A ladder coordination polymer based on Ca²⁺ and (4,5-di­cyano-1,2-phenyl­ene)bis­(phospho­nic acid): crystal structure and solution-state NMR study

The preparation of coordination polymers (CPs) based on either transition metal centres or rare-earth cations has grown considerably in recent decades. The different coordination chemistry of these metals allied to the use of a large variety of organic linkers has led to an amazing structural diversity. Most of these compounds are based on carb­oxy­lic acids or nitro­gen-containing ligands. More recently, a wide range of mol­ecules containing phospho­nic acid groups have been reported. For the particular case of Ca²⁺-based CPs, some inter­esting functional materials have been reported. A novel one-dimensional Ca²⁺-based coordination polymer with a new organic linker, namely poly[[di­aqua[μ₄-(4,5-di­cyano-1,2-phenyl­ene)bis­(phospho­nato)][μ₃-(4,5-di­cyano-1,2-phenyl­ene)bis(phospho­nato)]­dicalcium(II)] tetra­hydrate], {[Ca₂(C₈H₄N₂O₆P₂)₂(H₂O)₂]·4H₂O}_n, has been prepared at ambient temperature. The crystal structure features one-dimensional ladder-like _∞¹[Ca₂(H₂cpp)₂(H₂O)₂] polymers [H₂cpp is (4,5-di­cyano-1,2-phenyl­ene)bis­(phospho­nate)], which are created by two distinct coordination modes of the anionic H₂cpp²⁻ cyano­phospho­nate organic linkers: while one mol­ecule is only bound to Ca²⁺ cations via the phospho­nate groups, the other establishes an extra single connection via a cyano group. Ladders close pack with water mol­ecules through an extensive network of strong and highly directional O—H...O and O—H...N hydrogen bonds; the observed donor–acceptor distances range from 2.499 (5) to 3.004 (6) Å and the inter­action angles were found in the range 135–178°. One water mol­ecule was found to be disordered over three distinct crystallographic positions. A detailed solution-state NMR study of the organic linker is also provided.

Computing details

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b).

Poly[[diaqua[µ₄-(4,5-dicyano-1,2-phenylene)bis(phosphonato)][µ₃-(4,5-dicyano-1,2-phenylene)bis(phosphonato)]dicalcium(II)] tetrahydrate]

Crystal data

[Ca2(C8H4N2O6P2)2(H2O)2]·4H2O	F(000) = 1552
