Structure of calcinaksite KNa[Ca(H₂O)][Si₄O_l0], the first hydrous member of the litidionite group of silicates with [Si₈O₂₀]⁸⁻ tubes

Calcinaksite, KNa[Ca(H₂O)][Si₄O_l0], a new natural member of the litidionite group, was found in a calcic xenolith from alkaline basalt of the Bellerberg volcano, Eastern Eifel region, Rhineland–Palatinate, Germany. The crystal structure has been studied based on single-crystal X-ray diffraction data. Triclinic unit-cell parameters are: a = 7.021 (2), b = 8.250 (3), c = 10.145 (2) Å, α = 102.23 (2), β = 100.34 (2), γ = 115.09 (3)°, space group . The structure model was determined by the `charge-flipping' method and refined to R = 0.0527 in anisotropic approximation using 3057 I > 3σ(I). Calcinaksite is a hydrous calcium-dominant litidionite-group mineral. The crystal structure of calcinaksite (like other litidionite-group minerals and related compounds) is based on a heteropoly­hedral framework and is characterized by the presence of several types of channels. Calcium forms distorted CaO₅Ø (Ø = H₂O) octahedra while Na forms NaO₅ square pyramids. Nine-coordinated K atoms are located in a channel extending along [010]. Water molecules occupy a channel running along the [100] direction and are characterized by a rather high equivalent isotropic displacement parameter of 0.053 (2) Ų. In calcinaksite, there are three short distances between the water molecule and oxygen atoms, Ow...O3 [2.844 (5) Å], Ow...O9 [2.736 (4) Å] and Ow...Ow [2.843 (7) Å]. These distances correspond to three hydrogen bonds detected by IR data (the bands at 3340, 3170 and 3540 cm⁻¹).

S1. Experimental

S1.1. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

S2. Results and discussion

Computing details

Data collection: CrysAlis PRO, Agilent Technologies, Version 1.171.34.49 (release 20-01-2011 CrysAlis171 .NET) (compiled Jan 20 2011,15:58:25); cell refinement: CrysAlis PRO, Agilent Technologies, Version 1.171.34.49 (release 20-01-2011 CrysAlis171 .NET) (compiled Jan 20 2011,15:58:25); data reduction: CrysAlis PRO, Agilent Technologies, Version 1.171.34.49 (release 20-01-2011 CrysAlis171 .NET) (compiled Jan 20 2011,15:58:25).

Figures

(I)

Crystal data

CaKNaO11Si4	V = 495.4 (3) Å^3
Mr = 392.5	Z = 2
Triclinic, P1	F(000) = 388
Hall symbol: -P 1	Dx = 2.510 Mg m^−3
a = 7.021 (2) Å	Mo Kα radiation, λ = 0.7107 Å
b = 8.250 (3) Å	Cell parameters from 1903 reflections
c = 10.145 (2) Å	θ = 4.3–57.4°
α = 102.23 (2)°	µ = 1.62 mm^−1
β = 100.34 (2)°	T = 293 K
γ = 115.09 (3)°	0.25 × 0.18 × 0.13 mm

Data collection

Xcalibur, Sapphire3 diffractometer	11109 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3057 reflections with I > 3σ(I)
Graphite monochromator	Rint = 0.073
Detector resolution: 16.0628 pixels mm^-1	θmax = 57.6°, θmin = 4.3°
ω scans	h = −16→12
Absorption correction: multi-scan CrysAlis PRO, Agilent Technologies, Version 1.171.34.49 (release 20-01-2011 CrysAlis171 .NET) (compiled Jan 20 2011,15:58:25) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −16→19
Tmin = 0.737, Tmax = 1	l = −23→23
24923 measured reflections

Refinement

Refinement on F	0 constraints
R[F^2 > 2σ(F^2)] = 0.053	Weighting scheme based on measured s.u.'s w = 1/(σ^2(F) + 0.0025000002F^2)
wR(F^2) = 0.075	(Δ/σ)max = 0.047
S = 1.06	Δρmax = 0.54 e Å^−3
3057 reflections	Δρmin = −0.51 e Å^−3
164 parameters	Extinction correction: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974)
0 restraints	Extinction coefficient: −1100 (400)

