9 | 0.022 (3) | 0.040 (4) | 0.032 (4) | −0.007 (3) | −0.004 (3) | −0.003 (3) |
C10 | 0.050 (4) | 0.034 (4) | 0.027 (4) | −0.009 (3) | −0.007 (3) | 0.003 (3) |
C11 | 0.047 (4) | 0.090 (6) | 0.041 (5) | −0.011 (4) | −0.003 (4) | −0.008 (4) |
C12 | 0.085 (6) | 0.115 (8) | 0.030 (5) | −0.027 (6) | −0.014 (4) | −0.004 (5) |
C13 | 0.082 (6) | 0.077 (6) | 0.033 (5) | −0.023 (5) | 0.004 (4) | 0.007 (4) |
C14 | 0.060 (5) | 0.079 (6) | 0.049 (5) | −0.019 (5) | 0.011 (4) | −0.009 (4) |
C15 | 0.042 (4) | 0.064 (5) | 0.043 (4) | −0.012 (4) | −0.001 (3) | −0.004 (4) |
C16 | 0.032 (3) | 0.035 (3) | 0.022 (3) | −0.004 (3) | −0.001 (3) | −0.002 (3) |
C17 | 0.032 (3) | 0.029 (3) | 0.031 (4) | 0.002 (3) | 0.001 (3) | 0.001 (3) |
C18 | 0.030 (3) | 0.023 (3) | 0.031 (4) | 0.001 (3) | −0.001 (3) | −0.003 (3) |
Co1 | 0.0358 (5) | 0.0374 (5) | 0.0367 (5) | −0.0074 (4) | −0.0023 (4) | −0.0047 (4) |
Cl1 | 0.0377 (9) | 0.0444 (9) | 0.0440 (10) | −0.0008 (8) | −0.0085 (8) | −0.0048 (8) |
Cl2 | 0.0475 (10) | 0.0466 (10) | 0.0382 (10) | −0.0084 (8) | −0.0053 (8) | 0.0072 (8) |
Cl3 | 0.0408 (9) | 0.0566 (11) | 0.0487 (11) | −0.0156 (8) | 0.0076 (8) | −0.0109 (8) |
Cl4 | 0.0683 (12) | 0.0558 (11) | 0.0477 (11) | −0.0259 (10) | −0.0084 (9) | −0.0138 (8) |
N1 | 0.031 (3) | 0.021 (2) | 0.027 (3) | −0.004 (2) | −0.006 (2) | −0.006 (2) |
N2 | 0.023 (2) | 0.028 (3) | 0.028 (3) | −0.005 (2) | −0.002 (2) | −0.005 (2) |
O1 | 0.049 (3) | 0.030 (2) | 0.046 (3) | −0.017 (2) | 0.003 (2) | −0.007 (2) |
O2 | 0.064 (3) | 0.034 (2) | 0.046 (3) | 0.016 (2) | −0.022 (2) | −0.013 (2) |
O3 | 0.039 (2) | 0.035 (3) | 0.037 (3) | 0.005 (2) | −0.005 (2) | −0.008 (2) |
O4 | 0.067 (3) | 0.036 (2) | 0.040 (3) | −0.020 (2) | −0.010 (2) | 0.000 (2) |
O1W | 0.046 (3) | 0.062 (3) | 0.059 (3) | −0.010 (3) | −0.016 (2) | −0.016 (2) |
O2W | 0.050 (3) | 0.030 (2) | 0.069 (3) | −0.008 (2) | −0.012 (2) | 0.002 (2) |
P1 | 0.0409 (9) | 0.0271 (9) | 0.0281 (9) | −0.0029 (8) | −0.0048 (7) | −0.0074 (7) |
P2 | 0.0401 (9) | 0.0235 (8) | 0.0308 (9) | −0.0070 (7) | −0.0054 (7) | −0.0017 (7) |
Geometric parameters (Å, º) top
C1—C6 | 1.375 (9) | C13—H13 | 0.93 |
C1—C2 | 1.393 (9) | C14—C15 | 1.392 (10) |
C1—P1 | 1.795 (6) | C14—H14 | 0.93 |
C2—C3 | 1.378 (10) | C15—H15 | 0.93 |
C2—H2 | 0.93 | C16—N2 | 1.511 (7) |
C3—C4 | 1.354 (11) | C16—P2 | 1.817 (6) |
C3—H3 | 0.93 | C16—H16A | 0.97 |
C4—C5 | 1.374 (10) | C16—H16B | 0.97 |
C4—H4 | 0.93 | C17—N2 | 1.505 (7) |
C5—C6 | 1.396 (9) | C17—C18ii | 1.508 (8) |
C5—H5 | 0.93 | C17—H17A | 0.97 |
C6—H6 | 0.93 | C17—H17B | 0.97 |
C7—N1 | 1.512 (7) | C18—N2 | 1.494 (6) |
C7—P1 | 1.817 (5) | C18—C17ii | 1.508 (8) |
C7—H7A | 0.97 | C18—H18A | 0.97 |
C7—H7B | 0.97 | C18—H18B | 0.97 |
C8—N1 | 1.491 (6) | Co1—Cl3 | 2.2502 (16) |
