Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801005700/br6014sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801005700/br6014Isup2.hkl |
A mixture of (NH4)2HPO4, Sr(OH)2 and NiCl2 was ground together and heated to approximately 800 K. The molten mass was maintained at this temperature for two days and then cooled down to room temperature (El-Bali, 1993).
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).
SrNi3(P2O7)2 | F(000) = 588 |
Mr = 611.63 | Dx = 4.093 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.4116 (4) Å | Cell parameters from 39700 reflections |
b = 7.6542 (3) Å | θ = 3.8–37.3° |
c = 9.4486 (6) Å | µ = 11.69 mm−1 |
β = 112.194 (5)° | T = 173 K |
V = 496.30 (5) Å3 | Block, yellow |
Z = 2 | 0.24 × 0.18 × 0.16 mm |
Stoe IPDS II two-circle diffractometer | 2076 independent reflections |
Radiation source: fine-focus sealed tube | 2027 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.052 |
ω scans | θmax = 34.3°, θmin = 4.0° |
Absorption correction: empirical (using intensity measurements) (MULABS; Spek, 1990; Blessing, 1995) | h = −11→11 |
Tmin = 0.101, Tmax = 0.156 | k = −12→10 |
26742 measured reflections | l = −14→14 |
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)] = 0.021 | w = 1/[σ2(Fo2) + (0.0304P)2 + 0.4865P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.054 | (Δ/σ)max = 0.001 |
S = 1.13 | Δρmax = 0.78 e Å−3 |
2076 reflections | Δρmin = −0.78 e Å−3 |
104 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.096 (2) |
SrNi3(P2O7)2 | V = 496.30 (5) Å3 |
Mr = 611.63 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.4116 (4) Å | µ = 11.69 mm−1 |
b = 7.6542 (3) Å | T = 173 K |
c = 9.4486 (6) Å | 0.24 × 0.18 × 0.16 mm |
β = 112.194 (5)° |
Stoe IPDS II two-circle diffractometer | 2076 independent reflections |
Absorption correction: empirical (using intensity measurements) (MULABS; Spek, 1990; Blessing, 1995) | 2027 reflections with I > 2σ(I) |
Tmin = 0.101, Tmax = 0.156 | Rint = 0.052 |
26742 measured reflections |
R[F2 > 2σ(F2)] = 0.021 | 104 parameters |
wR(F2) = 0.054 | 0 restraints |
S = 1.13 | Δρmax = 0.78 e Å−3 |
2076 reflections | Δρmin = −0.78 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 | ||
Sr1 | 0.5000 | 1.0000 | 0.0000 | 0.01074 (7) | |
Ni1 | 0.18424 (3) | 0.62596 (3) | 0.02578 (2) | 0.00958 (7) | |
Ni2 | 0.0000 | 1.0000 | 0.0000 | 0.00934 (7) | |
P1 | 0.60256 (6) | 0.44098 (5) | 0.20097 (4) | 0.00920 (8) | |
