Poly[tris­(p-xylylenediaminium) [tetradeca-μ-oxo-hexa­deca­nona­molybdate(VI)] dihydrate]

Crystals of the title compound, {[C₈H₁₄N₂]₃[Mo₉O₃₀]·2H₂O}_n, were grown under mild hydro­thermal conditions in the presence of p-xylylenediamine. [Mo₉O₃₀]_n⁶ⁿ⁻ chains, constructed from [MoO₆] octa­hedra and [MoO₄] tetra­hedra, are separated by protonated p-xylylenediaminium cations and occluded water mol­ecules, creating an extensive hydrogen-bonding network. One cation posseses a centre of symmetry; the anion is also centrosymmetric and one Mo atom lies on a crystallographic twofold rotation axis.

Key indicators

• Single-crystal X-ray study
• T = 110 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.021
• wR factor = 0.047
• Data-to-parameter ratio = 14.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?

Alert level G
REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values
           From the CIF: _diffrn_reflns_theta_max           32.14
           From the CIF: _reflns_number_total               7576
           From the CIF: _diffrn_reflns_limit_ max hkl   23.   20.   30.
           From the CIF: _diffrn_reflns_limit_ min hkl  -24.  -20.  -26.
           TEST1: Expected hkl limits for theta max
           Calculated maximum hkl   25.   20.   32.
           Calculated minimum hkl  -25.  -20.  -32.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 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
   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
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2004); cell refinement: CrysAlis RED; data reduction: CrysAlis RED (Oxford Diffraction, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: ATOMS (Dowty, 2002); software used to prepare material for publication: CRYSTALS.

Poly[tris(p-xylylenediaminium) [tetradeca-µ-oxo- hexadecanonamolybdate(VI)] dihydrate]

Crystal data

(C8H14N2)3[Mo9O30]·2H2O	F(000) = 3464
Mr = 1794.13	Dx = 2.511 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 13373 reflections
a = 16.850 (3) Å	θ = 3.8–32.1°
b = 13.656 (3) Å	µ = 2.40 mm^−1
c = 21.441 (4) Å	T = 110 K
β = 105.908 (15)°	Plate, colorless
V = 4744.7 (16) Å^3	0.25 × 0.14 × 0.03 mm
Z = 4

Data collection

Oxford CrysAlis CCD area-detector diffractometer	4638 reflections with I > 3σ(I)
Graphite monochromator	Rint = 0.02
ω scans	θmax = 32.1°, θmin = 3.8°
Absorption correction: analytical (multifaceted crystal model; Clark & Reid, 1995)	h = −24→23
Tmin = 0.540, Tmax = 0.930	k = −20→20
49286 measured reflections	l = −26→30
7576 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.021	H-atom parameters constrained
wR(F^2) = 0.047	Method, part 1, Chebychev polynomial (Watkin, 1994; Prince, 1982), [weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)], where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = robust weighting (Prince, 1982) W = [weight] * [1-(δF/6*σF)^2]^2 Ai are: 0.344E + 05 -0.492E + 05 0.417E + 05 -0.161E + 05 0.755E + 04 Prince, E. (1982). Mathematical Techniques in Crystallography and Materials Science. New York: Springer-Verlag. Watkin, D. (1994). Acta Cryst. A50, 411–437.
S = 0.86	(Δ/σ)max = 0.001
4638 reflections	Δρmax = 0.58 e Å^−3
321 parameters	Δρmin = −0.56 e Å^−3
0 restraints

