One- and two-dimensional polymers from proline and calcium bromide

Reactions of calcium bromide with enanti­opure and racemic proline in aqueous solution lead to two solids in which the zwitterionic amino acid acts as a bridging ligand between neighbouring cations. Depending on the chirality of the amino acid, topologically very different products are obtained. With racemic proline, bromide acts as a simple uncoordinated counter-anion for the cationic heterochiral chains in catena-poly[[aqua­calcium(II)]-[mu]-aqua-[mu]₃-DL-proline-[mu]₂-DL-proline], {[Ca(C₅H₉NO₂)₂(H₂O)₂]Br₂}_n. In agreement with chemical intuition, only carboxyl­ate and aqua O atoms coordinate the alkaline earth cation in a low-symmetry arrangement. In contrast, L-proline affords the two-dimensional network poly[di­bromido­bis­([mu]₂-L-proline)calcium(II)], [CaBr₂(C₅H₉NO₂)₂]_n, with an unexpected CaBr₂ unit in a more regular coordination sphere.

Computing details

For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2008); data reduction: SAINT-Plus (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2015).

(1) catena-Poly[[aquacalcium(II)]-µ-aqua-µ₃-DL-proline-µ₂-DL-proline]

Crystal data

[Ca(C5H9NO2)2(H2O)2]Br2	F(000) = 936
Mr = 466.19	Dx = 1.861 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 13.5177 (13) Å	Cell parameters from 5444 reflections
b = 7.8151 (7) Å	θ = 2.3–30.2°
c = 16.3815 (16) Å	µ = 5.21 mm^−1
β = 105.988 (1)°	T = 100 K
V = 1663.6 (3) Å^3	Needle, colorless
Z = 4	0.26 × 0.10 × 0.09 mm

Data collection

Bruker d8 goniometer with an APEX CCD area detector diffractometer	4307 reflections with I > 2σ(I)
Radiation source: Incoatec microsource	Rint = 0.048
ω scans	θmax = 30.7°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −19→19
Tmin = 0.427, Tmax = 0.746	k = −11→10
24328 measured reflections	l = −23→23
4950 independent reflections

