The deformation electron density of the urea–phosphoric acid adduct has been studied from 100 K X-ray and neutron diffraction experiments. Data were interpreted according to the Hirshfeld model. The long hydrogen bonds show characteristics of electrostatic interaction. Deformation density maps on the short hydrogen bond shows hydrogen more strongly bonded to urea than to phosphoric acid, and peak maxima at almost midway between the two O—H bonds.
Supporting information
CCDC references: 166508; 166509
Data collection: XSCANS(Siemens, 1991) for X-ray. Cell refinement: XSCANS(Siemens, 1991) for X-ray. Data reduction: ARACOR (Lundgren, 1982) for neutron; P4red(Lundgren, 1982) for X-ray. Program(s) used to solve structure: DUPALS (Lundgren, 1982) for neutron. Program(s) used to refine structure: DUPALS (Lundgren, 1982) for neutron; DUPALS(Lundgren, 1982) for X-ray. Molecular graphics: ORTEP 3(Burnet & Johnson, 1996) for neutron; ORTEP-3 (Burnet and Johnson, 1996) and FOPLOT(Lundgren, 1982) for X-ray. For both compounds, software used to prepare material for publication: Ms-DOS 6.0 editor.
(neutron) urea phosphate
top
Crystal data top
CH7N2O5P | F(000) = 656 |
Mr = 159 | Dx = 1.820 Mg m−3 |
Orthorhombic, Pbca | Neutron radiation, λ = 1.207 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 9 reflections |
a = 17.43 (2) Å | θ = 18.9–30.9° |
b = 7.43 (2) Å | µ = 2.23 mm−1 |
c = 8.97 (2) Å | T = 100 K |
V = 1161 (4) Å3 | Prismatic, colorless |
Z = 8 | 3.8 × 2.2 × 1.0 mm |
Data collection top
Huber four circle diffractometer | 1579 reflections with I > −3σ(I) |
Radiation source: Studsvik (Sweden) reactor | Rint = 0.017 |
Cu(220) double system monochromator | θmax = 52°, θmin = 1° |
θ–2θ scans | h = −22→0 |
Absorption correction: analytical ? | k = −9→0 |
Tmin = 0.55, Tmax = 0.66 | l = 0→11 |
1762 measured reflections | 3 standard reflections every each 30 reflections reflections |
1599 independent reflections | intensity decay: less than 2 |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Refined anisotropically |
R[F2 > 2σ(F2)] = 0.053 | w = 1/[σ2(Fo2)] |
wR(F2) = 0.053 | (Δ/σ)max = 0.001 |
S = 1.35 | Δρmax = 0.38 e Å−3 |
1579 reflections | Δρmin = −0.19 e Å−3 |
151 parameters | Extinction correction: see text |
Crystal data top
CH7N2O5P | V = 1161 (4) Å3 |
Mr = 159 | Z = 8 |
Orthorhombic, Pbca | Neutron radiation, λ = 1.207 Å |
a = 17.43 (2) Å | µ = 2.23 mm−1 |
b = 7.43 (2) Å | T = 100 K |
