The crystal structure of poly[copper(II)-di-μ-hypophosphito-μ-urea], [Cu(H
2PO
2)
2(CH
4N
2O)]
n, has been determined at 293, 100 and 15 K. The geometry of the hypophosphite anion is very close to ideal, with point symmetry
mm2. Each Cu atom lies on an inversion centre and is coordinated to six O atoms from four hypophosphite anions and two urea molecules, forming a tetragonal bipyramid. The unique urea molecule lies on a twofold axis. Each hypophosphite anion in the structure is coordinated to two Cu atoms. The hypophosphite anions, urea molecules and Cu
II cations form polymeric ribbons. The Cu
II cations in the ribbon are linked together by two hypophosphite anions and a urea molecule, which is coordinated to Cu
via an O atom. The ribbons are linked to each other by N—H
O hydrogen bonds and form polymeric layers.
Supporting information
CCDC references: 169920; 169921; 169922
Compound (I) was synthesized by adding hypophosphorous acid, H3PO2 (2.3771 g
of 50% water solution in 35 ml of water), to basic copper carbonate,
CuCO3·Cu(OH)2 (1 g). The reacting mixture was evacuated until carbon
dioxide evolution had stopped (about 10 min). Next, a solution of urea (4.3852 g in 20 ml of water) was added to the solution of copper hypophosphite. The
molar ratios of the three starting materials were 1:4:16 for copper carbonate,
hypophosphorous acid and urea, respectively (QUERY). Crystals of (I) were
grown at 288 K from a water solution under a nitrogen atmosphere.
Data collection: SMART (Siemens, 1994) for Iat293K, Iat100K; MAD (Allibon, 1996) for Iat15K. Cell refinement: SAINT (Siemens, 1994) for Iat293K, Iat100K; RAFIN (Filhol et al., 1987) for Iat15K. Data reduction: SAINT for Iat293K, Iat100K; COLL5N (Lehmann et al., 1987) for Iat15K. For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1994); software used to prepare material for publication: SHELXL97.
(Iat293K) poly[copper(II)-di-µ-hypophosphito-µ-urea]
top
Crystal data top
[Cu(H2PO2)2(CH4N2O)] | F(000) = 508 |
Mr = 253.57 | Dx = 2.209 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 12.5540 (3) Å | Cell parameters from 2732 reflections |
b = 7.4686 (2) Å | θ = 3.2–29.1° |
c = 8.2628 (3) Å | µ = 3.26 mm−1 |
β = 100.2722 (13)° | T = 293 K |
V = 762.31 (4) Å3 | Irregular, blue |
Z = 4 | 0.54 × 0.30 × 0.22 mm |
Data collection top
Siemens SMART CCD area-detector diffractometer | 1014 independent reflections |
Radiation source: fine-focus sealed tube | 920 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
Detector resolution: 8.192 pixels mm-1 | θmax = 29.1°, θmin = 3.2° |
ω scans | h = −17→17 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −10→10 |
Tmin = 0.221, Tmax = 0.488 | l = −10→11 |
2894 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.026 | All H-atom parameters refined |
wR(F2) = 0.076 | w = 1/[σ2(Fo2) + (0.0471P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.12 | (Δ/σ)max < 0.001 |
1014 reflections | Δρmax = 0.40 e Å−3 |
70 parameters | Δρmin = −0.73 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.026 (2) |
Crystal data top
[Cu(H2PO2)2(CH4N2O)] | V = 762.31 (4) Å3 |