Mr = 760.40	Dx = 1.746 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.4384 (11) Å	Cell parameters from 9894 reflections
b = 25.2929 (18) Å	θ = 2.5–27.5°
c = 6.9599 (5) Å	µ = 0.70 mm^−1
β = 91.493 (3)°	T = 180 K
V = 2892.8 (4) Å^3	Needle, colourless
Z = 4	0.10 × 0.06 × 0.01 mm

Data collection

Bruker D8 QUEST diffractometer	5266 independent reflections
Radiation source: Sealed tube	4050 reflections with I > 2σ(I)
Multi-layer X-ray mirror monochromator	Rint = 0.065
Detector resolution: 10.4167 pixels mm^-1	θmax = 25.3°, θmin = 3.6°
ω / φ scans	h = −19→19
Absorption correction: multi-scan (SADABS; Bruker, 2001)	k = −30→30
Tmin = 0.665, Tmax = 0.746	l = −8→6
27705 measured reflections

Refinement

Refinement on F^2	17 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.051	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.133	w = 1/[σ^2(Fo^2) + (0.0456P)^2 + 10.5068P] where P = (Fo^2 + 2Fc^2)/3
S = 1.12	(Δ/σ)max < 0.001
5266 reflections	Δρmax = 1.11 e Å^−3
437 parameters	Δρmin = −0.46 e Å^−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)
Ca1	0.21357 (5)	0.48752 (4)	0.48298 (12)	0.0121 (2)
O1W	0.1289 (2)	0.41194 (14)	0.4757 (5)	0.0283 (9)
H1X	0.083 (2)	0.4128 (18)	0.556 (7)	0.042*
H1Y	0.149 (3)	0.3768 (8)	0.467 (8)	0.042*
Ca2	0.26293 (5)	0.55449 (4)	−0.01741 (12)	0.0129 (2)
O2W	0.3849 (2)	0.60987 (14)	0.0272 (5)	0.0251 (8)
H2X	0.416 (3)	0.605 (2)	−0.084 (4)	0.038*
H2Y	0.414 (3)	0.597 (2)	0.137 (4)	0.038*
P1	0.07803 (7)	0.57959 (5)	0.28875 (17)	0.0137 (3)
P2	0.27497 (7)	0.60345 (5)	0.47447 (16)	0.0123 (3)
P3	0.19620 (7)	0.44154 (5)	0.98306 (16)	0.0127 (3)
P4	0.38005 (7)	0.44944 (5)	0.76973 (16)	0.0133 (3)
O1	0.10166 (18)	0.54102 (12)	0.4433 (4)	0.0163 (7)
O2	0.11751 (18)	0.56490 (13)	0.0942 (4)	0.0159 (7)
H2	0.081 (2)	0.560 (2)	−0.012 (5)	0.024*
O3	−0.01218 (18)	0.58811 (13)	0.2597 (4)	0.0177 (7)
O4	0.27202 (18)	0.56479 (12)	0.3114 (4)	0.0156 (7)
O5	0.26030 (19)	0.57702 (13)	0.6615 (4)	0.0183 (7)
O6	0.35591 (19)	0.63571 (13)	0.4760 (5)	0.0236 (8)
H6	0.3892	0.6223	0.5558	0.035*
O7	0.19488 (18)	0.47961 (12)	0.8170 (4)	0.0137 (7)
O8	0.11072 (19)	0.41838 (13)	1.0214 (4)	0.0185 (7)
H8	0.0848	0.4147	0.9166	0.028*
