The one-dimensional coordination polymer poly[tetra-kis-[(4-chloro-phen-yl)methanaminium] [cadmate-μ-cyclo-hexa-phospho-rato]].

Cyclo-hexa-phospho-ric acid (P(6)O(18)H(6)) reacts with cadmium carbonate and 4-chloro-benzyl-amine (CBA) to give the mononuclear title complex, (C(7)H(9)ClN)(4)[Cd(P(6)O(18))](n), in which the Cd(II) atom, lying on an inversion centre, has an octa-hedral coordination built of six O atoms of two centrosymmetric P(6)O(18) rings. Each P(6)O(18) ligand acts as a bridge, linking two Cd(II) atoms and forming an anionic coordination polymer [Cd(P(6)O(18))(4-)](n) extending along [010]. Adjacent polymeric chains are connected through N-H⋯O and C-H⋯O hydrogen bonds, generating a three-dimensional supra-molecular network.

Related literature

For the crystal chemistry of condensed phosphates, see: Averbuch-Pouchot & Durif (1996 ▶); Durif (2005 ▶). For general background to supra­molecular complexes, see: Kolotuchin et al. (1995 ▶); Tong et al. (1999 ▶). For Cl⋯Cl inter­actions, see: Hathwar et al. (2010 ▶) and for π–π inter­actions, see: Janiak et al. (2000 ▶). For the synthesis, see: Schülke & Kayser (1985 ▶). For related structures, see: Du et al. (2010 ▶); Hu et al. (2008 ▶); Kontturi et al. (2005 ▶); Man et al. (2006 ▶).

Experimental

Crystal data

(C7H9ClN)4[Cd(P6O18)]

M = 1156.63

Triclinic,

a = 8.021 (4) Å

b = 8.1696 (16) Å

c = 17.919 (3) Å

α = 87.31 (5)°

β = 88.914 (19)°

γ = 70.100 (3)°

V = 1102.9 (6) Å3

Z = 1

Mo Kα radiation

μ = 1.03 mm−1

T = 293 K

0.22 × 0.20 × 0.18 mm

Data collection

Enraf–Nonius TurboCAD-4 diffractometer

3873 measured reflections

3770 independent reflections

3506 reflections with I > 2σ(I)

R int = 0.009

2 standard reflections every 120 min intensity decay: 1%

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.074

S = 1.14

3770 reflections

277 parameters

H-atom parameters constrained

Δρmax = 0.76 e Å−3

Δρmin = −0.57 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681104133X/ff2028sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681104133X/ff2028Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(C7H9ClN)4[Cd(P6O18)]	Z = 1
Mr = 1156.63	F(000) = 582
Triclinic, P1	Dx = 1.741 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.021 (4) Å	Cell parameters from 25 reflections
b = 8.1696 (16) Å	θ = 9.1–10.8°
c = 17.919 (3) Å	µ = 1.03 mm−1
α = 87.31 (5)°	T = 293 K
β = 88.914 (19)°	Prism, colourless
γ = 70.100 (3)°	0.22 × 0.20 × 0.18 mm
V = 1102.9 (6) Å3

Enraf–Nonius TurboCAD-4 diffractometer	Rint = 0.009
Radiation source: Enraf Nonius FR590	θmax = 28.0°, θmin = 2.3°
graphite	h = −9→10
non–profiled ω scans	k = 0→10
3873 measured reflections	l = −5→23
3770 independent reflections	2 standard reflections every 120 min
3506 reflections with I > 2σ(I)	intensity decay: 1%

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.074	H-atom parameters constrained
S = 1.14	w = 1/[σ2(Fo2) + (0.0373P)2 + 0.863P] where P = (Fo2 + 2Fc2)/3
3770 reflections	(Δ/σ)max = 0.022
277 parameters	Δρmax = 0.76 e Å−3
0 restraints	Δρmin = −0.57 e Å−3

