Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802005342/br6046sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802005342/br6046Isup2.hkl |
SrCO3, CoCO3 and (NH4)2HPO4 were mixed in a ratio of 1:3:2. The mixture was heated progressively in air at increasing temperatures up to 1173 K. Then, 100 mg iodine and 10 mg red phosphorous were added and the mixture was sealed in an evacuated silica ampoule. The ampoule was transferred to a tubular furnace where it was heated for a week at 973 K. The reaction product was washed with dilute NaOH and water and dried at 373 K. Two kinds of crystals were obtained: pink crystals have been identified as Co2P4O12 (Nord, 1982; Olbertz et al., 1998), dark red crystals were composed of the title compound.
Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991).
Co2P2O7 | F(000) = 560 |
Mr = 291.80 | Dx = 4.008 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.0022 (9) Å | Cell parameters from 10799 reflections |
b = 8.3634 (11) Å | θ = 3.2–30.0° |
c = 9.0114 (12) Å | µ = 7.50 mm−1 |
β = 113.600 (9)° | T = 173 K |
V = 483.59 (11) Å3 | Block, dark red |
Z = 4 | 0.29 × 0.18 × 0.12 mm |
Stoe IPDS II two-circle diffractometer | 1389 independent reflections |
Radiation source: fine-focus sealed tube | 1307 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
ω scans | θmax = 29.9°, θmin = 3.2° |
Absorption correction: empirical (MULABS; Spek, 1990; Blessing, 1995) | h = −9→9 |
Tmin = 0.200, Tmax = 0.406 | k = −11→11 |
7237 measured reflections | l = −11→12 |
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 | w = 1/[σ2(Fo2) + (0.0278P)2 + 0.0813P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.049 | (Δ/σ)max = 0.001 |
S = 1.12 | Δρmax = 0.50 e Å−3 |
1389 reflections | Δρmin = −0.47 e Å−3 |
101 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0252 (15) |
Co2P2O7 | V = 483.59 (11) Å3 |
Mr = 291.80 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.0022 (9) Å | µ = 7.50 mm−1 |
b = 8.3634 (11) Å | T = 173 K |
c = 9.0114 (12) Å | 0.29 × 0.18 × 0.12 mm |
β = 113.600 (9)° |
Stoe IPDS II two-circle diffractometer | 1389 independent reflections |
Absorption correction: empirical (MULABS; Spek, 1990; Blessing, 1995) | 1307 reflections with I > 2σ(I) |
Tmin = 0.200, Tmax = 0.406 | Rint = 0.048 |
7237 measured reflections |
R[F2 > 2σ(F2)] = 0.024 | 101 parameters |
wR(F2) = 0.049 | 0 restraints |
S = 1.12 | Δρmax = 0.50 e Å−3 |
1389 reflections | Δρmin = −0.47 e Å−3 |
Experimental. ; |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Co1 | 0.23247 (3) | 0.92882 (3) | 0.10884 (2) | 0.00799 (8) | |
Co2 | 0.69933 (3) | 0.44157 (2) | 0.82475 (2) | 0.00860 (8) | |
P1 | 0.94042 (6) | 0.76797 (4) | 0.75824 (4) | 0.00746 (9) | |
P2 | 0.53170 (5) | 0.77429 (4) | 0.46771 (4) | 0.00713 (9) | |
O1 | 0.74908 (16) | 0.82989 (14) | 0.60005 (12) | 0.0110 (2) | |
O2 | 0.37848 (17) | 0.76488 (13) | 0.54938 (13) | 0.0096 (2) | |
O3 | 1.11902 (16) | 0.75915 (12) | 0.70267 (13) | 0.0093 (2) | |