O9	0.23133 (18)	0.46456 (12)	1.1642 (4)	0.0153 (7)
O10	0.34371 (18)	0.46164 (13)	0.5742 (4)	0.0161 (7)
O11	0.36883 (18)	0.49098 (12)	0.9206 (4)	0.0150 (7)
O12	0.47252 (18)	0.43474 (13)	0.7524 (5)	0.0195 (7)
H12	0.4995	0.4622	0.7312	0.029*
N1	0.2182 (3)	0.84492 (17)	0.4633 (6)	0.0232 (9)
N2	−0.0175 (4)	0.8114 (2)	0.3213 (10)	0.0628 (18)
N3	0.4199 (3)	0.2033 (2)	0.8105 (8)	0.0445 (13)
N4	0.1946 (4)	0.1987 (2)	0.9551 (8)	0.0480 (14)
C1	0.1198 (3)	0.64455 (18)	0.3556 (6)	0.0145 (9)
C2	0.1994 (3)	0.65507 (18)	0.4251 (6)	0.0141 (9)
C3	0.2237 (3)	0.70717 (18)	0.4555 (6)	0.0174 (10)
H3	0.2778	0.7144	0.4992	0.021*
C4	0.1697 (3)	0.74911 (19)	0.4227 (6)	0.0199 (10)
C5	0.0894 (3)	0.73801 (19)	0.3647 (7)	0.0209 (11)
C6	0.0661 (3)	0.68640 (19)	0.3304 (7)	0.0192 (10)
H6A	0.0118	0.6793	0.2884	0.023*
C7	0.1968 (3)	0.8027 (2)	0.4459 (7)	0.0243 (11)
C8	0.0308 (4)	0.7803 (2)	0.3392 (8)	0.0324 (13)
C9	0.3783 (3)	0.34030 (19)	0.8153 (7)	0.0198 (10)
H9	0.4320	0.3420	0.7684	0.024*
C10	0.2573 (3)	0.38361 (18)	0.9209 (6)	0.0132 (9)
C11	0.3358 (3)	0.38678 (18)	0.8459 (6)	0.0156 (10)
C12	0.3442 (3)	0.2914 (2)	0.8519 (7)	0.0225 (11)
C13	0.2651 (3)	0.28838 (19)	0.9180 (7)	0.0221 (11)
C14	0.2224 (3)	0.33432 (19)	0.9546 (7)	0.0191 (10)
H14	0.1690	0.3323	1.0030	0.023*
C15	0.3892 (3)	0.2431 (2)	0.8245 (8)	0.0297 (12)
C16	0.2254 (3)	0.2379 (2)	0.9432 (8)	0.0275 (12)
O3W	0.43889 (19)	0.48070 (14)	1.2731 (5)	0.0200 (7)
H3X	0.411 (2)	0.481 (2)	1.152 (3)	0.030*
H3Y	0.401 (2)	0.479 (2)	1.373 (4)	0.030*
O4W	0.0320 (3)	0.5554 (3)	−0.2061 (6)	0.073 (2)
H4X	0.051 (4)	0.546 (4)	−0.328 (5)	0.109*
H4Y	−0.0246 (12)	0.562 (4)	−0.213 (10)	0.109*
O5W	0.4773 (2)	0.61236 (15)	0.7077 (5)	0.0267 (8)
H5X	0.502 (3)	0.5783 (8)	0.711 (9)	0.040*
H5Y	0.519 (2)	0.6385 (12)	0.706 (8)	0.040*
O6W	0.4021 (8)	0.7237 (5)	0.106 (2)	0.055 (2)*	0.375 (8)
O7W	0.4377 (11)	0.7206 (7)	0.296 (3)	0.055 (2)*	0.262 (8)
O8W	0.3948 (8)	0.7254 (5)	−0.046 (2)	0.055 (2)*	0.363 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ca1	0.0123 (4)	0.0148 (5)	0.0091 (4)	0.0004 (4)	0.0009 (3)	0.0008 (4)
O1W	0.034 (2)	0.022 (2)	0.030 (2)	−0.0097 (16)	0.0191 (16)	−0.0055 (16)
Ca2	0.0161 (5)	0.0137 (5)	0.0090 (4)	0.0008 (4)	0.0002 (3)	−0.0001 (4)