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

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
P1	0.67291 (7)	0.07788 (7)	0.58321 (4)	0.02160 (17)
P2	0.31753 (7)	0.30435 (7)	0.62408 (4)	0.02213 (17)
P3	0.21259 (7)	0.28764 (8)	0.46566 (4)	0.02360 (18)
O1	0.8257 (2)	0.0489 (2)	0.63383 (12)	0.0306 (5)
O2	0.6552 (2)	0.1994 (2)	0.51710 (12)	0.0278 (5)
O3	0.4957 (2)	0.1402 (2)	0.63318 (13)	0.0332 (5)
O4	0.6588 (2)	−0.1001 (2)	0.55819 (13)	0.0321 (6)
O5	0.3676 (2)	0.4624 (2)	0.60678 (11)	0.0265 (5)
O6	0.2085 (2)	0.3003 (2)	0.69060 (12)	0.0316 (5)
O7	0.2237 (3)	0.2579 (3)	0.55466 (12)	0.0354 (6)
O8	0.0311 (2)	0.3219 (2)	0.44049 (13)	0.0390 (6)
O9	0.3052 (2)	0.4116 (2)	0.43979 (12)	0.0295 (5)
Cd	0.5000	0.5000	0.5000	0.02314 (9)
N1	0.8521 (3)	0.3592 (3)	0.68090 (16)	0.0336 (6)
H1A	0.8605	0.2565	0.6633	0.050*
H1B	0.9603	0.3617	0.6892	0.050*
H1C	0.7969	0.4438	0.6476	0.050*
C1	0.7286 (4)	0.5549 (4)	0.7877 (2)	0.0373 (9)
C2	0.7656 (4)	0.6922 (4)	0.7522 (2)	0.0452 (10)
H2	0.8130	0.6803	0.7042	0.054*
C3	0.7325 (5)	0.8486 (5)	0.7875 (2)	0.0500 (10)
H3	0.7541	0.9424	0.7631	0.060*
C4	0.6673 (5)	0.8608 (5)	0.8592 (2)	0.0564 (12)
C5	0.6306 (6)	0.7272 (6)	0.8958 (3)	0.0661 (13)
H5	0.5852	0.7391	0.9442	0.079*
C6	0.6619 (5)	0.5735 (5)	0.8598 (2)	0.0522 (11)
H6	0.6377	0.4813	0.8844	0.063*
C7	0.7503 (5)	0.3849 (4)	0.7516 (2)	0.0502 (11)
H7A	0.8092	0.2893	0.7867	0.060*
H7B	0.6336	0.3799	0.7420	0.060*
Cl1	0.6261 (2)	1.05722 (18)	0.90321 (8)	0.1103 (6)
N2	0.8179 (3)	0.1736 (3)	0.37553 (14)	0.0286 (6)
H2A	0.7756	0.1534	0.4200	0.043*
H2B	0.8255	0.2800	0.3734	0.043*
H2C	0.9251	0.0952	0.3689	0.043*
C8	0.7590 (4)	0.1923 (4)	0.24011 (19)	0.0358 (8)
C9	0.8004 (5)	0.0633 (5)	0.1879 (2)	0.0564 (12)
H9	0.7943	−0.0456	0.2019	0.068*
C10	0.8495 (7)	0.0933 (6)	0.1169 (3)	0.0694 (15)
H10	0.8750	0.0059	0.0826	0.083*
C11	0.8614 (6)	0.2538 (6)	0.0958 (2)	0.0589 (12)
C12	0.8237 (5)	0.3838 (5)	0.1459 (2)	0.0558 (11)
H12	0.8325	0.4915	0.1317	0.067*
C13	0.7730 (4)	0.3532 (4)	0.2169 (2)	0.0453 (10)
H13	0.7472	0.4416	0.2507	0.054*
C14	0.6978 (4)	0.1610 (4)	0.3163 (2)	0.0401 (9)
H14A	0.5808	0.2454	0.3244	0.048*
H14B	0.6877	0.0460	0.3198	0.048*
Cl2	0.9233 (3)	0.2940 (2)	0.00535 (8)	0.1069 (6)