O4 | 0.97662 (17) | 0.90145 (13) | 0.88165 (13) | 0.0095 (2) | |
O5 | 0.88706 (18) | 0.61064 (14) | 0.81112 (14) | 0.0126 (2) | |
O6 | 0.48086 (17) | 0.90934 (13) | 0.34431 (13) | 0.0092 (2) | |
O7 | 0.55344 (17) | 0.61280 (14) | 0.39749 (13) | 0.0097 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.00769 (12) | 0.00809 (12) | 0.00812 (12) | 0.00033 (6) | 0.00307 (9) | 0.00007 (6) |
Co2 | 0.00846 (11) | 0.00823 (12) | 0.00975 (11) | −0.00018 (6) | 0.00431 (8) | 0.00030 (6) |
P1 | 0.00673 (16) | 0.00807 (17) | 0.00767 (16) | −0.00038 (11) | 0.00298 (13) | −0.00058 (11) |
P2 | 0.00668 (16) | 0.00790 (17) | 0.00660 (15) | −0.00011 (11) | 0.00244 (13) | −0.00014 (11) |
O1 | 0.0080 (5) | 0.0128 (5) | 0.0092 (5) | 0.0003 (3) | 0.0004 (4) | −0.0007 (4) |
O2 | 0.0098 (5) | 0.0102 (5) | 0.0102 (4) | −0.0013 (4) | 0.0054 (4) | −0.0008 (4) |
O3 | 0.0083 (5) | 0.0101 (5) | 0.0102 (4) | −0.0003 (3) | 0.0044 (4) | −0.0001 (4) |
O4 | 0.0097 (5) | 0.0103 (5) | 0.0083 (5) | 0.0010 (4) | 0.0034 (4) | −0.0016 (4) |
O5 | 0.0137 (5) | 0.0099 (5) | 0.0166 (5) | −0.0018 (4) | 0.0085 (4) | −0.0004 (4) |
O6 | 0.0096 (5) | 0.0091 (5) | 0.0083 (4) | −0.0007 (3) | 0.0031 (4) | 0.0013 (3) |
O7 | 0.0100 (5) | 0.0090 (5) | 0.0095 (5) | 0.0008 (4) | 0.0032 (4) | −0.0012 (4) |
Co1—O4i | 2.0655 (11) | P1—O1 | 1.6019 (11) |
Co1—O3ii | 2.0869 (11) | P2—O6 | 1.5239 (11) |
Co1—O2iii | 2.0966 (11) | P2—O7 | 1.5248 (12) |
Co1—O4iv | 2.1253 (12) | P2—O2 | 1.5268 (11) |
Co1—O6 | 2.1445 (11) | P2—O1 | 1.5817 (11) |
Co1—O7v | 2.1649 (12) | O2—Co2x | 2.0643 (11) |
Co2—O5 | 1.9677 (12) | O2—Co1vi | 2.0965 (11) |
Co2—O6vi | 2.0352 (11) | O3—Co2xi | 2.0636 (11) |
Co2—O3vii | 2.0636 (11) | O3—Co1xii | 2.0869 (11) |
Co2—O2viii | 2.0643 (11) | O4—Co1i | 2.0655 (11) |
Co2—O7ix | 2.1242 (11) | O4—Co1xiii | 2.1253 (11) |
P1—O5 | 1.4968 (12) | O6—Co2iii | 2.0352 (11) |
P1—O4 | 1.5237 (12) | O7—Co2ix | 2.1242 (11) |
P1—O3 | 1.5237 (12) | O7—Co1xiv | 2.1649 (12) |
O4i—Co1—O3ii | 96.30 (5) | O4—P1—O3 | 110.90 (6) |
O4i—Co1—O2iii | 165.45 (4) | O5—P1—O1 | 109.94 (7) |
O3ii—Co1—O2iii | 79.93 (5) | O4—P1—O1 | 104.36 (6) |
O4i—Co1—O4iv | 77.05 (5) | O3—P1—O1 | 103.14 (6) |
O3ii—Co1—O4iv | 89.91 (4) | O6—P2—O7 | 112.75 (7) |
O2iii—Co1—O4iv | 88.84 (4) | O6—P2—O2 | 112.71 (6) |
O4i—Co1—O6 | 108.59 (4) | O7—P2—O2 | 111.13 (6) |
O3ii—Co1—O6 | 80.29 (4) | O6—P2—O1 | 101.86 (6) |
O2iii—Co1—O6 | 84.77 (4) | O7—P2—O1 | 110.33 (6) |
O4iv—Co1—O6 | 169.10 (5) | O2—P2—O1 | 107.55 (6) |
O4i—Co1—O7v | 91.29 (5) | P2—O1—P1 | 141.76 (8) |
O3ii—Co1—O7v | 157.83 (4) | P2—O2—Co2x | 128.23 (6) |
O2iii—Co1—O7v | 97.40 (4) | P2—O2—Co1vi | 132.20 (6) |
O4iv—Co1—O7v | 112.13 (4) | Co2x—O2—Co1vi | 98.61 (5) |
O6—Co1—O7v | 77.54 (4) | P1—O3—Co2xi | 129.05 (6) |
O5—Co2—O6vi | 96.27 (5) | P1—O3—Co1xii | 131.70 (6) |
O5—Co2—O3vii | 93.70 (5) | Co2xi—O3—Co1xii | 98.95 (5) |
O6vi—Co2—O3vii | 169.76 (4) | P1—O4—Co1i | 128.33 (7) |
O5—Co2—O2viii | 151.47 (5) | P1—O4—Co1xiii | 127.72 (7) |
