catena-Poly[piperazinium(2+) [ferrate(III)-μ-hydroxo-κ²O:O-di-μ-sulfato-κ⁴O:O′] monohydrate]

In the crystal structure of the title compound, {(C₄H₁₂N₂)[Fe(OH)(SO₄)₂]·H₂O}_n, the anion exists as a linear chain that propagates in a zigzag manner along the c axis of the monoclinic unit cell. The organic cations, the polyanions and non-coordinated water mol­ecules inter­act through O—H...O and N—H...O hydrogen bonds, forming a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.039
• wR factor = 0.098
• Data-to-parameter ratio = 13.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          6
PLAT731_ALERT_1_C Bond    Calc     0.85(3), Rep   0.850(10) ......       3.00 su-Rat
              O1W  -H1W2    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.85(3), Rep   0.850(10) ......       3.00 su-Rat
              N1   -H1N2    1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(3), Rep   0.850(10) ......       3.00 su-Rat
              O1W  -H2#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(3), Rep   0.850(10) ......       3.00 su-Rat
              N1   -H4#     1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     1.86(3), Rep   1.860(10) ......       3.00 su-Rat
              H3#  -O2      1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     1.93(3), Rep   1.930(10) ......       3.00 su-Rat
              H4#  -O8      1.555   4.676
PLAT736_ALERT_1_C H...A   Calc     2.02(3), Rep   2.020(10) ......       3.00 su-Rat
              H6#  -O3      1.555   4.575

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

   9 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
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

catena-Poly[piperazinium(2+) [ferrate(III)-µ-hydroxo-κ²O:O- di-µ-sulfato-κ⁴O:O'] monohydrate]

Crystal data

(C4H12N2)[Fe(OH)(SO4)2]·H2O	F(000) = 764
Mr = 371.15	Dx = 2.052 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3698 reflections
a = 9.2570 (6) Å	θ = 2.2–28.0°
b = 18.318 (1) Å	µ = 1.66 mm^−1
c = 7.1562 (4) Å	T = 295 K
β = 98.094 (1)°	Rod, yellow
V = 1201.4 (1) Å^3	0.26 × 0.07 × 0.06 mm
Z = 4

Data collection

Bruker APEX area-detector diffractometer	2743 independent reflections
Radiation source: fine-focus sealed tube	2452 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
φ and ω scans	θmax = 27.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
Tmin = 0.776, Tmax = 0.907	k = −23→23
13166 measured reflections	l = −9→9

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)] = 0.039	Hydrogen site location: difmap (O-H) and geom (others)
wR(F^2) = 0.098	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0533P)^2 + 1.0669P] where P = (Fo^2 + 2Fc^2)/3
2743 reflections	(Δ/σ)max = 0.001
200 parameters	Δρmax = 0.59 e Å^−3
10 restraints	Δρmin = −0.38 e Å^−3