c = 8.97 (2) Å | 3.8 × 2.2 × 1.0 mm |
Data collection top
Huber four circle diffractometer | 1579 reflections with I > −3σ(I) |
Absorption correction: analytical ? | Rint = 0.017 |
Tmin = 0.55, Tmax = 0.66 | 3 standard reflections every each 30 reflections reflections |
1762 measured reflections | intensity decay: less than 2 |
1599 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.053 | Refined anisotropically |
S = 1.35 | Δρmax = 0.38 e Å−3 |
1579 reflections | Δρmin = −0.19 e Å−3 |
151 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
P | 0.31097 (8) | 0.2798 (2) | 0.3096 (2) | 0.0081 (7) | |
O1 | 0.33979 (8) | 0.0912 (2) | 0.3620 (2) | 0.0117 (7) | |
O2 | 0.27752 (8) | 0.3861 (2) | 0.4378 (1) | 0.0101 (6) | |
O3 | 0.24495 (8) | 0.2515 (2) | 0.1954 (2) | 0.0118 (7) | |
O4 | 0.37978 (8) | 0.3693 (2) | 0.2372 (2) | 0.0114 (7) | |
O5 | 0.44844 (8) | 0.6367 (2) | 0.3098 (2) | 0.0121 (7) | |
N1 | 0.50979 (5) | 0.7845 (1) | 0.4931 (1) | 0.0131 (5) | |
N2 | 0.39770 (5) | 0.6329 (1) | 0.5442 (1) | 0.0143 (5) | |
C | 0.45156 (6) | 0.6836 (2) | 0.4487 (1) | 0.0092 (6) | |
H1 | 0.2975 (1) | 0.0091 (3) | 0.3944 (3) | 0.024 (1) | |
H3 | 0.2591 (1) | 0.1980 (4) | 0.0962 (3) | 0.023 (1) | |
H4 | 0.4113 (1) | 0.5116 (4) | 0.2826 (3) | 0.025 (1) | |
H11 | 0.5526 (2) | 0.8112 (4) | 0.4195 (3) | 0.026 (1) | |
H12 | 0.5142 (2) | 0.8217 (4) | 0.6004 (3) | 0.029 (1) | |
H21 | 0.3520 (1) | 0.5595 (4) | 0.5086 (3) | 0.027 (1) | |
H22 | 0.3995 (2) | 0.6734 (4) | 0.6509 (3) | 0.031 (1) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P | 0.0093 (7) | 0.0093 (7) | 0.0058 (7) | 0.0003 (5) | −0.0007 (5) | −0.0007 (6) |
O1 | 0.0121 (6) | 0.0090 (6) | 0.0139 (7) | 0.0005 (6) | −0.0020 (5) | 0.0010 (5) |
O2 | 0.0129 (6) | 0.0109 (6) | 0.0064 (6) | 0.0007 (5) | 0.0005 (5) | −0.0008 (5) |
O3 | 0.0108 (6) | 0.0161 (6) | 0.0084 (7) | 0.0009 (5) | −0.0016 (5) | −0.0032 (6) |
O4 | 0.0130 (6) | 0.0106 (6) | 0.0104 (7) | −0.0029 (5) | 0.0030 (5) | −0.0013 (5) |
O5 | 0.0155 (7) | 0.0135 (7) | 0.0074 (7) | −0.0038 (5) | 0.0005 (5) | −0.0009 (5) |
N1 | 0.0131 (4) | 0.0143 (4) | 0.0117 (5) | −0.0033 (3) | 0.0001 (4) | −0.0024 (4) |
N2 | 0.0144 (5) | 0.0175 (5) | 0.0111 (5) | −0.0047 (4) | 0.0039 (3) | −0.0027 (4) |
C | 0.0103 (5) | 0.0097 (5) | 0.0077 (6) | −0.0002 (4) | 0.0001 (4) | 0.0002 (4) |
H1 | 0.025 (1) | 0.019 (1) | 0.028 (1) | −0.002 (1) | −0.001 (1) | 0.003 (1) |
H3 | 0.023 (1) | 0.030 (1) | 0.017 (1) | 0.000 (1) | −0.002 (1) | −0.005 (1) |