	U11	U22	U33	U12	U13	U23
P1	0.0171 (2)	0.0128 (2)	0.0337 (4)	−0.0031 (2)	0.0003 (3)	−0.0040 (3)
P2	0.0190 (2)	0.0152 (3)	0.0315 (4)	−0.0047 (2)	0.0032 (3)	−0.0051 (3)
P3	0.0204 (2)	0.0144 (3)	0.0364 (4)	−0.0057 (2)	−0.0049 (3)	−0.0045 (4)
O1	0.0246 (8)	0.0235 (8)	0.0421 (13)	−0.0050 (7)	−0.0056 (8)	−0.0079 (10)
O2	0.0262 (8)	0.0182 (8)	0.0356 (13)	−0.0035 (6)	0.0047 (8)	−0.0001 (10)
O3	0.0249 (8)	0.0201 (8)	0.0471 (15)	0.0005 (7)	0.0114 (9)	0.0041 (11)
O4	0.0235 (7)	0.0152 (7)	0.0566 (16)	−0.0043 (6)	−0.0065 (9)	−0.0078 (11)
O5	0.0288 (8)	0.0161 (7)	0.0355 (12)	−0.0084 (6)	0.0038 (8)	−0.0060 (10)
O6	0.0268 (8)	0.0288 (9)	0.0387 (13)	−0.0085 (7)	0.0084 (8)	−0.0065 (11)
O7	0.0427 (10)	0.0386 (11)	0.0354 (14)	−0.0273 (9)	−0.0031 (9)	−0.0022 (12)
O8	0.0230 (8)	0.0293 (9)	0.0635 (17)	−0.0050 (7)	−0.0104 (9)	−0.0154 (12)
O9	0.0334 (8)	0.0195 (8)	0.0392 (13)	−0.0133 (7)	−0.0079 (9)	−0.0007 (10)
Cd	0.02384 (11)	0.01532 (11)	0.03217 (18)	−0.00887 (9)	−0.00109 (10)	−0.00258 (13)
N1	0.0303 (10)	0.0249 (10)	0.0464 (17)	−0.0101 (9)	−0.0057 (11)	−0.0041 (13)
C1	0.0316 (12)	0.0382 (15)	0.043 (2)	−0.0126 (12)	−0.0013 (13)	−0.0018 (19)
C2	0.0535 (17)	0.0464 (18)	0.042 (2)	−0.0242 (15)	0.0066 (16)	−0.012 (2)
C3	0.068 (2)	0.0419 (17)	0.047 (3)	−0.0273 (17)	0.0068 (18)	−0.006 (2)
C4	0.074 (2)	0.050 (2)	0.049 (3)	−0.0237 (19)	0.009 (2)	−0.015 (2)
C5	0.091 (3)	0.070 (3)	0.042 (3)	−0.032 (2)	0.017 (2)	−0.012 (3)
C6	0.066 (2)	0.049 (2)	0.044 (3)	−0.0245 (18)	0.006 (2)	0.008 (2)
C7	0.0545 (18)	0.0404 (17)	0.062 (3)	−0.0249 (15)	0.0130 (18)	−0.008 (2)
Cl1	0.1789 (15)	0.0753 (8)	0.0887 (11)	−0.0554 (9)	0.0468 (10)	−0.0485 (9)
N2	0.0239 (9)	0.0246 (10)	0.0353 (15)	−0.0048 (8)	0.0001 (9)	−0.0065 (12)
C8	0.0382 (13)	0.0338 (14)	0.0370 (19)	−0.0138 (12)	−0.0073 (13)	−0.0016 (17)
C9	0.081 (2)	0.0355 (17)	0.053 (3)	−0.0185 (17)	−0.008 (2)	−0.010 (2)
C10	0.112 (3)	0.048 (2)	0.045 (3)	−0.022 (2)	0.002 (2)	−0.015 (3)
C11	0.082 (3)	0.064 (2)	0.030 (2)	−0.025 (2)	0.0006 (19)	0.003 (3)
C12	0.072 (2)	0.0465 (19)	0.054 (3)	−0.0269 (18)	−0.006 (2)	0.000 (2)
C13	0.0578 (18)	0.0387 (17)	0.045 (2)	−0.0227 (15)	0.0010 (16)	−0.009 (2)
C14	0.0350 (13)	0.0433 (16)	0.048 (2)	−0.0211 (12)	−0.0060 (14)	−0.0035 (19)
Cl2	0.1687 (16)	0.1080 (12)	0.0444 (8)	−0.0486 (12)	0.0145 (9)	−0.0017 (10)

