1,3-Propane­diammonium triaqua­(sulfato-κO)bis(sulfato-κ²O,O′)zirconate(IV)

The eight-coordinate Zr^IV atom in the title compound, (C₃H₁₂N₂)[Zr(SO₄)₃(H₂O)₃], has an approximate square-anti­prismatic coordination geometry. In the dianion, one of the sulfate groups is unidentate whereas the other two chelate the metal atom. In the crystal strucure, cations and anions are linked into a three-dimensional network architecture by hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](N-C) = 0.007 Å
• Disorder in solvent or counterion
• R factor = 0.038
• wR factor = 0.122
• Data-to-parameter ratio = 13.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         S3
PLAT243_ALERT_4_C High  'Solvent' Ueq as Compared to Neighbors for         C3
PLAT243_ALERT_4_C High  'Solvent' Ueq as Compared to Neighbors for        C3'
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         N2
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      29.00 Perc.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........         16

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C3 H18 N2 O15 S3 Zr1
            Atom count from _chemical_formula_moiety:

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

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

Computing details

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2006).

(I)

Crystal data

(C3H12N2)[Zr(SO4)3(H2O)3]	F(000) = 1032
Mr = 509.59	Dx = 2.160 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3634 reflections
a = 7.9124 (5) Å	θ = 2.4–28.4°
b = 20.464 (1) Å	µ = 1.18 mm^−1
c = 10.4195 (7) Å	T = 295 K
β = 111.727 (1)°	Block, colorless
V = 1567.26 (16) Å^3	0.16 × 0.14 × 0.09 mm
Z = 4

Data collection

Bruker APEX area-detector diffractometer	3532 independent reflections
Radiation source: fine-focus sealed tube	3079 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
φ and ω scans	θmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan SADABS (Sheldrick, 1996)	h = −9→10
Tmin = 0.833, Tmax = 0.901	k = −26→10
8512 measured reflections	l = −13→13

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	w = 1/[σ^2(Fo^2) + (0.0601P)^2 + 2.5754P] where P = (Fo^2 + 2Fc^2)/3
3532 reflections	(Δ/σ)max = 0.001
260 parameters	Δρmax = 0.77 e Å^−3
30 restraints	Δρmin = −0.63 e Å^−3