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

	x	y	z	Uiso*/Ueq
Ca1	0.25729 (13)	0.73567 (11)	0.08326 (7)	0.0171 (3)
K	−0.14714 (16)	0.20147 (13)	0.49142 (10)	0.0263 (3)
Si1	0.11132 (17)	0.39963 (13)	0.24679 (10)	0.0138 (3)
Na	0.7505 (3)	0.6953 (3)	0.08325 (18)	0.0255 (7)
Si2	0.57768 (17)	0.71073 (13)	0.36451 (10)	0.0144 (3)
Si3	0.25070 (17)	1.10137 (13)	0.30732 (10)	0.0141 (3)
Si4	0.33754 (17)	0.61793 (14)	−0.24708 (10)	0.0150 (3)
O1	−0.0968 (4)	0.3939 (4)	0.3013 (3)	0.0183 (10)
O2	0.1242 (5)	0.8828 (4)	0.2283 (3)	0.0205 (10)
O3	0.3028 (5)	0.4210 (4)	−0.3485 (3)	0.0224 (11)
O4	0.1143 (5)	1.2081 (4)	0.2586 (3)	0.0239 (11)
O5	0.2893 (5)	1.1384 (4)	0.4772 (3)	0.0215 (10)
O6	0.5844 (5)	0.8104 (4)	0.2484 (3)	0.0224 (11)
O7	0.3270 (5)	0.5800 (4)	0.3673 (3)	0.0217 (10)
O8	0.4969 (5)	1.2081 (4)	0.2892 (3)	0.0207 (10)
O9	0.4137 (5)	0.6427 (4)	−0.0846 (3)	0.0207 (11)
O10	0.0952 (5)	0.4206 (4)	0.0948 (3)	0.0192 (10)
O_wat	0.2839 (8)	0.9805 (5)	−0.0292 (4)	0.0529 (19)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ca1	0.0181 (3)	0.0208 (3)	0.0150 (3)	0.0113 (3)	0.0056 (2)	0.0058 (2)
K	0.0280 (5)	0.0229 (4)	0.0297 (4)	0.0111 (3)	0.0089 (4)	0.0145 (3)
Si1	0.0139 (4)	0.0146 (4)	0.0164 (4)	0.0075 (3)	0.0066 (3)	0.0081 (3)
Na	0.0205 (8)	0.0322 (9)	0.0243 (8)	0.0133 (7)	0.0074 (7)	0.0080 (7)
Si2	0.0148 (4)	0.0142 (4)	0.0143 (4)	0.0066 (3)	0.0049 (3)	0.0054 (3)
Si3	0.0149 (4)	0.0133 (4)	0.0150 (4)	0.0065 (3)	0.0055 (3)	0.0061 (3)
Si4	0.0140 (4)	0.0163 (4)	0.0167 (4)	0.0073 (3)	0.0063 (3)	0.0075 (3)
O1	0.0135 (11)	0.0249 (12)	0.0204 (11)	0.0100 (10)	0.0072 (9)	0.0115 (10)
O2	0.0221 (13)	0.0148 (10)	0.0228 (12)	0.0072 (10)	0.0090 (10)	0.0047 (9)
O3	0.0207 (14)	0.0201 (12)	0.0267 (13)	0.0119 (11)	0.0059 (11)	0.0045 (10)
O4	0.0227 (14)	0.0213 (12)	0.0318 (15)	0.0128 (11)	0.0077 (12)	0.0124 (11)
O5	0.0269 (14)	0.0191 (11)	0.0148 (11)	0.0072 (11)	0.0068 (10)	0.0064 (9)
O6	0.0227 (13)	0.0266 (13)	0.0202 (12)	0.0109 (11)	0.0085 (10)	0.0123 (10)
O7	0.0161 (12)	0.0247 (12)	0.0210 (12)	0.0071 (10)	0.0062 (10)	0.0066 (10)
O8	0.0169 (12)	0.0193 (11)	0.0265 (13)	0.0064 (10)	0.0097 (10)	0.0113 (10)
O9	0.0217 (13)	0.0253 (13)	0.0195 (12)	0.0125 (11)	0.0079 (10)	0.0116 (10)
O10	0.0214 (13)	0.0199 (11)	0.0185 (11)	0.0089 (10)	0.0082 (10)	0.0106 (9)
O_wat	0.068 (3)	0.0262 (17)	0.0371 (19)	0.0049 (18)	−0.0008 (19)	0.0117 (15)