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

	x	y	z	Uiso*/Ueq
Fe1	0.69457 (4)	0.74694 (2)	0.59073 (5)	0.0127 (1)
S1	0.93587 (7)	0.66313 (3)	0.88744 (9)	0.0136 (2)
S2	0.51170 (7)	0.63322 (4)	0.81211 (9)	0.0140 (2)
O1	0.8424 (2)	0.6726 (1)	0.7021 (3)	0.0208 (4)
O2	1.0630 (3)	0.7088 (1)	0.8969 (4)	0.0357 (6)
O3	0.9774 (2)	0.5867 (1)	0.9109 (3)	0.0242 (5)
O4	0.8490 (2)	0.6824 (1)	1.0406 (3)	0.0271 (5)
O5	0.5370 (2)	0.6764 (1)	0.6427 (3)	0.0191 (4)
O6	0.5342 (2)	0.6821 (1)	0.9796 (3)	0.0208 (4)
O7	0.6098 (3)	0.5717 (1)	0.8414 (3)	0.0300 (5)
O8	0.3597 (2)	0.6089 (1)	0.7830 (3)	0.0261 (5)
O9	0.6936 (2)	0.7053 (1)	0.3383 (3)	0.0159 (4)
O1w	0.7209 (4)	0.5483 (2)	0.2447 (4)	0.0465 (7)
N1	1.1949 (4)	0.8377 (2)	0.9563 (4)	0.0353 (7)
N2	1.2013 (3)	0.9573 (1)	0.7027 (4)	0.0229 (5)
C1	1.0666 (4)	0.8863 (2)	0.9123 (5)	0.0316 (8)
C2	1.1112 (3)	0.9612 (2)	0.8584 (4)	0.0262 (7)
C3	1.3313 (4)	0.9105 (2)	0.7529 (5)	0.0307 (7)
C4	1.2846 (4)	0.8349 (2)	0.8010 (5)	0.0382 (9)
H9o	0.694 (4)	0.6596 (6)	0.332 (5)	0.03 (1)*
H1w1	0.710 (6)	0.564 (2)	0.133 (3)	0.09 (2)*
H1w2	0.673 (4)	0.509 (1)	0.249 (6)	0.06 (1)*
H1n1	1.161 (4)	0.795 (1)	0.968 (5)	0.06 (1)*
H1n2	1.242 (4)	0.852 (2)	1.061 (3)	0.04 (1)*
H2n1	1.237 (3)	0.998 (1)	0.680 (4)	0.03 (1)*
H2n2	1.150 (3)	0.941 (2)	0.604 (3)	0.02 (1)*
H1a	1.0158	0.8897	1.0217	0.038*
H1b	0.9999	0.8655	0.8093	0.038*
H2a	1.0249	0.9903	0.8188	0.031*
H2b	1.1666	0.9847	0.9671	0.031*
H3a	1.3936	0.9312	0.8602	0.037*
H3b	1.3867	0.9081	0.6476	0.037*
H4a	1.2286	0.8129	0.6906	0.046*
H4b	1.3701	0.8049	0.8384	0.046*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.0143 (2)	0.0163 (2)	0.0076 (2)	−0.0006 (1)	0.0012 (1)	0.0007 (1)
S1	0.0128 (3)	0.0145 (3)	0.0129 (3)	0.0018 (2)	0.0004 (2)	−0.0011 (2)
S2	0.0143 (3)	0.0152 (3)	0.0122 (3)	−0.0021 (2)	0.0007 (2)	0.0008 (2)
O1	0.022 (1)	0.027 (1)	0.013 (1)	0.008 (1)	−0.001 (1)	−0.001 (1)
O2	0.025 (1)	0.031 (1)	0.049 (2)	−0.012 (1)	−0.003 (1)	0.004 (1)
O3	0.029 (1)	0.016 (1)	0.026 (1)	0.006 (1)	−0.003 (1)	−0.001 (1)
O4	0.031 (1)	0.037 (1)	0.014 (1)	0.018 (1)	0.004 (1)	0.002 (1)
O5	0.019 (1)	0.024 (1)	0.014 (1)	−0.006 (1)	0.002 (1)	0.002 (1)
O6	0.024 (1)	0.025 (1)	0.014 (1)	−0.008 (1)	0.003 (1)	−0.002 (1)
O7	0.034 (1)	0.022 (1)	0.035 (1)	0.009 (1)	0.006 (1)	0.003 (1)
O8	0.019 (1)	0.036 (1)	0.023 (1)	−0.011 (1)	0.000 (1)	0.005 (1)
O9	0.023 (1)	0.015 (1)	0.010 (1)	0.002 (1)	0.003 (1)	0.000 (1)
O1w	0.071 (2)	0.034 (2)	0.031 (2)	−0.007 (1)	−0.005 (1)	0.008 (1)
N1	0.048 (2)	0.022 (1)	0.030 (2)	−0.013 (1)	−0.019 (1)	0.009 (1)
N2	0.028 (1)	0.023 (1)	0.018 (1)	−0.006 (1)	0.003 (1)	0.003 (1)
C1	0.025 (2)	0.047 (2)	0.022 (2)	−0.013 (2)	0.001 (1)	0.006 (1)
C2	0.027 (2)	0.029 (2)	0.023 (2)	0.003 (1)	0.007 (1)	0.001 (1)
C3	0.024 (2)	0.042 (2)	0.027 (2)	0.004 (1)	0.006 (1)	−0.006 (1)
C4	0.045 (2)	0.030 (2)	0.034 (2)	0.012 (2)	−0.013 (2)	−0.011 (2)