Refinement

Refinement on F^2	12 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.061	w = 1/[σ^2(Fo^2) + (0.022P)^2 + 0.9P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
4950 reflections	Δρmax = 0.66 e Å^−3
214 parameters	Δρmin = −0.44 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
Ca1	−0.03024 (3)	0.73199 (5)	−0.03630 (2)	0.00994 (8)
Br1	0.39471 (2)	0.09604 (3)	0.21768 (2)	0.01529 (6)
Br2	0.25796 (2)	0.51410 (3)	−0.14487 (2)	0.01390 (5)
O1	0.13614 (11)	0.71883 (18)	0.06342 (9)	0.0134 (3)
O2	0.17880 (11)	0.44177 (18)	0.09274 (9)	0.0133 (3)
C1	0.19681 (15)	0.5995 (3)	0.09691 (12)	0.0113 (4)
C2	0.30554 (15)	0.6591 (3)	0.14306 (12)	0.0116 (4)
H2	0.3027	0.7641	0.1772	0.014*
C3	0.36813 (16)	0.6948 (3)	0.07862 (13)	0.0157 (4)
H3A	0.3223	0.6991	0.0200	0.019*
H3B	0.4056	0.8047	0.0915	0.019*
C4	0.44328 (16)	0.5450 (3)	0.08921 (14)	0.0166 (4)
H4A	0.4103	0.4439	0.0564	0.020*
H4B	0.5052	0.5767	0.0714	0.020*
C5	0.46954 (16)	0.5122 (3)	0.18362 (14)	0.0167 (4)
H5A	0.5017	0.3984	0.1984	0.020*
H5B	0.5160	0.6014	0.2161	0.020*
N1	0.36515 (14)	0.5202 (2)	0.19917 (11)	0.0126 (3)
H1N	0.3719 (19)	0.542 (3)	0.2524 (11)	0.015*
H2N	0.3339 (18)	0.426 (2)	0.1853 (15)	0.015*
O3	0.07574 (11)	0.82890 (19)	−0.12582 (9)	0.0146 (3)
O4	0.05729 (11)	1.0672 (2)	−0.05780 (9)	0.0169 (3)
C6	0.10168 (15)	0.9775 (3)	−0.10027 (12)	0.0108 (4)
C7	0.19624 (15)	1.0570 (3)	−0.11861 (13)	0.0118 (4)
H7	0.1749	1.1590	−0.1562	0.014*
C8	0.27868 (16)	1.1100 (3)	−0.03832 (14)	0.0157 (4)
H8A	0.2658	1.2267	−0.0201	0.019*
H8B	0.2820	1.0289	0.0088	0.019*
C9	0.37676 (16)	1.1036 (3)	−0.06692 (15)	0.0195 (5)
H9A	0.3828	1.2062	−0.1007	0.023*
H9B	0.4384	1.0959	−0.0176	0.023*
C10	0.36426 (16)	0.9424 (3)	−0.12097 (14)	0.0164 (4)
H10A	0.4018	0.9525	−0.1648	0.020*
H10B	0.3898	0.8406	−0.0854	0.020*
N2	0.24971 (13)	0.9306 (2)	−0.16118 (11)	0.0125 (3)
H3N	0.2416 (19)	0.947 (3)	−0.2149 (11)	0.015*
H4N	0.2262 (18)	0.831 (2)	−0.1566 (15)	0.015*
O5	−0.03995 (11)	0.53197 (19)	0.08375 (9)	0.0119 (3)
H1W	−0.0034 (17)	0.555 (3)	0.1264 (12)	0.014*
H2W	−0.0915 (15)	0.516 (3)	0.0947 (16)	0.014*
O6	−0.15013 (11)	0.93335 (19)	−0.13128 (9)	0.0131 (3)
H3W	−0.140 (2)	1.023 (2)	−0.1128 (16)	0.016*
H4W	−0.2080 (13)	0.920 (3)	−0.1470 (15)	0.016*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ca1	0.00831 (17)	0.01124 (18)	0.01027 (18)	−0.00012 (14)	0.00258 (14)	−0.00103 (14)
Br1	0.01326 (10)	0.01502 (11)	0.01546 (10)	−0.00064 (7)	0.00038 (7)	−0.00028 (8)
Br2	0.01601 (10)	0.01203 (10)	0.01506 (10)	0.00101 (7)	0.00660 (8)	−0.00014 (7)
O1	0.0123 (7)	0.0132 (7)	0.0134 (7)	0.0022 (5)	0.0014 (5)	0.0011 (5)
O2	0.0118 (7)	0.0125 (7)	0.0153 (7)	−0.0013 (5)	0.0033 (6)	−0.0008 (6)
C1	0.0094 (8)	0.0156 (10)	0.0090 (8)	0.0002 (7)	0.0026 (7)	−0.0012 (7)
C2	0.0104 (9)	0.0120 (9)	0.0106 (9)	0.0006 (7)	0.0001 (7)	0.0004 (7)
C3	0.0143 (10)	0.0200 (11)	0.0131 (9)	−0.0012 (8)	0.0042 (8)	0.0027 (8)
C4	0.0143 (10)	0.0177 (10)	0.0188 (10)	−0.0032 (8)	0.0064 (8)	−0.0053 (8)
C5	0.0088 (9)	0.0191 (11)	0.0208 (11)	0.0004 (8)	0.0016 (8)	0.0005 (8)
N1	0.0126 (8)	0.0134 (9)	0.0102 (8)	−0.0012 (7)	0.0005 (6)	−0.0010 (7)
O3	0.0146 (7)	0.0110 (7)	0.0201 (7)	−0.0021 (6)	0.0081 (6)	−0.0001 (6)
O4	0.0139 (7)	0.0205 (8)	0.0170 (7)	0.0003 (6)	0.0053 (6)	−0.0064 (6)
C6	0.0101 (9)	0.0122 (9)	0.0092 (8)	0.0003 (7)	0.0011 (7)	0.0010 (7)
C7	0.0107 (9)	0.0104 (9)	0.0149 (9)	0.0003 (7)	0.0046 (7)	−0.0001 (7)
C8	0.0147 (10)	0.0121 (10)	0.0181 (10)	−0.0002 (8)	0.0006 (8)	−0.0017 (8)
C9	0.0120 (10)	0.0141 (10)	0.0293 (12)	−0.0009 (8)	0.0007 (9)	0.0003 (9)
C10	0.0098 (9)	0.0175 (10)	0.0224 (11)	0.0016 (8)	0.0052 (8)	0.0028 (8)
N2	0.0125 (8)	0.0121 (8)	0.0149 (8)	−0.0016 (6)	0.0070 (7)	0.0002 (7)
O5	0.0089 (7)	0.0154 (7)	0.0115 (7)	−0.0018 (6)	0.0028 (5)	−0.0015 (6)
O6	0.0104 (7)	0.0124 (7)	0.0154 (7)	−0.0020 (6)	0.0017 (6)	−0.0013 (6)