Mr = 253.57 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 12.5540 (3) Å | µ = 3.26 mm−1 |
b = 7.4686 (2) Å | T = 293 K |
c = 8.2628 (3) Å | 0.54 × 0.30 × 0.22 mm |
β = 100.2722 (13)° | |
Data collection top
Siemens SMART CCD area-detector diffractometer | 1014 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 920 reflections with I > 2σ(I) |
Tmin = 0.221, Tmax = 0.488 | Rint = 0.030 |
2894 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.076 | All H-atom parameters refined |
S = 1.12 | Δρmax = 0.40 e Å−3 |
1014 reflections | Δρmin = −0.73 e Å−3 |
70 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 0 | 0 | 1/2 | 0.01994 (17) | |
P1 | 0.17206 (4) | −0.12420 (7) | 0.29901 (6) | 0.02362 (18) | |
H1 | 0.259 (2) | −0.227 (4) | 0.332 (4) | 0.036 (7)* | |
H2 | 0.204 (2) | 0.056 (5) | 0.337 (4) | 0.044 (8)* | |
O1 | 0.09677 (12) | −0.17305 (18) | 0.41699 (17) | 0.0245 (3) | |
O2 | 0.12775 (12) | −0.1344 (2) | 0.11669 (18) | 0.0278 (3) | |
O3 | 0 | 0.1676 (3) | 1/4 | 0.0262 (4) | |
C1 | 0 | 0.3358 (4) | 1/4 | 0.0248 (5) | |
N1 | 0.0690 (2) | 0.4284 (3) | 0.3625 (3) | 0.0390 (5) | |
H3 | 0.062 (3) | 0.529 (5) | 0.380 (4) | 0.033 (8)* | |
H4 | 0.099 (4) | 0.382 (6) | 0.437 (6) | 0.069 (14)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0259 (2) | 0.0190 (2) | 0.0146 (2) | −0.00243 (10) | 0.00285 (13) | −0.00262 (10) |
P1 | 0.0253 (3) | 0.0269 (3) | 0.0178 (3) | 0.00247 (18) | 0.00147 (18) | 0.00155 (18) |
O1 | 0.0345 (7) | 0.0190 (7) | 0.0208 (6) | 0.0029 (5) | 0.0069 (6) | 0.0027 (5) |
O2 | 0.0328 (7) | 0.0322 (8) | 0.0180 (6) | 0.0100 (6) | 0.0032 (6) | 0.0028 (5) |
O3 | 0.0422 (11) | 0.0149 (9) | 0.0212 (9) | 0 | 0.0051 (8) | 0 |
C1 | 0.0351 (14) | 0.0193 (12) | 0.0231 (12) | 0 | 0.0133 (11) | 0 |
N1 | 0.0571 (13) | 0.0207 (10) | 0.0380 (11) | −0.0077 (9) | 0.0050 (10) | −0.0063 (8) |
Geometric parameters (Å, º) top
Cu1—O1i | 1.9784 (14) | P1—H1 | 1.32 (3) |
Cu1—O1 | 1.9784 (14) | P1—H2 | 1.42 (4) |
Cu1—O2ii | 1.9895 (14) | O2—Cu1ii | 1.9895 (14) |
Cu1—O2iii | 1.9895 (14) | O3—C1 | 1.256 (3) |
Cu1—O3 | 2.4153 (10) | O3—Cu1ii | 2.4154 (10) |
Cu1—O3i | 2.4153 (10) | C1—N1 | 1.344 (3) |
Cu1—Cu1ii | 4.1314 (2) | C1—N1ii | 1.344 (3) |
P1—O1 | 1.5184 (15) | N1—H3 | 0.77 (3) |
P1—O2 | 1.5119 (15) | N1—H4 | 0.75 (5) |
| | | |
O1i—Cu1—O1 | 180.0 | O3—Cu1—Cu1ii | 31.21 (4) |
O1i—Cu1—O2ii | 90.34 (6) | O3i—Cu1—Cu1ii | 148.79 (4) |
O1—Cu1—O2ii | 89.66 (6) | O1—P1—O2 | 117.84 (8) |
O1i—Cu1—O2iii | 89.66 (6) | O1—P1—H1 | 108.5 (13) |
O1—Cu1—O2iii | 90.34 (6) | O2—P1—H1 | 108.5 (14) |
O2ii—Cu1—O2iii | 180.00 (6) | O1—P1—H2 | 105.5 (13) |
O1i—Cu1—O3 | 92.96 (5) | O2—P1—H2 | 107.8 (14) |
O1—Cu1—O3 | 87.04 (5) | H1—P1—H2 | 108.3 (17) |
O2ii—Cu1—O3 | 88.28 (5) | P1—O1—Cu1 | 123.82 (8) |
O2iii—Cu1—O3 | 91.72 (5) | P1—O2—Cu1ii | 125.38 (9) |
O1i—Cu1—O3i | 87.04 (5) | C1—O3—Cu1ii | 121.21 (4) |
O1—Cu1—O3i | 92.96 (5) | C1—O3—Cu1 | 121.21 (4) |
O2ii—Cu1—O3i | 91.72 (5) | Cu1ii—O3—Cu1 | 117.57 (8) |
O2iii—Cu1—O3i | 88.28 (5) | O3—C1—N1 | 120.97 (15) |
O3—Cu1—O3i | 180.0 | O3—C1—N1ii | 120.97 (15) |
O1i—Cu1—Cu1ii | 117.14 (4) | N1—C1—N1ii | 118.1 (3) |