Geometric parameters (Å, º)

Ca1—Ca1^i	3.760 (5)	K—O3^ix	2.821 (4)
Ca1—K^ii	4.481 (2)	K—O5^ii	2.661 (4)
Ca1—Na^iii	3.430 (3)	K—O7^ii	2.896 (4)
Ca1—Na	3.617 (3)	Si1—O1	1.639 (4)
Ca1—Na^iv	3.571 (4)	Si1—O4^x	1.618 (4)
Ca1—O2	2.283 (4)	Si1—O7	1.630 (3)
Ca1—O6	2.333 (4)	Si1—O10	1.577 (3)
Ca1—O9	2.351 (4)	Na—Na^iv	3.400 (5)
Ca1—O10	2.394 (4)	Na—O2^xi	2.377 (4)
Ca1—O10^i	2.398 (4)	Si2—O3^iv	1.631 (4)
K—K^v	4.714 (4)	Si2—O5^xii	1.621 (3)
K—K^vi	4.614 (3)	Si2—O6	1.569 (4)
K—K^ii	4.409 (5)	Si2—O7	1.638 (4)
K—Si1	3.598 (2)	Si3—O2	1.567 (3)
K—Si1^ii	3.647 (3)	Si3—O4	1.633 (4)
K—Na^vii	4.384 (3)	Si3—O5	1.636 (3)
K—Si2^viii	3.471 (4)	Si3—O8	1.640 (4)
K—Si2^vii	3.694 (3)	Si4—O1^i	1.635 (3)
K—Si3^ii	3.478 (2)	Si4—O3	1.620 (4)
K—Si4^ix	3.661 (4)	Si4—O8^xiii	1.618 (4)
K—Si4^i	3.495 (2)	Si4—O9	1.579 (3)
K—O1	2.726 (4)
Ca1^i—Ca1—K^ii	92.34 (4)	Si2^viii—K—Si2^vii	99.88 (6)
Ca1^i—Ca1—Na^iii	59.35 (5)	Si2^viii—K—Si3^ii	53.34 (4)
Ca1^i—Ca1—Na	111.96 (6)	Si2^viii—K—Si4^ix	144.34 (6)
Ca1^i—Ca1—Na^iv	55.72 (5)	Si2^viii—K—Si4^i	110.36 (5)
Ca1^i—Ca1—O2	97.99 (8)	Si2^viii—K—O1	118.59 (7)
Ca1^i—Ca1—O6	128.08 (9)	Si2^viii—K—O3^ix	123.75 (10)
Ca1^i—Ca1—O9	89.49 (7)	Si2^viii—K—O5^ii	26.72 (7)
Ca1^i—Ca1—O10	38.36 (8)	Si2^viii—K—O7^ii	122.97 (7)
Ca1^i—Ca1—O10^i	38.29 (9)	Si2^vii—K—Si3^ii	81.44 (5)
K^ii—Ca1—Na^iii	65.75 (4)	Si2^vii—K—Si4^ix	49.21 (4)
K^ii—Ca1—Na	112.11 (4)	Si2^vii—K—Si4^i	128.04 (5)
K^ii—Ca1—Na^iv	115.95 (5)	Si2^vii—K—O1	101.23 (7)
K^ii—Ca1—O2	38.88 (9)	Si2^vii—K—O3^ix	24.64 (8)
K^ii—Ca1—O6	72.31 (9)	Si2^vii—K—O5^ii	87.92 (9)
K^ii—Ca1—O9	151.85 (10)	Si2^vii—K—O7^ii	122.79 (7)
K^ii—Ca1—O10	75.45 (8)	Si3^ii—K—Si4^ix	98.86 (5)
K^ii—Ca1—O10^i	108.36 (9)	Si3^ii—K—Si4^i	150.31 (5)
Na^iii—Ca1—Na	170.17 (6)	Si3^ii—K—O1	171.93 (6)
Na^iii—Ca1—Na^iv	115.07 (6)	Si3^ii—K—O3^ix	92.75 (9)
