Poly[3-methyl­pyridinium [(μ₂-di­hydrogen phosphito)bis(μ₃-hydrogen phosphito)dizinc]]

In the title compound, {(C₆H₈N)[Zn₂(HPO₃)₂(H₂PO₃)]}_n, the constituent ZnO₄, HPO₃ and H₂PO₃ polyhedra of the inorganic component are linked into (010) sheets by Zn—O—P bonds (mean angle = 134.4°) and the layers are reinforced by O—H...O hydrogen bonds. The protonated templates are anchored to the inorganic sheets via bifurcated N—H...(O,O) hydrogen bonds.

Key indicators

Structure: I

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.008 Å
• R factor = 0.050
• wR factor = 0.134
• Data-to-parameter ratio = 18.0

checkCIF/PLATON results

No syntax errors found



Alert level A
DIFF019_ALERT_1_A  _diffrn_standards_number is missing
            Number of standards used in measurement.

Author Response: not applicable for area-detector data

DIFF020_ALERT_1_A  _diffrn_standards_interval_count and
            _diffrn_standards_interval_time are missing. Number of measurements
            between standards or time (min) between standards.

Author Response: not applicable for area-detector data

DIFF022_ALERT_1_A  _diffrn_standards_decay_% is missing
            Percentage decrease in standards intensity.

Author Response: not apploicable for area-detector data

Alert level C
PLAT250_ALERT_2_C Large U3/U1 Ratio for <U(i,j)> Tensor(Resd    1)        2.3 Note
PLAT250_ALERT_2_C Large U3/U1 Ratio for <U(i,j)> Tensor(Resd    2)        2.1 Note
PLAT341_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0082 Ang.
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      3.252 Check
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600         11 Report
               -4  2 10,  -3  2 10,  -2  0 11,  -1  0 11,  -2  1 11,  -1  1 11,
                0  1 11,  -2  2 11,  -1  2 11,  -2  3 11,  -1  3 11,
PLAT973_ALERT_2_C Check Calcd Positive Resid. Density on       Zn1       1.14 eA-3
PLAT973_ALERT_2_C Check Calcd Positive Resid. Density on       Zn2       1.08 eA-3
PLAT977_ALERT_2_C Check Negative Difference Density on H2        .      -0.39 eA-3

Alert level G
PLAT004_ALERT_5_G Polymeric Structure Found with Maximum Dimension          2 Info
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          5 Report
              H1    H1O   H2    H3    H1B
PLAT760_ALERT_1_G CIF Contains no Torsion Angles .................          ? Info
PLAT794_ALERT_5_G Tentative Bond Valency for Zn1       (II)      .       2.15 Info
PLAT794_ALERT_5_G Tentative Bond Valency for Zn2       (II)      .       2.10 Info
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600        683 Note
PLAT941_ALERT_3_G Average HKL Measurement Multiplicity ...........        4.3 Low
PLAT969_ALERT_5_G The 'Henn et al.' R-Factor-gap value ...........       2.67 Note
              Predicted wR2: Based on SigI   2  5.03 or SHELX Weight 13.57       
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          0 Info

   3 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   8 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   9 ALERT level G = General information/check it is not something unexpected

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

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Computing details

Poly[3-methylpyridinium [(µ₂-dihydrogen phosphito)bis(µ₃-hydrogen phosphito)dizinc]]

Crystal data

(C6H8N)[Zn2(HPO3)2(H2PO3)]	Z = 2
Mr = 465.82	F(000) = 464
Triclinic, P1	Dx = 2.099 Mg m^−3
a = 8.8428 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.2779 (6) Å	Cell parameters from 6732 reflections
c = 9.9343 (4) Å	θ = 2.1–29.4°
α = 79.126 (4)°	µ = 3.62 mm^−1
β = 82.732 (4)°	T = 173 K
γ = 67.279 (6)°	Bar, colourless
V = 736.99 (8) Å^3	0.12 × 0.03 × 0.01 mm

Data collection

Rigaku XtaLAB P200K diffractometer	2491 reflections with I > 2σ(I)
Radiation source: Rotating Anode	Rint = 0.066
ω scans	θmax = 29.6°, θmin = 2.1°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2024)	h = −11→12
Tmin = 0.850, Tmax = 1.000	k = −12→12
14787 measured reflections	l = −13→12
3442 independent reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.050	H-atom parameters constrained
wR(F^2) = 0.134	w = 1/[σ^2(Fo^2) + (0.0819P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
3442 reflections	Δρmax = 1.43 e Å^−3
191 parameters	Δρmin = −0.89 e Å^−3
0 restraints

