CsTiP₂O₇

From single-crystal X-ray data, cesium titanium pyrophos­phate, CsTiP₂O₇, is found to crystallize in the KAlP₂O₇ structure type. It possesses a three-dimensional tunnel structure built by the corner-sharing of distorted TiO₆ octahedra and P₂O₇ pyrophosphate groups. The Cs⁺ cations are in the tunnels.

Computing details

Data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL/PC (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1997); software used to prepare material for publication: SHELXTL/PC.

'caesium titanium pyrophosphate'

Crystal data

CsTiP2O7	F(000) = 652
Mr = 354.75	Dx = 3.699 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.7247 (6) Å	Cell parameters from 4699 reflections
b = 10.2237 (7) Å	θ = 2.7–27.0°
c = 8.3429 (6) Å	µ = 7.46 mm^−1
β = 104.788 (1)°	T = 153 K
V = 637.05 (8) Å^3	Plate, purple-blue
Z = 4	0.23 × 0.20 × 0.09 mm

Data collection

Bruker Smart 1000 CCD diffractometer	1279 independent reflections
Radiation source: standard-focus sealed tube	1272 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
ω scans	θmax = 27.0°, θmin = 2.7°
Absorption correction: numerical face indexed (SHELXTL/PC; Sheldrick, 1997)	h = −9→10
Tmin = 0.198, Tmax = 0.520	k = −12→12
4699 measured reflections	l = −10→10

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.023	w = 1/[σ^2(Fo^2) + (0.0400Fo^2)^2]
wR(F^2) = 0.068	(Δ/σ)max = 0.001
S = 1.42	Δρmax = 1.15 e Å^−3
1279 reflections	Δρmin = −1.14 e Å^−3
101 parameters	Extinction correction: SHELXTL/PC (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0082 (7)

Special details

Experimental. X-ray data were collected on a Bruker Smart- 1000 CCD system. The crystal-to-detector distance was 5.023 cm. Crystal decay was monitored by recollecting 50 initial frames at the end of data collection. Each exposure was 10 s and covered -0.3° in ω. Data were collected in groups of 606, 435, 230 frames at φ settings of 0°, 90°, and 180°.

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. Anisotropic displacement parameters were used for all atoms. All sites are fully occupied.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cs	0.19698 (2)	0.800752 (16)	0.04465 (2)	0.01042 (14)
Ti	0.23894 (7)	0.39850 (4)	0.25875 (6)	0.00422 (16)
P1	0.13198 (10)	0.09468 (6)	0.33116 (9)	0.00459 (18)
P2	0.42723 (9)	0.12928 (6)	0.18254 (9)	0.00494 (18)
O1	0.0063 (3)	0.50010 (16)	0.2667 (2)	0.0056 (4)
O2	0.0908 (2)	0.23357 (18)	0.2678 (2)	0.0074 (4)
O3	0.1571 (3)	0.41543 (18)	0.0153 (3)	0.0080 (4)
O4	0.3206 (2)	0.05270 (18)	0.2972 (2)	0.0073 (4)
O5	0.3213 (3)	0.10378 (17)	0.0055 (3)	0.0096 (4)
O6	0.4368 (3)	0.27299 (18)	0.2293 (3)	0.0073 (4)
O7	0.6125 (2)	0.07001 (18)	0.2253 (2)	0.0075 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cs	0.00989 (19)	0.01156 (18)	0.00913 (19)	−0.00092 (5)	0.00120 (11)	0.00256 (4)
Ti	0.0056 (3)	0.0040 (3)	0.0032 (3)	0.00026 (16)	0.0014 (2)	0.00017 (15)
P1	0.0056 (4)	0.0041 (3)	0.0045 (4)	−0.0009 (2)	0.0021 (3)	0.0001 (2)
P2	0.0059 (3)	0.0046 (3)	0.0048 (4)	0.0003 (2)	0.0022 (3)	0.0001 (2)
O1	0.0061 (9)	0.0050 (9)	0.0063 (9)	0.0022 (6)	0.0028 (7)	0.0011 (6)
O2	0.0091 (9)	0.0053 (8)	0.0075 (9)	−0.0005 (7)	0.0016 (7)	0.0010 (7)
O3	0.0088 (9)	0.0091 (9)	0.0063 (9)	0.0018 (7)	0.0023 (8)	0.0003 (7)
O4	0.0074 (9)	0.0063 (8)	0.0094 (10)	0.0014 (7)	0.0041 (7)	0.0017 (6)
O5	0.0122 (10)	0.0088 (10)	0.0066 (10)	−0.0001 (7)	0.0007 (7)	−0.0005 (7)
O6	0.0069 (9)	0.0065 (8)	0.0100 (10)	0.0001 (7)	0.0045 (7)	−0.0003 (7)
O7	0.0066 (9)	0.0077 (9)	0.0090 (9)	0.0012 (7)	0.0036 (7)	0.0003 (7)