Geometric parameters (Å, º)

Ca1—O4^i	2.2984 (15)	C5—H5B	0.9900
Ca1—O2^ii	2.3894 (14)	N1—H1N	0.868 (16)
Ca1—O1	2.3903 (14)	N1—H2N	0.850 (16)
Ca1—O3	2.4360 (15)	O3—C6	1.251 (2)
Ca1—O6	2.4768 (16)	O4—C6	1.251 (2)
Ca1—O5^ii	2.4832 (15)	O4—Ca1^i	2.2984 (15)
Ca1—O5	2.5437 (15)	C6—C7	1.524 (3)
Ca1—O4	2.9355 (16)	C7—N2	1.504 (3)
Ca1—C6	2.998 (2)	C7—C8	1.528 (3)
Ca1—Ca1^ii	3.8334 (8)	C7—H7	1.0000
Ca1—Ca1^i	4.3698 (9)	C8—C9	1.524 (3)
O1—C1	1.263 (2)	C8—H8A	0.9900
O2—C1	1.255 (2)	C8—H8B	0.9900
O2—Ca1^ii	2.3894 (14)	C9—C10	1.523 (3)
C1—C2	1.528 (3)	C9—H9A	0.9900
C2—N1	1.505 (3)	C9—H9B	0.9900
C2—C3	1.549 (3)	C10—N2	1.509 (3)
C2—H2	1.0000	C10—H10A	0.9900
C3—C4	1.528 (3)	C10—H10B	0.9900
C3—H3A	0.9900	N2—H3N	0.865 (16)
C3—H3B	0.9900	N2—H4N	0.853 (16)
C4—C5	1.510 (3)	O5—Ca1^ii	2.4832 (15)
C4—H4A	0.9900	O5—H1W	0.758 (16)
C4—H4B	0.9900	O5—H2W	0.777 (16)
C5—N1	1.503 (3)	O6—H3W	0.762 (16)
C5—H5A	0.9900	O6—H4W	0.760 (16)
O4^i—Ca1—O2^ii	112.06 (5)	C2—C3—H3B	110.8
O4^i—Ca1—O1	82.22 (5)	H3A—C3—H3B	108.9
O2^ii—Ca1—O1	140.57 (5)	C5—C4—C3	102.00 (17)
O4^i—Ca1—O3	114.84 (5)	C5—C4—H4A	111.4
O2^ii—Ca1—O3	120.98 (5)	C3—C4—H4A	111.4
O1—Ca1—O3	79.98 (5)	C5—C4—H4B	111.4
O4^i—Ca1—O6	77.88 (5)	C3—C4—H4B	111.4
O2^ii—Ca1—O6	77.48 (5)	H4A—C4—H4B	109.2
O1—Ca1—O6	141.84 (5)	N1—C5—C4	101.52 (16)
O3—Ca1—O6	79.39 (5)	N1—C5—H5A	111.5
O4^i—Ca1—O5^ii	157.25 (5)	C4—C5—H5A	111.5
O2^ii—Ca1—O5^ii	76.09 (5)	N1—C5—H5B	111.5
O1—Ca1—O5^ii	79.02 (5)	C4—C5—H5B	111.5
O3—Ca1—O5^ii	74.40 (5)	H5A—C5—H5B	109.3
O6—Ca1—O5^ii	124.85 (5)	C5—N1—C2	107.24 (16)
O4^i—Ca1—O5	81.34 (5)	C5—N1—H1N	109.5 (17)
O2^ii—Ca1—O5	74.52 (5)	C2—N1—H1N	111.1 (17)
O1—Ca1—O5	71.61 (5)	C5—N1—H2N	109.8 (17)
O3—Ca1—O5	145.15 (5)	C2—N1—H2N	108.6 (17)
O6—Ca1—O5	135.39 (5)	H1N—N1—H2N	110 (2)
O5^ii—Ca1—O5	80.62 (5)	C6—O3—Ca1	104.14 (12)
O4^i—Ca1—O4	67.36 (6)	C6—O4—Ca1^i	160.85 (14)
O2^ii—Ca1—O4	141.66 (5)	C6—O4—Ca1	80.65 (12)
O1—Ca1—O4	77.64 (5)	Ca1^i—O4—Ca1	112.64 (6)