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zr1	0.38179 (5)	0.452032 (18)	0.22355 (4)	0.01721 (14)
S1	0.42897 (14)	0.33109 (5)	0.36724 (11)	0.0247 (2)
S2	0.77173 (13)	0.46493 (5)	0.30988 (10)	0.0213 (2)
S3	0.33649 (14)	0.61484 (5)	0.12587 (10)	0.0226 (2)
O1	0.3456 (4)	0.34326 (15)	0.2140 (3)	0.0293 (7)
O2	0.4558 (4)	0.40149 (15)	0.4166 (3)	0.0273 (7)
O3	0.6001 (5)	0.29773 (17)	0.4014 (4)	0.0402 (8)
O4	0.3069 (5)	0.29846 (17)	0.4202 (4)	0.0410 (8)
O5	0.6347 (4)	0.42140 (15)	0.2057 (3)	0.0255 (6)
O6	0.6468 (4)	0.50364 (14)	0.3611 (3)	0.0236 (6)
O7	0.9042 (5)	0.42775 (17)	0.4172 (4)	0.0392 (8)
O8	0.8547 (4)	0.50903 (16)	0.2397 (3)	0.0277 (7)
O9	0.3458 (5)	0.54112 (14)	0.1172 (3)	0.0289 (7)
O10	0.4852 (5)	0.64178 (17)	0.0921 (4)	0.0443 (9)
O11	0.1628 (5)	0.63582 (17)	0.0278 (4)	0.0442 (9)
O12	0.3620 (5)	0.63221 (17)	0.2671 (3)	0.0398 (8)
O1W	0.3017 (4)	0.42292 (16)	0.0050 (3)	0.0280 (7)
H1w1	0.268 (6)	0.4560 (15)	−0.047 (4)	0.034*
H1w2	0.386 (5)	0.4030 (19)	−0.011 (5)	0.034*
O2W	0.2970 (4)	0.51707 (15)	0.3571 (3)	0.0245 (6)
H2w1	0.314 (6)	0.5098 (18)	0.4408 (17)	0.029*
H2w2	0.305 (7)	0.5575 (7)	0.343 (4)	0.029*
O3W	0.0879 (4)	0.44305 (17)	0.1527 (3)	0.0310 (7)
H3w1	0.024 (5)	0.466 (2)	0.186 (4)	0.037*
H3w2	0.017 (5)	0.422 (2)	0.083 (3)	0.037*
N1	0.7089 (5)	0.2301 (2)	0.6655 (4)	0.0364 (9)
H1n1	0.661 (6)	0.2072 (18)	0.713 (4)	0.044*
H1n2	0.691 (7)	0.2088 (18)	0.590 (3)	0.044*
H1n3	0.646 (6)	0.2657 (13)	0.643 (4)	0.044*
N2	1.1902 (6)	0.3570 (2)	0.6203 (4)	0.0390 (10)
H2n1	1.235 (6)	0.338 (2)	0.567 (4)	0.047*
H2n2	1.272 (5)	0.377 (2)	0.683 (4)	0.047*
H2n3	1.107 (5)	0.3834 (19)	0.572 (4)	0.047*
C1	0.9053 (6)	0.2396 (3)	0.7371 (6)	0.0496 (14)
H1a	0.9664	0.1977	0.7603	0.059*
H1b	0.9294	0.2640	0.8219	0.059*
C2	0.9747 (11)	0.2779 (4)	0.6385 (7)	0.049 (2)	0.66 (1)
H2a	1.0183	0.2472	0.5867	0.059*	0.66 (1)
H2b	0.8747	0.3023	0.5731	0.059*	0.66 (1)
C3	1.1217 (14)	0.3231 (4)	0.7135 (9)	0.062 (3)	0.66 (1)
H3a	1.0770	0.3548	0.7625	0.074*	0.66 (1)
H3b	1.2201	0.2990	0.7811	0.074*	0.66 (1)
C2'	0.999 (2)	0.3011 (6)	0.7327 (15)	0.049 (2)	0.34 (1)
H2'c	1.0925	0.3093	0.8225	0.059*	0.34 (1)