O1—Cu1—Cu1ii | 62.86 (4) | C1—N1—H3 | 123 (2) |
O2ii—Cu1—Cu1ii | 70.07 (4) | C1—N1—H4 | 120 (3) |
O2iii—Cu1—Cu1ii | 109.93 (4) | H3—N1—H4 | 111 (4) |
| | | |
N1—C1—O3—Cu1 | 47.74 (12) | | |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x, y, −z+1/2; (iii) x, −y, z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H4···O2iii | 0.75 (5) | 2.36 (5) | 3.037 (3) | 152 (4) |
P1—H2···O3 | 1.42 (4) | 2.66 (3) | 3.0442 (14) | 91.2 (13) |
P1—H2···O2iii | 1.42 (4) | 2.72 (3) | 3.3840 (16) | 105.4 (17) |
N1—H3···O1iv | 0.77 (3) | 2.27 (4) | 3.021 (3) | 162 (3) |
P1—H1···O1v | 1.32 (3) | 2.61 (3) | 3.7139 (15) | 139 (2) |
Symmetry codes: (iii) x, −y, z+1/2; (iv) x, y+1, z; (v) −x+1/2, −y−1/2, −z+1. |
(Iat100K) poly[copper(II)-di-µ-hypophosphito-µ-urea]
top
Crystal data top
[Cu(H2PO2)2(CH4N2O)] | F(000) = 508 |
Mr = 253.57 | Dx = 2.260 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 12.3589 (3) Å | Cell parameters from 2798 reflections |
b = 7.4464 (2) Å | θ = 3.2–29.1° |
c = 8.2199 (2) Å | µ = 3.34 mm−1 |
β = 99.8369 (14)° | T = 100 K |
V = 745.35 (3) Å3 | Irregular, blue |
Z = 4 | 0.54 × 0.30 × 0.22 mm |
Data collection top
Siemens SMART CCD area-detector diffractometer | 996 independent reflections |
Radiation source: fine-focus sealed tube | 935 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
Detector resolution: 8.192 pixels mm-1 | θmax = 29.1°, θmin = 3.2° |
ω scans | h = −16→16 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −10→10 |
Tmin = 0.297, Tmax = 0.480 | l = −10→11 |
2849 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.022 | All H-atom parameters refined |
wR(F2) = 0.057 | w = 1/[σ2(Fo2) + (0.0296P)2 + 0.9238P] where P = (Fo2 + 2Fc2)/3 |
S = 1.12 | (Δ/σ)max < 0.001 |
996 reflections | Δρmax = 0.57 e Å−3 |
70 parameters | Δρmin = −0.39 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0104 (9) |
Crystal data top
[Cu(H2PO2)2(CH4N2O)] | V = 745.35 (3) Å3 |
Mr = 253.57 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 12.3589 (3) Å | µ = 3.34 mm−1 |
b = 7.4464 (2) Å | T = 100 K |
c = 8.2199 (2) Å | 0.54 × 0.30 × 0.22 mm |
β = 99.8369 (14)° | |
Data collection top
Siemens SMART CCD area-detector diffractometer | 996 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 935 reflections with I > 2σ(I) |
Tmin = 0.297, Tmax = 0.480 | Rint = 0.020 |
2849 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.022 | 0 restraints |
wR(F2) = 0.057 | All H-atom parameters refined |
S = 1.12 | Δρmax = 0.57 e Å−3 |
996 reflections | Δρmin = −0.39 e Å−3 |
70 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 0 | 0 | 1/2 | 0.00715 (12) | |
P1 | 0.17446 (3) | −0.12486 (6) | 0.29780 (5) | 0.00878 (13) | |
H1 | 0.263 (2) | −0.227 (4) | 0.334 (3) | 0.015 (6)* | |
H2 | 0.2168 (19) | 0.043 (3) | 0.338 (3) | 0.010 (5)* | |
O1 | 0.09674 (10) | −0.17611 (16) | 0.41549 (15) | 0.0098 (2) | |
O2 | 0.13054 (10) | −0.13429 (16) | 0.11367 (15) | 0.0107 (2) | |
O3 | 0 | 0.1643 (2) | 1/4 | 0.0102 (3) | |
C1 | 0 | 0.3341 (3) | 1/4 | 0.0097 (4) | |
N1 | 0.07099 (13) | 0.4268 (2) | 0.3624 (2) | 0.0138 (3) | |