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

	x	y	z	Uiso*/Ueq
Mo1	0.408393 (16)	0.257935 (19)	0.472504 (13)	0.0086
Mo2	0.301918 (16)	0.196539 (18)	0.572155 (13)	0.0073
Mo3	0.411198 (16)	0.397174 (19)	0.634565 (13)	0.0095
Mo4	0.286744 (16)	0.085325 (19)	0.396419 (13)	0.0089
Mo5	0.5000	0.20978 (3)	0.7500	0.0091
O1	0.46174 (15)	0.35696 (18)	0.45346 (12)	0.0136
O2	0.48257 (15)	0.17106 (18)	0.50317 (12)	0.0143
O3	0.36024 (14)	0.19431 (17)	0.39051 (11)	0.0112
O4	0.38761 (14)	0.29922 (17)	0.55139 (11)	0.0104
O5	0.29480 (13)	0.18163 (16)	0.48069 (10)	0.0079
O6	0.20782 (14)	0.14115 (17)	0.57166 (11)	0.0111
O7	0.37353 (15)	0.10969 (17)	0.60591 (11)	0.0127
O8	0.31047 (14)	0.29309 (16)	0.63656 (11)	0.0098
O9	0.41504 (16)	0.45189 (19)	0.70698 (12)	0.0174
O10	0.48208 (14)	0.45859 (18)	0.60490 (13)	0.0155
O11	0.31234 (14)	0.46316 (16)	0.58439 (11)	0.0105
O12	0.48242 (15)	0.28520 (17)	0.67780 (11)	0.0131
O13	0.35860 (15)	0.00460 (17)	0.44126 (12)	0.0137
O14	0.26930 (16)	0.04663 (18)	0.31806 (12)	0.0164
O15	0.41626 (15)	0.13630 (19)	0.74873 (12)	0.0164
O16	0.36658 (19)	0.5249 (3)	0.81254 (14)	0.0319
N1	0.48612 (18)	0.9706 (2)	0.58688 (14)	0.0148
N2	0.25633 (19)	0.6726 (2)	0.77284 (15)	0.0171
N3	0.11391 (17)	0.0423 (2)	0.01168 (14)	0.0127
C1	0.3143 (2)	0.7526 (3)	0.69065 (16)	0.0163
C2	0.3144 (2)	0.8535 (3)	0.69991 (16)	0.0145
C3	0.3771 (2)	0.9111 (2)	0.68846 (15)	0.0122
C4	0.4406 (2)	0.8687 (2)	0.66712 (16)	0.0126
C5	0.4410 (2)	0.7674 (3)	0.65840 (19)	0.0205
C6	0.3777 (3)	0.7100 (3)	0.66968 (19)	0.0205
C7	0.2441 (3)	0.6933 (3)	0.70184 (18)	0.0215
C8	0.5080 (2)	0.9320 (3)	0.65526 (17)	0.0160
C9	0.2227 (2)	0.3459 (2)	−0.00901 (17)	0.0145
C10	0.1827 (2)	0.2791 (3)	0.02159 (17)	0.0148
C11	0.2096 (2)	0.1828 (2)	0.03035 (16)	0.0134
C12	0.1669 (2)	0.1086 (3)	0.06180 (16)	0.0163
H1	0.42077	0.5516	0.83862	0.0376*
H2	0.37373	0.4929	0.77247	0.0376*
H3	0.2692	0.8847	0.71492	0.0176*
H4	0.3767	0.9835	0.69538	0.0147*
H5	0.4866	0.7360	0.64403	0.0257*
H6	0.3780	0.6376	0.66296	0.0262*
H7	0.5175	0.9886	0.68604	0.0200*
H8	0.5597	0.8924	0.66304	0.0200*
H9	0.43458	1.0106	0.57882	0.0186*
H10	0.53207	1.0124	0.58056	0.0186*
H11	0.47678	0.9144	0.55582	0.0186*
H12	0.1915	0.7304	0.68479	0.0259*
H13	0.2407	0.6297	0.67810	0.0259*
H14	0.25954	0.7359	0.79679	0.0228*
H15	0.30883	0.6352	0.79010	0.0228*
H16	0.20898	0.6331	0.77885	0.0228*
H17	0.2027	0.4151	−0.01551	0.0167*
H18	0.1347	0.3006	0.03714	0.0178*
H19	0.1316	0.1436	0.08528	0.0198*
H20	0.2093	0.0687	0.09333	0.0198*
H21	0.07143	0.0821	−0.01987	0.0151*
H22	0.14912	0.0071	−0.01182	0.0151*
H23	0.08588	−0.0065	0.03322	0.0151*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mo1	0.00755 (11)	0.00671 (11)	0.01247 (11)	−0.00065 (9)	0.00424 (9)	−0.00068 (9)