Na^iii—Ca1—O2	43.67 (8)	Si3^ii—K—O5^ii	26.94 (7)
Na^iii—Ca1—O6	137.87 (10)	Si3^ii—K—O7^ii	94.63 (8)
Na^iii—Ca1—O9	136.63 (8)	Si4^ix—K—Si4^i	103.98 (5)
Na^iii—Ca1—O10	83.60 (11)	Si4^ix—K—O1	88.53 (6)
Na^iii—Ca1—O10^i	46.54 (10)	Si4^ix—K—O3^ix	24.88 (8)
Na—Ca1—Na^iv	56.45 (6)	Si4^ix—K—O5^ii	121.30 (8)
Na—Ca1—O2	140.45 (8)	Si4^ix—K—O7^ii	75.76 (7)
Na—Ca1—O6	42.27 (10)	Si4^i—K—O1	27.03 (7)
Na—Ca1—O9	42.41 (9)	Si4^i—K—O3^ix	115.77 (9)
Na—Ca1—O10	86.58 (11)	Si4^i—K—O5^ii	134.62 (7)
Na—Ca1—O10^i	130.22 (10)	Si4^i—K—O7^ii	73.25 (8)
Na^iv—Ca1—O2	147.26 (9)	O1—K—O3^ix	92.64 (9)
Na^iv—Ca1—O6	86.39 (10)	O1—K—O5^ii	145.05 (9)
Na^iv—Ca1—O9	44.96 (9)	O1—K—O7^ii	90.31 (11)
Na^iv—Ca1—O10	44.07 (10)	O3^ix—K—O5^ii	107.36 (12)
Na^iv—Ca1—O10^i	80.46 (10)	O3^ix—K—O7^ii	100.27 (10)
O2—Ca1—O6	98.85 (12)	O5^ii—K—O7^ii	113.06 (11)
O2—Ca1—O9	167.10 (13)	K—Si1—K^ii	74.96 (5)
O2—Ca1—O10	103.36 (13)	K—Si1—O1	45.95 (13)
O2—Ca1—O10^i	89.27 (12)	K—Si1—O4^x	64.10 (13)
O6—Ca1—O9	84.53 (12)	K—Si1—O7	95.75 (13)
O6—Ca1—O10	89.90 (12)	K—Si1—O10	150.25 (12)
O6—Ca1—O10^i	165.64 (13)	K^ii—Si1—O1	56.46 (10)
O9—Ca1—O10	89.03 (12)	K^ii—Si1—O4^x	131.97 (12)
O9—Ca1—O10^i	90.17 (12)	K^ii—Si1—O7	50.43 (15)
O10—Ca1—O10^i	76.65 (12)	K^ii—Si1—O10	113.72 (14)
Ca1^ii—K—K^v	62.54 (4)	O1—Si1—O4^x	104.25 (19)
Ca1^ii—K—K^vi	97.43 (3)	O1—Si1—O7	104.00 (17)
Ca1^ii—K—K^ii	99.41 (4)	O1—Si1—O10	113.23 (19)
Ca1^ii—K—Si1	151.00 (4)	O4^x—Si1—O7	108.51 (18)
Ca1^ii—K—Si1^ii	48.31 (3)	O4^x—Si1—O10	114.30 (18)
Ca1^ii—K—Na^vii	45.52 (4)	O7—Si1—O10	111.78 (16)
Ca1^ii—K—Si2^viii	97.03 (4)	Ca1—Na—Ca1^xi	170.17 (8)
Ca1^ii—K—Si2^vii	92.66 (4)	Ca1—Na—Ca1^iv	123.55 (6)
Ca1^ii—K—Si3^ii	48.51 (3)	Ca1—Na—K^vii	112.72 (6)
Ca1^ii—K—Si4^ix	71.24 (4)	Ca1—Na—Na^iv	61.10 (7)
Ca1^ii—K—Si4^i	122.90 (4)	Ca1—Na—O2^xi	132.96 (13)