H3 | 0.069 (2) | 0.530 (4) | 0.378 (3) | 0.016 (6)* | |
H4 | 0.107 (2) | 0.367 (3) | 0.441 (3) | 0.014 (6)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.00992 (17) | 0.00583 (16) | 0.00567 (16) | −0.00081 (9) | 0.00120 (10) | −0.00116 (9) |
P1 | 0.0104 (2) | 0.0090 (2) | 0.0066 (2) | 0.00057 (14) | 0.00073 (14) | 0.00043 (14) |
O1 | 0.0140 (5) | 0.0073 (5) | 0.0084 (5) | 0.0006 (4) | 0.0028 (4) | 0.0008 (4) |
O2 | 0.0132 (5) | 0.0115 (5) | 0.0072 (5) | 0.0030 (4) | 0.0014 (4) | 0.0008 (4) |
O3 | 0.0172 (8) | 0.0050 (7) | 0.0084 (7) | 0 | 0.0024 (6) | 0 |
C1 | 0.0132 (10) | 0.0080 (10) | 0.0090 (10) | 0 | 0.0054 (8) | 0 |
N1 | 0.0208 (7) | 0.0065 (7) | 0.0134 (7) | −0.0022 (6) | 0.0010 (6) | −0.0018 (5) |
Geometric parameters (Å, º) top
Cu1—O1 | 1.9788 (12) | P1—H1 | 1.32 (2) |
Cu1—O1i | 1.9788 (12) | P1—H2 | 1.38 (3) |
Cu1—O2ii | 1.9901 (12) | O2—Cu1ii | 1.9901 (12) |
Cu1—O2iii | 1.9901 (12) | O3—C1 | 1.264 (3) |
Cu1—O3i | 2.3917 (8) | O3—Cu1ii | 2.3917 (8) |
Cu1—O3 | 2.3917 (8) | C1—N1 | 1.3502 (19) |
Cu1—Cu1ii | 4.1100 (1) | C1—N1ii | 1.3502 (19) |
P1—O1 | 1.5236 (12) | N1—H3 | 0.78 (3) |
P1—O2 | 1.5198 (13) | N1—H4 | 0.85 (3) |
| | | |
O1—Cu1—O1i | 180.0 | O3i—Cu1—Cu1ii | 149.23 (3) |
O1—Cu1—O2ii | 89.55 (5) | O3—Cu1—Cu1ii | 30.77 (3) |
O1i—Cu1—O2ii | 90.45 (5) | O1—P1—O2 | 117.66 (7) |
O1—Cu1—O2iii | 90.45 (5) | O1—P1—H1 | 107.5 (11) |
O1i—Cu1—O2iii | 89.55 (5) | O2—P1—H1 | 109.7 (11) |
O2ii—Cu1—O2iii | 180.00 (9) | O1—P1—H2 | 109.4 (10) |
O1—Cu1—O3i | 92.94 (4) | O2—P1—H2 | 109.6 (10) |
O1i—Cu1—O3i | 87.06 (4) | H1—P1—H2 | 101.7 (15) |
O2ii—Cu1—O3i | 91.56 (4) | P1—O1—Cu1 | 122.76 (7) |
O2iii—Cu1—O3i | 88.44 (4) | P1—O2—Cu1ii | 124.56 (7) |
O1—Cu1—O3 | 87.06 (4) | C1—O3—Cu1ii | 120.77 (3) |
O1i—Cu1—O3 | 92.94 (4) | C1—O3—Cu1 | 120.77 (3) |
O2ii—Cu1—O3 | 88.44 (4) | Cu1ii—O3—Cu1 | 118.46 (7) |
O2iii—Cu1—O3 | 91.56 (4) | O3—C1—N1 | 120.74 (11) |
O3i—Cu1—O3 | 180.0 | O3—C1—N1ii | 120.74 (11) |
O1—Cu1—Cu1ii | 62.98 (3) | N1—C1—N1ii | 118.5 (2) |
O1i—Cu1—Cu1ii | 117.02 (3) | C1—N1—H3 | 126 (2) |
O2ii—Cu1—Cu1ii | 70.67 (3) | C1—N1—H4 | 116.9 (17) |
O2iii—Cu1—Cu1ii | 109.33 (3) | H3—N1—H4 | 114 (3) |
| | | |
N1—C1—O3—Cu1 | 48.15 (8) | | |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x, y, −z+1/2; (iii) x, −y, z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H4···O2iii | 0.85 (3) | 2.23 (3) | 3.005 (2) | 153 (2) |
P1—H2···O3 | 1.38 (3) | 2.80 (2) | 3.0250 (12) | 85.6 (10) |
P1—H2···O2iii | 1.38 (3) | 2.75 (2) | 3.3527 (13) | 103.6 (12) |
N1—H3···O1iv | 0.78 (3) | 2.23 (3) | 2.998 (2) | 169 (3) |
P1—H1···O1v | 1.32 (2) | 2.56 (3) | 3.6701 (13) | 139.7 (16) |
Symmetry codes: (iii) x, −y, z+1/2; (iv) x, y+1, z; (v) −x+1/2, −y−1/2, −z+1. |
(Iat15K) poly[copper(II)-di-µ-hypophosphito-µ-urea]
top
Crystal data top
[Cu(H2PO2)2(CH4N2O)] | F(000) = 508 |
Mr = 253.57 | Dx = 2.280 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 12.297 (3) Å | Cell parameters from 24 reflections |
b = 7.435 (1) Å | θ = 8–12° |
c = 8.197 (2) Å | µ = 3.37 mm−1 |
β = 99.72 (1)° | T = 15 K |
V = 738.7 (3) Å3 | Irregular, blue |
Z = 4 | 0.27 × 0.21 × 0.15 mm |
Data collection top