H4 | 0.029 (1) | 0.028 (1) | 0.018 (1) | 0.004 (1) | 0.006 (1) | 0.001 (1) |
H11 | 0.025 (1) | 0.028 (1) | 0.024 (1) | −0.007 (1) | 0.005 (1) | −0.000 (1) |
H12 | 0.032 (1) | 0.037 (1) | 0.017 (1) | −0.009 (1) | −0.001 (1) | −0.008 (1) |
H21 | 0.022 (1) | 0.034 (1) | 0.026 (1) | −0.011 (1) | 0.003 (1) | −0.003 (1) |
H22 | 0.034 (1) | 0.043 (2) | 0.016 (1) | −0.008 (1) | 0.007 (1) | −0.008 (1) |
Geometric parameters (Å, º) top
P—O1 | 1.562 (2) | N1—H12 | 1.004 (3) |
P—O2 | 1.512 (2) | N2—H21 | 1.017 (3) |
P—O4 | 1.517 (2) | N2—H22 | 1.003 (3) |
P—O3 | 1.554 (2) | O1—H1 | 1.000 (3) |
C—O5 | 1.295 (2) | O3—H3 | 1.005 (3) |
C—N1 | 1.323 (1) | O4—H4 | 1.259 (3) |
C—N2 | 1.325 (1) | O5—H4 | 1.160 (3) |
N1—H11 | 1.016 (3) | | |
| | | |
O1—P—O2 | 111.4 (1) | C—N1—H11 | 118.6 (2) |
O1—P—O3 | 108.3 (1) | C—N1—H12 | 120.2 (2) |
O1—P—O4 | 105.5 (1) | H11—N1—H12 | 120.8 (2) |
O2—P—O3 | 106.6 (1) | C—N2—H21 | 120.4 (2) |
O2—P—O4 | 113.6 (1) | C—N2—H22 | 120.5 (2) |
O3—P—O4 | 111.3 (1) | H21—N2—H22 | 119.0 (2) |
P—O1—H1 | 113.5 (2) | O5—C—N1 | 118.3 (1) |
P—O3—H3 | 117.0 (2) | O5—C—N2 | 121.0 (1) |
P—O4—H4 | 125.1 (2) | N1—C—N2 | 120.8 (1) |
C—O5—H4 | 116.2 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 1.000 (3) | 1.643 (3) | 2.639 (2) | 174.4 (3) |
O3—H3···O2ii | 1.005 (3) | 1.584 (3) | 2.589 (2) | 177.4 (3) |
O4—H4···O5 | 1.259 (3) | 1.160 (3) | 2.410 (2) | 170.2 (3) |
N1—H11···O4iii | 1.016 (3) | 1.885 (3) | 2.893 (2) | 171.4 (2) |
N1—H12···O5iv | 1.004 (3) | 2.221 (3) | 3.090 (2) | 143.9 (2) |
N2—H21···O2 | 1.017 (3) | 1.936 (3) | 2.943 (2) | 170.1 (2) |
N2—H22···O5iv | 1.003 (4) | 2.180 (3) | 3.064 (2) | 146.2 (2) |
Symmetry codes: (i) −x+1/2, y−1/2, z; (ii) x, −y+1/2, z−1/2; (iii) −x+1, y+1/2, −z+1/2; (iv) x, −y+3/2, z+1/2. |
(X-ray) urea phosphate
top
Crystal data top
CH7N2O5P | F(000) = 656.0 |
Mr = 159.0 | Dx = 1.815 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 98 reflections |
a = 17.4527 (7) Å | θ = 12–20° |
b = 7.4465 (5) Å | µ = 0.43 mm−1 |
c = 8.9589 (4) Å | T = 100 K |
V = 1164.31 (9) Å3 | Almost spherical, colorless |
Z = 8 | 0.19 mm (radius) |
Data collection top
SIEMENS P4 diffractometer | 7257 reflections with I > 0.0σ(I) |
Radiation source: sealed tube | Rint = 0.013 |
Graphite monochromator | θmax = 60°, θmin = 1° |
θ–2θ scans | h = −1→41 |
Absorption correction: analytical ? | k = −1→17 |
Tmin = 0.87, Tmax = 0.89 | l = −1→21 |
8472 measured reflections | 3 standard reflections every each 400 reflections reflections |
