Buy article online - an online subscription or single-article purchase is required to access this article.
The title salt, C
7H
9ClN
+·H
2PO
4−, is monoclinic (
P2
1/
c). The ions are held together by O—H
O and N—H
O hydrogen bonds. The O—H
O bonds interconnect the dihydrogenphosphates into sheets which are parallel to the (100) plane. In each sheet, there are centrosymmetric pairs of dihydrogenphosphates held together by O—H
O bonds. In addition, the dihydrogenphosphates are interconnected by —NH
3 groups. Each H atom from an —NH
3 group is donated to a different dihydrogenphosphate ion. A differential scanning calorimetry experiment showed no anomaly between 98 and 420 K.
Supporting information
CCDC reference: 180774
Key indicators
- Single-crystal X-ray study
- T = 290 K
- Mean (C-C) = 0.008 Å
- R factor = 0.045
- wR factor = 0.170
- Data-to-parameter ratio = 16.3
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
RINTA_01 Alert C The value of Rint is greater than 0.10
Rint given 0.141
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
Data collection: KM4B8 (Gałdecki et al., 1997); cell refinement: LATCO (Allmann, 1988); data reduction: JANA2000 (Petříček & Dušek, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996).
Crystal data top
C7H9ClN+·H2PO4− | F(000) = 496 |
Mr = 239.59 | In the setting corresponding to C1121/b it has nearly orthorhombic setting. |
Monoclinic, P21/c | Dx = 1.497 Mg m−3 |
Hall symbol: -P2ybc | Mo Kα radiation, λ = 0.710688 Å |
a = 16.603 (4) Å | Cell parameters from 18 reflections |
b = 8.339 (3) Å | θ = 2.8–15.8° |
c = 7.903 (4) Å | µ = 0.50 mm−1 |
β = 103.76 (6)° | T = 290 K |
V = 1062.8 (7) Å3 | Plate, colourless |
Z = 4 | 0.30 × 0.14 × 0.06 mm |
Data collection top
Kuma KM-4 diffractometer | Rint = 0.141 |
ω–2θ scans | θmax = 26.3°, θmin = 1.3° |
Absorption correction: integration Gaussian integration (Coppens, 1965) | h = −20→20 |
Tmin = 0.919, Tmax = 0.977 | k = −10→0 |
4283 measured reflections | l = −9→9 |
2151 independent reflections | 3 standard reflections every 200 reflections |
911 reflections with I > 2σ(I) | intensity decay: 9.8% |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.045 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.170 | w = 1/[σ2(Fo2) + (0.1P)2 + ] where P = (Fo2 + 2Fc2)/3 |
S = 0.82 | (Δ/σ)max = 0.001 |
2151 reflections | Δρmax = 0.23 e Å−3 |
132 parameters | Δρmin = −0.27 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: 0.014 (3) |
Special details top
Experimental. The diffractions of the studied crystals were invariably split except for the
diffractions 00 l. No domains, however, were observed in the microscope in the
polarized light. Because of this splitting the lattice parameters were
determined from the powder pattern. The powder diffractometer used is a
locally adapted parallel beam HUBER powder diffractometer equipped with Goebel
mirror and double crystal monochromator in reflected beam. The source is
rotation-anode (Cu) radiation generated by 55 kV/300 mA; step scan mode with 5
- s step 0.02 ° in 2θ. The data collection was performed in the unit cell
with C-centered orthorhombic metric (see the section _publ_section_comment).
The parameters of the scan were chosen so the split peaks fell between the
background regions, and therefore they were integrated together. |
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 | 0.43529 (8) | 0.03782 (14) | 0.20760 (16) | 0.0370 (4) | |
O3 | 0.52042 (19) | 0.0964 (4) | 0.2029 (4) | 0.0407 (8) | |
O1 | 0.4420 (3) | −0.1045 (4) | 0.3391 (5) | 0.0508 (9) | |
H1 | 0.4610 | −0.1834 | 0.3003 | 0.076* | |
O2 | 0.3906 (2) | −0.0258 (5) | 0.0236 (4) | 0.0537 (10) | |
H2 | 0.4250 | −0.0429 | −0.0334 | 0.081* | |
O4 | 0.3801 (2) | 0.1578 (4) | 0.2637 (4) | 0.0479 (9) | |
Cl | 0.02954 (12) | 0.7927 (3) | −0.0569 (3) | 0.1069 (8) | |