H2'd	0.9123	0.3368	0.7118	0.059*	0.34 (1)
C3'	1.083 (3)	0.2983 (7)	0.6255 (19)	0.062 (3)	0.34 (1)
H3'c	1.1619	0.2603	0.6434	0.074*	0.34 (1)
H3'd	0.9872	0.2923	0.5357	0.074*	0.34 (1)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zr1	0.0185 (2)	0.0181 (2)	0.0156 (2)	0.00142 (14)	0.00705 (15)	−0.00090 (14)
S1	0.0306 (5)	0.0215 (5)	0.0227 (5)	−0.0024 (4)	0.0106 (4)	0.0016 (4)
S2	0.0184 (5)	0.0249 (5)	0.0207 (5)	0.0030 (4)	0.0076 (4)	0.0018 (4)
S3	0.0267 (5)	0.0206 (5)	0.0194 (5)	0.0033 (4)	0.0072 (4)	0.0005 (4)
O1	0.0378 (17)	0.0236 (16)	0.0217 (15)	−0.0016 (13)	0.0054 (13)	−0.0001 (12)
O2	0.0360 (16)	0.0248 (15)	0.0184 (14)	−0.0041 (13)	0.0071 (12)	−0.0011 (12)
O3	0.0435 (19)	0.0370 (19)	0.042 (2)	0.0160 (16)	0.0179 (16)	0.0113 (16)
O4	0.051 (2)	0.040 (2)	0.040 (2)	−0.0134 (17)	0.0250 (17)	−0.0009 (16)
O5	0.0215 (14)	0.0325 (17)	0.0202 (15)	0.0022 (12)	0.0051 (11)	−0.0080 (12)
O6	0.0240 (14)	0.0250 (15)	0.0256 (15)	0.0002 (12)	0.0134 (12)	−0.0034 (12)
O7	0.0313 (17)	0.0399 (19)	0.042 (2)	0.0093 (16)	0.0078 (15)	0.0130 (17)
O8	0.0221 (14)	0.0359 (18)	0.0253 (15)	0.0014 (13)	0.0091 (12)	0.0042 (13)
O9	0.0436 (19)	0.0192 (15)	0.0281 (16)	0.0033 (13)	0.0182 (14)	0.0018 (12)
O10	0.053 (2)	0.0282 (18)	0.065 (2)	−0.0063 (17)	0.038 (2)	−0.0060 (17)
O11	0.0398 (19)	0.0334 (19)	0.041 (2)	0.0133 (16)	−0.0060 (16)	−0.0032 (16)
O12	0.069 (2)	0.0280 (17)	0.0233 (16)	0.0068 (17)	0.0184 (16)	−0.0007 (14)
O1w	0.0332 (16)	0.0279 (17)	0.0249 (16)	0.0081 (13)	0.0130 (13)	0.0017 (13)
O2w	0.0299 (15)	0.0252 (15)	0.0204 (14)	−0.0006 (13)	0.0115 (12)	−0.0013 (12)
O3w	0.0183 (14)	0.045 (2)	0.0253 (16)	0.0006 (13)	0.0037 (12)	−0.0139 (14)
N1	0.041 (2)	0.037 (2)	0.034 (2)	−0.0071 (19)	0.0166 (19)	0.0014 (18)
N2	0.032 (2)	0.044 (3)	0.035 (2)	0.0045 (19)	0.0052 (18)	−0.003 (2)
C1	0.034 (3)	0.060 (4)	0.050 (3)	−0.002 (3)	0.011 (3)	0.002 (3)
C2	0.048 (4)	0.066 (6)	0.031 (4)	−0.022 (4)	0.012 (3)	−0.004 (4)
C3	0.104 (8)	0.041 (5)	0.052 (5)	−0.016 (5)	0.043 (6)	0.000 (4)
C2'	0.048 (4)	0.066 (6)	0.031 (4)	−0.022 (4)	0.012 (3)	−0.004 (4)
C3'	0.104 (8)	0.041 (5)	0.052 (5)	−0.016 (5)	0.043 (6)	0.000 (4)