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
Zn1	−0.15526 (6)	0.48844 (6)	0.17897 (5)	0.02409 (17)
Zn2	0.24043 (6)	0.62310 (6)	0.40311 (5)	0.02507 (18)
P1	0.12600 (13)	0.63180 (14)	0.10765 (11)	0.0231 (3)
H1	0.096928	0.778451	0.046688	0.028*
P2	0.57579 (14)	0.67732 (15)	0.38453 (12)	0.0249 (3)
H2	0.585406	0.817529	0.343455	0.030*
P3	−0.05587 (14)	0.79747 (15)	0.60236 (12)	0.0268 (3)
H3	−0.092835	0.950694	0.595471	0.032*
O1	0.2488 (4)	0.5969 (4)	0.2136 (3)	0.0339 (8)
O2	0.2100 (4)	0.5268 (4)	−0.0006 (3)	0.0354 (8)
O3	−0.0360 (4)	0.6260 (4)	0.1659 (4)	0.0336 (8)
O4	0.6946 (4)	0.5953 (4)	0.4998 (3)	0.0292 (7)
O5	0.6265 (4)	0.5929 (4)	0.2609 (3)	0.0347 (8)
O6	0.3994 (4)	0.7076 (4)	0.4335 (3)	0.0296 (7)
O7	0.0241 (4)	0.7586 (4)	0.4650 (3)	0.0374 (8)
O8	0.0481 (4)	0.7208 (4)	0.7225 (4)	0.0386 (8)
O9	−0.2216 (4)	0.7747 (5)	0.6275 (4)	0.0495 (10)
H1O	−0.248833	0.714280	0.588686	0.059*
C1	0.5538 (6)	0.2241 (8)	0.0263 (6)	0.0480 (15)
H1A	0.501366	0.270784	−0.057545	0.058*
C2	0.6748 (6)	0.0729 (7)	0.0373 (5)	0.0398 (13)
C3	0.7424 (6)	0.0139 (6)	0.1628 (5)	0.0365 (12)
H3A	0.822779	−0.090250	0.177280	0.044*
C4	0.6958 (7)	0.1029 (7)	0.2676 (5)	0.0424 (13)
H4	0.745714	0.061680	0.352982	0.051*
C5	0.5791 (7)	0.2484 (7)	0.2484 (6)	0.0462 (15)
H5	0.546317	0.311069	0.320035	0.055*
C6	0.7301 (10)	−0.0189 (10)	−0.0812 (7)	0.076 (2)
H6A	0.645693	0.024450	−0.148650	0.113*
H6B	0.747583	−0.130136	−0.047771	0.113*
H6C	0.832992	−0.010706	−0.124466	0.113*
N1	0.5110 (5)	0.3034 (5)	0.1310 (6)	0.0501 (13)
H1B	0.432689	0.397922	0.121074	0.060*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0207 (3)	0.0390 (3)	0.0137 (3)	−0.0117 (2)	0.0011 (2)	−0.0071 (2)
Zn2	0.0217 (3)	0.0384 (3)	0.0167 (3)	−0.0109 (2)	0.0002 (2)	−0.0094 (2)
P1	0.0208 (6)	0.0313 (6)	0.0170 (6)	−0.0083 (5)	−0.0011 (4)	−0.0064 (5)
P2	0.0231 (6)	0.0367 (7)	0.0183 (6)	−0.0141 (5)	−0.0002 (5)	−0.0067 (5)
P3	0.0226 (6)	0.0356 (7)	0.0231 (6)	−0.0106 (5)	0.0001 (5)	−0.0079 (5)
O1	0.0318 (18)	0.056 (2)	0.0185 (17)	−0.0173 (16)	−0.0047 (14)	−0.0113 (15)
O2	0.0284 (17)	0.058 (2)	0.0178 (17)	−0.0078 (16)	−0.0033 (14)	−0.0176 (16)
O3	0.0247 (17)	0.0344 (18)	0.044 (2)	−0.0114 (15)	0.0067 (15)	−0.0161 (16)
O4	0.0279 (17)	0.0387 (19)	0.0237 (17)	−0.0145 (15)	−0.0031 (14)	−0.0055 (14)
O5	0.0205 (16)	0.066 (2)	0.0187 (16)	−0.0148 (16)	0.0025 (13)	−0.0153 (16)
O6	0.0215 (16)	0.046 (2)	0.0266 (17)	−0.0132 (15)	0.0041 (13)	−0.0192 (15)
O7	0.0236 (17)	0.054 (2)	0.0286 (19)	−0.0059 (16)	0.0002 (14)	−0.0126 (16)
O8	0.045 (2)	0.043 (2)	0.0290 (19)	−0.0170 (17)	−0.0059 (16)	−0.0032 (16)
O9	0.034 (2)	0.080 (3)	0.052 (2)	−0.033 (2)	0.0135 (17)	−0.038 (2)
C1	0.026 (3)	0.069 (4)	0.040 (3)	−0.017 (3)	−0.007 (2)	0.016 (3)
C2	0.036 (3)	0.057 (4)	0.033 (3)	−0.025 (3)	0.008 (2)	−0.014 (3)
C3	0.025 (2)	0.033 (3)	0.043 (3)	−0.007 (2)	0.000 (2)	0.005 (2)
C4	0.046 (3)	0.057 (4)	0.029 (3)	−0.029 (3)	−0.004 (2)	0.005 (3)
C5	0.054 (4)	0.052 (4)	0.044 (4)	−0.034 (3)	0.029 (3)	−0.021 (3)
C6	0.088 (5)	0.115 (6)	0.053 (4)	−0.062 (5)	0.024 (4)	−0.047 (4)
N1	0.030 (2)	0.033 (2)	0.066 (4)	0.000 (2)	0.024 (2)	−0.001 (2)

