Square network based upon the mol­ecular salt of the tetra­protonated photo­product rtct-tetra­kis­(pyri­din-4-yl)cyclo­butane and the sulfate anion

The formation and crystal structure of a hydrated mol­ecular salt that results in a square network is reported. The crystalline solid is based upon the tetra­pro­ton­ated photo­product rtct-tetra­kis­(pyri­din-4-yl)cyclo­butane (4H-rtct-TPCB)⁴⁺ along with two sulfate anions (SO₄²⁻) and eight waters of hydration, namely, 4,4′,4′′,4′′′-(cyclo­butane-1,2,3,4-tetra­yl)tetra­pyri­dinium bis­(sulfate) octa­hydrate, C₂₄H₂₄N₄⁴⁺·2SO₄²⁻·8H₂O. The fully protonated photo­product acts as a four-connecting node within the square network by engaging in four charge-assisted N⁺—H...O hydrogen bonds to the sulfate anion. The observed hydrogen-bonding pattern in this square network is akin to T-silica, which is a metastable form of SiO₂. The included water mol­ecules and sulfate anions engage in numerous O—H...O hydrogen bonds to form various hydrogen-bonded ring structures.

Computing details

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

4,4',4'',4'''-(Cyclobutane-1,2,3,4-tetrayl)tetrapyridinium bis(sulfate) octahydrate

Crystal data

C24H24N4^4+·2SO4^2^−·8H2O	F(000) = 744
Mr = 704.72	Dx = 1.526 Mg m^−3
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
a = 9.7415 (6) Å	Cell parameters from 3517 reflections
b = 16.3378 (8) Å	θ = 2.3–24.9°
c = 9.6396 (5) Å	µ = 0.26 mm^−1
β = 91.680 (2)°	T = 100 K
V = 1533.53 (14) Å^3	Block, colourless
Z = 2	0.37 × 0.31 × 0.25 mm