Ca1^ii—K—O1	138.23 (8)	Ca1^xi—Na—Ca1^iv	64.93 (6)
Ca1^ii—K—O3^ix	83.88 (8)	Ca1^xi—Na—K^vii	68.73 (5)
Ca1^ii—K—O5^ii	73.75 (8)	Ca1^xi—Na—Na^iv	127.09 (9)
Ca1^ii—K—O7^ii	50.02 (7)	Ca1^xi—Na—O2^xi	41.54 (10)
K^v—K—K^vi	97.64 (5)	Ca1^iv—Na—K^vii	96.64 (7)
K^v—K—K^ii	129.75 (5)	Ca1^iv—Na—Na^iv	62.45 (7)
K^v—K—Si1	139.72 (4)	Ca1^iv—Na—O2^xi	101.32 (13)
K^v—K—Si1^ii	91.17 (5)	K^vii—Na—Na^iv	122.17 (8)
K^v—K—Na^vii	99.49 (5)	K^vii—Na—O2^xi	41.93 (9)
K^v—K—Si2^viii	53.48 (4)	Na^iv—Na—O2^xi	158.61 (15)
K^v—K—Si2^vii	136.50 (5)	K^xiv—Si2—K^vii	80.12 (5)
K^v—K—Si3^ii	55.19 (4)	K^xiv—Si2—O3^iv	124.92 (10)
K^v—K—Si4^ix	133.19 (5)	K^xiv—Si2—O5^xii	47.55 (13)
K^v—K—Si4^i	95.15 (4)	K^xiv—Si2—O6	64.65 (10)
K^v—K—O1	121.29 (7)	K^xiv—Si2—O7	123.75 (14)
K^v—K—O3^ix	143.66 (8)	K^vii—Si2—O3^iv	46.15 (9)
K^v—K—O5^ii	52.32 (9)	K^vii—Si2—O5^xii	64.73 (15)
K^v—K—O7^ii	69.51 (7)	K^vii—Si2—O6	105.89 (14)
K^vi—K—K^ii	132.20 (4)	K^vii—Si2—O7	140.03 (15)
K^vi—K—Si1	96.70 (4)	O3^iv—Si2—O5^xii	104.11 (18)
K^vi—K—Si1^ii	134.19 (4)	O3^iv—Si2—O6	112.9 (2)
K^vi—K—Na^vii	66.17 (5)	O3^iv—Si2—O7	107.94 (18)
K^vi—K—Si2^viii	52.06 (4)	O5^xii—Si2—O6	112.16 (16)
K^vi—K—Si2^vii	47.82 (4)	O5^xii—Si2—O7	105.79 (17)
K^vi—K—Si3^ii	55.37 (4)	O6—Si2—O7	113.24 (18)
K^vi—K—Si4^ix	95.06 (5)	K^ii—Si3—O2	61.58 (13)
K^vi—K—Si4^i	139.02 (4)	K^ii—Si3—O4	129.50 (13)
K^vi—K—O1	121.05 (8)	K^ii—Si3—O5	47.47 (12)
K^vi—K—O3^ix	71.96 (9)	K^ii—Si3—O8	120.16 (15)
K^vi—K—O5^ii	45.50 (9)	O2—Si3—O4	112.94 (17)
K^vi—K—O7^ii	147.44 (8)	O2—Si3—O5	108.82 (17)
K^ii—K—Si1	53.03 (4)	O2—Si3—O8	113.5 (2)
K^ii—K—Si1^ii	52.01 (4)	O4—Si3—O5	107.17 (19)
K^ii—K—Na^vii	96.19 (5)	O4—Si3—O8	108.03 (19)
K^ii—K—Si2^viii	161.90 (4)	O5—Si3—O8	106.01 (16)
K^ii—K—Si2^vii	86.91 (5)	K^xv—Si4—K^i	76.02 (5)
K^ii—K—Si3^ii	144.74 (4)	K^xv—Si4—O1^i	56.00 (11)