Fddd (Copley et al., 1997) diffractometer | 980 reflections with I > 2σ(I) |
Radiation source: rotating anode | Rint = 0.025 |
Graphite monochromator | θmax = 29.1°, θmin = 3.2° |
ω scans | h = −16→16 |
Absorption correction: empirical (using intensity measurements) (XPREP; Siemens, 1995) | k = −1→10 |
Tmin = 0.407, Tmax = 0.604 | l = −2→11 |
1355 measured reflections | 3 standard reflections every 100 reflections |
993 independent reflections | intensity decay: none |
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)] = 0.024 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.063 | All H-atom parameters refined |
S = 1.23 | w = 1/[σ2(Fo2) + (0.0347P)2 + 1.2895P] where P = (Fo2 + 2Fc2)/3 |
993 reflections | (Δ/σ)max < 0.001 |
69 parameters | Δρmax = 0.99 e Å−3 |
0 restraints | Δρmin = −0.48 e Å−3 |
Crystal data top
[Cu(H2PO2)2(CH4N2O)] | V = 738.7 (3) Å3 |
Mr = 253.57 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 12.297 (3) Å | µ = 3.37 mm−1 |
b = 7.435 (1) Å | T = 15 K |
c = 8.197 (2) Å | 0.27 × 0.21 × 0.15 mm |
β = 99.72 (1)° | |
Data collection top
Fddd (Copley et al., 1997) diffractometer | 980 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) (XPREP; Siemens, 1995) | Rint = 0.025 |
Tmin = 0.407, Tmax = 0.604 | 3 standard reflections every 100 reflections |
1355 measured reflections | intensity decay: none |
993 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.024 | 0 restraints |
wR(F2) = 0.063 | All H-atom parameters refined |
S = 1.23 | Δρmax = 0.99 e Å−3 |
993 reflections | Δρmin = −0.48 e Å−3 |
69 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 0 | 0 | 1/2 | 0.00621 (11) | |
P1 | 0.17508 (3) | −0.12519 (5) | 0.29767 (5) | 0.00739 (12) | |
H1 | 0.261 (2) | −0.227 (3) | 0.326 (3) | 0.010 (5)* | |
H2 | 0.217 (2) | 0.042 (4) | 0.340 (3) | 0.009 (5)* | |
O1 | 0.09670 (10) | −0.17693 (16) | 0.41505 (14) | 0.0085 (2) | |
O2 | 0.13132 (10) | −0.13403 (16) | 0.11318 (14) | 0.0089 (2) | |
O3 | 0 | 0.1634 (2) | 1/4 | 0.0090 (3) | |
C1 | 0 | 0.3335 (3) | 1/4 | 0.0085 (4) | |
N1 | 0.07136 (12) | 0.4262 (2) | 0.36231 (18) | 0.0106 (3) | |
H3 | 0.067 (2) | 0.535 (4) | 0.379 (3) | 0.010 (6)* | |
H4 | 0.104 (2) | 0.370 (4) | 0.435 (3) | 0.014 (6)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.00608 (16) | 0.00646 (16) | 0.00596 (16) | −0.00019 (8) | 0.00061 (10) | −0.00079 (8) |
P1 | 0.0069 (2) | 0.0087 (2) | 0.0064 (2) | 0.00020 (13) | 0.00053 (14) | 0.00003 (12) |
O1 | 0.0091 (5) | 0.0086 (5) | 0.0080 (5) | 0.0009 (4) | 0.0021 (4) | 0.0002 (4) |
O2 | 0.0087 (5) | 0.0109 (5) | 0.0067 (5) | 0.0018 (4) | 0.0007 (4) | 0.0012 (4) |
O3 | 0.0113 (7) | 0.0069 (7) | 0.0087 (7) | 0 | 0.0012 (6) | 0 |
C1 | 0.0084 (9) | 0.0095 (9) | 0.0082 (9) | 0 | 0.0035 (7) | 0 |
N1 | 0.0130 (6) | 0.0080 (6) | 0.0100 (6) | 0.0002 (5) | −0.0005 (5) | −0.0003 (5) |
Geometric parameters (Å, º) top
Cu1—O1 | 1.9771 (12) | P1—H1 | 1.29 (2) |
Cu1—O1i | 1.9771 (12) | P1—H2 | 1.37 (3) |
Cu1—O2ii | 1.9889 (12) | O2—Cu1iii | 1.9889 (12) |
Cu1—O2iii | 1.9889 (12) | O3—C1 | 1.265 (3) |
Cu1—O3 | 2.3824 (10) | O3—Cu1iii | 2.3824 (10) |