Mo2	0.00767 (11)	0.00573 (10)	0.00816 (11)	0.00030 (8)	0.00175 (8)	0.00017 (9)
Mo3	0.00909 (11)	0.00741 (11)	0.01025 (11)	−0.00087 (9)	−0.00043 (9)	−0.00040 (9)
Mo4	0.01003 (11)	0.00639 (11)	0.01091 (11)	0.00002 (9)	0.00380 (9)	−0.00092 (9)
Mo5	0.00901 (16)	0.00682 (15)	0.01054 (16)	0.0000	0.00114 (13)	0.0000
O1	0.0131 (11)	0.0114 (10)	0.0186 (12)	−0.0039 (9)	0.0083 (9)	−0.0001 (9)
O2	0.0119 (10)	0.0118 (10)	0.0201 (12)	0.0025 (9)	0.0060 (9)	−0.0009 (9)
O3	0.0117 (10)	0.0089 (10)	0.0152 (11)	−0.0002 (8)	0.0073 (8)	−0.0008 (8)
O4	0.0111 (10)	0.0088 (10)	0.0112 (10)	−0.0027 (8)	0.0029 (8)	−0.0025 (8)
O5	0.0070 (9)	0.0075 (9)	0.0091 (9)	0.0000 (7)	0.0019 (7)	0.0009 (7)
O6	0.0131 (10)	0.0088 (10)	0.0117 (10)	−0.0007 (8)	0.0039 (8)	0.0018 (8)
O7	0.0146 (11)	0.0107 (10)	0.0109 (10)	0.0031 (8)	0.0005 (8)	0.0009 (8)
O8	0.0138 (10)	0.0068 (9)	0.0085 (9)	0.0009 (8)	0.0026 (8)	−0.0010 (8)
O9	0.0181 (12)	0.0161 (12)	0.0148 (12)	0.0038 (9)	−0.0007 (9)	−0.0038 (9)
O10	0.0103 (10)	0.0124 (11)	0.0213 (12)	−0.0033 (9)	−0.0001 (9)	0.0044 (9)
O11	0.0108 (10)	0.0080 (10)	0.0116 (10)	0.0000 (8)	0.0010 (8)	0.0010 (8)
O12	0.0138 (11)	0.0121 (11)	0.0116 (10)	0.0016 (8)	0.0006 (8)	0.0019 (8)
O13	0.0122 (11)	0.0099 (10)	0.0203 (12)	0.0007 (8)	0.0067 (9)	0.0019 (9)
O14	0.0245 (13)	0.0115 (11)	0.0145 (11)	−0.0026 (9)	0.0073 (10)	−0.0021 (9)
O15	0.0158 (12)	0.0157 (11)	0.0183 (12)	−0.0061 (9)	0.0055 (9)	−0.0029 (10)
O16	0.0250 (15)	0.052 (2)	0.0167 (13)	0.0185 (14)	0.0014 (11)	0.0024 (13)
N1	0.0135 (13)	0.0145 (13)	0.0185 (14)	0.0042 (10)	0.0080 (11)	0.0041 (11)
N2	0.0205 (14)	0.0145 (13)	0.0205 (14)	0.0001 (11)	0.0126 (12)	−0.0004 (11)
N3	0.0116 (12)	0.0095 (12)	0.0157 (13)	−0.0036 (10)	0.0015 (10)	−0.0003 (10)
C1	0.0220 (16)	0.0145 (15)	0.0125 (14)	−0.0038 (13)	0.0049 (12)	0.0008 (12)
C2	0.0156 (15)	0.0163 (15)	0.0128 (14)	−0.0006 (12)	0.0059 (12)	−0.0007 (12)
C3	0.0164 (14)	0.0106 (13)	0.0101 (13)	0.0021 (11)	0.0046 (11)	−0.0006 (11)
C4	0.0142 (14)	0.0118 (14)	0.0115 (14)	0.0008 (11)	0.0030 (11)	−0.0008 (11)
C5	0.0276 (19)	0.0133 (15)	0.0253 (18)	0.0056 (14)	0.0150 (15)	0.0010 (13)
C6	0.0315 (19)	0.0095 (14)	0.0232 (18)	0.0029 (14)	0.0124 (15)	0.0002 (13)
C7	0.0299 (19)	0.0171 (16)	0.0171 (16)	−0.0070 (15)	0.0058 (14)	0.0023 (14)
C8	0.0154 (15)	0.0180 (16)	0.0150 (15)	0.0027 (12)	0.0047 (12)	0.0001 (12)
C9	0.0151 (14)	0.0094 (14)	0.0178 (15)	−0.0006 (12)	0.0026 (12)	−0.0032 (12)
C10	0.0112 (14)	0.0152 (15)	0.0188 (16)	−0.0003 (11)	0.0054 (12)	−0.0050 (12)
C11	0.0126 (14)	0.0133 (14)	0.0135 (14)	−0.0055 (11)	0.0021 (12)	−0.0023 (11)
C12	0.0211 (16)	0.0158 (15)	0.0119 (14)	−0.0063 (13)	0.0044 (12)	−0.0037 (12)