7433 independent reflections | intensity decay: 1.1% |
Refinement top
Refinement on F2 | Hydrogen fixed from neutron |
Least-squares matrix: full | w = 1/[σ2(Fo2) + 0.0068Fo2 + 34.9λ/sen(θ)-0.00055Fo2λ/sen(θ)] |
R[F2 > 2σ(F2)] = 0.058 | (Δ/σ)max = 0.001 |
wR(F2) = 0.053 | Δρmax = 0.61 e Å−3 |
S = 0.69 | Δρmin = −0.62 e Å−3 |
7257 reflections | Extinction correction: see text |
215 parameters | |
Crystal data top
CH7N2O5P | V = 1164.31 (9) Å3 |
Mr = 159.0 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 17.4527 (7) Å | µ = 0.43 mm−1 |
b = 7.4465 (5) Å | T = 100 K |
c = 8.9589 (4) Å | 0.19 mm (radius) |
Data collection top
SIEMENS P4 diffractometer | 7257 reflections with I > 0.0σ(I) |
Absorption correction: analytical ? | Rint = 0.013 |
Tmin = 0.87, Tmax = 0.89 | 3 standard reflections every each 400 reflections reflections |
8472 measured reflections | intensity decay: 1.1% |
7433 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.058 | 215 parameters |
wR(F2) = 0.053 | Hydrogen fixed from neutron |
S = 0.69 | Δρmax = 0.61 e Å−3 |
7257 reflections | Δρmin = −0.62 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
P | 0.311006 (9) | 0.27977 (2) | 0.30966 (2) | 0.00835 | |
O1 | 0.33980 (3) | 0.09073 (8) | 0.36199 (7) | 0.01296 | |
O2 | 0.27739 (3) | 0.38618 (8) | 0.43782 (6) | 0.01059 | |
O3 | 0.24492 (3) | 0.25128 (8) | 0.19524 (6) | 0.01337 | |
O4 | 0.37975 (4) | 0.36869 (8) | 0.23724 (6) | 0.01262 | |
O5 | 0.44835 (4) | 0.63663 (8) | 0.30980 (8) | 0.01380 | |
N1 | 0.50967 (4) | 0.78421 (9) | 0.49287 (7) | 0.01389 | |
N2 | 0.39746 (4) | 0.63295 (9) | 0.54387 (8) | 0.01559 | |
C | 0.45132 (4) | 0.68355 (8) | 0.44853 (9) | 0.00993 | |
H1 | 0.29755 | 0.00911 | 0.39445 | 0.02384 | |
H3 | 0.25912 | 0.19804 | 0.09619 | 0.02348 | |
H4 | 0.41127 | 0.51156 | 0.28258 | 0.02507 | |
H11 | 0.55260 | 0.81118 | 0.41950 | 0.02600 | |
H12 | 0.51423 | 0.82167 | 0.60044 | 0.02865 | |
H21 | 0.35197 | 0.55954 | 0.50861 | 0.02731 | |
H22 | 0.39954 | 0.67336 | 0.65086 | 0.03132 | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P | 0.00824 (6) | 0.00962 (6) | 0.00719 (6) | −0.00015 (4) | 0.00004 (4) | −0.00067 (4) |
O1 | 0.0111 (2) | 0.0101 (1) | 0.0177 (2) | 0.0003 (1) | −0.0007 (1) | 0.0010 (1) |
O2 | 0.0124 (1) | 0.0119 (1) | 0.0075 (1) | 0.0007 (1) | 0.0010 (1) | −0.0009 (1) |
O3 | 0.0107 (1) | 0.0200 (2) | 0.0094 (1) | 0.0013 (1) | −0.0023 (1) | −0.0037 (1) |