O2W	0.0251 (19)	0.028 (2)	0.0225 (18)	−0.0025 (16)	−0.0002 (15)	0.0023 (16)
P1	0.0114 (6)	0.0153 (6)	0.0143 (6)	0.0002 (5)	0.0008 (4)	−0.0004 (5)
P2	0.0145 (6)	0.0125 (6)	0.0098 (5)	−0.0017 (5)	−0.0009 (4)	0.0003 (5)
P3	0.0131 (6)	0.0150 (6)	0.0100 (5)	−0.0017 (5)	0.0015 (4)	0.0006 (5)
P4	0.0120 (6)	0.0153 (6)	0.0127 (5)	0.0006 (5)	0.0007 (4)	0.0003 (5)
O1	0.0146 (16)	0.0156 (17)	0.0188 (16)	0.0004 (13)	0.0005 (13)	0.0027 (13)
O2	0.0138 (16)	0.0210 (18)	0.0129 (15)	−0.0006 (13)	−0.0001 (12)	−0.0028 (13)
O3	0.0132 (16)	0.0242 (19)	0.0158 (16)	0.0008 (14)	0.0002 (13)	−0.0004 (14)
O4	0.0192 (17)	0.0173 (17)	0.0103 (15)	0.0012 (13)	0.0013 (13)	−0.0008 (13)
O5	0.0252 (18)	0.0179 (18)	0.0120 (15)	0.0010 (14)	0.0013 (13)	0.0018 (13)
O6	0.0158 (17)	0.0222 (19)	0.032 (2)	−0.0029 (14)	−0.0074 (15)	0.0064 (16)
O7	0.0141 (16)	0.0139 (17)	0.0132 (15)	0.0000 (12)	0.0018 (12)	0.0000 (13)
O8	0.0144 (16)	0.0270 (19)	0.0141 (16)	−0.0046 (14)	0.0009 (13)	0.0006 (15)
O9	0.0160 (16)	0.0183 (17)	0.0118 (15)	−0.0017 (13)	0.0016 (12)	−0.0006 (13)
O10	0.0144 (16)	0.0226 (18)	0.0115 (15)	0.0009 (13)	0.0028 (12)	0.0010 (13)
O11	0.0119 (15)	0.0172 (17)	0.0158 (16)	0.0006 (13)	0.0005 (12)	−0.0012 (13)
O12	0.0135 (16)	0.0217 (19)	0.0235 (18)	0.0022 (13)	0.0013 (14)	−0.0011 (15)
N1	0.031 (2)	0.018 (2)	0.021 (2)	−0.0016 (19)	0.0066 (18)	−0.0019 (18)
N2	0.053 (4)	0.043 (4)	0.092 (5)	0.023 (3)	−0.013 (3)	−0.016 (3)
N3	0.048 (3)	0.023 (3)	0.062 (4)	0.013 (2)	−0.002 (3)	−0.005 (3)
N4	0.061 (4)	0.030 (3)	0.053 (3)	−0.012 (3)	−0.007 (3)	0.005 (3)
C1	0.019 (2)	0.014 (2)	0.010 (2)	−0.0018 (19)	0.0021 (18)	−0.0012 (18)
C2	0.019 (2)	0.018 (2)	0.006 (2)	−0.0012 (19)	0.0037 (17)	0.0014 (18)
C3	0.024 (3)	0.017 (2)	0.012 (2)	−0.004 (2)	0.0039 (19)	0.0016 (19)
C4	0.034 (3)	0.014 (2)	0.012 (2)	−0.002 (2)	0.004 (2)	−0.0014 (19)
C5	0.026 (3)	0.021 (3)	0.016 (2)	0.008 (2)	0.003 (2)	0.001 (2)
C6	0.019 (2)	0.021 (3)	0.017 (2)	0.001 (2)	−0.0007 (19)	0.001 (2)
C7	0.035 (3)	0.024 (3)	0.014 (2)	0.004 (2)	0.006 (2)	−0.001 (2)
C8	0.038 (3)	0.021 (3)	0.038 (3)	0.009 (3)	−0.004 (3)	−0.005 (2)
C9	0.023 (3)	0.020 (3)	0.016 (2)	0.003 (2)	−0.0018 (19)	0.000 (2)
C10	0.019 (2)	0.012 (2)	0.008 (2)	0.0015 (18)	−0.0020 (17)	0.0001 (17)