O3—Ca1—O4	47.70 (4)	O4—C6—O3	124.95 (19)
O6—Ca1—O4	64.73 (5)	O4—C6—C7	115.98 (17)
O5^ii—Ca1—O4	120.16 (5)	O3—C6—C7	119.04 (17)
O5—Ca1—O4	138.55 (5)	O4—C6—Ca1	75.03 (11)
O4^i—Ca1—C6	90.99 (6)	O3—C6—Ca1	51.99 (10)
O2^ii—Ca1—C6	138.23 (5)	C7—C6—Ca1	160.37 (13)
O1—Ca1—C6	74.22 (5)	N2—C7—C6	111.10 (16)
O3—Ca1—C6	23.87 (5)	N2—C7—C8	104.32 (16)
O6—Ca1—C6	73.92 (5)	C6—C7—C8	113.16 (17)
O5^ii—Ca1—C6	96.13 (5)	N2—C7—H7	109.4
O5—Ca1—C6	145.67 (5)	C6—C7—H7	109.4
O4—Ca1—C6	24.32 (5)	C8—C7—H7	109.4
O4^i—Ca1—Ca1^ii	119.83 (4)	C9—C8—C7	102.50 (17)
O2^ii—Ca1—Ca1^ii	70.56 (4)	C9—C8—H8A	111.3
O1—Ca1—Ca1^ii	70.56 (4)	C7—C8—H8A	111.3
O3—Ca1—Ca1^ii	111.73 (4)	C9—C8—H8B	111.3
O6—Ca1—Ca1^ii	147.41 (4)	C7—C8—H8B	111.3
O5^ii—Ca1—Ca1^ii	40.90 (3)	H8A—C8—H8B	109.2
O5—Ca1—Ca1^ii	39.73 (3)	C10—C9—C8	103.84 (17)
O4—Ca1—Ca1^ii	145.37 (3)	C10—C9—H9A	111.0
C6—Ca1—Ca1^ii	128.11 (4)	C8—C9—H9A	111.0
O4^i—Ca1—Ca1^i	38.32 (4)	C10—C9—H9B	111.0
O2^ii—Ca1—Ca1^i	136.42 (4)	C8—C9—H9B	111.0
O1—Ca1—Ca1^i	77.58 (4)	H9A—C9—H9B	109.0
O3—Ca1—Ca1^i	76.63 (4)	N2—C10—C9	103.91 (16)
O6—Ca1—Ca1^i	66.60 (4)	N2—C10—H10A	111.0
O5^ii—Ca1—Ca1^i	145.35 (4)	C9—C10—H10A	111.0
O5—Ca1—Ca1^i	115.11 (4)	N2—C10—H10B	111.0
O4—Ca1—Ca1^i	29.04 (3)	C9—C10—H10B	111.0
C6—Ca1—Ca1^i	52.91 (4)	H10A—C10—H10B	109.0
Ca1^ii—Ca1—Ca1^i	144.53 (2)	C7—N2—C10	108.90 (16)
C1—O1—Ca1	134.82 (13)	C7—N2—H3N	115.6 (17)
C1—O2—Ca1^ii	135.17 (13)	C10—N2—H3N	105.2 (17)
O2—C1—O1	127.49 (18)	C7—N2—H4N	108.8 (16)
O2—C1—C2	118.15 (17)	C10—N2—H4N	112.3 (17)
O1—C1—C2	114.27 (17)	H3N—N2—H4N	106 (2)
N1—C2—C1	111.27 (16)	Ca1^ii—O5—Ca1	99.38 (5)
N1—C2—C3	104.18 (16)	Ca1^ii—O5—H1W	106 (2)
C1—C2—C3	110.43 (16)	Ca1—O5—H1W	113.9 (19)
N1—C2—H2	110.3	Ca1^ii—O5—H2W	112.3 (19)
C1—C2—H2	110.3	Ca1—O5—H2W	121.4 (19)
C3—C2—H2	110.3	H1W—O5—H2W	103 (3)
C4—C3—C2	104.80 (17)	Ca1—O6—H3W	109 (2)
C4—C3—H3A	110.8	Ca1—O6—H4W	124 (2)
C2—C3—H3A	110.8	H3W—O6—H4W	108 (3)
C4—C3—H3B	110.8