C8—C9i | 1.495 (7) | Co1—Cl4 | 2.2509 (17) |
C8—H8A | 0.97 | Co1—Cl1 | 2.2935 (18) |
C8—H8B | 0.97 | Co1—Cl2 | 2.3148 (18) |
C9—C8i | 1.495 (7) | N1—H1 | 0.91 |
C9—N1 | 1.514 (7) | N2—H2A | 0.91 |
C9—H9A | 0.97 | O1—P1 | 1.551 (4) |
C9—H9B | 0.97 | O1—H1A | 0.82 |
C10—C11 | 1.365 (9) | O2—P1 | 1.494 (4) |
C10—C15 | 1.398 (8) | O3—P2 | 1.553 (4) |
C10—P2 | 1.781 (6) | O3—H3A | 0.82 |
C11—C12 | 1.394 (10) | O4—P2 | 1.486 (4) |
C11—H11 | 0.93 | O1W—H1W | 0.85 |
C12—C13 | 1.370 (10) | O1W—H2W | 0.85 |
C12—H12 | 0.93 | O2W—H3W | 0.85 |
C13—C14 | 1.349 (10) | O2W—H4W | 0.85 |
| | | |
C6—C1—C2 | 120.3 (6) | C10—C15—H15 | 119.8 |
C6—C1—P1 | 119.7 (5) | N2—C16—P2 | 113.7 (4) |
C2—C1—P1 | 119.9 (5) | N2—C16—H16A | 108.8 |
C3—C2—C1 | 119.7 (7) | P2—C16—H16A | 108.8 |
C3—C2—H2 | 120.1 | N2—C16—H16B | 108.8 |
C1—C2—H2 | 120.1 | P2—C16—H16B | 108.8 |
C4—C3—C2 | 119.9 (8) | H16A—C16—H16B | 107.7 |
C4—C3—H3 | 120.1 | N2—C17—C18ii | 110.3 (5) |
C2—C3—H3 | 120.1 | N2—C17—H17A | 109.6 |
C3—C4—C5 | 121.4 (7) | C18ii—C17—H17A | 109.6 |
C3—C4—H4 | 119.3 | N2—C17—H17B | 109.6 |
C5—C4—H4 | 119.3 | C18ii—C17—H17B | 109.6 |
C4—C5—C6 | 119.6 (7) | H17A—C17—H17B | 108.1 |
C4—C5—H5 | 120.2 | N2—C18—C17ii | 112.1 (4) |
C6—C5—H5 | 120.2 | N2—C18—H18A | 109.2 |
C1—C6—C5 | 119.1 (7) | C17ii—C18—H18A | 109.2 |
C1—C6—H6 | 120.4 | N2—C18—H18B | 109.2 |
C5—C6—H6 | 120.4 | C17ii—C18—H18B | 109.2 |
N1—C7—P1 | 116.8 (3) | H18A—C18—H18B | 107.9 |
N1—C7—H7A | 108.1 | Cl3—Co1—Cl4 | 112.62 (7) |
P1—C7—H7A | 108.1 | Cl3—Co1—Cl1 | 108.26 (7) |
N1—C7—H7B | 108.1 | Cl4—Co1—Cl1 | 120.58 (7) |
P1—C7—H7B | 108.1 | Cl3—Co1—Cl2 | 109.02 (7) |
H7A—C7—H7B | 107.3 | Cl4—Co1—Cl2 | 103.41 (7) |
N1—C8—C9i | 111.0 (4) | Cl1—Co1—Cl2 | 101.79 (7) |
N1—C8—H8A | 109.4 | C8—N1—C7 | 113.4 (4) |
C9i—C8—H8A | 109.4 | C8—N1—C9 | 109.9 (4) |
N1—C8—H8B | 109.4 | C7—N1—C9 | 114.0 (4) |
C9i—C8—H8B | 109.4 | C8—N1—H1 | 106.3 |
H8A—C8—H8B | 108.0 | C7—N1—H1 | 106.3 |
C8i—C9—N1 | 109.2 (5) | C9—N1—H1 | 106.3 |
C8i—C9—H9A | 109.8 | C18—N2—C17 | 108.6 (4) |
N1—C9—H9A | 109.8 | C18—N2—C16 | 110.0 (4) |
C8i—C9—H9B | 109.8 | C17—N2—C16 | 113.0 (4) |
N1—C9—H9B | 109.8 | C18—N2—H2A | 108.4 |
H9A—C9—H9B | 108.3 | C17—N2—H2A | 108.4 |
C11—C10—C15 | 118.6 (6) | C16—N2—H2A | 108.4 |
C11—C10—P2 | 121.2 (5) | P1—O1—H1A | 109.5 |
C15—C10—P2 | 120.2 (5) | P2—O3—H3A | 109.5 |
C10—C11—C12 | 120.8 (7) | H1W—O1W—H2W | 105.7 |
C10—C11—H11 | 119.6 | H3W—O2W—H4W | 106.1 |
C12—C11—H11 | 119.6 | O2—P1—O1 | 115.7 (2) |
C13—C12—C11 | 119.4 (7) | O2—P1—C1 | 112.9 (3) |
C13—C12—H12 | 120.3 | O1—P1—C1 | 108.1 (3) |
C11—C12—H12 | 120.3 | O2—P1—C7 | 110.1 (3) |
C14—C13—C12 | 121.2 (7) | O1—P1—C7 | 103.1 (2) |
C14—C13—H13 | 119.4 | C1—P1—C7 | 106.2 (2) |
C12—C13—H13 | 119.4 | O4—P2—O3 | 117.4 (3) |