Geometric parameters (Å, º)

Cs—O2^i	2.9840 (18)	P1—O4	1.612 (2)
Cs—O6^ii	2.9859 (19)	P1—Cs^ix	3.6488 (8)
Cs—O2^iii	3.105 (2)	P1—Cs^i	3.6556 (8)
Cs—O1^iv	3.1544 (18)	P1—Cs^xi	3.9508 (7)
Cs—O7^ii	3.1577 (18)	P2—O7	1.511 (2)
Cs—O1^iii	3.2186 (19)	P2—O5	1.517 (2)
Cs—O7^v	3.267 (2)	P2—O6	1.517 (2)
Cs—O5^vi	3.2843 (18)	P2—O4	1.615 (2)
Cs—O4^vi	3.3105 (19)	P2—Cs^x	3.6479 (7)
Cs—O3^i	3.452 (2)	P2—Cs^xi	3.8372 (7)
Cs—P2^ii	3.6479 (7)	P2—Cs^v	3.9166 (8)
Cs—P1^iii	3.6488 (8)	O1—P1^iii	1.5155 (19)
Ti—O3	1.974 (2)	O1—Cs^viii	3.1544 (18)
Ti—O5^vii	1.994 (2)	O1—Cs^ix	3.2186 (19)
Ti—O2	2.0499 (19)	O2—Cs^i	2.9840 (18)
Ti—O6	2.058 (2)	O2—Cs^ix	3.105 (2)
Ti—O7^ii	2.0810 (19)	O3—P1^xii	1.503 (2)
Ti—O1	2.091 (2)	O3—Cs^i	3.452 (2)
Ti—Cs^viii	3.9552 (5)	O4—Cs^xi	3.3105 (19)
Ti—Cs^i	4.1887 (5)	O5—Ti^xii	1.994 (2)
Ti—Cs^ix	4.2247 (6)	O5—Cs^xi	3.2843 (18)
Ti—Cs^x	4.3619 (6)	O6—Cs^x	2.9859 (19)
P1—O3^vii	1.503 (2)	O7—Ti^x	2.0810 (19)
P1—O1^ix	1.5155 (19)	O7—Cs^x	3.1577 (18)
P1—O2	1.5201 (19)	O7—Cs^v	3.267 (2)
O2^i—Cs—O6^ii	156.22 (6)	O6—Ti—Cs^ix	126.07 (6)
O2^i—Cs—O2^iii	86.82 (5)	O7^ii—Ti—Cs^ix	130.97 (6)
O6^ii—Cs—O2^iii	110.22 (5)	O1—Ti—Cs^ix	47.83 (5)
O2^i—Cs—O1^iv	47.90 (5)	Cs^viii—Ti—Cs^ix	75.736 (10)
O6^ii—Cs—O1^iv	135.65 (5)	Cs^i—Ti—Cs^ix	61.449 (9)
O2^iii—Cs—O1^iv	104.67 (5)	O3—Ti—Cs^x	115.71 (6)
O2^i—Cs—O7^ii	124.81 (5)	O5^vii—Ti—Cs^x	65.43 (6)
O6^ii—Cs—O7^ii	47.61 (5)	O2—Ti—Cs^x	108.12 (5)
O2^iii—Cs—O7^ii	79.11 (5)	O6—Ti—Cs^x	36.96 (5)
O1^iv—Cs—O7^ii	170.66 (5)	O7^ii—Ti—Cs^x	71.79 (5)
O2^i—Cs—O1^iii	98.86 (5)	O1—Ti—Cs^x	152.37 (5)
O6^ii—Cs—O1^iii	104.66 (5)	Cs^viii—Ti—Cs^x	100.318 (10)
O2^iii—Cs—O1^iii	52.56 (5)	Cs^i—Ti—Cs^x	133.444 (12)
O1^iv—Cs—O1^iii	75.90 (6)	Cs^ix—Ti—Cs^x	128.209 (13)
O7^ii—Cs—O1^iii	112.68 (5)	O3—Ti—Cs	62.36 (6)
O2^i—Cs—O7^v	79.13 (5)	O5^vii—Ti—Cs	113.30 (5)
O6^ii—Cs—O7^v	87.31 (5)	O2—Ti—Cs	142.06 (5)
O2^iii—Cs—O7^v	160.61 (5)	O6—Ti—Cs	120.48 (6)
O1^iv—Cs—O7^v	55.95 (5)	O7^ii—Ti—Cs	39.79 (5)
O7^ii—Cs—O7^v	119.94 (6)	O1—Ti—Cs	65.15 (5)