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

(2) Poly[dibromidobis(µ₂-L-proline)calcium(II)]

Crystal data

[CaBr2(C5H9NO2)2]	F(000) = 856
Mr = 430.16	Dx = 1.852 Mg m^−3
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
a = 20.598 (4) Å	Cell parameters from 2371 reflections
b = 7.6790 (14) Å	θ = 3.0–24.5°
c = 9.7974 (17) Å	µ = 5.60 mm^−1
β = 95.553 (3)°	T = 100 K
V = 1542.4 (5) Å^3	Needle, colorless
Z = 4	0.21 × 0.11 × 0.10 mm

Data collection

Bruker d8 goniometer with an APEX CCD area detector diffractometer	3368 reflections with I > 2σ(I)
Radiation source: microsource	Rint = 0.045
ω scans	θmax = 28.0°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −27→27
Tmin = 0.557, Tmax = 0.746	k = −10→10
10314 measured reflections	l = −12→12
3717 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)] = 0.042	w = 1/[σ^2(Fo^2) + (0.050P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.098	(Δ/σ)max < 0.001
S = 1.03	Δρmax = 1.43 e Å^−3
3717 reflections	Δρmin = −0.79 e Å^−3
184 parameters	Absolute structure: Flack x determined using 1392 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons & Flack, 2004)
7 restraints	Absolute structure parameter: 0.053 (8)

Special details

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.