P2 | 0.88811 (6) | 0.70400 (5) | 0.19372 (4) | 0.00911 (8) | |
O1 | 0.39757 (18) | 0.47873 (17) | 0.19242 (14) | 0.0113 (2) | |
O2 | 0.62427 (18) | 0.31912 (17) | 0.08281 (14) | 0.01178 (19) | |
O3 | 0.73161 (18) | 0.38239 (16) | 0.36484 (14) | 0.01116 (19) | |
O4 | 0.67992 (17) | 0.62943 (16) | 0.17742 (14) | 0.0112 (2) | |
O5 | 0.97336 (18) | 0.57480 (16) | 0.11291 (14) | 0.01094 (19) | |
O6 | 0.99820 (18) | 0.71065 (16) | 0.36620 (13) | 0.01111 (19) | |
O7 | 0.84443 (18) | 0.87709 (16) | 0.11085 (14) | 0.0112 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sr1 | 0.01043 (10) | 0.01129 (10) | 0.01150 (10) | −0.00001 (6) | 0.00528 (7) | 0.00012 (6) |
Ni1 | 0.00949 (10) | 0.00950 (10) | 0.01023 (10) | 0.00014 (6) | 0.00425 (7) | 0.00016 (6) |
Ni2 | 0.00950 (13) | 0.00890 (13) | 0.01007 (12) | 0.00003 (8) | 0.00420 (10) | 0.00001 (8) |
P1 | 0.00881 (16) | 0.00958 (16) | 0.00973 (16) | −0.00004 (12) | 0.00408 (12) | 0.00005 (12) |
P2 | 0.00937 (15) | 0.00872 (15) | 0.00969 (15) | −0.00011 (12) | 0.00413 (12) | 0.00005 (12) |
O1 | 0.0095 (4) | 0.0126 (5) | 0.0128 (5) | 0.0006 (4) | 0.0051 (4) | 0.0010 (4) |
O2 | 0.0124 (5) | 0.0120 (5) | 0.0119 (4) | −0.0005 (4) | 0.0055 (4) | −0.0019 (4) |
O3 | 0.0108 (4) | 0.0118 (5) | 0.0101 (4) | 0.0001 (4) | 0.0031 (4) | 0.0006 (3) |
O4 | 0.0092 (4) | 0.0106 (5) | 0.0138 (5) | −0.0014 (4) | 0.0046 (4) | 0.0005 (4) |
O5 | 0.0118 (5) | 0.0103 (4) | 0.0120 (4) | 0.0001 (4) | 0.0059 (4) | −0.0009 (4) |
O6 | 0.0125 (5) | 0.0103 (5) | 0.0098 (4) | −0.0007 (4) | 0.0033 (4) | −0.0004 (3) |
O7 | 0.0116 (5) | 0.0104 (5) | 0.0125 (4) | 0.0004 (4) | 0.0055 (4) | 0.0013 (4) |
Sr1—O7 | 2.5453 (12) | Ni2—O3vi | 2.1164 (12) |
Sr1—O7i | 2.5453 (12) | Ni2—Sr1vii | 3.7058 (2) |
Sr1—O2ii | 2.6234 (13) | P1—O2 | 1.5094 (13) |
Sr1—O2iii | 2.6234 (13) | P1—O1 | 1.5184 (13) |
Sr1—O3iv | 2.6541 (13) | P1—O3 | 1.5474 (13) |
Sr1—O3v | 2.6541 (13) | P1—O4 | 1.5985 (13) |
Sr1—O1v | 2.7169 (13) | P1—Sr1viii | 3.2230 (4) |
Sr1—O1iv | 2.7169 (13) | P2—O7 | 1.5105 (13) |
Sr1—P1v | 3.2229 (4) | P2—O6 | 1.5231 (12) |
Sr1—P1iv | 3.2229 (4) | P2—O5 | 1.5247 (13) |
Sr1—O4i | 3.3083 (12) | P2—O4 | 1.5971 (13) |
Sr1—O4 | 3.3083 (12) | O1—Sr1viii | 2.7169 (13) |
Ni1—O6vi | 2.0415 (12) | O2—Ni1iii | 2.0841 (12) |
Ni1—O5vii | 2.0606 (12) | O2—Sr1ix | 2.6234 (13) |
Ni1—O5iii | 2.0704 (12) | O3—Ni2viii | 2.1164 (12) |
Ni1—O2iii | 2.0841 (12) | O3—Ni1viii | 2.1961 (12) |
Ni1—O1 | 2.0901 (13) | O3—Sr1viii | 2.6541 (13) |