C11	0.016 (2)	0.018 (3)	0.013 (2)	0.0002 (19)	−0.0016 (18)	−0.0023 (19)
C12	0.029 (3)	0.018 (3)	0.020 (2)	0.006 (2)	−0.001 (2)	0.001 (2)
C13	0.030 (3)	0.017 (3)	0.020 (2)	−0.002 (2)	−0.003 (2)	0.003 (2)
C14	0.022 (3)	0.018 (3)	0.017 (2)	−0.003 (2)	0.0001 (19)	−0.001 (2)
C15	0.036 (3)	0.022 (3)	0.030 (3)	0.002 (2)	−0.005 (2)	−0.002 (2)
C16	0.032 (3)	0.021 (3)	0.029 (3)	−0.003 (2)	−0.005 (2)	0.001 (2)
O3W	0.0147 (17)	0.030 (2)	0.0157 (16)	0.0005 (14)	0.0019 (13)	0.0027 (15)
O4W	0.024 (2)	0.173 (6)	0.021 (2)	0.030 (3)	−0.0032 (17)	−0.023 (3)
O5W	0.0198 (19)	0.025 (2)	0.035 (2)	−0.0024 (15)	−0.0017 (16)	0.0026 (17)

Geometric parameters (Å, º)

Ca1—O1	2.294 (3)	O6—H6	0.8400
Ca1—O4	2.496 (3)	O7—Ca2^ii	2.470 (3)
Ca1—O5	2.685 (3)	O8—H8	0.8400
Ca1—O7	2.362 (3)	O9—Ca1^ii	2.319 (3)
Ca1—O9^i	2.319 (3)	O9—Ca2^ii	2.660 (3)
Ca1—O10	2.310 (3)	O11—Ca2^ii	2.416 (3)
Ca1—O1W	2.365 (3)	O12—H12	0.8400
Ca1—Ca2^ii	3.9334 (12)	N1—C7	1.130 (6)
Ca1—Ca2	3.9753 (12)	N1—Ca2^iv	2.651 (4)
O1W—H1X	0.947 (10)	N2—C8	1.122 (7)
O1W—H1Y	0.949 (10)	N3—C15	1.130 (7)
Ca2—O2	2.546 (3)	N4—C16	1.117 (7)
Ca2—O4	2.304 (3)	C1—C6	1.386 (7)
Ca2—O5^i	2.306 (3)	C1—C2	1.409 (6)
Ca2—O7^i	2.469 (3)	C2—C3	1.392 (6)
Ca2—O9^i	2.660 (3)	C3—C4	1.399 (7)
Ca2—O11^i	2.416 (3)	C3—H3	0.9500
Ca2—N1^iii	2.651 (4)	C4—C5	1.398 (7)
Ca2—O2W	2.459 (4)	C4—C7	1.434 (7)
O2W—H2X	0.948 (10)	C5—C6	1.379 (7)
O2W—H2Y	0.946 (10)	C5—C8	1.449 (7)
P1—O1	1.496 (3)	C6—H6A	0.9500
P1—O3	1.507 (3)	C9—C12	1.384 (7)
P1—O2	1.562 (3)	C9—C11	1.388 (7)
P1—C1	1.836 (5)	C9—H9	0.9500
P2—O5	1.489 (3)	C10—C14	1.395 (6)
P2—O4	1.498 (3)	C10—C11	1.406 (6)
P2—O6	1.561 (3)	C12—C13	1.392 (7)
P2—C2	1.828 (5)	C12—C15	1.445 (7)
P3—O9	1.492 (3)	C13—C14	1.385 (7)
P3—O7	1.504 (3)	C13—C16	1.448 (7)
P3—O8	1.552 (3)	C14—H14	0.9500
P3—C10	1.834 (5)	O3W—H3X	0.946 (10)
P3—Ca2^ii	3.0603 (15)	O3W—H3Y	0.945 (10)
P4—O11	1.500 (3)	O4W—H4X	0.946 (10)
P4—O10	1.504 (3)	O4W—H4Y	0.945 (10)
P4—O12	1.573 (3)	O5W—H5X	0.949 (10)
P4—C11	1.828 (5)	O5W—H5Y	0.949 (10)
O2—H2	0.947 (10)	O6W—O8W	1.061 (16)
O5—Ca2^ii	2.306 (3)	O6W—O7W	1.44 (2)
O1—Ca1—O4	78.35 (11)	O9—P3—Ca2^ii	60.36 (13)
O1—Ca1—O5	77.14 (11)	O7—P3—Ca2^ii	53.09 (12)
O1—Ca1—O7	92.53 (11)	O8—P3—Ca2^ii	132.75 (14)