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

	x	y	z	Uiso*/Ueq
Br1	0.37540 (4)	1.09421 (9)	0.15097 (8)	0.02143 (19)
Br2	0.10606 (3)	1.00362 (10)	0.25148 (8)	0.02170 (19)
Ca1	0.24385 (7)	1.07014 (19)	0.24436 (14)	0.0139 (3)
O1	0.2716 (3)	0.9454 (7)	0.4504 (5)	0.0209 (12)
O2	0.2708 (3)	0.8369 (7)	0.6609 (5)	0.0211 (12)
C1	0.2904 (4)	0.9420 (10)	0.5743 (7)	0.0158 (15)
C3	0.4312 (4)	1.0180 (13)	0.7985 (8)	0.0256 (17)
H3A	0.4409	0.9220	0.8647	0.031*
H3B	0.4559	1.1229	0.8316	0.031*
C2	0.3396 (4)	1.0783 (11)	0.6270 (7)	0.0189 (15)
H2	0.3195	1.1961	0.6121	0.023*
C4	0.4476 (5)	0.9670 (15)	0.6575 (10)	0.041 (3)
H4A	0.4938	0.9928	0.6462	0.049*
H4B	0.4396	0.8413	0.6411	0.049*
C5	0.4034 (4)	1.0742 (15)	0.5621 (8)	0.034 (2)
H5A	0.3974	1.0203	0.4699	0.041*
H5B	0.4210	1.1932	0.5537	0.041*
N1	0.3596 (3)	1.0545 (9)	0.7784 (7)	0.0210 (15)
H1A	0.355 (5)	1.158 (7)	0.810 (9)	0.025*
H1B	0.329 (3)	1.018 (13)	0.825 (8)	0.025*
O3	0.2091 (3)	1.2300 (7)	0.0488 (5)	0.0168 (11)
O4	0.2576 (3)	1.3016 (7)	−0.1370 (5)	0.0171 (11)
C6	0.2177 (4)	1.2171 (9)	−0.0749 (7)	0.0150 (14)
C7	0.1793 (3)	1.0762 (11)	−0.1614 (7)	0.0153 (14)
H8	0.2095	0.9779	−0.1773	0.018*
C8	0.0625 (4)	1.0712 (17)	−0.1556 (9)	0.039 (3)
H9A	0.0524	1.1906	−0.1259	0.047*
H9B	0.0258	0.9932	−0.1391	0.047*
C9	0.0761 (4)	1.0679 (14)	−0.3068 (8)	0.034 (2)
H10A	0.0729	0.9483	−0.3445	0.041*
H10B	0.0456	1.1447	−0.3632	0.041*
C10	0.1457 (4)	1.1358 (10)	−0.3005 (8)	0.0232 (17)
H11A	0.1459	1.2644	−0.3072	0.028*
H11B	0.1683	1.0871	−0.3766	0.028*
N2	0.1246 (3)	1.0075 (10)	−0.0836 (6)	0.0183 (12)
H2A	0.119 (4)	0.898 (6)	−0.098 (9)	0.022*
H2B	0.123 (4)	1.028 (12)	0.003 (5)	0.022*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0230 (4)	0.0175 (4)	0.0243 (4)	0.0003 (3)	0.0049 (3)	0.0019 (3)
Br2	0.0191 (3)	0.0229 (4)	0.0238 (4)	0.0015 (3)	0.0057 (3)	0.0023 (3)
Ca1	0.0197 (7)	0.0097 (7)	0.0124 (6)	0.0002 (6)	0.0019 (5)	−0.0001 (5)
O1	0.032 (3)	0.018 (3)	0.012 (2)	−0.002 (2)	−0.001 (2)	0.000 (2)
O2	0.033 (3)	0.015 (3)	0.016 (3)	−0.003 (2)	0.005 (2)	0.006 (2)
C1	0.020 (4)	0.014 (3)	0.015 (3)	0.006 (3)	0.007 (3)	0.004 (3)
C3	0.023 (4)	0.029 (4)	0.024 (4)	0.005 (4)	−0.001 (3)	−0.002 (4)
C2	0.028 (4)	0.017 (3)	0.012 (3)	−0.004 (3)	0.001 (3)	0.000 (3)
C4	0.030 (5)	0.049 (7)	0.045 (6)	0.012 (5)	0.014 (4)	0.004 (5)
C5	0.038 (5)	0.047 (6)	0.020 (4)	−0.015 (5)	0.010 (3)	−0.002 (4)
N1	0.023 (3)	0.021 (4)	0.019 (3)	0.004 (3)	0.000 (3)	−0.008 (3)
O3	0.023 (3)	0.011 (2)	0.016 (3)	−0.001 (2)	0.002 (2)	0.003 (2)
O4	0.021 (3)	0.013 (2)	0.018 (3)	0.002 (2)	0.006 (2)	0.004 (2)
C6	0.018 (3)	0.009 (3)	0.018 (4)	0.004 (3)	0.002 (3)	0.004 (3)
C7	0.016 (3)	0.014 (3)	0.017 (3)	0.001 (3)	0.008 (3)	0.004 (3)
C8	0.022 (4)	0.071 (8)	0.025 (4)	0.004 (5)	0.002 (3)	0.012 (5)
C9	0.034 (5)	0.044 (6)	0.023 (4)	−0.001 (4)	−0.002 (3)	0.003 (4)
C10	0.029 (4)	0.018 (4)	0.023 (4)	−0.001 (3)	0.003 (3)	−0.007 (3)
N2	0.023 (3)	0.015 (3)	0.017 (3)	−0.006 (3)	0.005 (2)	0.000 (3)

Geometric parameters (Å, º)