Geometric parameters (Å, º)

Zn1—O3	1.923 (3)	P3—O9	1.543 (3)
Zn1—O8^i	1.930 (4)	P3—H3	1.3200
Zn1—O2^ii	1.939 (3)	O9—H1O	0.8542
Zn1—O5^iii	1.945 (3)	C1—N1	1.318 (8)
Zn2—O6	1.931 (3)	C1—C2	1.392 (8)
Zn2—O1	1.931 (3)	C1—H1A	0.9500
Zn2—O7	1.938 (3)	C2—C3	1.374 (8)
Zn2—O4^iv	1.967 (3)	C2—C6	1.504 (8)
P1—O3	1.493 (3)	C3—C4	1.375 (8)
P1—O1	1.511 (3)	C3—H3A	0.9500
P1—O2	1.513 (3)	C4—C5	1.341 (8)
P1—H1	1.3200	C4—H4	0.9500
P2—O6	1.507 (3)	C5—N1	1.304 (8)
P2—O5	1.509 (3)	C5—H5	0.9500
P2—O4	1.533 (3)	C6—H6A	0.9800
P2—H2	1.3200	C6—H6B	0.9800
P3—O8	1.492 (4)	C6—H6C	0.9800
P3—O7	1.496 (3)	N1—H1B	0.8800
O3—Zn1—O8^i	114.37 (14)	P1—O3—Zn1	138.2 (2)
O3—Zn1—O2^ii	112.19 (15)	P2—O4—Zn2^iv	128.89 (18)
O8^i—Zn1—O2^ii	109.65 (15)	P2—O5—Zn1^v	129.60 (18)
O3—Zn1—O5^iii	107.88 (14)	P2—O6—Zn2	134.27 (19)
O8^i—Zn1—O5^iii	111.45 (15)	P3—O7—Zn2	134.0 (2)
O2^ii—Zn1—O5^iii	100.45 (13)	P3—O8—Zn1^i	138.6 (2)
O6—Zn2—O1	111.84 (14)	P3—O9—H1O	125.5
O6—Zn2—O7	108.97 (14)	N1—C1—C2	120.7 (5)
O1—Zn2—O7	112.00 (13)	N1—C1—H1A	119.6
O6—Zn2—O4^iv	108.32 (13)	C2—C1—H1A	119.6
O1—Zn2—O4^iv	102.86 (14)	C3—C2—C1	115.7 (5)
O7—Zn2—O4^iv	112.73 (14)	C3—C2—C6	122.1 (6)
O3—P1—O1	114.3 (2)	C1—C2—C6	122.1 (6)
O3—P1—O2	115.04 (19)	C2—C3—C4	121.2 (5)
O1—P1—O2	107.52 (19)	C2—C3—H3A	119.4
O3—P1—H1	106.4	C4—C3—H3A	119.4
O1—P1—H1	106.4	C5—C4—C3	119.5 (5)
O2—P1—H1	106.4	C5—C4—H4	120.3
O6—P2—O5	112.30 (17)	C3—C4—H4	120.3
O6—P2—O4	112.74 (18)	N1—C5—C4	119.7 (5)
O5—P2—O4	112.38 (19)	N1—C5—H5	120.2
O6—P2—H2	106.3	C4—C5—H5	120.2
O5—P2—H2	106.3	C2—C6—H6A	109.5
O4—P2—H2	106.3	C2—C6—H6B	109.5
O8—P3—O7	116.5 (2)	H6A—C6—H6B	109.5
O8—P3—O9	111.5 (2)	C2—C6—H6C	109.5
O7—P3—O9	111.4 (2)	H6A—C6—H6C	109.5
O8—P3—H3	105.5	H6B—C6—H6C	109.5
O7—P3—H3	105.5	C5—N1—C1	123.2 (5)
O9—P3—H3	105.5	C5—N1—H1B	118.4
P1—O1—Zn2	136.5 (2)	C1—N1—H1B	118.4
P1—O2—Zn1^ii	135.1 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O1	0.88	2.20	2.992 (6)	150
N1—H1B···O2	0.88	2.24	2.947 (6)	138
O9—H1O···O4^iii	0.85	1.78	2.630 (4)	177
C1—H1A···O5^vi	0.95	2.34	3.285 (6)	175
C5—H5···O4^iv	0.95	2.59	3.368 (6)	140
C5—H5···O6^iv	0.95	2.52	3.300 (7)	140

Symmetry codes: (iii) x−1, y, z; (iv) −x+1, −y+1, −z+1; (vi) −x+1, −y+1, −z.