O1^iii—Cs—O7^v	116.29 (5)	Cs^viii—Ti—Cs	61.065 (8)
O2^i—Cs—O5^vi	101.28 (5)	Cs^i—Ti—Cs	103.961 (11)
O6^ii—Cs—O5^vi	84.18 (5)	Cs^ix—Ti—Cs	112.939 (11)
O2^iii—Cs—O5^vi	121.60 (5)	Cs^x—Ti—Cs	108.977 (10)
O1^iv—Cs—O5^vi	53.95 (5)	O3^vii—P1—O1^ix	113.33 (12)
O7^ii—Cs—O5^vi	131.48 (5)	O3^vii—P1—O2	112.37 (11)
O1^iii—Cs—O5^vi	69.07 (5)	O1^ix—P1—O2	110.66 (10)
O7^v—Cs—O5^vi	49.87 (5)	O3^vii—P1—O4	105.96 (11)
O2^i—Cs—O4^vi	132.62 (5)	O1^ix—P1—O4	106.26 (11)
O6^ii—Cs—O4^vi	66.37 (5)	O2—P1—O4	107.81 (11)
O2^iii—Cs—O4^vi	88.78 (5)	O3^vii—P1—Cs^ix	70.53 (8)
O1^iv—Cs—O4^vi	88.31 (4)	O1^ix—P1—Cs^ix	94.31 (8)
O7^ii—Cs—O4^vi	100.40 (5)	O2—P1—Cs^ix	57.34 (8)
O1^iii—Cs—O4^vi	45.05 (5)	O4—P1—Cs^ix	158.43 (7)
O7^v—Cs—O4^vi	90.95 (5)	O3^vii—P1—Cs^i	141.01 (9)
O5^vi—Cs—O4^vi	44.37 (5)	O1^ix—P1—Cs^i	58.98 (7)
O2^i—Cs—O3^i	53.98 (5)	O2—P1—Cs^i	52.47 (7)
O6^ii—Cs—O3^i	128.21 (5)	O4—P1—Cs^i	112.88 (7)
O2^iii—Cs—O3^i	44.65 (5)	Cs^ix—P1—Cs^i	72.100 (14)
O1^iv—Cs—O3^i	95.89 (5)	O3^vii—P1—Cs^xi	124.29 (8)
O7^ii—Cs—O3^i	80.72 (5)	O1^ix—P1—Cs^xi	50.94 (8)
O1^iii—Cs—O3^i	90.51 (5)	O2—P1—Cs^xi	123.22 (8)
O7^v—Cs—O3^i	129.68 (5)	O4—P1—Cs^xi	55.32 (7)
O5^vi—Cs—O3^i	146.15 (5)	Cs^ix—P1—Cs^xi	144.71 (2)
O4^vi—Cs—O3^i	132.81 (5)	Cs^i—P1—Cs^xi	82.611 (15)
O2^i—Cs—P2^ii	141.76 (4)	O7—P2—O5	113.84 (12)
O6^ii—Cs—P2^ii	23.87 (4)	O7—P2—O6	110.28 (10)
O2^iii—Cs—P2^ii	97.90 (4)	O5—P2—O6	113.30 (11)
O1^iv—Cs—P2^ii	156.46 (4)	O7—P2—O4	105.14 (10)
O7^ii—Cs—P2^ii	24.31 (4)	O5—P2—O4	105.27 (11)
O1^iii—Cs—P2^ii	114.14 (4)	O6—P2—O4	108.41 (11)
O7^v—Cs—P2^ii	101.41 (4)	O7—P2—Cs^x	59.36 (7)
O5^vi—Cs—P2^ii	108.00 (4)	O5—P2—Cs^x	146.68 (8)
O4^vi—Cs—P2^ii	85.55 (3)	O6—P2—Cs^x	52.79 (7)
O3^i—Cs—P2^ii	104.93 (3)	O4—P2—Cs^x	107.95 (7)
O2^i—Cs—P1^iii	76.27 (4)	O7—P2—Cs^xi	93.35 (7)
O6^ii—Cs—P1^iii	112.45 (4)	O5—P2—Cs^xi	57.60 (7)
O2^iii—Cs—P1^iii	24.35 (4)	O6—P2—Cs^xi	155.96 (7)
O1^iv—Cs—P1^iii	110.68 (4)	O4—P2—Cs^xi	59.06 (7)
O7^ii—Cs—P1^iii	69.29 (4)	Cs^x—P2—Cs^xi	147.335 (19)
O1^iii—Cs—P1^iii	76.39 (3)	O7—P2—Cs^v	54.06 (8)