O4 | 0.0129 (2) | 0.0132 (2) | 0.0117 (2) | −0.0032 (1) | 0.0040 (1) | −0.0022 (1) |
O5 | 0.0168 (2) | 0.0160 (2) | 0.0086 (1) | −0.0057 (2) | 0.0008 (1) | −0.0005 (1) |
N1 | 0.0119 (2) | 0.0167 (2) | 0.0131 (2) | −0.0041 (2) | 0.0004 (1) | −0.0019 (2) |
N2 | 0.0142 (2) | 0.0204 (3) | 0.0121 (2) | −0.0060 (2) | 0.0046 (2) | −0.0036 (2) |
C | 0.0096 (2) | 0.0105 (2) | 0.0097 (2) | −0.0006 (1) | 0.0002 (1) | −0.0000 (1) |
H1 | 0.024998 | 0.018751 | 0.027763 | −0.002416 | −0.000650 | 0.003265 |
H3 | 0.023347 | 0.030052 | 0.017041 | 0.000250 | −0.001957 | −0.005255 |
H4 | 0.028995 | 0.028516 | 0.017700 | 0.003885 | 0.006139 | 0.001524 |
H11 | 0.025276 | 0.028459 | 0.024263 | −0.007124 | 0.005188 | −0.000453 |
H12 | 0.031773 | 0.036946 | 0.017236 | −0.008599 | −0.001259 | −0.008311 |
H21 | 0.021820 | 0.034235 | 0.025889 | −0.010745 | 0.002788 | −0.003251 |
H22 | 0.034504 | 0.043219 | 0.016248 | −0.008118 | 0.006685 | −0.008459 |
Geometric parameters (Å, º) top
P—O1 | 1.566 (1) | O3—H3 | 1.003 (1) |
P—O2 | 1.513 (1) | O4—H4 | 1.265 (1) |
P—O4 | 1.516 (1) | H4—O5 | 1.160 (1) |
P—O3 | 1.558 (1) | N1—H11 | 1.017 (1) |
C—N1 | 1.325 (1) | N1—H12 | 1.006 (1) |
C—N2 | 1.325 (1) | N2—H21 | 1.014 (1) |
C—O5 | 1.292 (1) | N2—H22 | 1.005 (1) |
O1—H1 | 0.999 (1) | | |
| | | |
O1—P—O2 | 111.58 (3) | C—N1—H11 | 118.95 (6) |
O1—P—O3 | 108.19 (3) | C—N1—H12 | 120.29 (7) |
O1—P—O4 | 105.46 (3) | H11—N1—H12 | 120.41 (7) |
O2—P—O3 | 106.48 (3) | C—N2—H21 | 120.52 (7) |
O2—P—O4 | 113.75 (3) | C—N2—H22 | 120.26 (7) |
O3—P—O4 | 111.33 (3) | H21—N2—H22 | 119.12 (7) |
P—O1—H1 | 113.40 (5) | O5—C—N1 | 118.17 (7) |
P—O3—H3 | 116.95 (4) | O5—C—N2 | 120.98 (6) |
P—O4—H4 | 125.04 (4) | N1—C—N2 | 120.85 (7) |
C—O5—H4 | 116.22 (6) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 0.999 (1) | 1.643 (1) | 2.639 (1) | 174.58 (4) |
O3—H3···O2ii | 1.003 (1) | 1.584 (1) | 2.586 (1) | 177.31 (4) |
O4—H4···O5 | 1.265 (1) | 1.160 (1) | 2.416 (1) | 170.25 (4) |
N1—H11···O4iii | 1.017 (1) | 1.884 (1) | 2.893 (1) | 171.35 (4) |
N1—H12···O5iv | 1.006 (1) | 2.222 (1) | 3.091 (1) | 143.73 (4) |
N2—H21···O2 | 1.014 (1) | 1.940 (1) | 2.945 (1) | 170.27 (4) |
N2—H22···O5iv | 1.005 (1) | 2.181 (1) | 3.067 (1) | 146.20 (5) |
Symmetry codes: (i) −x+1/2, y−1/2, z; (ii) x, −y+1/2, z−1/2; (iii) −x+1, y+1/2, −z+1/2; (iv) x, −y+3/2, z+1/2. |
Experimental details
| (neutron) | (X-ray) |
Crystal data |
Chemical formula | CH7N2O5P | CH7N2O5P |
Mr | 159 | 159.0 |