Geometric parameters (Å, º)

Mo1—O1	1.733 (2)	N1—H11	1.000
Mo1—O2	1.718 (2)	N2—C7	1.506 (5)
Mo1—O3	1.929 (2)	N2—H14	1.000
Mo1—O4	1.904 (2)	N2—H15	1.000
Mo1—O5	2.228 (2)	N2—H16	1.000
Mo1—O6^i	2.369 (2)	N3—C12	1.499 (4)
Mo2—O4	2.145 (2)	N3—H21	1.000
Mo2—O5	1.942 (2)	N3—H22	1.000
Mo2—O5^i	2.386 (2)	N3—H23	1.000
Mo2—O6	1.754 (2)	C1—C2	1.391 (5)
Mo2—O7	1.705 (2)	C1—C6	1.395 (5)
Mo2—O8	1.886 (2)	C1—C7	1.507 (5)
Mo3—O4	2.177 (2)	C2—C3	1.392 (5)
Mo3—O8	2.223 (2)	C2—H3	1.000
Mo3—O9	1.708 (2)	C3—C4	1.399 (4)
Mo3—O10	1.718 (2)	C3—H4	1.000
Mo3—O11	1.939 (2)	C4—C5	1.395 (5)
Mo3—O12	2.007 (2)	C4—C8	1.503 (5)
Mo4—O3	1.962 (2)	C5—C6	1.396 (5)
Mo4—O5	2.209 (2)	C5—H5	1.000
Mo4—O8^i	2.303 (2)	C6—H6	1.000
Mo4—O11^i	1.942 (2)	C7—H12	1.000
Mo4—O13	1.723 (2)	C7—H13	1.000
Mo4—O14	1.708 (2)	C8—H7	1.000
Mo5—O12	1.815 (2)	C8—H8	1.000
Mo5—O12^ii	1.815 (2)	C9—C10	1.400 (5)
Mo5—O15	1.726 (2)	C9—C11^iii	1.397 (5)
Mo5—O15^ii	1.726 (2)	C9—H17	1.000
O16—H1	1.000	C10—C11	1.386 (5)
O16—H2	1.000	C10—H18	1.000
N1—C8	1.506 (4)	C11—C12	1.505 (5)
N1—H9	1.000	C12—H19	1.000
N1—H10	1.000	C12—H20	1.000
O1—Mo1—O2	105.01 (11)	Mo1—O5—Mo4	94.33 (8)
O1—Mo1—O3	104.62 (11)	Mo2—O5—Mo4	149.46 (12)
O2—Mo1—O3	96.77 (11)	Mo2^i—O5—Mo4	98.39 (8)
O1—Mo1—O4	102.22 (11)	Mo1^i—O6—Mo2	113.47 (11)
O2—Mo1—O4	98.98 (11)	Mo2—O8—Mo3	109.78 (10)
O3—Mo1—O4	143.99 (9)	Mo2—O8—Mo4^i	111.96 (10)
O1—Mo1—O5	153.58 (10)	Mo3—O8—Mo4^i	90.90 (8)
O2—Mo1—O5	101.39 (10)	Mo3—O11—Mo4^i	112.43 (11)
O3—Mo1—O5	72.86 (9)	Mo3—O12—Mo5	139.78 (14)
O1—Mo1—O6^i	82.95 (10)	H1—O16—H2	109.467
O2—Mo1—O6^i	171.69 (10)	C8—N1—H9	109.19
O3—Mo1—O6^i	78.62 (9)	C8—N1—H10	109.86
O4—Mo1—O5	72.39 (9)	H9—N1—H10	109.476
O4—Mo1—O6^i	81.36 (9)	C8—N1—H11	109.35
O5—Mo1—O6^i	70.72 (8)	H9—N1—H11	109.476
O4—Mo2—O5	73.61 (9)	H10—N1—H11	109.475
O4—Mo2—O5^i	81.76 (8)	C7—N2—H14	109.25
O5—Mo2—O5^i	75.44 (9)	C7—N2—H15	109.4
O4—Mo2—O6	159.94 (10)	H14—N2—H15	109.476
O5—Mo2—O6	98.23 (10)	C7—N2—H16	109.79
O5^i—Mo2—O6	78.42 (9)	H14—N2—H16	109.476
O4—Mo2—O7	96.00 (10)	H15—N2—H16	109.475
O5—Mo2—O7	101.32 (10)	C12—N3—H21	109.38
O5^i—Mo2—O7	176.46 (10)	C12—N3—H22	109.41
O6—Mo2—O7	103.65 (11)	H21—N3—H22	109.476
O4—Mo2—O8	76.96 (9)	C12—N3—H23	109.61
O5—Mo2—O8	141.60 (9)	H21—N3—H23	109.476
O5^i—Mo2—O8	76.44 (9)	H22—N3—H23	109.476
O6—Mo2—O8	101.15 (10)	C2—C1—C6	119.2 (3)