Cu1—O3i | 2.3824 (10) | C1—N1 | 1.3486 (19) |
Cu1—Cu1iii | 4.0985 (10) | C1—N1iii | 1.3486 (19) |
P1—O1 | 1.5218 (12) | N1—H3 | 0.83 (3) |
P1—O2 | 1.5186 (13) | N1—H4 | 0.78 (3) |
| | | |
O1—Cu1—O1i | 180.00 (6) | O3—Cu1—Cu1iii | 30.66 (4) |
O1—Cu1—O2ii | 90.48 (5) | O3i—Cu1—Cu1iii | 149.34 (4) |
O1i—Cu1—O2ii | 89.52 (5) | O1—P1—O2 | 117.57 (7) |
O1—Cu1—O2iii | 89.52 (5) | O1—P1—H1 | 109.2 (10) |
O1i—Cu1—O2iii | 90.48 (5) | O2—P1—H1 | 107.1 (11) |
O2ii—Cu1—O2iii | 180.00 (5) | O1—P1—H2 | 108.9 (10) |
O1—Cu1—O3 | 87.08 (4) | O2—P1—H2 | 110.2 (10) |
O1i—Cu1—O3 | 92.92 (4) | H1—P1—H2 | 102.9 (15) |
O2ii—Cu1—O3 | 91.59 (4) | P1—O1—Cu1 | 122.50 (7) |
O2iii—Cu1—O3 | 88.41 (4) | P1—O2—Cu1iii | 124.48 (7) |
O1—Cu1—O3i | 92.92 (4) | C1—O3—Cu1iii | 120.66 (4) |
O1i—Cu1—O3i | 87.08 (4) | C1—O3—Cu1 | 120.66 (4) |
O2ii—Cu1—O3i | 88.41 (4) | Cu1iii—O3—Cu1 | 118.67 (7) |
O2iii—Cu1—O3i | 91.59 (4) | O3—C1—N1 | 120.70 (11) |
O3—Cu1—O3i | 180.0 | O3—C1—N1iii | 120.70 (11) |
O1—Cu1—Cu1iii | 63.02 (3) | N1—C1—N1iii | 118.6 (2) |
O1i—Cu1—Cu1iii | 116.98 (3) | C1—N1—H3 | 124.0 (18) |
O2ii—Cu1—Cu1iii | 109.23 (4) | C1—N1—H4 | 116 (2) |
O2iii—Cu1—Cu1iii | 70.77 (4) | H3—N1—H4 | 116 (3) |
| | | |
N1—C1—O3—Cu1 | 48.23 (8) | | |
Symmetry codes: (i) −x, −y, −z+1; (ii) x, −y, z+1/2; (iii) −x, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H4···O2ii | 0.78 (3) | 2.27 (3) | 2.9963 (19) | 155 (3) |
P1—H2···O3 | 1.37 (3) | 2.80 (2) | 3.0180 (13) | 85.7 (11) |
P1—H2···O2ii | 1.37 (3) | 2.72 (2) | 3.3411 (13) | 104.7 (12) |
N1—H3···O1iv | 0.83 (3) | 2.18 (3) | 2.991 (2) | 166 (2) |
P1—H1···O1v | 1.29 (2) | 2.61 (2) | 3.6543 (14) | 136.2 (15) |
Symmetry codes: (ii) x, −y, z+1/2; (iv) x, y+1, z; (v) −x+1/2, −y−1/2, −z+1. |
Experimental details
| (Iat293K) | (Iat100K) | (Iat15K) |
Crystal data |
Chemical formula | [Cu(H2PO2)2(CH4N2O)] | [Cu(H2PO2)2(CH4N2O)] | [Cu(H2PO2)2(CH4N2O)] |
Mr | 253.57 | 253.57 | 253.57 |
Crystal system, space group | Monoclinic, C2/c | Monoclinic, C2/c | Monoclinic, C2/c |
Temperature (K) | 293 | 100 | 15 |
a, b, c (Å) | 12.5540 (3), 7.4686 (2), 8.2628 (3) | 12.3589 (3), 7.4464 (2), 8.2199 (2) | 12.297 (3), 7.435 (1), 8.197 (2) |
β (°) | 100.2722 (13) | 99.8369 (14) | 99.72 (1) |
V (Å3) | 762.31 (4) | 745.35 (3) | 738.7 (3) |
Z | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 3.26 | 3.34 | 3.37 |
Crystal size (mm) | 0.54 × 0.30 × 0.22 | 0.54 × 0.30 × 0.22 | 0.27 × 0.21 × 0.15 |
|
Data collection |
Diffractometer | Siemens SMART CCD area-detector diffractometer | Siemens SMART CCD area-detector diffractometer | Fddd (Copley et al., 1997) diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) | Empirical (using intensity measurements) (XPREP; Siemens, 1995) |
Tmin, Tmax | 0.221, 0.488 | 0.297, 0.480 | 0.407, 0.604 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2894, 1014, 920 | 2849, 996, 935 | 1355, 993, 980 |
Rint | 0.030 | 0.020 | 0.025 |
(sin θ/λ)max (Å−1) | 0.684 | 0.684 | 0.685 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.076, 1.12 | 0.022, 0.057, 1.12 | 0.024, 0.063, 1.23 |
No. of reflections | 1014 | 996 | 993 |
No. of parameters | 70 | 70 | 69 |