Br1—Ca1	2.9485 (16)	C5—H5B	0.9900
Br2—Ca1	2.8914 (16)	N1—H1A	0.86 (4)
Ca1—O1	2.257 (5)	N1—H1B	0.86 (4)
Ca1—O2^i	2.281 (5)	O3—C6	1.246 (9)
Ca1—O4^ii	2.314 (5)	O4—C6	1.250 (9)
Ca1—O3	2.329 (5)	O4—Ca1^iv	2.314 (5)
O1—C1	1.239 (9)	C6—C7	1.544 (11)
O2—C1	1.264 (9)	C7—N2	1.515 (9)
O2—Ca1^iii	2.281 (5)	C7—C10	1.538 (11)
C1—C2	1.513 (11)	C7—H8	1.0000
C3—N1	1.495 (10)	C8—N2	1.483 (11)
C3—C4	1.505 (12)	C8—C9	1.535 (11)
C3—H3A	0.9900	C8—H9A	0.9900
C3—H3B	0.9900	C8—H9B	0.9900
C2—N1	1.512 (9)	C9—C10	1.520 (12)
C2—C5	1.514 (11)	C9—H10A	0.9900
C2—H2	1.0000	C9—H10B	0.9900
C4—C5	1.489 (14)	C10—H11A	0.9900
C4—H4A	0.9900	C10—H11B	0.9900
C4—H4B	0.9900	N2—H2A	0.86 (4)
C5—H5A	0.9900	N2—H2B	0.86 (4)
O1—Ca1—O2^i	92.8 (2)	H5A—C5—H5B	108.9
O1—Ca1—O4^ii	91.1 (2)	C3—N1—C2	108.9 (6)
O2^i—Ca1—O4^ii	171.5 (2)	C3—N1—H1A	105 (6)
O1—Ca1—O3	172.0 (2)	C2—N1—H1A	102 (7)
O2^i—Ca1—O3	79.58 (19)	C3—N1—H1B	129 (6)
O4^ii—Ca1—O3	96.11 (19)	C2—N1—H1B	115 (6)
O1—Ca1—Br2	93.87 (15)	H1A—N1—H1B	91 (9)
O2^i—Ca1—Br2	88.84 (15)	C6—O3—Ca1	134.2 (5)
O4^ii—Ca1—Br2	83.34 (14)	C6—O4—Ca1^iv	134.7 (5)
O3—Ca1—Br2	83.63 (14)	O3—C6—O4	126.4 (7)
O1—Ca1—Br1	98.25 (15)	O3—C6—C7	118.5 (6)
O2^i—Ca1—Br1	103.42 (15)	O4—C6—C7	115.0 (6)
O4^ii—Ca1—Br1	83.49 (14)	N2—C7—C10	104.9 (6)
O3—Ca1—Br1	85.98 (14)	N2—C7—C6	109.5 (6)
Br2—Ca1—Br1	162.24 (6)	C10—C7—C6	116.2 (6)
C1—O1—Ca1	156.0 (5)	N2—C7—H8	108.7
C1—O2—Ca1^iii	155.4 (5)	C10—C7—H8	108.7
O1—C1—O2	125.5 (7)	C6—C7—H8	108.7
O1—C1—C2	117.1 (6)	N2—C8—C9	102.9 (7)
O2—C1—C2	117.3 (6)	N2—C8—H9A	111.2
N1—C3—C4	103.6 (6)	C9—C8—H9A	111.2
N1—C3—H3A	111.0	N2—C8—H9B	111.2
C4—C3—H3A	111.0	C9—C8—H9B	111.2
N1—C3—H3B	111.0	H9A—C8—H9B	109.1
C4—C3—H3B	111.0	C10—C9—C8	102.4 (7)
H3A—C3—H3B	109.0	C10—C9—H10A	111.3
C1—C2—N1	111.2 (6)	C8—C9—H10A	111.3
C1—C2—C5	115.0 (7)	C10—C9—H10B	111.3
N1—C2—C5	104.1 (6)	C8—C9—H10B	111.3
C1—C2—H2	108.8	H10A—C9—H10B	109.2
N1—C2—H2	108.8	C9—C10—C7	106.0 (6)
C5—C2—H2	108.8	C9—C10—H11A	110.5
C5—C4—C3	104.7 (8)	C7—C10—H11A	110.5
C5—C4—H4A	110.8	C9—C10—H11B	110.5
C3—C4—H4A	110.8	C7—C10—H11B	110.5
C5—C4—H4B	110.8	H11A—C10—H11B	108.7
C3—C4—H4B	110.8	C8—N2—C7	107.2 (6)
H4A—C4—H4B	108.9	C8—N2—H2A	98 (6)
C4—C5—C2	104.5 (7)	C7—N2—H2A	111 (6)
C4—C5—H5A	110.8	C8—N2—H2B	107 (6)
C2—C5—H5A	110.8	C7—N2—H2B	122 (6)
C4—C5—H5B	110.8	H2A—N2—H2B	109 (9)
C2—C5—H5B	110.8

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