O6vi—Co2—O2viii | 91.04 (4) | Co1i—O4—Co1xiii | 102.95 (5) |
O3vii—Co2—O2viii | 81.23 (5) | P1—O5—Co2 | 155.46 (8) |
O5—Co2—O7ix | 114.85 (5) | P2—O6—Co2iii | 123.59 (6) |
O6vi—Co2—O7ix | 80.87 (5) | P2—O6—Co1 | 129.67 (6) |
O3vii—Co2—O7ix | 92.85 (4) | Co2iii—O6—Co1 | 101.99 (5) |
O2viii—Co2—O7ix | 93.51 (5) | P2—O7—Co2ix | 113.39 (6) |
O5—P1—O4 | 113.67 (7) | P2—O7—Co1xiv | 145.67 (7) |
O5—P1—O3 | 113.85 (6) | Co2ix—O7—Co1xiv | 98.47 (5) |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x−1, −y+3/2, z−1/2; (iii) x, −y+3/2, z−1/2; (iv) x−1, y, z−1; (v) −x+1, y+1/2, −z+1/2; (vi) x, −y+3/2, z+1/2; (vii) −x+2, y−1/2, −z+3/2; (viii) −x+1, y−1/2, −z+3/2; (ix) −x+1, −y+1, −z+1; (x) −x+1, y+1/2, −z+3/2; (xi) −x+2, y+1/2, −z+3/2; (xii) x+1, −y+3/2, z+1/2; (xiii) x+1, y, z+1; (xiv) −x+1, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | Co2P2O7 |
Mr | 291.80 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 173 |
a, b, c (Å) | 7.0022 (9), 8.3634 (11), 9.0114 (12) |
β (°) | 113.600 (9) |
V (Å3) | 483.59 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 7.50 |
Crystal size (mm) | 0.29 × 0.18 × 0.12 |
Data collection | |
Diffractometer | Stoe IPDS II two-circle diffractometer |
Absorption correction | Empirical (MULABS; Spek, 1990; Blessing, 1995) |
Tmin, Tmax | 0.200, 0.406 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7237, 1389, 1307 |
Rint | 0.048 |
(sin θ/λ)max (Å−1) | 0.702 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.049, 1.12 |
No. of reflections | 1389 |
No. of parameters | 101 |
Δρmax, Δρmin (e Å−3) | 0.50, −0.47 |
Computer programs: X-AREA (Stoe & Cie, 2001), X-AREA, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP in SHELXTL-Plus (Sheldrick, 1991).
Co1—O4i | 2.0655 (11) | Co2—O7ix | 2.1242 (11) |
Co1—O3ii | 2.0869 (11) | P1—O5 | 1.4968 (12) |
Co1—O2iii | 2.0966 (11) | P1—O4 | 1.5237 (12) |
Co1—O4iv | 2.1253 (12) | P1—O3 | 1.5237 (12) |
Co1—O6 | 2.1445 (11) | P1—O1 | 1.6019 (11) |
Co1—O7v | 2.1649 (12) | P2—O6 | 1.5239 (11) |
Co2—O5 | 1.9677 (12) | P2—O7 | 1.5248 (12) |
Co2—O6vi | 2.0352 (11) | P2—O2 | 1.5268 (11) |
Co2—O3vii | 2.0636 (11) | P2—O1 | 1.5817 (11) |
Co2—O2viii | 2.0643 (11) | ||
P2—O1—P1 | 141.76 (8) |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x−1, −y+3/2, z−1/2; (iii) x, −y+3/2, z−1/2; (iv) x−1, y, z−1; (v) −x+1, y+1/2, −z+1/2; (vi) x, −y+3/2, z+1/2; (vii) −x+2, y−1/2, −z+3/2; (viii) −x+1, y−1/2, −z+3/2; (ix) −x+1, −y+1, −z+1. |
The original structure of the title compound was reported by Krishnamachari & Calvo (1972) using the unconventional space group B21/c for comparison with the structure of Mg2P2O7 (Calvo, 1967). In addition, the magnetic structure of the title compound had been determined (Forsyth et al., 1989). We used the conventional space group P21/c for rerefinement. A perspective view of the title compound is shown in Fig. 1. Both structures agree well, but the present work is of improved precision.