K^ii—K—Si4^ix	50.29 (4)	K^xv—Si4—O3	47.12 (13)
K^ii—K—Si4^i	53.69 (4)	K^xv—Si4—O8^xiii	122.71 (11)
K^ii—K—O1	43.33 (6)	K^xv—Si4—O9	124.15 (11)
K^ii—K—O3^ix	65.87 (9)	K^i—Si4—O1^i	49.27 (12)
K^ii—K—O5^ii	171.22 (7)	K^i—Si4—O3	102.18 (13)
K^ii—K—O7^ii	64.36 (7)	K^i—Si4—O8^xiii	57.64 (13)
Si1—K—Si1^ii	105.04 (5)	K^i—Si4—O9	144.59 (15)
Si1—K—Na^vii	120.73 (5)	O1^i—Si4—O3	102.75 (16)
Si1—K—Si2^viii	111.61 (5)	O1^i—Si4—O8^xiii	104.22 (19)
Si1—K—Si2^vii	78.44 (4)	O1^i—Si4—O9	114.03 (19)
Si1—K—Si3^ii	152.07 (5)	O3—Si4—O8^xiii	109.27 (18)
Si1—K—Si4^ix	82.39 (5)	O3—Si4—O9	112.7 (2)
Si1—K—Si4^i	51.69 (4)	O8^xiii—Si4—O9	113.08 (14)
Si1—K—O1	25.60 (8)	K—O1—Si1	108.45 (18)
Si1—K—O3^ix	76.63 (8)	K—O1—Si4^i	103.71 (14)
Si1—K—O5^ii	132.51 (9)	Si1—O1—Si4^i	141.8 (2)
Si1—K—O7^ii	112.52 (8)	Ca1—O2—Na^iii	94.79 (11)
Si1^ii—K—Na^vii	68.05 (5)	Ca1—O2—Si3	122.60 (19)
Si1^ii—K—Si2^viii	141.79 (5)	Na^iii—O2—Si3	127.6 (2)
Si1^ii—K—Si2^vii	97.61 (5)	K^xv—O3—Si2^iv	109.21 (12)
Si1^ii—K—Si3^ii	96.63 (5)	K^xv—O3—Si4	108.00 (19)
Si1^ii—K—Si4^ix	50.08 (4)	Si2^iv—O3—Si4	140.87 (19)
Si1^ii—K—Si4^i	84.01 (5)	Si1^xvi—O4—Si3	149.87 (18)
Si1^ii—K—O1	90.59 (8)	K^ii—O5—Si2^xii	105.73 (17)
Si1^ii—K—O3^ix	74.58 (9)	K^ii—O5—Si3	105.59 (14)
Si1^ii—K—O5^ii	121.88 (9)	Si2^xii—O5—Si3	146.5 (2)
Si1^ii—K—O7^ii	25.71 (6)	Ca1—O6—Si2	120.13 (16)
Na^vii—K—Si2^viii	100.73 (6)	K^ii—O7—Si1	103.86 (18)
Na^vii—K—Si2^vii	47.18 (4)	K^ii—O7—Si2	113.12 (15)
Na^vii—K—Si3^ii	52.27 (5)	Si1—O7—Si2	131.9 (2)
Na^vii—K—Si4^ix	46.82 (4)	Si3—O8—Si4^xiii	145.0 (3)
Na^vii—K—Si4^i	148.52 (5)	Ca1—O9—Si4	124.8 (2)
Na^vii—K—O1	134.67 (6)	Ca1—O10—Ca1^i	103.35 (15)
Na^vii—K—O3^ix	44.23 (8)	Ca1—O10—Si1	116.90 (14)
Na^vii—K—O5^ii	75.11 (8)	Ca1^i—O10—Si1	119.90 (17)
Na^vii—K—O7^ii	86.00 (8)

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