P1—O1	1.4846 (19)	C3—C4	1.372 (6)
P1—O2	1.486 (2)	C3—H3	0.9300
P1—O4	1.5822 (16)	C4—C5	1.362 (6)
P1—O3	1.607 (2)	C4—Cl1	1.748 (3)
P2—O6	1.471 (2)	C5—C6	1.383 (5)
P2—O5	1.4947 (18)	C5—H5	0.9300
P2—O7	1.5909 (19)	C6—H6	0.9300
P2—O3	1.5975 (18)	C7—H7A	0.9700
P3—O8	1.4614 (18)	C7—H7B	0.9700
P3—O9	1.499 (2)	N2—C14	1.478 (3)
P3—O4i	1.6009 (16)	N2—H2A	0.8900
P3—O7	1.601 (2)	N2—H2B	0.8900
O2—Cd	2.3534 (18)	N2—H2C	0.8900
O4—P3i	1.6009 (16)	C8—C9	1.392 (4)
O5—Cd	2.230 (2)	C8—C13	1.401 (5)
O9—Cd	2.2432 (17)	C8—C14	1.482 (5)
Cd—O5ii	2.230 (2)	C9—C10	1.361 (6)
Cd—O9ii	2.2432 (17)	C9—H9	0.9300
Cd—O2ii	2.3534 (18)	C10—C11	1.382 (7)
N1—C7	1.478 (4)	C10—H10	0.9300
N1—H1A	0.8900	C11—C12	1.374 (5)
N1—H1B	0.8900	C11—Cl2	1.735 (5)
N1—H1C	0.8900	C12—C13	1.365 (5)
C1—C2	1.380 (5)	C12—H12	0.9300
C1—C6	1.383 (5)	C13—H13	0.9300
C1—C7	1.515 (4)	C14—H14A	0.9700
C2—C3	1.393 (4)	C14—H14B	0.9700
C2—H2	0.9300
O1—P1—O2	117.93 (12)	C3—C2—H2	119.7
O1—P1—O4	111.66 (10)	C4—C3—C2	118.4 (4)
O2—P1—O4	109.88 (11)	C4—C3—H3	120.8
O1—P1—O3	107.43 (12)	C2—C3—H3	120.8
O2—P1—O3	109.96 (11)	C5—C4—C3	122.2 (3)
O4—P1—O3	98.11 (10)	C5—C4—Cl1	119.5 (3)
O6—P2—O5	118.97 (11)	C3—C4—Cl1	118.2 (3)
O6—P2—O7	107.58 (11)	C4—C5—C6	118.8 (4)
O5—P2—O7	111.28 (13)	C4—C5—H5	120.6
O6—P2—O3	106.68 (13)	C6—C5—H5	120.6
O5—P2—O3	108.08 (11)	C5—C6—C1	121.0 (4)
O7—P2—O3	102.99 (12)	C5—C6—H6	119.5
O8—P3—O9	118.36 (13)	C1—C6—H6	119.5
O8—P3—O4i	111.32 (9)	N1—C7—C1	114.6 (3)
O9—P3—O4i	104.99 (10)	N1—C7—H7A	108.6
O8—P3—O7	110.18 (13)	C1—C7—H7A	108.6
O9—P3—O7	110.64 (11)	N1—C7—H7B	108.6
O4i—P3—O7	99.62 (12)	C1—C7—H7B	108.6
P1—O2—Cd	131.47 (10)	H7A—C7—H7B	107.6
P2—O3—P1	131.59 (16)	C14—N2—H2A	109.5
P1—O4—P3i	138.76 (11)	C14—N2—H2B	109.5
P2—O5—Cd	122.36 (10)	H2A—N2—H2B	109.5
P2—O7—P3	139.86 (14)	C14—N2—H2C	109.5
P3—O9—Cd	129.75 (13)	H2A—N2—H2C	109.5
O5—Cd—O5ii	180.0	H2B—N2—H2C	109.5
O5—Cd—O9	88.19 (7)	C9—C8—C13	117.2 (4)
O5ii—Cd—O9	91.81 (7)	C9—C8—C14	121.0 (3)
O5—Cd—O9ii	91.81 (7)	C13—C8—C14	121.8 (3)
O5ii—Cd—O9ii	88.19 (7)	C10—C9—C8	121.4 (4)
O9—Cd—O9ii	180.00 (10)	C10—C9—H9	119.3
O5—Cd—O2	83.53 (8)	C8—C9—H9	119.3
O5ii—Cd—O2	96.47 (8)	C9—C10—C11	119.8 (3)
O9—Cd—O2	83.70 (7)	C9—C10—H10	120.1
O9ii—Cd—O2	96.30 (7)	C11—C10—H10	120.1
O5—Cd—O2ii	96.47 (8)	C12—C11—C10	120.5 (4)
O5ii—Cd—O2ii	83.53 (8)	C12—C11—Cl2	119.2 (4)
O9—Cd—O2ii	96.30 (7)	C10—C11—Cl2	120.3 (3)
O9ii—Cd—O2ii	83.70 (7)	C13—C12—C11	119.3 (4)
O2—Cd—O2ii	180.000 (1)	C13—C12—H12	120.3
C7—N1—H1A	109.5	C11—C12—H12	120.3
C7—N1—H1B	109.5	C12—C13—C8	121.7 (3)
H1A—N1—H1B	109.5	C12—C13—H13	119.2
C7—N1—H1C	109.5	C8—C13—H13	119.2
H1A—N1—H1C	109.5	N2—C14—C8	113.1 (2)
H1B—N1—H1C	109.5	N2—C14—H14A	109.0
C2—C1—C6	118.9 (3)	C8—C14—H14A	109.0
C2—C1—C7	123.9 (3)	N2—C14—H14B	109.0
C6—C1—C7	117.2 (3)	C8—C14—H14B	109.0
C1—C2—C3	120.7 (3)	H14A—C14—H14B	107.8
C1—C2—H2	119.7