Geometric parameters (Å, º)

Zr1—O1	2.242 (3)	O3w—H3w2	0.86 (3)
Zr1—O2	2.142 (3)	N1—C1	1.467 (5)
Zr1—O5	2.170 (3)	N1—H1n1	0.86 (2)
Zr1—O6	2.311 (3)	N1—H1n2	0.86 (2)
Zr1—O9	2.097 (3)	N1—H1n3	0.87 (2)
Zr1—O1w	2.207 (3)	N2—C3	1.452 (7)
Zr1—O2w	2.202 (3)	N2—C3'	1.484 (8)
Zr1—O3w	2.171 (3)	N2—H2n1	0.86 (2)
S1—O3	1.438 (3)	N2—H2n2	0.84 (2)
S1—O4	1.442 (3)	N2—H2n3	0.86 (2)
S1—O1	1.505 (3)	C1—C2'	1.468 (9)
S1—O2	1.518 (3)	C1—C2	1.546 (7)
S2—O7	1.435 (3)	C1—H1A	0.9700
S2—O8	1.462 (3)	C1—H1B	0.9700
S2—O5	1.509 (3)	C2—C3	1.465 (8)
S2—O6	1.510 (3)	C2—H2A	0.9700
S3—O11	1.441 (3)	C2—H2B	0.9700
S3—O12	1.454 (3)	C3—H3A	0.9700
S3—O10	1.455 (4)	C3—H3B	0.9700
S3—O9	1.515 (3)	C2'—C3'	1.499 (9)
O1w—H1w1	0.85 (3)	C2'—H2'C	0.9700
O1w—H1w2	0.85 (3)	C2'—H2'D	0.9700
O2w—H2w1	0.85 (3)	C3'—H3'C	0.9700
O2w—H2w2	0.85 (3)	C3'—H3'D	0.9700
O3w—H3w1	0.85 (3)
O1—Zr1—O2	63.1 (1)	Zr1—O1w—H1w2	113 (3)
O1—Zr1—O5	79.4 (1)	H1w1—O1w—H1w2	110 (4)
O1—Zr1—O6	123.6 (1)	Zr1—O2w—H2w1	125 (3)
O1—Zr1—O9	148.2 (1)	Zr1—O2w—H2w2	115 (3)
O1—Zr1—O1w	72.7 (1)	H2w1—O2w—H2w2	111 (4)
O1—Zr1—O2w	124.4 (1)	Zr1—O3w—H3w1	122 (3)
O1—Zr1—O3w	78.3 (1)	Zr1—O3w—H3w2	128 (3)
O2—Zr1—O5	90.1 (1)	H3w1—O3w—H3w2	109 (4)
O2—Zr1—O6	76.6 (1)	C1—N1—H1n1	113 (3)
O2—Zr1—O9	148.5 (1)	C1—N1—H1n2	109 (3)
O2—Zr1—O1w	135.5 (1)	H1n1—N1—H1n2	107 (2)
O2—Zr1—O2w	74.9 (1)	C1—N1—H1n3	115 (3)
O2—Zr1—O3w	99.5 (1)	H1n1—N1—H1n3	107 (2)
O5—Zr1—O6	62.1 (1)	H1n2—N1—H1n3	107 (2)
O5—Zr1—O9	98.9 (1)	C3—N2—H2n1	124 (4)
O5—Zr1—O1w	75.8 (1)	C3'—N2—H2n2	131 (4)
O5—Zr1—O2w	137.3 (1)	H2n1—N2—H2n2	110 (2)
O5—Zr1—O3w	148.4 (1)	C3—N2—H2n3	107 (4)
O6—Zr1—O9	81.1 (1)	C3'—N2—H2n3	102 (4)
O6—Zr1—O1w	127.7 (1)	H2n1—N2—H2n3	109 (2)
O6—Zr1—O2w	75.6 (1)	H2n2—N2—H2n3	110 (2)
O6—Zr1—O3w	149.4 (1)	N1—C1—C2	107.4 (5)
O9—Zr1—O1w	76.0 (1)	C2'—C1—H1A	123.7
O9—Zr1—O2w	78.2 (1)	N1—C1—H1A	110.2
O9—Zr1—O3w	88.6 (1)	C2—C1—H1A	110.2
O1w—Zr1—O2w	141.0 (1)	N1—C1—H1B	110.2
O1w—Zr1—O3w	76.3 (1)	C2—C1—H1B	110.2
O2w—Zr1—O3w	74.2 (1)	H1A—C1—H1B	108.5
O3—S1—O4	112.8 (2)	C3—C2—C1	111.9 (5)
O3—S1—O1	110.1 (2)	C3—C2—H2A	109.2
O4—S1—O1	113.0 (2)	C1—C2—H2A	109.2
O3—S1—O2	111.5 (2)	C3—C2—H2B	109.2
O4—S1—O2	109.8 (2)	C1—C2—H2B	109.2
O1—S1—O2	98.85 (17)	H2A—C2—H2B	107.9
O7—S2—O8	112.56 (19)	N2—C3—C2	111.4 (6)
O7—S2—O5	111.8 (2)	N2—C3—H3A	109.3
O8—S2—O5	109.93 (18)	C2—C3—H3A	109.3
O7—S2—O6	112.77 (19)	N2—C3—H3B	109.3
O8—S2—O6	109.10 (18)	C2—C3—H3B	109.3
O5—S2—O6	100.01 (16)	H3A—C3—H3B	108.0
O11—S3—O12	112.6 (2)	C1—C2'—C3'	111.0 (8)
O11—S3—O10	111.1 (2)	C1—C2'—H2'C	109.4