Data collection

Bruker D8 Venture diffractometer	2665 reflections with I > 2σ(I)
Radiation source: Mo microsource	Rint = 0.025
phi– and ω–scans	θmax = 25.1°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −11→11
Tmin = 0.873, Tmax = 0.928	k = −19→19
6517 measured reflections	l = −11→11
2715 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.033	w = 1/[σ^2(Fo^2) + (0.0429P)^2 + 2.9664P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.089	(Δ/σ)max < 0.001
S = 1.02	Δρmax = 0.20 e Å^−3
2715 reflections	Δρmin = −0.38 e Å^−3
236 parameters	Absolute structure: Flack x determined using 1231 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
5 restraints	Absolute structure parameter: 0.04 (3)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	0.72188 (9)	0.16567 (9)	0.78936 (9)	0.0139 (2)
O1	0.7919 (3)	0.20197 (18)	0.9113 (3)	0.0205 (6)
O3	0.5857 (3)	0.13548 (19)	0.8243 (3)	0.0234 (7)
O2	0.7072 (3)	0.22694 (19)	0.6766 (3)	0.0212 (6)
O4	0.8047 (3)	0.09612 (19)	0.7381 (3)	0.0227 (6)
N1	0.5290 (4)	0.5207 (2)	0.8328 (3)	0.0160 (7)
H1	0.4542	0.5453	0.8081	0.019*
O6	0.9329 (4)	0.5482 (2)	0.6231 (4)	0.0387 (9)
H6A	0.8474	0.5587	0.6198	0.058*
H6B	0.9618	0.5694	0.6990	0.058*
N2	1.1749 (4)	0.2878 (2)	0.5495 (4)	0.0201 (7)
O5	0.6317 (3)	0.2555 (2)	1.1456 (4)	0.0332 (8)
O7	0.6661 (5)	0.5672 (2)	0.5399 (4)	0.0420 (10)
H7A	0.6263	0.5212	0.5303	0.063*
H7B	0.6868	0.5809	0.4580	0.063*
C8	1.0804 (4)	0.3728 (2)	0.7710 (4)	0.0132 (7)
C4	0.7572 (4)	0.5284 (2)	0.9187 (4)	0.0167 (8)
H4	0.8317	0.5599	0.9490	0.020*
O9	0.5000	0.2909 (4)	0.5000	0.0436 (13)
C5	0.7673 (4)	0.4430 (2)	0.9147 (4)	0.0125 (7)
C3	0.6365 (4)	0.5650 (2)	0.8774 (4)	0.0181 (8)
H3	0.6292	0.6217	0.8804	0.022*
C7	1.0346 (4)	0.4197 (2)	0.8947 (4)	0.0116 (7)
H7	1.0404	0.4786	0.8770	0.014*
C11	1.1564 (4)	0.4122 (3)	0.6701 (4)	0.0198 (8)
H11	1.1755	0.4679	0.6771	0.024*
C9	1.0532 (4)	0.2900 (3)	0.7561 (4)	0.0168 (8)
H9	1.0014	0.2628	0.8212	0.020*
C6	0.8956 (4)	0.3987 (2)	0.9610 (4)	0.0125 (7)
H6	0.8798	0.3395	0.9550	0.015*
C10	1.1033 (4)	0.2483 (2)	0.6442 (4)	0.0170 (8)
H10	1.0870	0.1925	0.6347	0.020*
C12	1.2025 (5)	0.3671 (3)	0.5595 (4)	0.0244 (9)
H12	1.2534	0.3925	0.4916	0.029*
C2	0.6532 (4)	0.3986 (2)	0.8670 (4)	0.0178 (8)