C13—C14—C15 | 119.7 (7) | O4—P2—C10 | 114.3 (3) |
C13—C14—H14 | 120.2 | O3—P2—C10 | 106.2 (3) |
C15—C14—H14 | 120.2 | O4—P2—C16 | 108.3 (2) |
C14—C15—C10 | 120.3 (7) | O3—P2—C16 | 104.0 (2) |
C14—C15—H15 | 119.8 | C10—P2—C16 | 105.6 (3) |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···O4 | 0.85 | 2.45 | 3.049 (6) | 128 |
O1W—H2W···Cl2 | 0.85 | 2.82 | 3.248 (5) | 113 |
O1W—H2W···Cl1 | 0.85 | 2.54 | 3.351 (5) | 159 |
O1—H1A···O4 | 0.82 | 1.71 | 2.532 (5) | 176 |
N2—H2A···O1W | 0.91 | 1.83 | 2.734 (6) | 174 |
O2W—H4W···Cl2iii | 0.85 | 2.54 | 3.382 (4) | 169 |
O2W—H3W···Cl3ii | 0.85 | 2.39 | 3.217 (5) | 163 |
O3—H3A···O2iv | 0.82 | 1.71 | 2.486 (6) | 157 |
N1—H1···O2Wv | 0.91 | 1.80 | 2.698 (6) | 167 |
Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) −x, −y+1, −z+1; (iv) x+1, y, z; (v) x, y−1, z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | (C18H26N2O4P2)[CdCl4]·2H2O | (C18H26N2O4P2)[CoCl4]·2H2O |
Mr | 686.58 | 633.11 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 6.6159 (3), 14.5242 (7), 14.5449 (7) | 6.6448 (4), 14.4213 (14), 14.4804 (16) |
α, β, γ (°) | 87.035 (4), 81.713 (4), 76.947 (4) | 87.523 (8), 80.727 (7), 76.990 (7) |
V (Å3) | 1347.03 (11) | 1334.3 (2) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.36 | 1.20 |
Crystal size (mm) | 0.30 × 0.25 × 0.20 | 0.30 × 0.25 × 0.20 |
|
Data collection |
Diffractometer | Agilent Xcalibur (Atlas, Gemini ultra) diffractometer | Agilent Xcalibur (Atlas, Gemini ultra) diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2011) | Multi-scan (CrysAlis PRO; Agilent, 2011) |
Tmin, Tmax | 0.686, 0.772 | 0.715, 0.795 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10146, 4832, 3928 | 10695, 4786, 2993 |
Rint | 0.036 | 0.061 |
(sin θ/λ)max (Å−1) | 0.599 | 0.599 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.069, 1.01 | 0.069, 0.157, 0.99 |
No. of reflections | 4832 | 4786 |
No. of parameters | 300 | 300 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.36, −0.53 | 1.06, −0.37 |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···O4 | 0.85 | 2.43 | 3.038 (3) | 128.7 |
O1W—H2W···Cl2 | 0.85 | 2.82 | 3.237 (2) | 111.8 |
O1W—H2W···Cl1 | 0.85 | 2.55 | 3.346 (3) | 155.3 |
O1—H1A···O4 | 0.82 | 1.72 | 2.533 (3) | 175.0 |
N2—H2A···O1W | 0.91 | 1.82 | 2.732 (3) | 177.6 |
O2W—H4W···Cl2i | 0.85 | 2.49 | 3.323 (2) | 166.6 |
O2W—H3W···Cl3ii | 0.85 | 2.36 | 3.198 (3) | 167.1 |
O3—H3A···O2iii | 0.82 | 1.69 | 2.482 (3) | 160.6 |
N1—H1···O2Wiv | 0.91 | 1.81 | 2.708 (3) | 166.6 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x+1, y, z; (iv) x, y−1, z. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···O4 | 0.85 | 2.45 | 3.049 (6) | 128.1 |
O1W—H2W···Cl2 | 0.85 | 2.82 | 3.248 (5) | 113.2 |