N | 0.3438 (2) | 0.4280 (4) | 0.0670 (5) | 0.0388 (10) | |
H1N | 0.3849 | 0.4935 | 0.1173 | 0.058* | |
H2N | 0.3518 | 0.3944 | −0.0346 | 0.058* | |
H3N | 0.3428 | 0.3440 | 0.1360 | 0.058* | |
C1 | 0.2655 (3) | 0.5128 (6) | 0.0384 (6) | 0.0403 (12) | |
C2 | 0.1921 (3) | 0.4343 (6) | −0.0326 (7) | 0.0530 (14) | |
C3 | 0.1192 (4) | 0.5239 (8) | −0.0615 (8) | 0.0675 (17) | |
H3 | 0.0687 | 0.4749 | −0.1108 | 0.081* | |
C4 | 0.1210 (4) | 0.6838 (8) | −0.0179 (8) | 0.0659 (17) | |
C5 | 0.1936 (4) | 0.7599 (8) | 0.0538 (10) | 0.0760 (19) | |
H5 | 0.1943 | 0.8679 | 0.0834 | 0.091* | |
C6 | 0.2665 (4) | 0.6728 (6) | 0.0817 (8) | 0.0597 (16) | |
H6 | 0.3167 | 0.7228 | 0.1303 | 0.072* | |
C7 | 0.1901 (4) | 0.2564 (7) | −0.0783 (10) | 0.080 (2) | |
H1C7 | 0.2294 | 0.2352 | −0.1472 | 0.120* | |
H2C7 | 0.1355 | 0.2277 | −0.1433 | 0.120* | |
H3C7 | 0.2042 | 0.1942 | 0.0268 | 0.120* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P1 | 0.0497 (8) | 0.0241 (6) | 0.0401 (7) | 0.0002 (6) | 0.0162 (5) | 0.0005 (6) |
O3 | 0.048 (2) | 0.0318 (17) | 0.0438 (19) | −0.0026 (16) | 0.0132 (15) | −0.0031 (14) |
O1 | 0.080 (3) | 0.0277 (17) | 0.052 (2) | 0.0044 (18) | 0.0301 (18) | 0.0022 (15) |
O2 | 0.049 (2) | 0.067 (2) | 0.0457 (19) | −0.013 (2) | 0.0132 (16) | −0.0116 (19) |
O4 | 0.063 (2) | 0.0342 (18) | 0.053 (2) | 0.0111 (17) | 0.0264 (18) | 0.0071 (16) |
Cl | 0.0742 (13) | 0.1020 (16) | 0.1401 (18) | 0.0406 (12) | 0.0167 (12) | 0.0085 (13) |
N | 0.047 (2) | 0.031 (2) | 0.041 (2) | −0.0005 (18) | 0.0144 (18) | 0.0045 (16) |
C1 | 0.043 (3) | 0.037 (3) | 0.043 (3) | 0.002 (2) | 0.015 (2) | 0.002 (2) |
C2 | 0.053 (4) | 0.048 (3) | 0.057 (3) | −0.004 (3) | 0.011 (3) | −0.001 (3) |
C3 | 0.053 (4) | 0.070 (4) | 0.076 (4) | −0.003 (3) | 0.010 (3) | −0.003 (3) |
C4 | 0.053 (4) | 0.071 (4) | 0.071 (4) | 0.018 (3) | 0.010 (3) | 0.010 (3) |
C5 | 0.072 (5) | 0.046 (3) | 0.108 (5) | 0.007 (3) | 0.017 (4) | −0.006 (4) |
C6 | 0.052 (4) | 0.036 (3) | 0.087 (4) | −0.003 (3) | 0.007 (3) | −0.006 (3) |
C7 | 0.071 (5) | 0.053 (4) | 0.109 (5) | −0.016 (3) | 0.009 (4) | −0.025 (4) |
Geometric parameters (Å, º) top
P1—O4 | 1.493 (4) | C1—C2 | 1.379 (7) |
P1—O3 | 1.504 (3) | C2—C3 | 1.395 (8) |
P1—O2 | 1.560 (4) | C2—C7 | 1.526 (8) |
P1—O1 | 1.564 (3) | C3—C4 | 1.376 (9) |
O1—H1 | 0.8200 | C3—H3 | 0.9300 |
O2—H2 | 0.8200 | C4—C5 | 1.362 (9) |
Cl—C4 | 1.732 (6) | C6—C5 | 1.383 (8) |
N—C1 | 1.449 (6) | C6—H6 | 0.9300 |
N—H1N | 0.8900 | C5—H5 | 0.9300 |
N—H2N | 0.8900 | C7—H1C7 | 0.9600 |
N—H3N | 0.8900 | C7—H2C7 | 0.9600 |
C1—C6 | 1.376 (7) | C7—H3C7 | 0.9600 |
| | | |
O4—P1—O3 | 115.8 (2) | C3—C2—C7 | 120.9 (6) |
O4—P1—O2 | 108.4 (2) | C4—C3—C2 | 120.8 (6) |
O3—P1—O2 | 109.2 (2) | C4—C3—H3 | 119.6 |
O4—P1—O1 | 105.2 (2) | C2—C3—H3 | 119.6 |
O3—P1—O1 | 110.2 (2) | C5—C4—C3 | 121.3 (6) |
O2—P1—O1 | 107.7 (2) | C5—C4—Cl | 118.8 (5) |
P1—O1—H1 | 109.5 | C3—C4—Cl | 119.8 (5) |
P1—O2—H2 | 109.5 | C1—C6—C5 | 120.8 (5) |
C1—N—H1N | 109.5 | C1—C6—H6 | 119.6 |
C1—N—H2N | 109.5 | C5—C6—H6 | 119.6 |
H1N—N—H2N | 109.5 | C4—C5—C6 | 118.5 (6) |
C1—N—H3N | 109.5 | C4—C5—H5 | 120.8 |
H1N—N—H3N | 109.5 | C6—C5—H5 | 120.8 |
H2N—N—H3N | 109.5 | C2—C7—H1C7 | 109.5 |
C6—C1—C2 | 121.2 (5) | C2—C7—H2C7 | 109.5 |
C6—C1—N | 118.5 (5) | H1C7—C7—H2C7 | 109.5 |
C2—C1—N | 120.3 (4) | C2—C7—H3C7 | 109.5 |
C1—C2—C3 | 117.5 (5) | H1C7—C7—H3C7 | 109.5 |
C1—C2—C7 | 121.7 (5) | H2C7—C7—H3C7 | 109.5 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3i | 0.82 | 1.86 | 2.611 (4) | 151 |
O2—H2···O3ii | 0.82 | 1.84 | 2.644 (5) | 166 |
N—H1N···O3iii | 0.89 | 2.04 | 2.900 (5) | 162 |
N—H2N···O4iv | 0.89 | 1.82 | 2.704 (5) | 173 |
N—H3N···O4 | 0.89 | 1.88 | 2.722 (5) | 158 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1, −y, −z; (iii) −x+1, y+1/2, −z+1/2; (iv) x, −y+1/2, z−1/2. |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.