H2A	0.6573	0.3418	0.8630	0.021*
C1	0.5344 (4)	0.4387 (3)	0.8255 (4)	0.0197 (9)
H1A	0.4586	0.4091	0.7928	0.024*
O8	0.5000	0.4487 (4)	0.5000	0.088 (3)
H8A	0.4801	0.4814	0.5650	0.132*	0.5
H5A	0.675 (5)	0.255 (6)	1.070 (3)	0.09 (3)*
H5B	0.558 (3)	0.228 (3)	1.141 (6)	0.039 (15)*
H9A	0.560 (5)	0.275 (4)	0.567 (4)	0.08 (3)*
H8B	0.5000	0.3906 (4)	0.5000	0.09 (4)*
H2	1.196 (5)	0.254 (3)	0.485 (6)	0.029 (13)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0155 (4)	0.0116 (4)	0.0148 (4)	0.0013 (4)	0.0020 (3)	0.0018 (4)
O1	0.0276 (16)	0.0160 (12)	0.0177 (14)	−0.0044 (12)	0.0010 (12)	0.0004 (11)
O3	0.0193 (15)	0.0267 (15)	0.0242 (15)	−0.0017 (12)	0.0015 (12)	0.0083 (12)
O2	0.0259 (16)	0.0184 (13)	0.0194 (15)	0.0032 (12)	0.0041 (12)	0.0072 (11)
O4	0.0241 (15)	0.0188 (14)	0.0248 (15)	0.0114 (12)	−0.0055 (12)	−0.0053 (12)
N1	0.0160 (17)	0.0191 (16)	0.0130 (16)	0.0072 (13)	0.0001 (13)	0.0015 (12)
O6	0.045 (2)	0.039 (2)	0.0319 (18)	0.0035 (17)	−0.0040 (16)	−0.0031 (16)
N2	0.0231 (19)	0.0222 (17)	0.0151 (16)	0.0035 (15)	0.0025 (13)	−0.0071 (15)
O5	0.0280 (19)	0.0405 (19)	0.0315 (18)	−0.0104 (15)	0.0071 (15)	−0.0115 (16)
O7	0.060 (3)	0.041 (2)	0.0266 (18)	0.0171 (19)	0.0192 (17)	0.0030 (16)
C8	0.0094 (17)	0.0182 (19)	0.0118 (17)	0.0035 (15)	−0.0015 (13)	0.0007 (15)
C4	0.019 (2)	0.0168 (19)	0.0146 (18)	−0.0008 (16)	−0.0013 (15)	−0.0008 (15)
O9	0.032 (3)	0.048 (3)	0.050 (3)	0.000	−0.015 (3)	0.000
C5	0.0153 (19)	0.0146 (18)	0.0077 (16)	0.0023 (14)	0.0029 (14)	0.0014 (13)
C3	0.025 (2)	0.0122 (17)	0.0168 (19)	0.0048 (16)	−0.0016 (16)	−0.0016 (15)
C7	0.0132 (18)	0.0087 (16)	0.0129 (17)	0.0009 (14)	−0.0002 (14)	0.0012 (14)
C11	0.023 (2)	0.0171 (19)	0.020 (2)	−0.0008 (16)	0.0047 (16)	−0.0003 (16)
C9	0.018 (2)	0.0153 (18)	0.017 (2)	−0.0004 (15)	0.0005 (15)	−0.0003 (16)
C6	0.0145 (18)	0.0111 (17)	0.0120 (17)	−0.0002 (14)	0.0005 (14)	0.0000 (14)
C10	0.020 (2)	0.0145 (19)	0.0170 (19)	0.0008 (15)	0.0000 (16)	−0.0030 (15)
C12	0.027 (2)	0.026 (2)	0.021 (2)	−0.0009 (19)	0.0083 (18)	−0.0001 (17)
C2	0.017 (2)	0.0129 (17)	0.023 (2)	0.0003 (15)	−0.0017 (16)	−0.0017 (15)
C1	0.019 (2)	0.020 (2)	0.020 (2)	−0.0009 (17)	−0.0024 (17)	−0.0009 (16)
O8	0.101 (6)	0.052 (5)	0.112 (7)	0.000	0.013 (6)	0.000