Ni1—O3iv | 2.1961 (12) | O5—Ni1x | 2.0606 (12) |
Ni2—O6iv | 2.0458 (12) | O5—Ni1iii | 2.0704 (12) |
Ni2—O6vi | 2.0458 (12) | O6—Ni1xi | 2.0416 (12) |
Ni2—O7i | 2.0552 (12) | O6—Ni2viii | 2.0458 (12) |
Ni2—O7vii | 2.0552 (12) | O7—Ni2x | 2.0552 (12) |
Ni2—O3iv | 2.1163 (12) | ||
O7—Sr1—O7i | 180.0 | O1—Ni1—O3iv | 97.34 (5) |
O7—Sr1—O2ii | 92.11 (4) | O6vi—Ni1—Sr1 | 75.48 (4) |
O7i—Sr1—O2ii | 87.89 (4) | O5vii—Ni1—Sr1 | 138.98 (3) |
O7—Sr1—O2iii | 87.89 (4) | O5iii—Ni1—Sr1 | 137.70 (3) |
O7i—Sr1—O2iii | 92.11 (4) | O2iii—Ni1—Sr1 | 42.18 (3) |
O2ii—Sr1—O2iii | 180.00 (6) | O1—Ni1—Sr1 | 98.45 (4) |
O7—Sr1—O3iv | 114.02 (4) | O3iv—Ni1—Sr1 | 43.74 (3) |
O7i—Sr1—O3iv | 65.98 (4) | O6iv—Ni2—O6vi | 180.0 |
O2ii—Sr1—O3iv | 112.97 (4) | O6iv—Ni2—O7i | 94.60 (5) |
O2iii—Sr1—O3iv | 67.03 (4) | O6vi—Ni2—O7i | 85.40 (5) |
O7—Sr1—O3v | 65.98 (4) | O6iv—Ni2—O7vii | 85.40 (5) |
O7i—Sr1—O3v | 114.02 (4) | O6vi—Ni2—O7vii | 94.60 (5) |
O2ii—Sr1—O3v | 67.03 (4) | O7i—Ni2—O7vii | 180.0 |
O2iii—Sr1—O3v | 112.97 (4) | O6iv—Ni2—O3iv | 100.20 (5) |
O3iv—Sr1—O3v | 180.0 | O6vi—Ni2—O3iv | 79.80 (5) |
O7—Sr1—O1v | 107.09 (4) | O7i—Ni2—O3iv | 85.52 (5) |
O7i—Sr1—O1v | 72.91 (4) | O7vii—Ni2—O3iv | 94.48 (5) |
O2ii—Sr1—O1v | 100.84 (4) | O6iv—Ni2—O3vi | 79.80 (5) |
O2iii—Sr1—O1v | 79.16 (4) | O6vi—Ni2—O3vi | 100.20 (5) |
O3iv—Sr1—O1v | 124.39 (4) | O7i—Ni2—O3vi | 94.48 (5) |
O3v—Sr1—O1v | 55.61 (4) | O7vii—Ni2—O3vi | 85.52 (5) |
O7—Sr1—O1iv | 72.91 (4) | O3iv—Ni2—O3vi | 180.00 (7) |
O7i—Sr1—O1iv | 107.09 (4) | O6iv—Ni2—Sr1 | 103.11 (3) |
O2ii—Sr1—O1iv | 79.16 (4) | O6vi—Ni2—Sr1 | 76.89 (3) |
O2iii—Sr1—O1iv | 100.84 (4) | O7i—Ni2—Sr1 | 41.10 (3) |
O3iv—Sr1—O1iv | 55.61 (4) | O7vii—Ni2—Sr1 | 138.90 (3) |
O3v—Sr1—O1iv | 124.39 (4) | O3iv—Ni2—Sr1 | 44.61 (3) |
O1v—Sr1—O1iv | 180.0 | O3vi—Ni2—Sr1 | 135.39 (3) |
O7—Sr1—P1v | 83.14 (3) | O6iv—Ni2—Sr1vii | 76.89 (3) |
O7i—Sr1—P1v | 96.86 (3) | O6vi—Ni2—Sr1vii | 103.11 (3) |
O2ii—Sr1—P1v | 87.62 (3) | O7i—Ni2—Sr1vii | 138.90 (3) |
O2iii—Sr1—P1v | 92.38 (3) | O7vii—Ni2—Sr1vii | 41.10 (3) |
O3iv—Sr1—P1v | 151.52 (3) | O3iv—Ni2—Sr1vii | 135.40 (3) |
O3v—Sr1—P1v | 28.48 (3) | O3vi—Ni2—Sr1vii | 44.61 (3) |
O1v—Sr1—P1v | 28.00 (3) | Sr1—Ni2—Sr1vii | 180.0 |
O1iv—Sr1—P1v | 152.00 (3) | O2—P1—O1 | 117.54 (7) |
O7—Sr1—P1iv | 96.86 (3) | O2—P1—O3 | 111.27 (7) |
O7i—Sr1—P1iv | 83.14 (3) | O1—P1—O3 | 109.65 (7) |
O2ii—Sr1—P1iv | 92.38 (3) | O2—P1—O4 | 108.09 (7) |