O7^v—Cs—P1^iii	153.90 (3)	O5—P2—Cs^v	80.94 (8)
O5^vi—Cs—P1^iii	144.62 (4)	O6—P2—Cs^v	87.37 (8)
O4^vi—Cs—P1^iii	112.16 (4)	O4—P2—Cs^v	158.15 (7)
O3^i—Cs—P1^iii	24.23 (4)	Cs^x—P2—Cs^v	69.153 (13)
P2^ii—Cs—P1^iii	92.654 (17)	Cs^xi—P2—Cs^v	111.030 (18)
O3—Ti—O5^vii	175.64 (8)	P1^iii—O1—Ti	142.48 (14)
O3—Ti—O2	94.29 (8)	P1^iii—O1—Cs^viii	96.70 (8)
O5^vii—Ti—O2	89.21 (8)	Ti—O1—Cs^viii	95.74 (7)
O3—Ti—O6	89.12 (8)	P1^iii—O1—Cs^ix	107.61 (10)
O5^vii—Ti—O6	93.73 (8)	Ti—O1—Cs^ix	103.38 (6)
O2—Ti—O6	85.99 (8)	Cs^viii—O1—Cs^ix	104.10 (6)
O3—Ti—O7^ii	91.06 (8)	P1—O2—Ti	135.41 (11)
O5^vii—Ti—O7^ii	85.33 (8)	P1—O2—Cs^i	103.70 (9)
O2—Ti—O7^ii	174.00 (8)	Ti—O2—Cs^i	111.28 (8)
O6—Ti—O7^ii	96.83 (8)	P1—O2—Cs^ix	98.31 (9)
O3—Ti—O1	86.36 (8)	Ti—O2—Cs^ix	108.35 (8)
O5^vii—Ti—O1	91.34 (8)	Cs^i—O2—Cs^ix	89.80 (5)
O2—Ti—O1	85.13 (7)	P1^xii—O3—Ti	165.86 (14)
O6—Ti—O1	169.71 (8)	P1^xii—O3—Cs^i	85.25 (8)
O7^ii—Ti—O1	92.50 (7)	Ti—O3—Cs^i	97.30 (7)
O3—Ti—Cs^viii	119.87 (6)	P1—O4—P2	126.54 (12)
O5^vii—Ti—Cs^viii	55.94 (5)	P1—O4—Cs^xi	101.08 (8)
O2—Ti—Cs^viii	119.00 (6)	P2—O4—Cs^xi	96.20 (8)
O6—Ti—Cs^viii	137.26 (6)	P2—O5—Ti^xii	163.30 (13)
O7^ii—Ti—Cs^viii	55.61 (6)	P2—O5—Cs^xi	99.45 (9)
O1—Ti—Cs^viii	52.52 (5)	Ti^xii—O5—Cs^xi	93.86 (6)
O3—Ti—Cs^i	54.83 (6)	P2—O6—Ti	130.21 (11)
O5^vii—Ti—Cs^i	127.86 (6)	P2—O6—Cs^x	103.34 (9)
O2—Ti—Cs^i	41.59 (5)	Ti—O6—Cs^x	118.56 (8)
O6—Ti—Cs^i	97.56 (6)	P2—O7—Ti^x	145.76 (12)
O7^ii—Ti—Cs^i	142.51 (5)	P2—O7—Cs^x	96.33 (9)
O1—Ti—Cs^i	72.29 (5)	Ti^x—O7—Cs^x	115.27 (7)
Cs^viii—Ti—Cs^i	124.438 (13)	P2—O7—Cs^v	103.95 (9)
O3—Ti—Cs^ix	110.01 (6)	Ti^x—O7—Cs^v	92.68 (7)
O5^vii—Ti—Cs^ix	70.86 (6)	Cs^x—O7—Cs^v	83.96 (4)
O2—Ti—Cs^ix	44.22 (6)

Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1, y+1/2, −z+1/2; (iii) −x, y+1/2, −z+1/2; (iv) x, −y+3/2, z−1/2; (v) −x+1, −y+1, −z; (vi) x, y+1, z; (vii) x, −y+1/2, z+1/2; (viii) x, −y+3/2, z+1/2; (ix) −x, y−1/2, −z+1/2; (x) −x+1, y−1/2, −z+1/2; (xi) x, y−1, z; (xii) x, −y+1/2, z−1/2.