O1—Ca1—O9^i	98.80 (11)	C10—P3—Ca2^ii	123.16 (15)
O1—Ca1—O10	159.06 (12)	O11—P4—O10	115.88 (18)
O1—Ca1—O1W	90.25 (13)	O11—P4—O12	110.84 (18)
O4—Ca1—O5	56.78 (9)	O10—P4—O12	109.95 (18)
O7—Ca1—O4	126.80 (11)	O11—P4—C11	110.31 (19)
O7—Ca1—O5	70.05 (10)	O10—P4—C11	106.76 (19)
O7—Ca1—O1W	82.00 (12)	O12—P4—C11	102.1 (2)
O9^i—Ca1—O4	71.26 (11)	O11—P4—Ca1	95.65 (12)
O9^i—Ca1—O5	127.75 (11)	O12—P4—Ca1	140.23 (13)
O9^i—Ca1—O7	160.64 (12)	C11—P4—Ca1	95.34 (15)
O9^i—Ca1—O1W	82.29 (12)	P1—O1—Ca1	131.58 (18)
O10—Ca1—O4	89.32 (11)	P1—O2—Ca2	134.73 (17)
O10—Ca1—O5	81.95 (11)	P1—O2—H2	116 (3)
O10—Ca1—O7	81.29 (10)	Ca2—O2—H2	110 (3)
O10—Ca1—O9^i	93.05 (11)	P2—O4—Ca2	145.71 (19)
O10—Ca1—O1W	108.50 (13)	P2—O4—Ca1	98.86 (15)
O1W—Ca1—O4	148.95 (12)	Ca2—O4—Ca1	111.77 (13)
O1W—Ca1—O5	148.50 (11)	P2—O5—Ca2^ii	163.6 (2)
Ca1—O1W—H1X	116 (3)	P2—O5—Ca1	91.42 (15)
Ca1—O1W—H1Y	124 (3)	Ca2^ii—O5—Ca1	103.77 (12)
H1X—O1W—H1Y	109.7 (16)	P2—O6—H6	109.5
O2—Ca2—O9^i	75.34 (10)	P3—O7—Ca1	144.20 (18)
O2—Ca2—N1^iii	69.80 (12)	P3—O7—Ca2^ii	97.78 (15)
O4—Ca2—O2	73.89 (10)	Ca1—O7—Ca2^ii	108.99 (12)
O4—Ca2—O5^i	159.04 (12)	P3—O8—H8	109.5
O4—Ca2—O7^i	124.54 (11)	P3—O9—Ca1^ii	148.31 (19)
O4—Ca2—O9^i	68.47 (10)	P3—O9—Ca2^ii	90.47 (14)
O4—Ca2—O11^i	102.96 (11)	Ca1^ii—O9—Ca2^ii	105.75 (12)
O4—Ca2—N1^iii	87.27 (12)	P4—O10—Ca1	130.54 (17)
O4—Ca2—O2W	77.21 (12)	P4—O11—Ca2^ii	133.87 (17)
O5^i—Ca2—O2	106.02 (11)	P4—O12—H12	109.5
O5^i—Ca2—O7^i	74.96 (11)	C7—N1—Ca2^iv	176.2 (4)
O5^i—Ca2—O9^i	132.30 (11)	C6—C1—C2	118.8 (4)
O5^i—Ca2—O11^i	89.23 (11)	C6—C1—P1	114.8 (3)
O5^i—Ca2—N1^iii	73.48 (12)	C2—C1—P1	126.4 (4)
O5^i—Ca2—O2W	88.64 (12)	C3—C2—C1	119.4 (4)
O7^i—Ca2—O2	78.71 (10)	C3—C2—P2	117.2 (3)
O7^i—Ca2—O9^i	58.29 (10)	C1—C2—P2	123.4 (4)
O7^i—Ca2—N1^iii	126.21 (12)	C2—C3—C4	121.0 (4)
O11^i—Ca2—O2	144.08 (11)	C2—C3—H3	119.5
O11^i—Ca2—O7^i	74.13 (10)	C4—C3—H3	119.5
O11^i—Ca2—O9^i	70.54 (10)	C5—C4—C3	119.1 (4)
O11^i—Ca2—N1^iii	146.04 (12)	C5—C4—C7	120.7 (5)
O11^i—Ca2—O2W	79.17 (11)	C3—C4—C7	120.2 (5)
O2W—Ca2—O2	132.19 (11)	C6—C5—C4	119.7 (4)
O2W—Ca2—O7^i	148.61 (11)	C6—C5—C8	119.8 (5)
O2W—Ca2—O9^i	126.56 (11)	C4—C5—C8	120.5 (5)
O2W—Ca2—N1^iii	71.58 (13)	C5—C6—C1	121.9 (4)