O2iii—Sr1—P1iv | 87.62 (3) | O1—P1—O4 | 103.01 (7) |
O3iv—Sr1—P1iv | 28.48 (3) | O3—P1—O4 | 106.39 (7) |
O3v—Sr1—P1iv | 151.52 (3) | O2—P1—Sr1viii | 149.48 (5) |
O1v—Sr1—P1iv | 152.00 (3) | O1—P1—Sr1viii | 57.14 (5) |
O1iv—Sr1—P1iv | 28.00 (3) | O3—P1—Sr1viii | 54.89 (5) |
P1v—Sr1—P1iv | 180.0 | O4—P1—Sr1viii | 102.20 (5) |
O7—Sr1—O4i | 132.46 (3) | O7—P2—O6 | 116.65 (7) |
O7i—Sr1—O4i | 47.54 (3) | O7—P2—O5 | 110.95 (7) |
O2ii—Sr1—O4i | 51.81 (3) | O6—P2—O5 | 113.68 (7) |
O2iii—Sr1—O4i | 128.19 (3) | O7—P2—O4 | 104.68 (7) |
O3iv—Sr1—O4i | 108.93 (3) | O6—P2—O4 | 102.87 (7) |
O3v—Sr1—O4i | 71.07 (3) | O5—P2—O4 | 106.73 (7) |
O1v—Sr1—O4i | 60.68 (3) | O7—P2—Sr1 | 37.37 (5) |
O1iv—Sr1—O4i | 119.32 (3) | O6—P2—Sr1 | 121.93 (5) |
P1v—Sr1—O4i | 67.61 (2) | O5—P2—Sr1 | 124.07 (5) |
P1iv—Sr1—O4i | 112.39 (2) | O4—P2—Sr1 | 67.41 (5) |
O7—Sr1—O4 | 47.54 (3) | P1—O1—Ni1 | 126.85 (7) |
O7i—Sr1—O4 | 132.46 (3) | P1—O1—Sr1viii | 94.87 (6) |
O2ii—Sr1—O4 | 128.19 (3) | Ni1—O1—Sr1viii | 126.85 (5) |
O2iii—Sr1—O4 | 51.81 (3) | P1—O2—Ni1iii | 121.48 (7) |
O3iv—Sr1—O4 | 71.07 (3) | P1—O2—Sr1ix | 132.26 (7) |
O3v—Sr1—O4 | 108.93 (3) | Ni1iii—O2—Sr1ix | 105.58 (5) |
O1v—Sr1—O4 | 119.32 (3) | P1—O3—Ni2viii | 124.43 (7) |
O1iv—Sr1—O4 | 60.68 (3) | P1—O3—Ni1viii | 133.49 (7) |
P1v—Sr1—O4 | 112.39 (2) | Ni2viii—O3—Ni1viii | 93.50 (5) |
P1iv—Sr1—O4 | 67.61 (2) | P1—O3—Sr1viii | 96.63 (6) |
O4i—Sr1—O4 | 180.00 (4) | Ni2viii—O3—Sr1viii | 101.34 (5) |
O6vi—Ni1—O5vii | 90.51 (5) | Ni1viii—O3—Sr1viii | 101.36 (5) |
O6vi—Ni1—O5iii | 85.70 (5) | P2—O4—P1 | 133.89 (8) |
O5vii—Ni1—O5iii | 77.30 (5) | P2—O4—Sr1 | 86.12 (5) |
O6vi—Ni1—O2iii | 84.75 (5) | P1—O4—Sr1 | 138.34 (6) |
O5vii—Ni1—O2iii | 174.47 (5) | P2—O5—Ni1x | 126.67 (7) |
O5iii—Ni1—O2iii | 99.46 (5) | P2—O5—Ni1iii | 123.84 (7) |
O6vi—Ni1—O1 | 173.91 (5) | Ni1x—O5—Ni1iii | 102.70 (5) |
O5vii—Ni1—O1 | 93.94 (5) | P2—O6—Ni1xi | 138.60 (8) |
O5iii—Ni1—O1 | 99.32 (5) | P2—O6—Ni2viii | 120.71 (7) |
O2iii—Ni1—O1 | 91.01 (5) | Ni1xi—O6—Ni2viii | 100.46 (5) |
O6vi—Ni1—O3iv | 78.03 (5) | P2—O7—Ni2x | 127.88 (7) |
O5vii—Ni1—O3iv | 96.04 (5) | P2—O7—Sr1 | 121.52 (7) |
O5iii—Ni1—O3iv | 162.42 (5) | Ni2x—O7—Sr1 | 106.84 (5) |
O2iii—Ni1—O3iv | 85.77 (5) |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) x, y+1, z; (iii) −x+1, −y+1, −z; (iv) −x+1, y+1/2, −z+1/2; (v) x, −y+3/2, z−1/2; (vi) x−1, −y+3/2, z−1/2; (vii) x−1, y, z; (viii) −x+1, y−1/2, −z+1/2; (ix) x, y−1, z; (x) x+1, y, z; (xi) x+1, −y+3/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | SrNi3(P2O7)2 |