Geometric parameters (Å, º)

Fe1—O1	2.014 (2)	C1—C2	1.499 (4)
Fe1—O4^i	1.999 (2)	C3—C4	1.504 (5)
Fe1—O5	2.023 (2)	O9—H9o	0.84 (1)
Fe1—O6^i	2.048 (2)	O1w—H1w1	0.85 (1)
Fe1—O9	1.960 (2)	O1w—H1w2	0.85 (1)
Fe1—O9^ii	1.977 (2)	N1—H1n1	0.85 (1)
S1—O2	1.437 (2)	N1—H1n2	0.85 (1)
S1—O3	1.455 (2)	N2—H2n1	0.85 (1)
S1—O1	1.488 (2)	N2—H2n2	0.85 (1)
S1—O4	1.490 (2)	C1—H1a	0.97
S2—O7	1.444 (2)	C1—H1b	0.97
S2—O8	1.463 (2)	C2—H2a	0.97
S2—O6	1.487 (2)	C2—H2b	0.97
S2—O5	1.493 (2)	C3—H3a	0.97
N1—C4	1.479 (5)	C3—H3b	0.97
N1—C1	1.482 (5)	C4—H4a	0.97
N2—C3	1.481 (4)	C4—H4b	0.97
N2—C2	1.484 (4)
O1—Fe1—O4^i	92.6 (1)	N1—C4—C3	110.5 (3)
O1—Fe1—O5	87.8 (1)	Fe1—O9—H9o	116 (2)
O1—Fe1—O6^i	176.4 (1)	Fe1^i—O9—H9o	113 (2)
O1—Fe1—O9	90.9 (1)	H1w1—O1w—H1w2	110 (2)
O1—Fe1—O9^ii	91.9 (1)	C4—N1—C1	112.3 (3)
O4^i—Fe1—O6^i	91.0 (1)	C4—N1—H1n1	107 (3)
O4^i—Fe1—O5	179.3 (1)	C1—N1—H1n1	106 (3)
O4^i—Fe1—O9	89.9 (1)	C4—N1—H1n2	114 (3)
O4^i—Fe1—O9^ii	88.2 (1)	C1—N1—H1n2	107 (3)
O5—Fe1—O6^i	88.6 (1)	H1n1—N1—H1n2	110 (2)
O5—Fe1—O9	90.6 (1)	C3—N2—H2n1	104 (2)
O5—Fe1—O9^ii	91.4 (1)	C2—N2—H2n1	112 (2)
O6^i—Fe1—O9	88.9 (1)	C3—N2—H2n2	110 (2)
O6^i—Fe1—O9^ii	88.4 (1)	C2—N2—H2n2	109 (2)
O9—Fe1—O9^ii	176.6 (1)	H2n1—N2—H2n2	110 (2)
O2—S1—O3	110.7 (1)	N1—C1—H1a	109.4
O2—S1—O1	110.1 (1)	C2—C1—H1a	109.4
O3—S1—O1	109.0 (1)	N1—C1—H1b	109.4
O2—S1—O4	110.6 (2)	C2—C1—H1b	109.4
O3—S1—O4	107.7 (1)	H1a—C1—H1b	108.0
O1—S1—O4	108.8 (1)	N2—C2—H2a	109.5
O7—S2—O8	110.8 (1)	C1—C2—H2a	109.5
O7—S2—O6	109.8 (1)	N2—C2—H2b	109.5
O8—S2—O6	108.7 (1)	C1—C2—H2b	109.5
O7—S2—O5	111.3 (1)	H2a—C2—H2b	108.1
O8—S2—O5	107.7 (1)	N2—C3—H3a	109.7
O6—S2—O5	108.4 (1)	C4—C3—H3a	109.7