N1^iii—Ca2—O9^i	141.94 (11)	C5—C6—H6A	119.1
Ca2—O2W—H2X	106 (3)	C1—C6—H6A	119.1
Ca2—O2W—H2Y	107 (3)	N1—C7—C4	179.7 (6)
H2X—O2W—H2Y	109.9 (16)	N2—C8—C5	176.7 (7)
O1—P1—O3	115.22 (18)	C12—C9—C11	121.3 (5)
O1—P1—O2	111.24 (18)	C12—C9—H9	119.4
O3—P1—O2	110.33 (17)	C11—C9—H9	119.4
O1—P1—C1	108.25 (19)	C14—C10—C11	119.9 (4)
O3—P1—C1	105.4 (2)	C14—C10—P3	116.4 (3)
O2—P1—C1	105.74 (19)	C11—C10—P3	123.7 (3)
O3—P1—Ca1	140.12 (14)	C9—C11—C10	118.7 (4)
O2—P1—Ca1	84.33 (12)	C9—C11—P4	118.9 (4)
C1—P1—Ca1	105.64 (15)	C10—C11—P4	122.2 (3)
O5—P2—O4	111.50 (18)	C9—C12—C13	119.8 (5)
O5—P2—O6	112.72 (19)	C9—C12—C15	121.3 (5)
O4—P2—O6	110.94 (19)	C13—C12—C15	118.9 (5)
O5—P2—C2	111.11 (19)	C14—C13—C12	119.7 (5)
O4—P2—C2	108.38 (19)	C14—C13—C16	119.1 (5)
O6—P2—C2	101.7 (2)	C12—C13—C16	121.1 (5)
O5—P2—Ca1	59.91 (13)	C13—C14—C10	120.4 (5)
O4—P2—Ca1	52.64 (12)	C13—C14—H14	119.8
O6—P2—Ca1	140.52 (14)	C10—C14—H14	119.8
C2—P2—Ca1	117.31 (15)	N3—C15—C12	174.7 (6)
O9—P3—O7	113.39 (18)	N4—C16—C13	177.3 (6)
O9—P3—O8	109.54 (18)	H3X—O3W—H3Y	110.3 (16)
O7—P3—O8	112.27 (18)	H4X—O4W—H4Y	110.4 (17)
O9—P3—C10	107.99 (19)	H5X—O5W—H5Y	109.4 (16)
O7—P3—C10	109.11 (18)	O8W—O6W—O7W	162.5 (16)
O8—P3—C10	104.0 (2)
O3—P1—O1—Ca1	152.6 (2)	P1—C1—C2—P2	−3.6 (6)
O2—P1—O1—Ca1	26.1 (3)	O5—P2—C2—C3	102.5 (4)
C1—P1—O1—Ca1	−89.7 (3)	O4—P2—C2—C3	−134.6 (3)
O1—P1—O2—Ca2	−60.0 (3)	O6—P2—C2—C3	−17.6 (4)
O3—P1—O2—Ca2	170.9 (2)	Ca1—P2—C2—C3	168.6 (3)
C1—P1—O2—Ca2	57.3 (3)	O5—P2—C2—C1	−78.7 (4)
Ca1—P1—O2—Ca2	−47.3 (2)	O4—P2—C2—C1	44.2 (4)
O5—P2—O4—Ca2	165.4 (3)	O6—P2—C2—C1	161.1 (4)
O6—P2—O4—Ca2	−68.1 (4)	Ca1—P2—C2—C1	−12.6 (4)
C2—P2—O4—Ca2	42.7 (4)	C1—C2—C3—C4	1.6 (6)
Ca1—P2—O4—Ca2	153.5 (4)	P2—C2—C3—C4	−179.5 (3)
O5—P2—O4—Ca1	11.8 (2)	C2—C3—C4—C5	2.1 (7)
O6—P2—O4—Ca1	138.38 (16)	C2—C3—C4—C7	−177.0 (4)
C2—P2—O4—Ca1	−110.76 (17)	C3—C4—C5—C6	−3.6 (7)
O4—P2—O5—Ca2^ii	147.1 (7)	C7—C4—C5—C6	175.5 (4)
O6—P2—O5—Ca2^ii	21.6 (8)	C3—C4—C5—C8	176.8 (5)
C2—P2—O5—Ca2^ii	−91.9 (7)	C7—C4—C5—C8	−4.1 (7)
Ca1—P2—O5—Ca2^ii	158.0 (8)	C4—C5—C6—C1	1.3 (7)
O4—P2—O5—Ca1	−10.87 (19)	C8—C5—C6—C1	−179.0 (5)
O6—P2—O5—Ca1	−136.43 (16)	C2—C1—C6—C5	2.5 (7)
C2—P2—O5—Ca1	110.16 (18)	P1—C1—C6—C5	−176.6 (4)
O9—P3—O7—Ca1	141.4 (3)	O9—P3—C10—C14	105.1 (4)