Mr | 611.63 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 173 |
a, b, c (Å) | 7.4116 (4), 7.6542 (3), 9.4486 (6) |
β (°) | 112.194 (5) |
V (Å3) | 496.30 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 11.69 |
Crystal size (mm) | 0.24 × 0.18 × 0.16 |
Data collection | |
Diffractometer | Stoe IPDS II two-circle diffractometer |
Absorption correction | Empirical (using intensity measurements) (MULABS; Spek, 1990; Blessing, 1995) |
Tmin, Tmax | 0.101, 0.156 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 26742, 2076, 2027 |
Rint | 0.052 |
(sin θ/λ)max (Å−1) | 0.794 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.021, 0.054, 1.13 |
No. of reflections | 2076 |
No. of parameters | 104 |
Δρmax, Δρmin (e Å−3) | 0.78, −0.78 |
Computer programs: X-AREA (Stoe & Cie, 2001), X-AREA, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP in SHELXTL-Plus (Sheldrick, 1991).
Sr1—O7 | 2.5453 (12) | Ni1—O2vi | 2.0841 (12) |
Sr1—O2i | 2.6234 (13) | Ni1—O1 | 2.0901 (13) |
Sr1—O3ii | 2.6541 (13) | Ni1—O3ii | 2.1961 (12) |
Sr1—O1iii | 2.7169 (13) | Ni2—O6ii | 2.0458 (12) |
Ni1—O6iv | 2.0415 (12) | Ni2—O7vii | 2.0552 (12) |
Ni1—O5v | 2.0606 (12) | Ni2—O3ii | 2.1163 (12) |
Symmetry codes: (i) x, y+1, z; (ii) −x+1, y+1/2, −z+1/2; (iii) x, −y+3/2, z−1/2; (iv) x−1, −y+3/2, z−1/2; (v) x−1, y, z; (vi) −x+1, −y+1, −z; (vii) −x+1, −y+2, −z. |
Pyrophosphates are of interest because of their complex network architecture and several structures have been previously determined. The title compound, SrNi3(P2O7)2, has already been investigated by powder diffraction (El-Bali, 1993), but since its single-crystal structure has not been determined yet, it is presented here.
The Sr and one of the Ni ions are located on a crystallographic centre of inversion. All other atoms occupy general positions. The structure consists of infinite zigzag chains of NiO6 octahedra sharing either trans or skew edges. These chains are connected by P2O7 moieties to form a three-dimensional network into which the Sr ions are incorporated via connections to eight O atoms. The structure of SrNi3(P2O7)2 is isostructural with all other metal pyrophosphates having the same stoichiometry: Ni3Pb(P2O7)2 (Krasnikov et al., 1985), CaNi3(P2O7)2, CaCo3(P2O7)2 and SrFe3(P2O7)2 (Lii et al., 1993), and PbCo3(P2O7)2 and PbFe3(P2O7)2 (Elmarzouki et al., 1995).