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.89	1.91	2.785 (3)	167
N1—H1B···O6iii	0.89	1.88	2.740 (3)	162
N1—H1C···O9ii	0.89	1.93	2.809 (4)	168
N2—H2A···O2	0.89	1.96	2.814 (4)	160
N2—H2B···O5ii	0.89	2.19	2.866 (3)	133
N2—H2C···O1iv	0.89	1.95	2.824 (3)	169
C3—H3···O1v	0.93	2.56	3.339 (5)	142
C13—H13···O6ii	0.93	2.53	3.394 (4)	154
C14—H14B···O3i	0.97	2.56	3.410 (4)	147

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1	0.89	1.91	2.785 (3)	167
N1—H1B⋯O6i	0.89	1.88	2.740 (3)	162
N1—H1C⋯O9ii	0.89	1.93	2.809 (4)	168
N2—H2A⋯O2	0.89	1.96	2.814 (4)	160
N2—H2B⋯O5ii	0.89	2.19	2.866 (3)	133
N2—H2C⋯O1iii	0.89	1.95	2.824 (3)	169
C3—H3⋯O1iv	0.93	2.56	3.339 (5)	142
C13—H13⋯O6ii	0.93	2.53	3.394 (4)	154
C14—H14B⋯O3v	0.97	2.56	3.410 (4)	147

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .