Caesium gadolinium polyphosphate, CsGd(PO₃)₄

Crystals of CsGd(PO₃)₄ have been grown by the flux technique from a mixture of CsH₂PO₄, Gd₂O₃ and H₃PO₄. CsGd(PO₃)₄ crystallizes in structure type IV of the M^IM^III(PO₃)₄ (M^I = alkali metal, M^III = rare earth or Bi) family of compounds. The structure consists of a three-dimensional framework made up of spiral (PO₃)_n chains linked by GdO₈ polyhedra. Two infinite (PO₃)_n chains with a period of eight tetra­hedra run along the [101] direction. Gd and Cs cations are surrounded by eight and eleven O atoms, respectively.

Key indicators

• Single-crystal X-ray study
• T = 292 K
• Mean [sigma](P-O) = 0.002 Å
• R factor = 0.018
• wR factor = 0.046
• Data-to-parameter ratio = 42.6

checkCIF/PLATON results

No syntax errors found



Alert level G
ABSTM02_ALERT_3_G  The ratio of expected to reported Tmax/Tmin(RR) is > 1.10
            Tmin and Tmax reported:      0.177     0.271
            Tmin and Tmax expected:      0.084     0.171
            RR =      1.329
            Please check that your absorption correction is appropriate.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   0 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97.

Caesium gadolinium polyphosphate

Crystal data

CsGd(PO3)4	F(000) = 1100
Mr = 606.04	Dx = 4.070 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9641 reflections
a = 10.3229 (2) Å	θ = 2–40°
b = 8.9307 (2) Å	µ = 11.04 mm^−1
c = 11.1826 (2) Å	T = 292 K
β = 106.371 (1)°	Needle, colourless
V = 989.13 (3) Å^3	0.26 × 0.20 × 0.16 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	6980 independent reflections
Radiation source: fine-focus sealed tube	5595 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.071
Detector resolution: 9 pixels mm^-1	θmax = 42.1°, θmin = 3.0°
ω scans	h = −14→19
Absorption correction: analytical (de Meulenaer & Tompa, 1965)	k = −16→15
Tmin = 0.177, Tmax = 0.271	l = −21→20
19421 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Primary atom site location: heavy-atom method
R[F^2 > 2σ(F^2)] = 0.018	Secondary atom site location: difference Fourier map
wR(F^2) = 0.046	w = 1/[σ^2(Fo^2) + (0.0187P)^2 + 2.8091P] where P = (Fo^2 + 2Fc^2)/3
S = 1.24	(Δ/σ)max = 0.001
6980 reflections	Δρmax = 0.89 e Å^−3
164 parameters	Δρmin = −0.58 e Å^−3

Special details

Experimental. Data were corrected for Lorentz-polarization effects and an analytical absorption correction (Meulenaer & Tompa, 1965) was applied. The structure was solved in the P 1 2₁/n 1 space group by the Patterson method (Cs and Gd) and subsequent difference Fourier syntheses (all other atoms).

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 (Ų)

	x	y	z	Uiso*/Ueq
Gd	0.497879 (11)	0.273491 (14)	0.180789 (11)	0.00726 (4)
Cs	0.67903 (2)	0.56590 (3)	0.459719 (19)	0.01910 (6)
P1	0.64512 (6)	−0.09227 (9)	0.25790 (7)	0.00809 (11)
P2	0.45955 (7)	−0.32517 (9)	0.13266 (7)	0.00799 (11)
P3	0.24454 (6)	−0.47205 (9)	0.21423 (6)	0.00771 (11)
P4	0.17229 (6)	−0.60738 (9)	−0.02627 (7)	0.00818 (11)
O1	0.13635 (19)	−0.5429 (3)	0.09486 (19)	0.0106 (3)
O2	0.3514 (2)	−0.5836 (3)	0.2739 (2)	0.0111 (3)
O3	0.5209 (2)	−0.2067 (3)	0.2421 (2)	0.0116 (3)
O4	0.6009 (2)	0.0399 (3)	0.1762 (2)	0.0123 (3)
O5	0.4394 (2)	−0.2544 (3)	0.0091 (2)	0.0133 (3)
O6	0.1682 (2)	−0.4037 (3)	0.2944 (2)	0.0121 (3)
O7	0.7638 (2)	−0.1780 (3)	0.2463 (2)	0.0139 (4)
O8	0.0641 (2)	−0.7111 (3)	−0.0963 (2)	0.0126 (4)
O9	0.3129 (2)	−0.6654 (3)	0.0140 (2)	0.0135 (4)
O10	0.5363 (2)	−0.4673 (3)	0.1652 (2)	0.0130 (4)
O11	0.31122 (19)	−0.3412 (3)	0.1532 (2)	0.0106 (3)
O12	0.6668 (2)	−0.0479 (3)	0.4002 (2)	0.0139 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Gd	0.00551 (6)	0.00778 (7)	0.00655 (6)	0.00047 (3)	−0.00147 (4)	0.00069 (3)
Cs	0.02011 (9)	0.02358 (11)	0.01103 (9)	−0.00406 (6)	0.00018 (6)	0.00080 (6)
P1	0.0065 (2)	0.0081 (3)	0.0074 (2)	−0.00007 (18)	−0.00168 (17)	−0.0006 (2)
P2	0.0073 (2)	0.0076 (3)	0.0073 (2)	−0.00007 (18)	−0.00079 (17)	−0.0001 (2)
P3	0.0062 (2)	0.0087 (3)	0.0065 (2)	0.00102 (18)	−0.00098 (17)	−0.00025 (19)
P4	0.0060 (2)	0.0095 (3)	0.0063 (2)	−0.00002 (18)	−0.00268 (17)	0.0001 (2)
O1	0.0076 (6)	0.0161 (9)	0.0064 (7)	−0.0018 (6)	−0.0009 (5)	−0.0022 (6)
O2	0.0095 (7)	0.0126 (8)	0.0099 (8)	0.0037 (6)	0.0003 (5)	0.0013 (6)
O3	0.0120 (7)	0.0113 (8)	0.0096 (8)	−0.0041 (6)	−0.0003 (6)	−0.0031 (6)
O4	0.0157 (8)	0.0096 (8)	0.0104 (8)	0.0018 (6)	0.0018 (6)	0.0037 (6)
O5	0.0115 (7)	0.0174 (9)	0.0104 (8)	0.0024 (7)	0.0022 (6)	0.0024 (7)
O6	0.0113 (7)	0.0144 (9)	0.0108 (8)	0.0036 (6)	0.0034 (6)	−0.0011 (7)
O7	0.0083 (7)	0.0158 (10)	0.0150 (9)	0.0027 (6)	−0.0009 (6)	−0.0015 (7)
O8	0.0114 (8)	0.0129 (9)	0.0114 (8)	−0.0033 (6)	−0.0002 (6)	−0.0040 (7)
O9	0.0071 (6)	0.0220 (11)	0.0093 (8)	0.0051 (6)	−0.0013 (5)	0.0016 (7)
O10	0.0088 (7)	0.0102 (9)	0.0184 (10)	0.0011 (6)	0.0012 (6)	0.0018 (7)
O11	0.0062 (6)	0.0117 (8)	0.0122 (8)	−0.0008 (5)	0.0000 (5)	0.0026 (6)
O12	0.0193 (9)	0.0115 (9)	0.0074 (8)	0.0006 (7)	−0.0018 (6)	−0.0024 (6)

Geometric parameters (Å, º)

Gd—O9^i	2.327 (2)	P2—Cs^vii	3.7855 (7)
Gd—O4	2.349 (2)	P2—Cs^x	3.8451 (7)
Gd—O10^i	2.363 (2)	P3—O6	1.481 (2)
Gd—O5^ii	2.394 (3)	P3—O2	1.497 (2)
Gd—O7^iii	2.403 (2)	P3—O11	1.603 (2)
Gd—O6^iv	2.406 (2)	P3—O1	1.609 (2)
Gd—O2^i	2.426 (2)	P3—Cs^viii	3.6052 (7)
Gd—O8^v	2.456 (2)	P4—O9	1.487 (2)
Gd—Cs	4.0936 (3)	P4—O8	1.492 (2)
Gd—Cs^vi	4.4703 (3)	P4—O12^xi	1.605 (3)
Gd—Cs^vii	4.6417 (3)	P4—O1	1.608 (2)
Cs—O4^iii	3.077 (2)	P4—Cs^xi	4.0992 (8)
Cs—O2^viii	3.086 (2)	O2—Gd^x	2.426 (2)
Cs—O5^ix	3.087 (2)	O2—Cs^viii	3.086 (2)
Cs—O6^viii	3.115 (2)	O2—Cs^x	3.684 (2)
Cs—O10^i	3.220 (2)	O3—Cs^x	3.236 (2)
Cs—O3^i	3.237 (2)	O4—Cs^vi	3.077 (2)
Cs—O11^ix	3.305 (2)	O5—Gd^ii	2.394 (3)
Cs—O7^iii	3.341 (3)	O5—Cs^vii	3.087 (2)
Cs—O8^v	3.379 (3)	O6—Gd^xii	2.406 (2)
Cs—O12^i	3.509 (3)	O6—Cs^viii	3.115 (2)
Cs—O7^i	3.588 (3)	O7—Gd^vi	2.403 (2)
Cs—P3^viii	3.6052 (7)	O7—Cs^vi	3.341 (3)
P1—O7	1.481 (2)	O7—Cs^x	3.588 (3)
P1—O4	1.484 (2)	O8—Gd^xi	2.456 (2)
P1—O12	1.593 (2)	O8—Cs^xi	3.379 (3)
P1—O3	1.610 (2)	O9—Gd^x	2.327 (2)
P1—Cs^vi	3.7017 (8)	O10—Gd^x	2.363 (2)
P1—Cs^x	3.7537 (8)	O10—Cs^x	3.220 (2)
P2—O5	1.480 (3)	O11—Cs^vii	3.305 (2)
P2—O10	1.486 (2)	O12—P4^v	1.605 (3)
P2—O3	1.607 (2)	O12—Cs^x	3.509 (3)
P2—O11	1.617 (2)
O9^i—Gd—O4	117.72 (9)	O3^i—Cs—O7^i	42.74 (5)
O9^i—Gd—O10^i	80.10 (9)	O11^ix—Cs—O7^i	80.11 (6)
O4—Gd—O10^i	141.43 (8)	O7^iii—Cs—O7^i	80.407 (7)
O9^i—Gd—O5^ii	70.82 (8)	O8^v—Cs—O7^i	127.81 (6)
O4—Gd—O5^ii	71.35 (9)	O12^i—Cs—O7^i	41.36 (6)
O10^i—Gd—O5^ii	84.91 (9)	O4^iii—Cs—P3^viii	120.02 (4)
O9^i—Gd—O7^iii	139.47 (9)	O2^viii—Cs—P3^viii	24.29 (4)
O4—Gd—O7^iii	74.98 (9)	O5^ix—Cs—P3^viii	90.83 (5)
O10^i—Gd—O7^iii	70.81 (8)	O6^viii—Cs—P3^viii	24.07 (4)
O5^ii—Gd—O7^iii	78.88 (8)	O10^i—Cs—P3^viii	156.86 (5)
O9^i—Gd—O6^iv	78.25 (9)	O3^i—Cs—P3^viii	145.75 (5)
O4—Gd—O6^iv	76.14 (8)	O11^ix—Cs—P3^viii	65.08 (4)
O10^i—Gd—O6^iv	142.42 (8)	O7^iii—Cs—P3^viii	120.98 (4)
O5^ii—Gd—O6^iv	115.80 (9)	O8^v—Cs—P3^viii	86.26 (4)
O7^iii—Gd—O6^iv	140.72 (8)	O12^i—Cs—P3^viii	113.98 (4)
O9^i—Gd—O2^i	75.57 (8)	O7^i—Cs—P3^viii	142.77 (4)
O4—Gd—O2^i	144.84 (8)	O7—P1—O4	118.41 (15)
O10^i—Gd—O2^i	69.77 (8)	O7—P1—O12	109.23 (13)
O5^ii—Gd—O2^i	140.80 (8)	O4—P1—O12	110.44 (14)
O7^iii—Gd—O2^i	117.49 (8)	O7—P1—O3	108.38 (14)
O6^iv—Gd—O2^i	75.27 (9)	O4—P1—O3	109.87 (13)
O9^i—Gd—O8^v	142.91 (8)	O12—P1—O3	98.69 (14)
O4—Gd—O8^v	79.78 (8)	O7—P1—Cs^vi	64.44 (11)
O10^i—Gd—O8^v	107.00 (8)	O4—P1—Cs^vi	54.15 (10)
O5^ii—Gd—O8^v	144.76 (8)	O12—P1—Cs^vi	127.20 (10)
O7^iii—Gd—O8^v	74.38 (8)	O3—P1—Cs^vi	133.87 (9)
O6^iv—Gd—O8^v	74.77 (8)	O7—P1—Cs^x	72.13 (11)
O2^i—Gd—O8^v	73.30 (8)	O4—P1—Cs^x	167.86 (10)
O9^i—Gd—Cs	123.81 (7)	O12—P1—Cs^x	68.84 (10)
O4—Gd—Cs	118.09 (5)	O3—P1—Cs^x	59.10 (9)
O10^i—Gd—Cs	51.77 (6)	Cs^vi—P1—Cs^x	136.53 (2)
O5^ii—Gd—Cs	122.79 (6)	O5—P2—O10	121.21 (15)
O7^iii—Gd—Cs	54.71 (7)	O5—P2—O3	110.56 (15)
O6^iv—Gd—Cs	121.25 (6)	O10—P2—O3	107.91 (13)
O2^i—Gd—Cs	62.83 (5)	O5—P2—O11	106.33 (12)
O8^v—Gd—Cs	55.56 (6)	O10—P2—O11	110.51 (13)
O9^i—Gd—Cs^vi	109.91 (6)	O3—P2—O11	97.80 (13)
O4—Gd—Cs^vi	40.24 (6)	O5—P2—Cs^vii	51.39 (10)
O10^i—Gd—Cs^vi	102.88 (6)	O10—P2—Cs^vii	157.79 (9)
O5^ii—Gd—Cs^vi	40.87 (5)	O3—P2—Cs^vii	93.82 (9)
O7^iii—Gd—Cs^vi	53.14 (7)	O11—P2—Cs^vii	60.54 (8)
O6^iv—Gd—Cs^vi	113.24 (6)	O5—P2—Cs^x	152.39 (10)
O2^i—Gd—Cs^vi	170.37 (5)	O10—P2—Cs^x	54.57 (10)
O8^v—Gd—Cs^vi	103.94 (6)	O3—P2—Cs^x	56.10 (9)
Cs—Gd—Cs^vi	107.850 (4)	O11—P2—Cs^x	99.80 (8)
O9^i—Gd—Cs^vii	55.10 (7)	Cs^vii—P2—Cs^x	143.27 (2)
O4—Gd—Cs^vii	70.48 (5)	O6—P3—O2	117.10 (14)
O10^i—Gd—Cs^vii	135.15 (5)	O6—P3—O11	108.81 (14)
O5^ii—Gd—Cs^vii	79.02 (6)	O2—P3—O11	108.89 (13)
O7^iii—Gd—Cs^vii	143.41 (7)	O6—P3—O1	107.52 (12)
O6^iv—Gd—Cs^vii	37.88 (6)	O2—P3—O1	111.11 (13)
O2^i—Gd—Cs^vii	97.94 (5)	O11—P3—O1	102.39 (12)
O8^v—Gd—Cs^vii	110.20 (6)	O6—P3—Cs^viii	59.08 (9)
Cs—Gd—Cs^vii	157.736 (7)	O2—P3—Cs^viii	58.04 (9)
Cs^vi—Gd—Cs^vii	91.678 (5)	O11—P3—Cs^viii	127.03 (8)
O4^iii—Cs—O2^viii	140.42 (6)	O1—P3—Cs^viii	130.57 (9)
O4^iii—Cs—O5^ix	53.32 (6)	O9—P4—O8	117.73 (15)
O2^viii—Cs—O5^ix	96.88 (6)	O9—P4—O12^xi	110.27 (15)
O4^iii—Cs—O6^viii	98.08 (6)	O8—P4—O12^xi	110.76 (13)
O2^viii—Cs—O6^viii	48.36 (6)	O9—P4—O1	107.87 (12)
O5^ix—Cs—O6^viii	84.10 (7)	O8—P4—O1	110.37 (13)
O4^iii—Cs—O10^i	71.13 (6)	O12^xi—P4—O1	98.02 (14)
O2^viii—Cs—O10^i	148.23 (6)	O9—P4—Cs^xi	68.78 (11)