Geometric parameters (Å, º)

S1—O1	1.467 (3)	O9—O9^i	0.000 (12)
S1—O3	1.464 (3)	O9—H9A	0.9000 (15)
S1—O2	1.482 (3)	C5—C6	1.501 (5)
S1—O4	1.487 (3)	C5—C2	1.394 (6)
N1—H1	0.8600	C3—H3	0.9300
N1—C3	1.333 (6)	C7—H7	0.9800
N1—C1	1.343 (5)	C7—C6	1.552 (5)
O6—H6A	0.8505	C7—C6^ii	1.568 (5)
O6—H6B	0.8501	C11—H11	0.9300
N2—C10	1.331 (5)	C11—C12	1.382 (6)
N2—C12	1.326 (6)	C9—H9	0.9300
N2—H2	0.86 (6)	C9—C10	1.377 (6)
O5—H5A	0.8500 (16)	C6—C7^ii	1.568 (5)
O5—H5B	0.8499 (16)	C6—H6	0.9800
O7—H7A	0.8499	C10—H10	0.9300
O7—H7B	0.8504	C12—H12	0.9300
C8—C7	1.497 (5)	C2—H2A	0.9300
C8—C11	1.396 (5)	C2—C1	1.379 (6)
C8—C9	1.385 (5)	C1—H1A	0.9300
C4—H4	0.9300	O8—H8A	0.8500
C4—C5	1.400 (5)	O8—H8B	0.9501 (15)
C4—C3	1.368 (6)
O1—S1—O2	110.32 (17)	C8—C7—C6^ii	117.6 (3)
O1—S1—O4	109.34 (17)	C6—C7—H7	110.1
O3—S1—O1	110.82 (17)	C6^ii—C7—H7	110.1
O3—S1—O2	109.14 (17)	C6—C7—C6^ii	87.0 (3)
O3—S1—O4	108.86 (18)	C8—C11—H11	120.6
O2—S1—O4	108.29 (17)	C12—C11—C8	118.8 (4)
C3—N1—H1	119.1	C12—C11—H11	120.6
C3—N1—C1	121.8 (4)	C8—C9—H9	120.2
C1—N1—H1	119.1	C10—C9—C8	119.5 (4)
H6A—O6—H6B	104.4	C10—C9—H9	120.2
C10—N2—H2	109 (3)	C5—C6—C7^ii	119.6 (3)
C12—N2—C10	122.2 (4)	C5—C6—C7	120.0 (3)
C12—N2—H2	129 (3)	C5—C6—H6	109.3
H5A—O5—H5B	113 (6)	C7—C6—C7^ii	87.5 (3)
H7A—O7—H7B	104.5	C7^ii—C6—H6	109.3
C11—C8—C7	119.7 (3)	C7—C6—H6	109.3
C9—C8—C7	121.4 (3)	N2—C10—C9	120.2 (4)
C9—C8—C11	118.8 (4)	N2—C10—H10	119.9
C5—C4—H4	120.4	C9—C10—H10	119.9
C3—C4—H4	120.4	N2—C12—C11	120.5 (4)
C3—C4—C5	119.2 (4)	N2—C12—H12	119.7
O9^i—O9—H9A	0 (10)	C11—C12—H12	119.7
C4—C5—C6	122.1 (3)	C5—C2—H2A	119.9
C2—C5—C4	118.2 (4)	C1—C2—C5	120.2 (4)
C2—C5—C6	119.7 (3)	C1—C2—H2A	119.9
N1—C3—C4	121.1 (4)	N1—C1—C2	119.5 (4)
N1—C3—H3	119.4	N1—C1—H1A	120.2
C4—C3—H3	119.4	C2—C1—H1A	120.2
C8—C7—H7	110.1	H8A—O8—H8B	128.9
C8—C7—C6	119.9 (3)
C8—C7—C6—C5	−92.0 (4)	C11—C8—C7—C6^ii	−110.1 (4)
C8—C7—C6—C7^ii	145.0 (3)	C11—C8—C7—C6	146.4 (4)
C8—C11—C12—N2	0.1 (6)	C11—C8—C9—C10	1.1 (6)
C8—C9—C10—N2	−1.4 (6)	C9—C8—C7—C6	−35.8 (5)
C4—C5—C6—C7	−55.8 (5)	C9—C8—C7—C6^ii	67.7 (5)
C4—C5—C6—C7^ii	49.8 (5)	C9—C8—C11—C12	−0.5 (6)
C4—C5—C2—C1	−0.2 (6)	C6—C5—C2—C1	179.3 (4)
C5—C4—C3—N1	−0.4 (6)	C6^ii—C7—C6—C5	147.7 (3)
C5—C2—C1—N1	−0.6 (6)	C6^ii—C7—C6—C7^ii	24.7 (3)
C3—N1—C1—C2	1.0 (6)	C10—N2—C12—C11	−0.4 (7)
C3—C4—C5—C6	−178.8 (3)	C12—N2—C10—C9	1.0 (6)
C3—C4—C5—C2	0.7 (6)	C2—C5—C6—C7	124.7 (4)
C7—C8—C11—C12	177.3 (4)	C2—C5—C6—C7^ii	−129.7 (4)
C7—C8—C9—C10	−176.7 (4)	C1—N1—C3—C4	−0.4 (6)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4^iii	0.86	1.79	2.647 (4)	174
O6—H6A···O7	0.85	1.91	2.716 (6)	157
O6—H6B···O3^iv	0.85	2.00	2.800 (5)	157
O7—H7A···O8	0.85	1.73	2.545 (7)	161
O7—H7B···O4^v	0.85	1.91	2.744 (4)	166
O5—H5A···O1	0.85 (1)	2.12 (4)	2.917 (4)	155 (8)
O5—H5B···O3^vi	0.85 (1)	2.09 (2)	2.907 (5)	160 (5)
O9—H9A···O2	0.90 (1)	1.92 (2)	2.804 (4)	167 (6)
O8—H8B···O9	0.95 (1)	1.63 (1)	2.579 (10)	180 (1)
N2—H2···O2^vii	0.86 (6)	1.89 (6)	2.683 (5)	151 (5)

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