O1W—H2W···Cl1 | 0.85 | 2.54 | 3.351 (5) | 158.7 |
O1—H1A···O4 | 0.82 | 1.71 | 2.532 (5) | 176.1 |
N2—H2A···O1W | 0.91 | 1.83 | 2.734 (6) | 173.8 |
O2W—H4W···Cl2i | 0.85 | 2.54 | 3.382 (4) | 169.0 |
O2W—H3W···Cl3ii | 0.85 | 2.39 | 3.217 (5) | 163.1 |
O3—H3A···O2iii | 0.82 | 1.71 | 2.486 (6) | 157.3 |
N1—H1···O2Wiv | 0.91 | 1.80 | 2.698 (6) | 166.7 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x+1, y, z; (iv) x, y−1, z. |
Organophosphorus compounds have attracted considerable attention because of their unique chemical, biochemical and physical properties (Miller et al., 2008; Moll et al., 2012; Leonova et al., 2010; Sharma & Clearfield, 2000). Special attention has been focused on diphosphonate ligands containing N atoms (sometimes called aminoalkyl/arylorganophosphonic acids), which have been extensively studied for a long time. Recent work on this topic has been devoted to different areas. They comprise pharmaceutically active compounds, such as sodium alendronate, which may act as potent inhibitors of bone resorption and as highly selective bone-targeting agents (Lenin et al., 2013). In coordination chemistry, piperazine-based fragments have been successfully used as building blocks for the design of polydentate ligands which may give rise to a variety of structures with many metal cations, including common transition metals (Arnold et al., 2002; Groves et al., 2005a or Groves et al., 2005b ?; Li et al., 2005; Soghomonian et al., 1995; Taddei et al., 2010), lanthanide metals (Du et al., 2006; Groves, Miller et al., 2006 or Groves, Stephens et al., 2006; Mowat et al., 2009; Wharmby et al., 2010) and main group metals (Du et al., 2009; Ma et al., 2010; Serre et al., 2006; Zhang et al., 2008, 2010). Applications in the realm of agrochemicals (Kong et al., 2008) are also possible. Many organophosphorus compounds represent well known halogen-free flame retardants and thus enable another important application in industry. For safety reasons, such compounds have been used to improve the flame retardancy of polymers in many fields, especially with the rapid development of the construction, aerospace and electronics industries (Lin, 2004; Lin et al., 2010; Lu & Hamerton, 2002). Several studies indicate that a significant improvement in flame-retardant efficiency is observed when the elements phosphorus and nitrogen coexist in the polymer system (Allcock & Harris, 1983; Allcock et al., 2000; Allcock & Laredo, 2001; Chang & Ma, 2004; Parvez et al., 1991; Taylor & Allcock, 2000). We therefore decided to explore new phosphorus–nitrogen containing halogen-free flame retardants, and among them, [piperazine-1,4-diylbis(methylene)]bis(phenylphosphinic acid) (hereinafter abbreviated as PBPA), is an excellent candidate.