H-atom treatment | All H-atom parameters refined | All H-atom parameters refined | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.40, −0.73 | 0.57, −0.39 | 0.99, −0.48 |
Selected geometric parameters (Å, º) for (Iat293K) topCu1—O1 | 1.9784 (14) | P1—O2 | 1.5119 (15) |
Cu1—O2i | 1.9895 (14) | P1—H1 | 1.32 (3) |
Cu1—O3 | 2.4153 (10) | P1—H2 | 1.42 (4) |
Cu1—Cu1ii | 4.1314 (2) | O3—C1 | 1.256 (3) |
P1—O1 | 1.5184 (15) | C1—N1 | 1.344 (3) |
| | | |
O1—Cu1—O2i | 90.34 (6) | H1—P1—H2 | 108.3 (17) |
O1—Cu1—O3 | 87.04 (5) | P1—O1—Cu1 | 123.82 (8) |
O2i—Cu1—O3 | 91.72 (5) | P1—O2—Cu1ii | 125.38 (9) |
O1—P1—O2 | 117.84 (8) | C1—O3—Cu1 | 121.21 (4) |
O1—P1—H1 | 108.5 (13) | Cu1ii—O3—Cu1 | 117.57 (8) |
O2—P1—H1 | 108.5 (14) | O3—C1—N1 | 120.97 (15) |
O1—P1—H2 | 105.5 (13) | N1—C1—N1ii | 118.1 (3) |
O2—P1—H2 | 107.8 (14) | | |
| | | |
N1—C1—O3—Cu1 | 47.74 (12) | | |
Symmetry codes: (i) x, −y, z+1/2; (ii) −x, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) for (Iat293K) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H4···O2i | 0.75 (5) | 2.36 (5) | 3.037 (3) | 152 (4) |
N1—H3···O1iii | 0.77 (3) | 2.27 (4) | 3.021 (3) | 162 (3) |
Symmetry codes: (i) x, −y, z+1/2; (iii) x, y+1, z. |
Selected geometric parameters (Å, º) for (Iat100K) topCu1—O1 | 1.9788 (12) | P1—O2 | 1.5198 (13) |
Cu1—O2i | 1.9901 (12) | P1—H1 | 1.32 (2) |
Cu1—O3 | 2.3917 (8) | P1—H2 | 1.38 (3) |
Cu1—Cu1ii | 4.1100 (1) | O3—C1 | 1.264 (3) |
P1—O1 | 1.5236 (12) | C1—N1 | 1.3502 (19) |
| | | |
O1—Cu1—O2i | 90.45 (5) | H1—P1—H2 | 101.7 (15) |
O1—Cu1—O3 | 87.06 (4) | P1—O1—Cu1 | 122.76 (7) |
O2i—Cu1—O3 | 91.56 (4) | P1—O2—Cu1ii | 124.56 (7) |
O1—P1—O2 | 117.66 (7) | C1—O3—Cu1 | 120.77 (3) |
O1—P1—H1 | 107.5 (11) | Cu1ii—O3—Cu1 | 118.46 (7) |
O2—P1—H1 | 109.7 (11) | O3—C1—N1 | 120.74 (11) |
O1—P1—H2 | 109.4 (10) | N1—C1—N1ii | 118.5 (2) |
O2—P1—H2 | 109.6 (10) | | |
| | | |
N1—C1—O3—Cu1 | 48.15 (8) | | |
Symmetry codes: (i) x, −y, z+1/2; (ii) −x, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) for (Iat100K) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H4···O2i | 0.85 (3) | 2.23 (3) | 3.005 (2) | 153 (2) |
N1—H3···O1iii | 0.78 (3) | 2.23 (3) | 2.998 (2) | 169 (3) |
Symmetry codes: (i) x, −y, z+1/2; (iii) x, y+1, z. |
Selected geometric parameters (Å, º) for (Iat15K) topCu1—O1 | 1.9771 (12) | P1—O2 | 1.5186 (13) |
Cu1—O2i | 1.9889 (12) | P1—H1 | 1.29 (2) |
Cu1—O3 | 2.3824 (10) | P1—H2 | 1.37 (3) |
Cu1—Cu1ii | 4.0985 (10) | O3—C1 | 1.265 (3) |
P1—O1 | 1.5218 (12) | C1—N1 | 1.3486 (19) |
| | | |
O1—Cu1—O2i | 90.48 (5) | O2—P1—H2 | 110.2 (10) |
O1—Cu1—O3 | 87.08 (4) | H1—P1—H2 | 102.9 (15) |
O2i—Cu1—O3 | 91.59 (4) | P1—O1—Cu1 | 122.50 (7) |
O2ii—Cu1—O3 | 88.41 (4) | P1—O2—Cu1ii | 124.48 (7) |
O1—P1—O2 | 117.57 (7) | C1—O3—Cu1 | 120.66 (4) |
O1—P1—H1 | 109.2 (10) | Cu1ii—O3—Cu1 | 118.67 (7) |
O2—P1—H1 | 107.1 (11) | O3—C1—N1 | 120.70 (11) |
O1—P1—H2 | 108.9 (10) | N1—C1—N1ii | 118.6 (2) |
| | | |
N1—C1—O3—Cu1 | 48.23 (8) | | |
Symmetry codes: (i) x, −y, z+1/2; (ii) −x, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) for (Iat15K) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H4···O2i | 0.78 (3) | 2.27 (3) | 2.9963 (19) | 155 (3) |