O5^ix—Cs—O10^i	110.95 (6)	O8—P4—Cs^xi	51.52 (10)
O6^viii—Cs—O10^i	146.29 (6)	O12^xi—P4—Cs^xi	147.33 (10)
O4^iii—Cs—O3^i	87.83 (6)	O1—P4—Cs^xi	113.58 (10)
O2^viii—Cs—O3^i	121.78 (6)	P4—O1—P3	124.64 (13)
O5^ix—Cs—O3^i	91.24 (6)	P3—O2—Gd^x	128.98 (13)
O6^viii—Cs—O3^i	168.04 (6)	P3—O2—Cs^viii	97.67 (11)
O10^i—Cs—O3^i	45.60 (6)	Gd^x—O2—Cs^viii	133.35 (8)
O4^iii—Cs—O11^ix	98.82 (6)	P3—O2—Cs^x	117.04 (12)
O2^viii—Cs—O11^ix	57.71 (6)	Gd^x—O2—Cs^x	81.30 (5)
O5^ix—Cs—O11^ix	45.50 (6)	Cs^viii—O2—Cs^x	76.36 (5)
O6^viii—Cs—O11^ix	75.83 (6)	P2—O3—P1	129.22 (17)
O10^i—Cs—O11^ix	136.34 (6)	P2—O3—Cs^x	99.57 (11)
O3^i—Cs—O11^ix	93.04 (6)	P1—O3—Cs^x	95.63 (9)
O4^iii—Cs—O7^iii	46.53 (6)	P1—O4—Gd	139.09 (15)
O2^viii—Cs—O7^iii	141.67 (6)	P1—O4—Cs^vi	102.84 (11)
O5^ix—Cs—O7^iii	99.49 (6)	Gd—O4—Cs^vi	110.23 (8)
O6^viii—Cs—O7^iii	99.30 (6)	P2—O5—Gd^ii	142.75 (16)
O10^i—Cs—O7^iii	49.74 (6)	P2—O5—Cs^vii	106.61 (12)
O3^i—Cs—O7^iii	92.32 (6)	Gd^ii—O5—Cs^vii	108.63 (8)
O11^ix—Cs—O7^iii	144.65 (5)	P3—O6—Gd^xii	149.17 (14)
O4^iii—Cs—O8^v	96.15 (6)	P3—O6—Cs^viii	96.85 (10)
O2^viii—Cs—O8^v	95.79 (6)	Gd^xii—O6—Cs^viii	113.81 (8)
O5^ix—Cs—O8^v	141.91 (6)	P1—O7—Gd^vi	148.91 (15)
O6^viii—Cs—O8^v	77.96 (6)	P1—O7—Cs^vi	91.98 (12)
O10^i—Cs—O8^v	71.86 (6)	Gd^vi—O7—Cs^vi	89.35 (8)
O3^i—Cs—O8^v	111.88 (5)	P1—O7—Cs^x	84.74 (12)
O11^ix—Cs—O8^v	151.33 (6)	Gd^vi—O7—Cs^x	94.45 (7)
O7^iii—Cs—O8^v	51.83 (6)	Cs^vi—O7—Cs^x	176.20 (7)
O4^iii—Cs—O12^i	88.42 (6)	P4—O8—Gd^xi	128.81 (15)
O2^viii—Cs—O12^i	97.18 (6)	P4—O8—Cs^xi	108.26 (11)
O5^ix—Cs—O12^i	58.71 (6)	Gd^xi—O8—Cs^xi	87.61 (7)
O6^viii—Cs—O12^i	127.37 (6)	P4—O9—Gd^x	146.63 (15)
O10^i—Cs—O12^i	85.11 (6)	P2—O10—Gd^x	139.94 (13)
O3^i—Cs—O12^i	41.99 (5)	P2—O10—Cs^x	103.33 (12)
O11^ix—Cs—O12^i	51.61 (5)	Gd^x—O10—Cs^x	93.03 (7)
O7^iii—Cs—O12^i	120.93 (6)	P3—O11—P2	131.48 (15)
O8^v—Cs—O12^i	153.46 (5)	P3—O11—Cs^vii	132.32 (10)
O4^iii—Cs—O7^i	50.73 (6)	P2—O11—Cs^vii	94.24 (10)
O2^viii—Cs—O7^i	136.04 (6)	P1—O12—P4^v	134.56 (18)
O5^ix—Cs—O7^i	53.70 (6)	P1—O12—Cs^x	86.12 (10)
O6^viii—Cs—O7^i	136.57 (5)	P4^v—O12—Cs^x	139.26 (12)
O10^i—Cs—O7^i	60.35 (6)

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