Crystal system, space group | Orthorhombic, Pbca | Orthorhombic, Pbca |
Temperature (K) | 100 | 100 |
a, b, c (Å) | 17.43 (2), 7.43 (2), 8.97 (2) | 17.4527 (7), 7.4465 (5), 8.9589 (4) |
V (Å3) | 1161 (4) | 1164.31 (9) |
Z | 8 | 8 |
Radiation type | Neutron, λ = 1.207 Å | Mo Kα |
µ (mm−1) | 2.23 | 0.43 |
Crystal size (mm) | 3.8 × 2.2 × 1.0 | 0.19 (radius) |
|
Data collection |
Diffractometer | Huber four circle diffractometer | SIEMENS P4 diffractometer |
Absorption correction | Analytical | Analytical |
Tmin, Tmax | 0.55, 0.66 | 0.87, 0.89 |
No. of measured, independent and observed reflections | 1762, 1599, 1579 [I > −3σ(I)] | 8472, 7433, 7257 [I > 0.0σ(I)] |
Rint | 0.017 | 0.013 |
(sin θ/λ)max (Å−1) | 0.653 | 1.218 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.053, 1.35 | 0.058, 0.053, 0.69 |
No. of reflections | 1579 | 7257 |
No. of parameters | 151 | 215 |
No. of restraints | 0 | ? |
H-atom treatment | Refined anisotropically | Hydrogen fixed from neutron |
Δρmax, Δρmin (e Å−3) | 0.38, −0.19 | 0.61, −0.62 |
Selected geometric parameters (Å, º) for (neutron) topP—O1 | 1.562 (2) | N1—H12 | 1.004 (3) |
P—O2 | 1.512 (2) | N2—H21 | 1.017 (3) |
P—O4 | 1.517 (2) | N2—H22 | 1.003 (3) |
P—O3 | 1.554 (2) | O1—H1 | 1.000 (3) |
C—O5 | 1.295 (2) | O3—H3 | 1.005 (3) |
C—N1 | 1.323 (1) | O4—H4 | 1.259 (3) |
C—N2 | 1.325 (1) | O5—H4 | 1.160 (3) |
N1—H11 | 1.016 (3) | | |
| | | |
O1—P—O2 | 111.4 (1) | C—N1—H11 | 118.6 (2) |
O1—P—O3 | 108.3 (1) | C—N1—H12 | 120.2 (2) |
O1—P—O4 | 105.5 (1) | H11—N1—H12 | 120.8 (2) |
O2—P—O3 | 106.6 (1) | C—N2—H21 | 120.4 (2) |
O2—P—O4 | 113.6 (1) | C—N2—H22 | 120.5 (2) |
O3—P—O4 | 111.3 (1) | H21—N2—H22 | 119.0 (2) |
P—O1—H1 | 113.5 (2) | O5—C—N1 | 118.3 (1) |
P—O3—H3 | 117.0 (2) | O5—C—N2 | 121.0 (1) |
P—O4—H4 | 125.1 (2) | N1—C—N2 | 120.8 (1) |
C—O5—H4 | 116.2 (2) | | |
Hydrogen-bond geometry (Å, º) for (neutron) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 1.000 (3) | 1.643 (3) | 2.639 (2) | 174.4 (3) |
O3—H3···O2ii | 1.005 (3) | 1.584 (3) | 2.589 (2) | 177.4 (3) |
O4—H4···O5 | 1.259 (3) | 1.160 (3) | 2.410 (2) | 170.2 (3) |
N1—H11···O4iii | 1.016 (3) | 1.885 (3) | 2.893 (2) | 171.4 (2) |
N1—H12···O5iv | 1.004 (3) | 2.221 (3) | 3.090 (2) | 143.9 (2) |
N2—H21···O2 | 1.017 (3) | 1.936 (3) | 2.943 (2) | 170.1 (2) |
N2—H22···O5iv | 1.003 (4) | 2.180 (3) | 3.064 (2) | 146.2 (2) |
Symmetry codes: (i) −x+1/2, y−1/2, z; (ii) x, −y+1/2, z−1/2; (iii) −x+1, y+1/2, −z+1/2; (iv) x, −y+3/2, z+1/2. |