O12—S3—O10	109.3 (2)	C3'—C2'—H2'C	109.4
O11—S3—O9	108.0 (2)	C1—C2'—H2'D	109.4
O12—S3—O9	108.20 (18)	C3'—C2'—H2'D	109.4
O10—S3—O9	107.5 (2)	H2'C—C2'—H2'D	108.0
S1—O1—Zr1	96.82 (15)	N2—C3'—C2'	114.5 (9)
S1—O2—Zr1	100.64 (15)	N2—C3'—H3'C	108.6
S2—O5—Zr1	101.99 (15)	C2'—C3'—H3'C	108.6
S2—O6—Zr1	95.93 (14)	N2—C3'—H3'D	108.6
S3—O9—Zr1	146.54 (19)	C2'—C3'—H3'D	108.6
Zr1—O1w—H1w1	111 (3)	H3'C—C3'—H3'D	107.6
O3—S1—O1—Zr1	−110.50 (19)	O1—Zr1—O5—S2	−136.92 (17)
O4—S1—O1—Zr1	122.35 (19)	O6—Zr1—O5—S2	0.46 (13)
O2—S1—O1—Zr1	6.34 (18)	O7—S2—O6—Zr1	−118.25 (18)
O9—Zr1—O1—S1	−179.63 (18)	O8—S2—O6—Zr1	115.89 (15)
O2—Zr1—O1—S1	−4.97 (14)	O5—S2—O6—Zr1	0.59 (16)
O3w—Zr1—O1—S1	−111.99 (18)	O9—Zr1—O6—S2	−105.57 (15)
O5—Zr1—O1—S1	90.54 (16)	O2—Zr1—O6—S2	96.86 (15)
O2w—Zr1—O1—S1	−50.5 (2)	O3w—Zr1—O6—S2	−177.20 (19)
O1w—Zr1—O1—S1	168.86 (19)	O5—Zr1—O6—S2	−0.46 (13)
O6—Zr1—O1—S1	44.7 (2)	O2w—Zr1—O6—S2	174.44 (16)
O3—S1—O2—Zr1	109.09 (19)	O1w—Zr1—O6—S2	−41.0 (2)
O4—S1—O2—Zr1	−125.11 (19)	O1—Zr1—O6—S2	52.54 (18)
O1—S1—O2—Zr1	−6.70 (19)	S1—Zr1—O6—S2	74.51 (13)
O9—Zr1—O2—S1	179.59 (18)	O11—S3—O9—Zr1	−122.6 (4)
O3w—Zr1—O2—S1	76.67 (17)	O12—S3—O9—Zr1	−0.5 (5)
O5—Zr1—O2—S1	−73.09 (16)	O10—S3—O9—Zr1	117.4 (4)
O2w—Zr1—O2—S1	147.34 (18)	O2—Zr1—O9—S3	−10.1 (6)
O1w—Zr1—O2—S1	−3.4 (3)	O3w—Zr1—O9—S3	95.8 (4)
O1—Zr1—O2—S1	4.98 (14)	O5—Zr1—O9—S3	−115.0 (4)
O6—Zr1—O2—S1	−134.28 (17)	O2w—Zr1—O9—S3	21.6 (4)
O7—S2—O5—Zr1	118.94 (19)	O1w—Zr1—O9—S3	172.1 (4)
O8—S2—O5—Zr1	−115.31 (17)	O1—Zr1—O9—S3	160.7 (3)
O6—S2—O5—Zr1	−0.64 (18)	O6—Zr1—O9—S3	−55.4 (4)
O9—Zr1—O5—S2	75.35 (17)	N1—C1—C2—C3	145.1 (8)
O2—Zr1—O5—S2	−74.31 (16)	C1—C2—C3—N2	177.9 (7)
O3w—Zr1—O5—S2	177.31 (19)	N1—C1—C2'—C3'	−97.3 (15)
O2w—Zr1—O5—S2	−6.8 (3)	C1—C2'—C3'—N2	−176.3 (13)
O1w—Zr1—O5—S2	148.40 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H1w1···O8^i	0.85 (3)	2.01 (3)	2.763 (4)	148 (5)
O1w—H1w2···O10^i	0.85 (3)	1.80 (2)	2.624 (5)	164 (5)
O2w—H2w1···O6^ii	0.85 (2)	1.99 (1)	2.834 (4)	178 (4)
O2w—H2w2···O12	0.85 (3)	1.85 (2)	2.656 (5)	158 (4)
O3w—H3w1···O8^iii	0.85 (3)	1.85 (4)	2.700 (4)	171 (4)
O3w—H3w2···O11^iv	0.85 (3)	1.88 (2)	2.705 (5)	162 (5)
N1—H1n1···O3^v	0.86 (2)	2.19 (3)	2.945 (6)	146 (4)
N1—H1n2···O10^vi	0.86 (2)	2.34 (3)	3.126 (6)	152 (4)
N1—H1n3···O12^ii	0.87 (2)	2.30 (3)	3.007 (6)	139 (4)
N2—H2n1···O4^vii	0.86 (2)	1.99 (2)	2.839 (6)	172 (4)
N2—H2n2···O6^viii	0.84 (2)	2.60 (5)	3.106 (5)	120 (4)
N2—H2n3···O7	0.86 (2)	2.02 (2)	2.855 (5)	164 (4)

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