Over recent decades, a large number of crystal structures of organoammonium tetrachloridometallates have been reported. In most of them, various organoammonium cations balance the charge of the tetrachloridometallates, in which the metals are common divalent transition metals, such as MnII, CoII, NiII, CuII, ZnII, CdII and HgII, and others (Beleaga et al., 2011; Espallargas et al., 2006; Korupoju et al., 2005; Matthews et al., 2003; Tremelling et al., 2009). However, only a few structures of aminoalkylorganophosphinic acid salts containing organoammonium cations and tetrahalogenometallate anions have been reported to date. To the best of our knowledege, only four structures of protonated bis(dialkylaminomethyl)phosphinic acids acting as cations and tetrachloridocuprate(II), tetrachloridocobaltate(II) or tetrachloridozincate(II) acting as counter-anions have been published (Kasparek et al., 2002; Kubicek et al., 2007). No single-crystal structure of a piperazine-ring based aminophenylphosphinic acid or its derivatives have yet been reported. Here, we describe the first preparation of PBPA, which crystallizes as a hydrochloride with poor solubility in water and most organic solvents due to the high polarity of its doubly charged ionic constituents. Fortunately, the tetrachloridocadmate(II) and tetrachloridocobaltate(II) salts, viz. (H2PBPA)[CdCl4].2H2O, (I), and (H2PBPA)[CoCl4].2H2O, (II), were obtained by reaction of PBPA hydrochloride with CdCl2.2.5H2O and CoCl2.6H2O, respectively, in concentrated hydrochloric acid. Single-crystal X-ray diffraction study of these derivatives confirms the first examples of PBPA salts with complex tetrachloridometallate(II) anions.
The diffraction experiments revealed that both (I) and (II) are isostructural and crystallize in the triclinic space group P1. The asymmetric unit contains one [MCl4]2- anion, two half fully protonated PBPA cations on crystallographic inversion centres and two solvent water molecules. Displacement ellipsoid plots showing the arrangement of the residues are given in Figs. 1 and 2. The metal atoms adopt a distorted tetrahedral geometry with four chloride ligands, with M—Cl bond lengths ranging from 2.2502 (17) to 2.3148 (18) Å in (I), and from 2.4111 (11) to 2.5313 (8) Å in (II). The Cl—M—Cl angles vary between 108 and 110°, very close to the expected value for a regular tetrahedron, consistent with similar compounds (Chen & Beatty, 2007; Daoud, 1976). The PBPA groups are located on crystallographic centres of inversion, with the piperazine rings in chair conformations; all bonds in these rings fall in the normal range [Standard reference?]. The P atoms show distorted tetrahedral geometry. The P—O bond lengths range between 1.482 (2) and 1.553 (4) Å, in agreement with P═ O and P—OH bonds, respectively. The Ueq values for the C atoms of the peripheral phenyl rings are slightly higher than those for the central heterocycle.
Charge balance requires protonation of all N atoms, and additional evidence comes from the hydrogen bonds. Detailed hydrogen-bond parameters are listed in Tables 1 and 2. Each half PBPA fragment is linked to two adjacent half PBPA fragments by O3i—H3Ai···O2—P1—O1—H1A···O4—P2—O3 hydrogen bonds [symmetry code: (i) x - 1, y, z], thus generating one-dimensional zigzag chains along a. These chains are interconnected by piperazine rings in the b direction, thus forming two-dimensional corrugated layers parallel to the ab plane, as shown in Fig. 3. The solvent water molecules and tetrachloridometallate(II) complex anions are linked to the layers by additonal hydrogen bonds (Tables 1 and 2) and fill the voids. The main difference between these isostructural compounds is the size of the [MCl4]2- tetrahedra, due to the different average M—Cl bond lengths.