N1—H3···O1iii | 0.83 (3) | 2.18 (3) | 2.991 (2) | 166 (2) |
Symmetry codes: (i) x, −y, z+1/2; (iii) x, y+1, z. |
The present paper reports the results of a multiple-temperature single-crystal structural analysis for a urea complex of copper(II) hypophosphite, (I). No structural data for this compound have been reported previously, despite the great importance of the complex in many technological processes (Lomovsky & Boldyrev, 1994). The synthesis of the urea complex of copper(II) hypophosphite by adding different amounts of urea to copper(II) hypophosphite in solution was described by Yagodin (1985, 1988). Our studies have shown that different starting ratios of the hypophosphite and urea components (from 1:1 to 1:8) always give the same crystals with an equal ratio (1:1) of copper(II) hypophosphite and urea. \sch
The geometry of the hypophosphite anion in the crystal structure of (I) is very close to the ideal, with point symmetry mm2. Each Cu atom is coordinated to six O atoms from four hypophosphite anions and two urea molecules, forming a tetragonal bipyramid. Each hypophosphite anion in the structure is coordinated to two Cu atoms. Two different types of Cu—O bonds are observed. The hypophosphite anions, urea and CuII cations form polymeric ribbons in the [001] direction (Fig. 1). The CuII cations in the ribbon are linked together by two hypophosphite anions and a urea molecule, which is coordinated to Cu via an O atom. The ribbons are linked to each other via N—H3···O1iii hydrogen bonds [symmetry code: (iii) x, 1 + y, z] along the [010] direction and form polymeric layers in the (100) plane (Fig. 1). The urea molecule is rotated in a special way, to form an N—H4···O2i hydrogen bond [symmetry code: (i) x, -y, 1/2 + z] with the nearest hypophosphite anion in the ribbon. The different layers are linked to each other by van der Waals interactions (Fig. 2).
On cooling to 15 K, the structure of (I) contracted anisotropically. The contractions were calculated from the change in the cell parameters between 293 and 100 K, since the same diffractometer was used for data collection. On cooling from 100 to 15 K the character of the contractions was the same. The direction of minimum contraction [-0.297 (2)%; axis 1 of the strain tensor in Fig. 1] coincides with the crystallographic b axis. The direction of this minimum contraction can be correlated with the N—H3···O1iii hydrogen bonds between different ribbons. The direction of medium contraction [-0.321 (4)%; axis 2 of the strain tensor in Fig. 1] is close to the crystallographic c axis. The direction of the medium contraction can be correlated with the contraction of long Cu—O distances on cooling, and both these shorter contractions lie essentially within the layer. The direction of maximum contraction [-1.620 (2)%; axis 3 of the strain tensor in Fig. 1] lies near the crystallographic a axis. This maximum contraction can be correlated with the decrease of the distance between layers in the crystallographic a direction.