O8—P3—O7—Ca1	−93.8 (3)	O7—P3—C10—C14	−131.3 (3)
C10—P3—O7—Ca1	21.0 (4)	O8—P3—C10—C14	−11.3 (4)
Ca2^ii—P3—O7—Ca1	138.7 (3)	Ca2^ii—P3—C10—C14	170.9 (3)
O9—P3—O7—Ca2^ii	2.8 (2)	O9—P3—C10—C11	−74.0 (4)
O8—P3—O7—Ca2^ii	127.57 (16)	O7—P3—C10—C11	49.7 (4)
C10—P3—O7—Ca2^ii	−117.63 (17)	O8—P3—C10—C11	169.7 (4)
O7—P3—O9—Ca1^ii	119.5 (4)	Ca2^ii—P3—C10—C11	−8.1 (4)
O8—P3—O9—Ca1^ii	−6.8 (4)	C12—C9—C11—C10	1.9 (7)
C10—P3—O9—Ca1^ii	−119.5 (4)	C12—C9—C11—P4	−173.3 (4)
Ca2^ii—P3—O9—Ca1^ii	122.0 (4)	C14—C10—C11—C9	−3.0 (6)
O7—P3—O9—Ca2^ii	−2.54 (18)	P3—C10—C11—C9	176.1 (3)
O8—P3—O9—Ca2^ii	−128.81 (16)	C14—C10—C11—P4	172.1 (3)
C10—P3—O9—Ca2^ii	118.48 (17)	P3—C10—C11—P4	−8.9 (5)
O11—P4—O10—Ca1	−52.1 (3)	O11—P4—C11—C9	−137.4 (4)
O12—P4—O10—Ca1	−178.8 (2)	O10—P4—C11—C9	95.9 (4)
C11—P4—O10—Ca1	71.2 (3)	O12—P4—C11—C9	−19.6 (4)
O10—P4—O11—Ca2^ii	32.3 (3)	Ca1—P4—C11—C9	124.5 (4)
O12—P4—O11—Ca2^ii	158.5 (2)	O11—P4—C11—C10	47.5 (4)
C11—P4—O11—Ca2^ii	−89.1 (3)	O10—P4—C11—C10	−79.2 (4)
Ca1—P4—O11—Ca2^ii	8.7 (2)	O12—P4—C11—C10	165.4 (4)
O1—P1—C1—C6	−135.0 (3)	Ca1—P4—C11—C10	−50.5 (4)
O3—P1—C1—C6	−11.2 (4)	C11—C9—C12—C13	0.9 (7)
O2—P1—C1—C6	105.7 (3)	C11—C9—C12—C15	−178.5 (5)
Ca1—P1—C1—C6	−165.9 (3)	C9—C12—C13—C14	−2.8 (7)
O1—P1—C1—C2	45.9 (4)	C15—C12—C13—C14	176.7 (5)
O3—P1—C1—C2	169.7 (4)	C9—C12—C13—C16	175.1 (5)
O2—P1—C1—C2	−73.4 (4)	C15—C12—C13—C16	−5.5 (7)
Ca1—P1—C1—C2	15.0 (4)	C12—C13—C14—C10	1.7 (7)
C6—C1—C2—C3	−3.9 (6)	C16—C13—C14—C10	−176.2 (4)
P1—C1—C2—C3	175.1 (3)	C11—C10—C14—C13	1.2 (7)
C6—C1—C2—P2	177.3 (3)	P3—C10—C14—C13	−177.9 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1X···O3^v	0.95	1.76	2.693 (4)	169
O1W—H1Y···N4^vi	0.95	2.06	3.004 (6)	178
O2W—H2X···O5W^i	0.95	1.79	2.725 (5)	167
O2W—H2Y···O12^vii	0.95	2.16	2.988 (5)	146
O3W—H3X···O11	0.95	1.76	2.696 (4)	171
O3W—H3Y···O10^ii	0.95	1.77	2.691 (4)	166
O4W—H4X···O1^i	0.95	1.82	2.747 (5)	167
O4W—H4Y···O8^v	0.95	2.04	2.785 (5)	135
O5W—H5X···O3W^viii	0.95	1.79	2.729 (5)	171
O5W—H5Y···N3^ix	0.95	1.93	2.860 (6)	166
O2—H2···O4W	0.95	1.56	2.499 (5)	171
O6—H6···O5W	0.84	1.79	2.600 (5)	162
O8—H8···O3^v	0.84	1.69	2.513 (4)	165
O12—H12···O3W^viii	0.84	1.76	2.596 (5)	171

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