O7—Mo2—O8	105.80 (10)	C2—C1—C7	118.7 (3)
O4—Mo3—O8	69.76 (8)	C6—C1—C7	122.1 (3)
O4—Mo3—O9	165.08 (11)	C1—C2—C3	120.4 (3)
O8—Mo3—O9	95.80 (11)	C1—C2—H3	119.8
O4—Mo3—O10	89.20 (11)	C3—C2—H3	119.83
O8—Mo3—O10	158.63 (11)	C2—C3—C4	120.6 (3)
O9—Mo3—O10	105.43 (13)	C2—C3—H4	119.74
O4—Mo3—O11	83.97 (9)	C4—C3—H4	119.64
O8—Mo3—O11	76.33 (9)	C3—C4—C5	119.0 (3)
O9—Mo3—O11	96.53 (11)	C3—C4—C8	119.8 (3)
O10—Mo3—O11	98.42 (10)	C5—C4—C8	121.1 (3)
O4—Mo3—O12	82.07 (9)	C4—C5—C6	120.1 (3)
O8—Mo3—O12	82.36 (9)	C4—C5—H5	119.9
O9—Mo3—O12	92.55 (11)	C6—C5—H5	120.0
O10—Mo3—O12	98.89 (11)	C1—C6—C5	120.6 (3)
O11—Mo3—O12	157.54 (10)	C1—C6—H6	119.6
O3—Mo4—O5	72.71 (9)	C5—C6—H6	119.7
O3—Mo4—O8^i	80.90 (9)	N2—C7—C1	111.5 (3)
O5—Mo4—O8^i	72.60 (8)	N2—C7—H12	109.0
O3—Mo4—O11^i	150.07 (9)	C1—C7—H12	109.0
O5—Mo4—O11^i	83.88 (9)	N2—C7—H13	108.93
O8^i—Mo4—O11^i	74.36 (9)	C1—C7—H13	108.9
O3—Mo4—O13	99.32 (10)	H12—C7—H13	109.467
O5—Mo4—O13	92.77 (10)	N1—C8—C4	111.8 (3)
O8^i—Mo4—O13	164.71 (10)	N1—C8—H7	108.92
O3—Mo4—O14	96.47 (11)	C4—C8—H7	108.95
O5—Mo4—O14	160.78 (10)	N1—C8—H8	108.75
O8^i—Mo4—O14	90.28 (10)	C4—C8—H8	108.91
O11^i—Mo4—O13	100.20 (10)	H7—C8—H8	109.467
O11^i—Mo4—O14	100.18 (11)	C10—C9—C11^iii	120.8 (3)
O13—Mo4—O14	104.84 (12)	C10—C9—H17	119.63
O12—Mo5—O12^ii	110.84 (15)	C11^iii—C9—H17	119.58
O12—Mo5—O15	112.02 (12)	C9—C10—C11	120.0 (3)
O12^ii—Mo5—O15	106.56 (11)	C9—C10—H18	120.18
O12—Mo5—O15^ii	106.56 (11)	C11—C10—H18	119.80
O12^ii—Mo5—O15^ii	112.02 (12)	C9^iii—C11—C10	119.2 (3)
O15—Mo5—O15^ii	108.88 (18)	C9^iii—C11—C12	119.4 (3)
Mo1—O3—Mo4	113.46 (11)	C10—C11—C12	121.4 (3)
Mo1—O4—Mo2	106.79 (10)	N3—C12—C11	110.5 (3)
Mo1—O4—Mo3	150.79 (12)	N3—C12—H19	109.26
Mo2—O4—Mo3	102.34 (9)	C11—C12—H19	109.13
Mo1—O5—Mo2	102.35 (9)	N3—C12—H20	109.22
Mo1—O5—Mo2^i	97.25 (8)	C11—C12—H20	109.28
Mo2—O5—Mo2^i	104.56 (9)	H19—C12—H20	109.467

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O16—H1···O10^ii	1.00	2.16	2.825 (4)	122
O16—H2···O9	1.00	1.82	2.792 (4)	164
N1—H9···O7^iv	1.00	1.89	2.792 (4)	149
N1—H10···O13^v	1.00	2.03	2.862 (4)	139
N1—H11···O2^v	1.00	1.98	2.883 (4)	149
N2—H15···O16	1.00	1.79	2.716 (4)	153
N2—H16···O15^vi	1.00	2.03	2.860 (4)	139
N3—H21···O1^vii	1.00	1.96	2.876 (4)	150
N3—H22···O11^viii	1.00	1.94	2.891 (4)	158

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