S1—O1—Fe1	135.1 (1)	N2—C3—H3b	109.7
S1—O4—Fe1^ii	139.4 (1)	C4—C3—H3b	109.7
S2—O5—Fe1	133.4 (1)	H3a—C3—H3b	108.2
S2—O6—Fe1^ii	135.0 (1)	N1—C4—H4a	109.6
Fe1—O9—Fe1^i	130.8 (1)	C3—C4—H4a	109.6
C3—N2—C2	111.7 (2)	N1—C4—H4b	109.6
N1—C1—C2	111.3 (3)	C3—C4—H4b	109.6
N2—C2—C1	110.7 (3)	H4a—C4—H4b	108.1
N2—C3—C4	109.8 (3)
O2—S1—O1—Fe1	−80.3 (2)	O1—Fe1—O5—S2	48.8 (2)
O3—S1—O1—Fe1	158.2 (2)	O6^i—Fe1—O5—S2	−131.5 (2)
O4—S1—O1—Fe1	41.0 (2)	O7—S2—O6—Fe1^ii	71.9 (2)
O9—Fe1—O1—S1	168.6 (2)	O8—S2—O6—Fe1^ii	−166.8 (2)
O9^ii—Fe1—O1—S1	−9.5 (2)	O5—S2—O6—Fe1^ii	−50.0 (2)
O4^i—Fe1—O1—S1	78.7 (2)	O4^i—Fe1—O9—Fe1^i	−44.5 (1)
O5—Fe1—O1—S1	−100.8 (2)	O1—Fe1—O9—Fe1^i	−137.2 (1)
O2—S1—O4—Fe1^ii	85.3 (3)	O5—Fe1—O9—Fe1^i	135.0 (1)
O3—S1—O4—Fe1^ii	−153.7 (2)	O6^i—Fe1—O9—Fe1^i	46.4 (1)
O1—S1—O4—Fe1^ii	−35.7 (3)	C4—N1—C1—C2	−54.3 (4)
O7—S2—O5—Fe1	−74.6 (2)	C3—N2—C2—C1	−56.5 (3)
O8—S2—O5—Fe1	163.8 (2)	N1—C1—C2—N2	53.7 (4)
O6—S2—O5—Fe1	46.3 (2)	C2—N2—C3—C4	58.1 (3)
O9—Fe1—O5—S2	139.7 (2)	C1—N1—C4—C3	55.9 (4)
O9^ii—Fe1—O5—S2	−43.1 (2)	N2—C3—C4—N1	−57.1 (4)

Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) x, −y+3/2, z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9o···O1w	0.84 (1)	2.16 (1)	2.971 (3)	164 (3)
O1w—H1w1···O7^iii	0.85 (1)	2.16 (2)	2.955 (4)	155 (4)
O1w—H1w2···O8^iv	0.85 (1)	2.19 (2)	2.974 (4)	153 (4)
N1—H1n1···O2	0.85 (1)	1.86 (1)	2.666 (4)	158 (3)
N1—H1n2···O8^v	0.85 (1)	1.93 (1)	2.783 (4)	173 (3)
N2—H2n1···O7^vi	0.85 (1)	1.97 (2)	2.775 (3)	157 (3)
N2—H2n2···O3^i	0.85 (1)	2.02 (1)	2.844 (3)	162 (3)

Symmetry codes: (i) x, −y+3/2, z−1/2; (iii) x, y, z−1; (iv) −x+1, −y+1, −z+1; (v) x+1, −y+3/2, z+1/2; (vi) −x+2, y+1/2, −z+3/2.